Redox-switchable breathing behavior in tetrathiafulvalene-based metal–organic frameworks

Su, Jian; Yuan, Shuai; Wang, Hai-Ying; Huang, Lan; Ge, Jing-Yuan; Joseph, Elizabeth; Qin, Junsheng; Cagin, Tahir; Zuo, Jing-Lin; Zhou, Hong-Cai

doi:10.1038/s41467-017-02256-y

Title: Redox-switchable breathing behavior in tetrathiafulvalene-based metal–organic frameworks

Journal Article · 07 December 2017 · Nature Communications

DOI: https://doi.org/10.1038/s41467-017-02256-y · OSTI ID:1470031

Su, Jian ^[1]; Yuan, Shuai ^[2]; Wang, Hai-Ying ^[1];

^[2]; Ge, Jing-Yuan ^[1]; Joseph, Elizabeth ^[2]; Qin, Junsheng ^[2]; Cagin, Tahir ^[2];

^[1];

^[2]

Nanjing Univ. (China)
Texas A & M Univ., College Station, TX (United States)

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.

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Research Organization:: Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC)

Sponsoring Organization:: USDOE SC Office of Basic Energy Sciences (SC-22)

Grant/Contract Number:: EE0007049; FE0026472; SC0001015

OSTI ID:: 1470031

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 8; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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