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Here, we report a topology\u2010driven conformational constraint strategy to enable high\u2010temperature organic phosphorescence. A hydrogen\u2010bonded supramolecular framework constructed from melamine and terephthalic acid serves as a rigid scaffold that imposes topological confinement on embedded terphenyl\u2010based emitters. Comparative studies using emitters with linear, bent, and trigonal\u2010like geometries reveal a clear geometry\u2010dependent trend in phosphorescence performance, suggesting that increased connectivity within the hydrogen\u2010bonded network strengthens conformational constraint and reduces non\u2010radiative relaxation pathways. Consistent with this topology\u2013phosphorescence relationship, the system integrating trigonal\u2010like emitters exhibits persistent phosphorescence with a lifetime of up to 1.22 s at room temperature and retains long\u2010lived emission of 344\u00a0ms even at 150\u00b0C. Benefiting from the excellent environmental stability, the phosphorescent materials can be integrated into polymer matrices to fabricate flexible luminescent films that operate under high\u2010temperature conditions. This work highlights topology\u2010driven conformational constraint as an effective design strategy for developing environmentally robust organic phosphorescent materials.<\/jats:p>","DOI":"10.1002\/anie.7657305","type":"journal-article","created":{"date-parts":[[2026,4,24]],"date-time":"2026-04-24T05:12:18Z","timestamp":1777007538000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Topology\u2010Driven Conformational Constraint Enables High\u2010Temperature Organic Phosphorescence"],"prefix":"10.1002","volume":"65","author":[{"given":"Tongyue","family":"Wu","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chengshuo","family":"Xu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5396-0820","authenticated-orcid":false,"given":"Weijiang","family":"Guan","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9715-4449","authenticated-orcid":false,"given":"Zhiqin","family":"Yuan","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7841-7477","authenticated-orcid":false,"given":"Chao","family":"Lu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing China"},{"name":"Pingyuan Laboratory College of Chemistry Zhengzhou University  Zhengzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,4,23]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010024\u201045811\u20100"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202306725"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.202513575"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/smtd.202401083"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/advs.202506507"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202421036"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202514446"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010024\u201045678\u20101"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c09165"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010023\u201035930\u20105"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.202505113"},{"key":"e_1_2_8_13_1","doi-asserted-by":"crossref","unstructured":"D.Chen Y. E.Shi S.Shen S.Liu D.Yan andZ.Wang \u201cAchieving High\u2010Temperature Resistant Afterglow by Modulating Dual\u2010Mode Emission of Organic Emitters Through Defects Engineering \u201d Small21(2025):2409689.","DOI":"10.1002\/smll.202409689"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cej.2025.164264"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202416397"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202205556"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202319694"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010026\u201068468\u20103"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/smll.202408303"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.adk3354"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.5c10894"},{"key":"e_1_2_8_22_1","first-page":"744","article-title":"Advances in Organic Room\u2010Temperature Phosphorescence: Design Strategies, Physical Mechanisms, and Emerging Applications Materials","volume":"9","author":"Yang Y.","year":"2025","journal-title":"Chemistry Frontiers"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2023.05.023"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.5c01735"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202423650"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202304722"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/adom.201901727"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.macromol.4c01857"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b03867"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.7657305","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.7657305","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.7657305","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,5]],"date-time":"2026-09-05T16:46:22Z","timestamp":1788626782000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.7657305"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,4,23]]},"references-count":28,"journal-issue":{"issue":"24","published-print":{"date-parts":[[2026,6,8]]}},"alternative-id":["10.1002\/anie.7657305"],"URL":"https:\/\/doi.org\/10.1002\/anie.7657305","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,4,23]]},"assertion":[{"value":"2026-03-11","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-04-15","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-04-23","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e7657305"}}