{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,7]],"date-time":"2026-02-07T11:30:06Z","timestamp":1770463806022,"version":"3.49.0"},"reference-count":57,"publisher":"Wiley","issue":"8","license":[{"start":{"date-parts":[[2023,1,19]],"date-time":"2023-01-19T00:00:00Z","timestamp":1674086400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2023,4,17]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Photochemical activation by triplet photosensitizers is highly expedient for a green focus society. In this work, we have theoretically probed excited state characteristics of thioxanthone and its derivatives for their triplet harvesting efficiency using density functional theory (DFT) and time\u2010dependent density functional theory (TDDFT). Absorption and triplet energies corroborate well with the available experimental data. Our results predict that both the S<jats:sub>1<\/jats:sub> and T<jats:sub>1<\/jats:sub> states are \u03c0\u2010\u03c0<jats:sup>*<\/jats:sup> in nature, which renders a high oscillator strength for S<jats:sub>0<\/jats:sub> to S<jats:sub>1<\/jats:sub> transition. Major triplet exciton conversion occurs through intersystem crossing (ISC) channel between the S<jats:sub>1<\/jats:sub> (<jats:sup>1<\/jats:sup>\u03c0\u2010\u03c0<jats:sup>*<\/jats:sup>) and high energy <jats:sup>3<\/jats:sup><jats:italic>n<\/jats:italic>\u2010 \u03c0<jats:sup>*<\/jats:sup> state. Apart from that, there is both radiative and non\u2010radiative channel from S<jats:sub>1<\/jats:sub> to S<jats:sub>0<\/jats:sub>, which competes with the ISC channel and reduces the triplet harvesting efficiency. For thioxanthones with \u2212OMe (Me=Methyl) or \u2212F substitution at 2 or 2\u2019 positions, the ISC channel is not energetically feasible, causing sluggish intersystem crossing quantum yield (\u03a6<jats:sub>ISC<\/jats:sub>). For unsubstituted thioxanthone and for isopropyl substitution at 2\u2019 position, the S<jats:sub>1<\/jats:sub>\u2010T<jats:sub>1<\/jats:sub> gap is slightly positive (<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/cphc202200753-math-0001.png\" xlink:title=\"urn:x-wiley:14394235:media:cphc202200753:cphc202200753-math-0001\"\/>\n), rendering a lower triplet harvesting efficiency. For systems with \u2212OMe or \u2212F substitution at 3 or 3\u2019 position of thioxanthone, because of buried \u03c0 state and high energy \u03c0<jats:sup>*<\/jats:sup> state, the S<jats:sub>1<\/jats:sub>\u2010<jats:sup>3<\/jats:sup><jats:italic>n<\/jats:italic>\u03c0<jats:sup>*<\/jats:sup> gap becomes negative. This leads to a high \u03a6<jats:sub>ISC<\/jats:sub> (&gt;0.9), which is key to being an effective photocatalyst.<\/jats:p>","DOI":"10.1002\/cphc.202200753","type":"journal-article","created":{"date-parts":[[2022,12,10]],"date-time":"2022-12-10T01:48:46Z","timestamp":1670636926000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Unraveling the Efficiency of Thioxanthone Based Triplet Sensitizers: A Detailed Theoretical Study"],"prefix":"10.1002","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2258-0002","authenticated-orcid":false,"given":"Bidhan","family":"Chandra Garain","sequence":"first","affiliation":[{"name":"Theoretical Sciences Unit School of Advanced Materials (SAMat) Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR)  Bangalore 560064 India."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5124-7455","authenticated-orcid":false,"given":"Swapan K.","family":"Pati","sequence":"additional","affiliation":[{"name":"Theoretical Sciences Unit School of Advanced Materials (SAMat) Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR)  Bangalore 560064 India."}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,1,19]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/b915340c"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3cs35531d"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201200223"},{"key":"e_1_2_9_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201200223"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs35203f"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35250H"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201106162"},{"key":"e_1_2_9_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201106162"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201002992"},{"key":"e_1_2_9_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201002992"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201102306"},{"key":"e_1_2_9_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201102306"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja047649e"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0553497"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35216H"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1751-1097.2009.00585.x"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2010.01.003"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201101102"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cp23900k"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2jm33654e"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/C1RA00665G"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs35171d"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0427101"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr078381n"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/C1CS15159B"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.83"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.6b00915"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules27030891"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp001348j"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.200690207"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1OB00221J"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c05069"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(89)87234-3"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-007-0310-x"},{"key":"e_1_2_9_33_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3359469"},{"key":"e_1_2_9_34_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1558471"},{"key":"e_1_2_9_35_1","volume-title":"Gaussian 16 Rev. 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