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Represented herein is to report an unexpected cracking of PS to C6\u2010C8 aromatic products in CH\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>2<\/jats:sub>\n                    without any additional photocatalysts under an O\n                    <jats:sub>2<\/jats:sub>\n                    atmosphere and 365\u2010415\u00a0nm irradiation. Remarkably, this photocatalyst\u2010free system achieves a maximum generation rate of 15.9\u00a0\u00b5mol\/h for C6\u2010C8 aromatic products, competitive with state\u2010of\u2010the\u2010art systems that rely on external photocatalysts. Radical scavenging experiments and EPR spectra reveal that chlorine (Cl\u2022) radicals generated from CH\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>2<\/jats:sub>\n                    under irradiation contribute to the cleavage of C\u2500H\/C\u2500C bonds in PS, leading to the formation of C6\u2010C8 aromatic products. Under aerobic conditions, these Cl\u2022 radicals also promote the transformation of PS into carbonylated intermediates as the light\u2010absorbing species with an absorption range of 300\u2010500\u00a0nm, thereby accelerating the activation of PS and derivatives. Importantly, this work identifies, for the first time, CH\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>2<\/jats:sub>\n                    as a vital photochemical reagent in PS conversion to value\u2010added aromatics even under visible light irradiation.\n                  <\/jats:p>","DOI":"10.1002\/anie.5578835","type":"journal-article","created":{"date-parts":[[2026,6,9]],"date-time":"2026-06-09T12:02:03Z","timestamp":1781006523000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Photocracking of Polystyrene into Aromatic Products in CH\n                    <sub>2<\/sub>\n                    Cl\n                    <sub>2<\/sub>"],"prefix":"10.1002","volume":"65","author":[{"given":"Kaiyi","family":"Su","sequence":"first","affiliation":[{"name":"Key Laboratory of Supramolecular Photochemistry &amp; CAS\u2010HKU Joint Laboratory on New Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P.R. China"},{"name":"School of Future Technology University of Chinese Academy of Sciences  Beijing P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tengshijie","family":"Gao","sequence":"additional","affiliation":[{"name":"Key Laboratory of Supramolecular Photochemistry &amp; CAS\u2010HKU Joint Laboratory on New Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P.R. China"},{"name":"School of Future Technology University of Chinese Academy of Sciences  Beijing P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haixia","family":"Liu","sequence":"additional","affiliation":[{"name":"Key Laboratory of Supramolecular Photochemistry &amp; CAS\u2010HKU Joint Laboratory on New Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P.R. China"},{"name":"School of Future Technology University of Chinese Academy of Sciences  Beijing P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zeyang","family":"Zhang","sequence":"additional","affiliation":[{"name":"National Engineering Research Center of Engineering Plastics and Ecological Plastics Technical Institute of Physics and Chemistry Chinese Academy of Sciences  Beijing P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhi\u2010Jun","family":"Li","sequence":"additional","affiliation":[{"name":"Key Laboratory of Supramolecular Photochemistry &amp; CAS\u2010HKU Joint Laboratory on New Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P.R. China"},{"name":"School of Future Technology University of Chinese Academy of Sciences  Beijing P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Boxiang","family":"Liu","sequence":"additional","affiliation":[{"name":"Key Laboratory of Supramolecular Photochemistry &amp; CAS\u2010HKU Joint Laboratory on New Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P.R. China"},{"name":"School of Future Technology University of Chinese Academy of Sciences  Beijing P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Min","family":"Jiang","sequence":"additional","affiliation":[{"name":"School of Material, Chemistry and Chemical Engineering Hangzhou Normal University Hangzhou Zhejiang P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mingxuan","family":"Gao","sequence":"additional","affiliation":[{"name":"Key Laboratory of Supramolecular Photochemistry &amp; CAS\u2010HKU Joint Laboratory on New Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P.R. China"},{"name":"School of Future Technology University of Chinese Academy of Sciences  Beijing P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhiyuan","family":"Huang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Supramolecular Photochemistry &amp; CAS\u2010HKU Joint Laboratory on New Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P.R. China"},{"name":"School of Future Technology University of Chinese Academy of Sciences  Beijing P.R. 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