{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Chan AY"],"funding":["NIGMS NIH HHS"],"pagination":["191-197"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10690870"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["382(6667)"],"pubmed_abstract":["Second- and third-row transition metal complexes are widely employed in photocatalysis, whereas earth-abundant first-row transition metals have found only limited use because of the prohibitively fast decay of their excited states. We report an unforeseen reactivity mode for productive photocatalysis that uses cobalt polypyridyl complexes as photocatalysts by exploiting Marcus inverted region behavior that couples increases in excited-state energies with increased excited-state lifetimes. These cobalt (III) complexes can engage in bimolecular reactivity by virtue of their strong redox potentials and sufficiently long excited-state lifetimes, catalyzing oxidative C(sp<sup>2</sup>)-N coupling of aryl amides with challenging sterically hindered aryl boronic acids. More generally, the results imply that chromophores can be designed to increase excited-state lifetimes while simultaneously increasing excited-state energies, providing a pathway for the use of relatively abundant metals as photoredox catalysts."],"journal":["Science (New York, N.Y.)"],"pubmed_title":["Exploiting the Marcus inverted region for first-row transition metal-based photoredox catalysis."],"pmcid":["PMC10690870"],"funding_grant_id":["R35 GM134897"],"pubmed_authors":["Ghosh A","Chan AY","Yarranton JT","Twilton J","Jin J","McCusker JK","MacMillan DWC","Arias-Rotondo DM","Sakai HA"],"additional_accession":[]},"is_claimable":false,"name":"Exploiting the Marcus inverted region for first-row transition metal-based photoredox catalysis.","description":"Second- and third-row transition metal complexes are widely employed in photocatalysis, whereas earth-abundant first-row transition metals have found only limited use because of the prohibitively fast decay of their excited states. We report an unforeseen reactivity mode for productive photocatalysis that uses cobalt polypyridyl complexes as photocatalysts by exploiting Marcus inverted region behavior that couples increases in excited-state energies with increased excited-state lifetimes. These cobalt (III) complexes can engage in bimolecular reactivity by virtue of their strong redox potentials and sufficiently long excited-state lifetimes, catalyzing oxidative C(sp<sup>2</sup>)-N coupling of aryl amides with challenging sterically hindered aryl boronic acids. More generally, the results imply that chromophores can be designed to increase excited-state lifetimes while simultaneously increasing excited-state energies, providing a pathway for the use of relatively abundant metals as photoredox catalysts.","dates":{"release":"2023-01-01T00:00:00Z","publication":"2023 Oct","modification":"2025-04-04T09:39:33.86Z","creation":"2025-04-04T09:39:33.86Z"},"accession":"S-EPMC10690870","cross_references":{"pubmed":["37824651"],"doi":["10.1126/science.adj0612"]}}