{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,13]],"date-time":"2026-02-13T09:08:39Z","timestamp":1770973719093,"version":"3.50.1"},"reference-count":43,"publisher":"Wiley","issue":"68","license":[{"start":{"date-parts":[[2024,10,29]],"date-time":"2024-10-29T00:00:00Z","timestamp":1730160000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2024,12,5]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Thiophene polycyclic derivatives are widely used in organic light\u2010emitting diodes, photovoltaics, and medicinal chemistry applications. Understanding the electronic and structural factors controlling their intersystem crossing rates is paramount for these applications to be successful. This study investigates the photophysical, electronic structure, and excited state dynamics of 1,2\u2010benzodiphenylene sulfide, benzo[<jats:italic>b<\/jats:italic>]naphtho[1,2\u2010<jats:italic>d<\/jats:italic>]thiophene, and benzo[<jats:italic>b<\/jats:italic>]naphtho[2,3\u2010<jats:italic>d<\/jats:italic>]thiophene in polar aprotic and non\u2010polar solvents. Steady\u2010state absorption and emission spectroscopy, femtosecond transient absorption spectroscopy, and DFT and TD\u2010DFT calculations are employed. Low fluorescence quantum yields of 1.2 to 2.7\u2009% are measured in acetonitrile and cyclohexene, evidencing that the primary relaxation pathways in these thiophene derivatives are nonradiative. Linear interpolation of internal coordinates calculations predict that an S\u2212C bond elongation reaction coordinate facilitates the efficient intersystem crossing to the T<jats:sub>1<\/jats:sub> state. Excitation of 1,2\u2010benzodiphenylene sulfide and benzo[<jats:italic>b<\/jats:italic>]naphtho[1,2\u2010<jats:italic>d<\/jats:italic>]thiophene at 350\u2005nm or benzo[<jats:italic>b<\/jats:italic>]naphtho[2,3\u2010<jats:italic>d<\/jats:italic>]thiophene at 365\u2005nm, populates the lowest\u2010energy <jats:sup>1<\/jats:sup>\u03c0\u03c0* state, which relaxes to the <jats:sup>1<\/jats:sup>\u03c0\u03c0* minimum in tens of picoseconds or intersystem crosses to the triplet manifold in ca. 500\u2005ps to 1.1\u2005ns depending on the position at which the benzene rings are added. Excitation at 266\u2005nm does not affect the intersystem crossing rates. Laser photodegradation experiments demonstrate that the thiophene polycyclic derivatives are highly photostable.<\/jats:p>","DOI":"10.1002\/chem.202402721","type":"journal-article","created":{"date-parts":[[2024,8,26]],"date-time":"2024-08-26T07:30:10Z","timestamp":1724657410000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Structural and Electronic Factors Controlling the Efficiency and Rate of Intersystem Crossing to the Triplet State in Thiophene Polycyclic Derivatives"],"prefix":"10.1002","volume":"30","author":[{"given":"Cameron","family":"Griffrith","sequence":"first","affiliation":[{"name":"Department of Chemistry Case Western Reserve University  Cleveland, Ohio 44106 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sarah E.","family":"Krul","sequence":"additional","affiliation":[{"name":"Department of Chemistry Case Western Reserve University  Cleveland, Ohio 44106 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sean J.","family":"Hoehn","sequence":"additional","affiliation":[{"name":"Department of Chemistry Case Western Reserve University  Cleveland, Ohio 44106 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tram","family":"Phan","sequence":"additional","affiliation":[{"name":"Department of Chemistry Case Western Reserve University  Cleveland, Ohio 44106 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3594-0890","authenticated-orcid":false,"given":"Carlos E.","family":"Crespo\u2010Hern\u00e1ndez","sequence":"additional","affiliation":[{"name":"Department of Chemistry Case Western Reserve University  Cleveland, Ohio 44106 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,10,29]]},"reference":[{"key":"e_1_2_10_1_1","volume-title":"Semiconducting Polymers: Chemistry, Physics and Engineering","author":"Hadziioannou G.","year":"2000"},{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1080\/10426509408034296"},{"key":"e_1_2_10_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/b401209g"},{"key":"e_1_2_10_4_1","volume-title":"Handbook of Oligo- and Polythiophene","author":"Fichou D.","year":"1999"},{"key":"e_1_2_10_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3cs60108k"},{"key":"e_1_2_10_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.progpolymsci.2013.09.005"},{"key":"e_1_2_10_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200500461"},{"key":"e_1_2_10_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.8b18240"},{"key":"e_1_2_10_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CP00019J"},{"key":"e_1_2_10_10_1","first-page":"1","volume":"27","author":"Kubrak T. 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