Albalad Jorge, Peralta Ricardo A, Huxley Michael T, Tsoukatos Steven, Shi Zhaolin, Zhang Yue-Biao, Evans Jack D, Sumby Christopher J, Doonan Christian J
Centre for Advanced Nanomaterials and Department of Chemistry, The University of Adelaide North Terrace Adelaide SA 5000 Australia
School of Physical Science and Technology, ShanghaiTech University Shanghai 201210 China.
Chem Sci. 2021 Oct 14;12(44):14893-14900. doi: 10.1039/d1sc04712d. eCollection 2021 Nov 17.
Stimuli-responsive metal-organic frameworks (MOFs) exhibit dynamic, and typically reversible, structural changes upon exposure to external stimuli. This process often induces drastic changes in their adsorption properties. Herein, we present a stimuli-responsive MOF, ·[CuCl], that shows temperature dependent switching from a rigid to flexible phase. This conversion is associated with a dramatic reversible change in the gas adsorption properties, from Type-I to S-shaped isotherms. The structural transition is facilitated by a novel mechanism that involves both a change in coordination number (3 to 2) and geometry (trigonal planar to linear) of the post-synthetically added Cu(i) ion. This process serves to 'unlock' the framework rigidity imposed by metal chelation of the bis-pyrazolyl groups and realises the intrinsic flexibility of the organic link.
刺激响应性金属有机框架（MOF）在受到外部刺激时会表现出动态且通常可逆的结构变化。这一过程常常会使其吸附特性发生剧烈变化。在此，我们展示了一种刺激响应性MOF，即·[CuCl]，它表现出随温度从刚性相转变为柔性相的特性。这种转变与气体吸附特性从I型等温线到S型等温线的显著可逆变化相关。结构转变是由一种新机制促成的，该机制涉及合成后添加的Cu(i)离子的配位数（从3到2）和几何构型（从三角平面到线性）的变化。这一过程有助于“解锁”由双吡唑基的金属螯合作用所施加的框架刚性，并实现有机连接体的固有柔性。
