Absorption Spectra of Protonated Corroles: Two Distinct Patterns Due to Peripheral Substitution Architecture

Abstract

The origin of individual features in the ground state absorption spectra of two protonated corroles differing in the architecture of peripheral substitution (either Cm-aryl or Cb-alkyl) have been studied in detail with the ground state absorption spectroscopy and density functional theory calculations. The geometry optimization, molecular orbitals and absorption spectra calculation have been carried out. It was found that protonation leads to the saddle type macrocycle conformation in contrast with the wave type conformation known for the parent-free base corroles. The mean plane deviation parameter Δ23 for the macrocycle, pyrrole tilting angles and the degree of pyramidalization λ2 of all four pyrrole nitrogens was found to depend on the peripheral substitution architecture. Macrocycle conformation of the protonated forms has distinct asymmetrical features which are reflected by the sets of values of the tilting angles and values of pyramidalization degree. The pair of pyrroles B and C has smaller tilting angles and higher pyramidalization degree values, whereas the opposite trend was found for the pair of pyrroles A and D. Electronic effects and structural differences induced by substitution lead to the pronounced shifts of the molecular orbitals. In the Cb-alkylated corrole, almost-degenerated HOMO and HOMO-1 molecular orbitals lead to enhancement of the configuration interaction. As a result, the Qx transition oscillator strength goes down, becoming comparable to that of the Qy one. A large HOMO-HUMO-1gap in the Cm-aryl corrole minimizes the configuration interaction, giving rise to Qx band domination in the visible range spectrum.