Department of Physical Chemistry of Coordination Compounds

The Head of Department – MANORIK P.A.

Doctor hab, Senior Research Scientist

tel. +38 (044) 525-65-66

e-mail: lizabeth@svitonline.com

The Department of Physical Chemistry of Coordination Compounds was established in 1961 by academician K.B.Yatsimirskii at the V.I.Vernadskii Institute of General and Inorganic Chemistry of the Academy of Sciences of URSR. In 1969, the department, led by academician K.B.Yatsimirskii, moved to the L.V. Pisarzhevskii Institute of Physical Chemistry of the Academy of Sciences of URSR. From 1985 to 1996 his supervisor was Prof. A.P.Filippov. From the very beginning the main work of the department focused on the study of structure, stability and reactivity of different classes of coordination compounds of d-, f-metals, the study of their spectral characteristics and electronic structure, studies of the kinetics and mechanisms of fast reactions and development of kinetic methods of analysis. In the 70’s the department began research in bioinorganic chemistry, including coordination compounds with different classes of biomolecules and macrocyclic ligands, compounds able to bind molecular nitrogen, oxygen, oscillatory chemical reactions. The main results of this research are summarized in more than 20 monographs.In the early 90’s, the department begun to study the physicochemical characteristics of heterogeneous systems formed by coordination compounds or composites based on them, the study of heterogeneous reactions involving them, the synthesis and study of polynuclear coordination compounds, porous materials, development of piezoresonance sensors for detection of ecologically important small molecules, methods and means of testing, non-destructive leak tester.

Main research

– molecular design of mononuclear, homo-, heteropolynuclear mixed-ligands coordination compounds, study their structure and physico-chemical properties, development of methods of their use as components of coatings of sensitive optical and piezoelectric sensors for determination of water ammonia and hydrocarbons vapors, as precursors for preparation of mesoporous (TiO2, SiO2), nanocomposites and films;

– study of porosity and sorption properties of metal-organic frameworks based macrocyclic complexes of transition metals, aromatic carboxylates and polyoxometalates;

– preparation and study composites containing functionalized ligands or coordination compounds, kinetics and mechanisms of heterogeneous reactions with their participation;

–  synthesis and study of dispersed porous materials (ТiO2, SiO2) as sorbents, photocatalysts, catalysts and development of approaches to the formation of ordered mesoporous films and nanocomposites based on titanium and silicon dioxides;

–  Synthesis of dispersed porous materials (TiO2, SiO2) of different morphology, ordered film mesoporous nanocomposites and study of their sorption, catalytic and photocatalytic properties.

The most important results in recent years
New mixed-ligand complexes of Co, Ni, Cu, Zn with pyridine derivatives of different structure have been obtained. It was shown that they display high selectivity towards aromatic hydrocarbons in the presence of aliphatic ones which depends on the composition and the structure of the complexes and the structure of analytes

Sensitivity of coatings based on the complexes CoPPP4Cl2, NiPPP4Cl2 and ZnPPP2Cl2 towards hydrocarbon vapors at 20 °C and the image of the surface of quartz crystal microbalance electrode without and with sensitive coating

– The methods for the formation of sensitive and selective toward aromatic analytes coatings based on these complexes as well as on their composites with TiO2, SiO2 on the surfaces of piesoquartz resonators have been developed.

– The technology for preparation of thermally stable nanocrystalline mesoporous titania (anatase) as spherical morphologically uniform particles with the size 1÷4 μm, mesopore diameters 5÷11 nm, specific surface 120÷155 m2/g, pore volumes 0,3o÷0,46 cm3/g was elaborated. These materials are prospective for use as fuel cell elements, ion-lithium batteries, photocatalysts.

Uniform mesoporous (dpore = 5÷11 nm, Sspec = 120÷155 m2/g , Vpore = 0,30÷0,46 cm3/g ) microspheres of TiO2 (anatase)

– The reduction of Ag, Au salts with Fuzarium Oxisporum proteins was shown to results in the formation of monodisperse Ag, Au nanoparticles that are stable in sol-gel processes of the formation of nanocomposites ТіО2/M under the conditions of thermo- and ultrasound treatment. Based on them film-forming blends for the formation of the layers of photocatalysts for effective cleaning of environment from organic pollutants have been developed.

SPR spectra of heat-treated (373 – 673 K) nanocomposite TiO2/Ag and SEM image of nanocomposite TiO2/Ag film

– Small-sized hardware based on regulated magnetic clampers for emergency blocking of the leaks of environmentally hazardous substances from steel tanks or other reservoirs has been constructed.

Leaks blocking device for hollow constructions

– New porous crystalline materials based on coordination polymers and ionic species characterized by the presence of channels with the diameters of 0,5÷1,6 nm, void volumes up to 45% of unit cells and specific area of 600 m2/g have been prepared. It was shown that some of these materials represent themselves selective adsorbents for a number of polar molecules with the sorption capacity reaching 40 molecules of the adsorbate per formula unit.

Visualization of the cavities in crystal lattice of coordination polymer [Ni(mc)(dphdc)]n

This type of compounds was shown to display reducing properties towards noble metal cations (Ag, Au, Pd) allowing to prepare composite materials with metal nanoclusters which are localized on the surfaces of reductant crystallite.

  TEM image of the composite Ag@[(CuL)3(PMo12O40)2]

 Scientific cooperations

• Professor V. Arion, Institute of Inorganic Chemistry, University of Vienna (Austria)
• Doctor S. Shova, “Petru Poni Institute of Macrovolecular Chemistry, Romania
• Professor Р. Comba, Anorganisch-Chemisches Institut, University of Heidelberg (Germany)
• Professor Ph. Lightfoot, School of Chemistry, University of St. Andrews (UK).

Research Scientists of the Department

• Andriichuk Iryna L., Сandidate of Chemical Sciences (PhD),Research Scientist. Tel. 38(044)525 25 70, E-mail: andriichuk@gmail.com
• Gavrish Sergey P. Сandidate of Chemical Sciences (PhD),Research Scientist,. Tel.  38 (044) 525 25 70, E-mail: gavrish_sp@ukr.net
• Grebennikov Volodymyr, candidate of chemical sciences, Researcher; tel: 38(044)525 65 85, E-mail: _vng@ukr.net
• Ermokhina Natalia I., Сandidate of Сhemical Sciences (PhD),Research Scientist. Tel. 38(044)52-66 50, E-mail: nat.ermokhina@gmail.com
• Lampeka Yaroslaw D., Doctor hab., Professor in Inorganic Chemistry, Corresponding Member of the National Academy of Sciences of Ukraine. Tel. 38(044)525 65 40, E-mail lampeka@adamant.net
• Tsymbal Lyudmyla V. Candidate of Chemical Sciences(PhD), Senior Research Scientist. Tel.  38(044)525 25 70, Е-mail: ltsymbal@ukr.net.
• Shulzhenko Alexander Vasilyevich, Junior Research Fellow; Tel.  38(044)52-66 50 Е-mail: vng@ukr.net

The list of developments that may present potential interest

1. Gavrish S.P., Lampeka Ya.D., Lightfoot P., Arion V.B., Keppler B.K., Woźniak K. Solid state structural variations in copper(II) complexes of open-chain and macrocyclic malonamide-derived ligands / Cryst. Growth Des., 2012, 12(9), 4388–4396 https://dx.doi.org/10.1021/cg300554r

2. Lampeka Ya.D., Tsymbal L.V., Barna A.V., Shuĺga Yu.L., Shova S., Arion V.B. Catenation control in the two-dimensional coordination polymers based on tritopic carboxylate linkers and azamacrocyclic nickel(II) complexes / Dalton Trans. 2012, 41(14), 4118–4125 https://dx.doi.org/10.1021/cg300554r

3. Tsymbal L.V., Lampeka Ya.D., Boyko V.I., Kalchenko V.I., Shishkina S.V., Shishkin O.V. A ladder-type coordination polymer constructed from two macrocyclic units – calix[4]arene tetracarboxylate and azamacrocyclic nickel(II) complex / CrystEngComm., 2014, 16(18), 3707–3711 https://doi.org/10.1039/C3CE42279H

4. Лампека Я.Д., Цымбал Л.В. Нанокомпозиты двумерных дихалькогенидов молибдена и вольфрама с частицами металлов: получение, свойства и перспективы применения / Теор. эксперим. химия, 2015, 51(3), 133-155

5. Stroyuk AL, Ermokhina NI, Korzhak AV, Andryushina NS, Kozyt- skiy AV, Manorik PA, Ilyin VG, Puziy AM, Sapsai VI, Shcherbatyuk NN Photocatalytic and photoelectrochemical char-acteristics of mesoporous titanium dioxide microspheres. Theor Exp Chem 2015, 51(3):183–190. https://doi.org/10.1007/s11237-015-9414-x

6. Gavrish S.P., Lampeka Ya.D., Lightfoot P. Metal-dependent structural variations and the peculiarities of hydrogen-bonded networks in the highly hydrated copper(II), nickel(II), and palladium(II) complexes of bis-dioxocyclam / Cryst. Growth Des., 2015, 15(4), 2024–2032 https://dx.doi.org/10.1021/acs.cgd.5b00217

7.  Лампека Я.Д., Цымбал Л.В. Получение, строение и функциональные свойства нанокомпозитов MoS2 и WS2 с неорганическими халькогенидными полупроводниками (обзор) / Теор. эксперим. химия, 2017, 53(4) 201–222

8.  Stroyuk OL, Ermokhina NI, Korzhak GV, Andryushina NS, Shvalagin VV, Kozytskiy AV, Manoryk PA, Barakov RY, Kuchmiy SY, Shcherbatyuk M, Sapsay VI, Puziy AM Photocatalytic and photoelectrochemical properties of hierarchical mesoporous TiO2 microspheres produced using a crown template. J Photo- chem Photobiol A Chem 2017, 334:26–35. https://doi.org/10.1016/j.jphotochem.2016.10.039.

9. Ermokhina NI, Shvalagin VV, Romanovska NI, Sydorova NA, Manoryk PA, Barakov RY, Shcherbatyuk MM, Klymchuk DO, Puziy AM Photocatalytic activity of mesoporous titanium dioxide stabilized with lanthanum in the gas-phase oxidation of ethanol. Theor Exp Chem 2018, 53(6):395–401. https://doi.org/10. 1007/s11237-018-9537-y

10. Gavrish S. P., Lampeka Ya. D., Babak M. V., Arion V. B. Palladium complexes of N,N′-bis(2-aminoethyl)oxamide (H2L): structural (PdIIL, PdII2L2, and PdIVLCl2), electrochemical, dynamic 1H NMR and cytotoxicity studies / Inorg. Chem., 2018, 57(3), 1288–1297 https://dx.doi.org/10.1021/acs.inorgchem.7b02732

11. Shvalagin V, Ermokhina N, Romanovska N, Barakov R, ManorikP, Sapsay V, Shcherbakov S, Poddubnaya O, Puziy A Mesoporous TiO2 microspheres with improved efficiency for photooxidation of volatile organic compounds. Res Chem Intermed 2019, 45(8):4133–4148. https://doi.org/10.1007/s11164-019-03896-z

12. Gavrish S.P., Shova S., Cazacu M., Lampeka Ya. D. A 2D coordination polymer assembled from a nickel(II) tetraazamacrocyclic cation and 4,4′-(dimethylsilanediyl)diphthalate(3-) linker / Acta Crystallogr. Sect. C, 2020, C76(5), 419–426 https://dx.doi.org/10.1107/S2053229620005008

13. N. I. Ermokhina, V. V. Shvalagin, N. I. Romanovska, P. A. Manoryk, R. Yu. Barakov, M. O. Kompanets, V. I. Sapsay, D. O. Klymchuk, A. M. Puziy. Synthesis and characterization of diferent binary and ternary phasemixtures of mesoporous nanocrystalline titanium dioxide. SN Applied Sciences 2021, 3:491 | https://doi.org/10.1007/s42452-021-04474-y

14. Tsymbal L.V., Rodik R.V., Danylyuk O., Suwinska K., Lipkowski J., Kalchenko V. I., Lampeka Ya. D. Supramolecular interactions in the heteroarylimine-substituted calix[4]arenes: the formation of cyclic dodecanuclear palladium aggregates / Supramol. Chem., 2021 https://dx.doi.org/10.1080/10610278.2021.1944632

15. Tsymbal L.V., Andriichuk I.L., Shova S., Trzybiński D., Woźniak K., Arion V.B., Lampeka Ya D. Coordination polymers of the macrocyclic nickel(II) and copper(II) complexes with isomeric benzenedicarboxylates: the case of spatial complementarity between the bis-macrocyclic complexes and o-phthalate / Cryst. Growth Des., 2021, 21(4), 2355–2370 https://dx.doi.org/10.1021/acs.cgd.1c00011

 Scientific and technical workings out of department

1. Magnetic piezoquartz microbalances

Desighned magnetic piezoquartz microbalances- the device for studying by a method piezoquartz microweighings in a non-uniform magnetic field of magnetic properties of the thin layers or films of materials, weight is no more 10-6-10-7 g, and chemical processes at their participation.

2. Piezoelectriс sensors on ammonia and materials for sorbtion-sensitive coatings

3. Piezoelectriс sensors on water vapors and materials for sorbtion-sensitive coatings

4. Piezoelectriс sensors on toluene vapors and materials for sorbtion-sensitive coatings

5. Universal remedies of fast emergency hermetic sealing of locally damaged walls of steel tanks and the pipelines which are under superfluous pressure of ecologically harmful substances.