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Topological Impact on the Kinetic Stability of Supramolecular Polymers
Atsuhito Suzuki1, Keisuke Aratsu1, Sougata Datta2
1Division of Advanced Science and Engineering, Graduate School of Engineering , Chiba University , 1-33 Yayoi-cho, Inage-ku , Chiba 263-8522 , Japan.
Journal of the American Chemical Society
|July 27, 2019
Summary
Topological differences in metastable supramolecular polymers significantly impact their kinetic stability. Cyclized polymers exhibit greater stability than open-ended ones, enabling controlled transformations into thermodynamic structures.
Area of Science:
- Supramolecular Chemistry
- Polymer Science
- Materials Science
Background:
- Metastable molecular assemblies are crucial in supramolecular polymer research.
- Distinguishing kinetic stabilities of similar supramolecular motifs is challenging.
- Topological variations can influence assembly dynamics.
Purpose of the Study:
- To investigate the topological effect on kinetic stabilities of metastable supramolecular polymers.
- To differentiate the kinetic stability between cyclized and open-ended supramolecular polymers.
- To explore controlled transformations into thermodynamically stable structures.
Main Methods:
- Formation of azobenzene-containing monomer mixtures in nonpolar solvents.
- Thermal treatment to induce kinetic and thermodynamic assembly formation.
- Atomic Force Microscopy (AFM) for direct visualization of molecular assemblies.
- Photoinduced structural changes to probe kinetic stability.
Main Results:
- Kinetically formed complex mixtures of supramolecular polymers with cyclized and open-ended topologies were generated.
- Thermodynamically stable twisted fibrils were obtained upon further heating.
- Cyclized supramolecular polymers demonstrated superior kinetic stability against thermal transformation compared to open-ended counterparts.
- Photoinduced opening successfully converted metastable cyclized species into thermodynamic structures.
Conclusions:
- Topology plays a critical role in determining the kinetic stability of metastable supramolecular polymers.
- The absence of aggregate termini in cyclized structures enhances their kinetic stability.
- Controlled photoinduced transformations offer a pathway to manipulate supramolecular polymer states.
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