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Ultrafast intersystem crossing (ISC) is observed in the iodinated (IDMICE) as well as brominated (BDMICE) analogues of the eumelanin monomer derivative in solution. The triplet quantum yields (<jats:italic>\u03c6<jats:sub>T<\/jats:sub><\/jats:italic>) and intersystem crossing rates (<jats:italic>k<jats:sub>ISC<\/jats:sub><\/jats:italic>) of the halogenated eumelanin derivatives are \n=25.4\u00b11.1\u2009%; \n=1.95\u00d710<jats:sup>9<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup> and \n=59.1\u00b11.6\u2009%; \n1.36\u00d710<jats:sup>10<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup>, as monitored using transient absorption spectroscopy. Theoretical calculations based on nuclear ensemble method reveal that computed <jats:italic>k<jats:sub>ISC<\/jats:sub><\/jats:italic> and spin\u2010orbit coupling matrix elements for eumelanin derivatives are larger for IDMICE relative to BDMICE. The halogen and \u03c0\u2010\u03c0 interactions, with distinct excitonic coupling and higher ISC rate promote phosphorescence in IDMICE molecular crystals. Accessing triplet excited states and resultant photoluminescence through structural modification of eumelanin scaffolds paves way for exploring the versatility of eumelanin\u2010inspired molecules as bio\u2010functional materials.<\/jats:p>","DOI":"10.1002\/chem.202400499","type":"journal-article","created":{"date-parts":[[2024,3,19]],"date-time":"2024-03-19T13:29:25Z","timestamp":1710854965000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Room Temperature Phosphorescence in Crystalline Iodinated Eumelanin Monomer"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7537-0335","authenticated-orcid":false,"given":"Kavya","family":"Vinod","sequence":"first","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER TVM), Maruthamala P.O., Vithura, Thiruvananthapuram  695551 Kerala India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sohan D.","family":"Jadhav","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER TVM), Maruthamala P.O., Vithura, Thiruvananthapuram  695551 Kerala India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3237-6235","authenticated-orcid":false,"given":"Mahesh","family":"Hariharan","sequence":"additional","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram (IISER TVM), Maruthamala P.O., Vithura, Thiruvananthapuram  695551 Kerala India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,4,12]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1038\/1821427a0"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200803786"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp903190k"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja806345q"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz400437q"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.aaq1293"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c12322"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202106289"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-023-01175-4"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja905162s"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja501499q"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1751-1097.2007.00290.x"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3cc48376b"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz100729w"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41578-020-0223-z"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5SC03766B"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0BM00819B"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8TC01007B"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja401769g"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC04646A"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC06755A"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201705945"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3CC00923H"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8RA06148C"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/j150576a013"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00484"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00484G"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.8b01003"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.9b00766"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz100052m"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.6b12027"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201810209"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms6241"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1038\/srep41532"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.2212343119"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00843a004"},{"key":"e_1_2_8_37_1","unstructured":"J. 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