Tailoring the Intersystem Crossing and Triplet Dynamics of Free-Base Octaalkyl-β-oxo-Substituted Porphyrins: Competing Effects of Spin–Vibronic and NH Tautomerism Relaxation Channels

[Image: see text] We demonstrate that β-oxo-substitution provides effective fine-tuning of both steady-state and transient electronic properties of octaalkyl-β-mono-oxochlorin and all isomers of the β,β′-dioxo-substituted chromophores. The addition of a carbonyl group increases the Q(y) oscillator strength and red-shifts the absorption spectra. Each oxo-substitution results in a 2-fold increase in the singlet to triplet state intersystem crossing (ISC) rates, resulting in a 4-fold ISC rate increase for the dioxo-substituted chromophores. The effects of oxo-substitution on the ISC rate are thus additive. The progressive increase in the ISC rates correlates directly with the spin–vibronic channels provided by the C=O out-of-plane distortion modes, as evidenced by density functional theory (DFT) modeling. The triplet states, however, were not evenly affected by β-oxo-substitution, and reduction in the triplet lifetime seems to be influenced instead by the presence of NH tautomers in the dioxoisobacteriochlorins.