The Photophysics and Photochemistry of First-row Transition Metal Complexes: Quantum Coherence, the Marcus Inverted Region, and Applications in Excited-state Chemistry

There has been considerable renewed interest in the photophysical properties of first-row transition metal complexes, driven in part by a long-standing desire to shift to earth-abundant materials for a variety of photolytic applications. A significant challenge to achieving this goal is the fundamental difference in the excited-state properties of first-row metal complexes as compared to their second- and third-row congeners subsequent to light absorption. [1] Our group has been working on understanding the origins of this difference in an effort to develop design principles that will assist in overcoming these intrinsic challenges and develop new paradigms for the creation of photo-active first-row chromophores for applications in solar energy conversion strategies as well as photoredox catalysis. This presentation will provide a brief survey of the work we have been engaged in over the past several years employing a combination of synthetic chemistry and ultrafast spectroscopy.[2-6]


References
1. McCusker, J.K. Science 2019, 363, 484-488.
2. Sinha, N.; Wenger, O. J. Am. Chem. Soc. 2023,145, 4503-4520.
3. Paulus, B.C.; Adelman, S.L.; Jamula, L.L.; McCusker, J.K.; Nature 2020, 582, 214-218.
4. Alowakennu, M.M.; Ghosh, A.; McCusker, J.K.; J. Am. Chem. Soc. 2023, 145, 20786-20791.
5. Ghosh, A.; Yarranton, J.T.; McCusker, J.K.; Nat. Chem. 2024, 16, 1665-1672.
6. Chan, A.Y.; Ghosh, A.; Yarranton, J.T.; Twilton, J.; Jin, J.; Arias-Rotondo, D.M.; Sakai, H.A.; McCusker, J.K.; MacMillan, D.W.C.; Science 2023, 382, 191-197.