Synthesis, crystal structure and spectral characterization, of a new phaseof tris(phthalocyaninato)dibismuth(III), Bi-2(Pc)(3)

Direct-template synthesis and purification of a new phase of the triple-dec ker bismuth(III) phthalocyanine Bi-2(Pc)(3), prepared from bismuth acetate and phthalonitrile, are described. X-ray analysis shows a triple-decker mol ecular structure involving three phthalocyanine rings and two bismuth atoms that are 3.838(9) Angstrom apart. The coordination polyhedron is a distort ed square anti-prism. The average distances between the bismuth(III) and th e isoindolic nitrogens are 2.336 Angstrom and 2.726 Angstrom, respectively, for the external saucer-shape ring and the more planar inner ring. The int ramolecular distance between two neighbouring 4N(iso) mean-planes is 3.17 A ngstrom, the inner Pc ring being rotated by 38.3 degrees with respect to th e peripheral ones. The shortest intermolecular distance between two carbon atoms in the crystal packing is 3.284 Angstrom. This black phase is a regul ar stack of phthalocyanine rings that have their pi system all overlapping. UV/Visible and FT-IR spectra are discussed in relation to the molecular st ructure and fully characterize this triple-decker compound.