Giant anisotropic thermal expansion actuated by thermodynamically assisted reorientation of imidazoliums in a single crystal

Zi-Shuo Yao (), Hanxi Guan, Yoshihito Shiota, Chun-Ting He, Xiao-Lei Wang, Shu-Qi Wu, Xiaoyan Zheng, Sheng-Qun Su, Kazunari Yoshizawa, Xueqian Kong, Osamu Sato () and Jun Tao ()
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Zi-Shuo Yao: Beijing Institute of Technology
Hanxi Guan: Zhejiang University
Yoshihito Shiota: Kyushu University
Chun-Ting He: Jiangxi Normal University
Xiao-Lei Wang: Beijing Institute of Technology
Shu-Qi Wu: Kyushu University
Xiaoyan Zheng: Beijing Institute of Technology
Sheng-Qun Su: Kyushu University
Kazunari Yoshizawa: Kyushu University
Xueqian Kong: Zhejiang University
Osamu Sato: Kyushu University
Jun Tao: Beijing Institute of Technology

Nature Communications, 2019, vol. 10, issue 1, 1-8

Abstract: Abstract Materials demonstrating unusual large positive and negative thermal expansion are fascinating for their potential applications as high-precision microscale actuators and thermal expansion compensators for normal solids. However, manipulating molecular motion to execute huge thermal expansion of materials remains a formidable challenge. Here, we report a single-crystal Cu(II) complex exhibiting giant thermal expansion actuated by collective reorientation of imidazoliums. The circular molecular cations, which are rotationally disordered at a high temperature and statically ordered at a low temperature, demonstrate significant reorientation in the molecular planes. Such atypical molecular motion, revealed by variable-temperature single crystal X-ray diffraction and solid-state NMR analyses, drives an exceptionally large positive thermal expansion and a negative thermal expansion in a perpendicular direction of the crystal. The consequent large shape change (~10%) of bulk material, with remarkable durability, suggests that this complex is a strong candidate as a microscale thermal actuating material.

Date: 2019
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DOI: 10.1038/s41467-019-12833-y

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