10.1021/ic302045m.s001 Qi Li Qi Li Jinzhen Lu Jinzhen Lu John F. Boas John F. Boas Daouda A. K. Traore Daouda A. K. Traore Matthew C. J. Wilce Matthew C. J. Wilce Fuzhi Huang Fuzhi Huang Lisandra L. Martin Lisandra L. Martin Tadaharu Ueda Tadaharu Ueda Alan M. Bond Alan M. Bond Spontaneous Redox Synthesis of the Charge Transfer Material TTF<sub>4</sub>[SVMo<sub>11</sub>O<sub>40</sub>] American Chemical Society 2012 EPR spectra material Spontaneous Redox Synthesis Scanning electron microscopy images 2.6 K TTF V atom positionally state reactions bond lengths Mo atoms TCNQ voltammetric analysis redox reaction state phases Spectral evidence semiconducting range SVMo 11O Raman spectra support 4N room temperature 2012-12-03 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Spontaneous_Redox_Synthesis_of_the_Charge_Transfer_Material_TTF_sub_4_sub_SVMo_sub_11_sub_O_sub_40_sub_/2464630 The charge-transfer material TTF-SV<sup>IV</sup>Mo<sub>11</sub>O<sub>40</sub> (TTF = tetrathiafulvalene) was prepared by a spontaneous redox reaction between TTF and the vanadium-substituted polyoxometalate (n-Bu<sub>4</sub>N)<sub>3</sub>[SV<sup>V</sup>Mo<sub>11</sub>O<sub>40</sub>] in both solution and solid state phases. Single crystal X-ray diffraction gave the stoichiometry TTF<sub>4</sub>[SVMo<sub>11</sub>O<sub>40</sub>]·2H<sub>2</sub>O·2CH<sub>2</sub>Cl<sub>2</sub>, with the single V atom positionally disordered with eight Mo atoms over the whole α-Keggin polyanion [SVMo<sub>11</sub>O<sub>40</sub>]<sup>4‑</sup>. 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<sub>4</sub>N)<sub>3</sub>[SV<sup>V</sup>Mo<sub>11</sub>O<sub>40</sub>] 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<sup>IV</sup>Mo<sub>11</sub>O<sub>40</sub> materials prepared from either solution or solid state reactions are equivalent. The newly isolated TTF-SV<sup>IV</sup>Mo<sub>11</sub>O<sub>40</sub> material represents a new class of TTF-polyoxometalate compound having dual electrical and magnetic functionality derived from both the cationic and anionic components.