Two Unprecedented POM-Based Inorganic–Organic Hybrids with Concomitant Heteropolytungstate and Molybdate

Two novel POM-based inorganic–organic hybrids, [Cu 6 II (2,2′-bipy) 6 (Mo 6 O 22 )(SiW 12 O 40 )] n ( 1 ), and {[Cu 6 II (ppz) 6 (H 2 O) 5 (MoO 4 )(SiW 12 O 40 )]·4H 2 O} n ( 2 ) (2,2′-bipy = 2,2′-bipyridine, Hppz = 3-(pyrid-2-yl)pyrazole), have been constructed from heteropolytungstates and molybdates. Two compounds have been identified by single crystal X-ray diffraction, elemental analysis, and FT-IR. Compound 1 shows a 1D (one-dimensional) chain structure constructed from classical Keggin heteropolytungstate [SiW 12 O 40 ] 4– clusters and [Cu 6 (2,2′-bipy) 6 ] modified isopolymolybdates [Mo 6 O 22 ] 8– . Compound 2 also represents a 1D chain-like motif built from classical Keggin heteropolytungstate [SiW 12 O 40 ] 4– clusters and [Cu 8 (ppz) 6 (H 2 O) 5 ] modified molybdates MoO 4 2– . Compound 1 represents the first example of POM-based inorganic–organic hybrid with mixed heteropolytungstates and isopolymolybdates. ESI-MS (electrospray ionization mass spectrometry) technique was employed to reveal the species and their evolutions in the hydrothermal reaction, whereby trivacant [SiW 9 ] building block gradually transforms to classical Keggin [SiW 12 ] during assembly process. Furthermore, the electrocatalytic and magnetic properties were discussed in details.