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Here, we report the first investigation of the simplest triplet alkyl nitrene bearing a pyridine\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010oxide moiety. Direct irradiation (\u03bb\u2009&gt;\u2009350\u2009nm) of 4\u2010azidomethyl\u2010pyridine\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010oxide in an Ar matrix (15\u2009K) generated the target triplet 4\u2010nitrenemethyl\u2010pyridine\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010oxide\n                    <jats:sup>\n                      <jats:bold>3<\/jats:bold>\n                    <\/jats:sup>\n                    <jats:bold>2<\/jats:bold>\n                    , along with\n                    <jats:italic>E<\/jats:italic>\n                    and\n                    <jats:italic>Z<\/jats:italic>\n                    isomers of 4\u2010iminomethyl\u2010pyridine\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010oxide\n                    <jats:bold>3<\/jats:bold>\n                    . Results from subsequent irradiations (\u03bb\u2009&gt;\u2009325\u2009nm) enabled the discrimination of the IR spectroscopic signatures of these species, allowing their unequivocal identification with support from DFT\u2010B3LYP computations. Triplet nitrene\n                    <jats:sup>\n                      <jats:bold>3<\/jats:bold>\n                    <\/jats:sup>\n                    <jats:bold>2<\/jats:bold>\n                    was found to be stable in dark Ar matrices, demonstrating that quantum tunneling 1,2\u2010H shift to imine\n                    <jats:bold>3<\/jats:bold>\n                    is not operative on the experimental timescale. Computations show that this reaction is thermodynamically favorable on the triplet surface but involves a high\u2010energy barrier (~36\u2009kcal\u2009mol\n                    <jats:sup>\u22121<\/jats:sup>\n                    ), explaining the absence of H\u2010tunneling. As the pyridine\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010oxide moiety can act as an anchoring site for complexation with calix[4]pyrrole derivatives, our findings open new perspectives for investigating alkyl nitrene reactivity and tunneling phenomena under supramolecular confinement conditions.\n                  <\/jats:p>","DOI":"10.1002\/poc.70074","type":"journal-article","created":{"date-parts":[[2026,3,16]],"date-time":"2026-03-16T11:29:34Z","timestamp":1773660574000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Triplet 4\u2010Nitrenemethyl\u2010Pyridine\u2010\n                    <i>N<\/i>\n                    \u2010Oxide: A Model Alkyl Nitrene Isolated in Cryogenic Matrices"],"prefix":"10.1002","volume":"39","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8511-1230","authenticated-orcid":false,"given":"Cl\u00e1udio\u00a0M.","family":"Nunes","sequence":"first","affiliation":[{"name":"University of Coimbra, CQC\u2010IMS, Department of Chemistry  Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5953-976X","authenticated-orcid":false,"given":"A.\u00a0J.\u00a0Lopes","family":"Jesus","sequence":"additional","affiliation":[{"name":"CQC\u2010IMS, Faculty of Pharmacy  Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-0467-3614","authenticated-orcid":false,"given":"Tatiana","family":"Caneca","sequence":"additional","affiliation":[{"name":"University of Coimbra, CQC\u2010IMS, Department of Chemistry  Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2405-0278","authenticated-orcid":false,"given":"Gemma","family":"Aragay","sequence":"additional","affiliation":[{"name":"Institute of Chemical Research of Catalonia (ICIQ) the Barcelona Institute of Science and Technology (BIST)  Tarragona Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8377-6610","authenticated-orcid":false,"given":"Pablo","family":"Ballester","sequence":"additional","affiliation":[{"name":"Institute of Chemical Research of Catalonia (ICIQ) the Barcelona Institute of Science and Technology (BIST)  Tarragona Spain"},{"name":"ICREA  Barcelona Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8264-6854","authenticated-orcid":false,"given":"Rui","family":"Fausto","sequence":"additional","affiliation":[{"name":"University of Coimbra, CQC\u2010IMS, Department of Chemistry  Coimbra Portugal"},{"name":"Spectroscopy@IKU, Faculty Sciences and Letters, Department of Physics Istanbul Kultur University  Istanbul 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