MainDEPARTMENTSDEPARTMENT OF PHYSICO-INORGANIC CHEMISTRY

DEPARTMENT OF PHYSICO-INORGANIC CHEMISTRY

The Department Head -MANORIK PETER.A.

Doctor of Chemistry (habilitat), Senior Research Scientist

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

E-mail lizabeth@svitonline.com

The Department 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-metals and lanthanides, 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, synthesis and study of new materials for modern technology.

Main research areas

  • molecular design of mononuclear, homo-, heteropolynuclear mixed-ligands coordination compounds, study their structure and redox 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 materials (TiO2, SiO2) and their highly ordered films;
  •  study of porosity and sorption properties of metal-organic frameworks based macrocyclic complexes of transition metals, aromatic carboxylates and polyoxometalates;
  •  preparation and study of heterogeneous systems including composites containing functionalized ligands or coordination compounds, kinetics and mechanisms of heterogeneous reactions with their participation;
  •  synthesis and study of dispersed porous materials as sorbents, photocatalysts, catalysts and development of approaches to the formation of ordered mesoporous films and nanocomposites based on titanium and silicon dioxides;
  •  development of methods for investigation of heterogeneous solid-gas reactions, study the applicability new materials for sensitive sensor coatings forecologically important small molecules.

The most important results in recent years

New hetero-and homonuclear complexes of cobalt, nickel, copper, zinc, and some lanthanides with aminopolycarboxylates, hydroxyacids, carboxylic acids, benzene and pyridine derivatives have been obtained and their composition, structure, and redox properties have been studied. Sensitive coating of piesoresonance sensors based on ternary mono-and heteronuclear complexes of 3d metals or their composites with TiO2 and SiO2 have been prepared. The influence of the structure of complexes and weak interligand interactions on sensory characteristics (sensitivity, selectivity, response time and relaxation) towards the vapors of ammonia, water and hydrocarbon in heterophase processes have been established. The composition of sensitive coating is protected by patents.

r1

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

New approaches to the creation of high-performance photocatalyst for hydrogen production based on nanoperiodical mesoporous titania using macrocyclic compounds as templates have been developed. The mesoporous TiO2 samples characterized by a high content of anatase, specific surface area of 100 m2/g and the pore diameter of 10 nm was shown to possess high photocatalytic activity in the formation of molecular hydrogen from water-alcohol solutions. Semiconductor nanostructured composites TiO2/Ni operating on the principle of "two in one" (without dark stage catalyst Pd/SiO2) have been synthesized by chemical and photochemical reduction which demonstrate high quantum yields (γ=0,4-0,5) significantly exceeding that of commercial Degussa P-25.

r2

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

Fast universal emergency sealing for locally damaged walls of high-pressure steel tanks and piping with environmentally harmful substances have been developed, tested and patented.

r4

Leaks blocking device for hollow constructions

New method – piezoelectric quartz microweighting (PKMW) in an inhomogeneous magnetic field (NMP), based on the linear dependence of the change of mass-frequency characteristics of the resonator coated with sensing material (10-6 - 10-7 g ) have been developed and corresponding device have been constructed. Since the response of PKMW for different magnetic materials in NMP differ significantly from those in the absence of the field, it was proposed to use this difference to determine the magnetic properties of thin layers or films of materials of different nature.

The conditions of template sol-gel synthesis and experimental parameters of making of thin and transparent mesoporous films based on silicon and titanium dioxides with different pore geometry have been established. The infrared spectroscopic method of control of the structure of films has been developed.

The possibility of creating functional nanocomposites based on the quasi-amorphous mesoporous silicon and titanium oxides films and guest molecules have been shown.

In order to create new materials able to accumulate small gaseous molecules, in particular molecular hydrogen, new porous crystalline compounds based on azamacrocyclic nickel (II), copper (II) complexes and aromatic carboxylates or polyoxometalates have been obtained. It was shown that, depending on the chemical structure of the building blocks, the diameter of the channels in their crystal lattices vary in the range from 4 to 15 Å and these materials absorb up to 1% of dihydrogen by weight.

r5

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

It was found that the metal-organic frameworks obtained stoichiometrically interact with ammonia gas, both in hydrated and dehydrated state. Some of them characterized by a high adsorption capacity, up to 40 of the ammonia molecules per formula unit of the complex. A promising feature of these systems is that they, unlike most known sorbents react with ammonia, even in the absence of water vapor. It was shown that these complexes exhibit sorption properties towards other polar molecules (methanol, ethanol, acetonitrile), and the thermodynamic and kinetic characteristics of their behavior depend strongly on the chemical composition.

 Scientific cooperations

Institute of Physics, Lithuania.

Vienna University, Austria

Center of Microbiology and tumor biology at the Karolinska Institute.

Technical University of Georgia.

 Researcher in the Department

Barna Andrey, cand. chem. Science, Research Associate

Gavrish Sergey, cand. chem., Research Scientist

Grebennikov Vladimir, cand. chem., Research Scientist

Yermokhina Natalia, cand. chem, Research Scientist

Lampeka Yaroslaw , Doctor hab., Professor

Telbiz Herman , cand. chem. , senior research scientist

Tsymbal Lyudmila, cand. chem., , senior research scientist

 List of selected publications

  • Patent of Ukraine 23210. Device for the temporary sealing of hollow articles made of magnetically conductive material. Shulzhenko .V., Manoruk P.., Grebennikov V..  Publ. 10.05 2007, Bul. 6.- 6 p
  • Patent of Ukraine 23211. Magnetic lock. Shulzhenko .V., Manoruk P.. Publ. 10.05 2007, Bul. 6.- 6 p. 
  • Russian patent 2291839. Mesoporous titanium dioxide, process and intermediates for its preparation. P.. Manoruk, N.I Yermokhina, V.I. Litvin, V.G. Ilyin, S.Y. Kuchmiy, A.V. Shulzhenko, V.I. Yatskiv, .. Fedorenko, A.V. Korzhak, V.. Granchak, A.L. Stroyuk. Publ. 20.01.2007. – Bul.2.
  • Tetrazolecalix[4]arenes as new ligands for palladium(II) / V. Boiko, R. Rodik, L.Tsymbal, O.Danylyuk, Y.Lampeka, K.Suwinska, J.LipkowskI, V.Kalchenko. - Tetrahedron, 2006, .61, 52, p.12282-12287.
  • Encapsulation of cyanometalates by a tris-macrocyclic ligand tricopper(II) complex: syntheses, structural variation, and magnetic exchange coupling pathways. / M.Atanasov, P.Comba, Y.D.Lampeka, G.Linti, T.Malcherek, R.Miletich, A.I.Prikhodko, H.Pritzkow. - Chem. Eur. J., 2006, v.12, 3, p.737 – 748.
  • Posudievsky O. Y., Telbiz G. M., Rossokhaty V. K. Effect of solvent nature on liquid-phase self assembly of MEH-PPV/MCM-41 guest–host composites. -J. Mater. Chem., 2006, v.16, p.2485-2489.
  • Gavrish S.P., Lampeka YA.D., Lightfoot P., Pritzkow H. The crystal and molecular structures of the related nickel(II) complexes of open-chain and macrocyclic oxamide-based ligands and the peculiarities of water aggregates in their crystal lattices // Dalton Trans.- 2007.- N41.- P. 4708 – 4714.
  • N.A. Burlaenko, L.M. Pogorelaya, P.A. Manoruk, V.N. Grebennikov, A.V. Shulzhenko. Citrate complexes of copper (II), nickel (II) as sorption-active coating of piezoelectric sensors for ammonia // Ukrainian Journal of Chemistry.- 2007.- Vol.73,7.- P.26-30.
  • A.V. Korzhak, N.I. Ermokhina, A.L. Stroyuk, V.K. Bukhtiyarov, A.E. Raevskaya, V.I. Litvin, S.Ya. Kuchmiy, V.G. Ilyin, P.A. Manorik Photocatalytic hydrogen evolution over mesoporous TiO2/ metal nanocomposites // Journal of Photochemistry and Photobiology A: Chemistry 198- 2008. .126–134
  • O. V. Kravchenko, L. V. Tsymbal, Ya. D. Lampeka, Isocationic substitution of copper(II) complexes in anisotropic materials based on benzenetricarboxylate / Theor. Exper. Chem., 2007, v.43, N.2, p.124-129.
  • P. N. Boltovets, L. V. Tsymbal, B. A. Snopok, Ya. D. LampekaEffect of macrocyclic nickel(II) and copper(II) complexes on the reaction of trypsin with a soybean bioinhibitor /Theor. Exper. Chem., 2008, v.44, N.4, p.248-253