Conformation-Engineered B←N Macrocycles: A New Paradigm for Metal-Free Photocatalytic H2O2 Production
Gaoyan Lan , Kaibang Chen , Borui Zhang , Furong Yuan , Chenxin Chen , Yixin Lai , Yu Zhang , Qingtao Tu , Banglin Chen , Huadan Chen , Shengchang Xiang , Zhangjing Zhang
Chinese Journal of Chemistry ›› 2026, Vol. 44 ›› Issue (15) : 2553 -2562.
Supramolecular macrocycles, despite their ubiquity in molecular recognition, have remained largely unexplored in photocatalysis due to their intrinsic lack of continuous π-conjugation and inefficient charge-carrier separation. Here, we report a conformational engineering strategy to integrate dynamic B←N dative bonds into highly active photocatalytic macrocyclic architectures. By simply switching the boronate linker from meta to para geometry, we control the rotational freedom of B←N bonds to yield two isomeric frameworks-twisted BNF-80 and planar BNF-81-with well-defined supramolecular macrocyclic building units, as unequivocally confirmed by single-crystal X-ray diffraction. The planarized conformation of BNF-81 enforces extended π-conjugation and continuous π-π stacking, leading to markedly enhanced charge separation efficiency and charge transfer. As a result, BNF-81 achieves an outstanding photocatalytic H2O2 production rate of 4275 μmol·g–1·h–1 under visible light in pure water without any sacrificial agent, outperforming previously reported B←N-based photocatalysts. This work establishes linker conformation driven control as a powerful design principle, unlocking the latent photocatalytic potential of supramolecular macrocycles and opening a new avenue for developing efficient metal-free photocatalysts.
Hydrogen peroxide production / Photocatalytic / Porous framework materials / Dative B←N bonds / Supramolecular macrocycles
2026 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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