Photophysical Properties and Electronic Structure of Zinc(II) Porphyrins Bearing 0-4 -Phenyl Substituents: Zinc Porphine to Zinc Tetraphenylporphyrin (ZnTPP).

Six zinc(II) porphyrins bearing 0-4 -phenyl substituents have been examined spectroscopically and theoretically. Comparisons with previously examined free base analogues afford a deep understanding of the electronic and photophysical effects of systematic addition of phenyl groups in porphyrins containing a central zinc(II) ion versus two hydrogen atoms. Trends in the wavelengths and relative intensities of the absorption bands are generally consistent with predictions from time-dependent density functional theory calculations and simulations from Gouterman's four-orbital model. These trends derive from a preferential effect of the -phenyl groups to raise the energy of the highest occupied molecular orbital. The calculations reveal additional insights, such as a progressive increase in oscillator strength in the violet-red (B-Q) absorption manifold with increasing number of phenyls. Progressive addition of 0-4 phenyl substituents to the zinc porphyrins in O-free toluene engenders a reduction in the measured lifetime of the lowest singlet excited state (2.5-2.1 ns), an increase in the S → S fluorescence yield (0.022-0.030), a decrease in the yield of S → T intersystem crossing (0.93-0.88), and an increase in the yield of S → S internal conversion (0.048-0.090). The derived rate constants for S decay reveal significant differences in the photophysical properties of the zinc chelates versus free base forms. The unexpected finding of a larger rate constant for internal conversion for zinc chelates versus free bases is particularly exemplary. Collectively, the findings afford fundamental insights into the photophysical properties and electronic structure of -phenylporphyrins, which are widely used as benchmarks for tetrapyrrole-based architectures in solar energy and life sciences research.