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dc.contributor.authorHenke, Wade C.
dc.contributor.authorOtolski, Christopher J.
dc.contributor.authorMoore, William N. G.
dc.contributor.authorElles, Christopher G.
dc.contributor.authorBlakemore, James D.
dc.date.accessioned2020-10-20T21:39:45Z
dc.date.available2020-10-20T21:39:45Z
dc.date.issued2020-01-28
dc.identifier.citationHenke, W. C., Otolski, C. J., Moore, W., Elles, C. G., & Blakemore, J. D. (2020). Ultrafast Spectroscopy of [Mn(CO)3] Complexes: Tuning the Kinetics of Light-Driven CO Release and Solvent Binding. Inorganic chemistry, 59(4), 2178–2187. https://doi.org/10.1021/acs.inorgchem.9b02758en_US
dc.identifier.urihttp://hdl.handle.net/1808/30792
dc.descriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.9b02758.en_US
dc.description.abstractManganese tricarbonyl complexes are promising catalysts for CO2 reduction, but complexes in this family are often photo-sensitive and decompose rapidly upon exposure to visible light. In this report, synthetic and photochemical studies probe the initial steps of light-driven speciation for Mn(CO)3(Rbpy)Br complexes bearing a range of 4,4′-disubstituted-2,2′-bipyridyl ligands (Rbpy, R = tBu, H, CF3, NO2). Transient absorption spectroscopy measurements for the Mn(CO)3(Rbpy)Br coordination compounds with R = tBu, H, and CF3 in acetonitrile reveal ultrafast loss of a CO ligand on the femtosecond timescale, followed by solvent coordination on the picosecond timescale. The Mn(CO)3(NO2bpy)Br complex is unique among the four compounds in having a longer-lived excited state that does not undergo CO release or the subsequent solvent coordination. The kinetics of photolysis and solvent coordination for the light-sensitive complexes depend on the electronic properties of the di-substituted bipyridyl ligand. The results implicate roles for both metal-to-ligand charge transfer (MLCT) and dissociative ligand field (dd) excited states in the ultrafast photochemistry. Taken together, the findings suggest that more robust catalysts could be prepared with appropriately designed complexes that avoid crossing between the excited states that drive photochemical CO loss.en_US
dc.description.sponsorshipHall Chemical Research Fund at the University of Kansasen_US
dc.description.sponsorshipU.S. National Science Foundation (CHE-1151555)en_US
dc.description.sponsorshipNIH T32 GM008545-25en_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsCopyright © 2020 American Chemical Societyen_US
dc.titleUltrafast Spectroscopy of [Mn(CO)3] Complexes: Tuning the Kinetics of Light-Driven CO Release and Solvent Bindingen_US
dc.typeArticleen_US
kusw.kuauthorHenke, Wade C.
kusw.kuauthorOtolski, Christopher J.
kusw.kuauthorMoore, William N. G.
kusw.kuauthorElles, Christopher G.
kusw.kuauthorBlakemore, James D.
kusw.kudepartmentChemistryen_US
dc.identifier.doi10.1021/acs.inorgchem.9b02758en_US
dc.identifier.orcidhttps://orcid.org/0000-0002-1408-8360en_US
dc.identifier.orcidhttps://orcid.org/0000-0003-4172-7460en_US
kusw.oaversionScholarly/refereed, author accepted manuscripten_US
kusw.oapolicyThis item meets KU Open Access policy criteria.en_US
dc.identifier.pmidPMC7412560en_US
dc.rights.accessrightsembargoedAccessen_US


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