Mixed valence, tetradisordered structure of iodine-doped bismuth(III) diphthalocyanine

Abstract

Tetragonal crystals of iodine-doped bismuth(III) diphthalocyanine were grown directly by the reaction of bismuth with 1,2-dicyanobenzene in the presence of I 2 at 200°C. The structure of [BiPc 2]I 1.5 shows columnar stacks of BiPc 2 units and linear chains of iodine atoms. atoms. The BiPc 2 units and doped iodine atoms are tetradisordered in the crystal. The one-dimensional iodine and pseudo one-dimensional BiPc 2 aggregates are aligned along the c-axis of the crystal. The two Pc groups in the BiPc 2 unit are staggered at an angle of 39.4° and are 3.275 Å apart. The Bi 3+ ion, eight coordinated by N-isoindole atoms, does not lie between the Pc rings at the center. The BiN distances are 2.377(8) Å to one Pc unit and 2.760(8) Å to the other. The difference of the BiN bond lengths, similar to those found in other partially oxidized M(III) diphthalocyanine complexes, correlates with the binding of the internal metal to a Pc 2− ion and to partially oxidized Pc − ion.