stuba.sk · 2017. 5. 30. · Detection of lanthanide circularly polarized luminescence by Raman...

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

http://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: Milan MELNÍK

Chairman: Peter SEGĽA

Secretary: Miroslav TATARKO

Members: 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 Reception in Smolenice castle

16:00 Departure from Bratislava (bus 1)

18:30 Departure from Bratislava (bus 2)

18:00 Dinner 1

19:30 Dinner 2

MONDAY, June 5, 2017

7:15 Breakfast

9:00 Opening

9:15 – 12:30 Plenary session A

12:45 Lunch

14:30 – 18:00 Session A

19:00 Official Ceremony

19:30 Get-together Party

TUESDAY, June 6, 2017

7:15 Breakfast

8:15 – 12:30 Plenary session C

11:30 – 12:30 Session C

12:45 Lunch

14:30 – 17:45 Session B

18:00 Dinner

WEDNESDAY, June 7, 2017

7:15 Breakfast

8:15 – 12:30 Plenary session B

12:30 Lunch

13:25 Photography

13:30 – 17:30 Excursion

18:00 Dinner

20:00 – 21:30 Poster Session

THURSDAY, June 8, 2017

7:15 Breakfast

8:15 – 11:45 Plenary session D

12:45 Lunch

14:00 – 16:50 Young session

16:50 Closing

19:00 Banquet and Farewell Party

20:00 Concert

FRIDAY, June 9, 2017

7:15 Breakfast

8:00 Departure (bus 1)

9:00 Departure (bus 2)

7

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 Chairman: M. Melnik

9:15 – 10:00 M. Fujita (Japan) 42

Coordination self-assembly: from the origins to the latest advances

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 Coffee break

Room 1 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) 21

Structural diversity of copper(II) complexes derived from various

coordination modes of imidazoledioxide

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) 61

Understanding single-ion molecular magnetism

8

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) 27

QTAIM studies of biomimetic trigonal iron(IV) nitrido and imido

15:15 – 15:30 M. Gall (Slovakia) 43

Agostic Cu-H interaction – charge density study of bis(clonixato)

bis(imidazole)copper(II) complex

15:30 – 15:45 J. Pavlik (Slovakia) 84

Magnetic exchange interaction transmitted by H-bonds


Room 1 Part 2 Chairman: P. Baran

16:15 – 16:30 G. Ondrejovič (Slovakia) 82

Advanced structural analysis of coordination Cu4OX6L4 molecules

16:30 – 16:45 K. Ogasawara (Japan) 81

Multidimensional multiplet energy diagrams for Cr3+ in oxides based on

first-principles calculation

16:45 – 17:00 M. Lawson (Slovakia) 65

Study of copper(II) complexes with quercetin and rutin

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-pyridine-

methanol

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

9

TUESDAY, June 6, 2017

8.15 – 12.30 Plenary Session C

APPLIED INORGANIC AND COORDINATION CHEMISTRY

Room 1 Part 1 Chairman: M. Swart

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

10:00 – 10:30 P. Sobota (Poland) 103

Heterometallic nanomaterials with hierarchical structure for special

applications in materials engineering: design, synthesis and research


Room 1 Part 2 Chairman: M. Ruben

11:00 – 11:30 M. Swart (Spain) 108

The inner side of high-valent metal-oxo reactivity

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/Cu2O

nanoparticles

12:15 – 12:30 M. Szabados (Hungary) 111

Mechanochemical synthesis of zinc aluminate spinel

10

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 single-

molecule magnets

12:00 – 12:15 G. Varga (Hungary) 122

Co(II)-amino acid–CaAl-layered double hydroxide composites –

construction and characterization

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 Part 1 Chairman: R. Boča

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) 23

Homo and heterometallic molecular magnetic materials

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 Part 2 Chairman: G. Knör

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

11

16:00 – 16:15 R. Khattak (Pakistan) 54

Thermodynamic aspect: kinetics of the reduction of dicyano-

bis(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


Room 1 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 silver-

bismuth composite

14.30 – 17.45 Session B


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) 113

Metal ion binding of TACH-based polydentate tripodal ligands

15:15 – 15:30 M. Puchoňová (Slovakia) 88

New different salicylatocopper(II) complexes with isonicotinamide

12

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


Room 2 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) 101

New insight into Jablonski diagram

17:30 – 17:45 F. Matyuska (Hungary) 71

Transition metal complexes of mono- and trisubstituted tren-derivatives

13

WEDNESDAY, June 7, 2017

8.15 – 12.30 Plenary Session B


Room 1 Part 1 Chairman: A. Taglietti

8:15 – 9:00 F. Tuna (United Kingdom) 120

Quantum information with molecular nanomagnets

9:00 – 9:30 R. Boča (Slovakia) 24

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

9:30 – 10:00 G. Knör (Austria) 55

Photochemical enzyme models – state of the art

10:00 – 10:30 E. Lodyga-Chruscinska (Poland) 66

Physicochemical properties and biological activity of naringenin

thiosemicarbazone


Room 1 Part 2 Chairman: F. Tuna

11:00 – 11:30 F. Mohr (Germany) 77

Reactivity of coordinated azides

11:30 – 12:00 P. Sipos (Hungary) 100

Calcium complexation processes in hyperalkaline aqueous solutions

12:00 – 12:30 M. Mikuriya (Japan) 76

Trinuclear mixed-valent manganese complex with non-Schiff-base

tetradentate ligand showing a ferromagnetic coupling

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) 22

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

14

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) 60

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) 117

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

15

THURSDAY, June 8, 2017

8.15 – 11.45 Plenary Session D

COMPLEXES IN HUMAN MEDICINE AND THE ENVIRONMENT

Room 1 Part 1 Chairman: F. Mohr

8:15 – 8:45 M. Melnik (Slovakia) 73

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) 96

The redox qqueous chemistry of CuII/IATP


Room 1 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) 83

Rare earth metal complexes of polyether ionophores

11:15 – 11:30 I. Potočňák (Slovakia) 87

Structures and in vitro cytotoxic properties of Pd(II) complexes with 7-

bromo-quinolin-8-ol

11:30 – 11:45 Z. Vargová (Slovakia) 123

Complexing properties of 2-pyridinephosphonic acid

16

14.00 – 16.50 Young Session

Room 1 Part 1 Chairman: M. Drabik

14:00 – 14:10 A. A. Ádám (Hungary) 19

Synthesis and characterization of nickel nanoparticles

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) 89

DFT studies of the effectiveness of p-substituted diphenyl amine

antioxidants through their Cu(II) coordination ability

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


Room 1 Part 2 Chairman: I. Potočňák

15:30 – 15:40 M. Szczepańska (Poland) 112

Theoretical investigation of photochemical properties of

palladium(II)corrin

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) 40

Structural activation of NColE7-based artificial metallonucleases

17

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) 74

Half-sandwich rhodium(III) complexes formed with (N,N) ligands:

structural characterization and solution chemistry

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) 86

Spin crossover and high spin iron(III) Schiff base complexes


Room 2 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 Schiff-

base 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

18

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) 50

Complexation characteristics of a thionated cyanoxime ligand

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) 126

Towards new organometallic antimalarial drugs

16.50 Closing (Room 1)

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

19

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.


20

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.


21

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.


22

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.


23

Homo and heterometallic molecular magnetic materials

aA. Bieńko, bD. Bieńko

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

Wroclaw, Poland

[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 Organic-

Inorganic 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.

mailto:[email protected]


24

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.


25

The conjugate base of malonaldehyde as antenna-ligand towards

trivalent europium and terbium ions

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

a 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

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 antenna-

ligand for the sensitization of Tb(III) luminescence. The experimental data have been

rationalized of the basis of DFT calculations.


26

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 = 2,6-

bis(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 single-

molecule magnetism.


27

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.


28

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 Ca2+/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.


29

Phenanthroline-decorated iron(II) clathrochelates as ligands

towards other metals

aA. Burdukov, aM. Vershinin, aN. Pervukhina, aE. Boguslavskii, bI. Eltsov, cY.

Voloshin, dS. Selektor, dA. Shokurov

aNikolaev Institute of Inorganic Chemistry SB RAS, Lavrentiev Ave. 3,

630090 Novosibirsk, Russia bNovosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia cNesmeyanov Institute of Organoelement Compounds RAS, Vavilova str. 28,

119991 Moscow, Russia dA.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.

NH2

NH2

N

N

Fe2+N

N N

OOOB

OO

BO

N

F

F

N

N

Fe2+N

N N

OOOB

OO

BO

N

F

F

base

N

N

O

O

N

N N

N

N

N

Fe2+N

N N

OOOB

OO

BO

N

F

F

N

N N

N

MLL

M

-2L

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.


30

NIR-Photothermal properties of nickel-bis(dithiolene) complexes:

Cancer therapy, photoresponsive gels and photocontrolled drug

release

aK. Mebrouk, aS. Debnath, aF. Chotard, aM. Fourmigué, bC. Le Goff-Gaillard, bY.

Arlot-Bonnemains, aF. Camerel

a Institut des Sciences Chimiques de Rennes (ISCR), Université Rennes 1, 35042, Rennes b 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 nickel-

bis(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.


31

Steric and electronic control on the nitrite reduction

of the bio-inspired copper(I)-nitro complexes

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

a Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung

807, Taiwan bDepartment of Applied Chemistry, National University of Kaohsiung, Kaohsiung 804, Taiwan cDepartment 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.


32

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 tetragonal-

pyramidal 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).


33

Potentiometric, voltammetric and spectroscopic studies of fisetin

and its copper complexes

aL. Chruscinski, bM. I. Pilo, bA. Zucca, cM. Rowińska-Zyrek, dE. Lodyga-Chruscinska

aFaculty 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 cDepartment of Chemistry, University of Wroclaw, F. Joliot-Curie Street 14, 50-383 Wroclaw,

Poland dFaculty 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.


34

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, 40-

006 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.


35

Rationalization of the spin crossover (SCO) behavior in polypyridyl-

based iron(II) complexes

aK. 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 bICMol, Universidad de Valencia, C/ Cat. José Beltrán, 2, 46980 Paterna, Valencia, Spain.

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.


36

Strength and limitations of thermoanalytical research in materials

and solid state chemistry

aM. 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.



37

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-oxopentane-

dioate, 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 Ket2– underwent

deprotonation resulting in an enolate form after tautomerism. Temperature-dependent 1H 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 13C NMR spetroscopies.


38

5-Bromo-7-azaindole complexes with Pt(II) and Pd(II):

synthesis, vibrational spectroscopy and DFT calculations

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

a 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

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.



39

[FeFe]-hydrogenase models: synthesis, characterization and

catalytic activity of diselenolato diiron complexes

aM. El-Khateeb, bW. Weigand

aChemistry Department, Jordan University of Science and Technology, 22110 Irbid, JORDAN bInstitut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena,

Humboldt-Straße 1, 07743 Jena, GERMANY

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.


40

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 Zn2+ 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


41

Synthesis, crystal structure and cytotoxicity of zinc(II) complexes

with quinolin-8-ol chloroderivatives

aV. Farkasová, bR. Jendželovský, bM. Majerník, bP. Fedoročko, aI. Potočňák

aDepartment of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice,

Moyzesova 11, 041 54 Košice, Slovakia bDepartment of Cell Biology, Institute of Biology and Ecology, P. J. Šafárik University in

Košice, Šrobárova 2, 041 54 Košice, Slovakia

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.


42

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.


43

Agostic Cu-H interaction – charge density study of bis(clonixato)

bis(imidazole)copper(II) complex

aM.Gall, bJ. Kožíšek

aInstitute of Information Engineering, Automation, and Mathematics, Faculty of Chemical and

Food Technology, Slovak University of Technology, SK-812 37 Bratislava, Slovakia bInstitute 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 single-

crystal 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;


44

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 Zn2+-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 side-

chains. 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.


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

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

aDepartment of Material Science, Interdisciplinary Faculty of Science and Engineering,

Shimane University, Matsue 690-8504, Japan bDepartment 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.


46

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.


47

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.


48

Reactivity study of unsymmetrical ß-diketiminato copper(I)

and zinc(II) complexes: effect of chelating ring

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

aDepartment of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung

807, Taiwan; Department of Medical Research, Kaohsiung Medical University Hospital,

Kaohsiung 807, Taiwan bDepartment 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.


49

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 (2b(BF4)2), [Cp2Fe2(-SEt)2

(4-CNC6H4NH2)2](BF4)2 (2c(BF4)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.


50

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.


51

Novel dicarboxylato platinum(II) complexes as potential anticancer

agents

aM. Jakubowski, bJ. Sitkowski, aA. Wojtczak, aD. Śmiłowicz, aI. Łakomska

aNicolaus Copernicus University in Toruń, Faculty of Chemistry, Gagarina 7,

87-100 Toruń, Poland bNational Medicines Institute, Chełmska 30/34, 00-975 Warsaw, Poland

Mateusz Jakubowski, MSc; [email protected]; Ni

stuba.sk · 2017. 5. 30. · Detection of lanthanide circularly polarized luminescence by Raman...

Documents

Transcript of stuba.sk · 2017. 5. 30. · Detection of lanthanide circularly polarized luminescence by Raman...