Ionothermal Synthesis of Five Keggin-Type Polyoxometalate-Based Metal-Organic Frameworks.
Ionothermal Synthesis of Five Keggin-Type Polyoxometalate-Based Metal-Organic Frameworks.
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DOI：
10.1021/acs.inorgchem.8b02277
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发表时间：
2019-01
影响因子：
4.6
通讯作者：
Kun Lu;Alex Liebman Peláez;Luogang Wu;Yu Cao;Chengfeng Zhu;H. Fu
中科院分区：
文献类型：
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作者：
Kun Lu;Alex Liebman Peláez;Luogang Wu;Yu Cao;Chengfeng Zhu;H. Fu
在离子热条件下合成了5种独特的keggin型多金属氧酸盐（POM）基金属有机骨架（POMFs），分别为[CH2L1]2[(CuL12)(PMoVI9MoV3O40)](1)、[Zn0.5(H2O)(L1)][Zn(L1)1.5Cl][H2L1]0.5[PMo12O40]·1.25H2O(2)、（TBA）[Cu(H2O)2L12][PMo12O40](3)、[Cu2(H2O)2(L1)3][PMVI11MoVO40](4)、（H2L2）0.5[(CuIL2)2(PMo12O40)]·H2O(5)、L1 = 4,4'-双（（1h -1,2,4-三唑-1-基）甲基）-联苯、L2 = 1,4-双（（1h -1,2,4-三唑-1-基）甲基）-苯。根据单晶数据，1表现出一种新的机械互锁分子结构（MIMA），由二维（2D）互穿的聚轮烷层与独特的环烷(四阳离子viologen大环环双（百草草-对苯）（CBPQT4+体系）构成，形成一个h键三维超分子，是第一个在离子热条件下合成自组装环烷- pmofs。2显示了一种新的二维三重互穿聚轮烷主客体网络。1和2是第一个在离子热条件下合成的MIMA聚轮烷结构。电化学阻抗谱（EIS）表明，2、4和5由于其独特的结构性质而表现出较高的质子导电性。固体漫反射紫外可见近红外测量表明标题化合物是潜在的半导体材料。光催化研究表明，1-5在可见光照射下具有高且稳定的光催化H2生成和罗丹明B （rhodamine B, RhB）降解。
Five unique Keggin-type polyoxometalate (POM)-based metal-organic frameworks (POMFs), namely [CH2L1]2[(CuL12)(PMoVI9MoV3O40)] (1), [Zn0.5(H2O)(L1)][Zn(L1)1.5Cl][H2L1]0.5[PMo12O40]·1.25H2O (2), (TBA)[Cu(H2O)2L12][PMo12O40] (3), [Cu2(H2O)2(L1)3][PMVI11MoVO40] (4), (H2L2)0.5[(CuIL2)2(PMo12O40)]·H2O (5), L1 = 4,4'-bis((1H-1,2,4-triazol-1-yl)methyl)-biphenyl, L2 = 1,4-bis((1H-1,2,4-triazol-1-yl)methyl)-benzene, have been synthesized under ionothermal conditions. According to single-crystal data, 1 exhibits a novel mechanically interlocked molecular architecture (MIMA) constructed by two-dimensional (2D) interpenetrating polyrotaxane layers with unique cyclophanes (tetra-cationic viologen macrocycle cyclobis(paraquat- p-phenylene) (CBPQT4+ system)), resulting in an H-bonded 3D supermolecule, and is the first synthesis of self-assembled cyclophane-PMOFs under ionothermal conditions. 2 shows a novel 2D three-fold interpenetrating polyrotaxane host and guest network. 1 and 2 are presented as the first MIMA polyrotaxane structures to have been synthesized under ionothermal conditions. Electrochemical impedance spectroscopy (EIS) reveals that 2, 4, and 5 show high proton conductivity owing to their unique structural properties. Solid-state diffuse reflection UV-vis-NIR measurements show the title compounds are potentially semiconductor materials. Photocatalytic investigations indicate that 1-5 possess high and stable photocatalytic H2 evolution and rhodamine B (RhB) degradation under visible-light irradiation.