MACROANIONIC ELECTRON-ACCEPTORS FOR THE SYNTHESIS OF LOW-DIMENSIONAL ORGANIC CONDUCTORS - SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF IRON OXYCHLORIDE INTERCALATED WITH TETRASELENAFULVALENE, BIS(ETHYLENEDITHIO)TETRATHIAFULVALENE, AND BIS(PYRAZINO)TETRATHIAFULVALENE

The synthesis and structural characterization of FeOCl intercalated with the organic donors tetraselenafulvalene (TSF), bis(ethylenedithio)tetrathiafulvalene (ET), and bis(pyrazino)tetrathiafulvalene (BPTTF) are reported. X-ray powder diffraction studies of both microcrystalline powders and oriented films of the intercalates have been used to assess intercalate structure. Intercalation of the donor TSF into FeOCl results in the intercalate FeOCl(TSF)1/8.5, with lattice parameters a = 3.786 (5) angstrom, b = 3.323 (2) angstrom, and c = 26.98 (2) angstrom. In FeOCl(TSF)1/8.5, the donors are aligned with their molecular planes parallel to the interlayer c axis. Reaction of the electron donor ET with FeOCl in dimethoxyethane (DME) results in the intercalate FeOCl.(ET)1/4, with lattice parameters a = 3.783 (5) angstrom, b = 3.307 (4) angstrom, and c = 44.76 (1) angstrom. This intercalate exhibits a remarkably large interlayer spacing of 22.4 angstrom. The ET donors are probably oriented within their long axes slightly canted from the perpendicular to the FeOCl layers. The BPTTF intercalate has a stoichiometry of FeOCl(BPTTF)1/20, with the planar BPTTF molecules lying parallel to the FeOCl sheets.