The Dog That Didn't Bark: A New Interpretation of Hypsoporphyrin Spectra and the Question of Hypsocorroles

Abstract

Nearly a half-century after Gouterman classified the UV–vis–NIR spectra of porphyrin derivatives as normal, hyper, or hypso, we propose a heretofore unsuspected “mechanism” underlying hypso spectra. Hypsoporphyrins, which exhibit blueshifted optical spectra relative to normal porphyrins (such as Zn porphyrins), typically involve dn transition metal ions, where n > 6. The spectral blueshifts have been traditionally ascribed to elevated porphyrin eg LUMO (lowest unoccupied molecular orbital) energy levels as a result of antibonding interactions with metal dπ orbitals. Herein, we have found instead that the blueshifts reflect a lowering of the a_2u HOMO (highest occupied molecular orbital) energy levels. Electronegative metals such as Pd and Pt transfer smaller quantities of electron density to the porphyrin nitrogens, compared to a more electropositive metal such as Zn. With large amplitudes at the porphyrin nitrogens, the a_2u HOMOs of Pd(II) and Pt(II) porphyrins accordingly exhibit lower orbital energies than those of Zn(II) porphyrins, thus explaining the hypso effect. Hypso spectra are also observed for corroles: compared with six-coordinate Al(III) corroles, which may be thought of exhibiting normal spectra, Au(III) corroles, for instance, exhibit blueshifted or hypso spectra.