Stereochemistry-Dependent, Mechanoresponsive Supramolecular Host Assemblies for Fullerenes: A Guest-Induced Enhancement of Thixotropy

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• 作者：Arnab Dawn ; Tomohiro Shiraki ; Hiroshi Ichikawa ; Akihiko Takada ; Yoshiaki Takahashi ; Youichi Tsuchiya ; Le Thi Ngoc Lien ; Seiji Shinkai
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：February 1, 2012
• 年：2012
• 卷：134
• 期：4
• 页码：2161-2171
• 全文大小：509K
• 年卷期：v.134,no.4(February 1, 2012)
• ISSN：1520-5126

文摘

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. C₆₀ and C₇₀ 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. C₇₀ appears to be a superior guest in terms of property enhancement due to its better size fitting with the concave-shaped host.