Order-disorder transition of a rigid cage cation embedded in a cubic perovskite

Zhifang Shi; Zheng Fang; Jingshu Wu; Yi Chen; Qixi Mi

doi:10.1038/s41467-021-23917-z

Order-disorder transition of a rigid cage cation embedded in a cubic perovskite

Nat Commun. 2021 Jun 10;12(1):3548. doi: 10.1038/s41467-021-23917-z.

Authors

Zhifang Shi¹, Zheng Fang¹, Jingshu Wu¹, Yi Chen¹, Qixi Mi²

Affiliations

¹ School of Physical Science and Technology, ShanghaiTech University, Shanghai, China.
² School of Physical Science and Technology, ShanghaiTech University, Shanghai, China. miqx@shanghaitech.edu.cn.

Abstract

The structure and properties of organic-inorganic hybrid perovskites are impacted by the order-disorder transition, whose driving forces from the organic cation and the inorganic framework cannot easily be disentangled. Herein, we report the design, synthesis and properties of a cage-in-framework perovskite AthMn(N₃)₃, where Ath⁺ is an organic cation 4-azatricyclo[2.2.1.0^2,6]heptanium. Ath⁺ features a rigid and spheroidal profile, such that its molecular reorientation does not alter the cubic lattice symmetry of the Mn(N₃)₃^- host framework. This order-disorder transition is well characterized by NMR, crystallography, and calorimetry, and associated with the realignment of Ath⁺ dipole from antiferroelectric to paraelectric. As a result, an abrupt rise in the dielectric constant was observed during the transition. Our work introduces a family of perovskite structures and provides direct insights to the order-disorder transition of hybrid materials.

Abstract

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