Three hybrid networks based on octamolybdate building units, CuI8BBTZ6[(α-Mo8O26)(β-Mo8O26)] (1), (CuIBBTZ)4[Mo7CuIIO24(H2O)2]·6H2O (2), and CuIICuI2BBTZ5[β-Mo8O26] (3) (BBTZ = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), have been synthesized under ionothermal conditions and structurally characterized by single-crystal X-ray diffraction. 1 exhibits a rare 3D three-fold self-penetration network (SPN) structure, in which the interpenetrating polymer networks (IPN) formed by α-Mo8O26 units, CuI ions and BBTZ ligands are united by β-Mo8O26 units. 2 shows a classic 103-utp net built by transition-metal monosubstitution octamolybdate β-Mo7CuO26, CuI and BBTZ ligands. 3 displays an interesting interpenetrating network (IPN) structure formed by 2D poly-rings layers and 3D NaCl topology framework. IR, TG, and electrochemical studies were also conducted to further authenticate the identities of these compounds. Photocatalytic investigation indicates that compounds 1–3 are active for photocatalytic H2 evolution under UV irradiation.
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