12 Connecting Sites Linked Three-dimensional Covalent Organic Frameworks with Intrinsic Non-interpenetrated shp Topology for Photocatalytic HO Synthesis.

Developing high connectivity (>8) three-dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting high connectivity organic building blocks. This however represents the most important step towards promoting the diversity of COFs due to the still limited dynamic covalent bonds available for constructing COFs at this stage. Herein, highly connected phthalocyanine-based (Pc-based) 3D COFs MPc-THHI-COFs (M=H, Ni) were afforded from the reaction between 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine M(TAPc) (M=H, Ni) and 5,5',5'',5''',5'''',5'''''-(triphenylene-2,3,6,7,10,11-hexayl)hexa(isophthalohydrazide) (THHI) with 12 connecting sites. Powder X-ray diffraction analysis together with theoretical simulations and transmission electron microscopy reveals their crystalline nature with an unprecedented non-interpenetrated shp topology. Experimental and theoretical investigations disclose the broadened visible light absorption range and narrow optical band gap of MPc-THHI-COFs. This in combination with their 3D nanochannels endows them with efficient photocatalysis performance for HO generation from O and HO via 2e oxygen reduction reaction and 2e water oxidation reaction under visible-light irradiation (λ >400 nm). This work provides valuable result for the development of high connectivity functional COFs towards diverse application potentials.