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Herein, a heterobimetallic supramolecular catalyst (Fe\u2013Re SA) is constructed via electrostatic self\u2010assembly between a porphyrinic FeTCPP unit and a molecular Rebpy complex. Structural and spectroscopic analyses confirm that the Fe\u2013N\n                    <jats:sub>4<\/jats:sub>\n                    and Re(I) carbonyl coordination environments remain preserved after assembly, while density functional theory (DFT)\u2010supported interfacial charge redistribution induces an internal electric field that promotes directional charge transfer and suppresses carrier recombination. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals\n                    <jats:sup>*<\/jats:sup>\n                    CO\u2010related and C\u2013C coupling\u2010related features, supporting a tandem catalytic mechanism in which the Re site catalyzes CO generation and the Fe\u2010centered porphyrin promotes subsequent C\u2013C coupling. As a result, Fe\u2013Re SA exhibits enhanced photocatalytic CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction toward multicarbon products, achieving a C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    formation rate of 4967 \u00b5mol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    \u00a0h\n                    <jats:sup>\u22121<\/jats:sup>\n                    with a total C\n                    <jats:sub>2<\/jats:sub>\n                    selectivity of 57.2% (C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    selectivity of 47.5%) among carbon\u2010containing products. The catalyst also maintains decent activity under low CO\n                    <jats:sub>2<\/jats:sub>\n                    concentration (3% CO\n                    <jats:sub>2<\/jats:sub>\n                    in Ar) and under natural sunlight irradiation, highlighting its potential for practical solar\u2010driven CO\n                    <jats:sub>2<\/jats:sub>\n                    conversion.\n                  <\/jats:p>","DOI":"10.1002\/smll.76055","type":"journal-article","created":{"date-parts":[[2026,10,4]],"date-time":"2026-10-04T13:33:47Z","timestamp":1791120827000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Internal Electric Field\u2010Regulated Dual\u2010Site Fe\u2013Re Supramolecular Assembly for Photocatalytic CO\n                    <sub>2<\/sub>\n                    Reduction Toward Multicarbon Products"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0000-2099-3167","authenticated-orcid":false,"given":"Yajia","family":"Tian","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing P. 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China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xianjun","family":"Yin","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kefan","family":"Zhang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing Advanced Innovation Center for Soft Matter Science and Engineering College of Chemistry Beijing University of Chemical Technology  Beijing P. R. 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