期刊
CHEMISTRY OF MATERIALS
卷 31, 期 24, 页码 10236-10242出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.9b04232
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资金
- National Natural Science Foundation of China [21771037, 21805033]
- Natural Science Foundation of Jiangsu Province (JSNSF) [BK20170659]
Organic-inorganic hybrid molecular ferroelastics have gained widespread attention as a promising candidate for data storage, sensor, and mechanical switch applications. However, it remains a great challenge to construct new molecular ferroelastic materials. Based on the quasi-spherical theory, we designed and synthesized a new quasi-spherical cation [DMIE](+) ([DMIE](+) is dimethyl-isopropyl-ethyl-ammonium cation) to expect ferroelastic materials. Unfortunately, [DMIE][Cd(SCN)(3)] (1) undergoes a structural phase transition from the space group P6(3) to P6(3)/mmc, which is not among the 94 species of ferroelastic phase transitions as suggested by Aizu. Herein, by introducing electronegative halogen (F, Cl, or Br) atoms to the [DMIE](+) cation, the symmetry groups of the corresponding cadmium thiocyanate perovskites get efficiently lowered to orthorhombic Pbca to induce ferroelastic phase transitions with an Aizu notation of 6/mmmFmmm. The spontaneous strain value reduces from 0.0778 in a fluorinated product to 0.0428 in a brominated product. Accompanied by the introduction of halogen groups from F to Br, the phase transition temperature increases from 248.6 to 367.8 K. This work demonstrates that the strategy of combining a quasi-spherical molecule with specific electronegative groups provides an efficient way to offer molecular ferroelastic materials.
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