"Tree"-like Multidentate Ligand-Assisted Synthesis of Polymolybdate-Based Architectures with Multinuclear Metal...

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 Ag^I 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]⁴ 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.