Charge transfer and mixed-valence behavior in phtalocyanine-dimer cations

摘要

Phtalocyanine compounds deserved a considerable interest in recent times, particularly because of their possible use in the field of nanoelectronics. In particular, the charge mobility (of both electrons and holes) in phtalocyanine stacked arrangements has been recently extensively investigated. The present work focuses on the study of the hole-transfer mechanism between two phtalocyanine monomers. For an interdisk distance larger than 4.5 bohrs, the eclipsed dimer exhibits a mixed-valence behavior, with a saddle point transition state separating two equivalent minima. This behavior, however, is strongly dependent on the relative angle between the disks. In particular, the mixed-valence character of the compound is strongly enhanced for arrangements that are far from the eclipsed geometry. Moreover, for values of the angle close to π /8 and 3π /8, the ground and excited transition states have exactly the same energy, thus implying the presence of a conical intersection. These results can have deep implication in the charge transfer along phtalocyanine chains.