{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T00:58:14Z","timestamp":1760403494263,"version":"build-2065373602"},"reference-count":86,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2024,6,12]],"date-time":"2024-06-12T00:00:00Z","timestamp":1718150400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100019994","name":"Indian Institute of Technology Tirupati","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100019994","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2024,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Structurally\u2010rigid metal\u2010free organic molecules are of high demand for various triplet harvesting applications. However, inefficient intersystem crossing (ISC) due to large singlet\u2010triplet gap (\n) and small spin\u2010orbit coupling (SOC) between lowest excited singlet and triplet often limits their efficiency. Excited electronic states, fluorescence and ISC rates in several thiocarbonyl\u2010bridged N\u2010heterotriangulene (\nS\u2010HTG) with systematically increased thione content (\n0\u20133) are investigated implementing polarization consistent time\u2010dependent optimally\u2010tuned range\u2010separated hybrid. All \nS\u2010HTGs are dynamically stable and also thermodynamically feasible to synthesize. Relative energies of several low\u2010lying singlets (\n) and triplets (\n), and their excitation nature (i.\u2009e., \n or \n) and SOC are determined for these \nS\u2010HTGs in dichloromethane. Low\u2010energy optical peak displays gradual red\u2010shift with increasing thione content due to relatively smaller electronic gap resulted from greater degree of orbital delocalization. Significantly large SOC due to different orbital\u2010symmetry and heavy\u2010atom effect produces remarkably high ISC rates (\n ~10<jats:sup>12<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup>) for enthalpically favoured \n(\n) channel in these \nS\u2010HTGs, which outcompete radiative fluorescence rates (~10<jats:sup>8<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup>) even directly from higher lying optically bright \n singlets. Importantly, high energy triplet excitons of ~1.7\u2005eV resulting from such significantly large ISC rates from non\u2010fluorescent \n make these thiocarbonylated HTGs ideal candidates for energy efficient triplet harvest including triplet\u2010photosensitization.<\/jats:p>","DOI":"10.1002\/cphc.202400371","type":"journal-article","created":{"date-parts":[[2024,5,3]],"date-time":"2024-05-03T10:20:43Z","timestamp":1714731643000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Thiocarbonyl\u2010Bridged N\u2010Heterotriangulenes for Energy Efficient Triplet Photosensitization: A Theoretical Perspective"],"prefix":"10.1002","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8893-2288","authenticated-orcid":false,"given":"Arun K.","family":"Manna","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Tirupati  517619 Tirupati Andhra Pradesh 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