Spectroscopic and electrical properties of VO(dmit) sub 2 and V(dmit) sub 3 anion complexes and X-ray crystal structure of (NMP) sub 2 (V(dmit) sub 3 ) (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate, NMP = N-methylphenazinium)

Journal Article · Wed Dec 28 00:00:00 EST 1988 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00299a013· OSTI ID:5447551

Matsubayashi, Gen-etsu; Akiba, Kazuki; Tanaka, Toshio ^[1]

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1. Osaka Univ. (Japan)

V{sup IV}O(dmit){sub 2} and V{sup IV}(dmit){sub 3} anion complexes were prepared. Although they are essentially insulators, their oxidized complexes (N-methyphenazinium){sub 2}(V(dmit){sub 3}), (tetrathiafulvalenium){sub 2}(V(dmit){sub 3}), and (NBu{sup n}{sub 4}){sub 0.17}(V(dmit){sub 3}) as well as (N-methylpyridinium){sub 2}(VO(dmit){sub 2}){center dot}I{sub 4,2} and (NMu{sup n}{sub 4}){sub 2}(V(dmit){sub 3}){center dot}I{sub 5,4} exhibit semiconductive behavior with electrical conductivities of 1 {times} 10{sup {minus}8}-1 {times} 10{sup {minus}2} S cm{sup {minus}1}. Electronic, ESR, and X-ray photoelectron spectra of these complexes are discussed on the basis of interactions between the anion moieties. A single-crystal X-ray structure analysis of (N-methylphenazinium){sub 2}(V(dmit){sub 3}), (C{sub 13}H{sub 11}N{sub 2}){sub 2}(V-(C{sub 3}S{sub 5}){sub 3}), revealed a distorted-octahedral geometry of the V(dmit){sub 3} anion and a layer packing of the anions in the crystal phase. The orthorhombic crystal, space group Pbca, has cell dimensions a = 18.5299 (6) {angstrom}, b = 30.726 (2) {angstrom}, c = 14.826 (1) {angstrom}, V = 8441 (1) {angstrom}{sup 3}, and Z = 8. Block-diagonal least-squares refinement based on 5601 independent reflections with {vert bar}F{sub o}{vert bar} > 3{sigma}(F) yielded an R factor of 0.056.

• OSTI ID: 5447551
• Journal Information: Inorganic Chemistry; (USA), Vol. 27:26; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
LIGANDS
CRYSTAL STRUCTURE
STRUCTURAL CHEMICAL ANALYSIS
ANIONS
CHEMICAL STATE
COMPLEXES
ELECTRICAL PROPERTIES
INTERACTIONS
MOLECULAR STRUCTURE
OPTICAL PROPERTIES
OXIDATION
SPACE GROUPS
SPECTROSCOPY
SULFUR COMPOUNDS
CHARGED PARTICLES
CHEMICAL REACTIONS
IONS
PHYSICAL PROPERTIES
400201* - Chemical & Physicochemical Properties