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Nikolaev Institute of Inorganic Chemistry

Siberian Branch of Russian Academy of Sciences

SELECTED RESULTS OF COMPLETED RESEARCH STUDIES in 2009

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

Homo- and heterometal polyphosphide samarium complexes
(in collaboration with Karlsruhe Institute for Technology, Germany)

Reactions of Sm(II) compounds with white phosphorus and polyphosphide complexes of d-elements were investigated. Molecular polyphosphide complexes of the rare-earth element as well as heterometal polyphosphide complexes of both d- and f-elements were synthesized for the first time. It was shown that

  • Sm(II) compounds reduce P4 up to P84− and P43− with the formation of the [Cp*8Sm4P8] (1) and [Cp*6Sm3P4] (2) polynuclear complexes;
  • an interaction of Sm(II) compounds with the [Cp*Fe(cyclo-P5)] polyphosphide complex results in heterometal compounds with distorted (3) or dimeric (4) cyclo-P5 ligands.

The approach enabled to synthesize low-valence complexes containing the Sm, Fe, and P atoms together in one molecule. It may be extend to the other lanthanides and transition metals and to the heavier phosphorus analogues. The polyelemental complexes may be precursors of materials containing 15-group elements, rare-earth elements, and transition metals.

[Cp*<sub>8</sub>Sm<sub>4</sub>P<sub>8</sub>] (<b>1</b>)

[Cp*8Sm4P8] (1)

[Cp*<sub>6</sub>Sm<sub>3</sub>P<sub>4</sub>] (<b>2</b>)

[Cp*6Sm3P4] (2)

<b>3</b>

3

<b>4</b>

4

Konchenko S. N., Pushkarevsky N. A., Gamer M. T., Köppe R., Schnöckel H., Roesky P.J. Am. Chem. Soc., 2009, V. 131, P. 5740–5741.

Konchenko S. N., Sanden T., Pushkarevsky N. A., Köppe R., Roesky P.Chem. Eur. J., 2010, in press.

Chemical thermodynamic of inorganic systems

The structure of the ionic clathrate hydrate of tetrabutylammonium valerate (С4H9)44H9CO2·39.8H2O
(in collaboration with Institute of Physical Chemistry PAS, Warsaw, Poland)

Ionic clathrate hydrates of peralkylammonium salts are near related to gas hydrates. These compounds attract attention as material for storage, separation, and transportation of gases; for cold storage and cold transportation; as model systems for biomolecules hydration study. For the first time the detailed crystal structure of the ionic clathrate hydrate of tetrabutylammonium valerate (C4H9)4NC4H9CO2·39.8H2O has been determined by single crystal X-ray analysis. Detailed analysis of structural disordering of host and guest subsystems revealed new structural features of ionic clathrate hydrates. Received data extend modern conceptions of adaptation of host hydrate frameworks to guest particles and open new concepts of crystal design of similar supramolecular compounds.

The five compartment cavity in the host water framework

The five compartment cavity in the host water framework

The cavity with water molecule included

The cavity with water molecule included

Layer-by-layer arrangement of the polyhedral cavities in the host water framework

Layer-by-layer arrangement of the polyhedral cavities in the host water framework

Rodionova T., Komarov V., Lipkowski J., Kuratieva N.The structure of the ionic clathrate hydrate of tetrabutylammonium valerate (C4H9)4NC4H9CO2·39.8H2ONew Journal of Chemistry. 2010. V. 34. P.432-438

Crystal chemistry and electronic structure of inorganic compounds

Structural investigation of organometallic macromolecules
(in collaboration with Universität Regensburg, Regensburg, Germany)

The structures of giant organometallic macromolecules C60⊂[Cu26Cl26(H2O)2{Cp*Fe(η5-P5)}13(NCMe)9 and C2B10H12⊂[Cu20Cl20{Cp*Fe(η5-P5)}12] obtained by template synthesis were studied. The C60⊂[Cu26Cl26(H2O)2{Cp*Fe(η5-P5)}13(NCMe)9] compound is an unique supramolecular host-guest complex with the fullerene molecule as a quest. The C2B10H12⊂[Cu20Cl20{Cp*Fe(η5-P5)}12] compound crystallizes in an unusually high symmetrical space group, Fm3c. The giant pseudo-spherical [Cu20Cl20{Cp*Fe(η5-P5)}12] molecule has an idealized icosahedral symmetry and includes the C2B10H12 orthocarborane molecule. The host copper and phosphorus atoms form the 80-vertex Cu20(P5)12 polyhedron which is topologically identical to an icosahedral isomer of fullerene-80. It is interesting to note that according to quantum-chemical calculations icosahedral isomer of fullerene-80 is the most symmetrical but the least stable from all theoretically possible isomers. In case of organometallic compound the high idealized symmetry is a direct consequence of topological requirements generated by the coordination of copper atoms to the phosphorus atoms of the pentamerous P5 cycles. The guest molecule fits very well into the host cavity. The results have shown that a template-supported self-assembly of giant supramolecular assemblies occurs in such systems.

 

<b>C<sub>60</sub>⊂Cu<sub>26</sub>Cl<sub>26</sub>(H<sub>2</sub>O)<sub>2</sub>{Cp*Fe(η<sup>5</sup>-P<sub>5</sub>)}<sub>13</sub>(NCMe)<sub>9</sub></b><br>
Fullerene-60 molecule is shown in orange ball representation

C60⊂Cu26Cl26(H2O)2{Cp*Fe(η5-P5)}13(NCMe)9
Fullerene-60 molecule is shown in orange ball representation

M. Scheer, A. Schindler, R. Merkle, B. P. Johnson, M. Linseis, R. Winter, C. E. Anson, and A. V. VirovetsJ. Am. Chem. Soc. 2007, 129, 13386–13387

M. Scheer, A. Schindler, C. Gröger, A. V. Virovets, and E. V. PeresypkinaAngew. Chem. Int. Ed. 2009, 48, 5046–5049

Chemical fundamentals for separation and purification

Synthesis of microporous metal–organic coordination polymers for gas storage and separation
(in collaboration with Center for Smart Supramolecules, Pohang University of Science and Technology, South Korea, and Faculty of Chemistry, Moscow State University)

New microporous metal–organic coordination polymers with permanent porosity were synthesized and characterized by X-ray crystallography.

Microporous manganese and magnesium formates demonstrate not only high capacity for acetylene sorption (up to 50–60 cm3/g at 1,0 atm) but also remarkable selectivity over CO2, CH4, N2, O2, and H2 at room temperature.

Sorption of methane in microporous [Zn2(bdc)2(dabco)] has been studied. The material show a very high sorption capacity: 13.6 wt. % at 40 atm, that corresponds to 206 cm3/g.

The crystal structures determination of methane-adsorbed [Zn2(bdc)2(dabco)] and acetylene-adsorbed M(HCOO)2 (M = Mg, Mn) with using synchrotron radiation allowed to locate of sorption sites of the C2H2 and CH4 molecules inside the channels of the porous frameworks./img/science/results/2009/results2009-005.png

Gas sorption in Mg(HCOO)<sub>2</sub>

Gas sorption in Mg(HCOO)2

Sorption sites in microporous Mg(HCOO)<sub>2</sub>

Sorption sites in microporous Mg(HCOO)2

Gas sorption in [Zn<sub>2</sub>(bdc)<sub>2</sub>(dabco)]

Gas sorption in [Zn2(bdc)2(dabco)]

Sorption sites in microporous [Zn<sub>2</sub>(bdc)<sub>2</sub>(dabco)]

Sorption sites in microporous [Zn2(bdc)2(dabco)]

Samsonenko D. G., Kim H., Sun Y., Kim G.-H., Lee H.-S., Kim K. Microporous Magnesium and Manganese Formates for Acetylene Storage and SeparationChem. Asian J., 2007, V. 2, No. 4, P. 484–488.

Kim H., Samsonenko D. G., Das S., Kim G.-H., Lee H.-S., Dybtsev D. N., Berdonosova E. A., Kim K.Methane sorption and structural characterization of the sorption sites in Zn2(bdc)2(dabco) by single crystal X-ray crystallographyChem. Asian J., 2009, V. 4, No. 6, P. 886–891.

Chemistry and technology of functional materials

Hybrid nanomaterials based on carbon nanotube arrays and CdS nanoparticles

A technique has been developed for deposition of CdS nanoparticles onto the surface of carbon nanotubes aligned normally to the surface of a silicon substrate. A relationship between the structure of nanoparticles deposited and the conditions of their formation was studied. The CdS particles were revealed to exhibit electroluminescence arising in the process of field electron emission. The material obtained could be used in order to create new kinds of light-emitting elements, as well as in medical and biochemical research as the sensors and luminescent labels.

Full-scale photo of a carbon nanotube array (at the top left) and scanning electron micrograph demonstrating perpendicular orientation of nanotubes to the substrate surface (at the top right)

Full-scale photo of a carbon nanotube array (at the top left) and scanning electron micrograph demonstrating perpendicular orientation of nanotubes to the substrate surface (at the top right)

Scheme of the studies of electroluminescent properties of carbon nanotubes with deposited CdS particles (at the bottom left) and photo of a luminescent sample (at the bottom right).

Scheme of the studies of electroluminescent properties of carbon nanotubes with deposited CdS particles (at the bottom left) and photo of a luminescent sample (at the bottom right).