Сочетанием полимеризации металлосодержащих мономеров в твердой фазе и последующего контролируемого термолиза формирующихся металлополимеров получены металлополимерные нанокомпозиты, представляющие собой наночастицы металлов и (или) их оксидов и карбидов, равномерно распределенные в стабилизирующей их полимерной матрице. Методами рентгеновской дифракции, электронной микроскопии, ферромагнитного резонанса и ИК-спектроскопии показано, что наночастицы в такой системе имеют характерную структуру “ядро–оболочка”, которая включает в себя металлосодержащее ядро и поверхностный слой – полимерную оболочку; оценены параметры этих компонентов.

Metal-polymer nanocomposites, which comprise nanoparticles of metals and/or their oxides and carbides uniformly distributed in stabilizing polymer matrices, are prepared through solid-phase polymerization of metal-containing monomers followed by controlled thermolysis of synthesized metal-containing polymers. Using X-ray diffraction, electron microscopy, ferromagnetic resonance, and IR spectroscopy, it is shown that nanoparticles present in these systems have a characteristic core-shell structure that comprises a metal-containing core and a surface layer, i.e., a polymer shell. Parameters of the components are estimated.

The synthesis and properties of a new class of electroluminescent metal complexes based on quinoline ligands containing the sulfanylamino group in position 8 are described. These complexes contain C-N-M-N chains in the chelate cycles instead of the traditionally used C-O-M-N chains.

Polyacetylene- and carbon-nanotube-based composite materials are prepared by the method of polymerization filling for the first time. It is shown that the acetylene polymerization mainly occurs at catalytic centers attached to the carbon nanotubes. It follows from TEM data that in the case of single-wall nanotubes the polyacetylene fibriles are wound up onto the nanotubes. In the case of multi-wall nanotubes, polyacetylene can form separate bodies that are connected to the multi-wall nanotubes. The specific electrochemical capacity of the novel composite materials is nearly twice as large as compared with that of the composite prepared by mechanical mixing; it is by two orders of magnitude larger than the pure polyacetylene capacity. The reversibility of the Li+ intercalation-deintercalation electrode reaction appears significantly improved at the polyacetylene-carbon nanotubes composites.

Coordinated fullerene acts as a hydrogen acceptor in reactions with compounds having weakened C-H bonds (1,4-dihydropyridine and 9,10-dihydroanthracene). Metal fullerides are the dehydrogenation catalysts. They activate the C-H bonds of dihydroanthracene and diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate in positions 9,10 and 1,4, respectively. No activation of norbornane carbon-hydrogen bonds with metal fullerides was observed under mild conditions.

The reaction of ditoluenetitanium(0) with oxygen affords an intermediate oxidation product: a titanium(II) complex that catalyzes ethylene polymerization.

We studied the composition of products of the photochemical degradation of 3,6-dichloropicolinic acid (DCPA), the active principle of Lontrel, a herbicide broadly used in agriculture. Ultraviolet irradiation (mimicking the natural sunlight action) did not degrade DCPA completely to environmentally safe products. The rate of DCPA degradation was notably lower when distilled water was replaced by river water and even lower in sea water. Chromatomass spectrometry revealed 9 compounds among the photolysis products, in addition to undegraded DCPA.

A composite consisting of single-walled carbon nanotubes (2.4 wt %) covered by polyacetylene has been prepared. Polyacetylene synthesized directly on single-walled carbon nanotubes is a defectless long-chain polymer composed of trans and cis units with a sufficient length (60% trans and 40% cis isomers). An appreciable acceleration of the lithium ion intercalation-deintercalation corresponds to an increase in the conductivity of the composite material near the percolation threshold. The polyacetylene layer on single-walled carbon nanotubes plays the role of an electrochemically active ion-conductive membrane suitable for the transport of Li+ cations to the surface of nanotubes.

Photochemical transformation of polyphenylacetylene (PPA) was studied. Irradiation of a toluene solution of PPA with the light λ = 365 nm induces the cleavage of PPA polymeric chains and cis-transoidal—trans-cisoidal isomerization. Intense photoluminescence appears after irradiation of the polymer.

The interaction between acetylene and dibenzenetitanium(0) at a room temperature results in the acetylene polymerization and its reduction to ethylene, ethane, and methane at the expense of H atoms of the acetylene molecule. The catalytically active species capable of copolymerizing acetylene with ethylene that are formed during the reaction or are added into the system originate from the interaction of dibenzenetitanium(0) with acetylene.

9,10-Dihydroanthracene (C 14 H 12 reacts with platinum fulleride C 60 Pt at 513-623 K under anaerobic conditions to form anthracene and hydrofullerenes identified by IR and mass spectroscopy. The Pt 4 f 7/2 binding energy of platinum in the initial fulleride (72.4 eV) indicates partial charge transfer form Pt to C60, which agrees with the results of X-ray fluorescence spectroscopic study of C60Pt.

X-ray photoelectron spectra and catalytic properties of platinum fulleride C 60 Pt were studied. The value of the bond energy of Pt4f 7/2 (72.4 eV) found for platinum in the starting C 60 Pt suggests a partial charge transfer from Pt to C 60 . The interaction of solid platinum fulleride with gaseous deuterium leads to the formation of fullerene deuterides C 60 D x and Pt clusters.

Ditoluenetitanium is proposed as a catalyst for applying polyacetylene on various materials (polyethylene, lithium, carbon) used for preparing the negative electrode of lithium batteries. It is shown that Li+ may be reversibly intercalated into the carbon material through a polyacetylene coating without the electrolyte decomposition and concurrent gas evolution.

Fullerene hydrides of C60H18, C60H36 and C70H36 are studied by using IR, H-1 and C-13 NMR, X-ray photoelectron and electron energy loss spectroscopies, and magnetochemistry. The comparison of IR and solid state H-1 and C-13 NMR data for C60H36 With the theoretical ones allows the suggestion that fullerene hydride has a T symmetric structure and contains 4 isolated benzenoid rings located at tetrahedral positions on the surface of a closed skeleton of the molecule. The EELS revealed that the transition from fullerene to the hydride is accompanied by the decrease of the density of valence electrons. Magnetization measurements showed C60H36 to be a ferromagnet. The hydrogenated fullerenes were prepared by transfer hydrogenation procedures involving 9,10-dihydroanthracene. The compositions of the hydrides are determined by field desorption mass-spectral analysis.

The effect of an electron beam irradiation on cis—trans isomerization and oxidation in polyacetylene films is studied by IR spectroscopy. It is found that the irradiation treatment of the films results in the stabilization of the initial cis-conformation of polyacetylene and the decrease of the oxidation destruction of polymer chains. The effect of the conformation stabilization is most clearly seen in a long-duration storage of irradiated films under inert atmosphere at low temperatures. This effect is significantly less pronounced at high temperatures. The increase of the conformational stability of the irradiated polyacetylene films is supposed to be caused by the formation of transverse crosslinkages between the chains under irradiation.

Heating (100 °C, toluene) or photolysis (Nd3+ : YAG laser, λ = 532 mil, benzonitrile) of a mixture of ethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (Hantsch ester) (1) and fullerene C60 under anaerobic conditions results in the formation of fullerene hydrogenation products and ethyl 2,6-dimethylpyridine-3,5-dicarboxylate, which is the product of dehydrogenation of1, identified by IR spectroscopy and mass spectrometry. The triplet state of C60 is quenched by the Hantsch ester.

Fullerene hydrides were prepared by hydrogenation of fullerences C 60 and C 70 using proton transfer from 9,10-dihydroanthracene to fullerene and were studied by mass spectrometry (electron impact, field desorption), IR, UV, and 1 H and 13 C NMR spectroscopy. The main product of the hydrogenation of C 60 is C 60 H 36 , which is sufficiently stable. Hydrogenation of fullerene C 70 gives a series of polyhydrides C 70 H n ( n =36–46), and the main product is C 70 H 36 . The dehydrogenation of C 60 H 36 by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is not quantitative and results in the formation of fullerene derivatives along with C 60 . The comparison of the IR and 1 H and 13 C NMR spectral data for solid C 60 H 36 with the theoretical calculations suggests that the fullerene hydride has a T -symmetric structure and contains four isolated benzenoid rings located at tetrahedral positions on the surface of the closed skeleton of the molecule.

New charge transfer complexes: (TMDTDM-TTF)2C60(CS2)3, TMDTDM-TTF · C60 · C6H6, (EDTTTF)2C60CS2 were synthesized by the reaction of C60 with asymmetric donors in CS2 and benzene. XPS- and IR-spectroscopy show a weak charge transfer in these compounds. The influence of the solvents during the formation of the complexes was disscussed. The (TMDTDM-TTF)2C60(CS2)3 crystal structure reveals that it has a layered structure with alternating sheets of C60 and donor dimers.