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一种包含钌双(三联吡啶)配合物和葫芦[8]脲的编织超分子金属有机框架:对醇氧化的催化活性增强。

A Woven Supramolecular Metal-Organic Framework Comprising a Ruthenium Bis(terpyridine) Complex and Cucurbit[8]uril: Enhanced Catalytic Activity toward Alcohol Oxidation.

作者信息

Zhang Yun-Chang, Xu Zi-Yue, Wang Ze-Kun, Wang Hui, Zhang Dan-Wei, Liu Yi, Li Zhan-Ting

机构信息

Department of Chemistry Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 2205 Songhu Road, Shanghai, 200438, P. R. China.

Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California, 94720, USA.

出版信息

Chempluschem. 2020 Jul;85(7):1498-1503. doi: 10.1002/cplu.202000391.

Abstract

The self-assembly of a diamondoid woven supramolecular metal-organic framework wSMOF-1 has been achieved from intertwined [Ru(tpy) ] (tpy=2,2',6',2''-terpyridine) complex M1 and cucurbit[8]uril (CB[8]) in water, where the intermolecular dimers formed by the appended aromatic arms of M1 are encapsulated in CB[8]. wSMOF-1 exhibits ordered pore periodicity in both water and the solid state, as confirmed by a combination of H NMR spectroscopy, UV-vis absorption, isothermal titration calorimetry, dynamic light scattering, small angle X-ray scattering and selected area electron diffraction experiments. The woven framework has a pore aperture of 2.1 nm, which allows for the free access of both secondary and primary alcohols and tert-butyl hydroperoxide (TBHP). Compared with the control molecule [Ru(tpy) ]Cl , the [Ru(tpy) ] unit of wSMOF-1 exhibits a remarkably higher heterogeneous catalysis activity for the oxidation of alcohols by TBHP in n-hexane. For the oxidation of 1-phenylethan-1-ol, the yield of acetophenone was increased from 10 % to 95 %.

摘要

由相互缠绕的[Ru(tpy)](tpy = 2,2',6',2''-三联吡啶)配合物M1和葫芦[8]脲(CB[8])在水中实现了类金刚石编织超分子金属有机框架wSMOF-1的自组装,其中由M1的附加芳香臂形成的分子间二聚体被封装在CB[8]中。通过1H NMR光谱、紫外可见吸收、等温滴定量热法、动态光散射、小角X射线散射和选区电子衍射实验相结合,证实wSMOF-1在水和固态中均表现出有序的孔周期性。该编织框架的孔径为2.1 nm,允许仲醇、伯醇和叔丁基过氧化氢(TBHP)自由进入。与对照分子[Ru(tpy)]Cl相比,wSMOF-1的[Ru(tpy)]单元对TBHP在正己烷中氧化醇表现出显著更高的多相催化活性。对于1-苯基乙醇的氧化,苯乙酮的产率从10%提高到了95%。

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