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A particular example is the <jats:italic>C<\/jats:italic>\u2010phenyl\u2010nitrilimine, which exists as two energy minima that constitute bond\u2010shift isomers. To examine the effect of substituents in the phenyl ring, here we investigate the <jats:italic>meta<\/jats:italic> and <jats:italic>para<\/jats:italic> OH substituted derivatives. These two nitrile imines were generated in an argon matrix by UV\u2010irradiation of 2<jats:italic>H<\/jats:italic>\u2010tetrazole precursors and found to photoisomerize to carbodiimides <jats:italic>via<\/jats:italic> 1<jats:italic>H<\/jats:italic>\u2010diazirines. The different effects of the OH substitution in <jats:italic>meta<\/jats:italic> and <jats:italic>para<\/jats:italic> positions on the bond\u2010shift isomerism are rationalized with the support of Natural Resonance Theory and Hirshfeld atomic charges. The understanding of how substitution affects the structural characteristics of <jats:italic>C<\/jats:italic>\u2010phenyl\u2010nitrilimines, opens a door to modulate the chemistry of those compounds (<jats:italic>e.\u2009g<\/jats:italic>. in cycloaddition reactions) by appropriate tuning of their substitution (substituent type and position).<\/jats:p>","DOI":"10.1002\/ejoc.202300310","type":"journal-article","created":{"date-parts":[[2023,5,2]],"date-time":"2023-05-02T04:10:06Z","timestamp":1683000606000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["The <i>meta<\/i> and <i>para<\/i> OH Substitution Effect on <i>C<\/i>\u2010Phenyl\u2010Nitrilimine Bond\u2010Shift Isomers"],"prefix":"10.1002","volume":"26","author":[{"given":"Gil A.","family":"Ferreira","sequence":"first","affiliation":[{"name":"University of Coimbra CQC-IMS Department of Chemistry  3004-535 Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8511-1230","authenticated-orcid":false,"given":"Cl\u00e1udio M.","family":"Nunes","sequence":"additional","affiliation":[{"name":"University of Coimbra CQC-IMS Department of Chemistry  3004-535 Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5953-976X","authenticated-orcid":false,"given":"A. J.","family":"Lopes Jesus","sequence":"additional","affiliation":[{"name":"University of Coimbra CQC-IMS Faculty of Pharmacy  3000-548 Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8264-6854","authenticated-orcid":false,"given":"Rui","family":"Fausto","sequence":"additional","affiliation":[{"name":"University of Coimbra CQC-IMS Department of Chemistry  3004-535 Coimbra Portugal"},{"name":"Istanbul Kultur University Faculty Sciences and Letters Department of Physics  34158 Bakirkoy Istanbul Turkey"}]}],"member":"311","published-online":{"date-parts":[[2023,6,14]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo01088a034"},{"key":"e_1_2_8_2_1","doi-asserted-by":"crossref","unstructured":"C. Jamieson K. Livingstone The Nitrile Imine 1 3-Dipole: Properties Reactivity and Applications; Springer Cham 2020.","DOI":"10.1007\/978-3-030-43481-6"},{"key":"e_1_2_8_3_1","unstructured":"J.\u2005T. 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As our optical parametric oscillator has an intrinsic blind spot in the 370\u2013340\u2005nm region we carried out UV-irradiations at 330\u2005nm."},{"key":"#cr-split#-e_1_2_8_36_1.1","unstructured":"Note: (i) The most distinctive IR absorptions of3pare computed at 1814 [\u03bd(C=N)] 1616 [\u03bd(ring)] 1510 [\u03b4(CH) \u03bd(CO) and \u03bd(CCD)"},{"key":"#cr-split#-e_1_2_8_36_1.2","unstructured":"\"CD\" refers to the carbon atom of the diazirine fragment] 1268 [\u03bd(CO)] 1162 [\u03bd(ring) \u03b4(OH) and \u03b4(CH)] and 833 [\u03b3(CH)] cm\u22121 in good agreement with the experiment most intense bands observed at 1785 1615 1515 1273 1163 and 839\u2005cm\u22121 respectively. (ii) The most prominent IR bands4pare computed at 2117 [\u03bdas(NCN)] 1515 [\u03bd(ring) \u03b4(CH)] 1253 [\u03bd(CO)] 1164 [\u03b4(OH) \u03b4(CH)] and 884 [\u03b4(NH)] cm\u22121 in good agreement with the experimental most intense bands observed at 2152\/2119 1520 1265 1171 and 864\/855\u2005cm\u22121 respectively."},{"key":"#cr-split#-e_1_2_8_37_1.1","unstructured":"Note: (i) The most characteristic IR absorptions of3mare computed at 1817 [\u03bd(C=N)] 1453 [\u03bd(ring) \u03b4(CH)] 1267 [\u03bd(CO)] and 1169\u2005cm\u22121[\u03b4(OH)] in good agreement with the experimental most intense bands observed at 1787 1460 1275 and 1170\u2005cm\u22121 respectively."},{"key":"#cr-split#-e_1_2_8_37_1.2","unstructured":"(ii) The most distinctive IR absorptions of4mare computed at 2117 [\u03bdas(NCN)] 1607 [\u03bd(ring)] and 866\u2005cm\u22121[\u03b4(NH)] in agreement with the experimental most intense bands observed at 2138 1598 and 868\u2005cm\u22121 respectively."},{"key":"e_1_2_8_38_1","doi-asserted-by":"crossref","unstructured":"Following our previous finding on vibrationally excitation chemistry (see ref. 38a) we have also tried to interconvert2m\u2009Pand2mAby near-IR irradiations at the frequencies of their 2\u03bd(OH) and 2\u03bd(NH) overtone modes but no changes were observed. (38a) R. Fausto G.\u2005O. Ildiz C.\u2005M. Nunes Chem. Soc. Rev.2022 51 2853\u20132872.","DOI":"10.1039\/D1CS01026C"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF00549096"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.8b02740"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4901898"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.5b00443"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.8b02908"},{"key":"e_1_2_8_44_1","unstructured":"F.\u2005A. Carey R.\u2005J. Sundberg Advanced Organic Chemistry Part A: Structure and Mechanisms 4th ed. Kluwer Academics \/ Plenum Publishers New York 2000."},{"key":"e_1_2_8_45_1","unstructured":"Gaussian 09 Revision C.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone G.\u2005A. Petersson H. Nakatsuji X. Li M. Caricato A. 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Weinhold Theoretical Chemistry Institute University of Wisconsin Madison WI 2013."}],"container-title":["European Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejoc.202300310","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T12:08:26Z","timestamp":1760530106000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/ejoc.202300310"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,6,14]]},"references-count":65,"journal-issue":{"issue":"27","published-print":{"date-parts":[[2023,7,17]]}},"alternative-id":["10.1002\/ejoc.202300310"],"URL":"https:\/\/doi.org\/10.1002\/ejoc.202300310","archive":["Portico"],"relation":{},"ISSN":["1434-193X","1099-0690"],"issn-type":[{"type":"print","value":"1434-193X"},{"type":"electronic","value":"1099-0690"}],"subject":[],"published":{"date-parts":[[2023,6,14]]},"assertion":[{"value":"2023-04-05","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-06-14","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202300310"}}