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Organic PSs exhibiting thermally activated delayed fluorescence (TADF) are particularly promising owing to their ideal photophysics and well\u2010understood electron\u2010transfer mechanisms. However, rational improvement via structural design remains elusive. In this study, we present a comparative study on three TADF\u2010type PSs for precious\u2010metal\u2010free PCO\n                    <jats:sub>2<\/jats:sub>\n                    R. Our results reveal that the kinetic competition between intersystem crossing (ISC) and singlet excited\u2010state quenching determines the utilization efficiency of the long\u2010lived triplet state, a key species to enable high cage\u2010escape yield and eventually the PCO\n                    <jats:sub>2<\/jats:sub>\n                    R performance. Guided by this principle, we have developed a Br\u2010substituted PS derived from 1,3\u2010dicyano\u20102,4,5,6\u2010tetrakis(diphenylamino)\u2010benzene, in which the heavy\u2010atom effect ensures rapid ISC while avoids reinforcing singlet quenching. Such strong steering toward triplet utilizations has led to record\u2010high quantum yields near 50% for complete CO production with a cobalt catalyst, significantly surpassing the performances of precious\u2010metal benchmarks (Ru and Ir\u2010based) and most documented organic PS\u2010driven systems.\n                  <\/jats:p>","DOI":"10.1002\/anie.9417743","type":"journal-article","created":{"date-parts":[[2026,8,19]],"date-time":"2026-08-19T14:23:56Z","timestamp":1787149436000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Intrinsically Inhibiting Singlet Quenching of Organic Sensitizers for Enhanced CO\n                    <sub>2<\/sub>\n                    Photoreduction"],"prefix":"10.1002","volume":"65","author":[{"given":"Fan","family":"Ma","sequence":"first","affiliation":[{"name":"School of Chemical Engineering and Technology Sun Yat\u2010sen University, and Southern Marine Science and Engineering 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