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Mechanistic investigation indicates a fast protonation at phosphorus as evidenced by the isolation of the phosphonium intermediate, followed by a protophosphonylation reaction across the alkyne moiety. DFT calculations support our mechanistic proposal and indicate a reaction highly exergonic compared to our recently reported phosphinoauration. Photophysical measurements recorded fluorescence quantum yields up to 97\u2009% in solution for the phosphindolium core and fluorescence was observed in the solid state.<\/jats:p>","DOI":"10.1002\/chem.201700889","type":"journal-article","created":{"date-parts":[[2017,2,28]],"date-time":"2017-02-28T02:42:04Z","timestamp":1488249724000},"page":"5429-5433","source":"Crossref","is-referenced-by-count":31,"title":["Direct Access to \u03c0\u2010Extended Phosphindolium Salts by Simple Proton\u2010Induced Cyclization of (<i>o<\/i>\u2010Alkynylphenyl)phosphanes"],"prefix":"10.1002","volume":"23","author":[{"given":"Sebastian","family":"Arndt","sequence":"first","affiliation":[{"name":"Organisch-Chemisches Institut Universit\u00e4t Heidelberg  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Max M.","family":"Hansmann","sequence":"additional","affiliation":[{"name":"Organisch-Chemisches Institut Universit\u00e4t Heidelberg  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Frank","family":"Rominger","sequence":"additional","affiliation":[{"name":"Organisch-Chemisches Institut Universit\u00e4t Heidelberg  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matthias","family":"Rudolph","sequence":"additional","affiliation":[{"name":"Organisch-Chemisches Institut Universit\u00e4t Heidelberg  Im Neuenheimer Feld 270 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6720-8602","authenticated-orcid":false,"given":"A. 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