{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T07:55:32Z","timestamp":1790668532036,"version":"4.1.0"},"reference-count":75,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T00:00:00Z","timestamp":1790640000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"},{"start":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T00:00:00Z","timestamp":1790640000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100004794","name":"Centre National de la Recherche Scientifique","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100004794","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001665","name":"Agence Nationale de la Recherche","doi-asserted-by":"publisher","award":["ANR\u201011\u2010IDEX\u20100003\u201002"],"award-info":[{"award-number":["ANR\u201011\u2010IDEX\u20100003\u201002"]}],"id":[{"id":"10.13039\/501100001665","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The activation and reduction of molecular oxygen at transition metal centers are central to both enzymatic catalysis and energy conversion. Here, we report the first direct observation of a hydrogen\u2010bonding\u2010assisted, quasi\u2010reversible superoxo (Fe\n                    <jats:sup>III<\/jats:sup>\n                    \u2500O\n                    <jats:sub>2<\/jats:sub>\n                    \u02d9\u02c9)\/peroxo (Fe\n                    <jats:sup>III<\/jats:sup>\n                    \u2500O\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>2<\/jats:sup>\n                    \u02c9) redox couple in a heme model complex using conventional cyclic voltammetry. Urea groups installed in the second coordination sphere (SCS) of an iron\u2010porphyrin (\n                    <jats:bold>\n                      <jats:italic>\u03b1\u03b1<\/jats:italic>\n                      UrFe\n                    <\/jats:bold>\n                    ) form a hydrogen\u2010bonding network that stabilizes the Fe\n                    <jats:sup>III<\/jats:sup>\n                    \u2500O\n                    <jats:sub>2<\/jats:sub>\n                    \u02d9\u02c9 intermediate through interaction with a trapped water molecule. Spectroscopic studies and DFT calculations reveal that one\u2010electron reduction of the low\u2010spin end\u2010on Fe\n                    <jats:sup>III<\/jats:sup>\n                    \u2500O\n                    <jats:sub>2<\/jats:sub>\n                    \u02d9\u02c9 species generates a low\u2010spin end\u2010on Fe\n                    <jats:sup>III<\/jats:sup>\n                    \u2500O\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>2<\/jats:sup>\n                    \u02c9 adduct with minimal structural reorganization. These findings provide the first synthetic demonstration of a biologically relevant end\u2010on peroxo species stabilized by hydrogen\u2010bonding \u201cpull effect\u201d in the SCS and highlight the critical role of second\u2010sphere interactions in modulating O\n                    <jats:sub>2<\/jats:sub>\n                    activation pathways in bioinspired catalysts.\n                  <\/jats:p>","DOI":"10.1002\/chem.71748","type":"journal-article","created":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T07:06:20Z","timestamp":1790665580000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Direct Observation of a Hydrogen\u2010Bonding Assisted Quasi\u2010Reversible Superoxo\/Peroxo Interconversion in a Heme Model"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4495-4469","authenticated-orcid":false,"given":"Adelais","family":"Trapali","sequence":"first","affiliation":[{"name":"CNRS, Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris\u2010Saclay Orsay France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9003-0670","authenticated-orcid":false,"given":"R\u00e9gis","family":"Guillot","sequence":"additional","affiliation":[{"name":"CNRS, Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris\u2010Saclay Orsay France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2113-4625","authenticated-orcid":false,"given":"Christian","family":"Herrero","sequence":"additional","affiliation":[{"name":"CNRS, Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris\u2010Saclay Orsay France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6466-8830","authenticated-orcid":false,"given":"Sylvain","family":"Bertaina","sequence":"additional","affiliation":[{"name":"CNRS, IM2NP, UMR 7334 Aix\u2010Marseille Universit\u00e9  Marseille France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5682-2968","authenticated-orcid":false,"given":"Athanassios","family":"Coutsolelos","sequence":"additional","affiliation":[{"name":"Chemistry Department, Laboratory of Bioinorganic Chemistry University of Crete  Heraklion Greece"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9317-8005","authenticated-orcid":false,"given":"Maylis","family":"Orio","sequence":"additional","affiliation":[{"name":"CNRS, Centrale Med, iSm2 Aix\u2010Marseille Universit\u00e9 Marseille France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3080-9727","authenticated-orcid":false,"given":"Zakaria","family":"Halime","sequence":"additional","affiliation":[{"name":"CNRS, Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris\u2010Saclay Orsay France"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,29]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00220"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00299"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0680639"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00462"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1088\/0953\u20108984\/19\/44\/445010"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00407"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201106166"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/fsn3.3784"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr400415k"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9500500"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0307143"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900121s"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.trechm.2021.10.008"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9SC04388H"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9DT00136K"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00074"},{"key":"e_1_2_7_18_1","doi-asserted-by":"crossref","first-page":"283","DOI":"10.1002\/9781118094365.ch9","volume-title":"Copper\u2010Oxygen Chemistry","author":"Halime Z.","year":"2011"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9020993"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1038\/463168a"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c09566"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar9001685"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0122391"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021\u20109258(18)41536\u20100"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja992425v"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202004977"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja1001955"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202013791"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200904572"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b12571"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.0c01379"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b01804"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202010859"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b13654"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c02972"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.71.4.1326"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200390096"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja028548o"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c13552"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c02836"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc35162e"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00212"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b03329"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9006668"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.9b02079"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b01516"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b03157"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.4c00371"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b13756"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinorgbio.2024.112776"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic0105866"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b02640"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2012.11.011"},{"key":"e_1_2_7_54_1","doi-asserted-by":"publisher","DOI":"10.1142\/S108842461550025X"},{"key":"e_1_2_7_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00533a009"},{"key":"e_1_2_7_56_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr940053x"},{"key":"e_1_2_7_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja953694y"},{"key":"e_1_2_7_58_1","doi-asserted-by":"crossref","first-page":"47","DOI":"10.15227\/orgsyn.033.0047","article-title":"1,5\u2010Naphthalenedithiol","volume":"33","author":"Caesar P. D.","year":"1953","journal-title":"Organic Synthesis"},{"key":"e_1_2_7_59_1","unstructured":"G. M.Sheldrick SHELXS\u201097 Program for Crystal Structure Solution (University of G\u00f6ttingen 1997)."},{"key":"e_1_2_7_60_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"},{"key":"e_1_2_7_61_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889899006020"},{"key":"e_1_2_7_62_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jmr.2005.08.013"},{"key":"e_1_2_7_63_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1626543"},{"key":"e_1_2_7_64_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.10318"},{"key":"e_1_2_7_65_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.6b01041"},{"key":"e_1_2_7_66_1","doi-asserted-by":"crossref","first-page":"4597","DOI":"10.1063\/1.466059","article-title":"Relativistic Regular Two\u2010component Hamiltonians","volume":"99","author":"Lenthe E.","year":"1993","journal-title":"Journal of Chemical Physics"},{"key":"e_1_2_7_67_1","doi-asserted-by":"crossref","first-page":"9783","DOI":"10.1063\/1.467943","article-title":"Relativistic Total Energy Using Regular Approximations","volume":"101","author":"Lenthe E.","year":"1994","journal-title":"Journal of Chemical Physics"},{"key":"e_1_2_7_68_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct800047t"},{"key":"e_1_2_7_69_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct900090f"},{"key":"e_1_2_7_70_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3382344"},{"key":"e_1_2_7_71_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.21759"},{"key":"e_1_2_7_72_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.440939"},{"key":"e_1_2_7_73_1","first-page":"423","article-title":"Density\u2010Functional Theory of Spin Polarization and Spin Coupling in Iron\u2014Sulfur Clusters","volume":"38","author":"Noodleman L.","year":"1992","journal-title":"Advances in Inorganic Chemistry"},{"key":"e_1_2_7_74_1","doi-asserted-by":"publisher","DOI":"10.1016\/0301\u20100104(86)80192\u20106"},{"key":"e_1_2_7_75_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp9716997"},{"key":"e_1_2_7_76_1","unstructured":"Chemcraft\u2014graphical software for visualization of quantum chemistry computations. G. A. Andrienko Version 1.8 build 682 https:\/\/www.chemcraftprog.com."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.71748","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.71748","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.71748","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T07:06:23Z","timestamp":1790665583000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.71748"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,29]]},"references-count":75,"alternative-id":["10.1002\/chem.71748"],"URL":"https:\/\/doi.org\/10.1002\/chem.71748","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,29]]},"assertion":[{"value":"2026-07-16","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-23","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-29","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e71748"}}