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In this work, polyimides (PIs) exhibiting both ESIPT and room\u2010temperature phosphorescence (RTP) properties were designed and synthesized by end\u2010capping with 5\u2010amino\u20102\u2010(2\u2010hydroxyphenyl) benzothiazole (HBTA) and 5\u2010amino\u20102\u2010(2\u2010hydroxyphenyl) benzimidazole (HBIA), respectively. HBTA\u2010PI and HBIA\u2010PI exhibit bright yellow\u2010green and sky\u2010blue fluorescence at 510\u00a0nm and 470\u00a0nm, with a relatively high photoluminescence quantum yields of about 27.2% and 25.1%, respectively. Importantly, HBTA\u2010PI and HBIA\u2010PI show excellent RTP emissions at 520\u00a0nm and 485\u00a0nm, with decay lifetimes of 76.5\u00a0ms and 53.2\u00a0ms. The theoretical results indicate that the effective and large spin\u2010orbit coupling (SOC) constants from their keto forms in the excited state can enhance the intersystem crossing (ISC) process to produce triplet excitons. The rigid polyimide networks further inhibit the nonradiative decay of triplet excitons and enhance phosphorescence emission. Additionally, the excellent ESIPT properties of HBTA\u2010PI and HBIA\u2010PI enable the detection of HCl vapor, which induces multiple fluorescent and phosphorescent color changes. This work provides good examples of polyimides for organic polymers with ESIPT properties and multi\u2010stimulus response emissions.<\/jats:p>","DOI":"10.1002\/chem.202501038","type":"journal-article","created":{"date-parts":[[2025,4,16]],"date-time":"2025-04-16T08:19:21Z","timestamp":1744791561000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Polyimides with Excited\u2010State Intramolecular Proton Transfer and Room\u2010Temperature Phosphorescence Properties by End\u2010capping"],"prefix":"10.1002","volume":"31","author":[{"given":"Qiuyue","family":"Ding","sequence":"first","affiliation":[{"name":"School of Materials Science and Engineering Chongqing University of Technology  No. 69 Hongguang Avenue, Banan District Chongqing 400054 P. R. 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