title: Spontaneous redox synthesis of the charge transfer material TTF4[SVMo11O40].
abstract: The charge-transfer material TTF-SV(IV)Mo(11)O(40) (TTF = tetrathiafulvalene) was prepared by a spontaneous redox reaction between TTF and the vanadium-substituted polyoxometalate (n-Bu(4)N)(3)[SV(V)Mo(11)O(40)] in both solution  and solid state phases. Single crystal X-ray diffraction gave the stoichiometry TTF(4)[SVMo(11)O(40)]·2H(2)O·2CH(2)Cl(2), with the single V atom positionally disordered with eight Mo atoms over the whole α-Keggin polyanion [SVMo(11)O(40)](4-). Raman spectra support the 1+ charge assigned to the oxidized TTF deduced from bond lengths, and elemental and voltammetric analysis also are consistent with this formulation. Scanning electron microscopy images showed a rod-type morphology for the new charge-transfer material. The conductivity of the solid at room temperature is in the semiconducting range. The TTF and (n-Bu(4)N)(3)[SV(V)Mo(11)O(40)] solids also undergo a rapid interfacial reaction, as is the case with TTF and TCNQ (TCNQ = tetracyanoquinodimethane) solids. EPR spectra at temperatures down to 2.6 K confirm the presence of two paramagnetic species, V(IV) and the oxidized TTF radical. Spectral evidence shows that the TTF-SV(IV)Mo(11)O(40) materials prepared from either solution or solid state reactions are equivalent. The newly isolated TTF-SV(IV)Mo(11)O(40) material represents a new class of TTF-polyoxometalate compound having dual electrical and magnetic functionality derived from both the cationic and anionic components.
authors.affiliation: School of Chemistry, Monash University, Clayton, Victoria 3800, Australia.
authors.forename: Qi
authors.initials: Q
authors.lastname: Li
authors.forename: Jinzhen
authors.initials: J
authors.lastname: Lu
authors.forename: John F
authors.initials: JF
authors.lastname: Boas
authors.forename: Daouda A K
authors.initials: DA
authors.lastname: Traore
authors.forename: Matthew C J
authors.initials: MC
authors.lastname: Wilce
authors.forename: Fuzhi
authors.initials: F
authors.lastname: Huang
authors.forename: Lisandra L
authors.initials: LL
authors.lastname: Martin
authors.forename: Tadaharu
authors.initials: T
authors.lastname: Ueda
authors.forename: Alan M
authors.initials: AM
authors.lastname: Bond
mesh_terms: D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D013816:Thermodynamics; D014639:Vanadium / Q000737:chemistry*
chemical_list: D006571:Heterocyclic Compounds; D014639:Vanadium; D013455:Sulfur; D008982:Molybdenum; C063887:tetrathiafulvalene; D010100:Oxygen