Syntheses, structures, and physical properties of nickel bis(dithiolene) complexes containing tetrathiafulvalene (TTF) units

To contribute to the development of single-component molecular metals, several nickel complexes with cyclohexeno-condensed or ethylenedioxy-substituted TTF (tetrathiafulvalene) dithiolate ligands, (R4N)(n)[Ni(chdt)(2)] [R = Me, n = 2 (1); R = Bu-n, n = 1 (2); n = 0 (3)] and (R4N)(n)[Ni(eodt)(2)] [R = Me, n = 2 (4); R = Bu-n, n = 1 (5); n = 0 (6)], were prepared. X-ray structures were determined on the monoanionic species 2 and 5. The tetra-n-butylammonium complex of the monoanionic [Ni(chdt)21 (2) with a 1:1 composition revealed that its magnetic susceptibility gave a good agreement with the Bonner-Fisher model (J/k(B) = -28 K), which was derived from the one-dimensional chains of anions with a regular interval. On the other hand, the magnetic susceptibility of the tetra-n-butylammonium complex of the monoanionic [Ni(eodt)(2)] (5) showed the Curie-Weiss behavior (C = 0.376 K(.)emu(.)mol(-1) and Theta = -4.6 K). Both of the monoanionic species 2 and 5 indicate that they belong to the S = 1/2 magnetic system and have relatively large and anisotropic g-values, suggesting the contribution of the nickel 3d orbital. Electrical resistivity measurements were performed on the compressed pellets of the neutral species 3 and 6. Fairly large conductivities were obtained (sigma(n) = 1-10 S(.)cm(-1)). In addition, despite the measurements on the compressed pellets of powder samples, the neutral species 6 showed metallic behavior down to ca. 120 K and retained high conductivity even at 0.6 K [sigma(0.6 K)/sigma(rt) approximate to 1/30], suggesting the crystal to be essentially metallic down to very low temperature. The electrical behavior and Pauli paramagnetism of 6 indicate the system to be a new single-component metal.