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

Jian Su, Shuai Yuan, Hai-Ying Wang, Lan Huang, Jing-Yuan Ge, Elizabeth Joseph, Junsheng Qin, Tahir Cagin, Jing-Lin Zuo () and Hong-Cai Zhou ()
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Jian Su: Nanjing University
Shuai Yuan: Texas A&M University
Hai-Ying Wang: Nanjing University
Lan Huang: Texas A&M University
Jing-Yuan Ge: Nanjing University
Elizabeth Joseph: Texas A&M University
Junsheng Qin: Texas A&M University
Tahir Cagin: Texas A&M University
Jing-Lin Zuo: Nanjing University
Hong-Cai Zhou: Texas A&M University

Nature Communications, 2017, vol. 8, issue 1, 1-8

Abstract: 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.

Date: 2017
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DOI: 10.1038/s41467-017-02256-y

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