Catena-poly[fac-triiodobismuth(III)-tris-(A mu-ethane-1,2-diylbis(diphenylphosphane oxide-kappa O-2,O'))], a 2-D sheet network of BiI3 was synthesized from BiI3 and ethane-1,2-diylbis(diphenylphosphane oxide) (DppeO(2)) in tetrahydrofuran. The crystal structure revealed a trigonal structure with three-fold symmetry at Bi. Bismuth centers show fac-BiI3O3 coordination, with Bi-I = 2.9416(2) and Bi-O = 2.4583(17) . The I-Bi-I and O-Bi-O angles (95.520(7)A degrees and 79.04(6)A degrees, respectively) indicate trigonal distortion in the Bi octahedron. Bridging DppeO(2) ligands centered on inversion centers give rise to a 2-D sheet polymer. The 8.3 thick sheets consist of three layers in a sandwich structure. The outer layers are composed of phenyl rings and BiI3 groups with the iodide atoms pointing outward. The central layer consists of the O=PCH2CH2P=O bridging groups. Computational results suggest that semi-conducting behavior arises from Bi(III) centers. A halide to DppeO(2) pi* transition is suggested by theoretical results.
Available at: http://works.bepress.com/robert-pike/145/