{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,21]],"date-time":"2026-09-21T15:07:10Z","timestamp":1790003230207,"version":"4.0.1"},"reference-count":44,"publisher":"Wiley","issue":"39","license":[{"start":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T00:00:00Z","timestamp":1785456000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T00:00:00Z","timestamp":1785456000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,9,21]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Cerium(IV) complexes are powerful photooxidants with broad applications in organic synthesis and environmental remediation. We employ broadband transient absorption spectroscopy spanning in time (fs\u2014\u00b5s) to map the influence of solvent and ligand identity on the excited\u2010state dynamics of cerium(IV) ammonium nitrate (CAN). In acetonitrile, photoexcitation triggers an LMCT event that generates a remarkably long\u2010lived (\u03c4 = 40 \u00b5s) charge\u2010separated state comprising free nitrate radicals (NO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2022<\/jats:sup>\n                    ) and a reduced Ce(III) center. In protic solvents, productive photochemistry is suppressed: methanol drives ultrafast deactivation (\u03c4 = 1.5\u00a0ps) arising from its mixed Ce(IV) coordination environment, whereas complete nitrate displacement in water enforces rapid geminate recombination (\u03c4 &lt; 100\u00a0ps). Crucially, exchanging the nitrate ligand for chloride in acetonitrile generates a more stable charge\u2010separated state (\u03c4 &gt; 100 \u00b5s) involving chloride radicals (Cl\n                    <jats:sup>\u2022<\/jats:sup>\n                    ), whose interaction with toluene is kinetically faster (\u03c4 = 4\u00a0ns vs. \u03c4 = 10 \u00b5s) than that of NO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2022<\/jats:sup>\n                    , consistent with the thermodynamically favorable adduct formation confirmed by DFT calculations. This enhanced reactivity translates into dramatically improved photocatalytic yields across a range of aromatic substrates. This work offers a rational basis for the design of more efficient earth\u2010abundant photocatalysts.\n                  <\/jats:p>","DOI":"10.1002\/anie.6538194","type":"journal-article","created":{"date-parts":[[2026,7,31]],"date-time":"2026-07-31T08:03:57Z","timestamp":1785485037000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Solvent and Ligand Control of Long\u2010Lived Charge\u2010Separated States in Cerium(IV) Photocatalysis"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2091-4507","authenticated-orcid":false,"given":"Manas R.","family":"Parida","sequence":"first","affiliation":[{"name":"Ultrafast Laser Spectroscopy Lab CIPR KFUPM  Dhahran Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3069-4675","authenticated-orcid":false,"given":"Amal Hassan","family":"Tolba","sequence":"additional","affiliation":[{"name":"Ultrafast Laser Spectroscopy Lab CIPR KFUPM  Dhahran Saudi Arabia"},{"name":"Chemistry Department Faculty of Science Assiut University  Assiut Egypt"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1710-9072","authenticated-orcid":false,"given":"Theis I.","family":"S\u00f8lling","sequence":"additional","affiliation":[{"name":"Ultrafast Laser Spectroscopy Lab CIPR KFUPM  Dhahran Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9380-1058","authenticated-orcid":false,"given":"Albaraa","family":"Al\u2010Nassar","sequence":"additional","affiliation":[{"name":"Ultrafast Laser Spectroscopy Lab CIPR KFUPM  Dhahran Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jakub","family":"Dostal","sequence":"additional","affiliation":[{"name":"ELI Beamlines Facility The Extreme Light Infrastructure ERIC  Doln\u00ed B\u0159e\u017eany Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6436-1452","authenticated-orcid":false,"given":"Andrej","family":"Hovan","sequence":"additional","affiliation":[{"name":"ELI Beamlines Facility The Extreme Light Infrastructure ERIC  Doln\u00ed B\u0159e\u017eany Czech Republic"}],"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 KFUPM  Dhahran Saudi 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