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Nikolaev Institute of Inorganic Chemistry

Siberian Branch of Russian Academy of Sciences

SELECTED RESULTS OF COMPLETED RESEARCH STUDIES in 2011

Content:

Chemistry of inorganic compounds including coordination, cluster, and supramolecular compounds

First example of iridium incorporation into polyoxometalates

A new approach for incorporation of kinetically inert Ir into polyoxometalates (POM) has been developed. Use of the hexafluoroiridate with labile fluoride ligands has allowed preparation of the first Ir complex with POM, namely, [PW11O39Ir(H2O)]4−. Complexes of noble metals with POM are highly efficient catalysts for a broad range of transformations, including oxidation of organic substrates and photocatalytic water decomposition.

Incorporation of Ir into phosphotungstate

Incorporation of Ir into phosphotungstate

Sokolov M.N., Adonin S.A., Mainichev D.A., Vicent C., Zakharchuk N.F., Danilenko A.M., Fedin V.P.«Synthesis and characterization of [PW11O39Ir(H2O)]4−: successful incorporation of Ir into polyoxometalate framework and study of the substitutional lability at the Ir(III) site»Chem. Commun. 2011. P. 7833-7835.

First application of free-radical reactions for modification of coordinated ligands

A fundamentally new approach to modification of coordinated ligands in boron-capped iron(II) tris-dioximate clathrochelates has been discovered – free-radical substitution of chlorine atoms with carbon-centered radicals affording carbon-carbon bonds. In presence of a radical initiator (including autogenous hydroperoxide) hydrogen atom is abstracted from the substrate, and the resulting radical undergoes addition to the double bond of the azomethine fragment of the clathrochelate framework. At the next step the chlorine atom is eliminated and participates in chain propagation (average propagation lengths achieves 5). The key distinction of this reaction from radical addition to double bonds C=C and C=N known in organic chemistry lays in the fact that extreme stability of the clathrochelate framework determines the reaction path as substitution but not as reductive addition. The reaction can be extended to alkylation with other cyclic ethers, cyclohexane, and alcohols. This is the first example of targeted application of free-radical reactions to modification of coordinated ligands.

Free-radical alkylation of an iron(II) tris-dioximate clathrochelate with 1,4-dioxane

Free-radical alkylation of an iron(II) tris-dioximate clathrochelate with 1,4-dioxane

Vershinin M.A., Burdukov A.B., Eltsov I.V., Reznikov V.A., Boguslavsky E.G., Voloshin Y.Z.«Unexpected radical substitution of the dichlorine-containing iron(II) clathrochelate with 1,4-dioxane derivatives: novel approach to functionalization of its macrobicyclic framework»Polyhedron. 2011. V. 30. N. 7. P. 1233-1237

Record luminescence characteristics among the octahedral clusters

A series of octahedral halide molybdenum cluster complexes coordinated with perfluorobutyrate ligands has been prepared. The iodide cluster {Mo6I8} shows record luminescence characteristics, including long decay time and high quantum yield. They emit red light, which property makes these clusters of potential interest for development of sensitizers for conversion of triplet oxygen molecules into singlet. Such complexes can be useful for photodynamic therapy.

Synthesis, structure and luminescence of [Mo6X8(n-C3F7COO)6]2– (X = Cl, Br, I)

Synthesis, structure and luminescence of [Mo6X8(n-C3F7COO)6]2– (X = Cl, Br, I)

Sokolov M.N., Mihailov M.A., Peresypkina E.V., Brylev K.A., Kitamura N., Fedin V.P.«Highly luminescent complexes [Mo6X8(n-C3F7COO)6]2– (X = Br, I)»Dalton Trans. 2011. V. 40. N. 24. P. 6375-6377

CoPt solid solutions with different superstructure ordering

Single phase disordered solid solutions Co0,50Pt0,50 with crystallite size less than 10 nm were prepared by thermolysis of complex precursor salt at relatively low temperatures (150-300°С). The conditions were found for controlled synthesis of solid solutions with different ordering degree: from entirely disordered to completely ordered intermetallic. It was shown that coercivity grows with long-range order increase. The samples of nanoscale (2–4 nm) solid solutions Co0,50Pt0,50 supported on ceria or alumina possess high catalytic activity and selectivity in reaction of hydrogen purification from CO.

Synthesis and some properties of Co0,50Pt0,50 nanoparticles

Synthesis and some properties of Co0,50Pt0,50 nanoparticles

Zadesenets A., Filatov E., Plyusnin P., Baidina I., Dalezky V., Shubin Y., Korenev S., Bogomyakov A.«Bimetallic single-source precursors [M(NH3)4][Co(C2O4)2(H2O)2]·2H2O (M = Pd, Pt) for the one run synthesis of CoPd and CoPt magnetic nanoalloys»Polyhedron. 2011. V 30. P. 1305-1312


Chemical thermodynamic of inorganic systems

Thermodynamic characterization of some precursors for CVD processes

The detailed characterization of a set of aminosilanes and silylorganoamines as precursors for chemical vapor deposition processes of functional silicon-based films (Si3N4, SiC, SiCxNy) was carried out using tenzimetric and thermodynamic simulation methods. Vapor pressure measurements have been used to determine the saturated vapor pressure as a function of temperature and calculate the thermodynamic characteristics of vaporization. Thermodynamic simulation of chemical vapor deposition processes has been performed for the purpose of predicting the phase composition of the deposits as a function of the nature precursors and process conditions.

Thermodynamic characterization of some precursors for CVD processes

Thermodynamic characterization of some precursors for CVD processes

Sysoev S.V., Nikulina L.D., Kosinova M.L., Rakhlin V.I., Tsirendorzhieva I.P., Lis A.V., Voronkov M.G.«Properties of Aminosilane Precursors for the Preparation of Si-C-N Films»Inorganic Materials. 2011. V. 47. No.12. P.1324-1329

Sysoev S.V., Nikulina L.D., Kolontaeva A.O., Kosinova M.L., Titov A.A., Rakhlin V.I., Tsirendorzhieva I.P., Lis A.V., Voronkov M.G.«N-Substituted Hexamethyldisilazanes as New Substances for the Synthesis of Fuctional Films in the System Si-Ge-C-N-H»Russian Journal of General Chemistry. 2011. Vol.81. No.12. P. 2501-2505

Crystal chemistry and electronic structure of inorganic compounds

Novel porous inorganic framework

In collaboration with University Rennes -1 (France) the novel porous inorganic framework based on tetrahedral molybdenum cluster complex was obtained. The synthesis was carried out in evacuated quartz ampoule at high temperature (900°C). Anionic framework is constructed from cuban cluster units linked by bridging chlorine atoms. The framework has the topology of zeolite MNT with diameters of small and large cavities about ~ 19 Å and ~ 22 Å respectively. These cavities include chlorine anions, cesium cations and nanoscale octahedral clusters [Mo6Cl14]2–. The resulting inorganic framework exhibits paramagnetic properties.

Porous inorganic framework based on tetrahedral molybdenum cluster

Porous inorganic framework based on tetrahedral molybdenum cluster

Shestopalov M.A., Ledneva A.Y., Cordier S., Hernandez O., Potell M., Naumov N.G., Perrin C.«Tetrahedral Mo4 clusters as building blocks for the design of clathrate-related giant frameworks»Angew. Chem., Int. Ed. 2011. V. 50. N. 32. P. 7300-7303

Flexible porous organometallic crystals

In collaboration with Universität Regensburg (Germany) an interesting phenomenon of reversible inclusion and release of solvent molecules in the single crystal of organometallic chain polymer [(CpR2Mo2P4S)CuI)4]n was discovered by X-ray structural analysis. The single crystal keeps its quality after complete solvent loss under vacuum and even after reverse solvatation in the CH2Cl2 solution. Unit cell parameters change during the process without single crystal destruction. The unit cell volume decreases by 908.6 Å3 (4.5%) after complete solvent loss. Therefore, helical chain polymer behaves like a spring.

Organometallic chain polymer [(CpR2Mo2P4S)3(CuI)4]n reversibly include CH2Cl2 molecules

Organometallic chain polymer [(CpR2Mo2P4S)3(CuI)4]n reversibly include CH2Cl2 molecules

Gröger C., Kalbitzer H. R., Pronold M., Piryazev D., Scheer M., Wachter J., Virovets A., Zabel M.«Novel Metal-Organic Frameworks Incorporating [Cp°2Mo2P4S] (Cp° = 1-tBu-3,4-Me2C5H2), P4S3 and Cu2I2 Building Blocks»Eur. J. Inorg. Chem. 2011. P. 785-793


Physical and chemical foundation of substances separation and purification

Nanoporous metal-organic coordination polymers for gas storage and separation

Methods of synthesis of new robust nanoporous metal-organic coordination polymers, perspective materials for gas storage and separation, were developed. Zn compound containing 1 nm channels (top left; dmf – N,N'-dimethylformamide, ndc – naphthalenedicarboxylate, ur – urotropine) adsorbs reversibly large amount of acetylene and carbon dioxide and does not adsorb carbon monooxide (top right). Novel approach for enhancing hydrogen sorption properties of metal-organic frameworks was developed. The approach is based on encapsulation of large negative charged metal clusters (bottom) inside nanopores, which decrease void volume and provide an extra surface polarization inside new hybrid material. It was shown that volumetric hydrogen uptake of new materials based on rhenium, molybdenum and tungsten clusters incorporated into mesoporous chromium terephthalate MIL-101 is better than one of pure MIL-101 at the same conditions.

Sorption properties of [Zn4(dmf)(ndc)4(ur)2] and scheme of cluster complexes incorporation into MIL-101

Sorption properties of [Zn4(dmf)(ndc)4(ur)2] and scheme of cluster complexes incorporation into MIL-101

Sapchenko S.A., Samsonenko D.G., Dybtsev D.N., Melgunov M.S., Fedin V.P.«Microporous sensor: gas sorption, guest exchange and guest-dependant luminescence of metal-organic framework»Dalton Trans. 2011. V. 40, No. 10. P. 2196-2203

Klyamkin S.N., Berdonosova E.A., Kogan E.V., Kovalenko K.A., Dybtsev D.N., Fedin V.P.«Influence of MIL-101 Doping by Ionic Clusters on Hydrogen Storage Performance up to 1900 Bar»Chem.–Asian J. 2011. V. 6. P. 1854-1859

Palladium extraction by thiacalixarenes

Palladium extraction by thiacalixarenes in a wide range of the metal concentration was quantitatively described. Shown that the coordination extraction of palladium depends on the acidity of water phase and can proceed either with the deprotonation of thiacalixarene lower rim (pH> 3) or without it. Quantum-chemical calculations showed that the donor ability of sulphur atoms in thiacalixarenes close to that in acyclic thioethers. Conformational changes of thiacalixarenes from "cone" to "1,3-alternate" leads to a significant redistribution of electron density between the donor atoms of sulfur and benzene rings, which correlates with the extraction properties of the macrocycle. The use of macrocyclic reagents based on the calix-and thiacalixarenes can increase the efficiency of noble metals extraction and can be used for single-reagent recovery schemes due to the bifunctional nature of these compounds.

Palladium extraction by thiacalixarenes

Palladium extraction by thiacalixarenes

Kostin G.A., Kryuchkova N.A., Mazalov L.N., Torgov V.G., Drapaylo A.B.«Influence of conformation on the electronic structure of thiacalixarenes according to DFT calculations and X-ray emission spectroscopy»J. Molec. Struct. 2011. V. 1006. P. 502-507


Chemistry and technology of functional materials

Influence of post deposition annealing under applied magnetic field on composition and morphology of phthalocyanine films

A comparative analysis of the influence of post deposition annealing process without and under applied magnetic field on composition and morphology of aluminium phthalocyanines (AlClPc) films (30-50 nm) has been carried out. It was shown that AlClPc films annealing under magnetic field of 1 T leads to the formation of (AlPc)2O films with elongated crystallites with a preferential orientation on the substrate surface. The AlClPc films heated without magnetic field did not demonstrate any preferential orientation. Thus, these results make it possible to develop the technique permitting to control the orientation of phthalocyanines layers which can be used as active layers in molecular transistors, diodes and chemical sensors.

Influence of post deposition annealing under applied magnetic field on composition and morphology of phthalocyanine films

Influence of post deposition annealing under applied magnetic field on composition and morphology of phthalocyanine films

Basova T., Plyashkevich V., Petrarki F., Peisert H., Chassè T.«Influence of post deposition annealing in magnetic field on the structure and composition of aluminium phthalocyanine films»J. Chem. Phys. 2011. V. 134. P. 124703

Novel optically transparent thin-film materials based on hydrogenated compounds SiCxNy: H and BCxNy: H

Novel optically transparent thin-film materials were obtained by plasma enhanced chemical vapor deposition (PECVD) from volatile silicon- and boron containing single-source precursors. The thin transparent films of hydrogenated boron carbonitride BCxNy: H were synthesized using a mixture of triethylborazine with H2 in the temperature range of 373 – 773 K. The thin transparent films of hydrogenated silicon carbonitride were grown using a mixture of tris(diethylamino)silane with helium in the temperature range of 373-773 K. The obtained films of SiCxNy: H and BCxNy: H are transparent (transmittance ~ 90%) over a wide wavelength range of 300-3500 nm. The transparency of the films depends on deposition temperature and the composition of the gas phase. Amorphous and nanocrystalline films SiCxNy: H and BCxNy: H are novel optically transparent materials promising for use in optical devices.

Novel optically transparent thin-film materials based on hydrogenated compounds SiCxNy: H and BCxNy: H

Novel optically transparent thin-film materials based on hydrogenated compounds SiCxNy: H and BCxNy: H

Румянцев Ю.М., Файнер Н.И., Аюпов Б.М., Рахлин В.И.«Плазмостимулированное химическое осаждение нанокристаллических пленок карбонитрида кремния из триметил(фениламино)силана»Физика и химия стекла. 2011. Т. 37, № 3. С. 424 -431

Effect of nitrogen doping on the field electron emission and electrochemical properties of carbon nanotubes (CNTs)

The methods of synthesis of nitrogen-doped carbon (CNx) nanotubes with certain content of nitrogen have been developed. The materials obtained were studied using the methods of electron microscopy, X-ray photoelectron and X-ray absorption spectroscopy, and quantum chemistry. The forms of nitrogen incorporated in CNT walls were determined and increase of the efficiency of field emission from CNTs with nitrogen doping was demonstrated. Incorporated nitrogen affects interaction of CNx nanotubes with lithium. It was found that electrochemical capacity of nitrogen-doped CNTs toward lithium ions is higher than that of pure CNTs. A portion of irreversible capacity, which increases with nitrogen doping, and binding energy of lithium ion with different nitrogen defects were determined. Enhanced reversible capacity and high stability of electrode with cycling indicate perspective of CNx nanotube materials utilization in lithium-ion batteries.

Effect of nitrogen defects on field emission and electrochemical properties of carbon nanotubes (CNTs)

Effect of nitrogen defects on field emission and electrochemical properties of carbon nanotubes (CNTs)

Bulusheva L.G., Okotrub A.V., Kurenya A.G., Zhang H., Chen X., Song H.«Electrochemical properties of nitrogen-doped carbon nanotube anode in Li-ion batteries»Carbon. 2011. V. 49. P. 4013-4023

Bulusheva L.G., Sedelnikova O.V., Okotrub A.V.«Substitutional sites of nitrogen atoms in carbon nanotubes and their influence on field emission characteristics»Int. J. Quant. Chem. 2011. V. 111. P. 2696-2704

Synthesis of films solid solutions in Hf-Sc-O system with the controllable content of scandium

On the base of kinetic dependences the synthesis of films solid solutions in Hf-Sc-O system with the controllable content of scandium was developed. The (HfO2)1-x(Sc2O3)x films were obtained by CVD method using the apparatus with separated zones of precursors evaporators and films growth. Concentration margins of the solid solution formation of unknown earlier orthorhombic structure were discovered in Hf-Sc-O system. The films are characterized by higher value of permittivity in comparison with monoclinic HfO2 (k=16) and cubic Sc2O3 (k=14) structural modifications. The films structure didn't change at annealing up to 900° C. An energy-gap width depends on Sc concentration and varies from 4.5 to 6.0 eV. The (HfO2)1-x(Sc2O3)x films are attractive material for nanoelectronic devices.

Synthesis of films solid solutions in Hf-Sc-O system with the controllable content of scandium

Synthesis of films solid solutions in Hf-Sc-O system with the controllable content of scandium

L.V. Yakovkina, T.P. Smirnova, V.O. Borisov, S. Jeong-Hwan, N.B. Morozova, V.N. Kitchai, A.V. Smirnov«Structure and Properties of Films based on HfO2–Sc2O3 Double Oxide»J. Struct. Chem. 2011. V. 52. № 4. P. 743-747