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XXVI. INTERNATIONAL CONFERENCE ON COORDINATION AND BIOINORGANIC CHEMISTRY Modern Trends in Coordination, Bioinorganic, and Applied Inorganic Chemistry June 4 – 9, 2017 Smolenice, Slovakia





www.iccbic.stuba.sk

Slovak Chemical Society Radlinského 9, 812 37 Bratislava Slovakia

Modern Trends in Coordination, Bioinorganic, and Applied Inorganic Chemistry M. Melník, P. Segľa, and M. Tatarko (Eds.) Book of Abstracts Monograph © 2017 by the Slovak Chemical Society. No part of this Book of Abstracts may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher. ISBN 978-80-89597-65-9 ISSN 1335-308X

This Book of Abstracts and USB-monograph contain the abstracts and full versions of contributions presented at the XXVI. International Conference on Coordination and Bioinorganic Chemistry organized by the Slovak Chemical Society, Slovak Academy of Sciences, and Slovak University of Technology in Bratislava, and held from June 4 to 9, 2017 in Smolenice Castle.

Abstracts of papers published in the Book of Abstracts are printed as submitted. Full papers published in USB-monograph were reviewed and the opinion of the referees was deciding for incorporating a paper into the monograph. The contributions have been edited by the editors only to the extent considered necessary and according to recommendations of the referees, naturally with the consent of the authors. The experimental data given in particular abstracts and/or papers, the conclusions expressed and the general style adopted remain, however, the responsibility of the named authors. Great care has been taken to maintain the accuracy of the information contained in the volume. However, neither Slovak Chemical Society nor the editors can be held responsible for errors, linguistic or numerical. Authors were themselves responsible for referring to appropriate and complete references and for obtaining the necessary permission to reproduce copyright materials and data from other sources.

PREFACE The XXVI. International Conference on Coordination and Bioinorganic Chemistry is organized in the Congress Centre of the Slovak Academy of Sciences in Smolenice Castle by the Slovak Chemical Society Slovak Academy of Sciences Slovak University of Technology in Bratislava

INTERNATIONAL ADVISORY BOARD Prof. Makoto FUJITA (Japan) Prof. Mario RUBEN (Germany) Dr. Floriana TUNA (United Kingdom)

ORGANIZING COMMITTEE Honour Chairman: Chairman: Secretary: Members:

Milan MELNÍK Peter SEGĽA Miroslav TATARKO Milan DRÁBIK Marian KOMAN Vladimír KUCHTANIN Ján PAVLIK Miroslava PUCHOŇOVÁ Jozef ŠVOREC Marián VALKO

This publication contains a complete scientific and social program. Moreover, the abstracts of the papers contributed to the Conference and presented as lectures and posters are contained in it and arranged in the alphabetical order according to the presenting authors. The name of the author presenting the contribution is underlined. At the end a list of authors is attached.

TIME TABLE SUNDAY, June 4, 2017 14:00 16:00 18:30 18:00 19:30

Reception in Smolenice castle Departure from Bratislava (bus 1) Departure from Bratislava (bus 2) Dinner 1 Dinner 2

MONDAY, June 5, 2017 7:15 9:00 9:15 – 12:30 12:45 14:30 – 18:00 19:00 19:30

Breakfast Opening Plenary session A Lunch Session A Official Ceremony Get-together Party

TUESDAY, June 6, 2017 7:15 8:15 – 12:30 11:30 – 12:30 12:45 14:30 – 17:45 18:00

Breakfast Plenary session C Session C Lunch Session B Dinner

WEDNESDAY, June 7, 2017 7:15 8:15 – 12:30 12:30 13:25 13:30 – 17:30 18:00 20:00 – 21:30

Breakfast Plenary session B Lunch Photography Excursion Dinner Poster Session

THURSDAY, June 8, 2017 7:15 8:15 – 11:45 12:45 14:00 – 16:50 16:50 19:00 20:00

Breakfast Plenary session D Lunch Young session Closing Banquet and Farewell Party Concert

FRIDAY, June 9, 2017 7:15 8:00 9:00

Breakfast Departure (bus 1) Departure (bus 2)

XXVI. INTERNATIONAL CONFERENCE ON COORDINATION AND BIOINORGANIC CHEMISTRY

SCIENTIFIC PROGRAM MONDAY, June 5, 2017 9.00

Opening (Room 1)

9.15 – 12.30

Plenary Session A ELECTRONIC, MOLECULAR, AND CRYSTAL STRUCTURES

Room 1

Part 1

9:15 – 10:00

M. Fujita (Japan)  42 Coordination self-assembly: from the origins to the latest advances

Chairman: M. Melnik

10:00 – 10:30 M. Handa (Japan)  45 Synthesis, structure, and properties of a lantern-type dinuclear rhodium(II) complex cis-[Rh2(4-Me-pf)2(O2CCMe3)2], 4-Me-pf– = N,N’-di-p-tolylformamidinate anion 10:30 – 11:00 Room 1

Coffee break Part 2

Chairman: M. Fujita

11:00 – 11:30 O. Kovalchukova (Russia)  57 Features of molecular and electronic structures of complex compounds derived from azopyrazolone derivatives 11:30 – 12:00 T. Wu (Czech Republic)  127 Detection of lanthanide circularly polarized luminescence by Raman optical activity instrumentation and its applications 12:00 – 12:30 P. Baran (USA) Structural diversity of copper(II) complexes derived from various coordination modes of imidazoledioxide

 21

14.30 – 18.00 Session A ELECTRONIC, MOLECULAR, AND CRYSTAL STRUCTURES Room 1

Part 1

Chairman: M. Handa

14:30 – 14:45 J. Krzystek (USA) Understanding single-ion molecular magnetism

7

 61

14:45 – 15:00 F. Conan (France)  35 Rationalization of the spin crossover (SCO) behavior in polypyridyl-based iron(II) complexes 15:00 – 15:15 M. Breza (Slovakia) QTAIM studies of biomimetic trigonal iron(IV) nitrido and imido

 27

15:15 – 15:30 M. Gall (Slovakia) Agostic Cu-H interaction – charge density study of bis(clonixato) bis(imidazole)copper(II) complex

 43

15:30 – 15:45 J. Pavlik (Slovakia) Magnetic exchange interaction transmitted by H-bonds

 84

15:45 – 16:15 Room 1

Coffee break Part 2

Chairman: P. Baran

16:15 – 16:30 G. Ondrejovič (Slovakia) Advanced structural analysis of coordination Cu4OX6L4 molecules

 82

16:30 – 16:45 K. Ogasawara (Japan)  81 Multidimensional multiplet energy diagrams for Cr 3+ in oxides based on first-principles calculation 16:45 – 17:00 M. Lawson (Slovakia) Study of copper(II) complexes with quercetin and rutin

 65

17:00 – 17:15 P. Segľa (Slovakia)  98 Structural, spectral and magnetic properties of copper(II) furan- and thiophencarboxylates: different coordination modes of 3- and 4-pyridinemethanol 17:15 – 17:30 J. Švorec (Slovakia)  107 A study of nitrobenzoatocopper(II) complexes with N-methylnicotinamide 17:30 – 17:45 J. Moncoľ (Slovakia)  78 Structurally diverse manganese(III)-salen complexes with bridging formate ligand 17:45 – 18:00 M. Koman (Slovakia)  56 Structural study of the three new groups Mn(III) and Fe(III) dipicolinate complexes

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TUESDAY, June 6, 2017 8.15 – 12.30

Plenary Session C APPLIED INORGANIC AND COORDINATION CHEMISTRY

Room 1

Part 1

8:15 – 9:00

M. Ruben (Germany)  92 If coordination chemistry meets quantum physics: metal complexes as nuclear spin qubits

9:00 – 9:30

A. Taglietti (Italy)  116 Inorganic nanochemistry for biomedical applications: going for silver and gold

9:30 – 10:00

F. Camerel (France)  30 NIR-Photothermal properties of nickel-bis(dithiolene) complexes: Cancer therapy, photoresponsive gels and photocontrolled drug release

Chairman: M. Swart

10:00 – 10:30 P. Sobota (Poland)  103 Heterometallic nanomaterials with hierarchical structure for special applications in materials engineering: design, synthesis and research 10:30 – 11:00 Room 1

Coffee break Part 2

Chairman: M. Ruben

11:00 – 11:30 M. Swart (Spain) The inner side of high-valent metal-oxo reactivity

 108

11:30 – 11:45 M. Drábik (Slovakia)  36 Strength and limitations of thermoanalytical research in materials and solid state chemistry 11:45 – 12:00 S. Muráth (Hungary)  79 Synthesis of layered double hydroxides in the presence of long-chained alcohols – structural characterization 12:00 – 12:15 K. Musza (Hungary)  80 The effect of the experimental parameters on the formation of Cu/Cu 2O nanoparticles 12:15 – 12:30 M. Szabados (Hungary) Mechanochemical synthesis of zinc aluminate spinel

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 111

11.30 – 12.30 Session C APPLIED INORGANIC AND COORDINATION CHEMISTRY Room 2

Chairman: P. Sobota

11:30 – 11:45 I. Šalitroš (Slovakia)  94 Photoactive spin-crossover iron(II) complexes with tridentate N-donor ligands 11:45 – 12:00 J. Titiš (Slovakia)  119 Metal complexes as units for spintronic devices: the quest for singlemolecule magnets 12:00 – 12:15 G. Varga (Hungary) Co(II)-amino acid–CaAl-layered double hydroxide composites – construction and characterization

 122

12:15 – 12:30 M. El-Khateeb (Jordan)  39 [FeFe]-hydrogenase models: synthesis, characterization and catalytic activity of diselenolato diiron complexes 14.30 – 17.45 Session B SOLUTION AND SOLID STATE REACTIVITY Room 1

Chairman: R. Boča

Part 1

14:30 – 14:45 S. Hsu (Taiwan)  48 Reactivity study of unsymmetrical ß-diketiminato copper(I) and zinc(II) complexes: effect of chelating ring 14:45 – 15:00 A. Bieńko (Poland) Homo and heterometallic molecular magnetic materials

 23

15:00 – 15:15 M. Bortoluzzi (Italy)  25 The conjugate base of malonaldehyde as antenna-ligand towards trivalent europium and terbium ions 15:15 – 15:30 V. Kuchtanin (Slovakia)  62 Nickel (II) Schiff base complexes: synthesis, characterization and magnetic properties Room 1

Chairman: G. Knör

Part 2

15:30 – 15:45 S. Kuznetsov (Russia)  64 The composition of the second coordination sphere and intervalence charge transfer for the Ti(IV)/Ti redox couple in chloride-fluoride melts 15:45 – 16:00 I. U. Khan (Pakistan)  53 3D heterometallic gadolinium(III)-sodium(I) and cerium(III) six-membered ring derived from pyridine-2,6-dicarboxylic acid

10

16:00 – 16:15 R. Khattak (Pakistan)  54 Thermodynamic aspect: kinetics of the reduction of dicyanobis(phen)iron(III) by acetylferrocene and methylferrocenemethanol 16:15 – 16:30 B. Kutus (Hungary)  63 Trinuclear complex formation between Ca2+ and L-gulonate ions in strongly alkaline medium 16:30 – 17:00 Room 1

Coffee break Part 3

Chairman: J. Krysztek

17:00 – 17:15 Á. Buckó (Hungary)  28 Temperature dependence of proton dissociation and complexation processes in the Ca2+/gluconate system under hyperalkaline conditions 17:15 – 17:30 C. Dudás (Hungary)  37 Acid-base properties and calcium complexation of α-ketoglutarate in strongly alkaline aqueous solutions 17:30 – 17:45 R. Mészáros (Hungary)  75 Characterization and a potential catalytic application of a novel silverbismuth composite 14.30 – 17.45 Session B SOLUTION AND SOLID STATE REACTIVITY Room 2

Part 1

Chairman: M. Mikuriya

14:30 – 14:45 T. Pintauer (USA)  85 Copper(I)-cyanide frameworks through thermal or photo decomposition of the free radical diazo initiator AIBN 14:45 – 15:00 J. C. Swarts (South Africa)  109 Carbon monoxide hydrogenation and polymerization reactions catalyzed by iron particles supported on two-dimensional silicon wafers and generated from [Cu(FcCOCHCOR)2] 15:00 – 15:15 A. Szorcsik (Hungary) Metal ion binding of TACH-based polydentate tripodal ligands 15:15 – 15:30 M. Puchoňová (Slovakia) New different salicylatocopper(II) complexes with isonicotinamide

11

 113  88

Room 2

Part 2

Chairman: P. Sipos

15:30 – 15:45 A. Burdukov (Russia)  29 Phenanthroline-decorated iron(II) clathrochelates as ligands towards other metals 15:45 – 16:00 M. Vershinin (Russia)  124 Decorating iron(II) clathrochelates with different functional groups 16:00 – 16:15 S. Ziegenheim (Hungary)  129 Cu(II)Cr(III)-LDH ‒ synthesis, characterization, intercalation properties and a catalytic application 16:15 – 16:30 Z. Timár (Hungary)  118 Intercalation of CaAl-layered double hydroxide with benzoate or acetate ion 16:30 – 17:00 Room 2

Coffee break Part 3

Chairman: F. Conan

17:00 – 17:15 M. Mazúr (Slovakia)  72 EPR spectroscopy of TEOS-based sol-gel process. An “U-spectra” type of Gd(III) EPR spectra analysis 17:15 – 17:30 R. Šípoš (Slovakia) New insight into Jablonski diagram

 101

17:30 – 17:45 F. Matyuska (Hungary)  71 Transition metal complexes of mono- and trisubstituted tren-derivatives

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WEDNESDAY, June 7, 2017 8.15 – 12.30

Plenary Session B SOLUTION AND SOLID STATE REACTIVITY

Room 1

Part 1

8:15 – 9:00

F. Tuna (United Kingdom) Quantum information with molecular nanomagnets

9:00 – 9:30

R. Boča (Slovakia) Recent progress in single-ion magnets: Co(II), Ni(II) and Cu(II)

 24

9:30 – 10:00

G. Knör (Austria) Photochemical enzyme models – state of the art

 55

Chairman: A. Taglietti  120

10:00 – 10:30 E. Lodyga-Chruscinska (Poland) Physicochemical properties and biological activity of naringenin thiosemicarbazone 10:30 – 11:00 Room 1

 66

Coffee break Part 2

Chairman: F. Tuna

11:00 – 11:30 F. Mohr (Germany) Reactivity of coordinated azides

 77

11:30 – 12:00 P. Sipos (Hungary)  100 Calcium complexation processes in hyperalkaline aqueous solutions 12:00 – 12:30 M. Mikuriya (Japan) Trinuclear mixed-valent manganese complex with non-Schiff-base tetradentate ligand showing a ferromagnetic coupling

 76

20.00 – 21.30 Poster Session 01

M. Almáši (Slovakia)  20 Non-equilibrium synthetic methods in the preparation of porous coordination polymers for gas adsorption and catalysis

02

S. Berdyugin (Russia) Substitution of chloride to hydroxide ligands in [RhCl6]3–

03

L. Chruscinski (Poland)  33 Potentiometric, voltammetric and spectroscopic studies of fisetin and its copper complexes

04

K. Dysz (Poland)  38 5-Bromo-7-azaindole complexes with Pt(II) and Pd(II): synthesis, vibrational spectroscopy and DFT calculations 13

 22

05

V. Farkasová (Slovakia)  41 Synthesis, crystal structure and cytotoxicity of zinc(II) complexes with quinolin-8-ol chloroderivatives

06

G. Henkel (Germany)  46 Phenanthroline - guanidine hybrid ligands: mimics of the cytochrome-c-to-CuA electron transport chain within cytochrome-c oxidase

07

J. Juráková (Slovakia)  52 Synthesis, structural and magnetic investigation of Co(II) coordination compounds with tridentate aromatic pyridine ligand

08

D. Krajčiová (Slovakia) Synthesis optimisation of selected ligands used in copper (II) complexes

09

A. Lükőová (Slovakia)  68 Synthesis, characterization and anticancer properties of Pd(II) ionic complexes with quinolin-8-ol halogenderivatives

10

C. Rajnák (Slovakia)  90 Field supported slow magnetic relaxation in hexacoordinate Co(II) complexes with easy plane anisotropy

11

E. Samoľová (Slovakia)  95 The study of heterobimetallic Cu(II)-Mn(II) compounds with N-derivatives of cyclam

12

A. Scrivanti (Italy)  97 Synthesis and characterization of yttrium, europium, terbium and dysprosium complexes containing a novel type of triazolyl-oxazoline ligand

13

A. Starikov (Russia)  104 Dispersion interactions in oligomerization of metal diketonates: quantum chemical calculations

14

S. Stoykova (Bulgaria)  106 M2L4 coordination nano-capsules as supramolecular hosts with guest-tunable anticancer activity

15

M. Tatarko (Slovakia) Manganese complexes with derivatives of pyridinecarboxylic acids

16

L. Xu (China)  128 Synthesis, structure and magnetic property of a tungstoantimonite cobalt(II) complex with 1-methylimidazole ligands

14

 60

 117

THURSDAY, June 8, 2017 8.15 – 11.45

Plenary Session D COMPLEXES IN HUMAN MEDICINE AND THE ENVIRONMENT

Room 1

Part 1

8:15 – 8:45

M. Melnik (Slovakia) Copper complexes as perspective cancerostatic drugs

8:45 – 9:15

Y. Hisaeda (Japan)  47 Bioinspired catalyst with vitamin B12 functions activated by photochemical or electrochemical methods

9:15 – 9:45

M. Tacke (Ireland)  115 Coinage metal NHC complexes as novel antibiotics and anticancer drugs

9:45 – 10:15

M. Saphier (Israel) The redox qqueous chemistry of CuII/IATP

10:15 – 10:45 Room 1

Chairman: F. Mohr  73

 96

Coffee break Part 2

Chairman: M. Tacke

10:45 – 11:00 B. Gyurcsik (Hungary)  44 Studying protein interactions through their metal ion binding properties by CD spectroscopy 11:00 – 11:15 I. Pantcheva (Bulgaria) Rare earth metal complexes of polyether ionophores

 83

11:15 – 11:30 I. Potočňák (Slovakia)  87 Structures and in vitro cytotoxic properties of Pd(II) complexes with 7bromo-quinolin-8-ol 11:30 – 11:45 Z. Vargová (Slovakia) Complexing properties of 2-pyridinephosphonic acid

15

 123

14.00 – 16.50 Young Session Room 1

Part 1

Chairman: M. Drabik

14:00 – 14:10 A. A. Ádám (Hungary) Synthesis and characterization of nickel nanoparticles

 19

14:10 – 14:20 P. J. Swarts (South Africa)  110 Electrochemical and computational studies on β-diketonato, β-diketoester and β-diketoamido [Rh(FcCOCHCOR)(cod)] complexes 14:20 – 14:30 J. Koziskova (Slovakia)  59 Charge density study of halogen-halogen interactions in Palladium(II) complex 14:30 – 14:40 S. Matejová (Slovakia)  70 Crystal structure of Ni(II) complexes synthetized with 4-methylpiperidine and tridentate Shiff base 14:40 – 14:50 I. Puškárová (Slovakia) DFT studies of the effectiveness of p-substituted diphenyl amine antioxidants through their Cu(II) coordination ability

 89

14:50 – 15:00 A. Starikova (Russia)  105 Computational design of magnetically active trinuclear heterometallic complexes on the basis of 1,3,5-triazapentadiene ligands 15:00 – 15:30 Room 1

Coffee break Chairman: I. Potočňák

Part 2

15:30 – 15:40 M. Szczepańska (Poland) Theoretical investigation of photochemical properties of palladium(II)corrin

 112

15:40 – 15:50 F. Varga (Slovakia)  121 Slow magnetic relaxation in a Co(II) octahedral-tetrahedral system formed of a [CoL3]2+ core with L = bis(diphenylphospanoxido)methane and tetrahedral [CoBr4]2– counter anion 15:50 – 16:00 L. Smolko (Slovakia)  102 Tetracoordinate Co(II) complexes with neocuproine: SMMs with potential biological activity 16:00 – 16:10 K. Ciura (Poland)  34 Photochemistry of 4-ethylphenylcobalamin, an antivitamin B12. DFT study. 16:10 – 16:20 Z. Fábián (Hungary) Structural activation of NColE7-based artificial metallonucleases

16

 40

16:20 – 16:30 M. Jakubowski (Poland)  51 Novel dicarboxylato platinum(II) complexes as potential anticancer agents 16:30 – 16:40 J. P. Mészáros (Hungary) Half-sandwich rhodium(III) complexes formed with (N,N) ligands: structural characterization and solution chemistry

 74

16:40 – 16:50 H. Repich (Ukraine)  91 Pi-coordination compounds of Pd(II) and Pt(II) as potential substitutes of cisplatin and its analogues 14.00 – 16.40 Young Session Room 2

Part 1

Chairman: Y. Hisaeda

14:00 – 14:10 B. Brachňaková (Slovakia)  26 The mononuclear Co(II) complexes as a potential single-molecule magnets 14:10 – 14:20 Y.-CH. Huang (Taiwan)  49 Stepwise and self-assembly synthesis of tetranuclear iron–thiolate– diisocyanide metallocyclophane complexes 14:20 – 14:30 Y.-L.Chang (Taiwan)  31 Steric and electronic control on the nitrite reduction of the bio-inspired Copper(I)-nitro complexes 14:30 – 14:40 D. Lomjanský (Slovakia)  67 Structure and magnetism of potential single-ion magnets based on Ni(II) and Co(II) complexes 14:40 – 14:50 P. Masárová (Slovakia)  69 Copper(II) dipicolinate compounds of potential catecholase activity 14:50 – 15:00 L. Pogány (Slovakia) Spin crossover and high spin iron(III) Schiff base complexes 15:00 – 15:30 Room 2

 86

Coffee break Part 2

Chairman: M. Mikuriya

15:30 – 15:40 M. Chegerev (Russia)  32 Theoretical and experimental investigation of redox-isomerism in 14th group bis-chelates 15:40 – 15:50 Y. Koyama (Japan)  58 Mixed-valent tetranuclear manganese complexes with pentadentate Schiffbase ligands having a Y-shaped core 15:50 – 16:00 F. Sibilla (Italy)  99 Reactions of azines with half-sandwich osmium complexes: preparation of metalated derivatives 17

16:00 – 16:10 M. Szpak (Poland)  114 Coordination abilities of N-methyl alkylaminomethane-1,1-diphosphonic acids towards zinc(II), magnesium(II) and calcium(II) metal ions. Equilibrium studies in aqueous solutions. 16:10 – 16:20 T. Hung (Hungary) Complexation characteristics of a thionated cyanoxime ligand

 50

16:20 – 16:30 A. Vráblová (Slovakia)  125 Solid solvates of a NiII Schiff base complex and its reactivity towards GdIII 16:30 – 16:40 S. Werner (Germany) Towards new organometallic antimalarial drugs

16.50

Closing (Room 1)

18

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis and characterization of nickel nanoparticles A. A. Ádám, K. Musza, M. Szabados, P. Sipos, I. Pálinkó Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-6720 Hungary  Prof. István Pálinkó, e-mail: [email protected], Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720 Hungary

Many research groups synthesized nanoparticles by the polyol process, but Au, Au-Pd core-shell nanoparticles and nanosized α-nickel hydroxide have been prepared successfully by the sonochemical method. Sonochemistry provides a route to materials without the need for long reaction time, high reaction temperature or pressure. The aim of this work was to prepare size-controlled nickel nanoparticles by applying ultrasound radiation of varying frequencies. Previously, nickel nanoparticles (NiNPs) were prepared by hydrazine reduction under wet chemical conditions; however, in our hands, nickel-chloride was reduced by hydrazine under ultrasound irradiation. During the reaction, room temperature was maintained and 2 h of sonication time was needed until the solution became dark. The obtained nanoparticles were characterized by XRD (X-ray diffractometry), SEM (scanning electron microscopy), EDX (energy-dispersive X-ray analysis) and TEM (transmission electron microscopy). The powder XRD diffractograms showed typical of (fcc) NiNPs and the shapes of the nanoparticles were studied by TEM. SEM results showed monodispersed system.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Non-equilibrium synthetic methods in the preparation of porous coordination polymers for gas adsorption and catalysis M. Almáši, V. Zeleňák Department of Inorganic Chemistry, Faculty of Science, P. J. Šafárik University, Moyzesova 11, 041 54 Košice, Slovak Republic  MSc. Miroslav Almáši, PhD.; [email protected]; Department of Inorganic Chemistry, Faculty of Science, P. J. Šafárik University, Moyzesova 11, 041 54 Košice, Slovak Republic

Non-equilibrium synthetic techniques such as hydro/solvothermal synthesis performed under autogenous pressure are frequently used in the preparation of porous solid materials called metal-organic frameworks (MOFs). These materials are constructed by three-dimensional porous polymeric framework, which consists of the inorganic building units (connectors), bridged by organic ligands (linkers). High porosity and high specific surface area of MOFs lead to many potential applications in gas storage and separation, ion exchange, catalysis, sensor technology and drug delivery. In our work, we have successfully prepared and characterized several MOFs constructed from tetrahedral linker, methanetetracarboxylic acid in combination with inner-transition metal ions. Materials were tested as adsorbents for carbon dioxide, methane or hydrogen. The results showed on the high adsorption capacities of MOFs toward to selected probes. These compounds were also tested as catalysts in Knoevenagel condensation of different bulky aldehydes with active methylene compounds and provide high catalytic activity, without significant loss in activity after several catalytic runs. Described interesting results of adsorption and catalytic measurements will be presented more in detail. Acknowledgement: Financial support was provided by KEGA 002UPJŠ-4/2015, VEGA 1/0745/17 and VVGS-2016-249.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Structural diversity of copper(II) complexes derived from various coordination modes of imidazoledioxide P. Baran, C. Taylor, A. Kensinger, N. Morgan, Y. Wojciechowski, D. Vu Juniata College, 1700 Moore Street, Huntingdon, PA 16652, USA  Prof. Peter Baran, PhD; [email protected]; 1700 Moore Street, Huntingdon, PA 16652, USA

3-Hydroxyimidazole-1-oxide is synthesized in high yield via condensation of glyoxal (1 equiv) with formaldehyde (1 equiv) and hydroxylammonium chloride (2 equiv). Upon reaction with chloride, nitrate, acetate, or sulfate salts of copper(II), it gets readily deprotonated and acts as an anionic bidentate ligand. Imidazoledioxide binds to metal cation in three different coordination modes. Each of the two oxygen donor atoms is capable of coordinating to one metal in a terminal fashion or two metal centers in a bridging mode. One or two of these bridging modes are observed in each of the seven crystallographically characterized copper(II) complexes which will be presented.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Substitution of chloride to hydroxide ligands in [RhCl6]3– S. Berdyugin, D. Vasiľchencko Nikolaev Institute of Inorganic Chemistry, Acad. Lavrentiev Ave.,3, Novosibirsk, 630090, Russia  Semen Berdyugin; [email protected]; Acad. Lavrentiev Ave.,3, Novosibirsk, 630090, Russia

Rhodium(III) chlorocomplexes was found to react with concentrated alkali solution forming quantitatively (according to potentiometric analysis of chloride content) hexahydroxorodiate(III) anion. Time dependence of optical density at 523 nm (minimum of absorption for [Rh(OH)6]3- and maximum for [RhCl6]3–) of potassium hexachlororhodiate(III) alkali solution was used to study the rate of the substitution [RhCl6]3–  [Rh(OH)6]3–. This reaction was found to proceed in 2 stages. The first and rate determines stage is substitution reaction [RhCl6]3–  [RhCl5(OH)]3–. Its activation energy of 110 kJ·mol–1 is in a good agreement with determined earlier activation energy of [RhCl6]3- hydration. The second observed stage is rapid substitution of the remaining chloride ligands in [RhCl5(OH)]3– which leads to formation of [Rh(OH)6]3–. This process is much faster than the first stage (10–15 times) which may correspond to labilization influence of hydroxide ligand. Homoleptic rhodium hydroxocomplex was isolated in solid phase as Sr3[Rh(OH)6]2 with strontium nitrate. This salt is isostructural to hydrogarnet type minerals according to X-ray diffraction. The catalytic activity of rhodium hydroxocomplex intercalated into brucite was studied on α-pinene oxidation reaction.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Homo and heterometallic molecular magnetic materials A. Bieńko, bD. Bieńko

a

a

Faculty of Chemistry, University of Wroclaw,14 F. Joliot - Curie, 50-383 Wroclaw, Poland Faculty of Chemistry, Wroclaw University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wroclaw, Poland b

 [email protected]

The main goal of our project is the synthesis and characterization by means of physicochemical methods of new multifunctional molecular magnetic materials with the highest possible temperature of transition to a state of long-range magnetic ordering. High magnetic anisotropy, characterized by the axial zero-field splitting parameter D and high – spin ground state are indispensable conditions to observe SMMs or SCMs behavior. However, even if suitable condition have been met the obtained compounds still exhibit too low blocking temperature TB. Thus, the synthesis and identification of new compounds being the candidates for molecular magnets is continually current challenge. At the first stage we synthetized mono-, di- and trinuclear compounds containing CoII or NiII ions to obtain the structures with relatively large values of D (ZFS). Significant results have been obtained for the Imidazolium Based OrganicInorganic Hybrids [C3N2H5]2[CoCl4]. The theoretical analysis of DC magnetic data revealed that this complex is highly anisotropic with a large value of D = –12 cm–1, which implies that the ground state is the ( 3/2). Therefore the magnetization possesses an easy axis as displayed by the 3D-diagram . The AC susceptibility as a function of frequency showed three peaks, proving a coexistence of three relaxation processes. At the next step we synthetized and study a) heterometallic multi-metal-core molecular materials with 3d elements, Ni3Fe2, Cu3Cr2, Ni3Cr2, constructing 3D networks or 2D layers (NiFe)Ni and exhibit slow relaxation proces, b) the complexes with 4f and 3d elements forming the heterometallic, NiIILnIII or CoII LnIII frameworks of different topology. The 4f electron metal have large angular orbital moment and a great plasticity of the coordination geometry what results in a large magnetic anisotropy, greater than in case of the compounds with d-electron metals. Project supported by Wroclaw Centre of Biotechnology, programme The Leading National Research Centre (KNOW) for years 2014-2018.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Recent progress in single-ion magnets: Co(II), Ni(II) and Cu(II) R. Boča University of SS Cyril and Methodius, Department of Chemistry, 91701 Trnava, Slovakia  Prof. Roman Boča; [email protected]; as above

Single molecule magnets (SMMs) based upon mononuclear tetra-, penta- and hexacoordinate Co(II) complexes are reported in detail. They exhibit a slow magnetic relaxation with a single, double or three relaxation channels. Some of them exhibit SMM behavior in the absence of magnetic field but majority of them are field supported SMMs. The effect of the magnetic field lies in preventing a fast magnetic tunneling among components of the spin-orbit multiplets as well as in formation of microdomains (finite chains, plates of blocks) in the solid state that disintegrate to monomers on heating. Completely novel is the discovery of the SMM behaviour in S = 1 and S = 1/2 spin systems [1, 2]. [1] J. Miklovič, D. Valigura, R. Boča, J. Titiš: Dalton Trans. 44 (2015) 12484. Mononuclear Ni(II) Complex: A Field Induced Single-Molecule Magnet Showing Two Slow Relaxation Processes. [2] R. Boča, C. Rajnák, J. Titiš, D. Valigura, Inorg. Chem. 56 (2017). Field Supported Slow Magnetic Relaxation in a Mononuclear Cu(II) Complex. 10.1021/acs.inorgchem.6b02535.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

The conjugate base of malonaldehyde as antenna-ligand towards trivalent europium and terbium ions a

M. Bortoluzzi, aA. Reolon, aA. Scrivanti, a,b,cF. Enrichi

Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Via Torino 155, 30170 Mestre (Ve), Italy b Museo Storico della Fisica e Centro Studi e Ricerche Enrico Fermi, Piazza del Viminale 1, 00184 Roma, Italy c Division of Materials Science, Department of Engineering Sciences and Mathematics, Luleå University of Technology, 971 87 Luleå, Sweden a

 Dr. Marco Bortoluzzi; e-mail: [email protected]

-diketonate lanthanide complexes are deeply investigated luminescent lanthanide compounds. Despite the comparable structure, the conjugate bases of β-dialdehydes have been less investigated as antenna-ligands towards lanthanide ions. In 2014 we reported the syntheses of some lanthanide complexes with the conjugate bases of nitromalonaldehyde (NMA) and bromomalonaldehyde (BrMA). Noticeable luminescence was exhibited by trivalent europium derivatives, and europium BrMA complexes showed metal-centered redox processes which allowed the electrochemical tuning of photoluminescence. In this communication we report the synthesis of new yttrium, europium and terbium complexes with the conjugate base of malonaldehyde (MA). Coordination compounds having formulae [M(MA)3]n and M(MA)(Me2Tp)2 (M = Y, Eu, Tb; MA = conjugate base of malonaldehyde; Me2Tp = tris(3,5-dimethyl-pyrazol-1-yl)borate) have been isolated. By comparing the herein reported photoluminescence data with those relative to analogous NMA and BrMA derivatives it appears that MA is a more efficient antennaligand for the sensitization of Tb(III) luminescence. The experimental data have been rationalized of the basis of DFT calculations.

25

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

The mononuclear Co(II) complexes as a potential single-molecule magnets B. Brachňaková, I. Šalitroš Institute of Inorganic Chemistry, Technology and Materials, Faculty of Chemical and Food Technology, Slovak University of Technology, SK-81237 Bratislava, Slovakia  Ing. Barbora Brachňaková; e-mail: [email protected]; Department of Inorganic Chemistry, Technology and Materials, Institute of Inorganic Chemistry, Slovak University of Technology, Radlinskeho 9, SK-81237 Bratislava, Slovakia

The field induced single molecule magnetism behavior was observed in new Co(II) complexes coordinated by a heterocyclic tridentate N, N´- donor ligands (L3 = 2,6bis(1-(3,5-ditertbutylbenzyl)-1H-benzimidazol-2-yl) pyridine) which create different coordination sphere. The direct-current measurements of magnetic susceptibility and magnetization confirm the paramagnetic behaviour for mononuclear complexes [Co(L3)Cl2] and [Co(L3)2]Br2 . 2CH3OH. Both metal centres exhibit a slow magnetic relaxation as proven by the AC susceptibility measurements. The activation energy of penta-coordinate complex [Co(L3)Cl2] is Ueff = 12 K (τ0 = 1.35×10−6 s) at BDC = 0.15 T and for hexa-coordinate complex is Ueff = 8.5 K (τ0 = 1.0×10−5 s) at BDC = 0.1 T. The frequency dependence of the maxima at the out-of-phase component of the magnetic susceptibility confirms a superparamagnetic behavior and possible singlemolecule magnetism.

26

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

QTAIM studies of biomimetic trigonal iron(IV) nitrido and imido complexes M. Breza Department of Physical Chemistry, Slovak Technical University, Bratislava, Slovakia  Martin Breza; e-mail: [email protected]; Department of Physical Chemistry, Slovak Technical University, Radlinského 9, SK-812 37 Bratislava, Slovakia

Geometries of four iron(IV) nitrido and imido complexes with tris(carbene)borate ligands in various spin states has been optimized at B3LYP/6-311G* level of theory. Neutral nitrido complexes prefer the singlet spin state whereas the imido cationic ones prefer the triplet spin state. Electron structure of the most stable spin states has been investigated in terms of Quantum Theory of Atoms in Molecules (QTAIM). The spin state preferences of the complexes can be ascribed to the donor properties of the imido and nitrido ligands. The σ-donor ability of the apical ligand is a sufficient parameter for tuning the spin states of d4 complexes in three-fold symmetry. We thank the Slovak Grant Agency VEGA (contract No. 1/0598/16) and Slovak Research and Development Agency (contract No. APVV-15-0079) for financial support. We thank the HPC center at the Slovak University of Technology in Bratislava, which is a part of the Slovak Infrastructure of High Performance Computing (SIVVP Project No. 26230120002, funded by the European Region Development Funds), for computing facilities.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Temperature dependence of proton dissociation and complexation processes in the Ca2+/gluconate system under hyperalkaline conditions Á. Buckó, B. Kutus, G. Peintler, I. Pálinkó, P. Sipos Institute of Chemistry, Materials and Solution Structure Research Group, University of Szeged, H–6720 Szeged Rerrich Béla tér 1.  Prof. Pál Sipos; [email protected]; H–6720 Szeged Dóm tér 7., Department of Inorganic and Analytical Chemistry

The complexation properties of various low molecular-weight sugar type ligands in strongly alkaline aqueous solutions are of relevance in, e.g., the cementitious pore water of radioactive waste repositories in in the hydrometallurgical extraction of metals, etc. A number of papers have been published by us within this topic. It was found, that D-gluconate (Gluc–) under hyperalkaline conditions forms high stability multinuclear complexes with Ca2+ [1]. Similar observations were made with using D-heptagluconate [2] and L-gulonate [3]. In the current work, the hyperalkaline complexation processes in the Ca 2+/D-gluconate system have been studied under hypersaline conditions (I = 4 M NaCl) and over the temperature range of 25 – 75 oC by pH potentiometry and 13C NMR spectroscopy. At first, to validate our method the pKw of the solutions have been determined at various temperatures and compared to the results given in the literature. Then the deprotonation of the alcoholic OH– group(s) of the ligand has been investigated. It was found that a second deprotonation of the anion should be taken into account at 4 M ionic strength, this is somewhat different from the speciation obtained at I = 1M. Finally, the temperature dependence of the stability constants of the complexes, forming in the Ca2+/Gluc–/OH– system has been compared. [1] A. Pallagi, É.G. Bajnóczi, S.E. Canton, T.B. Bolin, G. Peintler, B. Kutus, Z. Kele, I. Pálinkó and P. Sipos, Environmental Science & Technology, 2014, 48, 6604–6611. [2] A. Pallagi, Z. Csendes, B. Kutus, E. Czeglédi, G. Peintler, P. Forgó, I. Pálinkó and Sipos P, Dalton Transactions, 2013, 42, 8460–8467. [3] B. Kutus, in preparation.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Phenanthroline-decorated iron(II) clathrochelates as ligands towards other metals a

A. Burdukov, aM. Vershinin, aN. Pervukhina, aE. Boguslavskii, bI. Eltsov, cY. Voloshin, dS. Selektor, dA. Shokurov

a

Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentiev Ave. 3, 630090 Novosibirsk, Russia b Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia c Nesmeyanov Institute of Organoelement Compounds RAS, Vavilova str. 28, 119991 Moscow, Russia d A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Leninsky prospect 31, 119071 Moscow, Russia  Dr. Aleksei Burdukov; e-mail [email protected]; NIIC SB RAS, 3 Lavrentiev Ave., 630090 Novosibirsk, Russia

The reported ability of amine-substituted boron-capped tris-dioximate iron(II) clathrochelates to react with carbonyl compounds [1, 2] allowed us to elaborate the synthesis of a phenanthroline-decorated cage complex capable of binding other inner complexes of 3d and 4f metals. F

O

N

F

B

O

N

B

O O O N N N Fe2+ N N N OO O B F

NH2 base NH2

O O O N N N 2+ Fe N N N OO O B

L M L N

N

N

N

F

-2L

F B

O O O N N N Fe2+ N N N OO O B

N

N

N

N

M

F

Structural, electrochemical, and spectral features of the synthesized compounds will be presented. This study was partly supported by RFBR (grant 16-03-00408). Y.Z.V. thanks Russian Science Foundation (project 16-13-10475) for support of the spectral part of this work. [1] M.A.Vershinin et al., Inorg. Chim. Acta 2011, 366, 91-97. [2] A.B.Burdukov et al., J. Coord. Chem. 2015, 68(21), 3894-3902.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

NIR-Photothermal properties of nickel-bis(dithiolene) complexes: Cancer therapy, photoresponsive gels and photocontrolled drug release K. Mebrouk, aS. Debnath, aF. Chotard, aM. Fourmigué, bC. Le Goff-Gaillard, bY. Arlot-Bonnemains, aF. Camerel

a

a b

Institut des Sciences Chimiques de Rennes (ISCR), Université Rennes 1, 35042, Rennes Institut de Génétique et développement de Rennes (IGDR), Université Rennes 1, 35042, Rennes

 Dr. habil. Franck Camerel; e-mail: [email protected]

Metal-bis(dithiolene) complexes are known as strong NIR absorbers in a wide range of NIR wavelengths depending upon the choice of metal center and dithiolene substituents. However, in our recent works, we have also shown that nickelbis(dithiolene) complexes display strong photothermal activities under laser irradiation that can efficiently be used in material science and in biotechnologies. First, the photothermal activity of cholesterol functionalized metal-bis(dithiolene) organogelators can be used to control gelation processes under NIR irradiation. Proper functionalization of the complexes has also allowed good solubility in water and more importantly, in cellulo experiments have demonstrated that NIR-laser irradiation of cellular culture incubated with metal-bis(dithiolene) complexes can induced cell death, highlighting that such complexes can be good candidates for photothermal cancer therapies (PTT). Preliminary investigations have also demonstrated that NIR irradiation of amphiphilic nickel-bis(dithiolene) allows the fine control of fluorophores or drug release from self-assembled nanostructures in solution and that they can also act as efficient contrast agents for photoacoustic imaging.

30

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Steric and electronic control on the nitrite reduction of the bio-inspired copper(I)-nitro complexes a,c

Y.-L. Chang, aW.-J. Chuang, aY.-F. Lin, aM. Narwane, a,bJ. R. Carey, a H.-Y. Chen, a,cM. Y. Chiang, aS. C. N. Hsu

a

Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan b Department of Applied Chemistry, National University of Kaohsiung, Kaohsiung 804, Taiwan c Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan 804  Professor, Sodio C. N. Hsu; [email protected]; Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, 100 Shi-Chuan 1st Rd., San-Ming District, Kaohsiung 807, TAIWAN

Two copper(I)-nitro complexes [Tpm3-tBuCu(NO2)] and [(Ph3P)2N][Tp3-tBuCu(NO2)] have been synthesized and characterized and allow for the stoichiometric reduction of NO2- to NO with H+ addition. The results of this effort show the steric and electronic influences by nitrogen ligand environments will affect the nitrite reduction ability.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Theoretical and experimental investigation of redox-isomerism in 14th group bis-chelates M. G. Chegerev, A. V. Piskunov G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Laboratory of Organoelement Compounds, Tropinina Street 49, 603950 Nizhny Novgorod, Russian Federation  Mr. Maksim G. Chegerev; [email protected]

Using quantum chemical investigations we have shown of the possibility of the occurrence of valence-tautomerism (VT) in group 14 (E=Si, Ge, Sn, Pb) element derivatives with redox-active indophenols and aminophenols. It was shown that bis-chelate tin complex 1 on the basis of 4,6-di-tert-butyl-N-(tert-butyl)-aminophenol is characterized by a narrow energy gap between the pseudotetrahedral 1a and tetragonalpyramidal 1b electromeric forms and a low energy barrier for their interconversion and, therefore, was considered as a promising candidate for the observation of thermally driven valence tautomeric rearrangement.

According experiment we have found that 1 actually exists in two electromeric forms in non-polar solvents: diamagnetic 1a and paramagnetic 1b. The reversible redox-isomeric rearrangement between 1a and 1b was investigated in solid state and solution by means of magnetochemistry, EPR, UV-Vis and Mössbauer spectroscopy. This work was supported by the Russian Scientific Foundation (Grant 17-13-01428).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Potentiometric, voltammetric and spectroscopic studies of fisetin and its copper complexes L. Chruscinski, bM. I. Pilo, bA. Zucca, cM. Rowińska-Zyrek, d E. Lodyga-Chruscinska

a

a

Faculty of Process an Environmental Engineering, Lodz University of Technology, ul. Wólczańska 175, 90-924 Lodz, Poland b Dipartimento di Chimica e Farmacia, Universita di Sassari, Via Vienna 2, Sassari I-07100, Italy c Department of Chemistry, University of Wroclaw, F. Joliot-Curie Street 14, 50-383 Wroclaw, Poland d Faculty of Biotechnology and Food Chemistry, Lodz University of Technology, Stefanowskiego Street 4/10, 90-924 Lodz, Poland  Professor, Elzbieta Lodyga-Chruscinska; e-mail [email protected]; Correspondence Address: Lodz University of Technology, ul. Stefanowskiego 4/10, 90-924 Lodz, Poland

Fisetin is a naturally occurring bioactive plant compound of immense importance as a potentially useful therapeutic drug, for various free radical mediated as well as other diseases. The chelation of metals could be crucial in the prevention of radical generation which damage target biomolecules. Therefore, research on the metal flavonoid complexes is very helpful in developing new medicines, based on these complexes. Studies in solution are indispensable, because biologically active substances act in the cell compartments with different water contents, and therefore the information about the acid-base properties, the process of coordinating metal ions, give an idea, which chemical form of biomolecule may be involved in biochemical processes in the cells. Copper ions play an important role in biological systems and wherefore they are very popular in the area of biomedical research and bioinorganic chemistry. Therefore, copper was the subject of our investigation to determine chelating efficiency of fisetin. The purpose of these studies was to determine and characterize complexes formed in different pH range. Potentiometric titration, cyclic voltammetry and spectroscopic techniques: UV-Vis, ESI MS, CD were applied to characterize physicochemical properties of fisetin and copper complexes.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Photochemistry of 4-ethylphenylcobalamin, an antivitamin B12. DFT study. K. Ciura, P. Lodowski Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland  Karolina Ciura; [email protected]; Institute of Chemistry, University of Silesia, Szkolna 9, 40006 Katowice, Poland

Antivitamins B12 (Figure 1.) are photoactive antimetabolites acting antagonistically to vitamin B12 (CNCbl, cyanocobalamin). They are a new class of cobalamins designed to imitate cyanocobalamin deficiency. In respect of photochemical properties of antivitamins B12 they have a number of similarities to the biological forms B12 (MeCbl, AdoCbl, CNCbl) [1]. EtPhCbl (4-ethylphenylcobalamin) activated by visible light, with corresponding wavelength 550 nm, forms an excited state with a ca. 247 ps lifetime, which undergoes internal conversion to the ground state or forms a long-lived base-off form. The objective was to characterize the geometries, energetics and electronic structure of low-laying, singlet electronic states for base-on and base-off forms of EtPhCbl. On the base of calculational results a photochemical mechanism was proposed.

Figure 1. Molecular structure of vitamin B12 (CNCbl, R=CN) and 4-ethylphenylcobalamin (EtPhCbl, R=PhEty).

[1] N. A. Miller, T. E. Wiley, K. G. Spears, M. Ruetz, Ch. Kieninger, B. Kräutler, R. J. Sension, J. Am. Chem. Soc. 2016, 138, 14250–14256.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Rationalization of the spin crossover (SCO) behavior in polypyridylbased iron(II) complexes K. Déniel, aN. Cosquer, aF. Conan, aS. Triki, bC. J. Gómez-García.

a

UMR CNRS 6521, Université de Bretagne Occidentale, BP 809, F-29238 Brest Cedex3, France b ICMol, Universidad de Valencia, C/ Cat. José Beltrán, 2, 46980 Paterna, Valencia, Spain. a

 Professor, Conan; [email protected]; Correspondence Address : UMR CNRS 6521, Université de Bretagne Occidentale, BP 809, F-29238 Brest Cedex3, France

Switchable materials are characterized by two stable states which display distinct physical properties and can be figured out by + 1 and 0 bits. The interchanging from one to another of these two states can be easily reached via external stimuli such as chemical, photochemical or electrochemical stimuli. Therefore, these materials allow a wide range of applications for instance, in sensing, data storage, displays, and optics. Among them, spin crossover (SCO) materials and especially iron (II) systems are more extensively studied, and particularly those displaying photomagnetic properties. Actually, they exhibit two reversible and accessible spin states, one diamagnetic low spin (LS) state (S=O) and one paramagnetic high spin HS state (S=2). Such properties depend on several structural parameters such as the ligand features (donating atoms, denticity, steric hindrance) and are influenced by the intermolecular interactions which may exist within the lattice, as well. In this communication, we will detail the strategy which we have recently developed with the aim to better rationalize the physical properties of a series of new iron(II) complexes based on polypyridyl ligands, and consequently to tune their spin crossover properties. Syntheses, Structural characterizations and physical properties will be discussed.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Strength and limitations of thermoanalytical research in materials and solid state chemistry a

M. Drábik, bE. Chmielewská

a

Department of Inorganic Chemistry, Faculty of Science, Comenius University, Ilkovičova 6, 842 15 Bratislava, Slovakia b Department of Environmental Ecology, Faculty of Science, Comenius University, Ilkovičova 6, 842 15 Bratislava, Slovakia  Assoc. Prof. Milan Drábik, PhD; [email protected]

The contribution deals with the challenge of thermogravimetry (TG) and differential thermal analysis (DTA) in the fields of solid state & materials chemistry. The graphical presentation below displays both a general methodological outline and two case studies – knowledge gained on iron doped clinoptilolite (#) and macrodefectfree (MDF) materials (##).

Thermogravimetry (TG) and differential thermal analysis (DTA), however traditional these experimental techniques are, exert a valued usefulness for generation of the knowledge in materials/solid state chemistry. Usually critical awareness of the limits & limitations is needed and data needs to be supported by results of „twinned“ method. Authors acknowledge Peter Billik for accomplishing sophisticated mechanochemical experiments on the tests of macrodefectfree (MDF) procedures and materials.

36

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Acid-base properties and calcium complexation of α-ketoglutarate in strongly alkaline aqueous solutions C. Dudás, B. Kutus, R. Bélteki, A. Gácsi, I. Pálinkó, P. Sipos Institute of Chemistry, University of Szeged, Aradi vértanúk tere 1, H-6720 Szeged, Hungary  Prof. Dr. Pál Sipos, [email protected], Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 8., Szeged, Hungary, H-6720

In the present study the complex formation between α-ketoglutarate (2-oxopentanedioate, Ket2–) and calcium in neutral and in hyperalkaline medium was studied. From Ca-ISE potentiometry, the formation constants of CaKet0 and Ca2Ket2+ complexes formed in neutral solutions were determined to be logβ1,1 = 1.12  0.01 and logβ2,1 = 2.04  0.01, respectively. The deprotonation constant of Ket2– in highly alkaline medium was determined from UV-Vis spectrophotometry. It was found that the methylene group of Ket 2– underwent deprotonation resulting in an enolate form after tautomerism. Temperature-dependent 1 H NMR spectra revealed the presence of the enolate form. The deprotonation constant was found to be logKa = 15.3  0.1. The calcium-complexing behaviour of Ket2– was also studied in strongly alkaline medium by UV-Vis spectrophotometry. The formation constant of CaKet(OH) 22– was determined to be logβ1,1,2 = 4.67 0.02. The deptoronation as well as the calcium complexation were also studied by 1H and 13 C NMR spetroscopies.

37

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

5-Bromo-7-azaindole complexes with Pt(II) and Pd(II): synthesis, vibrational spectroscopy and DFT calculations a

K. Dysz, bD. Michalska, aB. Morzyk-Ociepa

Institute of Chemistry, Environmental Protection and Biotechnology, Jan Długosz University, Armii Krajowej 13/15 Ave., 42-200, Częstochowa, Poland b Faculty of Chemistry, Wrocław University of Technology, Smoluchowskiego 23, 50-370 Wrocław, Poland a

 Associate Professor, Barbara Morzyk-Ociepa; e-mail: [email protected], Armii Krajowej 13/15 Ave., 42-200, Częstochowa, Poland

In the last decade, the 7-azaindole derivatives and their metal complexes have attracted growing attention in medicine as a new class of promising anticancer agents. Recently, it has been reported that the trans-palladium complexes containing relatively large monodentate ligands (e.g. pyridine derivatives) show better antitumor activity than the cis-platinum isomers. Therefore, in this work we synthesized the Pt(II) and Pd(II) complexes with 5-bromo-7-azaindole (5Br7AI), cis-[PtCl2(5Br7AI)2] and trans-[PdCl2(7AI)2]. The FT-IR and FT-Raman spectra were measured. These complexes were characterized by elemental analysis, vibrational spectroscopy and DFT calculations. Comprehensive theoretical studies on cis-[PtCl2(5Br7AI)2] and trans-[PdCl2(7AI)2] have been performed by the B3LYP method using the 6-311G++(d,p)/LanL2DZ basis set. The results have shown that the platinum cation is bound to two pyridine nitrogen atoms of the 5Br7AI ligands and to two chloride ions, in a square-planar cis arrangement, while the palladium cation is also bound to the analogous atoms, but the 5Br7AI and Cl ligands are in a square-planar trans arrangement. The obtained results can be used in a further studies of new biologically active Pt(II) and Pd(II) complexes with pyridine-based ligands, by using vibrational spectroscopy.

38

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

[FeFe]-hydrogenase models: synthesis, characterization and catalytic activity of diselenolato diiron complexes a

M. El-Khateeb, bW. Weigand

a

Chemistry Department, Jordan University of Science and Technology, 22110 Irbid, JORDAN Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldt-Straße 1, 07743 Jena, GERMANY b

 Prof. Mohammad El-khateeb; [email protected]; Chemistry Department, Jordan University of Science and Technology, 22110 Irbid, JORDAN

Diiron hexacarbonyl complexes containing diselenolato ligands Fe2(μ-Se2C3H5R)(CO)6 (R= H, Me) have been prepared as models of the active site of [FeFe]-hydrogenases [1]. The displacement of terminal CO-ligands of these complexes by triphenylphosphine, trimethylphosphite, bis(diphenylphosphino)ethane (dppe) or bis(diphenylphosphino)methane (dppm) ligands is reported [2,3]. All the new complexes have been characterized by IR, 1H-, 13C-, 77Se-NMR spectroscopy, mass spectrometry and elemental analysis as well as by X-ray diffraction analysis. Recently, the reactions of the model complexes Fe2(μ-Se2C3H5R)(CO)6 by bis(diphenylphosphino)ferrocene (dppf) is also investigated to produce (-dppf)[Fe2(CO)4(μ-Se2C3H5R)] which was fully characterized. Protonation and cyclic voltammetric studies of the newly prepared complexes were investigated. These new complexes proved to be good catalysts for electrochemical reduction of protons from the weak acids to give molecular hydrogen. [1] M.K. Harb, T. Niksch, J. Windhager, H. Gorls, R. Holze, L. Lockettd, N. Okumurad, D.H. Evans, R. S. Glass, D.L. Lichtenberger, M. El-khateeb, W. Weigand. Organometallics, 2009, 28, 1039. [2] M.K. Harb, J. Windhager, A. Darawosheh, H. Görls, L.T. Okumura D.H. Evans, R.S. Glass, D.L. Lichtenberger, M. El-khateeb, W. Weigand, Eur. J. Inorg. Chem., 2009, 23, 3414. [3] M. El-khateeb, M. Harb, Q. Abu-Salem, H. Görls, W. Weigand. Polyhedron 2013, 61, 1.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Structural activation of NColE7-based artificial metallonucleases Z. Fábián, E. Németh, B. Gyurcsik University of Szeged, Department of Inorganic and Analytical Chemistry  Dr. Béla Gyurcsik; [email protected]; 6720 Szeged, Dóm tér 7, Hungary

The aim of our research group is to develop a catalytic metalloprotein with a control mechanism, which is able to cleave nucleic acids at a selected specific site. The nuclease domain of colicin E7 (NColE7) was selected to form the catalytic domain of novel zinc-finger (ZF) nucleases. In these proteins an array of three ZF motifs was joined to the selected N- and the C-terminal sequences of NColE7 by designed linkers. The solution structure of three such nucleases and their interaction with Zn 2+ and DNA were examined by circular dichroism spectroscopy, MS and electrophoretic assays. A remarkable feature of NColE7 is that the C- and the N-terminal units need to be close to each other in the active enzyme. W464 residue plays a major role in this. Changing this amino acid to alanine, the structure of the protein becomes disordered and the catalytic activity decreases significantly. The NColE7-like structure of the W mutant is restored by the substrate or immunity protein. To explore the induced structure the W/Im7 protein complex was synthesized and crystallization experiments were performed. The main goal of these experiments is to understand the particular role of the W464 residue and to apply it as a new possible control function in the optimization process of the new artificial nucleases. Acknowledgement: Supported by the ÚNKP-16-2 New National Excellence Program of the Ministry of Human Capacities

40

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis, crystal structure and cytotoxicity of zinc(II) complexes with quinolin-8-ol chloroderivatives V. Farkasová, bR. Jendželovský, bM. Majerník, bP. Fedoročko, aI. Potočňák

a

Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, Moyzesova 11, 041 54 Košice, Slovakia b Department of Cell Biology, Institute of Biology and Ecology, P. J. Šafárik University in Košice, Šrobárova 2, 041 54 Košice, Slovakia a

 Mgr. Veronika Farkasová; [email protected]; Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University, Moyzesova 11, 041 54 Košice, Slovakia

K[Zn(dClQ)3]∙2DMF (1), [Zn4Cl2(ClQ)6]∙DMF (2) and [Zn(ClQ)2(H2O)2] (3) (ClQ = 5-chloro-quinolin-8-ol, dClQ = 5,7-dichloro-quinolin-8-ol) were synthesized and characterized. X-ray structure analysis was performed on 1 and 2. Structure of 1 is ionic and the negative charge of the anion, in which Zn(II) atom is chelated by three bidentate dClQ molecules, is balanced by uncoordinated potassium cation. On the other hand, the structure of 2 is molecular and consists of tetranuclear units. The complex 2 creates complicated structure, in which all six chelate ClQ molecules exhibit also bridging function between two Zn(II) atoms in slightly distorted octahedral coordination and remaining two Zn(II) atoms are in distorted trigonal bipyramidal coordination ( = 0.68). Both compounds involve uncoordinated DMF molecules in their structures. We were unable to prepare complex 3 in a crystalline form, but we expect its molecular character with Zn(II) atoms hexacoordinated by two chelate ClQ ligands and two monodentate water molecules. All three complexes have shown high cytotoxicity against HCT116 colon cancer cell line as shown by MTT tests. The financial supports of Slovak grant agencies VEGA (1/0598/14), APVV (14-0078) and VVGS-2016-265 are gratefully acknowledged.

41

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Coordination self-assembly: from the origins to the latest advances M. Fujita Department of Applied Chemistry, The University of Tokyo  [email protected]

Molecular self-assembly based on coordination chemistry has made an explosive development in recent years. Over the last >25 years, we have been showing that the simple combination of transition-metal’s square planar geometry (90° coordination angle) with pyridine-based bridging ligands gives rise to the quantitative self-assembly of nano-sized, discrete organic frameworks. Representative examples include square molecules (1990), linked-ring molecules (1994), cages (1995), capsules (1999), and tubes (2004) that are self-assembled from simple and small components. Originated from these earlier works, current interests in our group focus on 1) molecular confinement effects in coordination cages, 2) solution chemistry in crystalline porous complexes (as applied to “crystalline sponge method”), and 3) giant self-assemblies, as disclosed in this lecture.

42

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Agostic Cu-H interaction – charge density study of bis(clonixato) bis(imidazole)copper(II) complex M.Gall, bJ. Kožíšek

a

a

Institute of Information Engineering, Automation, and Mathematics, Faculty of Chemical and Food Technology, Slovak University of Technology, SK-812 37 Bratislava, Slovakia b Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, SK-812 37 Bratislava, Slovakia  Ing. Marián Gall, PhD., [email protected], Institute of Information Engineering, Automation, and Mathematics, Faculty of Chemical and Food Technology, Slovak University of Technology, SK-812 37 Bratislava, Slovakia

The first agostic interaction from aromatic system in a copper(II) complex (I) is reported. The term of agostic interaction was defined by Brookhart and Green1. In bis(clonixato) bis(imidazole)copper(II) complex central Cu(II) atom in the center of symmetry is square-planar coordinated by the oxygen atom from clonixin anion and the nitrogen atom from imidazole. In apical position there is the hydrogen atom from aromatic π-system. The excellent quality single crystal was used for data collection on Stoe STADIVARI diffractometer at 100 K. Integration and the data reduction was performed by X-Area2 and EVAL153 software and for theoretical calculations we used Gaussian094 and AIM20005 software. The results of experimental and theoretical AIM analysis of the electronic structure will be discussed. A σ-back donation hydrogen bond is expected. Acknowledgements: This work was supported by Slovak Grant Agency VEGA under Contract No. 1/0598/16. [1] M. Brookhart, M. L. H. Green, J. Organomet. Chem. 250 (1983) 395. [2] STOE & Cie GmbH (2016). X-Area 1.76, software package for collecting singlecrystal data on STOE area-detector diffractometers, for image processing, scaling reflection intensities and for outlier rejection; Darmstadt, Germany. [3] EVAL15. [4] Gaussian 09, M.J. Frisch, et al., Gaussian, Inc., Wallingford CT, 2009. [5] F. Biegler-König, J. Schönbohm, D. Bayles, J. Comp. Chem. 22 (2001) 545;

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Studying protein interactions through their metal ion binding properties by CD spectroscopy B. Gyurcsik University of Szeged, Department of Inorganic and Analytical Chemistry  Dr. Béla Gyurcsik; [email protected]; 6720 Szeged, Dóm tér 7, Hungary

Metalloproteins containing -metal ion binding motifs show distinct modes of metal ion coordination, as well as function. In the nuclease domain of Colicin E7 the Zn 2+-ion is coordinated by three histidine side-chains and the fourth coordination site can be occupied by a water molecule or the DNA substrate. Such complex forms the active centre of the nuclease providing multiple functions for the metal ion in the catalytic mechanism. It can activate the coordinated water molecule either to be an efficient nucleophilic attacking agent or to provide proton to the leaving alcoholate in the cleavage reaction. It can also electrostatically activate the substrate and/or stabilize the transition state. On the other hand, the classical zinc finger proteins possess structurally similar motif, but the Zn2+-ion is coordinated by two histidine and two cysteine sidechains. These proteins do not have catalytic activity, but they control transcription through specific binding of selected DNA sequences in the major grove. It is intriguing that the metal ion binding properties of both types of the above proteins change dramatically in the presence of their interacting partners. Our aim was to explore the influencing factors, i.e. the overall structure and environment around the metal binding sites by circular dichroism spectroscopy. Acknowledgement: This work was financially supported by the research grants NKFIH K_16/120130 and GINOP 2.3.2-15-2016-00038.

44

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis, structure, and properties of a lantern-type dinuclear rhodium(II) complex cis-[Rh2(4-Me-pf)2(O2CCMe3)2], 4-Me-pf– = N,N’-di-p-tolylformamidinate anion a

M. Handa, aS. Nishiura, aT. Masuda, aN. Yano, bM. Mikuriya, aY. Kataoka

a

Department of Material Science, Interdisciplinary Faculty of Science and Engineering, Shimane University, Matsue 690-8504, Japan b Department of Applied Chemistry for Environment and Research Center for Coordination Molecule-based Devices, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan  Prof. Makoto Handa; [email protected]; Interdisciplinary Faculty of Science and Engineering, Shimane University

The carboxylato ligand substitution reaction from cis-[Rh2(4-Me-pf)2(O2CCF3)2] (1) to cis-[Rh2(4-Me-pf)2(O2CCMe3)2] (2) (4-Me-pf- = N,N’-di-p-tolylformamidinate anion) was successfully performed. The lantern-type dinuclear structure with cis-(2:2) arrangement of the two formamidinato and two carboxylato ligands was confirmed for (2)(MeCN)2 by X-ray crystal structure analysis. The complex 2 showed absorption bands at 613, 506, 435, and 344 in MeCN, while complex 1 showed the bands at 516, 460, and 326 nm in MeCN. All the bands observed for 1 and 2 could be reasonably assigned using the TD-DFT calculation results. The cyclic voltammogram (CV) measured for 2 revealed the Rh2II,II  Rh2III,III and Rh2II,II  Rh2III,III processes at E1/2 = 0.32 and 1.22 V (vs. SCE), respectively, in CH2Cl2, as well as at E1/2 = 0.17 and 1.15 V (vs. SCE), respectively, in MeCN/CH2Cl2 (1:1 vol./vol.). The introduced t-butyl group on the carboxylato bridge was concluded to give rise to the negative shifts in the redox potentials compared with the corresponding potentials observed for 1 (E1/2 = 0.70 and 1.47 V (vs. SCE) in CH2Cl2 and E1/2 = 0.54 and 1.38 V (vs. SCE) in MeCN.

45

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Phenanthroline - guanidine hybrid ligands: mimics of the cytochrome-c-to-CuA electron transport chain within cytochrome-c oxidase J. Ortmeyer, Y. Vukadinovic, G. Henkel University of Paderborn, Warburger Str. 100, 33098 Paderborn, Germany  Prof. Dr. Gerald Henkel; [email protected]; University of Paderborn, Department of Chemistry, Warburger Str. 100, 33098 Paderborn, Germany.

Life on earth is intimately associated with electron transport. Based on its unique redox properties, the CuA center plays a crucial role within one of the most fundamental biological pathways known as respiratory chain. It is a binuclear thiolate-bridged copper complex with a delocalized mixed-valent {Cu+1Cu+2} core in its oxidized state. This special cluster facilitates electron transport from cytochrome-c to molecular oxygen and thus helps to accomplish the fundamental cycle of biological electrons. Though CuA has structurally been characterized twenty years ago, its detailed function remained unclear. In a recent attempt towards a better understanding of CuA, we constructed an artificial device for the electron path from cytochrome-c to CuA. Based on an unprecedented Janus-type bis-bifunctional ligand with two guanidine functionalities attached to a phenanthroline framework, this system is able to anchor an optically responsive metal at the phenanthroline site as the electron source and Cu at the guanidine site as the electron sink. By using iridium as the potential electron donor, we were able to arrive at the first heterobinuclear complex of our tetradentate ligand. The remarkable features of this molecule will be discussed and compared to features of other complexes stabilized by this ligand.

46

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Bioinspired catalyst with vitamin B12 functions activated by photochemical or electrochemical methods Y. Hisaeda Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan  Professor, Yoshio Hisaeda; [email protected]; Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan

As part of a study directed toward design of good catalytic systems based upon a hydrophobic vitamin B12, we reported preparation of various nanomaterials with the vitamin B12 derivative and photosensitizers. These bioinspired materials can apply to the catalytic reactions for the degradation of organic halide pollutants and the molecular transformations via radical intermediates under irradiation with UV or visible light. Examples include a vitamin B12-titanium dioxide hybrid catalyst, a vitamin B12-Ru complex combined system, and so on. These bioinspired materials offer scope for applications that are of great interest in terms of green chemistry. Recently, we applied trifluoromethylation reactions catalyzed by vitamin B12 derivative (1) using electrochemical and photochemical activation. This catalytic system can apply to perfluoroalkylation reactions.

47

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Reactivity study of unsymmetrical ß-diketiminato copper(I) and zinc(II) complexes: effect of chelating ring a

S. C. N. Hsu, aW.-J. Chuang, aK. Chand, aC.-L. Tsai, bJ. R. Carey

a

Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan; Department of Medical Research, Kaohsiung Medical University Hospital, Kaohsiung 807, Taiwan b Department of Applied Chemistry, National University of Kaohsiung, Kaohsiung 804, Taiwan  Professor, Sodio C. N. Hsu; [email protected]; Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, 100 Shi-Chuan 1st Rd., San-Ming District, Kaohsiung 807, TAIWAN

The β-Diketiminate ligands are widely used supporting ligands in modern bioinspired chemistry and are capable of stabilizing various metal complexes in multiple oxidation states and coordination environments. A series of unsymmetrical N-aryl-N’-alkyl β-diketiminates, bearing a pendant pyridyl arm (L1H - L4H) were synthesized. Deprotonation of the L1H - L4H by CuOtBu or diethyl zinc give their corresponding copper and zinc complexes. Here we describe the synthesis and structural characterization of a series of asymmetrical N-aryl-N’-alkylpyridyl β-diketiminate copper(I) and znic(II) complexes (CuL1, Cu2(μ-L1)2, CuL2, CuL3, CuL4, Cu2(μ-L4)2, Zn2(Et)2(μ-L1)2, Zn(Et)L2, Zn2(Et)2(μ-L3)2, Zn(Et)L4) and discuss the structures and reactivity of these complexes with respect to length of the pyridyl arm. All of the aforementioned unsymmetrical ß-Diketiminato copper(I) complexes bind CO reversibly, and are stable to disproportionation. The binding ability of CO and the rate of pyridyl ligand decoordination of these copper(I) complexes are directly related to the competition between the degree of puckering of the chelate system and to the steric demands of N-aryl substituent.

48

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Stepwise and self-assembly synthesis of tetranuclear iron–thiolate–diisocyanide metallocyclophane complexes Y.-C. Huang, S. C. N. Hsu Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan  Research associate, Yen-Chung Huang; [email protected]; Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, 100 Shi-Chuan 1st Rd., San-Ming District, Kaohsiung 807, Taiwan

Treatment of known complex [Cp2Fe2(μ-SEt)2(CH3CN)2](BF4)2 1(BF4)2 with two equivalents of 1,4-bis(isocyanomethyl)benzene (1,4-CNCH2C6H4CH2NC; L1), 4,4’-diisocyanophenyl ether (4,4’-CNC6H4OC6H4NC; L2), 4-isocyanoaniline (4-CNC6H4NH2; L3), ethyl 4-isocyanobenzoate (4-CNC6H4COOEt; L4), and 4-isocyanobenzoic acid (4-CNC6H4COOH; L5) yield to the formation of five new types of diisocyanide complexes [Cp2Fe2(μ-SEt)2(1,4-CNCH2C6H4CH2NC)2](BF4)2 2a(BF4)2, [Cp2Fe2(-SEt)2(4,4’-CNC6H4OC6H4NC)2](BF4)2 (4-CNC6H4NH2)2](BF4)2

(2c(BF4)2),

(2b(BF4)2),

[Cp2Fe2(-SEt)2

[Cp2Fe2(-SEt)2(4-CNC6H4COOEt)2](BF4)2

2d(BF4)2, and [Cp2Fe2(-SEt)2(4,4’-4-CNC6H4COOH)2](BF4)2 2e(BF4)2 respectively. The twenty-four membered ring tetranuclear iron-thiolate-aryldiisocyanide metallocyclophane complex [Cp4Fe4(μ-SEt)4(μ-1,4-CNCH2C6H4CH2NC)2](BF4)4 3a(BF4)4 was synthesized by using a self-assembly reaction between equimolar amounts of 1(BF4)2 and 1,4-bis(isocyanomethyl)benzene or by a stepwise route involving mixing a 1:1 molar ratio of complexes 1(BF4)2 and 2a(BF4)2. Alternatively, mixture of equal molar ratio of complexes 1(BF4)2 and 2b(BF4)2 gives a thirty membered ring tetranuclear iron-thiolate-aryldiisocyanide metallocyclophane complex [Cp4Fe4 (-SEt)4(4,4’-CNC6H4OC6H4NC)2][BF4]4 3b(BF4)4. The spectroscopic and electrochemical properties of all four iron-sulfur core complexes were determined.

49

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Complexation characteristics of a thionated cyanoxime ligand T. N. Hung, G. Varga, P. Sipos, I. Pálinkó Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-6720 Hungary  Prof. István Pálinkó, e-mail: [email protected], Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720 Hungary

2-Cyano-2-(hydroxyimino)dithioacetic acid was prepared starting from cyanoacetic acid methylester via 2-cyano-2-(hydroxyimino)acetic acid methylester. Before thionation, the ester had to be hydrolyzed. The optimum conditions for each reaction were identified. P4S10 was found to be the efficient thionation reactant resulting in the formation of the dithionated product. Its structure was verified with IR, NMR and mass spectrometric measurements. The obtained and appropriately characterized ligand was used as ligand in complexation with Cu(I), Ag(I) and Co(II) as central ions. The pristine ligand, the precipitate as well as the solutions were studied by infrared as well Raman spectroscopies. The spectroscopic results were used for identifying the coordinating groups, which helped in constructing structural models.

50

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Novel dicarboxylato platinum(II) complexes as potential anticancer agents M. Jakubowski, bJ. Sitkowski, aA. Wojtczak, aD. Śmiłowicz, aI. Łakomska

a

Nicolaus Copernicus University in Toruń, Faculty of Chemistry, Gagarina 7, 87-100 Toruń, Poland b National Medicines Institute, Chełmska 30/34, 00-975 Warsaw, Poland a

 Mateusz Jakubowski, MSc; [email protected]; Nicolaus Copernicus University in Toruń, Gagarina 7, 87-100 Toruń (Poland)

Cisplatin (CDDP) is a first platinum-based anticancer agent, which has been used to treat ovarian, head and lung cancers. Unfortunately, therapeutic effectiveness of CDDP is reduced by poor water solubility, significant reactivity towards glutathione and wide range of side effects. The above-mentioned disadvantages of cisplatin are reasons for design novel, more specific platinum(II) complexes. Previous studies have demonstrated that insertion dicarboxylate as O-chelating leaving ligand and using N-donor heterocyclic ligands should improve an activity and bioavailability of inorganic cytostatic drugs. Being inspired by above scientific premises we insulated a series of novel mixed ligand platinum(II) complexes of general formula [Pt(mal)(dmso)(L)], where: mal – malonato, dmso – dimethyl sulfoxide, L – 5,7-dimethyl/phenyl/tertbutyl-1,2,4-triazolo[1,5a]pyrimidine (dmtp/dptp/dbtp). Our research focused on thorough spectroscopic characterization (1H, 13C, 15N, 195Pt NMR; IR; X-ray) and biological studies of novel compounds. We indicated that lipophilic complex with bulky group (phenyl or tertbutyl) in a heterocyclic ligand revealed considerable in vitro anticancer activity and less toxicity. Additionally, the platinum(II) complex with dptp exhibited smaller than CDDP reactivity towards glutathione.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis, structural and magnetic investigation of Co(II) coordination compound with tridentate aromatic pyridine ligand J. Juráková, I. Šalitroš, J. Moncoľ Faculty of Chemical and Food Technology STU in Bratislava, Radlinského 9, 812 37 Bratislava, Slovakia a

 Jana Juráková; [email protected]; Rekreačná 6, 91934 Biely Kostol

The poster discusses about synthesis, structural and magnetic investigation of Co(II) coordination compound with 2,6-bis(1H-benzimidazolyl)pyridine ligand. Ligand bzimpy (IUPAC: 2,6-bis(1H-benzimidazolyl)pyridine) and substituted ligand C12bzimpy (IUPAC: 2,2'-(2,6-pyridinediyl)bis(1-dodecyl-1H-benzimidazol), were prepared. C12bzimpy has been used for the synthesize of new complex [Co(C12bzimpy)Cl2]. The ligands were characterized by elemental analysis, infrared spectra and by NMR spectroscopy. The Co(II) complex was analyzed by elemental analysis, infrared spectra and single crystal X-ray diffraction analysis. Compound crystallizes in triclinic system, space group P-1, and unit cell parameters are a = 8.7609(6) Å, b = 14.5870(10) Å, c = 16.6456(12) Å, α = 95.622(2)°, β = 101.075(2)° , γ = 99.327(2)°, V = 2041.6(2) Å3. Central atom is coordinated by three N donor atoms of the ligand C12bzimpy and by two terminal chlorido ligands. Magnetic properties of our complex were investigated by MPMS SQUID magnetometer and revealed high spin and paramagnetic behavior of Co(II) central atom.

52

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

3D heterometallic gadolinium(III)-sodium(I) and cerium(III) six-membered ring derived from pyridine-2,6-dicaboxylic acid I. U. Khan, S. Sharif Materterials Chemistry Laboratory, Department of Chemistry, Govt. College University, Lahore, P.O. Box 54000 , Lahore - Pakistan.  Tenured Professor and Dean S & T, Islam Ullah Khan, [email protected]

Variety of coordination polymers having applications in gas/chemical storage and separation, luminescent sensors and magnetic materials can be assembled by using multidentae ligands. Pyridine-2-6-dicarboxylic (PDA) provides various coordination modes to coordinate through terminal or bridging building blocks. Single X-Ray Diffraction technique, FTIR spectroscopy, Elemental Analysis, Thermal and SQUID analysis were used to explore their coordination behavior and applications. In view of the excellent coordination capability of PDA ligand, we have reported number of coordination polymers. Herein, we are reporting 3D heterometallic coordination polymer and six membered ring derived from highly connective PDA under mild solvothermal conditions. X-ray structural analysis reveals that [GdNa3(PDA)3]n.H2O 1 is 3D heterometallic coordination polymer while [Ce8(PDA)12.(PDAH)4.22H2O].11H2O 2 is six membered ring. In both complexes, PDA adopts tri, tetra, penta, and heptadentate coordination to generate trigonal tricapped prismatic LnO6N3 (Ln= Gd, Ce1, Ce2) and mono capped triangular prismatic (Ce3O8N, Ce4O9) geometries and showing tridentate chelating and μ1, μ2, μ3 and μ5-bridging coordination modes. In 2 clusters are joined by O-H···O hydrogen bonds to generate 3D supramolecular network.

53

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Thermodynamic aspect: kinetics of the reduction of dicyanobis(phen)iron(III) by acetylferrocene and methylferrocenemethanol a,b

R. Khattak, cS. Summer, dM. Sayed, bM. Nazir, aA. Minhaz, bI. I. Naqvi

a

Department of Chemistry, Shaheed Benazir Bhutto Women University, Peshawar, Pakistan Department of Chemistry, University of Karachi, Karachi-75270, Pakistan c Department of Chemistry, Jinnah University for Women, V-C Nazimabad, Karachi, Pakistan d National Center of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan b

 Assistant Professor, Dr. Rozina Khattak; [email protected], [email protected]; Department of Chemistry, Shaheed Benazir Bhutto Women University, Peshawar, Pakistan

Protonation plays an important role in the redox reactions. We observed this leading role during the reduction of [FeIII(phen)2(CN)2]+ by FcCOMe and FcCHOHMe. The kinetic data helped to deduce that the reaction(s) followed a complex kinetics due to the formation of protonated acetylferrocene (FcC+OHMe), and protonated -methylferrocenemethanol (FcCHO+H2Me) in aqueous dioxane (80% v/v). We studied the effect of different factors to identify the reacting entities, which take part in the rate-determining step of each reaction. Together, these results suggested oxidation of FcC+OHMe and FcCHOHMe in the slow-step of each reaction, respectively. We refined our results by thermodynamic parameters of activation. The low values of the activation energy (Ea) and change in enthalpy of activation (ΔH#) confirmed that the reduction of [FeIII(phen)2(CN)2]+ hardly depends upon temperature when the reducing agent is FcCOMe. The outcomes justified that the rate of reaction depends upon the unsaturated FcC+OHMe. This intermediate species contain a ‘carbonium ion’, which is very reactive and energetic. We obtained comparatively high values of Ea and ΔH# for the reaction between [FeIII(phen)2(CN)2]+ and FcCHOHMe. We obtained these results because FcCHOHMe is a saturated and stable compound that leads the slow-step and controls the rate of reaction.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Photochemical enzyme models – state of the art G. Knör Johannes Kepler University Linz (JKU), Institute of Inorganic Chemistry - Center for Nanobionics and Photochemical Sciences (CNPS), Linz, Austria  Univ.-Prof. Dr. Günther Knör; [email protected];

 JKU, Altenbergerstr. 69, A-4040 Linz, Austria

The involvement of photochemical key-steps to substitute catalytic functions or to regulate enzyme-like activity on demand is a very powerful tool for the development of novel biomimetic and bio-inspired systems [1]. Visible-light driven reaction cascades with robust artificial enzymes based on non-precious metal coordination compounds can offer an attractive “green chemistry” strategy for environmentally benign one-pot multistep substrate conversions [2]. Moreover, such light-dependent enzyme model compounds can be employed as versatile photocatalysts for powering energetically uphill redox processes required for the direct chemical conversion and storage of solar energy [3]. In the present contribution, some recent developments and breakthroughs in this fascinating research area will be discussed including the unprecedented case of an artificial photosynthetic system fully substituting the role of native PS I [3] and the replacement of synthetically useful oxidoreductase catalyzed redox transformations and C-H activation processes with light-powered artificial enzymes [2]. Possible implications for various research topics in the field of life-sciences including molecular photomedicine, photopharmacology and bottom-up synthetic biology will also be briefly discussed. [1] G. Knör, ChemBioChem 2001, 2, 593; G. Knör, Chem. Eur. J. 2009, 15, 568. [2] G. Knör, Coord. Chem. Rev. 2016, 325, 102. [3] G. Knör, Coord. Chem. Rev. 2015, 304-305, 102.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Structural study of the three new groups Mn(III) and Fe(III) dipicolinate complexes a

M. Koman, aJ. Moncoľ, bR. Uhrecký,

Department of Inorganic Chemistry, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia b Institute of Inorganic Chemistry of the AS CR, v.v.i., 1001, 250 68 Husinec-Řež, Czech Republic a

 professor, Marian Koman; e-mail Address: [email protected]; Correspondence Address: Department of Inorganic Chemistry, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia

The chemistry of manganese and iron complexes has been investigated recently since these metals are present in a various biological redox systems including peroxidases, catalases, superoxide dismutases, dioxygenases and lipoxidases. Dipicolinic acid is known to be a major component of bacterial spores. The metal dipicolinate complexes are also used in environmentally friendly “green” catalysis. The most common include heterogeneous catalysis, oxidation reactions and degradation reactions of waste water. In this lecture we report the structural characterization of a three new groups manganese(III) and iron(III) dipicolinate ionic complexes with three types of cations. The general formula of anions in these complexes is [M(dipic) 2]-1 (M = Mn(III) and Fe(III)). Each of the dipic anions are coordinate to one central atom in a terdentate fashion manner, via two O atoms and the N atom (dipic = pyridine-2,6-dicarboxylate anion). The cations in these groups of complexes are 2-, 3- or 4-hydroxymethylpyridinium, 2- or 4-carbamoylpyridinium, 1,10-phenantrolin-1-ium, or 2-(pyridin-2-yl)pyridinium and theirs derivatives. Observed structural data are discussed and correlated with those of known Mn(II/III) and Fe(II/III) complexes found in Cambridge Crystallographic Data Base.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Features of molecular and electronic structures of complex compounds derived from azopyrazolone derivatives O. V. Kovalchukova, S. B. Strashnova Peoples’ Friendship University (RUDN University), 6, Miklukho Maklaya Street, 117198 Moscow, Russia  Professor, Olga V. Kovalchukova; [email protected]; 6, Miklukho Maklaya Street, 117198 Moscow, Russia

Features of molecular and electronic structures of complex compounds derived from azopyrazolone derivatives are reviewed. Despite metal containing azopyrazolone dyes are widely used for more than 2 centuries, a few information on their molecular structure was found. Our recent researches allowed introduce new coordination modes of azopyrazolone derivatives at complexation with metals. Together with the traditional bi- and tridentate coordination, the possibility of an N pyrazolone atom to be involved in coordination was also found. As a result, polymeric or polynuclear complexes were isolated and described by X Ray analysis, NMR, EPR, IR and UV spectroscopy. The analysis of the interatomic distances in the organic anions indicated that azopyrazolone derivatives do not undergo significant azo-hydrazo tautomeric transformations at ionization and complexation despite strong shifts of the absorption bands in their IR and UV-VIS spectra.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Mixed-valent tetranuclear manganese complexes with pentadentate Schiff-base ligands having a Y-shaped core M. Mikuriya, S. Kudo, C. Matsumoto, S. Kurahashi, S. Tomohara, Y. Koyama, D. Yoshioka, R. Mitsuhashi Department of Applied Chemistry for Environment, Kwansei Gakuin University, 2-1 Gakuen, Sanda, 669-1337, Japan  Professor, Masahiro Mikuriya; e-mail [email protected]; Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, 669-1337, Japan

Reaction of pentadentate Schiff-base ligands, 1,3-bis(3-methoxysalicylideneamino)-2propanol (H3msap) and 1,3-bis(5-bromo-3-methoxysalicylideneamino)-2-propanol (H3bmsap) with manganese(II) salt afforded mixed-valent tetranuclear manganese complexes, [Mn4(msap)2(CH3CO2)3(CH3O)(CH3OH)] (1), [Mn4(msap)2(C6H5CO2)3(CH3O)] (2), and [Mn4(bmsap)2(CH3CO2)3(CH3O)] (3), which were characterized by elemental analysis, infrared and diffused reflectance spectra and temperature dependence of magnetic susceptibilities (4.5—300 K). Single-crystal X-ray crystallography of these complexes showed that four manganese atoms are chelated by two Schiff-base ligands with syn-syn bridging, syn-anti bridging, and bidentate carboxylato groups, forming a Y-shaped cluster made up of two MnII and two MnIII. Diffused reflectance spectra are featureless, showing broad bands around at near UV and visible regions. Magnetic moments decrease with lowering of temperature, showing an antiferromagnetic behavior of these complexes.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Charge density study of halogen-halogen interactions in palladium(II) complex J. Koziskova, bP. Vranec, cI. Potočňák, aJ. Kožíšek

a

a b

Department of Physical Chemistry, Slovak University of Technology in Bratislava, Slovakia, Department of Inorganic Chemistry, P. J. Šafárik University, Košice, Slovakia

 Ing. Julia Koziskova; [email protected]; Department of Physical Chemistry, Slovak University of Technology in Bratislava, Slovakia

The studied [Pd(CQ)2] complex (1) (CQ = clioquinol (5-chloro-7-iodo-quinolin-8-ol)) was prepared as potential anticancer agent. Monocrystal X-ray structure analysis revealed that the palladium atom in the studied complex is coordinated by two pairs of nitrogen and oxygen atoms from two coplanar molecules of CQ in trans positions. Very low solubility of (1) in the polar or non-polar solvents was ascribed to the presence of nonbonding π-π interactions. In addition, halogen-halogen interactions known from the literature were assumed. To prove such interactions, additional charge density studies of (1) were performed. Data collection was performed on a Stoe STADIVARI diffractometer with a Dectris Pilatus 300K detector and with an Incoatec IμS Ag microfocus source (Ag-Kα, λ = 0.56083 Å) at 100 K using a nitrogen gas open-flow cooler Cobra from Oxford Cryosystems. After the multipole refinement a topological analysis of the charge density was done. Halogen-halogen interactions were compared with the literature. There are known values for iodine-iodine interaction in solid iodine, for F∙∙∙F intermolecular interaction and for Cl∙∙∙Cl interaction, which are comparable with values obtained from (1). [1]Vranec. P. et al. (2012) Polyhedron 39, 118–123. [2]Bertolotti. F. et al. (2014) Crystal Growth & Design 14, 3587-3595. [3]Hathwar V. R., Guru Row T. N. (2010) J. Phys. Chem. A ,114, 13434-13441.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis optimisation of selected ligands used in copper(II) complexes D. Krajčiová, aM. Melník, a,bP. Mikuš

a

a

Department of Pharmaceutical Analysis and Nuclear Pharmacy, Faculty of Pharmacy, Comenius University in Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovak Republic b Toxicological and Antidoping Center, Faculty of Pharmacy, Comenius University in Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovak Republic  Mgr., Dominika Krajčiová; [email protected]; Faculty of Pharmacy, Comenius University in Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovak Republic

Carbonic anhydrase (CA) is an ubiquitous enzyme, crucial for many physiological (respiration and transport of CO2/bicarbonate between metabolizing tissues and lungs, pH and CO2 homeostasis, electrolyte secretion in a variety of tissues/organs, bone resorption, calcification) and pathologic processes. There were discovered 16 isozyme forms of CA with different tissue and subcellular localisation until now. The application of CA inhibitors (CAI) is in ophthalmology, neurology, nephrology and exploitation in oncology and gastroenterology. Recently, a new field in CAI research has been opened according to the potent anti-tumor properties of an entire class of sulfonamide CAI. The present study deals with the design of new 1,3,5-triazinylsubstituted sulfonamide conjugates with amino acids, used as a potential CAI, and their optimization and comparison of synthetic procedures. Subsequently, these conjugates are subject of their modification to corresponding Cu (II) complexes.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Understanding single-ion molecular magnetism J. Krzystek National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL USA  Dr. J. Krzystek; [email protected]

We will discuss properties of certain metal coordination complexes that make them “single-ion” molecular magnets, or SIMs. In particular, we will concentrate on the role of magnetic anisotropy originating from zero-field splitting (zfs), and how it correlates (or not) with the particular magnetic properties characteristic to SIMs such as a presence of an out-of-phase component of the ac magnetic susceptibility, or the activation energy of the magnetization reversal. Means to accurately measure the zfs will also be discussed with the particular emphasis on high-frequency and -field EPR and frequency-domain Fourier-transform terahertz EPR.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Nickel (II) Schiff base complexes: synthesis, characterization and magnetic properties V. Kuchtanin, J. Moncoľ, P. Segľa Depertment of Inorganic Chemistry, Institute of Inorganic Chemistry, Technology and Materials, Slovak University of Technology, Radlinského 9, SK-81237 Bratislava, Slovakia  Ing. Vladimír Kuchtanin, PhD.; [email protected]; Department of Inorganic chemistry, Institute of Inorganic Chemistry, Technology and Materials, Slovak University of Technology, Radlinského 9, SK-81237 Bratislava, Slovakia

Schiff base ligands have been extensively studied in coordination chemistry mainly due to their facile syntheses, easily tunable steric and electronic properties as well as good solubility in common solvents [1]. Five new octahedral Ni(II) complexes, namely [Ni(L)(CH)(MeOH)]·MeOH (1-4) and [Ni(HL)2(CH)]·AcN (5), were synthetized from a O,N,O-tridentate Schiff base H2L, phenantroline or bipyridine (CH) and Ni(CH3COO)2·4H2O, using different solvents and their ratios (MeOH and/or acetone and acetonitrile). The complexes under study have been characterized by spectral methods (IR and UVVIS spectroscopy), variable temperature and field magnetic measurments, and single crystal X-ray analysis. Acknowledgements: The financial supports of Slovak grant agencies VEGA (1/0388/14) and APVV (14-0078) and STU Grant scheme for support Excellent team (BIOKA 1664) are acknowledged for the financial support. [1]Shi, Q.; Xu, L.; Ji, J.; Li, Y. ; Wang, R.; Zhou, Z.; Cao, R.; Hong, M.; Chan, A. S. C.; Inorg. Chem. Commun. 2004, 7, 1254

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Trinuclear complex formation between Ca2+ and L-gulonate ions in strongly alkaline medium a

B. Kutus, aC. Dudás, bG. Peintler, cI. Pálinkó, aP. Sipos

a

Department of Inorganic and Analytical Chemistry, University of Szeged, 7 Dóm tér, H–6720 Szeged, Hungary b Department of Physical Chemistry and Material Scinece, University of Szeged, 1 Rerrich B. tér, H–6720 Szeged, Hungary c Department of Organic Chemistry, University of Szeged, 8 Dóm tér, H–6720 Szeged, Hungary  Prof. Dr. Pál Sipos; [email protected]; 7 Dóm tér, H–6720 Szeged, Hungary

Polyhydroxy-carboxylates, like D-gluconate and D-heptagluconate form highly stable, multinuclear complexes with calcium(II) in strongly alkaline (pH > 11) aqueous solutions. In the present work, the experimental work was extended to L-gulonate (Gul– ), the diastereomer of D-gluconate (Gluc–), and a broad range of experimental methods were employed. Potentiometric titration curves at T = 25 °C and I = 1 M have proven the deprotonation of the anion (pK = 13.72 ± 0.01) which was confirmed by 13C NMR spectroscopic measurements (pK = 13.75 ± 0.01). In presence of Ca(II) ions, the formation of three species, [CaGulH–1]0, [Ca3Gul2H–3]+ and [Ca3Gul2H–4]0, was revealed. The corresponding stability products are log β11–1 = –11.77 ± 0.01, log β32–3 = –30.52 ± 0.02 and log β32–4 = –42.65 ± 0.01, respectively. The high extent of ion association was further attested via using freezing point depression measurements. CaCl2- and temperature-dependent 1H NMR experiments suggested the C2-OH and C4-OH groups to be the coordination sites of the ligand (beside the carboxylate anion). Polarimetric measurements proved the deprotonation occurs of the coordinated anion.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

The composition of the second coordination sphere and intervalence charge transfer for the Ti(IV)/Ti redox couple in chloride-fluoride melts S. A. Kuznetsov, D. A. Vetrova Institute of Chemistry, Kola Science Centre of Russian Academy of Sciences 184209 Apatity, Murmansk region, Russia  Prof., Sergey A. Kuznetsov; e-mail: [email protected];

The aim of the present investigation was study of charge transfer kinetics for the redox couple Ti(IV)/Ti(III) in the (NaCl-KCl)equimol.-NaF(10 wt.%)-K2TiF6 melt and the estimation of the alkaline earth metal cations influence on the standard rate constants of charge transfer (ks) for this redox couple. Method of cyclic voltammetry was employed for the determination of the standard rate constants of charge transfer. It was found that addition of alkaline earth metal cations (Mg2+, Ca2+, Sr2+ and Ba2+) to the initial alkali chloride-fluoride melt resulted in increasing of ks up to the certain mole ratio of Me2+/Ti(IV), which was inversely proportional to ionic potential of cations. Increase of ks is connected with substitution of Na+ and K+ cations by strongly polarizing cations in the second coordination sphere of titanium complexes that led to increasing of the bond distance between Ti and F- ligands and decreasing of titanium fluoride complexes strength. It was determined the linear dependence of ks on ionic potential of alkaline earth metal cations and the maximum value was obtained for complexes with outer sphere cation of magnesium.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Study of copper(II) complexes with quercetin and rutin a

M. Valko, a,bM. K. Lawson, bK. Jomova

a

Faculty of Chemical and Food Technology, Slovak Technical University, 812 37 Bratislava, Slovakia b Department of Chemistry, Constantine the Philosopher University in Nitra, Tr. A. Hlinku 1, 949 74 Nitra, Slovakia  M. K. Lawson: PhD., Michael Kenneth Lawson; [email protected]; Department of Chemistry, Constantine the Philosopher University in Nitra, Tr. A. Hlinku 1, 949 74 Nitra, Slovakia

Using the techniques of UV-vis and epr spectroscopy copper(II) ions were shown to react with quercetin, and to a lesser extent with rutin, in suitable solvents such as methanol and DMSO. Quercetin is insoluble in water but we were able to produce a copper-quercetin complex in a solution of largely water with a little methanol. The ratio of quercetin molecules to copper ions were determined using a Job’s plot and was different for different solvents and for different copper(II) salts used (that is CuSO 4 and CuCl2). DNA damage assays showed that the complexes had quite a powerful ability to cut DNA strands suggesting some prooxidative properties. Experiments using bathocuprin suggested that quercetin could to some degree reduce copper(II) to copper(I) suggesting catalytic prooxidative activity of the complex by decomposition of hydrogen peroxide to form free radicals. In contrast antioxidant properties were demonstrated by spin trapping experiments which showed that the complexes neutralized hydroxyl radicals. DPPH assays showed that the copper complexes of the flavonoid were more powerful than the flavonoid by itself, in the case of quercetin.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Physicochemical properties and biological activity of naringenin thiosemicarbazone a

E. Lodyga-Chruscinska, aK. Brodowska, aE. Klewicka, b E. Garribba, cL. Chruściński

a

Faculty of Biotechnology and Food Chemistry, Lodz University of Technology, ul. Stefanowskiego 4/10, 90-924 Lodz, Poland b Dipartimento di Chimica e Farmacia, Università di Sassari, via Vienna 2, I-07100 Sassari, Italy c Faculty of Process an Environmental Engineering, Lodz University of Technology, ul. Wólczańska 175, 90-924 Lodz, Poland  Professor, Elzbieta Lodyga-Chruscinska; e-mail: [email protected]; Correspondence Address: Lodz University of Technology, ul. Stefanowskiego 4/10, 90-924 Lodz, Poland

Thiosemicarbazones are well established as an important class of sulphur-donor Schiff base ligands that are particularly useful for transition metal ions. This is due to the remarkable biological activities of these compounds, which have been shown to be related to their metal complexing ability. It must be admitted that regardless of the amount of data on the activity of thiosemicarbazones and their metal complexes, there are still many unknown details about their mechanism of action. Hence, further studies are necessary to explain the observed phenomena and deepen the present knowledge in this field. The synthesis of new thiosemicarbazone derivative of naringenin, a natural flavanone, and its antioxidant activities were investigated in our previous studies. This work is devoted to reveal physicochemical properties and biological actions of naringenin thiosemicarbazone and its copper complexes forming in mixed solvent solutions. An equilibrium solution study has been performed on the complexes with the biologically essential transition-metal ion Cu(II) in DMSO /water mixture by means of pH-potentiometric, UV/Vis and EPR spectroscopic methods. Plasmid DNA studies have been undertaken to reveal biological effect of the ligand and the complex. An attempt to characterize their antibacterial and antifungal properties will be also reported.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Structure and magnetism of potential single-ion magnets based on Ni(II) and Co(II) complexes D. Lomjanský, aF. Varga, aC. Rajnák, bJ. Moncoľ, aR. Boča, aJ. Titiš

a

a

Department of Chemistry, Faculty of Natural Sciences, University of SS. Cyril and Methodius, Nám. J. Herdu 2, 917 01 Trnava, Slovakia b Institute of Inorganic Chemistry, Faculty of Chemical and Food Technology, Radlinského 9, 812 37 Bratislava 1, Slovakia  Dominik Lomjanský; [email protected]

Single-molecule magnets (SMMs) are one of the major scientific targets of the modern inorganic chemistry because of their potential applications in high-density magnetic memories and quantum computing devices. We have prepared a simple Co(II) complex [Co(qu)2Br2] and Ni(II) complex [Ni(PPh3)2Cl2] (qu = quinoline, PPh3 = triphenylphosphine) that have been structurally and spectrally characterized. Magnetic properties of these different spin systems (Kramers ion, S = 3/2) and (non-Kramers ion, S = 1)) were investigated using SQUID magnetometry. These complexes exhibit a moderate magnetic anisotropy expressed by zero-field splitting parameter D. The D-value is in both cases positive, D/hc = +5.94 cm-1 and D/hc = +12.76 cm-1. These results were supported by quantum chemical calculations. Acknowledgments: Slovak grant agencies (APVV-14-0078, APVV-14-0073 and VEGA 1/0534/16) are acknowledged for the financial support.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis, characterization and anticancer properties of Pd(II) ionic complexes with quinolin-8-ol halogenderivatives A. Lükőová, aV. Farkasová, bH. Paulíková, bT. Balašková, aI. Potočňák

a

Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, Moyzesova 11, 041 54 Košice, Slovakia b Department of Biochemistry and Microbiology, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia a

 Mgr. Andrea Lükőová; [email protected]; Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University, Moyzesova 11, 041 54 Košice, Slovakia

Six coordination compounds of general formula Cat[PdCl2(XQ)], where Cat is K+ or Cs+ and XQ are biologically active derivatives of quinolin-8-ol (5-chloro-7-iodoquinolin-8-ol, 5,7-dichloro-quinolin-8-ol (dClQ) and 5,7-dibromo-quinolin-8-ol) have been prepared by cationic exchange from formerly prepared NH2(CH3)2[PdCl2(XQ)] complexes. Prepared complexes were characterized using IR and UV-Vis spectroscopy, elemental and thermal analysis. The in vitro antitumor properties of the complexes on A2780 ovarian cancer cell line and L1210 leukemic cell line were studied by MTT assays and compared with direct cell counting (DCC) method; the results show that DCC method is more reliable in this case. Most of the complexes are more active than cisplatin (K[PdCl2(dClQ)] exhibited the highest activity) and moreover, are selective cytotoxic against studied cancer cell lines (mainly on L1210 cells) as confirmed by tests on non-cancerous HEK293 cell line. Activity of the complexes on A2780 cell line was compared with the activity of three starting NH2(CH3)2[PdCl2(XQ)] complexes. This work was supported by the VEGA grant 1/0598/14 and the grant VVGS-2016-265.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Copper(II) dipicolinate compounds of potential catecholase activity P. Masárová, aV. Kuchtanin, bM. Mazúr, aJ. Moncoľ

a

a

Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovak Republic b Department of Physical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovak Republic  Ing. Petra Masárová; [email protected]

Investigation of enzymatic activity plays an essential role in bioinorganic chemistry. One of the most important enzymes is catecholase, which catalyzes the oxidation of catechol to o-quinone. The native enzyme catecholase consists of two bridged Cu(II) atoms through OH group and each Cu(II) atom is coordinated via three nitrogen atoms of histidines. From this reason our attention was focused on copper(II) complexes with N- and N,O- donor ligands. Overall, seven copper(II) compounds of dipicolinic acid with N-donors (nicotinamide derivatives, substituted benzimidazoles) have been prepared, structurally characterized and studied by methods of EPR, UV/VIS and IR spectroscopy. X-ray diffraction analysis revealed that central copper(II) atoms are either five- or six-coordinated with distorted square-pyramidal or octahedral geometry depending on the coordination mode of dipicolinic acid. Three different binding modes of dipicolinic acid were observed in the compounds, tridentate chelating and tridentate chelating as well as bridging through one or more oxygen atoms of carboxylate group. Acting of dipicolinic acid as a bridging ligand resulted in the formation of polymeric compounds. Synthesized monomeric compounds will be object of our further research – study of enzyme mimetic activity.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Crystal structure of Ni(II) complexes synthetized with 4-methylpiperidine and tridentate Shiff base S. Matejová, V. Kuchtanin, V. Jorík Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radinského 9, 812 37 Bratislava, Slovakia  Ing. Simona Matejová; [email protected]

We have focused on characterization of new Ni(II) complexes synthetized with 4-methylpiperidine (B) and tridentate Shiff base (H2L) using methods of power diffraction. Crystal structure of [Ni(L)B] was solved by single crystal structural analysis. Using Le Bail method, it was found that the simulated diffraction pattern does not match the experimental diffraction pattern of the bulk powder sample. It was considered that this sample could be mixture of complex with already solved crystal structure and other yet unknown compound. Based on this observation, the syntheses with the same reactants at different experimental conditions were made. The products were evaluated with qualitative phase analysis and four different products were found. It has been shown that two of these products can form the already mentioned bulk sample. This work presents preliminary results of single crystal and powder structural analysis of the four samples and comparison of the crystal structures obtained from powder and single crystal analysis.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Transition metal complexes of mono- and trisubstituted trenderivatives a

F. Matyuska, aA. Szorcsik, cN. V. May, bÁ. Dancs, d É. Kováts, eA. Bényei, a,bT. Gajda

MTA-SZTE Bioinorganic Chemistry Research Group, Dóm tér 7, H-6720 Szeged, Hungary Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, H-6720 Szeged, Hungary. c Research Centre for Natural Sciences HAS, Magyar tudósok körútja 2, H-1117 Budapest, Hungary d Institute for Solid State Physics and Optics, Wigner Research Centre for Physics HAS, Konkoly Thege Miklós u. 29-33, H-1121 Budapest, Hungary e Department of Pharmaceutical Chemistry, University of Debrecen, Egyetem tér 1, Debrecen H-4032, Hungary a b

 Ferenc Matyuska, e-mail: [email protected], Dóm tér 7, H-6720 Szeged, Hungary

Tripodal ligands provide enhanced chelate effect and reduced number of relevant binding conformations, resulting higher stability of their metal complexes. Tren (tris-(2-aminoethyl)amine) based tripodal ligands are widely used to develop metal ion chelators for divergent purposes. Here, we report the synthesis of three differently substituted tren-derivatives (N,N’,N’’-tris[N-(3-pyridilmethyl)-21 aminoethyl]amine (L ), N-[N-(2-pyridilmet-hyl)]-(tris-(2-aminoethyl)amine) (L2), and N-[N-(9-anthracylmethyl)]-(tris-(2-aminoethyl)-amine) (L3)), and the equilibrium and structural studies of their metal complexes. In equimolar solution L1 forms only mononuclear complexes with trigonal bipyramidal geometry. At metal ion excess, the formation of a 3D polymer was observed with copper(II)/L1 ratio of 11/6. Within this MOF three distinctly different copper geometries can be identified: two square pyramidal and four trigonal bipyramidal copper centres create a hexanuclear subunit with a large inside cavity. These moieties are linked by tetrahedral copper(II) centres, constructing the 3D structure. L2 has high metal sequestering ability and forms octahedral MHL2 and trigonal bopyramidal ML2 complexes. L3 is a useful zinc(II) sensor and their metal complexes have enhanced the DNA binding ability.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

EPR spectroscopy of TEOS-based sol-gel process. An “U-spectra“ type of Gd(III) EPR spectra analysis M. Mazúr, P. Poprac, M. Valko Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinskeho 9, SK-812 37 Bratislava, Slovak Republic  Dr. Milan Mazur; [email protected]; Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinskeho 9, SK-812 37 Bratislava, Slovak Republic

In the present contribution, the various stages of the TEOS-based sol-gel process were studied using Gd(III) cations as a spin probe, by the EPR spectroscopy at both, the room and liquid nitrogen temperatures. Very similar 77 K Gd (III) EPR spectra (being ‘U-spectrum’ type) were recorded at the various defined stages of the sol-gel process. The analysis of the experimental Gd(III) EPR spectra showed that, as the solgel process proceeded the spin Hamiltonian parameters remained unchanged (within experimental error), but the relative amplitude of the α-line (recorded at g ~ 2.8) and β-line (recorded at g ~ 2.0) changed significantly, such that the α/β–ratio decreased progressively. Accordingly, those changes that occurred in the sol-gel reaction mixture during its liquid-state to solid-state transformation could be monitored on the basis of the changing α/β–ratio. This is the first report that the silica sol-to-gel transition from the low viscosity, starting reaction mixture to the high viscosity, colloid suspension, up to the viscoelastic gel and finally to the dry gel can be successfully monitored using Gd(III) EPR spectroscopy. Acknowledgement: This work was supported by the Slovak Research and Development Agency under the contact No. APVV-15-0053 and by the Scientific Grant Agency of the Slovak Republic (Projects VEGA 1/0041/15 and VEGA 1/0686/17).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Copper complexes as perspective cancerostatic drugs M. Melník, P. Mikuš, D. Krajčiová Faculty of Pharmacy, Comenius University in Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovak Republic  Prof. RNDr. Milan Melnik, DrSc.; e-mail Address; [email protected]

Medicinal chemistry is one of the most rapidly developing areas of pharmaceutical research. One of the fundamental goals in medicinal chemistry is the development of new anticancer and antimicrobial therapeutic agents. Cancer treatment using metalbased drugs is one of the very effective strategies as the metal ions are capable to binding the nucleic acids. One of such metal is copper which is an essential element with many physiological functions. It affects activity of many “blue” enzymes to date, genetic studies in model systems one biochemical, cell biology, and structural studies have identified many proteins involved in eukaryotic copper hemostasis and provided insights into their structures and mechanism of action. As we gain a better understanding of the factors affecting cancer etiology, we can design improved treatment strategies. Over the last four decades, there have been numerous successful efforts in recognizing important cellular proteins have been targeted for cancer treatment. Several reports in the literature have shown that both serum and tumor copper levels in cancer patients are significantly elevated. Copper plays an important role in tumor angiogenesis, especially at its early stages. A brief view on the usage of copper complexes in oncology will be presented. Some copper complexes were applied for the treatment of human leukemia cell and other applications for treatment of breast, lung, colon, kidney, pancreatic and prostate cancer, ovarian carcinoma, malignant melanoma-skin, renal carcinoma, osteogenetic sarcoma and mammary glace cancer.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Half-sandwich rhodium(III) complexes formed with (N,N) ligands: structural characterization and solution chemistry J. P. Mészáros, a,bO. Dömötör, cC. M. Hackl, cA. Roller, c W. Kandioller, cB. K. Keppler, aÉ. A. Enyedy

a

Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, H-6720 Szeged, Hungary b MTA-SZTE Bioinorganic Chemistry Research Group, Dóm tér 7, H-6720 Szeged, Hungary c Institute of Inorganic Chemistry, Faculty of Chemistry, University of Vienna, Währinger Str. 42, A-1090 Vienna, Austria a

 Dr. Éva A. Enyedy; e-mail: [email protected]

Cisplatin and its derivatives are frequently used in cancer chemotherapy. Due to their severe side effects other metallodrug candidates were developed and investigated in clinical trials. Ru(III)-based complexes (NAMI-A and NKP-1339) and organometallic half-sandwich Ru(II)-complexes (RAED and RAPTA) showed promising results. Their isoelectronic Os(II), Rh(III) and Ir(III) congeners are also synthesized and characterized. Herein we report the comparative X-ray structural and solution equilibrium study of six organometallic rhodium(III) complexes formed with (N,N) donor bidentate ligands, namely: ethylenediamine and its various methylated derivatives, 2-picolylamine, 2,2’-bipyridine and 1,10-phenanthroline. These studies were performed using pHpotentiometry, 1H NMR spectroscopy and UV-Vis spectrophotometry. Our results revealed high complex stability and chloride ion affinity. Probably these properties have influence on the mode of action in cells. We have also investigated the possible binding modes to human serum albumin and DNA via ultrafiltration/UV-vis spectrophotometry, spectrofluorometry and 1H NMR spectroscopy. This work was supported through the New National Excellence Program of the Ministry of Human Capacities; the National Research, Development and Innovation Office-NKFIH through project GINOP-2.3.2-15-2016-00038; OTKA PD103905 and TÉT_15-1-2016-0024.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Characterization and a potential catalytic application of a novel silver-bismuth composite R. Mészáros, a,bS. B. Ötvös, cG. Varga, aM. Kocsis, cI. Pálinkó, a,bF. Fülöp

a

Institute of Pharmaceutical Chemistry University of Szeged, Eötvös utca 6, Szeged H-6720 Hungary; b MTA-SZTE Stereochemistry Research Group, Eötvös utca 6, Szeged H-6720 Hungary c Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-6720 Hungary a

 Prof. István Pálinkó; [email protected], Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720 Hungary

 Dr. Sándor B. Ötvös ; [email protected], MTA-SZTE Stereochemistry Research Group, Eötvös utca 6., Szeged, H-6720 Hungary

Silver-catalyzed reactions are of significant importance in organic chemistry. Nevertheless, efficiently reusable silver-containing catalytic systems are scarce, soluble salts are employed typically as catalytic sources in such transformations. We developed a silver-bismuth composite as a novel heterogeneous silver catalyst. The composite was synthesized by means of urea-mediated homogeneous precipitation of the corresponding metal nitrates. The as-prepared material was characterized with numerous methods including X-ray diffractometry, IR spectroscopy, scanning electron microscopy and ICP analysis. Nitriles are useful ingredients in the synthesis of pharmaceuticals and natural products. Therefore, we investigated the catalytic activity of the silver-bismuth composite in nitrogenation reactions of various alkynes with TMSN3 as nitrogen source. After a thorough optimization study, we achieved high-yielding nitrile formation. Importantly, the solid catalyst could be filtered off and reused numerous times. In conclusion, we developed a heterogeneous silver-bismuth containing composite displaying excellent catalytic activity in nitrogenation of alkynes.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Trinuclear mixed-valent manganese complex with non-Schiff-base tetradentate ligand showing a ferromagnetic coupling M. Mikuriya, I. Matsushima, D. Yoshioka Department of Applied Chemistry for Environment and Research Center for Coordination Molecule-based Devices, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, 669-1337, Japan  Professor, Masahiro Mikuriya; e-mail [email protected]; Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, 669-1337, Japan

Mixed-valent trinuclear manganese complex with N,N’-bis(2-hydroxy3,5-dimethylbenzyl-1,2-ethanediamine (H2hdde), [Mn3(hdde)2(CH3CO2)2(CH3O)2], was synthesized. The crystal structure was determined by the single-crystal X-ray diffraction method at 123 K. It crystallizes in the monoclinic space group Pca21 with a = 23.573(3) Å, b = 20.057(2) Å, c = 22.416(3) Å, V = 10598(2) Å3, Dx = 1.361 g/cm3, and Z = 4. The R1 [I > 2(I)] and wR2 (all data) values are 0.0669 and 0.1264, respectively, for all 23266 independent reflections. The compound is composed of three manganese atoms, MnIII-MnII-MnIII, with nearly linear arrangement where two manganese atoms of each MnII-MnIII pair are bridged by µ-phenolato-oxygen atom of hdde2– ligand, µ-methanolato-oxygen, and µ-acetato ion. Temperature dependence of magnetic susceptibilities (4.5—300 K) showed an increasing of magnetic moment with lowering of temperature, showing a ferromagnetic coupling (J = 1.84 cm–1). The result will be discussed with the related dinuclear, trinuclear, and tetranuclear manganese complexes.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Reactivity of coordinated azides F. Mohr Anorganische Chemie, Bergische Universität Wuppertal, Gaussstr. 20, 42119, Wuppertal, Germany  Prof. Dr. Fabian Mohr; [email protected]; Anorganische Chemie, Bergische Universität Wuppertal, Gaussstr. 20, 42119, Wuppertal, Germany.

Metal-bound azido ligands can undergo 1,3-dipolar cycloaddition reactions with a variety of substrates including alkynes, isothiocyanates, nitriles and isonitriles. In most cases the resulting heterocycles remain coordinated to the metal. Depending on the nature of the substrate, the heterocycle may coordinate to the metal through carbon-, nitrogen- or sulfur-atoms. Thus, using this approach it is possible to build-up a heterocyclic ligand from a metal-bound azide in a simple and clean reaction. In this presentation we will illustrate various examples of this approach and also show its scope and limitations. We have examined cycloaddition reactions of metal complexes containing one, two and three azido ligands. Gold(I) azido species react with isothiocyanates to give products containing S-bound tetrazoles. A similar reaction occurs with palladium(II) and platinum(II) bis(azido) complexes. Surprisingly, gold(III) tris(azido) compounds either do not react at all or undergo cycloaddition reactions accompanied by reduction to gold(I). Most unusual is the reaction of dimeric azido-bridged palladium(II) complexes with methyl isothiocyanate, which leads to assembly of a thiotetraazapentalene ligand.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Structurally diverse manganese(III)-salen complexes with bridging formate ligand M. Schoeller, L. Neuwirthová, M. Izakovič, J. Moncoľ Department of Inorganic Chemistry, Institute of Inorganic Chemistry, Technology and Materials, Slovak University of Technology,SK-81237 Bratislava, Slovakia  Associate Professor, Jan Moncol; e-mail [email protected];

A series of formate-bridged manganese(III) complexes derived from Schiff based obtained by the condensation of salicylaldehyde, 5-bromo-salicylaldehyde, 5-chlorosalicylaldehyde, 3,5-dibromo-salicylaldehyde or 3,5-dichloro-salicylaldehyde and 1,2diamineethane have been synthesized and characterized using single-crystal X-ray crystallography in the cases of [Mn(salen)(HCO2)]n (1), [Mn(5-Brsalen)(HCO2)]n (2), [Mn(5-Clsalen)(HCO2)]n (3), [Mn(3,5-Br2salen)(HCO2)]n (4) and {[Mn(3,5-Cl2salen)(HCO2)].MeOH}n (5). The crystal structures of [Mn(salen)(HCO2)]n (1) in variety temperatures show two phase transitions.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis of layered double hydroxides in the presence of long-chained alcohols – structural characterization S. Muráth, P. Sipos, I. Pálinkó Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-6720 Hungary  Prof. István Pálinkó, [email protected], Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720 Hungary

Layered double hydroxides (LDHs) are versatile members of inorganic carrier materials with positively charged layers, varying metal composition and facile anion-exchange ability. The morphology of the LDHs depends on numerous factors, for example the synthetic method, synthesis temperature, rate of pH change, aging and the type LDH itself. Morphologies observed consist of hexagonal platelets, rosebuds, toroids, wires, etc. CaAl-LDH sheets exfoliated in octanol were restacked with aqueous treatment, and the resulting solid showed crystals with improved morphology. In our current work, we are investigating the regular structure of LDH prepared by co-precipitation method in the presence of non-miscible alcohols. The metals salts were dissolved in water, and the solution was saturated with various alcohols before the addition of the base to form a slurry mixture. The effect of organic material was determined by powder X-ray diffractometry, infrared spectroscopy and scanning electron microscopy.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

The effect of the experimental parameters on the formation of Cu/Cu2O nanoparticles K. Musza, A. A. Ádám, M. Szabados, P. Sipos, I. Pálinkó Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H–6720 Hungary  Prof. Dr. István Pálinkó; [email protected]; Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720 Hungary

The importance of metallic nanoparticles (NPs) is mainly due to their unique physical and chemical properties. This results in wide range of applications. Among the NPs, those made of copper are particularly attractive, because of their low cost (relative to other noble metals); however, their preparation is problematic they are sensitive to oxygen to a large extent. The actual method used for their preparation determines the structure of CuNPs, which strongly influences their catalytic properties. In the last two decades various methods (chemical, physical and biological techniques) were described in the literature for the synthesis of CuNPs. In this contribution, an attempt to synthesize Cu/Cu2O nanoparticles via using a chemical reduction method with CuCl2 as starting material and hydrazine as reducing agent in ethanolic medium is described. The effect of various experimental parameters on the properties of the Cu/Cu2ONPs thus synthesized has been systematically studied. The structural characteristics of the NP samples were determined by X-ray diffractometry (XRD) and scanning electron microscopy (SEM).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Multidimensional multiplet energy diagrams for Cr3+ in oxides based on first-principles calculation K. Ogasawara Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo, 669-1337, JAPAN  Professor, Kazuyoshi Ogasawara; [email protected];

 Department of Chemistry, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo, 6691337, JAPAN

The materials doped with d3 ions such as Cr3+ and Mn4+ have been utilized as luminescent materials such as solid-state lasers and phosphors. In the case of octahedral coordination, the relationship between the multiplet energies and the crystal field parameters can be understood based on the so-called Tanabe-Sugano diagram. However, for the theoretical design of novel luminescent materials with controlled absorption and emission wavelengths, it is indispensable to clarify the relationship between the absolute multiplet energies and the actual local structures. In this work, in order to provide such information for Cr3+ in oxides, the multiplet energy diagrams for CrO69- clusters with Oh, D4h, C4v symmetries were created by performing the systematic first-principles configuration-interaction (CI) calculations using the discrete variational multi-electron (DVME) code for the clusters with gradually changed bond lengths and bond angles. Since the number of the structural parameters increases for lower symmetry, the multidimentional diagrams were created for D4h and C4v. The influence of the tetragonal distortion and the bond lengths on the multiplet energy levels have been clarified based on these diagrams, which would be useful for the theoretical design of the novel solid-state laser or phosphor materials based on d3 ions.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Advanced structural analysis of coordination Cu4OX6L4 molecules G. Ondrejovič, J. Moncoľ Institute of Inorganic Chemistry, Technology and Materials, Faculty of Chemical and Food Technology , Slovak University of Technology, 812 37 Bratislava, Radlinského 9, Slovakia  Prof. Gregor Ondrejovič, [email protected]

Vector calculations applied usualy to mechanical and electrical macroconstructions are here applied to microconstructions represented by structures of Cu4OX6L4 (X = Cl, Br, L = O and N-donor ligands) molecules. Vector analysis is used to describe molecular structural dynamics and corresponding electron densities shifts. Each structure of the Cu4O1X6L4 molecules consists of two basic polyhedra: the central four bonding Cu4–O1 tetrahedron described by four bonding vectors Cu–O1, tCu and the non-bonding - distance X6∙∙∙O1 octahedron described by six distance vectors X∙∙∙O, ox. The origin of vectors of the complex molecules and their inner- and intermolecular contacts is given by the three dimensional Cartesian coordinate system with the central oxygen atom O1 placed in its origin 0. The vector analysis was applied to 16 structures of the Cu4OCl6L4 complex molecules with L = imidazole and its derivatives. Obtained results demonstrate interesting correlations between structural molecular parameters and supramolecular inner- and intermolecular contacts by hydrogen bonds and van der Waals interactions.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Rare earth metal complexes of polyether ionophores a

A. Nedzhib, bV. Ivanova, bI. Pantcheva

a

Department of Disaster Medicine and Toxicology, Military Medical Academy, Sofia, Bulgaria b Department of Analytical Chemistry, Faculty of Chemistry and Pharmacy, "St. Kl. Ohridski" University of Sofia, Sofia, Bulgaria  Assos. Prof. Ivayla N. Pantcheva, PhD; [email protected]

Natural polyether ionophorous antibiotics possess diverse activity against parasites, Gram-positive microorganisms, fungi, tumor cells, etc. Knowledge on their coordination chemistry has become important due to variety of complex species formed with mono- and divalent metal ions, and to enhanced biological activity of the ligands via complexation process. Recently we studied coordination ability of Monensin and Salinomycin to bind trivalent metal ions of rare earth elements and found that depending on the metal-to-ligand molar ratio one neutral and two positively charged complex species form in methanolic solutions. Neutral complexes were characterized by various spectroscopic methods in solution and in solid state. It is assumed that structure of compounds corresponds to the mononuclear complex species, containing three deprotonated ligands. Each ionophore monoanion is coordinated to the metal cation in bidentate mode via carboxylate moiety and hydroxyl function, both located at the opposite ends of the molecule. The cavity of ligands is occupied by water molecule coordinated to the metal center and participating in hydrogen bonds of different origin. Acknowledgements: This research has received funding from TÁMOP 4.2.4. A/2-11-12012-0001 „National Excellence Program – Elaborating and operating an inland student and researcher personal support system” key project (subsidized by the European Union and co-financed by the European Social Fund) and H2020-Twinning project (Materials Networking; 692146).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Magnetic exchange interaction transmitted by H-bonds J. Pavlik, aM. Puchoňová, aJ. Moncoľ, b,aD. Valigura

a

Department of Inorganic Chemistry, Slovak University of Technology, Radlinského 9, SK812 37, Bratislava, Slovakia b Department of Chemistry, University of SS Cyril and Methodius, Nám. J. Herdu 2, SK-917 01, Trnava, Slovakia a

 Dr. Ján Pavlik; [email protected]; Department of Inorganic Chemistry, Slovak University of Technology, Radlinského 9, SK-812 37, Bratislava, Slovakia

The hydrogen-bonds are being progressively recognized for their ability to transmit the magnetic exchange interaction. In presented work the magnetism of two new dimeric Cu(II) complexes is analyzed, where the H-bonds play a crucial role, namely [Cu(μ-menia)(3-Mesal)2(menia)(H2O)]2 (1), and [Cu(μ-nia)(5-Mesal)2(H2O)]2 (2), where menia stands for N-methylnicotineamide and 5-Mesal for 5-methylsalicylato anion. From the structural point of view the dimers are linked by the H-bonds resulting in a 1D chain supramolecular system. On the other hand, the DFT study showed that the superexchange pathway operates preponderantly at the intermolecular level via the H-bond linkers, making thus a distinction between the molecular and magnetic structure of the system. The parameters extracted from the magnetization fitting and calculated by the DFT approach are mutually in very good qualitative and quantitative accordance. The wave-function based calculations indicate that the H-bonds play active role in the communication of the magnetic Cu(II) centers. Acknowledgement: Grant Agencies (Slovakia: APVV-14-0078, APVV-14-0073, VEGA 1/0522/14, KEGA 017STU-4/2017) and STU Grant scheme for Support of Excellent Teams of Young Researchers are acknowledged for the financial support. We are also grateful to the HPC centre at the Slovak University of Technology in Bratislava (SIVVP project, ITMS code 26230120002, funded by the European region development funds, ERDF).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Copper(I)-cyanide frameworks through thermal or photo decomposition of the free radical diazo initiator AIBN T. Pintauer Duquesne University, Department of Chemistry and Biochemistry, 600 Forbes Avenue, 308 Mellon Hall, Pittsburgh, PA 15282, USA

Thermal or photodecomposition of the classical free radical generating diazo reagent 2,2′-azobis(2-methylpropionitrile) (AIBN) was used as a source of cyanide anions in the synthesis of copper(I)–cyanide frameworks. The reported methodology utilizes the direct reduction of CuII(aa)(NN)X (aa = deprotonated amino acid, NN = bidentate nitrogen-based ligand, X = Cl or Br) complexes by AIBN/ascorbic acid to yield seven novel coordination networks. Aromatic amines were directly incorporated into 1D CuI– CN chains. In the case of the aliphatic amine tetramethylethylenediamine (TMEDA), a 3D CuI–CN framework was obtained. This novel procedure is mild, applicable to a variety of nitrogen-based ligands, and represents an efficient alternative to currently used hydrothermal or solvothermal methods.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Spin crossover and high spin iron(III) Schiff base complexes L. Pogány, I. Šalitroš Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Bratislava SK-81237, Slovakia.  Pogány Lukáš; [email protected]; Department of Inorganic Chemistry, Faculty of Chemical and Food Technology, Radlinského 9, Bratislava SK-81237, Slovakia.

Reaction of various phenols with benzoyl chloride afforded derivatives of phenyl benzoate that subsequently underwent Fries rearrangement. Obtained 2-hydroxybenzophenone analogues were combined with linear aliphatic triamines which afforded formation of pentadentate Schiff base ligands. Eleven new iron(III) complexes of the general formula [Fe(Ln)X] (where Ln is dianion of pentadentate Schiff base ligand and X is chlorido, azido, isocyanato or isothiocyanato terminal ligand) have been synthesized and characterized by elemental analyses, IR, and UV–VIS and the crystal structures of all complexes have been determined by X-ray diffraction. Investigation of magnetic properties revealed high spin state behavior of nine reported compounds when symmetrical triamines 1,5-diamino-3-azapentane, 1,7-diamino4-azaheptane or 1,7-diamino-4-aza-4-methylheptane were introduced in the Schiff base ligand. DFT calculations and analysis of magnetic functions allowed to extract absolute values of zero field splitting parameters and exchange coupling constants. On the other hand, SCO phenomenon with transition temperature in above room temperature was observed in two other compounds that utilized asymmetrical triamine 1,6-diamino3-azahexane in ligand synthesis.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Structures and in vitro cytotoxic properties of Pd(II) complexes with 7-bromo-quinolin-8-ol a

I. Potočňák, bS. A. Drweesh, aV. Farkasová, aA. Lüköová, c A. Arsenijevic, cD. Djordjevic, cV. Volarevic

Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, Moyzesova 11, 04154 Košice, Slovakia b Department of Inorganic Chemistry, National Research Center, P.O. 12622, 33 Elbohoth St. (former Elthrir st.), Dokki, Giza, Egypt c Center for Molecular Medicine and Stem Cell Research, Faculty of Medical Sciences University of Kragujevac, 69 Svetozara Markovica, 34000 Kragujevac, Serbia a

 Assoc. Prof. Ivan Potočňák, PhD.; [email protected]; Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University, Moyzesova 11, 041 54 Košice, Slovakia

Two polymorphic complexes, [Pd(BrQ)2] (1a) and (1b), and HBrQ[PdCl2(dBrQ)] (2) complex (BrQ is 7-bromo-quinolin-8-ol (BrQ) have been prepared and characterized. X-ray structure analysis of 1a and 1b revealed that the molecular structures of these square-planar polymorphs are very similar, nevertheless their supramolecular structures slightly differ due to different intermolecular forces. The structure of 2 in DMSO solution was studied using NMR experiments which showed that the complex decomposes to BrQ ligand. Cytotoxic activities of 2 and BrQ ligand were tested on human colorectal cancer cells HCT116 and compared. Complex 2 is significantly more cytotoxic against HCT116 cells than cisplatin at all tested concentrations and this effect is particularly pronounced at low concentrations, however the BrQ ligand is even more active.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

New different salicylatocopper(II) complexes with isonicotinamide M. Puchoňová, aS. Matejová, aV. Jorík, aJ. Moncoľ, bD. Valigura

a

a

Department of Inorganic Chemistry, Slovak University of Technology in Bratislava, Radlinského 9, 812 37 Bratislava Slovakia b Department of Chemistry, University of SS Cyril and Methodius in Trnava, J. Herdu 2, 917 01 Trnava, Slovakia  Ing. Miroslava Puchoňová, PhD.; [email protected]

The dimeric complex [Cu(3-Mesal)2(inia)2]2 1, polymeric complex [Cu(4-MeOsal)2(inia)(H2O)]n 2 and monomeric compound [Cu(4-MeOsal)2]·H2O 3, (where 3-Mesal– = 3-methylsalicylato, 4-MeOsal– = 4-methoxylsalicylato, inia = izonicotinamide), were prepared and characterized in solid state and in solution. The solid state complexes were characterized by IR, UV-Vis, and EPR spectra. Moreover, the preliminary results of the X-ray structure determination are also presented. Coordination environment of compound 1 is different in comparison to complex 3, but in both compounds similar 2-D supramolecular frameworks build up in contrast to complex 2, where the chain structure was found. The cyclic voltammetry study, as well as the superoxide dismutase activity of prepared complexes in solution has been measured. The superoxide dismutase-like (SOD-like) activity of complexes was studied by NBT assay, and results are compared with the activity of the parent ligands, copper acetate and native SOD enzyme as well as with related copper complex containing non-steroidal anti-inflammatory drugs. SOD mimetic activity of the prepared compounds exhibited slightly different IC50 values for compounds. The SOD activity together with the redox stability is related to the composition, structure of the complexes.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

DFT studies of the effectiveness of p-substituted diphenyl amine antioxidants through their Cu(II) coordination ability I. Puškárová, M. Breza Department of Physical Chemistry, Slovak Technical University, Bratislava, Slovakia  Ingrid Puškárová; e-mail: [email protected]; Department of Physical Chemistry, Slovak Technical University, Radlinského 9, SK-812 37 Bratislava, Slovakia

Geometries of eight p-substituted diphenyl amine (Aox) antioxidants with Cu2+ ions bonded to amine nitrogen sites were optimized at B3LYP/6-311G* level of theory. The extent of electron density transfer between Aox and Cu2+ were evaluated in terms of Cu atomic charges, Cu spin densities and electron density Laplacians at Cu – N bond critical points which were correlated with corresponding Molar Antioxidant Effectiveness (AEM) data obtained experimentally by Šimon et al. at 25 °C and 130 °C in polystyrene-butadiene rubber. AEM values of three compounds are high (over 1000 kg/mol) and significantly depend on the temperature unlike AEM values of the remaining five compounds. The relations between AEM and the above electron density characteristics depend on the temperature as well. This work was supported by the Slovak Grant Agency VEGA under the contract no. 1/0598/16. We thank the HPC center at the Slovak University of Technology in Bratislava, which is a part of the Slovak Infrastructure of High Performance Computing (SIVVP Project No. 26230120002, funded by the European Region Development Funds), for computing facilities.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Field supported slow magnetic relaxation in hexacoordinate Co(II) complexes with easy plane anisotropy C. Rajnák, R. Boča Department of Chemistry, Faculty of Natural Sciences, University of SS. Cyril and Methodius, 917 01 Trnava, Slovakia  Dr. Cyril Rajnák; e-mail: [email protected]; University of Ss. Cyril and Methodius, Námestie J. Herdu 2, Trnava, 917 01, Slovak Republic

Single molecule magnets known up to date cover several classes of transition metal complexes: there are polynuclear and mononuclear, 3d and 4f, heteronuclear 3d-4f, field induced and field suppressed, with single mode and multimode relaxation channel systems. Over the past years an increased interest is paid to mononuclear 3d complexes mainly for their easy synthesis, stability, and low price. Two mononuclear cobalt(II) complexes containing four equatorial 4-benzylpyridine and two axial chlorido and/or thiocyanato ligands posses easy plane magnetic anisotropy as resulted from analysis of magnetic susceptibility and magnetization, and confirmed by ab initio calculations (D = +106 and +95 cm–1). The AC susceptibility measurements show a slow magnetic relaxation with two or three relaxation branches. The low-frequency pathway occurs at about 1 – 10 Hz and it disappears progressively on heating. The high-frequency mode exists at the frequency ranges above 500 Hz. The characteristics of these field-induced single molecule magnets strongly depend upon the applied magnetic field which causes a prolongation of the low-frequency relaxation time and shortening of the highfrequency one. At 1.0 T and 1.9 K the relaxation time for the low-frequency pathway is as slow as 756 ms and 164 ms, respectively. Acknowledgement: The grant agencies (Slovakia, APVV-0014-11) are acknowledged for the financial support. C.R. thanks to grant from the Research Support Fund of the UCM (FPPV).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Pi-coordination compounds of Pd(II) and Pt(II) as potential substitutes of cisplatin and its analogues a

H. H. Repich, aS. I. Orysyk, bA. A. Biluk, bL. V. Garmanchuk, c L. G. Palchykovska, aV. I. Pekhnyo, dM. V. Vovk

a

Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine Taras Shevchenko National University, Educational and Scientific Centre “Institute of Biology” c Institute of Molecular Biology and Genetics, NAS of Ukraine d Institute of Organic Chemistry, NAS of Ukraine b

 PhD, Hlib Repich; [email protected]; Ukraine, 03142-Kyiv, prospekt Akademika Palladina, 32/34

Resistance of cancer cells to anticancer drugs is one of the main problems which greatly limit the effectiveness of the drugs. One of the ways how cancer cells resist platinumbased drugs is associated with increased levels of thiol-rich species in cytoplasm. According to Lewis theory “soft” active Pt(II) complexes bind firmly to “soft” thiol groups that leads to lack of activity. Our idea is to lower the Pt(II) affinity to “soft” groups by use of the “antisymbiosis in the trans-influence” phenomenon, according to which two “soft” ligands in mutual trans-position will have a destabilizing effect on each other when attached to “soft” metal atoms. For design of novel anticancer complexes we used N-allylthioureas as carrier ligands bearing very soft C=S and C=C donor groups. The “antisymbiosis” phenomenon may lower affinity of Pt(II) to "soft" thiol groups and allow the Pt(II) active complexes to reach DNA - their main pharmaceutical target. A row of Pd(II) and Pt(II) π-coordination compounds with N-allylthioureas were synthesized and characterized by X-ray diffraction and NMR spectroscopy. All compounds possessed pronounced cytotoxicity, high proapoptotic, cytostatic influence and ability to bind to DNA. Obtained data were compared to cisplatin as etalon drug.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

If coordination chemistry meets quantum physics: metal complexes as nuclear spin qubits a,b

a b

M. Ruben

Institut of Nanotechnology and Institut of Inorganic Chemistry, KIT, Karlsruhe (Germany) IPCMS, Université de Strasbourg, Strasbourg (France)

 e-mail: [email protected]; web: www.ruben-group.de

Magnetic metal complexes have been proposed as Quantum Bits (Qubits) candidates units for Quantum Computing (QC) and Quantum Information Processing (QIP). Herein, we report on the implementation of metal complexes into nanometre-sized (single-) molecular spintronic devices by a combination of bottom-up self-assembly and top-down lithography techniques. The controlled generation of magnetic molecular nanostructures on conducting surfaces and electrodes will be shown, self-assembled on sp2-carbon nano-structures (SW-CNTs, graphene, etc.), or inside nano-gap gold junctions. The quantum properties of the metal complexes inside of the obtained supramolecular Quantum Devices (SMQD) are addressed at the single molecule level in view of their I-V-characteristics by means of UHV- and solution-based scanning probe and electromigration techniques.1–10 [1] S. Kyatskaya et. al. J. Am. Chem. Soc. 2009, 131, 15143-15151. [2] M. Urdampilleta et al. Nature Mater. 2011, 10, 502-506. [3] J. Schwöbel et. al. Nature Comms. 2012, 3, 953-956. [4] R. Vincent et al. Nature 2012, 488, 357-360. [5] M. Ganzhorn et al. Nature Nano. 2013, 8, 165–169. [6] M. Ruben et. al. Nature Nano. 2013, 8, 377–389. [7] S. Wagner et. al. Nature Nano. 2013, 8, 575–579. [8] S. Thiele, et al. Science 2014, 344, 1135-1138. [9] M. Ganzhorn, et. al. Nature Comms 2016, accepted. [10] C. Godfrain, F. Balestro, S. Klyatskaya, M. Ruben, W. Wernsdorfer, submit. 2017

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Сytotoxicity studies of zinc(II) and cadmium(II) iodide complexes with antipyrine, caffeine and 1,10-phenantroline A. E. Barmashov, aA. A. Rudakova, aМ. А. Baryshnikova, b N. S. Rukk, bA. Y. Skryabina aG. N. Apryshko

a

a

N.N. Blokhin Russian Cancer Research Center, Kashirskoye sh., 24, Moscow, 115478, Russian Federation b Moscow Technological University (MITHT), Vernadsky av. 86, 119571 Moscow, Russian Federation  Associate Professor Nataliya S. Rukk; e-mail Address [email protected]; Correspondence Address: Vernadsky av. 86, 119571 Moscow, RF

The cytotoxic activity of the zinc(II)- and cadmium(II) iodide complexes with antipyrine (AP), caffeine (caf) and 1,10-phenantroline (phen) as organic ligands was investigated and compared with that of the starting compounds. Cytotoxicity was determined by the methylthiazole tetrazolium (MTT) assay using five human tumor cell lines: prostate adenocarcinoma РС-3, colon cancer HCT-116, Т-cell leukemia Jurkat, breast adenocarcinoma MCF-7, and lung cancer А549. It has been found that all cadmium complexes demonstrate cytotoxic activity with respect to all cell lines with IC50 being in the range 5,5-84 mkM. The [Cd(phen)I2] complex was found to be the most active one (IC50 = 40, 10, 5,5, 41, 9,2 mkM for A549, PC3, Jurkat, HCT-116, MCF-7 cells, respectively), its activity being higher than that of phen (IC50 = 78,6, 58,3, 8,2, >100, 56,5 mkM for A549, PC3, Jurkat, HCT-116, MCF-7 cells, respectively). The [Zn(phen)I2] demonstrates significant activity towards three cell lines (IC50: >100, 47,4, 10, >100, 72,5 mkM for A549, PC3, Jurkat, HCT-116, MCF-7 cells, respectively). The Jurkat cells were found to be the most sensitive ones towards the studied compounds. It seems that zinc(II)- and cadmium(II) iodide complexes with organic ligands are the promising ones as potential antitumor drugs for further studies both in vitro and in vivo.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Photoactive spin-crossover iron(II) complexes with tridentate N-donor ligands a,b

I. Šalitroš, bO. Fuhr, bM. Ruben

a

Institute of Inorganic Chemistry, Technology and Materials, Faculty of Chemical and Food Technology, Slovak University of Technology, Bratislava, 81237, Slovak Republic. b Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-vonHelmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.  Email: [email protected]

The Spin-Crossover (SCO) phenomenon between low-spin (LS) and high-spin (HS) state presents one of the most spectacular examples of molecular bistability. The outstanding position of SCO materials is based on the number of external stimuli, by which change of the spin can be performed. Until now, the most investigated is thermally activated transition of spin, which can be influenced also by other triggers like pressure, magnetic orelectric field. Moreover, in the last three decades, the light induced LS  HS photoconversion (LIESST and reverse LIESST effect) attracts the research interest. Herein we present thermal and light-induced SCO investigation in iron(II)bis(pyrazolyl)pyridine complexes. In the case of mononuclear compounds, their thermal and photoinduced transition of spin was investigated by magnetic measurements as well as by various spectroscopic techniques (temperature variable Far-IR, Vis and Mössbauer spectroscopy). In addition, new photoactive anthracene-contained bis(pyrazolyl)pyridine ligand moieties were synthesized. The consecutive iron(II) complexation resulted in the formation of oligomeric polynuclear complexes with grid-like or hexagone-like molecular architecture. 1 I. Šalitroš et al.; Dalton Trans.,2012,41, 5163. 2 I. Šalitroš et al.; Eur. J. Inorg. Chem., 2013, 1049 3 B. Schäfer et al., Chem. Commun., 2013, 49, 10986. 4 I. Šalitroš et al.; Dalton Trans., 2014, 43 , 16584. 5. K.S Kumar et al.; J Mat Chem C, 2015, 3, 11635

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

The study of heterobimetallic Cu(II)-Mn(II) compounds with N-derivatives of cyclam E. Samoľová, J. Kuchár Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, Moyzesova 11,04154 Košice, Slovakia  Mgr. Erika Samoľová, [email protected], Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, Moyzesova 11,04154 Košice, Slovakia

Because of its interesting properties 1D bimetallic compounds are widely studied in the area of molecular magnetism. Chains of Mn(II) (S = 5/2) and Cu(II) (S = l/2) structurally ordered in an alternating manner are of intense interest as potential starting blocks in the synthesis of molecular-based ferromagnets [1]. In several compounds, for example MnCu(pbaOH)(H2O)3 (pbaOH = 2-hydroxy-l,3-propylenebis(oxamato)), ferrimagnetic behavior was observed at low temperatures [2]. Important step in the preparation of this compounds is the selection of appropriate ligands, which may support the formation of the chain structure. Building upon the steric preconditions, the derivatives of cyclam ligand (1,4,8,11-tetraazacyclotetradecane) appear to be suitable for this purpose. We have undertaken a study of a series copper(II) compounds in which Cu(II) atom is coordinated by the N-derivatives of cyclam and Mn(II) is tetracoordinated by four chloride ligands. Such arrangement allows the formation of Cu(II)-Mn(II) bimetallic chains with short bridge between the paramagnetic atoms consisted of one chloride ligand. Further details on the syntheses, characterizations and crystal structures of prepared ligands, and Cu(II) and Mn(II) complexes will be given. 1. H. O. Stumpf, Y. Pei, O. Kahn, J. Sletten, J. P. Renard, J. Am. Chem. Soc., 115, (1993), 6738. 2. O. Kahn, J. Am. Chem. Soc., 110, No. 3, (1988), 183 This work was supported by the Slovak grant agency APVV (APVV-14-0078 and APVV14-0073) and P. J. Šafárik University in Košice (VVGS-PF-2016-72623, VVGS-2016265).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

The redox aqueous chemistry of CuII/IATP a,b

M. Saphier, aA. Mesica, a,bI. Zilbermann, cO. Saphier, a,dD. Meyerstein

a

Chemistry Department, Ben-Gurion University of the Negev, Beer-Sheva, Israel Chemistry Department, Nuclear Research Centre Negev, Beer-Sheva, Israel c Sami Shamoon College of Engineering of the Negev –Israel d Chemical Sciences Department and the Schlesinger Family Center for Compact Accelerators, Radiation Sources and Applications, Ariel University, Ariel, Israel b

 D'r Magal Saphier; [email protected]

Our study focuses on the interaction of ATP with both Cu(II) and Cu(I) ions and the redox activity of the latter formed complexes in general, and their reactions with molecular oxygen, hydrogen peroxide and methyl radicals, the latter being the simplest example for .R formed in biological tissues. The methyl radicals were produced in vitro by continuous radiolysis of N2O saturated aqueous solutions containing DMSO. While Cu(II)ATP was prepared by mixing the reagents at neutral pH (excess of ATP), the Cu(I) ATP was prepared by comproportionation of Cu(II)ATP, ATP and Cu(0), as CV experiments showed thermodynamic stabilization of the Cu(II)ATP/Cu(I)ATP with E1/2  +0.078V vs. Ag/AgCl(at pH 7) and log K(Cu(I)ATP)  15 (at pH 3). CH3 reacted with Cu(I)ATP in a process in which the presumable metal carbon  bond transient formed, ATPCu(II)-CH3 decomposed heterolytically to give methane and Cu(II)ATP as the major products. Its divalent analogue produced ATPCu(I)-CH3, which decomposed to give methane and ethane as minor products and methanol as the major product together with Cu(I)ATP. Detailed data and mechanisms of reactions will be presented. .

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis and characterization of yttrium, europium, terbium and dysprosium complexes containing a novel type of triazolyloxazoline ligand A. Scrivanti, M. Bortoluzzi, R. Sole, V. Beghetto Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Via Torino 155, 30172 Mestre (VE), Italy  Professor Alberto Scrivanti; e-mail [email protected]; Via Torino 155, 30172 Mestre (VE) – Italy

We have developed the synthesis of a novel type of N,N-bidentate chiral ligand which structurally derives from the association of a 1,2,3-triazole ring with a chiral oxazoline. Yttrium and lanthanide nitrato-complexes of the new triazolyl-oxazoline ligand were prepared and characterized. The coordination mode of the ligand has been investigated in silico by means of DFT calculations. Trivalent europium and terbium derivatives resulted appreciably photoluminescent upon excitation with UV light, showing the typical 5D0→7FJ and 5D4→7FJ emissions, respectively. These species were successfully used for the preparation of luminescent doped polymeric materials (PMMA).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Structural, spectral and magnetic properties of copper(II) furanand thiophenecarboxylates: different coordination modes of 3- and 4-pyridinemethanol P. Segľa, V. Kuchtanin, J. Švorec, J. Moncoľ Department of Inorganic Chemistry, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia  Professor Peter Segľa; [email protected]; Department of Inorganic Chemistry, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia

Herein, the synthesis, structural, spectral and magnetic characterization of eighteen thiophene- and furancarboxylate copper(II) complexes, containing either water, 3or 4-pyridinemethanol as an auxiliary ligand were described. A relatively simple synthetic approach leads to the preparation of complexes with interesting structural variability. Complexes with the most acidic 5-nitro-2-furancarboxylic acid (pKa = 2.06) were found to prefer monomeric structure. In contrary, far less acidic furan- and thiophenecarboxylic acids as well as their methyl substituted derivatives (pKa values from 3.15 to 4.64) prefer dimeric structure. Ambidentate 3-pyridinemethanol can be used in the synthesis of coordination compounds as a flexible N,O-bridging ligand that can directly form a polymeric structure. Only one complex is known, where 3-pyridinemethanol is employed as a terminal N-donor ligand. On the other hand, 4-pyridinemethanol in complexes under study exists only as a terminal N-donor ligand. In these complexes a non-coordinated function group CH2OH of 4-pyridinemethanol is involved in the extensive system of O–H…O hydrogen bonds, thus forming an interesting supramolecular structure. Acknowledgement: Financial support received from Slovak Grant Agencies under grant no. APVV-14-0078 and KEGA 017STU-4/2017.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Reactions of azines with half-sandwich osmium complexes: preparation of metalated derivatives a

G. Albertin, aF. Sibilla, aS. Antoniutti, bJ. Castro

Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, via Torino 155, 30170 Venezia-Mestre, Italy b Departamento de Quimica Inorganica, Univesidade de Vigo, Facultade de Quimica, Edificio de Ciencias Experimentais, 36310 Vigo, Spain a

 Phd student, Francesca Sibilla; [email protected]

Azines, N–N linked diimine or 2,3-diazo analogous to 1,3-butadiene, are a class of useful compounds which undergo a variety of chemical processes and they may display significant biological properties. However, the coordination chemistry of azines is still relatively unexplored. Our research group is interested in the chemistry of diazo complexes of transition metals with d6 configuration and here we report the preparation of aldazine complexes of osmium stabilized by half-sandwich p-cymene fragments. Chloro compounds OsCl2(6-p-cymene)L (L= P(OMe)3, P(OEt)3) react with azine R1(H)C=N–N=C(H)R1 (R1= Ph, p-tolyl, 4-OCH3C6H4) in ethanol to form the azine derivatives (1, 2). Metallated

[OsCl(6-p-cymene){κ1-[N=C(H)(C6H4-p-R1)]N=C(H)(C6H4-p-R1)]}L]+ complexes

[Os{κ2-[(C6H3-p-R1)(H)C=N-N=C(H)(C6H4-p-R1)]}

(6-p-cymene){P(OR)3}]+ (3, 4) were prepared by allowing chloro compounds to react first with AgOTf and then with the appropriate azine. The complexes were characterized by IR and NMR spectroscopy and by X-ray crystal structure determination of compound N=C(H)(C6H5)]}{P(OEt)3}]BPh4.

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[OsCl(6-p-cymene){κ1-[N=C(H)(C6H5)]-

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Calcium complexation processes in hyperalkaline aqueous solutions B. Kutus, aC. Dudás, aA. Gácsi, aÁ. Buckó, aS. Ziegenheim, a É. Böszörményi, aT. Faragó, bG. Peintler, cI. Pálinkó, aP. Sipos, a

a

Department of Inorganic and Analytical Chemistry, University of Szeged, 7 Dóm tér, H–6720 Szeged, Hungary b Department of Physical Chemistry and Materials Science, University of Szeged, 1 Aradi vértanúk tere 1., H-6720 Szeged, Hungary a Department of Organic Chemistry, University of Szeged, 8 Dóm tér, H–6720 Szeged, Hungary  Prof. Dr. Pál Sipos; [email protected]; 7 Dóm tér, H–6720 Szeged, Hungary

In hyperalkaline (pH > 13) aqueous solutions, Ca2+ ions form unusual complexes with certain organic ligands containing carboxylate and alcohol(ate) donor groups (e.g., sugar carboxylates, like gluconate, heptagluconate, gulonate, isosaccharinate, etc. or small molecular hydroxy-carboxylates, like tartrate, citrate, etc.) The complexes formed are of unexpectedly high stability and predominantly multinuclear (bi- or trinuclear). Often, the predominant multinuclear complexes are charge-neutral. These Ca-complexes present in high-pH solutions may serve as precursors or templates to form ternary (heteropolynuclear) species of the CanLmM type (where M = Fe(III), Al(III), radionuclides, etc.), which has clear practical implications (e.g., in radioactive waste repositories, binding of Al(III) in the Bayer’s alumina-trihydrate production or interactions with Fe(III) of vat dyes in various dyeing processes.) In the current contribution, examples will be shown on the formation and stability of Ca-complexes present in hyperalkaline aqueous solutions. We will attempt to show, how the conventional solution chemical tools are made suitable to work in extremely alkaline solutions. The major chemical parameters affecting the stability and determining the structure of these complexes will also be discussed.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

New insight into Jablonski dDiagram R. Šípoš, J. Šima Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia  Ing. Rastislav Šípoš, PhD.; [email protected]; Dept. of Inorganic Chemistry, FCHPT STU, Radlinského 9, 81237 Bratislava

In the past, two approaches towards relationship of the rate constant of electronic deactivations (transitions lowering the electronic energy) and rotational-vibrational relaxation (lowering mainly vibrational energy within a given electronic state) have evolved. The first is Jablonski diagram, originally used in organic photochemistry, while second the thermally equilibrated excited (Thexi) state was introduced by Adamson. In both concepts, vibrational relaxation precedes the electronic deactivation processes of excited molecules. The experimental data accumulated up to the present using mainly time-resolved luminescence and transient absorption spectroscopy from the field of photophysics of transition metal compounds and different organic molecules have clearly demonstrated that even spin-forbidden electronic deactivations are faster processes that vibrational relaxation. New, modified approach towards these two solutions is discussed.

This study was supported by VEGA Agency projects 1/0543/15 and 1/0388/14.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Tetracoordinate Co(II) complexes with neocuproine: SMMs with potential biological activity a,b

L. Smolko, bJ. Černák, bJ. Kuchár, cD. Sabolová, dR. Boča

Department of Medical and Clinical Biochemistry, P.J. Šafárik University in Košice, Trieda SNP 1, 04154 Košice, Slovakia b Department of Inorganic Chemistry, P.J. Šafárik University in Košice, Moyzesova 11, 04154 Košice, Slovakia c Department of Biochemistry, P.J. Šafárik University in Košice, Moyzesova 11, 04154 Košice, Slovakia d Department of Chemistry, University of SS Cyril and Methodius, Nám. J. Herdu 2, 91707 Trnava, Slovakia a

 Dr. Lukáš Smolko, PhD.; lukas,[email protected]; Department of Clinical and Medical Biochemistry, Faculty of Medicine, P. J. Šafárik University in Košice, Trieda SNP 1, 04154 Košice

Series of three mononuclear tetracoordinate complexes [Co(dmphen)X2] (dmphen = 2,9-dimethyl-1,10-phenantroline; X = Cl, Br, I) have been prepared by solvothermal synthesis. X-ray structure analysis have shown that complexes possess analogous molecular structure, even though the chlorido complex crystallizes in a different crystal system and space group. Their crystal structures are stabilized through intermolecular hydrogen bonding interactions and π-π interactions between complex molecules. Although the crystal structures of the complexes within the series are fairly similar, their magnetic properties visibly differ in an applied external AC field; bromido and iodido complexes exhibit single-molecule magnet (SMM) behaviour with manifold relaxation channels; while chlorido complex exhibits antiferromagnetic interaction and does not display slow relaxation of magnetization. In addition binding of the complexes to calf thymus DNA (CT-DNA) was investigated using spectroscopic methods (electronic absorption, fluorescence and circular dichroism (CD) spectrophotometry) and the experimental results indicate that they are able to bind to CT-DNA via intercalation thus suggesting potential antimicrobial and antitumor activity of these complexes.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Heterometallic nanomaterials with hierarchical structure for special applications in materials engineering: design, synthesis and research P. Sobota Faculty of Chemistry, University of Wroclaw, 14 F. Joliot-Curie, 50-383 Wroclaw, Poland.  e-mail: [email protected]

Topic of lecture includes development of a new synthetic strategy for (nano)materials derived from heterometallic metalloligands, which constitute building blocks toward hierarchical structures that depend on the presence of non-conventional interactions between structural elements. These hierarchical (nano)materials possess specific properties such as high hardness, strength, chemical lability, thermal stability and other properties which make these materials an attractive in the field of modern industrial technology and development of new research directions in the area of science and materials engineering. This unique synthetic method comprises elimination of the cyclopentadienyl ring (as CpH) from Cp2MCl2 (M = Ti, Zr, Hf) in the presence of M’(OR)2 (M’ = Ca, Sr, Ba; ROH = CH3OCH2CH2OH), in an alcohol as a proton source. The resulting compounds are suitable for synthesis of aluminosilicates containing a Ba(Sr)−O−Al−O−Si arrangement of natural feldspar mineral as well as highly phase-pure perovskite-like oxides including BaTiO3, BaHfO3, SrHfO3, etc.1–4 The authors express their gratitude to the National Science Centre (Grant 2014/13/B/ST5/01512) for financial support. 1. Ł. John, P. Sobota, Acc.Chem. Res., 2014, 47 (2), 470–481. Synthesis of Heterometallic Compounds with Uncommon Combinations of Elements for Oxide Nanomaterials Using Organometallics. 2. A. Drąg-Jarząbek, R. Petrus, P.Sobota, Inorg. Chem., 2016, 55, 9524−9527. Synthesis of Aluminosilicates Containing a Ba(Sr)−O−Al−O−Si Arrangement of Natural Feldspar Mineral. 3. A. Drąg-Jarząbek, M. Kosińska, Ł.John, L. B. Jerzykiewicz, P. Sobota, Chem. Mater. 2011, 23, 4212–4219. Synthesis and Structural Characterization of a New Molecular Precursor for BaHfO3: A Simple Approach to Eu-Based Phosphors. 4. A. Drąg-Jarząbek, R. Petrus, P. Sobota, Inorg. Chem. 2016, 55, 9524−9527. Synthesis of Aluminosilicates Containing a Ba(Sr)−O−Al−O−Si Arrangement of Natural Feldspar Mineral. 103

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Dispersion interactions in oligomerization of metal diketonates: quantum chemical calculations A. G. Starikov, D. G. Ivanov, A. A. Starikova, V. I. Minkin Institute of Physical and Organic Chemistry at Southern Federal University, Stachka Ave., 194/2, 344090, Rostov-on-Don, Russian Federation  Dr. Andrey G. Starikov; [email protected]; Stachka Ave., 194/2, 344090, Rostov-on-Don, Russian Federation

The possibility of self-association is one of the unique properties of transition metal β-diketonates determining their physicochemical characteristics. In the search for the factors responsible for stabilization of oligomeric structures, a systematic density functional theory quantum chemical study (DFT B3LYP/6-311++G(d,p)) of Co, Ni, Cu and Zn diketonates has been performed. Dependence of stability of the bischelate oligomers on complexing metal and substituents in the ligands has been investigated with the use of approximations taking into account dispersion interactions (CAM and D3BJ). It has been shown that the greatest differences in calculated and experimental bond lengths of considered associates are predicted for intermolecular interactions. Inclusion of dispersion interactions into the calculation scheme has been shown to favour reducing the contacts of metal and oxygen atoms of adjacent molecules, which leads to increasing an accuracy of reproducing experimental parameters by quantum chemical calculations. At the same time approaches using dispersion corrections overestimate significantly the stabilization energy of the oligomers, which does not allow to recommend them for studying stability of analogous systems. Acknowledgements: This work has been financially supported by Russian Science Foundation (grant no. 14-13-00573).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Computational design of magnetically active trinuclear heterometallic complexes on the basis of 1,3,5-triazapentadiene ligands A. A. Starikova Institute of Physical and Organic Chemistry at Southern Federal University, Stachka Ave., 194/2, 344090, Rostov-on-Don, Russian Federation  Dr. Alyona A. Starikova; [email protected]; Stachka Ave., 194/2, 344090, Rostov-onDon, Russian Federation

Rational design of polynuclear metal coordination compounds with the spin states variable in the wide range represents a central topic of investigations in the area of molecular magnetism. A series of mixed-ligand complexes of two iron(II) 2,6-di(pyrazol-1-yl)pyridine moieties with a linker on the basis of 1,3,5-triazapentadiene transition metal (M=Co, Ni, Cu, Zn) bischelate has been computationally designed using the density functional theory TPSSh/6-311++G(d,p) calculations. The systems possessing complete (M=Co, Ni) and partial (M=Cu, Zn) two-step spin-crossover phenomenon at ferrous ions have been revealed. Two spin-state switching mechanisms determining by spin-crossover at iron centers and configurational isomerism at cobalt ion may simultaneously occur in solution of corresponding heterometallic compound (M=Co). The nature of the exchange interactions between paramagnetic metal centers is controlled by variation of a metal in bischelate linker (M=Co, Ni, Cu, Zn). Energy and magnetic characteristics of electromeric forms of the complexes with nickel and copper central metal ions (M=Co, Ni) allow to consider them as promising candidates for the design of molecular switches. Acknowledgements: This work has been supported by Russian Foundation for Basic Research (grant no. 16-33-60019 mol_a_dk).

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

M2L4 coordination nano-capsules as supramolecular hosts with guest-tunable anticancer activity a

S. Stoykova, aA. Ahmedova, aJ. Zaharieva, bD. Momekova, b R. Mihaylova, bG. Momekov, cP. Shestakova

a

Faculty of Chemistry and Pharmacy, University of Sofia, 1, J. Bourchier blvd., Sofia 1164, Bulgaria b Faculty of Pharmacy, Medical University, 2 Dunav Street, 1000 Sofia, Bulgaria c NMR Laboratory, Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str. Bl. 9, Sofia 1113, Bulgaria  Assos. Prof. Anife I. Ahmedova, PhD; [email protected]

Metallosupramolecules attract increasing attention due to their potential application as molecular containers and anticancer agents. Herein, we present our recent results on the anticancer activity of anthracene based coordination capsules that have recently been designed and synthesised by Yoshizawa and co-workers. The anticancer activity of the capsules against various human cancer cells (HT-29, T-24, HL-60 and its resistant counterparts HL-60/Dox and HL-60/CDDP) significantly altered upon guest encapsulation. The encapsulation of pyrene molecules causes a decrease in cytotoxicity of the Pt(II) capsule, which is stronger than that of the Pd(II) capsule. The cytotoxicity of the caffeine containing capsules is lower than that of the empty capsules (except for HL-60), but still superior to cisplatin under the same conditions. The observed trends in the anticancer activity of the capsules and their host-guest complexes correlate with the difference in their stabilities toward glutathione, as was estimated by NMR-based kinetic experiments. Mechanistic insights into the observed activity were obtained by fluorescence microscopic imaging of tumor cells treated with the capsules and their pyrene complexes. Acknowledgement: The National Science Fund of Bulgaria (contract: DFNI-B02/24) and the H2020-Twinning project (Materials Networking; 692146) are acknowledged for financial support. Authors are grateful to Dr. Michito Yoshizawa (Laboratory for Chemistry and Life Science, Tokyo Institute of Technology, Japan) for kindly providing the supramolecular capsules.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

A study of nitrobenzoatocopper(II) complexes with N-methylnicotinamide J. Švorec, aJ. Moncoľ, bZ. Vasková, cM. Mazúr, aD. Valigura

a

Department of Inorganic Chemistry, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia b Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-84536 Bratislava, Slovakia c Department of Physical Chemistry, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia a

 Dr. Jozef Švorec; e-mail [email protected]

Synthesis and characterization of six complexes [Cu(2-NO2bz)2(mna)2(H2O)2] (1), [Cu(3-NO2bz)2(mna)2(H2O)2] (2), [Cu(2-NO2bz)2(mna)2(H2O)2]∙2H2O (3), [Cu(3,5-(NO2)2bz)2(mna)2(H2O)2]∙2H2O (4), [Cu(4-NO2bz)2(mna)2(H2O)2]∙ 2(4-NO2bzH) (5) and [Cu(3,5-(NO2)2bz)2(mna)(H2O)3] (6) (mna = N-methylnicotinamide, 2-NO2bz = 2-nitrobenzoate, 3-NO2bz = 3-nitrobenzoate, 4-NO2bz = 4-nitrobenzoate, 3,5-(NO2)2bz = 3,5-dinitrobenzoate) is reported. All complexes were studied by infrared, electronic and EPR spectroscopy as well as their structure was determined by X-ray structural analysis. The complexes 1‒6 are monomeric with a square-bipyramidal stereochemistry around the copper(II) centre. Solid state EPR spectra confirmed monomeric character of all complexes showing axial symmetry of an EPR signal with (5‒6) or without resolved hyperfine splitting (1‒4). Density functional calculations using PBE0 functional have been carried out on the experimental geometries of the studied complexes in order to reproduce experimental EPR parameters. The computed values of g tensor show relatively good agreement with experimental ones. Acknowledgement: Financial support was received from Slovak Grant Agencies under grant no. APVV-14-0078 and KEGA 017STU-4/2017. We are grateful to the HPC center at the Slovak University of Technology in Bratislava, which is a part of the Slovak Infrastructure of High Performance Computing (SIVVP project, ITMS code 26230120002, funded by the European region development funds, ERDF), for the computational time and resources made available.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

The inner side of high-valent metal-oxo reactivity a,b

M. Swart, cK. Ray

ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain IQCC, Univ. Girona, Campus Montilivi (Ciències), 17003 Girona, Spain c Dept. Chem., Humboldt Univ. Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany a b

 Prof. Marcel Swart FRSC FYAE; e-mail [email protected]

Oxidation processes of hydrocarbons in a selective, efficient and environment-friendly manner remains one of the major challenges at present today,[1] as shown in reviews[2-4] of studies on the topic. The majority of these studies is based on experiment, and computational chemistry plays sometimes an important role,[5] in giving a description of e.g. spectroscopy[6] or transition state structures to lead to a deeper understanding of what is going on. This is in particular true for the influence of the spin state on reactivity.[4] The oxidation reactions on hydrocarbons usually involve high-valent metal-oxo (FeIV=O, MnV=O) or metal-hydroxo (FeIV-OH, NiIII-OH)[7-8] species. Here we explore iron(IV)-oxo complexes and how changes in the ligand sphere influence both the efficiency of the reactions and the pathways taken.[9] Moreover, we break down the reactivity patterns into two complementary building blocks: (i) the reactivity of the iron-oxo unit and coordinating atoms (through model systems), and (ii) variations thereof by the real ligand systems. This breakdown brings forward valuable new insights that can be used for the design of new ligands with desired selectivity or improved efficiency. Financial support from COST (H2020), GenCat and MINECO is greatly acknowledged. [1] Inorg. Chem. 2015, 54, 5053; [2] Chem. Rev. 2004, 104, 939; [3] J. Am. Chem. Soc. 2014, 136, 13942; [4] Spin states in Biochemistry and inorganic chemistry: Influence on Structure and Reactivity, Wiley, Chichester UK, 2015; [5] Acc. Chem. Res. 2016, 49, 2690; [6] Inorg. Chem. 2017, 56, 470; [7] J. Am. Chem. Soc. 2016, 138, 13143; [8] J. Am. Chem. Soc. 2016, 138, 14362; [9] submitted 108

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Carbon monoxide hydrogenation and polymerization reactions catalyzed by iron particles supported on two-dimensional silicon wafers and generated from [Cu(FcCOCHCOR)2] C. C. Joubert, J. C. Swarts University of the Free State, Nelson Mandela Drive, Bloemfontein, 9300, South Africa  Professor Jannie C. Swarts; [email protected]; University of the Free State, Nelson Mandela Drive, Bloemfontein, 9300, South Africa

CO and H2 react under suitable conditions to generate amongst others, aliphatic hydrocarbons. This process can be catalyzed by iron or cobalt and promoted by copper supported on a suitable soluble support. Three-dimensional solid supports are used industrially, but these suffer from characterization problems as it is notoriously difficult to characterize catalytic particles inside the pores of three-dimensional supports. Mechanistic studies of the catalytic process are also difficult due to the inaccessibility of reactions sites by analytical techniques. This study will show how bimetallic Fe-Cu catalysts can be prepared on a two dimensional modified silicon wafer support from [Cu(FcCOCHCOR)2] complexes (R = CH3 or Fc = ferrocenyl = FeII(C5H5)(C5H4)) having different Cu-Fe ratios and how successful they perform in CO hydrogenation and polymerisation. Characterization techniques used include single crystal X-ray diffraction and electrochemical methods, as well as surface analysis techniques such as XPS (X-ray-photoelectron spectroscopy) and ATR-FTIR.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Electrochemical and computational studies on β-diketonato, βdiketoester and β-diketoamido [Rh(FcCOCHCOR)(cod)] complexes P. J. Swarts, aE. Müller, aE. Erasmus, bI. Fernández

a

a

University of the Free State, Nelsen Mandela Drive, Bloemfontein, 9300, South Africa Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain b

 Mr Pieter J Swarts; [email protected]; University of the Free State, Nelson Mandela Drive, Bloemfontein, 9301, South Africa

A series of ferrocenyl-containing β-diketonato, β-ketoester and β-ketoamide ligands were synthesized, characterized and complexed with rhodium(I) to give complexes of the type [Rh(FcCOCHCOR)(cod)] with R = CH3, OEt, NH2 and Fc = FeII(C5H5)(C5H4). Electrochemical studies enabled us to observe for the first time experimentally by cyclic voltammetry that RhI initially starts to oxidise to RhII in an electrochemically irreversible redox process having large ∆E values. This innitiates simultaneous oxidation of FeII to FeIII just after RhII oxidation commenced. Only when FeII was completely oxidized in a 1e transfer process did RhI completely oxidize to RhII. These overlapping redox processes were found to be followed by the oxidation of RhII to RhIII. Computational studies enabled us to identify the most stable keto or enol isomer for the β-diketones, β-ketoester and β-ketoamides, and to confirm the observed sequence of redox processes found electrochemically.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Mechanochemical synthesis of zinc aluminate spinel M. Szabados, S. Erdei, V. Havasi, P. Sipos, I. Pálinkó Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-6720 Hungary  Prof. István Pálinkó; [email protected], Deapertment of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720 Hungary

Layered double hydroxides (LDHs) have numerous applications as catalysts, anionexchangers, polymer additives, etc. In our experimental work, aluminum-rich ZnAlLDHs were prepared and applied as precursors in the mechanochemical syntheses of zinc aluminate spinels. These oxides can be represented by the AB2O4 formula, where A and B are di- and trivalent metal ions. They can serve as catalysts, catalyst supports or high-voltage semiconductors. The synthesis method is based on the dehydration effect of mechanical impacts. The starting reagents LDHs were grinded in a mixer mill, and no further steps were required. This novel synthesis technique was also studied and compared in parallel to the commonly used high temperature preparation method. X-ray diffractometry was the main method of characterization and to follow the effects of grinding parameters (frequency, duration) of the obtained samples. Scanning electron microscopy, infrared spectroscopy and thermogravimetric analysis could also provide further information. To sum up, this one-step solid-state reaction route proved to be efficient in preparing zinc aluminate spinels from ZnAl-LDHs without applying high temperature heat treatment.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Theoretical investigation of photochemical properties of palladium(II)corrin M. Szczepańska, P. Lodowski, M. Jaworska University of Silesia in Katowice, Department of Theoretical Chemistry, Bankowa street 14, 40-001 Katowice  mgr Marzena Szczepańska ; [email protected]; Kalinowa street 61/30, 41-208 Sosnowiec, Poland.

The aim of this study was to characterize the vertical and adiabatic electronic excited states of corrin complex with palladium(II) as a central ion, which are involved in the mechanism of luminescence observed for this compound. Calculations for the [PdIIcorrin]+ complex, was performed by DFT and TD-DFT methods using B3LYP and BP86 functionals. The def2-TZVPP basis sets was used in all clalculations. Excitation energies and characters of the excited states were determined and calculational results are compared with experimental data. Experimental studies suggest that the structure of the luminescence spectrum is a result of the occurrence of vibrational progression. The study shown, that the main luminescence bands are associated with de-excitation from the lowest S1 and T1 excited states of the dyz→π* character. Simultaneously, it does not exclude the possibility of participation in the fluorescence and phosphorescence process of S2 and T2 excited states. In order to facilitate interpretation of the results, in the study was proposed a scheme for the mechanism of luminescence process.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Metal ion binding of TACH-based polydentate tripodal ligands A. Szorcsik, aF. Matyuska bÁ. Dancs, cN. V. May, bT. Gajda

a

MTA-SZTE Bioinorganic Chemistry Research Group, Dóm tér 7., H-6720 Szeged, Hungary Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7., H-6720 Szeged, Hungary. c Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok körútja 2, H-1117 Budapest, Hungary a b

 Dr. Attila Szorcsik, e-mail: [email protected];

The preorganized spatial distribution of donor atoms in tripodal ligands has been long time recognised and applied to develop efficient artificial receptors, metal sequestering agents, metal ion sensors, structural/functional models of metalloproteins, supramolecular assemblies etc. Such polydentate tripodal ligands are generally synthesized by derivatization of tridentate tripodal platforms, such as cis,cis-1,3,5triaminocyclohexane (tach), which may provide additional donor site(s), may influence the steric environment around the metal centre or may help to introduce further metal binding site(s). The tripodal 2-pyridylmethyl derivative of tach (tachpyr, L1) forms highly stable {6N} coordinated complexes with a range of transition metal ions, since the favourable position of pyridine nitrogens encapsulate the metal ions by fused chelate rings. This encapsulating effect is not present in the case of 3-pyridylmethyl-substituted derivative (tach3’pyr, L2). It provides a 3N metal binding sites for the metal ions, and its CuL2(OH) complex is an efficient phosphatise model. In order to develop {4N} coordinated oxidase models, we synthesized the mono-2-pyridylmethyl derivative L3 (tachmpyr), which creates strongly distorted coordination trigonal bipyramid/square pyramid environment around the metal ions.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Coordination abilities of N-methyl alkylaminomethane1,1-diphosphonic acids towards zinc(II), magnesium(II) and calcium(II) metal ions. Equilibrium studies in aqueous solutions a

M. Szpak, aB. Kurzak, bA. Kamecka, cW. Goldeman

a

Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland Institute of Chemistry, Siedlce Univerity of Natural Sciences and Humanities, 3 Maja 54, 08110 Siedlce, Poland c Department of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50370 Wrocław, Poland b

 prof. Barbara Kurzak; [email protected]; Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland

Bisphosphonates are chemically stable analogues of the naturally occurring pyrophosphate. These compounds are used in the treatment of several bone-related diseases including myeloma, hypercalcemia of malignancy, osteoporosis, Paget’s disease and osteolytic bone metastases. In my studies I would like to show the complex-formation abilities of a series of 7 ligands of N-methyl alkylaminomethane-1,1-diphosphonic acids with a common tertiary nitrogen atom (CH3-N-R) bearing linear or branched alkyl, cycloheptyl or phenylalkyl R substituent toward Zn(II), Mg(II) and Ca(II) in aqueous solution. In the investigation of these systems pH-potentiometry, ESI-MS spectrometry, 1H and 31P NMR methods were used. The obtained results indicate that in the all presented systems mononuclear protonated equimolar and bis complexes are formed. In acidic and neutral solution, the formation of the protonated dinuclear species has been also confirmed. The comparative analysis of the potentiometric and NMR data reveal that the nitrogen atom of (CH3)-NH+-R group remains protonated in the whole pH range studied and the Zn(II), Mg(II) and Ca(II) ions are coordinated exclusively through oxygen atoms of the phosphonate groups in all detected complex species.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Coinage metal NHC complexes as novel antibiotics and anticancer drugs M. Tacke School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland  Matthias Tacke, Associate Professor, PhD; [email protected]

The synthesis and biological evaluation against cancer cells and pathogenic bacteria as well as fungi of five coinage metal NHC complexes derived from copper (WBC4), silver (SBC1/SBC3) and gold (NHC-Au-Cl/NHC-Au-SR) is reviewed. The NHC ligand for these compounds is 1,3-dibenzyl-4,5-diphenylimidazol-2-ylidene or derivatives closely related, since this ligand is proven suitable for drug-like molecules. The NHCsilver acetate complex SBC1 failed as an anticancer drug candidate in vivo, while its highly related compound SBC3 succeeded in vivo as an experimental antibiotic in Galleria mellonella larvae showing survival advantage against pathogenic bacteria and fungi. The corresponding gold complexes of NHC-Au-Cl and NHC-Au-SR (R = thioglucoside) as well as the NHC-copper bromide derivative WBC4 exhibited significant growth inhibition, when tested against xenografted human renal-cell cancer Caki-1 in nude mice; WBC4 showed tolerable toxicity in the form of reversible body weight loss, while the two gold compounds did not induce body weight loss in the xenograft mouse model experiment. SBC1

WBC4

SBC3

OMe CH3 N

N Cu

Ag

Br

N CN

OMe

Ph

Ph Ph

N Au

Ph

Ag

N

N

Ph

N

OAc

N

O

Cl

Au Ph

Ph

OAc

N AcO

N Ph

NHC-Au-Cl

NHC-Au-SR

115

OAc

S OAc

OAc

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Inorganic nanochemistry for biomedical applications: going for silver and gold A. Taglietti INLab, Department of Chemistry Università di Pavia, Viale Taramelli 12, 27100 Pavia, Italy  Prof. Angelo Taglietti; [email protected]; Viale Taramelli 12, 27100 Pavia, Italy

Since the ancient times, the charm of Silver and Gold have never gone out of fashion. In the last two decades, anyway, the rise of nanotechnologies has boosted a new, enormous interest in these shiny elements. Au and Ag nano-objects of different dimensions and shapes are showing to function for a plethora of applications, particularly in the biomedical field. Starting from the description of our early results on antibacterial effects of spherical silver nanoparticles layers grafted on glass, the lecture will move to more complex systems involving anistropical objects like silver nanoplates and gold nanostars, able to exert intense photo-thermal effects causing localized hyperthermia. This allows to obtain active model surfaces (usable for coatings of biomedical devices) in which the long term antibacterial action of Ag can be substituted or coupled with a Laserswitchable photo-thermal action. In addition, the realization of Surface Enhanced Raman Spectroscopy (SERS) chips based on gold nanostars layers for sensing of molecules with biomedical importance will be shown. Moreover, theranostic SERS nanotags will be described, showing how plasmonic features of gold nano-objects, which cause SERS and photo-thermal effects, permit to build devices capable of targeting, imaging and destroying cancer cells.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Manganese complexes with derivatives of pyridinecarboxylic acids M. Tatarko, R. Brišák Department of Inorganic Chemistry, Slovak University of Technology, Radlinského 9, 812 37 Bratislava, Slovakia  [email protected]

Preparation and the study of manganese(II) and manganese(III) complexes based on the derivatives of pyridinecarboxylic acids and pyrazinecarboxylic acids. Complexes were prepared in aquatic media at various molar ratios of reactants. Prepared complexes were investigated by elemental analysis as well as IR spectroscopy. X-ray structural analysis confirmed the composition cis-[Mn(μ-3-OH-inic)2(H2O)2]n, cis-[Mn(-5-F-2,6-Cl2nic)2(H2O)2]n, cis-[Mn(-3-F-inic)2(H2O)2]n, and [Mn(H2O)6]2+{fac-[Mn(2,3-pyrH)3]–}2 (inic = isonicotinate anion, 2,3-pyr = pyrazine-2,3-dicarboxylate anion). Acknowledgement: Financial support received from Slovak Grant Agencies under grant no. APVV-14-0078 and KEGA 017STU-4/2017.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Intercalation of CaAl-layered double hydroxide with benzoate or acetate ion Z. Timár, M. Kocsis, G. Varga, P. Sipos, I. Pálinkó University of Szeged, Institute of Chemistry, University of Szeged, Szeged, H-6720 Hungary  Prof. István Pálinkó, e-mail: [email protected], Department of Organic Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-6720 Hungary

Layered double hydroxides (LDHs) consist of brucite- or hydrocalumite-like lamellae with two or three positively charged metal ions surrounded by hydroxide ions and water molecules. The layers have excess positive charge compensated by partially or fully hydrated exchangeable anions between the layers. Using these materials as nanoreactors is one of their many application possibilities. For this, as the first step, intercalation of the reactants is inevitable. During our experimental work leading to this contribution, benzoate or acetate anions were intercalated between the layers of CaAl-LDH. After preparing the CaAl-LDH with the co-precipitation method, the intercalation was performed with direct anion exchange. The host material as well as the host-guest composites were structurally characterized and the success of intercalation was checked by X-ray diffraction and infrared spectroscopy applying various detector types as well as scanning electron microscopy in order to obtain morphological information about the samples.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Metal complexes as units for spintronic devices: the quest for single-molecule magnets J. Titiš Department of Chemistry, Faculty of Natural Sciences, University of SS. Cyril and Methodius, 917 01 Trnava, Slovakia  Ján Titiš, [email protected], Nám. J. Herdu 2, 917 01 Trnava, Slovakia

Rationally designed magnetic molecules, such as single-molecule magnets (SMMs), are regarded as potential candidates for various applications in future molecular electronics. SMMs are above all transition metal and/or lanthanide complexes that, beside other interesting quantum phenomena, exhibit slow relaxation of the magnetization at the level of one molecule. We have studied a series of metal complexes containing Co(II), Ni(II) and Dy(III) ions. In these compounds the slow magnetic relaxation processes have been detected using AC susceptometry. We have applied contemporary methods of quantum chemistry, such as methods of density functional theory (DFT) and multiconfigurational ab initio calculations, to investigate the electronic and structural aspects of the SMM behaviour. Acknowledgments: Slovak grant agencies (APVV-14-0078, APVV-14-0073 and VEGA 1/0534/16) are acknowledged for the financial support.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Quantum information with molecular nanomagnets F. Tuna EPSRC National EPR Facility, School of Chemistry and Photon Science Institute, University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom  E-mail: [email protected]

Quantum information processing (QIP) offers one of the most exciting challenges in the study and development of molecular materials. Instead of operating with classical bits of information, a quantum computer will work with quantum bits (known as qubits). The implementation of such an advanced technology demands chemical systems with robust quantum states that can be individually controlled and measured, and are able to sustain coherent quantum manipulations. This lecture focuses on d- and f-block organometallic complexes that have potential for QIP as electron-spin qubits. We use electron paramagnetic resonance (ESEEM, ENDOR, HYSCORE, DEER) to measure and understand the quantum coherence properties of the compounds. We show that CASSCF ab-initio calculations can guide the synthesis of lanthanide and actinide single-ion magnets with magnetic relaxation barriers that reach 860 K, and the assembling of molecular spin qubits exhibiting coherent Rabi oscillations at room temperature and below. Magnetic hysteresis measurements, ac susceptibility studies, pulse-EPR and CASSCF calculations were all involved to study the dynamics of the magnetization in these compounds and to gain understanding of the relaxation mechanisms. [1] K.S. Pederson, et al., F. Tuna. Toward molecular 4f single-ion magnet qubits, J. Am. Chem. Soc. 2016, 138, 5801–5804. [2] M. Gregson, et al., F. Tuna. A monometallic lanthanide bis(methanediide) single molecule magnet with a large energy barrier and complex spin relaxation behavior. Chem. Sci. 2016,7, 155–165. [3] J. Ferrando-Soria, et al., F. Tuna. A modular design of molecular qubits to implement universal quantum gates. Nature Commun. 2016, 25, 7:11377. [4] A. Formanuik, et al., F. Tuna. Actinide covalency measured by pulsed EPR spectroscopy. Nature Chem. 2016, doi:10.1038/nchem.2692

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Slow magnetic relaxation in a Co(II) octahedral-tetrahedral system formed of a [CoL3]2+ core with L = bis(diphenylphospanoxido)methane and tetrahedral [CoBr4]2– counter anion a

F. Varga, aC. Rajnák, aJ. Titiš, bJ. Moncoľ, aR. Boča

a

Department of Chemistry, Faculty of Natural Sciences, University of SS. Cyril and Methodius, Nám. J. Herdu 2, 917 01 Trnava, Slovakia b Institute of Inorganic Chemistry, Faculty of Chemical and Food Technology, Radlinského 9, 812 37 Bratislava 1, Slovakia  Filip Varga; [email protected]; 253, Helcmanovce 055 63

A bimetallic Co(II) compound O,O [Co(dppm )3][CoBr4] has been prepared, structurally characterized and subjected to deep magnetochemical investigation. The title compound consists of two coordination polyhedra, a cationic hexacoordinate [CoL3]2+ core with L = bis(diphenylphosphanoxido)methane and [CoBr4]2– counter anions. It shows sizable magnetic anisotropy and field-supported slow magnetic relaxation with the relaxation time of τ = 0.1 – 0.3 s at T = 1.9 K. Quantum chemical calculations were performed to probe the relationship between magnetic anisotropy and geometric structure. Acknowledgments: Slovak grant agencies (APVV-14-0078, APVV-14-0073 and VEGA 1/0534/16) are acknowledged for the financial support.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Co(II)-amino acid–CaAl-layered double hydroxide composites – construction and characterization G. Varga, Z. Kónya, Á. Kukovecz, P. Sipos, I. Pálinkó Institute of Chemistry, University of Szeged, Aradi vértanúk tere 1, Szeged, Hungary, H-6720  Prof. István Pálinkó; [email protected]; Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, Hungary, H-6720

Many types of guest materials were incorporated among the layers of layered double hydroxides (LDHs); however only few studies can be identified in which the intercalation of transition metal complexes are presented. Moreover, the synthesis of composite materials having cobalt-amino acid complexes as guests has not been reported yet. This study describes the incorporation of Co(II)-amino acid complexes into CaAl-LDH. The main aim was to form composite materials containing the complexes overwhelmingly among the layers of the LDH. To achieve this goal, the synthesis conditions were varied systematically, and the optimum circumstances were identified. Due to the optimization efforts intercalated structure of high crystallinity was obtained without by-product formation. The success of intercalation was confirmed by relevant characterization methods such as X-ray diffractometry, IR-spectroscopy, scanning electron microscopy, UV-vis spectroscopy and the ICP-OES method.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Complexing properties of 2-pyridinephosphonic acid M. Rendošová, aZ. Vargová, aI. Rostášová, bR. Gyepes, a S. Saksová, cM. Vilková

a

Department of Inorganic chemistry, Institute of Chemistry, University of P.J.Šafárik, 04154 Košice, Slovak Republic b NMR laboratory, Institute of Chemistry, University of P.J.Šafárik, 04154 Košice, Slovak Republic c Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40 Praha, Czech Republic a

 Zuzana Vargová, PhD.; [email protected];

Metal complexes of phosphonates offer a new class of materials with interesting properties for applications in the field of catalysis, ions exchange, magnetic materials as well as materials for diagnostic or therapeutic applications in medicine (contrast, radiotherapeutic agents). Moreover, zinc(II), cobalt(II), copper(II) and cadmium(II) pyridinephosphonates were synthetized and characterized with aim to produce promising polymeric materials [1-3]. Contribution deals with 2-pyridinephosphonate (2-PYPO) behavior in aqueous solution in dependence on pH. We observed its species formation and ability to form complexes with Zn(II) and Ag(I) central atoms using potentiometric titration at 25 ± 0.1°C and an ionic strength of I = 0.1 M(KNO3). Firstly, protonation constants were determined and after that stability constants were estimated for binary system Zn(II)/Ag(I)-PYPO in molar ratio 1:1, 1:2 and 1:4. Overall stability constants indicate more stable complexing species formation in the case of Zn(II)-2-PYPO (logβ011 = 8.4(1)) than Ag(I)-2-PYPO (logβ011 = 4.7(5)). 1H and 31P NMR spectra were used to 2-pyridinephosphonate coordination mode identification. This work was supported by Slovak grant agencies (KEGA 002UPJŠ-4/2015, APVV15-0520). [1] Ma Y. S. et al. J. Solid State Chem. 2006, 179, 3017. [2] Perry H. et al. J. Solid State Chem. 2010, 183, 1165. [3] Ayyappan P. et al. Inorg. Chem. 2001, 40, 5954.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Decorating iron(II) clathrochelates with different functional groups M. Vershinin Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentiev Ave. 3, 630090 Novosibirsk, Russia  Dr. Mikhail Vershinin; e-mail [email protected]; NIIC SB RAS, 3 Lavrentiev Ave., 630090 Novosibirsk, Russia

The coordination to metal ion can significantly change reaction properties of organic molecules. This phenomenon allows obtaining substances difficult to prepare by methods of classical chemistry. In our work we use the reactions of the coordinated dioxime ligand for design of novel macrobicyclic cages of tris-dioximate iron(II) clathrochelates. In our research we use three different synthetic tactics: nucleophilic or radical substitution and electrophilic addition. Synthesis and characterization (single crystal X-ray crystallography, multi nuclear NMR spectroscopy, UV-VIS spectroscopy and CV) of the compounds obtained will be discussed in this work. F B

Ph

N

O N

Cl

N

Cl

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Ph N O

B F

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B F

F

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Fe2+ t-BuOOH CH3CN

Ph

OPh O

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N O

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This study was partly supported by RFBR (grant 16-03-00408).

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S

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O

Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Solid solvates of a NiII Schiff base complex and its reactivity towards GdIII a,b

A. Vráblová, aJ. Černák, bL. R. Falvello, cM. Tomás

Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, Moyzesova 11, 041 54 Košice, Slovakia b Instituto de Ciencia de Materiales de Aragón (ICMA) c Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) b,c Department of Inorganic Chemistry, University of Zaragoza-CSIC, Pedro Cerbuna 12, 50009 Zaragoza, Spain a

 Mgr. Anna Vráblová; [email protected]; Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, Moyzesova 11, 041 54 Košice, Slovakia

Schiff bases prepared from ortho-vanillin and various diamines are ligands in a rich diversity of complexes, from mononuclear species to polymers. The complexes have interesting properties in a variety of fields – among them magnetism, luminescence, chirality, and catalysis. We have used targeted synthesis to prepare discrete heterodinuclear complexes with 3d-4f metal centers connected by the Schiff base ligand (H2L), which is prepared by condensation of ortho-vanillin and ethylenediamine in molar ratio 2:1. In the first step of the synthesis we isolated two solid solvates of NiL, namely [NiL]·H2O·EtOH and [NiL]·H2O·iPrOH; and in a subsequent step we obtained the heteronuclear compounds [NiLGdCl3(H2O)] and [NiLGd(NO3)3]·4MeCN from the reaction system [NiL] – LnIII. We present the structures of all four products. Possible causes are presented for some noteworthy differences between the two solid forms of the [NiL] compound, including different stabilities and colors of their crystals. Acknowledgment: Financial support from Slovak grant agencies (APVV-14-0078, VEGA 1/0063/17) is gratefully acknowledged, as is support from the Ministerio de Ciencia e Innovación (Spain, Grant MAT2015-68200-C2-1-P), the European Union Regional Development Fund (FEDER) and the Diputación General de Aragón, E16. AV thanks to grants VVGS-PF-2016-72623 and VVGS-2016-265.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Towards new organometallic antimalarial drugs S. Werner, F. Mohr Anorganische Chemie, Bergische Universität Wuppertal, Gaußstraße 20, 42119 Wuppertal, Germany  Prof. Dr. Fabian Mohr; [email protected]; Anorganische Chemie, Bergische Universität Wuppertal, Gaußstraße 20, 42119 Wuppertal, Germany

Malaria is still one of the most devastating diseases in the world with an estimated 212 million cases and 429 000 deaths in 2015. Over a long time period Chloroquine (CQ) has been the most successful agent for the treatment of malaria but nowadays many strains of the malaria parasite are resistant against CQ. Recently several studies have shown that metal containing compounds of antimalarial drugs improved efficacy against both CQ-sensitive and, more remarkably, CQ-resistant Plasmodium strains. In this work we investigated a panel of new silver, gold, platinum and palladium complexes with new ligands based on the CQ-backbone. The mode of action of CQ is the inhibition of hemozoin (malaria pigment) formation from hemin as a detoxification mechanism of the parasite. As a proof of principle we are investigating the ability of our compounds to inhibit hemozoin formation using a spectrophotometric test assay.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Detection of lanthanide circularly polarized luminescence by Raman optical activity instrumentation and its applications a

T. Wu, bJ. Kapitán, aP. Bouř

Institute of Organic Chemistry and Biochemistry, Academy of Sciences, Flemingovo nám. 2, 16610 Prague, Czech Republic b Department of Optics, Palacký University Olomouc, 17. listopadu 12, 77146 Olomouc Czech Republic a

 Dr. Tao Wu; [email protected]; Institute of Organic Chemistry and Biochemistry, Academy of Sciences, Flemingovo nám. 2, 16610 Prague, Czech Republic

Luminescent lanthanide(III) compounds are quite sensitive to their environment. However, the signal is sometimes weak and covered by Raman scattering. Recently, we have demonstrated that europium(III) circularly polarized luminescence (CPL) can be detected by the Raman optical activity (ROA) spectrometer, too. 1 Later, we found another option, identification of achiral lanthanide compounds by using ROA instrumentation equipped with an external magnet.2 This was shown for Na3[Ln(DPA)3] (Ln = Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Er) complexes with 532 nm laser excitation. Weak bands sometimes invisible in unpolarized measurement could be detected as magnetic circularly polarized luminescence (MCPL). Observed transitions were confirmed to belong to f-transitions of lanthanide(III) ions with the aid of ligand-field theory. As an example, we show specific CPL signal of an achiral Eu(III) complex induced by sugar molecules (fructose, mannose, glucose, and galactose). Differences were also observed between bare Eu(III) ion and its complexes, when interacting with these sugars. The sensitivity and specificity of the detection promises future usage in probes of saccharides and glycoconjugate in chemical imaging and medical diagnosis. 1, Wu, T.; Kapitán, J.; Mašek, V.; Bouř, P. Angew. Chem. Int. Ed. 2015, 54, 14933. 2, Wu, T.; Kapitán, J.; Andrushchenko, V.; Bouř, P. Anal. Chem. in revision. 3, Wu, T.; Průša, J.; Kessler, J.; Dračínský, M.; Valenta, J.; Bouř, P. Anal. Chem. 2016, 88, 8878–8885.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Synthesis, structure and magnetic property of a tungstoantimonite cobalt(II) complex with 1-methylimidazole ligands L. Xu, H. Liu College of Chemistry, Northeast Normal University, Changchun, 130024 China  Professor, Lin Xu; [email protected]; College of Chemistry, Northeast Normal University, Changchun, 130024 China

A sandwich-type coordination compound of tungstoantimonite (polyoxometalate) with 1-methylimidazole ligand, Na9[{Na(H2O)2}3{Co(mim)}3(SbW9O33)2]·41H2O (mim = 1-methylimidazole), was synthesized in alkaline aqueous solution by using the conventional method, and then the blue–green crystals were formed about seven days later. The composition of this compound and crystal structure were established by elemental analyses, IR spectra, and single crystal X-ray diffraction. This complex consists of two tri-vacant [SbW9O33]9- moieties linked through three transitional metal ions and three Na+ ions. The coordinated 1-methylimidazole molecules display different orientation, resulting in polyanions with lower symmetries. In addition to tungstoantimonite ligands, 1-methylimidazoles also coordinate to sandwich transitional metal ions. Magnetic measurement indicated the existence of antiferromagnetic interaction between the trimeric transitional metal ions in the coordination compound.

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Book of Abstracts – XXVI. International Conference on Coordination and Bioinorganic Chemistry Modern trends in coordination, bioinorganic, and applied inorganic chemistry June 4 – 9, 2017, Smolenice, Slovakia

Cu(II)Cr(III)-LDH – synthesis, characterization, intercalation properties and a catalytic application S. Ziegenheim, G. Varga, M. Szabados, P. Sipos, I. Pálinkó Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged H-6720 Hungary  Prof. István Pálinkó, [email protected], Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720 Hungary

Layered double hydroxides (LDHs) belong to the group of anionic clays. Their positively charged layers consist of divalent and trivalent metal ions coordinated with OH groups in octahedral arrangement. The interlayer space contains water molecules as well as partially hydrated anions, which compensate the positive charge of the layers. The variability of the metal ions and the interlayer anions provides diverse opportunities in application (catalysts, carriers), thus, nowadays, they are in the focus of research interest. The aim of this study was to optimize a method for the synthesis of Cu(II)Cr(III)-LDH, and to investigate their intercalation and catalytic properties. For the optimization the molar ratio of the metal ions, the pH, the temperature and the ageing time were systematically varied. For the characterization of the products powder X-ray diffractometry, IR spectroscopy, scanning electron microscopy as well as thermal methods were used. To investigate the opportunities for anion exchange, L-proline was intercalated to the interlayer space with the direct anion-exchange method. The catalytic properties were investigated in the oxidation of allylic alcohol. The reaction parameters such as the solvant, oxidant and the catalysts treatment were varied.

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LIST OF AUTHORS Ádám A. A. 19, 80 Ahmedova A. 106 Albertin G. 99 Almáši M. 20 Antoniutti S. 99 Apryshko G. N. 93 Arlot-Bonnemains Y. 30 Arsenijevic A. 87 Balašková T. 68 Baran P. 21 Barmashov A. E. 93 Baryshnikova М. А. 93 Beghetto V. 97 Bélteki R. 37 Bényei A. 71 Berdyugin S. 22 Bieńko A. 23 Bieńko D. 23 Biluk A. A. 91 Boča R. 24, 67, 90, 102, 121 Boguslavskii E. 29 Bortoluzzi M. 25, 97 Böszörményi É. 100 Bouř P. 127 Brachňaková B. 26 Breza M. 27, 89 Brišák R. 117 Brodowska K. 66 Buckó Á. 28, 100 Burdukov A. 29 Camerel F. 30 Carey J. R. 31, 48 Castro J. 99 Černák J. 102, 125 Chand K. 48 Chang Y.-L. 31 Chegerev M. G. 32 Chen H.-Y. 31 Chiang M. Y. 31

Chmielewská E. 36 Chotard F. 30 Chruscinski L. 33, 66 Chuang W.-J. 31, 48 Ciura K. 34 Conan F. 35 Cosquer N. 35 Dancs Á. 71, 113 Debnath S. 30 Déniel K. 35 Djordjevic D. 87 Dömötör O. 74 Drábik M. 36 Drweesh S. A. 87 Dudás C. 37, 63, 100 Dysz K. 38 El-Khateeb M. 39 Eltsov I. 29 Enrichi F. 25 Enyedy É. A. 74 Erasmus E. 110 Erdei S. 111 Fábián Z. 40 Falvello L. R. 125 Faragó T. 100 Farkasová V. 41, 68, 87 Fedoročko P. 41 Fernández I. 110 Fourmigué M. 30 Fuhr O. 94 Fujita M. 42 Fülöp F. 75 Gácsi A. 37, 100 Gajda T. 71, 113 Gall M. 43 Garmanchuk L. V. 91 Garribba E. 66 Goldeman W. 114 Gómez-García. C. J. 35 130

Gyepes R. 123 Gyurcsik B. 40, 44 Hackl C. M. 74 Handa M. 45 Havasi V. 111 Henkel G. 46 Hisaeda Y. 47 Hsu S. C. N. 31, 48, 49 Huang Y.-C. 49 Hung T. N. 50 Ivanov D. G. 104 Ivanova V. 83 Izakovič M. 78 Jakubowski M. 51 Jaworska M. 112 Jendželovský R. 41 Jomova K. 65 Jorík V. 70, 88 Joubert C. C. 109 Juráková J. 52 Kamecka A. 114 Kandioller W. 74 Kapitán J. 127 Kataoka Y. 45 Kensinger A. 21 Keppler B. K. 74 Khan I. U. 53 Khattak R. 54 Klewicka E. 66 Knör G. 55 Kocsis M. 75, 118 Koman M. 56 Kónya Z. 122 Kovalchukova O. V. 57 Kováts É. 71 Koyama Y. 58 Kožíšek J. 43, 59 Koziskova J. 59 Krajčiová D. 60, 73 Krzystek J. 61 Kuchár J. 95, 102 Kuchtanin V. 62, 69, 70, 98

Kudo S. 58 Kukovecz Á. 122 Kurahashi S. 58 Kurzak B. 114 Kutus B. 28, 37, 63, 100 Kuznetsov S. A. 64 Łakomska I. 51 Lawson M. K. 65 Le Goff-Gaillard C. 30 Lin Y.-F. 31 Liu H. 128 Lodowski P. 34, 112 Lodyga-Chruscinska E. 33, 66 Lomjanský D. 67 Lükőová A. 68, 87 Majerník M. 41 Masárová P. 69 Masuda T. 45 Matejová S. 70, 88 Matsumoto C. 58 Matsushima I. 76 Matyuska F. 71, 113 May N. V. 71, 113 Mazúr M. 69, 72, 107 Mebrouk K. 30 Melník M. 60, 73 Mesica A. 96 Mészáros J. P. 74 Mészáros R. 75 Meyerstein D. 96 Michalska D. 38 Mihaylova R. 106 Mikuriya M. 45, 58, 76 Mikuš P. 60, 73 Minhaz A. 54 Minkin V. I. 104 Mitsuhashi R. 58 Mohr F. 77, 126 Momekov G. 106 Momekova D. 106 Moncoľ J. 52, 56, 62, 67, 69, 78, 82, 84, 88, 98, 107, 121 131

Morgan N. 21 Morzyk-Ociepa B. 38 Müller E. 110 Muráth S. 79 Musza K. 19, 80 Naqvi I. I. 54 Narwane M. 31 Nazir M. 54 Nedzhib A. 83 Németh E. 40 Neuwirthová L. 78 Nishiura S. 45 Ogasawara K. 81 Ondrejovič G. 82 Ortmeyer J. 46 Orysyk S. I. 91 Ötvös S. B. 75 Palchykovska L. G. 91 Pálinkó I. 19, 28, 37, 50, 63, 75, 79, 80, 100, 111, 118, 122, 129 Pantcheva I. 83 Paulíková H. 68 Pavlik J. 84 Peintler G. 28, 63, 100 Pekhnyo V. I. 91 Pervukhina N. 29 Pilo M. I. 33 Pintauer T. 85 Piskunov A. V. 32 Pogány L. 86 Poprac P. 72 Potočňák I. 41, 59, 68, 87 Puchoňová M. 84, 88 Puškárová I. 89 Rajnák C. 67, 90, 121 Ray K. 108 Rendošová M. 123 Reolon A. 25 Repich H. H. 91 Roller A. 74 Rostášová I. 123 Rowińska-Zyrek M. 33

Ruben M. 92, 94 Rudakova A. A. 93 Rukk N. S. 93 Sabolová D. 102 Saksová S. 123 Šalitroš I. 26, 52, 86, 94 Samoľová E. 95 Saphier M. 96 Saphier O. 96 Sayed M. 54 Schoeller M. 78 Scrivanti A. 25, 97 Segľa P. 62, 98 Selektor S. 29 Sharif S. 53 Shestakova P. 106 Shokurov A. 29 Sibilla F. 99 Šima J. 101 Sipos P. 19, 28, 37, 50, 63, 79, 80, 100, 111, 118, 122, 129 Šípoš R. 101 Sitkowski J. 51 Skryabina A. Y. 93 Śmiłowicz D. 51 Smolko L. 102 Sobota P. 103 Sole R. 97 Starikov A. G. 104 Starikova A. A. 104, 105 Stoykova S. 106 Strashnova S. B. 57 Summer S. 54 Švorec J. 98, 107 Swart M. 108 Swarts J. C. 109 Swarts P. J. 110 Szabados M. 19, 80, 111, 129 Szczepańska M. 112 Szorcsik A. 71, 113 Szpak M. 114 Tacke M. 115 132

Taglietti A. 116 Tatarko M. 117 Taylor C. 21 Timár Z. 118 Titiš J. 67, 119, 121 Tomás M. 125 Tomohara S. 58 Triki S. 35 Tsai C.-L. 48 Tuna F. 120 Uhrecký R. 56 Valigura D. 84, 88, 107 Valko M. 65, 72 Varga F. 67, 121 Varga G. 50, 75, 118, 122, 129 Vargová Z. 123 Vasiľchencko D. 22 Vasková Z. 107 Vershinin M. 29, 124 Vetrova D. A. 64 Vilková M. 123

Volarevic V. 87 Voloshin Y. 29 Vovk M. V. 91 Vráblová A. 125 Vranec P. 59 Vu D. 21 Vukadinovic Y. 46 Weigand W. 39 Werner S. 126 Wojciechowski Y. 21 Wojtczak A. 51 Wu T. 127 Xu L. 128 Yano N. 45 Yoshioka D. 58, 76 Zaharieva J. 106 Zeleňák V. 20 Ziegenheim S. 100, 129 Zilbermann I. 96 Zucca A. 33

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