Three novel polyoxometalate (POM)-based Cu(Ⅱ) and Cu(Ⅰ) hybrid materials with multi-dentate monoand bis-triazole derivatives,namely {[Cu(L1)2(Mo4O13)] ·2H2O}n (1),{[Cu1.5(L2)(HL2)(H2O)(Mo4O13)] ·2H2O}n (2),{[Cu2(L3)1.5(Mo4O13)] · H2O}n (3) (L1 =4-pyridine-2-1,2,4-triazole,HL2=3-(4H-1,2,4-triazol-4-yl)benzoic acid,L3=trans-4,4'-azo-1,2,4-triazole) have been designed and synthesized by hydrothermal method.The structures of 1～3 have been determined by single crystal X-ray diffraction,FT-IR infrared spectra and powder X-ray diffraction analyses.In 1,Mo4O132-anions and Cu(Ⅱ) centers are inter-linked by bidentate L1,which are arranged into 2D POMs-based Cu(Ⅱ)hybrid metal-organic framework.In 2,Mo4O132-anions and Cu(Ⅱ) centers are inter-linked via bridging aqua atoms (O18),bi-dentate HL2 and tri-dentate L2-,which are arranged into 3D POM-based Cu(Ⅱ) micro-porous metal-organic framework.In 3,L3 ligands bridge neighboring Cu(Ⅰ) centers and Mo4O132-anions,which ultimately forms unique two-fold interpenetrating 3D POM-based Cu(Ⅰ) hybrid coordination framework.Photocatalytic activities for decomposition of different organic dyes of rhodamine B (RhB),methylene blue (MB) and methyl orange (MO) have been investigated for 1 ～3,indicating that 1～3 are good candidates for photocatalytic degradation of the organic dyes.CCDC:1474258,1;1477985,2;1544278,3.%在水热条件下,利用多齿的单-和双-三唑衍生物,制备了3种基于多金属氧簇基(POM)的Cu(Ⅱ)和Cu(Ⅰ)杂化材料,即{[Cu(L1)2(Mo4O13)]·2H2O}n(1),{[Cu1.5(L2)(HL2)(H2O)(Mo4O13)]·2H2O}n(2),{[Cu2(L3)1.5(Mo4O13)]·H2O}n(3)(L1=4-pyridine-2-1,2,4-triazole,HL2=3-(4H-1,2,4-triazol-4-yl)benzoic acid,L3=trans-4,4'-azo-1,2,4-triazole).通过单晶X射线衍射、傅里叶变换红外光谱和粉末X射线衍射分析确定了它们的结构.在1中,Mo4O132-阴离子和Cu(Ⅱ)中心通过双齿L1相互连接,最终形成了二维(2D)POMs基的Cu(Ⅱ)杂化金属-有机骨架.在2中,Mo4O132-阴离子和Cu(Ⅱ)中心通过桥接水原子(O18),双齿HL和三齿L2-相互连接,最终形成了三维(3D)POMs基的Cu(Ⅱ)微孔金属-有机骨架.在3中,L3配体桥接相邻的Cu(Ⅰ)中心和Mo4O132-阴离子,最终形成独特的双重穿插结构的3DPOMs基的Cu(Ⅰ)杂化配位框架.光催化实验研究表明,样品1～3对于不同有机染料罗丹明B(RhB)、亚甲基蓝(MB)和甲基橙(MO)都具有很好的光催化降解能力.
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