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Here, we designed two amino\u2010functionalized, tetrafunctional nickel tetraaza[14]annulene (TAA) building blocks and incorporated them into two\u2010dimensional COFs. Notably, the peripheral benzene rings of the TAA moiety bear abundant proximal sites amenable to modification, allowing facile tuning of the central nickel ion's electronic state. To investigate the positional effect of substituents, we constructed a pair of isomeric COFs containing the same number of fluorine atoms either at proximal or distal positions. Combined experimental and computational studies reveal that proximal fluorination more effectively reduces electron density at the nickel sites and enhances electron affinity, substantially improving electrocatalytic oxygen evolution reaction (OER) performance. Consequently, the optimized COF achieves an overpotential of 380\u00a0mV at 10\u00a0mA\u00a0cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    , significantly outperforming its distal\u2010fluorine and fluorine\u2010free counterparts. This work establishes metal TAA macrocycles as a new class of building blocks for metal\u2010based COFs and demonstrates that precise substituent positioning is an effective strategy for modulating the electronic structure and catalytic performance of crystalline framework materials.\n                  <\/jats:p>","DOI":"10.1002\/anie.4973178","type":"journal-article","created":{"date-parts":[[2026,7,21]],"date-time":"2026-07-21T19:25:36Z","timestamp":1784661936000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Substituent Variation in Tetraaza[14]Annulene\u2010Based Covalent Organic Frameworks for Modulation of Electronic States"],"prefix":"10.1002","volume":"65","author":[{"given":"Yaoqian","family":"Feng","sequence":"first","affiliation":[{"name":"State Key Laboratory of Silicon and Advanced Semiconductor Materials Department of Polymer Science and Engineering Zhejiang University  Hangzhou 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