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Atomically precise metal clusters are attractive as highly efficient catalysts, but suffer from continuous efficiency deactivation in the catalytic process. Here, we report the development of an efficient strategy that enhances catalytic performance by electropolymerization (EP) of metal clusters into hybrid materials. Based on carbazole ligand protection, three polymerized metal‐cluster hybrid materials, namely Poly‐Cu14cba, Poly‐Cu6Au6cbz and Poly‐Cu6Ag4cbz, were prepared. Compared with isolated metal clusters, metal clusters immobilizing on a biscarbazole network after EP significantly improved their electron‐transfer ability and long‐term recyclability, resulting in higher catalytic performance. As a proof‐of‐concept, Poly‐Cu14cba was evaluated as an electrocatalyst for reducing nitrate (NO3−) to ammonia (NH3), which exhibited ≈4‐fold NH3 yield rate and ≈2‐fold Faraday efficiency enhancement compared to that of Cu14cba with good durability. Similarly, Poly‐Cu6Au6cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart. [ABSTRACT FROM AUTHOR]

A series of polyoxometalate (POM)-based metal–organic complexes containing multinuclear Cu(ii) clusters with a 4-amino-1,2,4-triazole (4-atrz) ligand, namely, [Cu3(4-atrz)8(PMo12O40)2(H2O)2]·2H2O (1), [Cu2(4-atrz)6(SiW12O40)(H2O)]·6H2O (2), [Cu2(4-atrz)4(μ2-OH)(CrMo6(OH)6O18)]·3H2O (3), [Cu3(4-atrz)3(Mo8O27)(H2O)4]·6H2O (4) and [Cu3(4-atrz)3(V10O30)0.5(μ3-OH)(H2O)]·H2O (5) have been synthesized by selectively adding additional citric acid or boric acid under hydrothermal conditions and have been structurally characterized by single-crystal X-ray diffraction and powder X-ray diffraction. Compound 1 has a zero-dimensional (0D) architecture, which is constructed from a linear trinuclear cluster [Cu3(4-atrz)8(H2O)2]6+ and two Keggin PMo12O403− anions. Compound 2 shows a 1D zigzag chain, in which the binuclear [Cu2(4-atrz)6(H2O)]4+ clusters and Keggin SiW12O404− anions connect to each other. Compound 3 is a 1D linear chain based on linear [Cu3(4-atrz)6]6+ clusters; the [CrMo6(OH)6O18]3− anions hang on two sides of the 1D chain. Compound 4 has a 2D layer constructed from trigonal [Cu3(4-atrz)3(H2O)4]6+ clusters and rare infinite [Mo8O27]n6n− chains. The [Mo8O27]6− anion is transformed from the Anderson-type [CoMo6(OH)6O18]3− anion, which is also rare in the POM-based reaction system. Compound 5 has a 3D framework constructed from trigonal trinuclear [Cu3(4-atrz)3(OH)]5+ clusters and rare [V10O30]10− polyanions, which represents the first example of a V10O30-based 3D metal–organic complex. Structural analyses indicate that different POMs show great effect on the various structures of 1–5 and the additional acids play an important role in the formation of 1–5. Photocatalytic experiments of 1–5 on degradation of three organic dyes (methylene blue, Rhodamine B and methyl orange) manifest that compounds 1–3 are good candidates for the photocatalytic degradation of methylene blue, and compound 1 is a good photocatalyst for the degradation of Rhodamine B. [ABSTRACT FROM AUTHOR]