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Andrei N Khlobystov

Publications and source records attributed to Andrei N Khlobystov.

12 recordsLinked to original sources

Synthesis and reactivity of N@C60O.

The endohedral fullerene epoxide N@C60O was synthesised, isolated by High Performance Liquid Chromatography (HPLC), and characterised by Electron Spin Resonance (ESR). This nitrogen radical displays predominantly axial symmetry characteristics as expected for a monoadduct, evidenced by a zero-field splitting D parameter of 6.6 MHz and an E parameter of 0.5 MHz in powder at 77 K. Photo- and thermally-activated silencing of the nitrogen radical were observed, the latter showing the evolution of a new spin signal during heating at 100 degrees C. We suggest that loss of nitrogen spin is due to coupling with a radical formed by opening of the epoxide ring. This implies that the reaction of C60O with C60 in the solid state proceeds via a radical, rather than ionic, intermediate.

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Noncovalent interactions of molecules with single walled carbon nanotubes.

In this critical review we survey non-covalent interactions of carbon nanotubes with molecular species from a chemical perspective, particularly emphasising the relationship between the structure and dynamics of these structures and their functional properties. We demonstrate the synergistic character of the nanotube-molecule interactions, as molecules that affect nanotube properties are also altered by the presence of the nanotube. The diversity of mechanisms of molecule-nanotube interactions and the range of experimental techniques employed for their characterisation are illustrated by examples from recent reports. Some practical applications for carbon nanotubes involved in non-covalent interactions with molecules are discussed.

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Coating carbon nanotubes with polymer in supercritical carbon dioxide.

A facile and efficient method has been developed for coating MWNTs with solvent resistant polymer in scCO2, which permits the selective deposition of high molecular weight fluorinated graft poly(methyl vinyl ether-alt-maleic anhydride) polymer onto MWNTs in scCO2 under 100-170 bar at 40 degrees C and forms quasi one-dimensional nanostructures with conducting cores and insulating surfaces.

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Molecules in carbon nanotubes.

This Account focuses on structural and dynamic behavior of molecules encapsulated in carbon nanotubes. The impact of the confinement on the molecular packing, orientation, translation, rotation, and reactivity is demonstrated for a range of fullerene and nonfullerene molecules. These phenomena are described and analyzed using the current understanding of molecule-nanotube and intermolecular interactions.

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Observation of ordered phases of fullerenes in carbon nanotubes.

We have assembled molecular arrays of C60 inside double-walled carbon nanotubes (DWNTs) with internal diameters of 11-26 A and directly observed the existence of different crystalline phases of C60 previously predicted theoretically. The structure of the encapsulated C60 crystal is defined by the internal diameter of the DWNT, as the molecules adjust their packing arrangement in order to maximize van der Waals interactions. We have also shown that fullerenes in C(60)@DWNT interact with the outer layer of DWNTs, as demonstrated by the efficient filling of DWNTs with internal diameters of less than 12 A.

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Selective host-guest interaction of single-walled carbon nanotubes with functionalised fullerenes.

Exohedrally functionalised fullerenes have been inserted in single-walled carbon nanotubes (SWNTs) with the aid of supercritical carbon dioxide to form peapods; C(61)(COOEt)(2) are encapsulated in SWNTs in high yield, whereas C(61)(COOH)(2) aggregate via hydrogen bonding to form a supramolecular complex, which sterically hinders encapsulation and causes it to adhere to the exterior surface of the SWNTs.

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Stereoselective association of binuclear metallacycles in coordination polymers.

A series of structurally related binuclear metallacycles [Cd(NO(3))(2)L](2), where L is an angular exo-bidentate ligand, have been synthesized. Each metallacycle contains two coordinatively unsaturated, chiral metal centers within a single molecule, and the assembly of these metallacycles into polymeric framework structures has been studied systematically for the first time. Stereoselective homochiral association of [Cd(NO(3))(2)L](2) leads to the formation of helical coordination polymers, whereas meso type association results in nonhelical chain structures. The type of stereoselective aggregation depends on the conditions of self-assembly as well as on ligand functionality. Both helical and nonhelical polymeric complexes have been isolated for the metallacycle [Cd(NO(3))(2)(2,4'-pyacph)](2) (2,4'-pyacph = 2,4'-(4-ethynylphenyl)bipyridyl). Homochiral association results in the formation of helical [Cd(NO(3))]( infinity ) chains which link the binuclear [Cd(NO(3))(2)(2,4'-pyacph)](2) metallacycles into racemic two-dimensional sheets which contain both P and M [Cd(NO(3))]( infinity ) helices. In contrast, meso-association leads to the formation of nonhelical one-dimensional chains. It is shown that the product of homochiral association is predominately formed at room temperature and that of meso-association is generated at elevated temperatures. Thus, it may be concluded that the homochiral association appears to be energetically less favorable than the meso-association, a conclusion that has been confirmed by theoretical calculations of the crystal lattice energy. Several high-yield syntheses of bipyridyl-type ligands used for metallacyclic assembly are also reported.

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