Temperature Control of Sequential Nucleation–Growth Mechanisms in Hierarchical Supramolecular Polymers. Issue 56 (9th September 2019)

• Record Type: Journal Article
• Authors: Osypenko, Artem; Moulin, Emilie; Gavat, Odile; Fuks, Gad; Maaloum, Mounir; Koenis, Mark A. J.; Buma, Wybren Jan; Giuseppone, Nicolas
• Is Part Of: Chemistry. Volume 25:Issue 56(2019)
• Page Start: 13008
• Page End: 13016
• Publication Date: 2019-09-09
• Subjects: hierarchical self-assembly -- organogelators -- pathway complexity -- supramolecular polymers; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201902898
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Upon cooling in solution, chiral triarylamine tris‐amide unimers produce organogels by stacking into helical supramolecular polymers, which subsequently bundle into larger fibers. Interestingly, circular dichroism, vibrational circular dichroism, and AFM imaging of the chiral self‐assemblies revealed that monocolumnar P ‐helical fibrils formed upon fast cooling, whereas bundled M ‐superhelical fibers formed upon slow cooling. The mechanistic study of this structural bifurcation reveals the presence of a strong memory effect, reminiscent of a complex stepwise combination of primary and secondary nucleation‐growth processes. These results highlight the instrumental role of sequential self‐assembly processes to control supramolecular architectures of multiple hierarchical order. Abstract : Chiral supramolecular polymers produce distinct hierarchical helical fibers that can be selectively accessed by controlling their sequential nucleation–growth mechanisms.