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The phosphinyl radical (\u2022PH\n                    <jats:sub>2<\/jats:sub>\n                    ) is a key intermediate in the photochemistry of PH\n                    <jats:sub>3<\/jats:sub>\n                    , and its reactions with O\n                    <jats:sub>2<\/jats:sub>\n                    yield phosphorus oxyacids as stable reservoirs via the intermediacy of yet elusive radicals. Herein, we report the identification of the simplest phosphinylperoxy radical H\n                    <jats:sub>2<\/jats:sub>\n                    POO\u2022 in gas phase reaction between \u2022PH\n                    <jats:sub>2<\/jats:sub>\n                    and O\n                    <jats:sub>2<\/jats:sub>\n                    . The characterization of H\n                    <jats:sub>2<\/jats:sub>\n                    POO\u2022 with matrix\u2010isolation IR and UV\u2010vis spectroscopy is supported by D\u2010 and\n                    <jats:sup>18<\/jats:sup>\n                    O\u2010isotope labeling experiments and quantum chemical calculations. Upon photoexcitation at 410\u00a0nm, the matrix\u2010isolated H\n                    <jats:sub>2<\/jats:sub>\n                    POO\u2022 undergoes successive hydrogen\u2010migration to form two isomers HP(O)OH\u2022 and \u2022P(OH)\n                    <jats:sub>2<\/jats:sub>\n                    . Further UV\u2010irradiation at 365\u00a0nm causes decomposition to yield the water complex of phosphorus monoxide (\u2022PO), which can be photolytically converted to metaphosphorous acid (HOPO). The disclosed photochemistry of these novel phosphorus\u2010bearing molecules helps in understanding the photochemical network of PH\n                    <jats:sub>3<\/jats:sub>\n                    in the atmospheric and interstellar phosphorus chemistry.\n                  <\/jats:p>","DOI":"10.1002\/anie.9795009","type":"journal-article","created":{"date-parts":[[2026,2,6]],"date-time":"2026-02-06T09:19:01Z","timestamp":1770369541000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["The Simplest Phosphinylperoxy Radical and Its Isomers in the Photochemical Phosphorus\u2010Hydrogen\u2010Oxygen Network"],"prefix":"10.1002","volume":"65","author":[{"given":"Junjie","family":"Jiang","sequence":"first","affiliation":[{"name":"Department of Chemistry Advanced Institute of Future Energy Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Fudan University  Shanghai 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