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Herein, we present an effective strategy to activate and enhance RTP in heavy\u2010atom\u2010free chromophores through external heavy\u2010atom engineering (HAE). By dispersing these chromophores within hydrophobic halogen\u2010rich polymer matrices, external HAE is employed to enhance spin\u2013orbit coupling and promote efficient ISC. The generality of this strategy is demonstrated across a series of polycyclic aromatic hydrocarbons and further extended to other heterocyclic chromophores, affording bright (phosphorescence quantum yields up to 61.6%) and long\u2010lived (phosphorescence lifetimes up to 273\u00a0ms) RTP materials under ambient conditions, with emission wavelengths spanning from 500 to 700\u00a0nm. This supramolecular approach circumvents the need for covalent introduction of heavy atoms to the luminophores, thereby preserving their intrinsic photophysical properties while unlocking desirable triplet\u2010state emissions. Overall, the current external HAE strategy provides a versatile platform for the construction of high\u2010performance organic RTP materials, offering new insights into the design principles of organic RTP systems and broadening the material landscape for optoelectronic and bioimaging applications.<\/jats:p>","DOI":"10.1002\/anie.202516177","type":"journal-article","created":{"date-parts":[[2025,11,20]],"date-time":"2025-11-20T07:33:38Z","timestamp":1763624018000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["Unlocking Room\u2010Temperature Phosphorescence of Polycyclic Aromatic Hydrocarbons and Beyond via External Heavy\u2010Atom Engineering"],"prefix":"10.1002","volume":"65","author":[{"given":"Ruicong","family":"Feng","sequence":"first","affiliation":[{"name":"Shenzhen Grubbs Institute Southern University of Science and Technology  Shenzhen 518055 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