Publication | Closed Access
{Cu<sub>8</sub>} Cluster-Sandwiched Polyoxotungstates and Their Polymers: Syntheses, Structures, and Properties
16
Citations
56
References
2021
Year
Four inorganic-organic hybrid octa-Cu cluster sandwiched polyoxotungstates (POTs), [Cu<sub>8</sub>(H<sub>2</sub>O)<sub>2</sub>(en)<sub>4</sub>(B-α-H<sub>2</sub>SiW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>] (<b>1</b>), [Cu<sub>8</sub>(H<sub>2</sub>O)<sub>2</sub>(en)<sub>4</sub>(B-α-H<sub>2</sub>GeW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>] (<b>2</b>), K<sub>2</sub>[Cu<sub>8</sub>(en)<sub>4</sub>(B-α-HSiW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]·6H<sub>2</sub>O (<b>3</b>), and K<sub>2</sub>[Cu<sub>8</sub>(en)<sub>4</sub>(B-α-HGeW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]·2H<sub>2</sub>O (<b>4</b>) (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 <b>1</b>/<b>2</b> is a discrete dimer built by two trivalent Keggin [B-α-XW<sub>9</sub>O<sub>34</sub>]<sup>10-</sup> (X = Si/Ge) fragments and one octa-Cu cluster, whereas <b>3</b> and <b>4</b> display a two-dimensional network built by octa-Cu-sandwiched POT units via substitution of coordinated water on polyanions of <b>1</b> and <b>2</b> and further expand into a three-dimensional framework via K cation bridges. Ultraviolet-visible diffuse reflectance spectra reveal that <b>1-4</b> are potential semiconductor materials. Moreover, its visible light-driven catalytic H<sub>2</sub> evolution activity, electrochemical properties, catalysis for oxygenation reactions of thioethers, and magnetic behaviors have been investigated in detail.
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