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  • Title: "Tree"-like Multidentate Ligand-Assisted Synthesis of Polymolybdate-Based Architectures with Multinuclear Metal Clusters: Supercapacitor and Electrochemical Sensing Performances.
    Author: Chen Y, Chang Z, Zhang Y, Chen K, Wang X.
    Journal: Inorg Chem; 2022 Oct 10; 61(40):16020-16027. PubMed ID: 36177812.
    Abstract:
    In this work, aiming for constructing multinuclear metal cluster-modified polymolybdate-based architectures with novel conformation, the "tree"-like multidentate ligand 5-(3-pyridyl)-1H-tetrazole) (3-ptzH) is introduced into the polymolybdate reaction system. Three new polymolybdate-based architectures with various multinuclear metal clusters, H4[Cu6(μ3-OH)2(3-ptz)6(γ-Mo8O28) (H2O)2]·2H2O (BOHU-1), H2[Ag4(3-ptz)2(Mo8O26)] (BOHU-2), and H4[Cu5(3-ptzH)2(3-ptz)2(MnMo9O32)2(H2O)4] (BOHU-3) (BOHU = Bohai University), have been prepared via the hydrothermal method and structurally characterized. In BOHU-1, a kind of pentanuclear copper cluster unit: [Cu5(μ3-OH)2(3-ptz)6]2+ is formed, which connects to construct a one-dimensional (1D) cluster-based chain. The 1D chains are extended to a two-dimensional (2D) layer via the Cu ions, which are further linked by the 4-connected [γ-Mo8O28]8- anions to build a three-dimensional (3D) framework. In BOHU-2, when a AgI ion was used as the central metal, the 3-ptz adopts different coordination modes to link the Ag ions, forming hexanuclear [Ag6(3-ptz)4]2+ cluster and finally 1D chains. These 1D cluster-based chains are connected by the 6-connected [γ-Mo8O26]4- anions to establish a 2D layer, which is further extended by [Mo8O26]n4n- 1D chains to a 3D framework. For BOHU-3, the chiral [MnMo9O32]6- anions are introduced and coordinated with the Cu ions to build left- and right-handed 1D chains, which are connected via the [Cu3(3-ptz)4]2+ cluster to form a 1D ladder-like chain. The effects of 3-ptz on the formation of multinuclear clusters, as well as the metals and polymolybdates on the multinuclear clusters and final structures of BOHU-1∼3, are discussed. The electrochemical performances of BOHU-1∼3 as electrode materials for supercapacitors and electrochemical sensors are investigated.
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