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Through comprehensive spectroscopic analyses and computational modeling, we discovered that in acetonitrile (MeCN), O\n                    <jats:sub>2<\/jats:sub>\n                    molecules directly bind to the metal complex using the sphere of action model with a separation distance of 2.35 \u00c5. This binding leads to significant emission quenching of the 4f \u2190 5d transition, driven by an ultrafast electron transfer from Ce (III) to bound molecular oxygen, leading to Ce (IV) and O\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>\u2022\u2500<\/jats:sup>\n                    (superoxide radical anion) in approximately 1.0\u00a0ps, as confirmed by femtosecond transient absorption spectroscopy. However, this distinctive O\n                    <jats:sub>2<\/jats:sub>\n                    interaction is disrupted by the presence of strong oxidizing substrates, such as 4\u2010fluoroiodobenzene, or when the complex is dissolved in protic solvents like methanol (MeOH) or water (H\n                    <jats:sub>2<\/jats:sub>\n                    O). In these protic media, MeOH or H\n                    <jats:sub>2<\/jats:sub>\n                    O solvent molecules displace the Cl\n                    <jats:sup>\u2212<\/jats:sup>\n                    ligands, and the extended hydrogen bonding network formed by MeOH or H\n                    <jats:sub>2<\/jats:sub>\n                    O ligand acts as an effective shield around the Ce (III) center. Our findings reveal how solvent selection can strategically modulate Ce (III) photochemistry, shifting the balance between emission\u2010dominated and redox\u2010active pathways, and providing a mechanistic foundation for optimizing cerium\u2010based photocatalytic systems.\n                  <\/jats:p>","DOI":"10.1002\/anie.202513444","type":"journal-article","created":{"date-parts":[[2025,8,26]],"date-time":"2025-08-26T10:57:52Z","timestamp":1756205872000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["The Crucial Role of Solvent and Bound Oxygen on the Interplay of Cerium (III) and Cerium (IV) Chloride in a Photocatalytic Cycle for Organic Transformations"],"prefix":"10.1002","volume":"64","author":[{"given":"Ravi Kumar","family":"Venkatraman","sequence":"first","affiliation":[{"name":"Ultrafast Laser Spectroscopy Lab CIPR, CPG, King Fahd University of Petroleum and Minerals (KFUPM) Dhahran 31261 Saudi Arabia"},{"name":"Department of Chemistry SRM Institute of Science and Technology  Kattankulathur Chengalpattu Tamil Nadu 603 203 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Deborin","family":"Ghosh","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Bristol  Cantock's Close Bristol BS8 1TS UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amal Hassan","family":"Tolba","sequence":"additional","affiliation":[{"name":"Ultrafast Laser Spectroscopy Lab CIPR, CPG, King Fahd University of Petroleum and Minerals (KFUPM) Dhahran 31261 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Theis I.","family":"S\u00f8lling","sequence":"additional","affiliation":[{"name":"Ultrafast Laser Spectroscopy Lab CIPR, CPG, King Fahd University of Petroleum and Minerals (KFUPM) Dhahran 31261 Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrew J.","family":"Orr\u2010Ewing","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Bristol  Cantock's Close Bristol BS8 1TS UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2901-5815","authenticated-orcid":false,"given":"Ahmed M.","family":"El\u2010Zohry","sequence":"additional","affiliation":[{"name":"Ultrafast Laser Spectroscopy Lab CIPR, CPG, King Fahd University of Petroleum and Minerals (KFUPM) Dhahran 31261 Saudi 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