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While various phosphonium\u2010containing five\u2010 or six\u2010membered\u2010ring compounds have been reported, the seven\u2010membered\u2010ring phosphepinium have not been fully studied yet. In this study, dithieno[3,2\u2010<jats:italic>b<\/jats:italic>;\u20092\u2032,3\u2032\u2010<jats:italic>f<\/jats:italic>]phosphepinium ions containing electron\u2010donating aminophenyl groups were synthesized. An X\u2010ray crystallographic analysis of the resulting donor\u2013acceptor\u2013donor dyes revealed a bent conformation of the central seven\u2010membered ring. These compounds exhibit fluorescence in the near\u2010infrared region with a bathochromic shift of ca. 70\u2005nm compared to a phosphepine oxide congener and a large Stokes shift. High fluorescence quantum yields were obtained even in polar solvents due to the suppression of the nonradiative decay process. A theoretical study revealed that the phosphepinium skeleton is highly electron\u2010accepting owing to the orbital interaction between a <jats:italic>p<jats:sub>x<\/jats:sub><\/jats:italic> orbital of the phosphonium moiety and a \u03c0* orbital of the 1,3,5\u2010hexatriene moiety. Due to the lower\u2010lying <jats:italic>p<\/jats:italic><jats:sub>x<\/jats:sub> orbital in the phosphonium moiety compared to that of the phosphine oxide and the bent conformation of the seven\u2010membered ring, the phosphepinium ring permits effective <jats:italic>p<\/jats:italic><jats:sub>x<\/jats:sub>\u2013\u03c0* conjugation. A large structural relaxation with a contribution of a quinoidal resonance structure is suggested in the excited state, which should be responsible for the bright emission with a large Stokes shift.<\/jats:p>","DOI":"10.1002\/anie.202410204","type":"journal-article","created":{"date-parts":[[2024,6,27]],"date-time":"2024-06-27T19:12:03Z","timestamp":1719515523000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Dithieno[3,2\u2010<i>b<\/i>;\u20092\u2032,3\u2032\u2010<i>f<\/i>]phosphepinium\u2010Based Near\u2010Infrared Fluorophores: <i>p<\/i><sub>x<\/sub>\u2013\u03c0* Conjugation Inherent to Seven\u2010Membered Phosphacycles"],"prefix":"10.1002","volume":"63","author":[{"given":"Keita","family":"Andoh","sequence":"first","affiliation":[{"name":"Department of Chemistry, Graduate School of Science, and Integrated Research Consortium on Chemical Sciences (IRCCS) Nagoya University, Furo, Chikusa  Nagoya 464-8602 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