Photoredox catalysis is one of the most rapidly expanding areas of chemistry. In addition to the exciting science being realized, photoredox catalysis represents a great example of how synergy between two formally disparate subareas of study - in this case synthetic organic and physical-inorganic chemistries - can enable new discoveries that can transform a field into something greater than the sum of its parts. The most widely used complexes that are employed to facilitate photoredox catalysis continue to be compounds such as [Ru(bpy)3]2+ and Ir(ppy)3 (where bpy and ppy are 2,2'-bipyridine and phenylpyridine, respectively), but there has been recent interest in exploring the use of chromophores of the first transition series as potential alternatives to their second- and third-row counterparts. Such compounds have the advantage of enhanced material availability (i.e., "earth abundant") and the potential to carry out unprecedented chemical transformations, but differences in the innate electronic structures of first- versus second- and third-row transition metal complexes gives rise to certain challenges in terms of probing the mechasnism of a given photoreaction, or even identifying the nature of photo-activated chemistry in the first place. This presentation will provide an overview of the origin of the challenges (and opportunities) first-row metal complexes present in the field of photoredox catalysis by describing the underlying differences in the intrinsic photophysics of these disparate classes of chromohores as well as the different approaches one must employ in order to elucidate mechanistic information about organic transformations that such systems can facilitate.

Considerations for mechanistic studies of photoredox catalysis employing first-row transition metal-based chromophores

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ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.