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Here, 16 C-, O-, S-, and Se-containing B\/N MR-TADF emitters with varied framework symmetries are investigated using density functional theory (DFT), time-dependent density functional theory (TD-DFT), and the thermal vibration correlation function (TVCF) formalism. We find that the conventional T1 \u2192 S1 pathway cannot explain the accelerated RISC because the S1\u2013T1 gap remains thermally unfavorable. Instead, a near-resonant high-lying T2 state provides an intrinsically fast spin-conversion pathway, although its productive contribution is governed by the competition between T2 \u2192 S1 RISC and T2 \u2192 T1 internal conversion. Chalcogen embedding and framework symmetry breaking cooperatively tune the T2 orbital character, enhance S1\u2013T2 spin\u2013orbit coupling (SOC), and yield direct T2 \u2192 S1 RISC rate constants from 8.65 \u00d7 107 to 8.77 \u00d7 109 s\u22121 for S- and Se-containing emitters with numerically stable T2-state vibronic parameters. Spectral simulations further show that the same heavy-atom perturbation can increase S1\/S0 relaxation, reorganization energy, and vibronic coupling, thereby broadening emission. The emission bandwidth correlates more closely with S1 \u2192 S0 reorganization energy than with global structural displacement, identifying vibronic reorganization as the key color-purity descriptor. Thus, S1\u2013T2 energy alignment and SOC govern the intrinsic spin-conversion capability, whereas framework rigidity, symmetry, and reorganization energy determine narrowband emission. Symmetric double locking with localized S or Se embedding, therefore, provides a practical strategy for balancing intrinsic spin-conversion capability and color purity.<\/jats:p>","DOI":"10.1063\/5.0349411","type":"journal-article","created":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T11:32:01Z","timestamp":1790595121000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Photophysics of heteroatom-doped B,N multiple-resonance emitters: A computational investigation"],"prefix":"10.1063","volume":"165","author":[{"ORCID":"https:\/\/orcid.org\/0009-0002-2433-3152","authenticated-orcid":false,"given":"Yaxin","family":"Wang","sequence":"first","affiliation":[{"name":"Guangdong Basic Research Center of Excellence for Aggregate Science, School of Science and Engineering, The Chinese University of Hong Kong 1 , Shenzhen, Guangdong 518172,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2674-6751","authenticated-orcid":false,"given":"Wensheng","family":"Yang","sequence":"additional","affiliation":[{"name":"Institute of Molecular Plus, Tianjin University 2 , Tianjin 300072,","place":["People\u2019s Republic of China"]},{"name":"Engineering Research Center for Nanomaterials, Henan University 3 , Kaifeng 475004,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3591-2451","authenticated-orcid":false,"given":"Xiaonan","family":"Ma","sequence":"additional","affiliation":[{"name":"Institute of Molecular Plus, Tianjin University 2 , Tianjin 300072,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3867-2331","authenticated-orcid":false,"given":"Zhigang","family":"Shuai","sequence":"additional","affiliation":[{"name":"Guangdong Basic Research Center of Excellence for Aggregate Science, School of Science and Engineering, The Chinese University of Hong Kong 1 , Shenzhen, Guangdong 518172,","place":["People\u2019s Republic of China"]},{"name":"MOE Key Laboratory of Organic OptoElectronics and Molecular Engineering, Department of Chemistry, Tsinghua University 4 , 100084 Beijing,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2026,9,28]]},"reference":[{"key":"2026092807315815900_c1","doi-asserted-by":"publisher","first-page":"913","DOI":"10.1063\/1.98799","volume":"51","year":"1987","journal-title":"Appl. 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