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Redox-switchable breathing behavior in tetrathiafulvalene-based metal-organic frameworks
Jian Su1, Shuai Yuan2, Hai-Ying Wang1
1State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093, China.
Nature Communications
|December 10, 2017
Summary
Researchers developed novel metal-organic frameworks (MOFs) exhibiting switchable breathing responses to guest molecules and redox conditions. This discovery advances stimuli-responsive materials design.
Area of Science:
- Materials Science
- Chemistry
- Nanotechnology
Background:
- Stimuli-responsive materials, particularly metal-organic frameworks (MOFs), are crucial for advanced applications.
- MOFs that respond to external stimuli like guest molecules or redox conditions offer unique functionalities.
- Integrating multiple responsive properties within a single framework presents a significant challenge.
Purpose of the Study:
- To design and synthesize novel MOFs with coupled redox-switchable and guest-molecule-induced breathing behaviors.
- To investigate the distinct breathing mechanisms of isomeric MOFs.
- To explore the potential of these MOFs in stimuli-responsive applications.
Main Methods:
- Topological design and synthesis of two flexible isomeric MOFs (compounds 1 and 2) using indium metal nodes and tetrathiafulvalene-based linkers.
- Characterization using single-crystal X-ray diffraction.
- Analysis of breathing mechanisms through molecular simulations.
- Investigation of redox-switchable properties via oxidation and reduction of tetrathiafulvalene moieties.
Main Results:
- Two isomeric MOFs, In(Me2NH2)(TTFTB), were successfully synthesized.
- Compound 1 exhibits breathing via metal-ligand bond bending and framework sliding, while compound 2 shows linker distortion.
- The breathing behavior of compound 2 is reversibly switched by the oxidation and reduction of the tetrathiafulvalene linker.
- Distinct responses to N2 gas were observed for the two MOFs.
Conclusions:
- The study successfully coupled redox-switchable properties with guest-induced breathing in MOFs.
- The findings provide insights into the mechanisms governing MOF breathing.
- This work paves the way for designing advanced stimuli-responsive MOFs with tunable behaviors.
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