Institute of Chemistry and Life Science , Changchun University of Technology Changchun , Jilin 130012 , P. R. China.
Advanced Light Source , Lawrence Berkeley National Laboratory Berkeley , California 94720 , United States.
Inorg Chem. 2019 Feb 4;58(3):1794-1805. doi: 10.1021/acs.inorgchem.8b02277. Epub 2019 Jan 14.
Five unique Keggin-type polyoxometalate (POM)-based metal-organic frameworks (POMFs), namely [CHL1][(CuL1)(PMoMoO)] (1), [Zn(HO)(L1)][Zn(L1)Cl][HL1][PMoO]·1.25HO (2), (TBA)[Cu(HO)L1][PMoO] (3), [Cu(HO)(L1)][PMMoO] (4), (HL2)[(CuL2)(PMoO)]·HO (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) (CBPQT 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 H evolution and rhodamine B (RhB) degradation under visible-light irradiation.
五种独特的 Keggin 型多金属氧酸盐（POM）基金属有机骨架（POMFs），即 [CHL1][(CuL1)(PMoMoO)]（1）、[Zn(HO)(L1)][Zn(L1)Cl][HL1][PMoO]·1.25HO（2）、(TBA)[Cu(HO)L1][PMoO]（3）、[Cu(HO)(L1)][PMMoO]（4）、(HL2)[(CuL2)(PMoO)]·HO（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，在离子热条件下合成。根据单晶数据，1 表现出一种新颖的由二维（2D）互穿聚轮烷层与独特的环芳（四阳离子重氮大环环 bis(paraquat- p-苯撑)（CBPQT 系统））构建的机械互锁分子结构（MIMA），导致氢键 3D 超分子，并且是离子热条件下自组装的环芳-PMOFs 的首次合成。2 表现出一种新颖的 2D 三重互穿聚轮烷主体和客体网络。1 和 2 被呈现为离子热条件下首次合成的 MIMA 聚轮烷结构。电化学阻抗谱（EIS）表明，2、4 和 5 由于其独特的结构特性而表现出高质子电导率。固态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 H 2 演化和罗丹明 B（RhB）降解性能。
