文摘
A complete series of dianionic, monoanionic, and neutral dithiolene complexes formulated as [Ni(Et-thiazdt)2]n, with n = 鈭?, 鈭?, 0, and Et-thiazdt: N-ethyl-1,3-thiazoline-2-thione-4,5-dithiolate, is prepared using an optimized procedure described earlier for the N鈥揗e derivatives. Electrochemical and spectroscopic properties confirm the electron-rich character of the Et-thiazdt dithiolate ligand. The three complexes are structurally characterized by single-crystal X-ray diffraction. The paramagnetic anionic complex [Ni(Et-thiazdt)2]鈭?, as Ph4P+ salt, exhibits side-by-side lateral interactions leading to a Heisenberg spin chain behavior. The solid-state structure of the neutral, diamagnetic [Ni(Et-thiazdt)2]0 complex shows a face-to-face organization with a large longitudinal shift, at variance with the structure of its radical and neutral gold dithiolene analogue described earlier and formulated as [Au(Et-thiazdt)2]鈥?/sup>. Comparison of the two structures, and those of the other few structurally characterized pairs of Ni/Au dithiolene complexes, demonstrates the important role played by overlap interactions between gold dithiolene radical species. Despite its closed-shell character, the neutral nickel complex [Ni(Et-thiazdt)2]0 exhibits a semiconducting behavior with a room-temperature conductivity 蟽RT 鈮?0.014 S cm鈥?.