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Entropy-driven self-assembly of chiral nematic liquid crystalline phases of AgNR@Cu2O hyper branched coaxial nanorods and thickness-dependent handedness transition

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Abstract

The chiral nematic liquid crystalline phase (CNLCP) of noble metal nanorods induces a strong chiroptical response due to their intrinsic physical and chemical properties. Here, we demonstrate that the formation of CNLCP of Ag nanorods (AgNRs) originates from their bent-shape and is the result of purely entropic effects. The chirality of the liquid crystalline phase of AgNR@Cu2O hyper branched coaxial nanorods (HBCNRs) can be switched from left-handed to right-handed by increasing Cu2O thickness. It is proposed that the increase of coating thickness decreases the curvature of nanorods, which induces variation of the twist constant (K2) and bend elastic constant (K3). The increased thickness also changes the direction of director with respect to the helical axis. In addition, hydrogen bonds can break the CNLCP, which can be attributed to their stronger effection compared to van der Waals forces and electrostatic interactions. In contrast to the variation of coating thickness, the surface morphology, constituents of the hybrid building blocks and polarity of the solvents do not play important roles in the handedness transition of the liquid crystalline phase. Furthermore, the results presented here give insight into the structure–property relationship and our strategy provides guidance for the synthesis of other inorganic chiral suprastructures driven by entropic effects.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 20971051 and 21621001), and the Education Department of Jilin Province (No. 2016407). We are very grateful to Prof. Xudong Zhao for helpful discussion.

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Authors and Affiliations

  1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, China

    Guiqing Cheng, Yu Wang & Jihong Yu

  2. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, China

    Kun Liu

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  1. Guiqing Cheng
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Correspondence to Yu Wang or Jihong Yu.

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12274_2017_1715_MOESM1_ESM.pdf

Entropy-driven self-assembly of chiral nematic liquid crystalline phases of AgNR@Cu2O hyper branched coaxial nanorods and thickness-dependent handedness transition

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Cheng, G., Wang, Y., Liu, K. et al. Entropy-driven self-assembly of chiral nematic liquid crystalline phases of AgNR@Cu2O hyper branched coaxial nanorods and thickness-dependent handedness transition. Nano Res. 11, 1018–1028 (2018). https://doi.org/10.1007/s12274-017-1715-z

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