Photochemical cycloaddition and temperature-dependent breathing in pillared-layer metal–organic frameworks  

作　　者：Qingqing Pang Binbin Tu Lingyi Yang Qiaowei Li 

机构地区：[1]Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and Shanghai Key Laboratory of Molecular Catalysis and InnovativeMaterials, Fudan University

出　　处：《Science Bulletin》2019年第24期1881-1889,共9页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China (21571037,21733003,and 21961132003);the National Key Research and Development Program of China (2018YFA0209400);the National Top-Notch Talent Program;the Science & Technology Commission of Shanghai Municipality (16520710100,17JC1400100);the China Postdoctoral Science Foundation (2018M632003)

摘　　要：Single crystallinity of metal–organic frameworks(MOFs) enables the studies of their flexible behaviors with atomic precision. Here, we investigated the structural transformations triggered by photochemical cycloaddition and with temperature-dependent breathing in a series of pillared-layer MOF structures using a variety of pyrazolecarboxylate linkers for the layers and bipyridyl linkers as the pillars. The ethylenic double bonds from the pillars in close proximity undergo quantitative and seteroselective photochemical [2 + 2] cycloaddition upon UV irradiation, transforming the MOFs into structures with cyclobutane-based pillars. Furthermore, reversible breathing of the new pillared-layer MOF was evidenced by the 10.8% unit cell parameter change along c axis upon temperature change between 298 and 173 K. As revealed by single crystal X-ray diffraction, this transformation originates from the relative flattening of the wavy layers upon cooling. These two different types of characteristic structural transformations responding to inherent reactions and external stimuli happen at single crystalline state, providing a well-defined robust system with controlled flexibility.Single crystallinity of metal–organic frameworks(MOFs) enables the studies of their flexible behaviors with atomic precision. Here, we investigated the structural transformations triggered by photochemical cycloaddition and with temperature-dependent breathing in a series of pillared-layer MOF structures using a variety of pyrazolecarboxylate linkers for the layers and bipyridyl linkers as the pillars. The ethylenic double bonds from the pillars in close proximity undergo quantitative and seteroselective photochemical [2 + 2] cycloaddition upon UV irradiation, transforming the MOFs into structures with cyclobutane-based pillars. Furthermore, reversible breathing of the new pillared-layer MOF was evidenced by the 10.8% unit cell parameter change along c axis upon temperature change between 298 and 173 K. As revealed by single crystal X-ray diffraction, this transformation originates from the relative flattening of the wavy layers upon cooling. These two different types of characteristic structural transformations responding to inherent reactions and external stimuli happen at single crystalline state, providing a well-defined robust system with controlled flexibility.

关 键 词：Pillared-layer MOF Photochemical cycloaddition Structural transformation Breathing MOF Reticular chemistry 

分 类 号：O64[理学—物理化学]