Red-Light-Active N,C,N-Pincer Bismuthinidene: Excited State Dynamics and Mechanism of Oxidative Addition into Aryl...

Despite the progress made in the field of synthetic organic photocatalysis over the past decade, the use of higher wavelengths, especially those in the deep-red portion of the electromagnetic spectrum, remains comparatively rare. We have previously disclosed that a well-defined N,C,N-pincer bismuthinidene (1a) can undergo formal oxidative addition into a wide range of aryl electrophiles upon absorption of low-energy red light. In this study, we map out the photophysical dynamics of 1a and glean insights into the nature of the excited state responsible for the activation of aryl electrophiles. Transient absorption and emission techniques reveal that, upon irradiation with red light, the complex undergoes a direct S₀ → S₁ metal-to-ligand charge transfer (MLCT) transition, followed by rapid intersystem crossing (ISC) to a highly reducing emissive triplet state (-2.61 V vs Fc^+/0 in MeCN). The low dissipative losses incurred during ISC (∼6% of the incident light energy) help rationalize the ability of the bismuthinidene to convert low-energy light into useful chemical energy. Spectroelectrochemical and computational data support a charge-separated excited-state structure with radical-anion character on the ligand and radical-cation character on bismuth. Kinetic studies and competition experiments afford insights into the mechanism of oxidative addition into aryl iodides; concerted and inner-sphere processes from the triplet excited state are ruled out, with the data strongly supporting a pathway that proceeds via outer-sphere dissociative electron transfer.