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

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 degrees C. The structure of [BiPc2]I-1.5 shows columnar stacks of BiPc2 units and linear chains of iodine atoms. The BiPc2 units and doped iodine atoms are tetradisordered in the crystal. The one-dimensional iodine and pseudo one-dimensional BiPc2 aggregates are aligned along the c-axis of the crystal. The two Pc groups in the BiPc2 unit are staggered at an angle of 39.4 degrees and are 3.275 Angstrom apart. The Bi3+ 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) Angstrom to one Pc unit and 2.760(8) Angstrom 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 Pc2- ion and to a partially oxidized Pc- ion. (C) 1998 Elsevier Science S.A. All rights reserved.