Stereochemistry-dependent, mechanoresponsive supramolecular host assemblies for fullerenes: A guest-induced enhancement of thixotropy

Arnab Dawn, Tomohiro Shiraki, Hiroshi Ichikawa, Akihiko Takada, Yoshiaki Takahashi, Youichi Tsuchiya, Le Thi Ngoc Lien, Seiji Shinkai

Research output: Contribution to journalArticle

78 Citations (Scopus)

Abstract

Self-assembly behaviors of a series of systems (G1, G2, and G3) possessing same organic building blocks based on a substituted anthracene have been investigated in decalin. G2 and G3 are dominated by head-to-tail (ht) and head-to-head (hh) type dimers of G1, respectively. G1 gives a thermoresponsive gel that behaves ideally, showing frequency-independent elastic and viscous moduli. Interestingly, G2 produces a thixotropic gel that shows the signature of structural relaxation, signifying the dynamic nature of the system. In contrast, G3 remains fluidlike. As investigated by scanning electron microscopy (SEM), in the assembly process of G2, first disklike nanoaggregates are formed, and in the second step these aggregates interact to construct the densely packed secondary assembly. A transition from secondary assembly to primary assembly under shear initiates the mechanoresponsive destruction of the gel. In the self-assembly process, G1 propagates in a one-dimensional fashion, whereas G2 and G3 can propagate in a two-dimensionional fashion. The same side orientation of the substituents in G3 facilitates the formation of a compact closed-shell-type structure, which results in the generation of isolated nanocrystals. The long-range weak interaction together with the capability of propagating in two dimensions is found to be essential for the construction of such a mechanoresponsive assembly. C 60 and C 70 could be incorporated successfully in G2 assembly to develop mechanoresponsive fullerene assemblies. The presence of fullerenes not only enhances the elastic properties of G2 but also intensifies the thixotropy. C 70 appears to be a superior guest in terms of property enhancement due to its better size fitting with the concave-shaped host.

Original languageEnglish
Pages (from-to)2161-2171
Number of pages11
JournalJournal of the American Chemical Society
Volume134
Issue number4
DOIs
Publication statusPublished - Feb 1 2012

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Stereochemistry-dependent, mechanoresponsive supramolecular host assemblies for fullerenes: A guest-induced enhancement of thixotropy'. Together they form a unique fingerprint.

  • Cite this