Fe2OCl6(2-) salt formed by electrochemical oxidation of ethylenedioxytetrathiafulvalenoquinone-1,3-dithiolemethide in the presence of FeCl4- ion with a silicon wafer electrode

Electrochemical oxidation of a bent donor molecule, ethylenedioxytetrathiafulvalenoquinone-1,3-dithiolmethide ( 2), in chlorobenzene (PhCl)/ethanol containing NBu 4FeCl 4 as a supporting electrolyte is performed using an undoped silicon wafer electrode. Black crystals of 2 6.Fe 2OCl 6.2PhCl are obtained that have a different molecular formula from that of 2 2.FeCl 4 crystals obtained previously using a platinum rod electrode. The new crystal has a structure composed of alternately stacked layers of 2 molecules and Fe 2OCl 6 (2-) ions, whose Fe-O-Fe bond is completely linear and for which the geometry around the Fe atom is almost tetrahedral. The electrical resistivity decreases with temperature until ca. 200 K, but below this temperature, it gently increases. The magnetic susceptibility (chi p) observed can be described by the sum of chi p obeying a Curie-Weiss law for the impurity spins and of chi p obeying a dimer model with a spin-exchange integral ( J approximately -180 K) in each Fe 2OCl 6 (2-) ion, which is also weakly coupled to neighboring Fe 2OCl 6 (2-) ions through an additional exchange interaction.