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

Qingqing Pang; Binbin Tu; Lingyi Yang; Qiaowei Li

doi:10.1016/j.scib.2019.10.001

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

Sci Bull (Beijing). 2019 Dec 30;64(24):1881-1889. doi: 10.1016/j.scib.2019.10.001. Epub 2019 Oct 3.

Authors

Qingqing Pang¹, Binbin Tu¹, Lingyi Yang¹, Qiaowei Li²

Affiliations

¹ Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China.
² Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China. Electronic address: qwli@fudan.edu.cn.

PMID: 36659583
DOI: 10.1016/j.scib.2019.10.001

Abstract

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.

Keywords: Breathing MOF; Photochemical cycloaddition; Pillared-layer MOF; Reticular chemistry; Structural transformation.