Flexible Zirconium Metal‐Organic Frameworks as Bioinspired Switchable Catalysts

• DOI: 10.1002/anie.201604313
• Publication Date: 2016-06-27T09:28:41Z
• Authors: Shuai Yuan; Lanfang Zou; Haixia Li; Ying‐Pin Chen; Junsheng Qin; Qiang Zhang; Weigang Lu; Michael B. Hall; Hong‐Cai Zhou
• Keywords: Cycloaddition Reaction; switchable catalysts; bioinspired catalysts; Molecular Conformation; flexible MOFs; 02 engineering and technology; Carbon Dioxide; 540; Catalysis; pore opening; epoxides; Epoxy Compounds; Zirconium; 0210 nano-technology; Metal-Organic Frameworks

AbstractFlexible metal–organic frameworks (MOFs) are highly desirable in host–guest chemistry owing to their almost unlimited structural/functional diversities and stimuli‐responsive pore architectures. Herein, we designed a flexible Zr‐MOF system, namely PCN‐700 series, for the realization of switchable catalysis in cycloaddition reactions of CO2 with epoxides. Their breathing behaviors were studied by successive single‐crystal X‐ray diffraction analyses. The breathing amplitudes of the PCN‐700 series were modulated through pre‐functionalization of organic linkers and post‐synthetic linker installation. Experiments and molecular simulations confirm that the catalytic activities of the PCN‐700 series can be switched on and off upon reversible structural transformation, which is reminiscent of sophisticated biological systems such as allosteric enzymes.