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In this work, we report a series of acetylene\u2010linked specialized donor\u2013acceptor (D\u2013A) type conjugated microporous polymers (CMPs) designed with tailored electronic structures to investigate their efficacy in photocatalytic CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction to methanol in an aqueous NaOH solution under visible light irradiation. Significantly, the optimized porous polymer TTT\u2010DEBP, featuring a strong electron\u2010accepting triazine ring and an extended \u03c0\u2010conjugated diethynyl biphenyl (DEBP) system, achieved a higher CH\n                    <jats:sub>3<\/jats:sub>\n                    OH production rate of 30.8\u00a0\u00b5mol\u00a0g\n                    <jats:sup>\u22121\u00a0<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    with 90.3% selectivity and excellent recyclability. Experimental and theoretical investigations revealed that the synergistic effect of triazine, biphenyl, and acetylene moieties of the porous network reduces exciton binding energy, enhancing charge separation and transfer, and reduces charge recombination for improved photocatalytic performance.\n                  <\/jats:p>","DOI":"10.1002\/anie.202511602","type":"journal-article","created":{"date-parts":[[2025,8,26]],"date-time":"2025-08-26T12:16:18Z","timestamp":1756210578000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Acetylene\u2010Linked Octupolar Conjugated Microporous Polymers for CO\n                    <sub>2<\/sub>\n                    Photoreduction to Methanol: Effect of Acceptor and \u03c0\u2010Bridge Modulation"],"prefix":"10.1002","volume":"64","author":[{"given":"Rupak","family":"Chatterjee","sequence":"first","affiliation":[{"name":"School of Materials Sciences Indian Association for the Cultivation of Science  Jadavpur, Kolkata 700032 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Samim","family":"Reza","sequence":"additional","affiliation":[{"name":"Department of Physics SRM University\u2010AP  Amaravati Andhra Pradesh 522 240 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Surajit","family":"Samui","sequence":"additional","affiliation":[{"name":"School of Materials Sciences Indian Association for the Cultivation of Science  Jadavpur, Kolkata 700032 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ranjit","family":"Thapa","sequence":"additional","affiliation":[{"name":"Department of Physics SRM University\u2010AP  Amaravati Andhra Pradesh 522 240 India"},{"name":"Centre for Computational and Integrative Sciences SRM University\u2010AP  Amaravati Andhra Pradesh 522, 240 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4907-7418","authenticated-orcid":false,"given":"Asim","family":"Bhaumik","sequence":"additional","affiliation":[{"name":"School of Materials Sciences Indian Association for the Cultivation of Science  Jadavpur, Kolkata 700032 India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,8,26]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"https:\/\/www.co2.earth\/daily\u2010co2. 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