New organic-donor inorganic-acceptor salts: [(TTF)6(XMo12O40) (Et4)], X = Si and P

Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene–polyoxometalate of approximate composition (TTF)5.3(Bu4N)0.7[P2W18O62]·3H2O

“…The solid electrodeposited onto an ITO electrode (at 0.2 V for 30 min), was, while still adhered to the surface, thoroughly rinsed with MeCN solvent to remove soluble excess starting materials and supporting electrolyte. [29][30][31] Assuming that the polyoxometalate anion is in its fully oxidized form as [P 2 W 18 O 62 ] 6À (consistent with the electrochemical conditions used in the electrodeposition as well as the voltammogram in DMSO and the EPR data discussed below), an oxidation level of +1 per TTF unit is implied. Elemental analysis reported C, 9.25; H, 0.97; N, 0.20; S 12.04%, corresponds to an approximate stoichiometry of (TTF) 5 11.97%).…”

“…The incorporation of tetraalkylammonium cations has been reported in other TTF-polyoxometalate salts. [29][30][31] Assuming that the polyoxometalate anion is in its fully oxidized form as [P 2 W 18 O 62 ] 6À (consistent with the electrochemical conditions used in the electrodeposition as well as the voltammogram in DMSO and the EPR data discussed below), an oxidation level of +1 per TTF unit is implied. Energy dispersion spectra (EDS) of the solid clearly showed the expected presence of S, W and P. This technique can provide semi-quantitative analysis for the abundant S and W elements.…”

“…Due to the tendency of planar TTF molecules to stack, most of the crystal structures containing TTF derivatives and polyoxometalate anions exhibit layered structures with alternating TTF and polyoxometalate stacks. 10,29,30 Morphology SEM images of the electrodeposited solid reveal the formation of a highly uniform microcrystalline film (Fig. 7).…”

Controlled assembly of polyoxometalate-based composite materials containing zero- and one-dimensional structures

“…1,2 As inorganic building blocks, they can be assembled to form supramolecular composite materials through charge compensating cations 14,15 or organic p-electron donors, such as tetrathiofulvalene (TTF) [16][17][18] and bi(ethylenedithio)tetrathiofulvalene (ET). [19][20][21][22][23] An effective strategy in the realization of this assembly relies on linking polyanions through metal complex cations acting as inorganic bridging ligands. 24 In some cases, this strategy results in successful syntheses of composite materials containing lower dimensional structures.…”

An unusual phase transition in the crystal structure and physical properties of (TTF)9[Mo(CN)8]2·4H2O, where TTF = tetrathiafulvalene

“…In the low energy part of the spectrum, the broad band corresponds to charge transfer between the inorganic [Mo IV (CN) 8 ] 4Ϫ donors and organic TTF ؒϩ acceptors and is characteristic of ion pairing. 22…”