Breakdown of the Kasha-Vavilov's rule in low-symmetry porphyrazines: Ultrafast intersystem crossing via high vibronic state.

Recently (Photochem Photobiol. 2023;100:1277-1289. doi:10.1111/php.13898), we described the anti-Kasha effect in tribenzo-6H-1,4-diazepinoporphyrazins with C_2v symmetry, where the ultrafast spin changes successfully compete with the internal conversion. In this study, we show the presence of this effect in 2 (3),9 (10),16(17),23(24)-tetra-tert-butyl-29H,31H-phthalocyanine (1) and 1,4-di-[2-(2-methoxyethoxy)ethoxy]-29H,31H-phthalocyanine (2), which also possess reduced molecular symmetry and do not bear 6H-1,4-diazepine fragments. The anti-Kasha effect in 1 and 2 supplemented by Mg(II) tribenzo-6H-1,4-diazepinoporphyrazinates 3 and 4 exhibits a close-to-linear dependence on energy gap value between the zero vibrational levels of two lowest singlet excited states S₁ ⁰ and S₂ ⁰ (these states are degenerate in D_4h symmetry) and enhances with increase. The theoretical kinetic model of excited state dynamics, which takes into account the observed effects and follows Fermi's golden rule, predicts the presence of an additional excited state with enhanced spin-orbit coupling compared to S₁ ⁰, S₂ ⁰ and the corresponding triplet states, which is not predicted by TDDFT calculations in the Born-Oppenheimer approximation. The combination of the above indicates that the key role in the observed anti-Kasha effect and the mechanism of dissipation of the excited state in porphyrazines and their analogs is played by vibronic excited states, which requires theoretical research methods beyond the Born-Oppenheimer approximation.