title: Dynamics of rhenium photocatalysts revealed through ultrafast multidimensional spectroscopy.
abstract: Rhenium catalysts have shown promise to promote carbon neutrality by reducing a prominent greenhouse gas, CO2, to CO and other starting materials. Much research has focused on identifying intermediates in the photocatalysis mechanism as well as time scales of relevant ultrafast processes. Recent studies have implemented multidimensional spectroscopies to characterize the catalyst's ultrafast dynamics as it undergoes the many steps of its photocycle. Two-dimensional infrared (2D-IR) spectroscopy is a powerful method to obtain molecular structure information while extracting time scales of dynamical processes with ultrafast resolution. Many observables result from 2D-IR experiments including vibrational lifetimes, intramolecular redistribution time scales, and, unique to 2D-IR, spectral diffusion, which is highly sensitive to solute-solvent interactions and motional dynamics. Spectral diffusion, a measure of how long a vibrational mode takes to sample its frequency space due to multiple solvent configurations, has various contributing factors. Properties of the solvent, the solute's structural flexibility, and electronic properties, as well as interactions between the solvent and solute, complicate identifying the origin of the spectral diffusion. With carefully chosen experiments, however, the source of the spectral diffusion can be unveiled. Within the context of a considerable body of previous work, here we discuss the spectral diffusion of several rhenium catalysts at multiple stages in the catalysis. These studies were performed in multiple polar liquids to aid in discovering the contributions of the solvent. We also performed electronic ground state 2D-IR and electronic excited state transient-2D-IR experiments to observe how spectral diffusion changes upon electronic excitation. Our results indicate that with the original Lehn catalyst in THF, relative to the ground state, the spectral diffusion slows by a factor of 3 in the equilibrated triplet metal-to-ligand charge transfer state. We attribute this slowdown to a decrease in dielectric friction as well as an increase in molecular flexibility. It is possible to partially simulate the charge transfer by altering the electron density moderately by adding electron donating or withdrawing substituents symmetrically to the bipyridine ligand. We find that unlike the significant electronic structure change induced by MLCT, such small substituent effects do not influence the spectral diffusion. A solvent study in THF, DMSO, and CH3CN found there to be an explicit solvent dependence that we can correlate to the solvent donicity, which is a measure of its nucleophilicity. Future studies focused on the solvent effects on spectral diffusion in the crucial photoinitiated state can illuminate the role the solvent plays in the catalysis.
authors.affiliation: Department of Chemistry, University of Michigan, 930 N. University Ave., Ann Arbor, Michigan 48109, United States.
authors.forename: Laura M
authors.initials: LM
authors.lastname: Kiefer
authors.affiliation: Department of Chemistry, University of Michigan, 930 N. University Ave., Ann Arbor, Michigan 48109, United States.
authors.forename: John T
authors.initials: JT
authors.lastname: King
authors.affiliation: Department of Chemistry, University of Michigan, 930 N. University Ave., Ann Arbor, Michigan 48109, United States.
authors.forename: Kevin J
authors.initials: KJ
authors.lastname: Kubarych