Preparation and characterization of metal complexes with an extended TTF dithiolato ligand, bis(propylenedithiotetrathiafulvalenedithiolato)-nickelate and -cuprate

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Abstract
Novel monoanionic nickel and dianionic copper complexes with the extended TTF dithiolato ligand, propylenedithiotetrathiafulvalenedithiolate [ptdt2 –=(S8C9H6)2– ], have been synthesized. Characterization of monoanionic tetraphenylphosphonium and tetramethylammonium salts of Ni(ptdt)2 – and the dianionic tetraphenylphosphonium salt of Cu(ptdt)2 2– have been performed, using cyclic voltammetry, electrical resistivity measurements, magnetic susceptibility measurements and X-ray crystal structure determination. The geometries around the Ni atoms are almost square planar. In both Ni complexes, one of the extended ligands of Ni(ptdt)2 – is overlapping with that of the adjacent anion separated by about half of the unit of the molecule, forming a one-dimensional chain. The adjacent chains are connected by transverse short S‥S contacts. Cu(ptdt)2 2– has a distorted tetrahedral geometry around the Cu atom and the dihedral angle between the planes of the dithiolato ligand is 54.2 °. The crystal structures of Ni(ptdt)2 – and Cu(ptdt)2 2– complexes show the possibility of novel 2D or 3D intermolecular contacts through ptdt ligands. The complex [Me4N][Ni(ptdt)2 ]·Me2CO is a semiconductor with a room temperature conductivity of 1.4×10–3 S cm–1 and activation energy of 9.9×10–2 eV.

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