Topological Impact on the Kinetic Stability of Supramolecular Polymers

Suzuki, Atsuhito; Aratsu, Keisuke; Datta, Sougata; Shimizu, Nobutaka; Takagi, Hideaki; Haruki, Rie; Adachi, Shin-ichi; Hollamby, Martin; Silly, Fabien; Yagai, Shiki

Abstract

Kinetically formed metastable molecular assemblies have attracted increasing interest especially in the field of supramolecular polymers. In most cases, metastable assemblies are ensemblies of aggregates based on the same supramolecular motif but with different lengths or sizes, and therefore their kinetic stabilities are experimentally indistinguishable. Herein, we demonstrate a topological effect on kinetic stabilities in a complex mixture of metastable supramolecular polymers. Our azobenzene-incorporated monomer upon heating in nonpolar solvent at ambient temperature kinetically forms complex mixtures of supramolecular polymers with cyclized and open-ended randomly coiled topologies. Upon further heating, we obtained thermodynamically stable twisted fibrils organizing into crystalline fibers. Through the direct visualization of the complex supramolecular polymer mixtures by atomic force microscopy, we demonstrate that the cyclized supramolecular polymer has superior kinetic stability compared to the open-ended species toward the thermal transformation into twisted fibrils. Since the superior kinetic stability of the cyclized species can be attributed to the absence of aggregate termini, we could convert them fully into the thermodynamic species through photoinduced opening of the cyclized structures.

Citation

Suzuki, A., Aratsu, K., Datta, S., Shimizu, N., Takagi, H., Haruki, R., …Yagai, S. (2019). Topological Impact on the Kinetic Stability of Supramolecular Polymers. Journal of the American Chemical Society, 141(33), 13196-13202. https://doi.org/10.1021/jacs.9b06029

• Journal Article Type: Article
• Online Publication Date: Jul 26, 2019
• Publication Date: Aug 21, 2019
• Deposit Date: Jun 16, 2023
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 141
• Issue: 33
• Pages: 13196-13202
• DOI: https://doi.org/10.1021/jacs.9b06029
• Keywords: Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis