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Two unprecedented POM-based inorganic-organic hybrids with concomitant heteropolytungstate and molybdate
Li, Yun-Wu ...
Two novel POM-based inorganic-organic hybrids, ▫${\rm [Cu_6^{II}(2,2' -\text{bipy})_6(Mo_6O_{22})(SiW_{12}O_{40})]_n}$▫ (1), and ▫${\rm \{[Cu_6^{II}(\text{ppz})_6(H_2O)_5(MoO_4)(SiW_{12}O_{40})] ...\cdot 4H_2O\}_n}$▫ (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 ▫${\rm [SiW_{12}O_{40}]^{4-}}$▫ clusters and ▫${\rm [C_6(2,2'- \text{bipy})_6]}$▫ modified isopolymolybdates ▫${\rm [Mo_6O_{22}]^{8-}}$▫. Compound 2 also represents a 1D chain-like motif built from classical Keggin heteropolytungstate ▫${\rm [SiW_{12}O_{40}]^{4-}}$▫ clusters and ▫${\rm \{[Cu_8 (\text{ppz})_6(H_2O)_5]}$▫ modified molybdates ▫${\rm MoO_4^{2-}}$▫. 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 ▫${\rm [SiW_9]}$▫ building block gradually transforms to classical Keggin ▫${\rm [SiW_{12}]}$▫ during assembly process. Furthermore, the electrocatalytic and magnetic properties were discussed in details.
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