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Herein, we disclose the isolation of a crystalline dicarbondiphosphide\u2010based \u03b2\u2010distonic radical cation salt <jats:bold>3<jats:sup>.+<\/jats:sup><\/jats:bold>(BARF) (BARF=[B(3,5\u2010(CF<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub>)<jats:sub>4<\/jats:sub>)]<jats:sup>\u2212<\/jats:sup>) stable at room temperature and formed by a one\u2010electron\u2010oxidation\u2010induced intramolecular skeletal rearrangement reaction. Such a species has been validated by electron paramagnetic resonance (EPR) spectroscopy, single\u2010crystal X\u2010ray diffraction, UV\/Vis spectroscopy and density functional theory (DFT) calculations. Compound <jats:bold>3<jats:sup>.+<\/jats:sup><\/jats:bold>(BARF) exhibits a large majority of spin density at a two\u2010coordinate phosphorus atom (0.74\u2005a.u.) and a cationic charge located predominantly at the four\u2010coordinate phosphorus atom (1.53\u2005a.u.), which are separated by one carbon atom. This species represents an isolable entity of a phosphorus radical cation that is the closest to a genuine phosphorus DRC to date.<\/jats:p>","DOI":"10.1002\/anie.202011677","type":"journal-article","created":{"date-parts":[[2020,9,14]],"date-time":"2020-09-14T07:45:48Z","timestamp":1600069548000},"page":"23830-23835","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":25,"title":["A Room\u2010Temperature Stable Distonic Radical Cation"],"prefix":"10.1002","volume":"59","author":[{"given":"Xiaodan","family":"Chen","sequence":"first","affiliation":[{"name":"College of Chemistry and Materials Science Jinan University  Guangzhou 510632 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4934-0367","authenticated-orcid":false,"given":"Liu Leo","family":"Liu","sequence":"additional","affiliation":[{"name":"Shenzhen Grubbs Institute and Department of Chemistry Southern University of Science and Technology  Shenzhen 518055 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shihua","family":"Liu","sequence":"additional","affiliation":[{"name":"Lehn Institute of Functional Materials (LIFM) School of Chemistry Sun Yat-Sen University  Guangzhou 510275 China"},{"name":"State Key Laboratory of Elemento-Organic Chemistry Nankai University  Tianjin 30071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1531-8906","authenticated-orcid":false,"given":"Hansj\u00f6rg","family":"Gr\u00fctzmacher","sequence":"additional","affiliation":[{"name":"Lehn Institute of Functional Materials (LIFM) School of Chemistry Sun Yat-Sen University  Guangzhou 510275 China"},{"name":"State Key Laboratory of Elemento-Organic Chemistry Nankai University  Tianjin 30071 China"},{"name":"Department of Chemistry and Applied Biosciences ETH Z\u00fcrich  Vladimir-Prelog-Weg 1 Z\u00fcrich 8093 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5599-6018","authenticated-orcid":false,"given":"Zhongshu","family":"Li","sequence":"additional","affiliation":[{"name":"Lehn Institute of Functional Materials (LIFM) School of Chemistry Sun Yat-Sen University  Guangzhou 510275 China"},{"name":"State Key Laboratory of Elemento-Organic Chemistry Nankai University  Tianjin 30071 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