TY - JOUR
T1 - Anisotropic flexibility and rigidification in a TPE-based Zr-MOFs with scu topology.
AU - Meng, Sha-Sha
AU - Xu, Ming
AU - Guan, Hanxi
AU - Chen, Cailing
AU - Cai, Peiyu
AU - Dong, Bo
AU - Tan, Wen-Shu
AU - Gu, Yu-Hao
AU - Tang, Wen-Qi
AU - Xie, Lan-Gui
AU - Yuan, Shuai
AU - Han, Yu
AU - Kong, Xueqian
AU - Gu, Zhi-Yuan
N1 - KAUST Repository Item: Exported on 2023-09-05
Acknowledgements: This work is supported by the National Natural Science Foundation of China (22174067, Z.-Y.G. and 22204078, M.X.), the Natural Science Foundation of Jiangsu Province of China (BK20220370, M.X.), Jiangsu Provincial Department of Education (22KJB150009, M.X.), the Priority Academic Program Development of Jiangsu Higher Education Institutions, State Key Laboratory of Analytical Chemistry for Life Science (SKLACLS2218, Z.-Y.G.), and the Postgraduate Research&Practice Innovation Program of Jiangsu Province (KYCX23_1684, S.-S.M.). This work is carried out with the support of Shanghai Synchrotron Radiation Facility Beamline BL17B1 (proposal 2021-NFPS-PT-006657).
PY - 2023/9/2
Y1 - 2023/9/2
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/694072
UR - https://www.nature.com/articles/s41467-023-41055-6
U2 - 10.1038/s41467-023-41055-6
DO - 10.1038/s41467-023-41055-6
M3 - Article
C2 - 37660056
SN - 2041-1723
VL - 14
JO - Nature Communications
JF - Nature Communications
IS - 1
ER -