Anisotropic flexibility and rigidification in a TPE-based Zr-MOFs with scu topology

Sha-Sha Meng, Ming Xu, Hanxi Guan, Cailing Chen, Peiyu Cai, Bo Dong, Wen-Shu Tan, Yu-Hao Gu, Wen-Qi Tang, Lan-Gui Xie, Shuai Yuan, Yu Han, Xueqian Kong and Zhi-Yuan Gu ()
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Sha-Sha Meng: Nanjing Normal University
Ming Xu: Nanjing Normal University
Hanxi Guan: Zhejiang University
Cailing Chen: King Abdullah University of Science and Technology
Peiyu Cai: Texas A&M University
Bo Dong: Nanjing Normal University
Wen-Shu Tan: Nanjing Normal University
Yu-Hao Gu: Nanjing Normal University
Wen-Qi Tang: Nanjing Normal University
Lan-Gui Xie: Nanjing Normal University
Shuai Yuan: Nanjing University
Yu Han: King Abdullah University of Science and Technology
Xueqian Kong: Zhejiang University
Zhi-Yuan Gu: Nanjing Normal University

Nature Communications, 2023, vol. 14, issue 1, 1-10

Abstract: Abstract Tetraphenylethylene (TPE)-based ligands are appealing for constructing metal-organic frameworks (MOFs) with new functions and responsiveness. Here, we report a non-interpenetrated TPE-based scu Zr-MOF with anisotropic flexibility, that is, Zr-TCPE (H4TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene), remaining two anisotropic pockets. The framework flexibility is further anisotropically rigidified by installing linkers individually at specific pockets. By individually installing dicarboxylic acid L1 or L2 at pocket A or B, the framework flexibility along the b-axis or c-axis is rigidified, and the intermolecular or intramolecular motions of organic ligands are restricted, respectively. Synergistically, with dual linker installation, the flexibility is completely rigidified with the restriction of ligand motion, resulting in MOFs with enhanced stability and improved separation ability. Furthermore, in situ observation of the flipping of the phenyl ring and its rigidification process is made by 2H solid-state NMR. The anisotropic rigidification of flexibility in scu Zr-MOFs guides the directional control of ligand motion for designing stimuli-responsive emitting or efficient separation materials.

Date: 2023
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DOI: 10.1038/s41467-023-41055-6

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