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

Abstract

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.