DEVELOPMENT OF RESEARCH OF CHEMISTRY OF COORDINATION COMPOUNDS IN V.I. VERNADSKY INSTITUTE OF GENERAL AND INORGANIC CHEMISTRY NAS OF UKRAINE: FROM THE 30'S TWENTIETH CENTURY(part1)

The review considers the main stages of development of the chemistry of coordination compounds at the Institute of General and Inorganic Chemistry. VI Vernadsky National Academy of Sciences of Ukraine on the occasion of the 90th anniversary of its founding. An overview of complex compounds of p, d, f-me­tals with different classes of ligands (inorganic and organic), features of their synthesis, study of the structure and properties of the obtained compounds, contains current material on the use of synthesized complexes to create functional materials for different purposes. Me­thods of synthesis have been developed, do­zens of new coordination compounds with derivatives of hydrazones, amines, azomethanes, and thiosemicarbazones have been synthesized and isolated in the individual state. Their composition, structure and physicochemical pro­perties are determined. The general regularities that take place in the process of comple­xation of metals with ligands, as well as factors influencing the composition, structure and physico­chemical properties of the obtained coordination compounds are established. For the long history of the Institute has accumulated a huge amount of material on the problems of modern coordination chemistry. Significant research in this area belongs to Ukrainian scientists who have worked long and fruitfully at the Institute: A.K. Babko, K.B. Yatsimirsky, Ya.A. Fialkov, I.A. Sheka, S.V. Volkov, N.A. Kostromina, and who created scientific schools, known not only in Ukraine but also abroad. To date, the attention of scientists of the Institute has shifted from classical monomeric to bigeteronuclear, polynuclear, multiligand complexes, which is primarily due to intensive research of new functional materials: optical and magnetic, biologically active substances, as well as effective adsorbents, chemical sensors, catalysts, catalysts, catalysts and biochemical processes.

SPIN-CROSSOVER IRON(II) COORDINATION COM­POUNDS: FABRICATION OF FUNCTIONAL MATERIALS AND THEIR INTEGRATION INTO MICRO- AND NANOCONSTRUCTIONS

Development of micro- and nanosized spin-crossover (SCO) materials has become an important research direction within the past decade. Such an interest is associated with high perceptive of practical application of these materials in nanoelectronic devices. Therefore, researches working in the field of SCO put considerable efforts to obtain SCO complexes in various functional forms, such as nanoparticles, thin films, etc. Fabrication of these materials is realized through different chemical and/or lithographical approaches, which allow to adjust size, shape and even organization of nanoobjects. In this review theoretical background of SCO phenomenon is described, additionally different classes of coordination compounds exhibiting spin crossover are covered. It is demonstrated that electric field, temperature and light irradiation can be effectively used for switching and control of spin state in nanosized SCO systems. Cooperative SCO with transition close to room temperature, wide hysteresis loop and distinct thermochromic effect is most often observed for Fe(II) coordination complexes. Therefore, Fe(II) SCO compounds form one of the most perspective classes of compounds for obtaining functional materials. It is shown that integration of Fe(II) compounds into micro- and nanohybrid devi­ces allows to combine unique functional pro­perties in one material due to synergy between SCO and physical properties (luminescent, electrical, etc.) of the other component. As a result, SCO compounds are interesting not only from the fundamental point of view, but also from practical, thanks to the possibility of integration of SCO Fe(II) complexes as active materials in devices of different configurations. It is expected that obtaining of new Fe(II) coordination polymers with unique SCO cha­racteristics will favor the development of new functional materials and devices on their basis in the nearest future.

HYDROTHERMAL EXTRACTION OF LITHIUM COMPOUNDS FROM PETALITE Li[AlSi4O10]

Based on studies of the decomposition of pe­ta­lite ore, the hydrothermal method for the extraction of lithium and aluminum compounds from lithium aluminosilicate Li[AlSi4O10] (petalite) has been developed. The studied sample of ore contains, wt. %: Li2O – 0.75 and Al2O3 – 14.65. For unenriched petalite ore with low lithium content, it is proposed to use the hydrochemical method of aluminosilicate processing – Ponomarev – Sazhin method. According to this method, the decomposition of ore is carried out directly in autoclaves by chemical interaction of ore components with NaOH solution in the presence of calcium oxide. The conditions (high temperature and pressure) for the destruction of petalite and the transition of lithium into the liquid phase are created exactly in the hydrothermal process. In this case, lithium and aluminum compounds pass into the solution, and calcium and silicon form a partially soluble compound in the solid phase – sodium-calcium hydrosilicateNa2O·2CaO·2SiO2·2H2O. The degree of extraction of lithium reaches 89–94 %, aluminum reaches 77–95 % within 1 hour at a tempe­rature of 240–280 °C, given caustic modulus 14–18, the concentration of the initial solution of 400–450 g/dm3 of Na2O and the ratio of CaO : SiO2 = 1 : 1 in the reaction mixture. Aluminate or lithium carbonate and other compounds can be obtained from an aluminate solution containing 1.5–2.5 g/dm3 of Li2O and 32–44 g/dm3 of Al2O3. The solid phase formed as a result of decomposition, with a high degree of extraction of lithium from the ore contains a small amount of Li2O in its composition and therefore can be used in the cement industry. Depending on the quality of the decomposed raw material, the course of the hydrothermal process is influenced by a set of factors. With a small content of lithium and aluminum in the ore, the caustic modulus of aluminate solutions (αк = 1,645*Na2O/Al2O3) formed after decomposition is important. Its calculation is required in order to determine the amount of alkaline solution of the required concentration to ensure almost complete decomposition of the ore. This value should be higher the lower the decomposition temperature and the concentration of the initial solution to achieve the same degree of recovery of useful components in the liquid phase. With the same caustic modulus, the efficiency of ore decomposition increases significantly with increasing process temperature and increasing the concentration of the initial solution. This can be seen in the values of the degree of extraction of aluminum, which increases by 12 % with increasing temperature from 240 to 280 °C, while the extraction of lithium remains practically unchanged.

EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE

Studies have shown the possibility of a long cycle of sulfur electrode with a high content of active material. The use of water-soluble binder material NV-1A leads to the realization of high current loads in the Li-S battery. Impedance spectroscopy has shown that the low coulombic efficiency in the cycling of the sulfur electrode is primarily due to the spontaneous dissolution of sulfur in the electrolyte, which requires high energy consumption when charging the Li-S battery. The reduction of the specific capacity during cycling is associated with the formation and accumulation of non-conductive films of short-chain polysulfides. On the basis of the conducted researches and the review of the literature sources ways of overcoming of this problem are offered. The ability of cycling the sulfur electrodes at the high current loads has been shown. The discharge capacity values of the sulfur electrodes at the current load 790 mA∙cm-2 are 500 і 420 mAh∙g-1 on the 5-th and 100-th cycles, accordingly. Using the method of impedance spectroscopy, it has been supposed that the formation and accumulation of unconductive Li2S2 / Li2S phases is the main process, which induce the quick capacity reduction of Li - S batteries upon cycling.

STRUCTURE AND SPECTRAL-LUMUINESCENT PROPERTIES OF LANTHANIDE-CONTAINING COMPLEXES WITH AZACROWN CALIXARENES

Lanthanide complexes with calix[4]arenes lower rim substituted with two azacrown ether fragments are reported. The size of the substituent cavity varied from 4 to 6 heteroatoms. The complexes were analyzed by means of IR, NMR, ESI mass spectroscopy. It is assumed that the coordination of Ln(III) ions occurs through the donor atoms of the lower rim; the counter anion and solvent molecule are also coordinated. Lanthanide-centered characteristic luminescence was observed in Eu(III), Tb(III) and Yb(III) complexes. The most efficient 4f-luminescence is observed for terbium-containing complexes with benzo-crown-derived ligands. The pathways of the sensitization of 4f-luminescence are discussed.

SPECTROSCOPIC STUDIES OF Cu (II) AND Co (II) COMPLEXES WITH RUTIN IN SOLUTIONS

Complexation in M (II) – Rut systems (M(II) = Co, Cu) was studied by electron absorption spectroscopy and pH-metric titration in water-ethanol solutions depending on the metal: ligand ratio (1: 1; 2: 1) and the pH of the medium. It was shown that the structure and stoichiometric composition of the complexation reaction products are influenced by such basic parameters as L:M and the pH value of the medium. Depending on the pH value, chelation involves certain binding sites, which primarily is associated with the redistribution of the electron density in the flavonoid molecule. In a weakly acidic or neutral medium, regardless of the M(II): Rut ratio, the formation of monoligand complexes of rutin with 3-d metals occurs with the participation of 5-OH and 4-C=O fragments of the A and C rings, and in an alkaline medium, chelation proceeds on the catecholic fragment of ring B rutin. Biligand complexes are formed with the participation of the gydroxo groups of the catechol fragment of each rutin molecule, and the formation of compounds with a ratio of 2:1 occurs both due to 5-OH and 4C=O and due to 3 ', 4'-OH groups. The calculated values of the stability constants of the complexes showed that the stability of the Co (II) complexes is several orders of magnitude lower than the stability of the corresponding Cu (II) complexes.

METHODS OF SYNTHESIS AND FEATURES OF USING SYSTEMS BASED ON MORIN-METAL COMPLEXES IN FLUORESCENT ANALYSIS METHODS

The review describes modern physicochemical systems based on complex compounds with organic ligands, which may have fluorescent properties when interacting with metal ions or proteins. Modern methods of synthesis of these compounds and their use in physical-chemical methods of analysis are given. Approaches to detecting the content of metals and proteins using the fluorescent properties of morin complex compounds are considered. Areas of use of the effects of amplification and quenching of fluorescence for the determination of organic compounds and metal ions, especially in the presence of DNA and RNA of different biological origin are described. The influence of surfactants on the fluorescence intensity of complexes with morin was analyzed separately.

HYDROSOL OF C70 FULLERENE: SYNTHESIS AND STABILITY IN ELECTROLYTIC SOLUTIONS

This article is devoted to the synthesis and characterization of the hydrosol of C70 of the son/nC70 type and to its coagulation by sodium chloride and cetyltrimethylammonium bromide (CTAB). At C70 concentration of 3.3×10–6 M, the electrokinetic potential is ζ= –40 ± 4 mV, the particle size expressed as Zeta-average is 97±3 nm; at higher C70 concentrations, 1.7×10–5 and 6.9×10–5 M, the size stays the same: 99 – 100 nm. The critical concentration of coagulation (CCC) values, were determined using the diameter increasing rate (DIR) on NaCl concentration. The CCCs are concentration-dependent: 250, 145, and 130 mM at C70 concentrations 3.3×10–6, 1.7×10–5, and 6.9×10–5 M, respectively. The CCC for the CTAB surfactant is much lower, about 5×10–3 mM. At 0.02 mM CTAB, however, the overcharging up to ζ = + 40 mV and stabilization of the colloidal particles take place. Interpretation of the hydrosol coagulation by NaCl using the Derjaguin–Landau–Verwey–Overbeek theory makes it possible to determine the Hamaker constant of the C70–C70 interaction in vacuum, if only electrostatic repulsion and molecular attraction are taking into account: AFF ≈ 7×10–20 J. On the other hand, if we use the value AFF = (16.0–16.6)×10–20 J, obtained earlier in the study of organosols, then the data for hydrosols can be explained only by the introduction of an additional type of interactions. Following the terms of Churaev and Derjaguin, one should take into account the structural contribution to the interaction energy, which stabilizes the hydrosol.

4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES

Isomeric ditopic corroles and complexes of Yb (III), Nd (III) and Er (III) based on them were synthesized and corrole-photosensitized 4f-luminescence in near infrared region was revealed. The structure of isomeric complexes allows adjusting the distance between the corrole core and lanthanide ion. The obtained results show that the sensitization mechanism changes drastically for both different lanthanides and isomeric forms.

ELECTROCHEMISTRY OF IMMOBILIZED MICROPARTICLES AND MICRODROPLETE: ACCESS TO FUNDAMENTAL DATA OF SOLID MATERIALS AND IONS

The idea to study the electrochemistry of immobilized microparticles has been published by this author for the first time in 1989. In the last 32 years, this approach has been shown to be very successful not only for analytical characterization of solid materials, but also applicable to extract thermodynamic and kinetic data, and even to determine the age of metal specimen. In 2000, it has been shown that the electrochemistry of immobilized microdroplets gives an elegant access to determine the Gibbs free energies of ion transfer between immiscible solvents. These measurements are performed with a standard 3-electrode potentiostate and can be used also for solvents, which cannot be used in experiments with the classical 4-electrode technique. The electrochemistry of microparticles and microdroplets share several common features with respect to the electrode mechanisms: in both cases three-phase electrodes are realized and ion and electron transfer proceed simultaneously. This talk reviews the activities of the speaker and his cooperation partners during the last 3 decades paying special attention to those results, which are of general interest.