{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,25]],"date-time":"2026-10-25T17:33:31Z","timestamp":1792949611760,"version":"4.5.0"},"reference-count":66,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2026,10,25]],"date-time":"2026-10-25T00:00:00Z","timestamp":1792886400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,10,25]],"date-time":"2026-10-25T00:00:00Z","timestamp":1792886400000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemistryEurope"],"published-print":{"date-parts":[[2026,11]]},"abstract":"<jats:p>\n                    The diphenylphosphinyl radical\n                    <jats:bold>1<\/jats:bold>\n                    was generated from iododiphenylphosphine by visible\u2010light photolysis and flash\u2010vacuum pyrolysis under cryogenic matrix isolation conditions and characterized by IR, UV\/Vis, and EPR spectroscopy. In solid\n                    <jats:italic>para<\/jats:italic>\n                    \u2010hydrogen (\n                    <jats:italic>p<\/jats:italic>\n                    \u2010H\n                    <jats:sub>2<\/jats:sub>\n                    ), photolysis proceeds markedly more efficiently than in argon and affords substantially narrower EPR signals. Simulation of the low\u2010field wing requires an effective Gaussian broadening of 0.83\u2009G in\n                    <jats:italic>p<\/jats:italic>\n                    \u2010H\n                    <jats:sub>2<\/jats:sub>\n                    , compared with 1.13\u2009G in normal hydrogen and 4.95\u2009G in argon. This enhanced resolution reveals a seven\u2010line proton hyperfine envelope that remained unresolved in previous studies of\n                    <jats:bold>1<\/jats:bold>\n                    in frozen solutions. Spectral simulations and quantum\u2010chemical calculations identify\n                    <jats:bold>1<\/jats:bold>\n                    as a\n                    <jats:italic>\u03c0<\/jats:italic>\n                    \u2010type radical with pronounced spin localization at phosphorus and additional spin density delocalized over the phenyl rings. Compared with the more rigid dibenzophospholyl radical\n                    <jats:bold>4<\/jats:bold>\n                    , radical\n                    <jats:bold>1<\/jats:bold>\n                    is less stabilized, more conformationally flexible, and exhibits photochemical H\u2010atom abstraction from molecular hydrogen. Ground\u2010state and vertical excited\u2010state calculations exclude a simple thermal or adiabatic photochemical pathway and instead suggest that nonadiabatic or secondary radical\u2010pair processes contribute to the reaction. These results establish solid\n                    <jats:italic>p<\/jats:italic>\n                    \u2010H\n                    <jats:sub>2<\/jats:sub>\n                    as a powerful medium for resolving otherwise inaccessible hyperfine structure in reactive phosphorus\u2010centered radicals.\n                  <\/jats:p>","DOI":"10.1002\/ceur.70380","type":"journal-article","created":{"date-parts":[[2026,10,25]],"date-time":"2026-10-25T16:46:29Z","timestamp":1792946789000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Enhanced Resolution in EPR Spectroscopy: Solid\n                    <i>para<\/i>\n                    \u2010Hydrogen Resolves Proton Hyperfine Splitting in the Diphenylphosphinyl Radical"],"prefix":"10.1002","volume":"4","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4946-8205","authenticated-orcid":false,"given":"Mika","family":"Maehara","sequence":"first","affiliation":[{"name":"Lehrstuhl f\u00fcr Organische Chemie II Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9859-4043","authenticated-orcid":false,"given":"Adri\u00e1n","family":"Portela\u2010Gonz\u00e1lez","sequence":"additional","affiliation":[{"name":"Lehrstuhl f\u00fcr Organische Chemie II Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0009-1664-2685","authenticated-orcid":false,"given":"Kristin","family":"Wulff","sequence":"additional","affiliation":[{"name":"Lehrstuhl f\u00fcr Organische Chemie II Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-6237-8543","authenticated-orcid":false,"given":"Julian","family":"E\u00dfer","sequence":"additional","affiliation":[{"name":"Lehrstuhl f\u00fcr Organische Chemie II Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1029-9272","authenticated-orcid":false,"given":"Andr\u00e9 K.","family":"Eckhardt","sequence":"additional","affiliation":[{"name":"Lehrstuhl f\u00fcr Organische Chemie II Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,10,25]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"crossref","first-page":"10049","DOI":"10.1021\/acs.chemrev.8b00081","article-title":"Phosphine Organocatalysis","volume":"118","author":"Guo H.","year":"2018","journal-title":"Chemical Reviews"},{"key":"e_1_2_9_3_1","doi-asserted-by":"crossref","first-page":"536","DOI":"10.1021\/acscentsci.0c01493","article-title":"Phosphorus\u2010Based Catalysis","volume":"7","author":"Xie C.","year":"2021","journal-title":"ACS Central Science"},{"key":"e_1_2_9_4_1","doi-asserted-by":"crossref","first-page":"4681","DOI":"10.1021\/cr040179m","article-title":"Organophosphorus \u03c0\u2010Conjugated Materials","volume":"106","author":"Baumgartner T.","year":"2006","journal-title":"Chemical Reviews"},{"key":"e_1_2_9_5_1","doi-asserted-by":"crossref","first-page":"6177","DOI":"10.1021\/cr030451c","article-title":"Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity","volume":"104","author":"Moonen K.","year":"2004","journal-title":"Chemical Reviews"},{"key":"e_1_2_9_6_1","doi-asserted-by":"crossref","first-page":"5234","DOI":"10.1039\/D4DT03582H","article-title":"Recent Advances in Heavier Group 15 (P, As, Sb, Bi) Radical Chemistry \u2013 Frameworks, Small Molecule Reactivity, and Catalysis","volume":"54","author":"Symes D. 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