Bonding Characteristics Mediated by Saddle-Shaped Porphyrin Deformation: A Theoretical Approach to the Control of Spin State of Iron(III) Porphyrins

Abstract

The novel concept of a “symmetry switch” for spin transfer is proposed. EHT and INDO calculations on a series of iron(III) porphyrin complexes indicate that factors that can contribute to the stability of the intermediate-spin state can be explained clearly with crystal-field theory. A decrease in symmetry causes the extensive hybridization of d and d (shown here) orbitals and induces large electronic structure asymmetry in the saddle-shaped iron(III) porphyrin complexes.