Three-Dimensional Phosphine Metal–Organic Frameworks Assembled from Cu(I) and Pyridyl Diphosphine
Three-Dimensional Phosphine Metal–Organic Frameworks Assembled from Cu(I) and Pyridyl Diphosphine
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DOI：
10.1021/cm202608f
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发表时间：
2012-01
影响因子：
8.6
通讯作者：
X. Tan;Lei Li;Jianyong Zhang;Xiao-Bo Han;Long Jiang;Fuwei Li;C. Su
中科院分区：
文献类型：
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作者：
X. Tan;Lei Li;Jianyong Zhang;Xiao-Bo Han;Long Jiang;Fuwei Li;C. Su
具有膦基配体的金属有机骨架（mof）在催化方面极具吸引力。本文首次成功地将磷化氢加入到三维（3D） MOFs中。mof是基于刚性的L2M2二聚体二级构建块，由Cu(I)和吡啶二膦配体，4-（3,5-双（二苯基膦）苯基）吡啶组装而成，以Br -(CuL-Br), Cl -(CuL-Br)或PF6 -(CuL-PF6)作为反阴离子。该结构具有4.122的净拓扑结构，可以进一步简化为64.82-qtz。mof包含一维同手性通道。在CuL-PF6的一维通道中，PF6 -阴离子可以很容易地与Br -或Cl -交换，同时保持骨架完整。材料表现出阴离子可调的柔性孔隙率。CuL-Br表现出对MeOH的逐渐吸附，而CuL-PF6表现出对MeOH的逐步吸附。在烷基化反应中，mof具有非均相路易斯酸催化活性。CuL-Br和CuL-PF6在乙二醇和纤维素的反应中具有活性。
Metal–organic frameworks (MOFs) with phosphine based ligands are extremely attractive for catalysis. In this paper, phosphine has been successfully incorporated for the first time into three-dimensional (3D) MOFs. The MOFs are based on rigid L2M2 dimeric secondary building blocks assembled from Cu(I) and a pyridyl diphosphine ligand, 4-(3,5-bis(diphenylphosphino)phenyl)pyridine, with Br– (CuL-Br), Cl– (CuL-Br), or PF6– (CuL-PF6) as counteranions. The structures have a 4.122 net topology, which can be further simplified to 64.82-qtz. The MOFs contain 1D homochiral channels. The PF6– anions hosted in the 1D channel of CuL-PF6 can be readily exchanged with Br– or Cl– while keeping the framework intact. The materials show anion-tunable flexible porosity. CuL-Br reveals gradual uptake of MeOH, while CuL-PF6 exhibits stepwise sorption for MeOH. The heterogeneous Lewis acid catalytic activity of the MOFs has been shown in ketalization reaction. CuL-Br and CuL-PF6 are active in the reactions between ethylene glyc...