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

被引：178

作者：

Su, Jian ^{[1
]}

Yuan, Shuai ^{[2
]}

Wang, Hai-Ying ^{[1
]}

Huang, Lan ^{[3
]}

Ge, Jing-Yuan ^{[1
]}

Joseph, Elizabeth ^{[2
]}

Qin, Junsheng ^{[2
]}

Cagin, Tahir ^{[2
,4
]}

Zuo, Jing-Lin ^{[1
]}

Zhou, Hong-Cai ^{[2
,3
]}

机构：

[1] Nanjing Univ, Sch Chem & Chem Engn, State Key Lab Coordinat Chem, Collaborat Innovat Ctr Adv Microstruct, Nanjing 210093, Jiangsu, Peoples R China

[2] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA

[3] Texas A&M Univ, Dept Mat Sci & Engn, College Stn, TX 77843 USA

[4] Texas A&M Univ, Artie McFerrin Dept Chem Engn, College Stn, TX 77843 USA

来源：

NATURE COMMUNICATIONS | 2017年 / 8卷

基金：

中国国家自然科学基金;

关键词：

METHANE STORAGE; FLEXIBILITY; ADSORPTION; CRYSTAL; GUEST; CO2;

D O I：

10.1038/s41467-017-02256-y

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

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 N-2. 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.

引用

页数：8

共 36 条

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