{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T13:55:04Z","timestamp":1790690104178,"version":"4.1.0"},"reference-count":73,"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:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"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\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22471196"],"award-info":[{"award-number":["22471196"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22171214"],"award-info":[{"award-number":["22171214"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["advanced.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Advanced Materials"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Near\u2010infrared (NIR)\u2010driven CO\n                    <jats:sub>2<\/jats:sub>\n                    photoreduction to multi\u2010carbon products remains highly challenging because effective utilization of low\u2010energy NIR photons requires not only extended light harvesting but also efficient charge separation and transport, structural robustness, and accessible sites for C\u2013C coupling. Although several bismuth halides exhibit narrow bandgaps and NIR absorption, translating such optical response into productive NIR photochemistry remains largely unexplored. Herein, we construct a covalent\u2010linked bismuth iodide framework, BiI(tadt) (tadt = 1,3,4\u2010thiadiazole\u20102,5\u2010dithiolate), in which Bi\u2013S covalent bonds bridge dimeric [Bi\n                    <jats:sub>2<\/jats:sub>\n                    I\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>4+<\/jats:sup>\n                    clusters with \u03c0\u2010conjugated tadt ligands to form an electronically delocalized framework. The Bi\u2013S linkages enhance structural robustness, facilitate inorganic\u2013organic orbital hybridization, and extend light absorption into the NIR region with a narrow bandgap of 1.44\u00a0eV. Photophysical studies and theoretical calculations reveal that linkage\u2010mediated electronic coupling promotes carrier transport and NIR response, while adjacent Bi\n                    <jats:sup>3+<\/jats:sup>\n                    sites within [Bi\n                    <jats:sub>2<\/jats:sub>\n                    I\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>4+<\/jats:sup>\n                    clusters facilitate *CO coupling and stabilize key *OCCO intermediates. Consequently, single\u2010component BiI(tadt) achieves NIR\u2010driven CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010C\n                    <jats:sub>2<\/jats:sub>\n                    photoreduction in aqueous solution with an apparent quantum yield of 0.14% at 750(\u00b1 15) nm. This work demonstrates that covalent engineering of inorganic\u2013organic connectivity bridges NIR absorption and productive multi\u2010electron photochemistry, providing a design principle for lead\u2010free metal halide photocatalysts utilizing low\u2010energy solar photons.\n                  <\/jats:p>","DOI":"10.1002\/adma.75198","type":"journal-article","created":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T12:56:40Z","timestamp":1790686600000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Covalent Linkage Engineering of a Bismuth Iodide Framework for Near\u2010Infrared\u2010Driven CO\n                    <sub>2<\/sub>\n                    \u2010to\u2010C\n                    <sub>2<\/sub>\n                    Photoreduction in Aqueous Solution"],"prefix":"10.1002","author":[{"given":"Ziyi","family":"Wang","sequence":"first","affiliation":[{"name":"Shanghai Key Laboratory of Chemical Assessment and Sustainability School of Chemical Science and Engineering Tongji University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yukong","family":"Li","sequence":"additional","affiliation":[{"name":"Shanghai Key Laboratory of Chemical Assessment and Sustainability School of Chemical Science and Engineering Tongji University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yilin","family":"Jiang","sequence":"additional","affiliation":[{"name":"Shanghai Key Laboratory of Chemical Assessment and Sustainability School of Chemical Science and Engineering Tongji University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1353-9921","authenticated-orcid":false,"given":"Honghan","family":"Fei","sequence":"additional","affiliation":[{"name":"Shanghai Key Laboratory of Chemical Assessment and Sustainability School of Chemical Science and Engineering Tongji University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,29]]},"reference":[{"issue":"35","key":"e_1_2_8_2_1","doi-asserted-by":"crossref","DOI":"10.1002\/adma.202405825","article-title":"Achieving Almost 100% Selectivity in Photocatalytic CO2 Reduction to Methane via in\u2010Situ Atmosphere Regulation Strategy","volume":"36","author":"Zhang W.","year":"2024","journal-title":"Advanced Materials"},{"issue":"15","key":"e_1_2_8_3_1","doi-asserted-by":"crossref","DOI":"10.1002\/ange.202217565","article-title":"Metal\u2013Organic Frameworks for Photocatalytic Water Splitting and CO2 Reduction","volume":"135","author":"Sun K.","year":"2023","journal-title":"Angewandte Chemie"},{"issue":"5","key":"e_1_2_8_4_1","doi-asserted-by":"crossref","first-page":"1004","DOI":"10.1016\/j.joule.2018.02.019","article-title":"Infrared Light\u2010Driven CO2 Overall Splitting at Room Temperature","volume":"2","author":"Liang L.","year":"2018","journal-title":"Joule"},{"issue":"5","key":"e_1_2_8_5_1","doi-asserted-by":"crossref","first-page":"653","DOI":"10.1021\/acscentsci.0c00325","article-title":"Broad\u2010Spectral\u2010Response Photocatalysts for CO2 Reduction","volume":"6","author":"Jiao X.","year":"2020","journal-title":"ACS Central Science"},{"issue":"1","key":"e_1_2_8_6_1","doi-asserted-by":"crossref","first-page":"423","DOI":"10.1021\/jacs.8b10692","article-title":"Ultrathin Conductor Enabling Efficient IR Light CO2 Reduction","volume":"141","author":"Li X.","year":"2018","journal-title":"Journal of the American Chemical Society"},{"issue":"3","key":"e_1_2_8_7_1","doi-asserted-by":"crossref","first-page":"1218","DOI":"10.1021\/jacs.1c10110","article-title":"Large \u03c0\u2010Conjugated Metal\u2013Organic Frameworks for Infrared\u2010Light\u2010Driven CO2 Reduction","volume":"144","author":"Zeng J. 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