Bismuth triple-decker phthalocyanine: synthesis and structure

摘要

Triclinic crystals of bismuth(III) triple-decker phthalocyanine, Bi_2Pc_3, Pc = C_(32)H_(16)N_8~(2-), were grown directly by the reaction of Bi_2Se_3 with 1,2-dicyanobenzene at 220 deg C. The Bi_2Pc_3 molecule is centrosymmetric with the bismuth atoms located closer to the peripheral phthalocyaninato(2-) rings than to the central ring. Each bismuth(III) ion is connected by four N-isoindole atoms to the peripheral and by four N-isoindole to the central Pc ring with average distances of 2.333 and 2.747 A. respectively. This indicates a stronger connection of Bi(III) to the peripheral saucer-shaped macrocyclic rings than to the central rings. The neighbouring phthalocyaninato(2-) moieties in the Bi_2Pc_3 molecule are separated by a distance of 3.101(5) A. The central Pc ring is rotated by 36.4 deg with respect to the peripheral ones. Differences in Bi-N bond lengths are a result of interaction of the bismuth ion with peripheral and central rings as well as the repulsion forces between two bismuth ions in the same Bi_2Pc_3 molecule, which are separated by a distance of 3.839(2) A. The crystal packing is characterized by a distance of 3.56 A between Pc rings of neighbouring Bi_2Pc_3 molecules.