journal article·2023-05

Covalent organic framework atropisomers with multiple gas-triggered structural flexibilities

Chengjun Kang, Zhaoqiang Zhang, Shinpei Kusaka, Kohei Negita, Adam K. Usadi, David C. Calabro, Lisa Saunders Baugh, Yuxiang Wang, Xiaodong Zou, Zhehao Huang, Ryotaro Matsuda, Dan Zhao

Nature Materials· Volume 22· Issue 5
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Abstract

Covalent organic frameworks (COFs) are emerging crystalline porous polymers, showing great potential for applications but lacking gas-triggered flexibility. Atropisomerism was experimentally discovered in 1922 but has rarely been found in crystals with infinite framework structures. Here we report atropisomerism in COF single crystals. The obtained COF atropisomers, namely COF-320 and COF-320-A, have identical chemical and interpenetrated structures but differ in the spatial arrangement of repeating units. In contrast to the rigid COF-320 structure, its atropisomer (COF-320-A) exhibits unconventional gas sorption behaviours with one or more sorption steps in isotherms at different temperatures. Single-crystal structures determined from continuous rotation electron diffraction and in situ powder X-ray diffraction demonstrate that these adsorption steps originate from internal pore expansion with or without changing the crystal space group. COF-320-A recognizes different gases by expanding its internal pores continuously (crystal-to-amorphous transition) or discontinuously (crystal-to-crystal transition) or having mixed transition styles, distinguishing COF-320-A from existing soft/flexible porous crystals. These findings extend atropisomerism from molecules to crystals and propel COFs into the covalently linked soft porous crystal regime, further advancing applications of soft porous crystals in gas sorption, separation and storage.
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Research context

OpenAlex topics: Covalent Organic Framework Applications · Metal-Organic Frameworks: Synthesis and Applications · Luminescence and Fluorescent Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

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