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Helicene Chemistry pp 247–265Cite as

Helicene Assemblies

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Abstract

This chapter describes the assembly behaviors of helicenes and the properties of aggregates. It was found that optically pure helicenes form ordered monolayer on Ni(111), while thia[11]helicene on gold surfaces can form the 2D ordered layer, and structures of the Au surfaces play an important role in the assembly behaviors. The repulsive interactions between (M)-[7]helicenes result in supramolecular chirality of the close-packed 2D layer on Cu(111); but for racemic [7]helicene, an unprecedented chirality amplification is observed. Similarly, (M)-[7]helicene-2-carboxylic acid self-assembles into island structures, while the racemates give nanowire-like aggregates. Besides the chiral discrimination, the hydrogen bonds, the dispersive forces in the metal surfaces, temperatures, and even substituents can influence the assembly behaviors of helicenes. It was also found that mixing the pseudoenantiomeric oligomers composed by [4]helicene units with the same helicity can result in two-component gel, in which the π-π interactions between the helicenes are the driving force. After ultrasonication, gelation of (M)-[4]helicene derivative can occur upon the diffusion of the gelator from THF phase to hexane phase. Moreover, (P)-[4]helicene-grafted SiO2 NPs can capture the hetero-double-helix of ethynylhelicene oligomers from the gelation procedure. Furthermore, it was found that enantiopure helicenebisquinone can self-assemble into fibers or a true hexagonal assembly of right-handed helices. Different linkers in cycloalkyne-[4]Helicene oligomers can control the intra- and intermolecular aggregation, and dynamic and reversible polymorphism exists in the cyclic bis(ethynylhelicene) oligomers. In addition, hydrogen bonds can also be utilized for the construction of screw-shaped fibrous assemblies, which exhibit excellent CPL properties.

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

    Chuan-Feng Chen & Yun Shen

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  1. Chuan-Feng Chen
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  2. Yun Shen
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Correspondence to Chuan-Feng Chen .

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Chen, CF., Shen, Y. (2017). Helicene Assemblies. In: Helicene Chemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-53168-6_13

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