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Here, we report a platinum(II) supramolecular system in which catalytic activity is uniquely associated with a far\u2010from\u2010equilibrium aggregate. The complex forms two emissive species: a kinetically trapped, orange\u2010emissive aggregate (\n                    <jats:bold>PtA<\/jats:bold>\n                    ), and a thermodynamically stable, blue\u2010emissive aggregate (\n                    <jats:bold>PtB<\/jats:bold>\n                    ). Only\n                    <jats:bold>PtA<\/jats:bold>\n                    is catalytically active, acting as a single\u2010component photocatalyst for hydrogen evolution in aqueous ascorbate without additional photosensitizers or co\u2010catalysts, whereas\n                    <jats:bold>PtB<\/jats:bold>\n                    is completely inactive.\n                  <\/jats:p>\n                  <jats:p>\n                    Continuous irradiation drives and maintains\n                    <jats:bold>PtA<\/jats:bold>\n                    in an active, out\u2010of\u2010equilibrium state by coupling energy input directly to photocatalytic turnover, thereby preventing its conversion into the inactive thermodynamic\n                    <jats:bold>PtB<\/jats:bold>\n                    form. Upon removal of light,\n                    <jats:bold>PtA<\/jats:bold>\n                    irreversibly relaxes to\n                    <jats:bold>PtB<\/jats:bold>\n                    , and all photocatalytic activity is lost.\n                  <\/jats:p>\n                  <jats:p>This system demonstrates how catalytic function can be confined to an out\u2010of\u2010equilibrium assembly and sustained only through ongoing energy dissipation.<\/jats:p>","DOI":"10.1002\/anie.9082267","type":"journal-article","created":{"date-parts":[[2026,3,10]],"date-time":"2026-03-10T09:13:03Z","timestamp":1773133983000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Out\u2010of\u2010Equilibrium Supramolecular Assembly Sustained by Photocatalysis"],"prefix":"10.1002","volume":"65","author":[{"given":"E.","family":"Pelorosso","sequence":"first","affiliation":[{"name":"Dipartimento Di Scienze Chimiche Universit\u00e0 degli Studi 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