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Herein, we strategically employ tritopic borate ligands bearing terminal \u2013Br substituents, rather than their ditopic counterparts, as precursors to construct a single\u2010crystalline COP (\n                    <jats:bold>JNP\u20107<\/jats:bold>\n                    ) featuring polycatenane\u2010like topological junctions. Specifically, B\u2010centered Lewis acceptors and N\u2010donor units initially assemble into 1D nanoribbons via dative B\u2190N linkages. By leveraging inter\u2010nanoribbon halogen\u00b7\u00b7\u00b7halogen interactions between the semi\u2010interlocked Br\u2010containing motifs, the architecture is further extended into 2D arrays, thereby elevating the geometric dimensionality of\n                    <jats:bold>JNP\u20107<\/jats:bold>\n                    . Critically, the resulting polycatenated halogen\u2010bonded network imparts exceptional structural rigidity, and the dative B\u2190N motifs are found to concurrently promote visible\u2010light harvesting and facilitate charge\u2010carrier migration. Consequently,\n                    <jats:bold>JNP\u20107<\/jats:bold>\n                    enables highly efficient H\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    production via both the oxygen reduction reaction (ORR) and water oxidation reaction (WOR) under ambient sunlight, operating without sacrificial agents, photosensitizers, or metal cocatalysts, and outperforming state\u2010of\u2010the\u2010art covalent organic frameworks (COFs) and metal\u2010organic frameworks (MOFs) in terms of photocatalytic activity and apparent quantum yield (AQY). By aligning molecular topology with catalytic function, this work establishes a generalizable framework for the rational development of topologically sophisticated, high\u2010performance COP systems.\n                  <\/jats:p>","DOI":"10.1002\/anie.8903215","type":"journal-article","created":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T03:58:14Z","timestamp":1790827094000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["A Polycatenane\u2011Topological Covalent Organic Polymer for High\u2011Performance Photocatalytic H\n                    <sub>2<\/sub>\n                    O\n                    <sub>2<\/sub>\n                    Production"],"prefix":"10.1002","author":[{"given":"Wen","family":"Yao","sequence":"first","affiliation":[{"name":"State Key Laboratory of Bioactive Molecules and Druggability Assessment Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs College of Chemistry and Materials Science Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry Jinan University  Guangzhou P. 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