{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,23]],"date-time":"2026-07-23T22:30:12Z","timestamp":1784845812841,"version":"3.55.0"},"reference-count":49,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2025,1,22]],"date-time":"2025-01-22T00:00:00Z","timestamp":1737504000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100010190","name":"Grand \u00c9quipement National De Calcul Intensif","doi-asserted-by":"publisher","award":["A0150810977"],"award-info":[{"award-number":["A0150810977"]}],"id":[{"id":"10.13039\/501100010190","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001665","name":"Agence Nationale de la Recherche","doi-asserted-by":"publisher","award":["ANR\u201019\u2010CE05\u20100020\u201002"],"award-info":[{"award-number":["ANR\u201019\u2010CE05\u20100020\u201002"]}],"id":[{"id":"10.13039\/501100001665","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["advanced.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Advanced Science"],"published-print":{"date-parts":[[2025,3]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    To efficiently capture, activate, and transform small molecules, metalloenzymes have evolved to integrate a well\u2010organized pocket around the active metal center. Within this cavity, second coordination sphere functionalities are precisely positioned to optimize the rate, selectivity, and energy cost of catalytic reactions. Inspired by this strategy, an artificial distal pocket defined by a preorganized 3D strap is introduced on an iron\u2010porphyrin catalyst (\n                    <jats:bold>sc\u2010Fe<\/jats:bold>\n                    ) for the CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010CO electrocatalytic reduction. Combined electrochemical, kinetic, and computational studies demonstrate that the adequate positioning of a carboxylate\/carboxylic group acting in synergy with a trapped water molecule within this distal pocket remarkably enhances the reaction turnover frequency (TOF) by four orders of magnitude compared to the perfluorinated iron\u2010tetraphenylporphyrin catalyst (\n                    <jats:bold>\n                      F\n                      <jats:sub>20<\/jats:sub>\n                      Fe\n                    <\/jats:bold>\n                    ) operating at a similar low overpotential. A proton\u2010coupled electron transfer (PCET) is found to be the key process responsible for the unexpected protonation of the coordinating carboxylate, which, upon CO\n                    <jats:sub>2<\/jats:sub>\n                    insertion, shifts from the first to the second coordination sphere to play a possible secondary role as a proton relay.\n                  <\/jats:p>","DOI":"10.1002\/advs.202500482","type":"journal-article","created":{"date-parts":[[2025,1,22]],"date-time":"2025-01-22T05:47:27Z","timestamp":1737524847000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO\n                    <sub>2<\/sub>\n                    Electroreduction at Low Overpotential"],"prefix":"10.1002","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6207-4430","authenticated-orcid":false,"given":"Adrien","family":"Smith","sequence":"first","affiliation":[{"name":"Universit\u00e9 Paris\u2010Saclay CNRS Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay  Orsay 91400 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2926-6016","authenticated-orcid":false,"given":"Philipp","family":"Gotico","sequence":"additional","affiliation":[{"name":"Institute for Integrative Biology of the Cell CEA CNRS Universit\u00e9 Paris\u2010Saclay  Gif\u2010sur\u2010Yvette 91191 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":"Universit\u00e9 Paris\u2010Saclay CNRS Institut de Chimie Mol\u00e9culaire et des 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