Assembly of Supramolecular Nanotubes from Molecular Triangles and 1,2-Dihalohydrocarbons

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• 作者：Zhichang Liu ; Guoliang Liu ; Yilei Wu ; Dennis Cao ; Junling Sun ; Severin T. Schneebeli ; Majed S. Nassar ; Chad A. Mirkin ; J. Fraser Stoddart
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：November 26, 2014
• 年：2014
• 卷：136
• 期：47
• 页码：16651-16660
• 全文大小：893K
• ISSN：1520-5126

文摘

Precise control of molecular assembly is a challenging goal facing supramolecular chemists. Herein, we report the highly specific assembly of a range of supramolecular nanotubes from the enantiomeric triangular naphthalenediimide-based macrocycles (RRRRRR)- and (SSSSSS)-NDI-螖 and a class of similar solvents, namely, the 1,2-dihalo-ethanes and -ethenes (DXEs). Three kinds of supramolecular nanotubes are formed from the columnar stacking of NDI-螖 units with a 60掳 mutual rotation angle as a result of cooperative [C鈥揌路路路O] interactions, directing interactions of the [X路路路X]-bonded DXE chains inside the nanotubes and lateral [X路路路蟺] or [蟺路路路蟺] interactions. They include (i) semiflexible infinite nanotubes formed in the gel state from NDI-螖 and (E)-1,2-dichloroethene, (ii) rigid infinite nonhelical nanotubes produced in the solid state from NDI-螖 and BrCH₂CH₂Br, ClCH₂CH₂Br, and ClCH₂CH₂I, and (iii) a pair of rigid tetrameric, enantiomeric single-handed (P)- and (M)-helical nanotubes formed in the solid state from the corresponding (RRRRRR)- and (SSSSSS)-NDI-螖 with ClCH₂CH₂Cl. In case (i), only the electron-rich C鈺怌 double bond of (E)-1,2-dichloroethene facilitates the gelation of NDI-螖. In cases (ii) and (iii), the lengths of anti-DXEs determine the translation of the chirality of NDI-螖 into the helicity of nanotubes. Only ClCH₂CH₂Cl induces single-handed helicity into the nanotubes. The subtle interplay of noncovalent bonding interactions, resulting from the tiny structural variations involving the DXE guests, is responsible for the diverse and highly specific assembly of NDI-螖. This research highlights the critical role that guests play in constructing assembled superstructures of hosts and offers a novel approach to creating supramolecular nanotubes.