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具有棒状配体的金属有机框架中的超快分子转子及其一氧化碳调谐

Ultrafast Molecular Rotors and Their CO Tuning in MOFs with Rod-Like Ligands.

作者信息

Bracco Silvia, Castiglioni Fabio, Comotti Angiolina, Galli Simona, Negroni Mattia, Maspero Angelo, Sozzani Piero

机构信息

Department of Materials Science and INSTM Consortium, University of Milano Bicocca, Via R. Cozzi 55, Milan, Italy.

Dipartimento di Scienza e Alta Tecnologia and INSTM Consortium, Università degli studi dell' Insubria, Via Valleggio 11, 22100, Como, Italy.

出版信息

Chemistry. 2017 Aug 22;23(47):11210-11215. doi: 10.1002/chem.201702930. Epub 2017 Aug 2.

Abstract

A metal organic framework (MOF) engineered to contain in its scaffold rod-like struts featuring ultrafast molecular rotors showed extremely rapid 180 ° flip reorientation with rotational rates of 10  Hz at 150 K. Crystal-pore accessibility of the MOF allowed the CO molecules to enter the cavities and control the rotor spinning speed down to 10  Hz at 150 K. Rotor dynamics, as modulated by CO loading/unloading in the porous crystals, was described by proton T and H NMR spectroscopy. This strategy enabled the regulation of rotary motion by the diffusion of the gas within the channels and the determination of the energetics of rotary dynamics in the presence of CO .

摘要

一种经过工程设计的金属有机框架(MOF),其支架中含有具有超快分子转子的棒状支柱,在150K时表现出极快的180°翻转重新取向,旋转速率为10Hz。MOF的晶体孔隙可及性使CO分子能够进入腔体,并将转子旋转速度控制在150K时低至10Hz。通过质子T和H NMR光谱描述了由多孔晶体中CO的加载/卸载调制的转子动力学。该策略能够通过气体在通道内的扩散来调节旋转运动,并确定存在CO时旋转动力学的能量学。

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