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Covalent organic frameworks (COFs) offer a versatile molecular platform for photocatalysis, while constructing efficient charge transfer pathways in COFs to achieve directional transport of photoexcited electrons and enhance photocatalytic performance remains highly challenging. Here, to address this limitation, a new strategy are proposed by incorporating phenanthroline motifs with rigid, conjugated skeletons into 2D triazine\u2010based COFs to enhance charge transfer pathways. Structural and spectroscopic analyses reveal that benzene \u03c0\u2010bridges in COF structures activate confined \u03c0\u2010electrons in the phenanthroline core, establishing a directional \u03c0\n                    <jats:sub>D<\/jats:sub>\n                    \u2010\u03c0\u2010A electron transfer pathway. This engineered charge transport system significantly accelerates photocurrent generation and markedly enhances electron mobility. The optimized material achieves an exceptional H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    production rate of 40.1\u00a0mmol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    under sacrificial conditions, representing a 4.8\u2010fold enhancement over the original COF. The system's versatility is further demonstrated through the complete oxidation of methyl phenyl sulfide within 2\u00a0h, with similar efficiency across diverse sulfide derivatives. These findings establish phenanthroline\u2010incorporated COFs as a promising class of photocatalysts for both photocatalytic H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    production and organic transformations.\n                  <\/jats:p>","DOI":"10.1002\/smll.202512201","type":"journal-article","created":{"date-parts":[[2025,12,8]],"date-time":"2025-12-08T11:10:39Z","timestamp":1765192239000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Unlocking Electronic Confinement in Phenanthroline\u2010\u03c0\u2010Bridged Covalent Organic Frameworks Enables Efficient Photocatalytic H\n                    <sub>2<\/sub>\n                    O\n                    <sub>2<\/sub>\n                    Generation and Oxidation of 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