Polyoxometalate-Induced New Self-Assemblies Based on Copper Ions and Bichelate-Bridging Ligands

The introduction of polyoxometalates (POMs) into the metal–organic complex synthetic system containing copper ions and bichelate-bridging ligands (bis­(3-(2-pyridyl)­pyrazole-1-ylmethyl)­benzene, bppmb) led to the isolation of three new organic–inorganic hybrid compounds [Cu<sup>II</sup>L<i>o</i>]<sub>2</sub>H­[BW<sub>12</sub>O<sub>40</sub>]·4H<sub>2</sub>O (<b>1</b>), [Cu<sup>I</sup>L<i>o</i>]<sub>4</sub>[SiW<sub>12</sub>O<sub>40</sub>]·5H<sub>2</sub>O (<b>2</b>), and [CuL<i>p</i>]<sub>3</sub>H<sub>2</sub>[BW<sub>12</sub>O<sub>40</sub>]·5H<sub>2</sub>O (<b>3</b>) (L<i>o</i> = 1,2-bppmb and L<i>p</i> = 1,4-bppmb). All three compounds were hydrothermally synthesized and characterized by elemental analyses, IR spectra, TG analyses, powder X-ray diffraction, and single-crystal X-ray diffraction analyses. In these compounds, the use of Keggin-type POMs induces the formation of a series of new metal–organic secondary building units based on the copper ions and bppmb ligands such as helical chain and chiral Möbius Strip, which further form interesting supramolecular self-assemblies with the polyoxoanions. The degradation of Rhodamine-B (RhB) under UV irradiation with compounds <b>1</b>–<b>3</b> as the heterogeneous photocatalysts was investigated, and these compounds show good photocatalytic properties for RhB degradation.