Li Yun-Wu, Guo Ling-Yu, Su Hai-Feng, Jagodič Marko, Luo Ming, Zhou Xiao-Qi, Zeng Su-Yuan, Tung Chen-Ho, Sun Di, Zheng Lan-Sun
School of Chemistry and Chemical Engineering, and Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, Liaocheng University , Liaocheng 252000, P. R. China.
Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University , Jinan 250100, P. R. China.
Inorg Chem. 2017 Mar 6;56(5):2481-2489. doi: 10.1021/acs.inorgchem.6b02601. Epub 2017 Feb 15.
Two novel POM-based inorganic-organic hybrids, [Cu(2,2'-bipy)(MoO)(SiWO)] (1), and {[Cu(ppz)(HO)(MoO)(SiWO)]·4HO} (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 [SiWO] clusters and [Cu(2,2'-bipy)] modified isopolymolybdates [MoO]. Compound 2 also represents a 1D chain-like motif built from classical Keggin heteropolytungstate [SiWO] clusters and [Cu(ppz)(HO)] modified molybdates MoO. 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] building block gradually transforms to classical Keggin [SiW] during assembly process. Furthermore, the electrocatalytic and magnetic properties were discussed in details.
两种新型的基于多金属氧酸盐的无机-有机杂化物，[Cu(2,2'-联吡啶)(MoO)(SiWO)] (1) 和 {[Cu(3-(吡啶-2-基)吡唑)(H₂O)(MoO)(SiWO)]·4H₂O} (2)（2,2'-联吡啶 = 2,2'-联吡啶，Hppz = 3-(吡啶-2-基)吡唑），由杂多钨酸盐和钼酸盐构建而成。通过单晶X射线衍射、元素分析和傅里叶变换红外光谱对这两种化合物进行了鉴定。化合物1呈现出一种一维链状结构，由经典的Keggin杂多钨酸盐[SiWO]簇和[Cu(2,2'-联吡啶)]修饰的同多钼酸盐[MoO]构成。化合物2也代表了一种由经典的Keggin杂多钨酸盐[SiWO]簇和[Cu(3-(吡啶-2-基)吡唑)(H₂O)]修饰的钼酸盐MoO构建的一维链状结构。化合物1是基于多金属氧酸盐的无机-有机杂化物中首个包含混合杂多钨酸盐和同多钼酸盐的例子。采用电喷雾电离质谱（ESI-MS）技术揭示水热反应中的物种及其演变，在此过程中，三缺位的[SiW]结构单元在组装过程中逐渐转变为经典的Keggin [SiW]。此外，还详细讨论了其电催化和磁性性质。
