Electronic Structure of Neutral and Anionic Iron-Nitrosyl Corrole. A Multiconfigurational and Density Matrix Renormalization Group Investigation.

ABSTRACT

An elaborate study with multireference second-order perturbation theory has been performed to elucidate the electronic structure and relative energy of three relevant states of FeNO corroles, namely the S = 0 ground state, the lowest S = 1 state, and the anion S = 1/2 state. On the basis of CASSCF and DMRG calculations with an active space including up to 37 orbitals, the electronic structure of the ground state was analyzed, with special emphasis on the diradical nature of the Fe-corrole and Fe-NO bonds. The results essentially confirm an earlier suggestion from B3LYP of a non-innocent corrole•2- bound to an {FeNO}7 unit, although the contribution of diradical character to the iron-corrole bond is found to be limited to 35%. This limited diradical character explains the high relative energy (16.5 kcal/mol) of the corresponding triplet state, where the corrole•2- is ferromagnetically coupled to the S = 1/2 {FeNO}7 unit. Consistent with experimental findings, reduction is found to take place at the corrole ligand, with a calculated electron affinity of 52.5 kcal/mol. The results obtained from the correlated calculations were also compared to DFT with a broad range of functionals.