Heterometallic complexes of transition metals

Previous and Current Research

An unconventional approach to the preparation of metal complexes (Direct synthesis), developed by the group, offers a one-pot synthesis of such compounds using metal powders or metal oxides as starting materials. An important advantage of Direct synthesis is the possibility to obtain complexes that are often inaccessible by traditional synthetic routes. The team has a huge experience in synthesis of metal complexes and their characterization by various physico-chemical methods.

Current research interests are focused on:

• development of synthetic procedures based on direct synthesis to obtain 1) heterometallic complexes of transition metals with Schiff base ligands generated in situ via condensation of aromatic aldehydes and their derivatives with compounds containing primary amino groups; 2) hybrids based on polyoxometalate anions (e.g. V₁₀O₂₈^6-, PMo₁₂O₄₀^3-, P₂Mo₃O₁₈^6-, P₂Mo₅O₂₃^6-, V₂Mo₆O₂₄^8-, PMo₈V₄O₄₀^7-) via oxidative dissolution of metal powders (Cu, Co, Mn) in liquid phase in the presence of organic ligands;

• characterization of novel compounds by elemental analysis, UV-Vis, IR, EPR, NMR, Mass spectrometry, thermal analysis, powder and single crystal X-ray diffraction.

International Research Projects and Grants

COST D8 "The Chemistry of Metals in Medicine"; COST D20 "Metal Compounds in the Treatment of Cancer and Viral Diseases"; COST CM1305 “Explicit Control Over Spin-states in Technology and Biochemistry”; INTAS project 03-51-4532 "Polymetallic complexes as molecular nanomagnets and novel homogeneous catalysts"; International project for mutual mobility between Taras Shevchenko National University and Uppsala University (Sweden) 00859/2009 "Direct synthesis of manganese containing complexes: searching for water oxidation catalysts" ("Visby" Program); FCT project PTDC/QEQ-QIN/3967/2014 "Catalytic Alkane Functionalization towards Sustainable Organic Synthesis"; the Ukrainian-Polish project “Multifunctional materials based on mixed-metal polyoxometalates”.

Future Projects and Goals

• Investigation of functional properties of heterometallic complexes (magnetic properties, catalytic activity, luminescence, photoconductivity of film composites; bioactivity);

• Examination of possible applications of obtained complexes as novel multifunctional materials:

-        catalysts of cycloalkanes oxidation;

-        catalysts of water oxidation;

-        photovoltaics;

-        magnetic materials;

-        antitumor and antimicrobial agents;

-        antioxidant additive

Methodological and Technical Expertise

Design, synthesis and characterization of heterometallic complexes.

Selected Publications

1.    Plyuta, N., Petrusenko, S., Kokozay, V.N., Cauchy, T., Lloret, F., Julve, M., Cano, J. and Avarvari, N., 2022. Field-induced mononuclear cobalt (II) single-molecule magnet (SMM) based on a benzothiadiazole-ortho-vanillin ligand. Dalton Transactions, 51(12), pp.4760-4771.

2.    Buvailo, H.I., Makhankova, V.G., Kokozay, V.N., Babaryk, A.A., Omelchenko, I.V., Shishkina, S.V., Bieńko, D.C., Jezierska, J. and Bieńko, A., 2022. Hybrid Cu-Containing Compounds Based on Lacunary Strandberg Anions: Synthesis under Mild Conditions, Crystal Structure, and Magnetic Properties. Inorganic Chemistry, 61(15), pp.5701-5714.

3.    Halyna I. Buvailo, Valeriya G. Makhankova, Vladimir N. Kokozay, Iryna V. Omelchenko, Svitlana V. Shishkina, Alina Bie´nko, Mariia V. Pavliuk and Sergii I. Shylin. Hybrid compound based on diethylenetriaminecopper(II) cations and scarce V-monosubstituted b-octamolybdate as water oxidation catalyst. RSC Adv., 2021, 11, 32119–32125.

4.    Olga Yu. Vassilyeva, Elena A. Buvaylo, Yevheniia V. Lobko, Rostyslav P. Linnik, Vladimir N. Kokozay, Brian W. Skelton. Organic–inorganic hybrid tetrachlorocadmates as promising fluorescent agents for cross-linked polyurethanes: synthesis, crystal structures and extended performance analysis. RSC Adv., 2021, 11, 7713–7722.

5.    Olga Yu. Vassilyeva, Elena A. Buvaylo, Vladimir N. Kokozay, Brian W. Skelton, Alexandre N. Sobolev, Alina Bieńko and Andrew Ozarowski. Ferro- vs. antiferromagnetic exchange between two Ni(II) ions in a series of Schiff base heterometallic complexes: what makes the difference? Dalton Trans., 2021, 50, 2841–2853.

6.    Oleh Stetsiuk, Nataliya Plyuta, Narcis Avarvari, Evgeny Goreshnik, Vladimir Kokozay, Svitlana Petrusenko, and Andrew Ozarowski. Mn(III) Chain Coordination Polymers Assembled by Salicylidene-2-ethanolamine Schiff Base Ligands: Synthesis, Crystal Structures, and HFEPR Study. Cryst. Growth Des. 2020, 20, 1491−1502.

7.    Oleh Stetsiuk, Svitlana R. Petrusenko, Lorenzo Sorace, Alexandru Lupan, Amr A. A. Attia, Vladimir N. Kokozay, Abdelkrim El-Ghayoury and Narcis Avarvari. Versatile coordination behaviour of the chlorotetrazine-picolylamine ligand: mixed-valence binuclear Cu(I)/Cu(II) complexes. Dalton Trans., 2019, 48, 11966–11977.

8.    Oleh Stetsiuk, Valentyn Synytsia, Svitlana R. Petrusenko, Vladimir N. Kokozay, Abdelkrim El-Ghayoury, Joan Cano, Francesc Lloret, Miguel Julve, Benoit Fleury and Narcis Avarvari. Co-existence of ferro- and antiferromagnetic interactions in a hexanuclear mixed-valence Co^III₂ Mn^II₂Mn^IV₂ cluster sustained by a multidentate Schiff base ligand. Dalton Trans., 2019, 48, 11862–11871.

9.    Olga Yu. Vassilyeva, Elena A. Buvaylo, Vladimir N. Kokozay, Brian W. Skelton, Cyril Rajnák, Ján Titiš and Roman Boča. Long magnetic relaxation time of tetracoordinate Co²⁺ in imidazo[1,5-a]pyridinium-based (C₁₃H₁₂N₃)₂[CoCl₄] hybrid salt and [Co(C₁₃H₁₂N₃)Cl₃] molecular complex. Dalton Trans., 2019, 48, 11278–11284.

10. Elena A. Buvaylo, Vladimir N. Kokozay, Valeriya G. Makhankova, Andrii K. Melnyk, Maria Korabik, Maciej Witwicki, Brian W. Skelton, Olga Yu. Vassilyeva. Synthesis, Characterization, and Magnetic Properties of a Series of Copper(II) Chloride Complexes of Pyridyliminebenzoic Acids. Eur. J. Inorg. Chem. 2018, 1603-1619.

11. Halyna I. Buvailo,Valeriya G. Makhankova, Vladimir N. Kokozay, Irina V. Omelchenko, Svitlana V. Shishkina, Julia Jezierska, Mariia V. Pavliuk and Sergii I. Shylin. Copper-containing hybrid compounds based on extremely rare [V₂Mo₆O₂₆]⁶– POM as water oxidation catalysts. Inorg. Chem. Front., 2019, 6, 1813–1823.

-        https://www.scopus.com/authid/detail.uri?authorId=7003807259

-        https://orcid.org/0000-0003-1834-3020

Contacts

Phone: +380632516722  

E-mail.: kokozay@univ.kiev.ua