含混合配体多酸超分子化合物的水热合成、晶体结构及催化活性

在水热条件下合成了四个含混合配体4,4’-bipy和2,2’-bipy/phen的多酸配位聚合物Cu(4,4’-bipy)(2,2’-bipy)2]2SiW12O40]?4H2O (1)，Ag4(4,4’-bipy)3(2,2’-bipy)2]SiW12O40]?2H2O (2)，Cu(4,4’-bipy)(phen)]2H3O]2SiW12O40]?8H2O (3)和Cu(4,4’-bipy-Cl)(phen)]2H3O]PW12O40]?H2O (4) (bipy = 联吡啶，phen = 邻菲罗啉)，通过红外光谱、热重、元素分析、X-单晶衍射对聚合物进行了表征，在苯乙烯催化环氧化反应中，3和4显示了较高的催化活性，这与结构中存在配位不饱和金属中心有关.

Hydrothermal Synthesis and Characterization of POM-based Supramolecular Complexes with Mixed Ligands

Four POM-based coordination polymers with mixed 4,4’-bipy and 2,2’-bipy/phen, Cu(4,4’-bipy)(2,2’-bipy)2]2SiW12O40]?4H2O (1), Ag4(4,4’-bipy)3(2,2’- bipy)2]SiW12O40]?2H2O (2), Cu(4,4’-bipy)(phen)]2H3O]2SiW12O40]?8H2O (3) and Cu(4,4’-bipy-Cl)(phen)]2H3O]PW12O40]?H2O (4) (bipy = bipyridine, phen = phenanthroline), were synthesized under hydrothermal condition and characterized by IR, TG, elemental analysis, and single-crystal X-ray diffraction. Compound 1 is crystallized in the monoclinic system, space group P21/n, with a = 1.2858(4) nm, b = 2.0890(7) nm, c = 1.5580(5) nm, β = 102.306(4)o, V = 4.089(2) nm3, Z = 2, R1 = 0.0451, wR2 = 0.0934. Compound 2 is crystallized in the monoclinic system, space group P21/n, with a = 1.2766(4) nm, b = 2.1258(6) nm, c = 1.4491(4) nm, β = 104.774(4)o, V = 3.803(2) nm3, Z = 2, R1 = 0.0429, wR2 = 0.0730. Compound 3 is crystallized in the monoclinic system, space group C2/m, with a = 1.9850(8) nm, b = 1.4072(6) nm, c = 1.2108(5) nm, β = 110.629(6)o, V = 3.165(2) nm3, Z = 2, R1 = 0.0885, wR2 = 0.1647. Compound 4 is crystallized in the monoclinic system, space group C2/m, with a = 2.0376(7) nm，b = 1.4031(5) nm, c = 1.3784(5) nm, β = 93.502(6)o, V = 3.933(2) nm3, Z = 2, R1 = 0.0561, wR2 = 0.1491. The catalytic activity of these compounds was tested in the epoxidation of styrene and compound 3 and 4 exhibited high conversion of styrene and selectivity to epoxide.