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Here, we show that tailoring alkyl\u2010chain topology renders room\u2010temperature phosphorescence (RTP) as a sensitive reporter of these microenvironments. Upon thermal annealing, photoinduction, or vacuum deoxygenation, the afterglow varies systematically with chain length and odd\u2013even parity, confirming that RTP monitors cavity\u2010restricted environments and aggregate structures. Theoretical calculations further reveal that longer chains strengthen intermolecular interactions, whereas odd\u2013even parity dictates packing modes and cavity distributions; together, these factors control oxygen diffusion and triplet deactivation. Thus, this work establishes the relation among chain topology, aggregation architecture, and RTP property, providing an efficient approach to decode subtle evolutions in branched aggregates.<\/jats:p>","DOI":"10.1002\/smll.76286","type":"journal-article","created":{"date-parts":[[2026,10,15]],"date-time":"2026-10-15T06:33:45Z","timestamp":1792046025000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Phosphorescence Lighting Aggregation Architectures in Alkyl\u2010Engineered Branched Luminogens"],"prefix":"10.1002","author":[{"given":"Guigui","family":"Ye","sequence":"first","affiliation":[{"name":"Hubei Key Lab on Organic and Polymeric Opto\u2010Electronic Materials Department of Chemistry Wuhan University  Wuhan China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wentao","family":"Yuan","sequence":"additional","affiliation":[{"name":"Hubei Key Lab on Organic and Polymeric Opto\u2010Electronic 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