Charge Transport in Stacking Metal and Metal-Free Phthalocyanine Iodides. Effects of Packing, Dopants, External Electric Field, Central Metals, Core Modification, and Substitutions

The charge-tran sport properties of the one-dimensional stacking metal phthalocyanine iodides (M(Pc)I, M = Fe, Co, Ni, Cu) and metal-free phthalocyanine iodide (H-2(Pc)I) have been theoretically investigated. On the basis of the tight-binding approximation and two-state theory, both the site-energy corrected energy splitting in dimer and Fock-matrix-based methods are used to calculate the transfer integral. The intermolecular motions, including interplanar translation, rotation, slip, and tilt, exert remarkable impacts oil the transfer integral. The order/disorder of the dopant stack and the long-range electrostatic interactions are also demonstrated to be crucial factors for modulation of charge-transport properties. The transfer integral undergoes slight changes under all applied electric field along the stacking direction in the range of 10(6)-10(7) V cm(-1). The change of central metals in MPc has little effect on the transfer integrals, but significantly affects the reorganization energies. The extension of the pi-conjugation in macrocyclic ligand brings about considerable influence oil the transfer integrals. Peripheral substitutions by animo, hydroxyl, and methyl lead to deviations from planarity of macromolecular rings, and hence affect the valence hands significantly. (C) 2009 Wiley Periodicals, Inc. J Comput Chem 30: 1959-1972, 2009