{Cu8} Cluster-Sandwiched Polyoxotungstates and Their Polymers: Syntheses, Structures, and Properties

Four inorganic-organic hybrid octa-Cu cluster sandwiched polyoxotungstates (POTs), [Cu₈(H₂O)₂(en)₄(B-α-H₂SiW₉O₃₄)₂] (1), [Cu₈(H₂O)₂(en)₄(B-α-H₂GeW₉O₃₄)₂] (2), K₂[Cu₈(en)₄(B-α-HSiW₉O₃₄)₂]·6H₂O (3), and K₂[Cu₈(en)₄(B-α-HGeW₉O₃₄)₂]·2H₂O (4) (en = ethylenediamine), were hydrothermally made and characterized by single-crystal X-ray diffraction, infrared spectra, powder X-ray diffraction, and thermogravimetric analysis, respectively. Structure analysis reveals that the polyoxoanion of 1/2 is a discrete dimer built by two trivalent Keggin [B-α-XW₉O₃₄]^10- (X = Si/Ge) fragments and one octa-Cu cluster, whereas 3 and 4 display a two-dimensional network built by octa-Cu-sandwiched POT units via substitution of coordinated water on polyanions of 1 and 2 and further expand into a three-dimensional framework via K cation bridges. Ultraviolet-visible diffuse reflectance spectra reveal that 1-4 are potential semiconductor materials. Moreover, its visible light-driven catalytic H₂ evolution activity, electrochemical properties, catalysis for oxygenation reactions of thioethers, and magnetic behaviors have been investigated in detail.