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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 d  n   transition metal ions, where  n  > 6. The spectral blueshifts have been traditionally ascribed to elevated porphyrin e g  LUMO (lowest unoccupied molecular orbital) energy levels as a result of antibonding interactions with metal d π  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.

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