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Royal Society of Chemistry, Journal of Materials Chemistry, 31(15), p. 3187

DOI: 10.1039/b505724h

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Multistability in a family of DT-TTF organic radical based compounds (DT-TTF)4[M(L)2]3 (M = Au, Cu; L = pds, pdt, bdt)

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Abstract

The preparation of new charge transfer salts based on the DT-TTF donor and monoanionic square planar transition metal bisdichalcogenide complexes M(L) 2 (M = Au, Cu; L = pds, pdt, bdt, where pds = pyrazine-1,2-diselenolate, pdt = pyrazine-1,2-dithiolate, bdt = benzene-1,2-dithiolate) are reported and these salts are characterized by X-ray diffraction, EPR spectroscopy, electrical conductivity, thermoelectric power and static magnetization measurements, as well as tight-binding band structure calculations. Three compounds, (DT-TTF)4[AuIII(bdt) 2]3, (DT-TTF)4[CuIII(pds) 2]3, (DT-TTF)4[CuIII(pdt) 2]3, are members of a general family of compounds of DT-TTF with stoichiometry 4: 3 as the previously reported (DT-TTF) 4[AuIII(pds)2]3. Although not strictly isostructural, all members of this family present a similar crystal packing motif of the donor and acceptor units and present a common pattern of first- and second-order phase transitions as seen in electrical transport and magnetic properties. The second-order phase transition is ascribed to a variation from dynamic to static charge ordering. With [Cu III(pdt)2] and DT-TTF a 1: 1 salt with formula (DT-TTF)[CuIII(pdt)2] was also obtained. The structural differences and similarities between the four compounds (DT-TTF) 4[M(L)2]3 (M = Au, Cu; L = pds, pdt, bdt), that are related to their physical properties, and the reversible phase transitions observed are discussed.