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; Zhi-Yuan Gu

doi:10.1038/s41467-023-41055-6

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, Zhi-Yuan Gu

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5 Scopus citations

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.

Original language	English (US)
Journal	Nature Communications
Volume	14
Issue number	1
DOIs	https://doi.org/10.1038/s41467-023-41055-6
State	Published - Sep 2 2023

Bibliographical note

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).

ASJC Scopus subject areas

General Biochemistry, Genetics and Molecular Biology
General Chemistry
General Physics and Astronomy

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10.1038/s41467-023-41055-6

https://repository.kaust.edu.sa/bitstream/10754/694072/1/s41467-023-41055-6.pdf

Cite this

@article{e4b0ed6d0baf4352bfd6a0bcece6f7da,

title = "Anisotropic flexibility and rigidification in a TPE-based Zr-MOFs with scu topology.",

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.",

author = "Sha-Sha Meng and Ming Xu and Hanxi Guan and Cailing Chen and Peiyu Cai and Bo Dong and Wen-Shu Tan and Yu-Hao Gu and Wen-Qi Tang and Lan-Gui Xie and Shuai Yuan and Yu Han and Xueqian Kong and Zhi-Yuan Gu",

note = "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).",

year = "2023",

month = sep,

day = "2",

doi = "10.1038/s41467-023-41055-6",

language = "English (US)",

volume = "14",

journal = "Nature Communications",

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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 -

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

Abstract

Bibliographical note

ASJC Scopus subject areas

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