stuba.sk · 2017. 5. 30. · detection of lanthanide circularly polarized luminescence by raman...
TRANSCRIPT
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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
http://www.iccbic.stuba.sk/
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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.
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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.
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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)
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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
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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
15:45 – 16:15 Coffee break
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
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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
10:30 – 11:00 Coffee break
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
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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
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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
16:30 – 17:00 Coffee break
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
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) 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
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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 Coffee break
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
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WEDNESDAY, June 7, 2017
8.15 – 12.30 Plenary Session B
SOLUTION AND SOLID STATE REACTIVITY
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
10:30 – 11:00 Coffee break
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
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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
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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
10:15 – 10:45 Coffee break
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
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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
15:00 – 15:30 Coffee break
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
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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
15:00 – 15:30 Coffee break
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
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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)
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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
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.
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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
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.
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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
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.
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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
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.
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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
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
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]
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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
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.
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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
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.
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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
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.
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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
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.
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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
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.
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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
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.
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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
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.
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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
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.
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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
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).
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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
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.
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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
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.
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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
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.
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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
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.
mailto:[email protected]
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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
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.
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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
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.
mailto:[email protected]
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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
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.
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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
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
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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
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.
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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
42
Coordination self-assembly: from the origins to the latest advances
M. Fujita
Department of Applied Chemistry, The University of Tokyo
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.
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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
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;
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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
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.
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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
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.
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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
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.
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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
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.
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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
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.
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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
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.
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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
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.
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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
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