Redox-switchable breathing behavior in tetrathiafulvalene-based metal–organic frameworks
Abstract
Metal–organic frameworks (MOFs) that respond to external stimuli such as guest molecules, temperature, or redox conditions are highly desirable. Herein, we coupled redox-switchable properties with breathing behavior induced by guest molecules in a single framework. Guided by topology, two flexible isomeric MOFs, compounds 1 and 2, with a formula of In(Me2NH2) (TTFTB), were constructed via a combination of [In(COO)4]- metal nodes and tetratopic tetrathiafulvalene-based linkers (TTFTB). The two compounds show different breathing behaviors upon the introduction of N2. Single-crystal X-ray diffraction, accompanied by molecular simulations, reveals that the breathing mechanism of 1 involves the bending of metal–ligand bonds and the sliding of interpenetrated frameworks, while 2 undergoes simple distortion of linkers. Reversible oxidation and reduction of TTF moieties changes the linker flexibility, which in turn switches the breathing behavior of 2. The redox-switchable breathing behavior can potentially be applied to the design of stimuli-responsive MOFs.
- Publication Date:
- Research Org.:
- Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1470031
- Grant/Contract Number:
- EE0007049; FE0026472; SC0001015
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 1; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)
Citation Formats
Su, Jian, Yuan, Shuai, Wang, Hai-Ying, Huang, Lan, Ge, Jing-Yuan, Joseph, Elizabeth, Qin, Junsheng, Cagin, Tahir, Zuo, Jing-Lin, and Zhou, Hong-Cai. Redox-switchable breathing behavior in tetrathiafulvalene-based metal–organic frameworks. United States: N. p., 2017.
Web. doi:10.1038/s41467-017-02256-y.
Su, Jian, Yuan, Shuai, Wang, Hai-Ying, Huang, Lan, Ge, Jing-Yuan, Joseph, Elizabeth, Qin, Junsheng, Cagin, Tahir, Zuo, Jing-Lin, & Zhou, Hong-Cai. Redox-switchable breathing behavior in tetrathiafulvalene-based metal–organic frameworks. United States. https://doi.org/10.1038/s41467-017-02256-y
Su, Jian, Yuan, Shuai, Wang, Hai-Ying, Huang, Lan, Ge, Jing-Yuan, Joseph, Elizabeth, Qin, Junsheng, Cagin, Tahir, Zuo, Jing-Lin, and Zhou, Hong-Cai. Fri .
"Redox-switchable breathing behavior in tetrathiafulvalene-based metal–organic frameworks". United States. https://doi.org/10.1038/s41467-017-02256-y. https://www.osti.gov/servlets/purl/1470031.
@article{osti_1470031,
title = {Redox-switchable breathing behavior in tetrathiafulvalene-based metal–organic frameworks},
author = {Su, Jian and Yuan, Shuai and Wang, Hai-Ying and Huang, Lan and Ge, Jing-Yuan and Joseph, Elizabeth and Qin, Junsheng and Cagin, Tahir and Zuo, Jing-Lin and Zhou, Hong-Cai},
abstractNote = {Metal–organic frameworks (MOFs) that respond to external stimuli such as guest molecules, temperature, or redox conditions are highly desirable. Herein, we coupled redox-switchable properties with breathing behavior induced by guest molecules in a single framework. Guided by topology, two flexible isomeric MOFs, compounds 1 and 2, with a formula of In(Me2NH2) (TTFTB), were constructed via a combination of [In(COO)4]- metal nodes and tetratopic tetrathiafulvalene-based linkers (TTFTB). The two compounds show different breathing behaviors upon the introduction of N2. Single-crystal X-ray diffraction, accompanied by molecular simulations, reveals that the breathing mechanism of 1 involves the bending of metal–ligand bonds and the sliding of interpenetrated frameworks, while 2 undergoes simple distortion of linkers. Reversible oxidation and reduction of TTF moieties changes the linker flexibility, which in turn switches the breathing behavior of 2. The redox-switchable breathing behavior can potentially be applied to the design of stimuli-responsive MOFs.},
doi = {10.1038/s41467-017-02256-y},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {12}
}
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Figures / Tables:
Fig. 1: Topology-guided design of compounds 1 and 2. a [In(COO)4]− inorganic building unit as a tetrahedral node; b TTFTB organic linker as a square planar node; c pts topology; d, e two networks derived from pts topology; f, g structure of compounds 1 and 2. Color scheme: In, cyan;more »
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