Three-Dimensional Phosphine Metal鈥揙rganic Frameworks Assembled from Cu(I) and Pyridyl Diphosphine
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- 作者：Xin Tan ; Lei Li ; Jianyong Zhang ; Xiaorui Han ; Long Jiang ; Fuwei Li ; Cheng-Yong Su
- 刊名：Chemistry of Materials
- 出版年：2012
- 出版时间：February 14, 2012
- 年：2012
- 卷：24
- 期：3
- 页码：480-485
- 全文大小：322K
- 年卷期：v.24,no.3(February 14, 2012)
- ISSN：1520-5002
文摘
Metal鈥搊rganic 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鈥?/sup> (CuL-Br), Cl鈥?/sup> (CuL-Br), or PF6鈥?/sup> (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鈥?/sup> anions hosted in the 1D channel of CuL-PF6 can be readily exchanged with Br鈥?/sup> or Cl鈥?/sup> 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 glycol and 2-butanone/cyclohexanone, up to 93% yield with 0.2 mol % catalyst loading. In contrast, no reaction happens between ethylene glycol and bulky benzophenone, suggesting profound size selectivity. The catalysts can be reused with the framework left intact for three runs without loss of activity.