Understanding Hyperporphyrin Spectra: TDDFT Calculations on Diprotonated Tetrakis(p-aminophenyl)porphyrin

[Image: see text] A detailed TDDFT study (with all-electron STO-TZ2P basis sets and the COSMO solvation model) has been carried out on the effect of diprotonation on the UV–vis–NIR spectra of free-base tetraphenylporphyrin and tetrakis(p-aminophenyl)porphyrin. The diprotonated forms have been modeled as their bis-formate complexes, i.e., as so-called porphyrin diacids. The dramatic redshift of the Q-band of the TAPP diacid has been explained in terms of an elevated “a(2u)” HOMO and lowered LUMOs, both reflecting infusion of aminophenyl character into the otherwise classic Gouterman-type frontier MOs. The exercise has also yielded valuable information on the performance of different exchange–correlation functionals. Thus, the hybrid B3LYP functional was found to yield a substantially better description of key spectral features, especially the diprotonation-induced redshifts, than the pure OLYP functional. Use of the range-separated CAMY-B3LYP functional, on the other hand, did not result in improvements relative to B3LYP.