Subtly tuning intermolecular hydrogen bonds in hybrid crystals to achieve ultrahigh-temperature molecular ferroelastic.
Hui YeXiao-Xian ChenDe-Xuan LiuBing-Qing ZhaoYao-Bin LiYing ZengWei-Xiong ZhangXiao-Ming ChenPublished in: Chemical science (2022)
Molecular-based ferroic phase-transition materials have attracted increasing attention in the past decades due to their promising potential as sensors, switches, and memory. One of the long-term challenges in the development of molecular-based ferroic materials is determining how to promote the ferroic phase-transition temperature ( T c ). Herein, we present two new hexagonal molecular perovskites, (nortropinonium)[CdCl 3 ] (1) and (nortropinium)[CdCl 3 ] (2), to demonstrate a simple design principle for obtaining ultrahigh- T c ferroelastic phase transitions. They consist of same host inorganic chains but subtly different guest organic cations featuring a rigid carbonyl and a flexible hydroxyl group in 1 and 2, respectively. With stronger hydrogen bonds involving the carbonyl but a relatively lower decomposition temperature ( T d , 480 K), 1 does not exhibit a crystalline phase transition before its decomposition. The hydroxyl group subtly changes the balance of intermolecular interactions in 2 via reducing the attractive hydrogen bonds but increasing the repulsive interactions between adjacent organic cations, which finally endows 2 with an enhanced thermal stability ( T d = 570 K) and three structural phase transitions, including two ferroelastic phase transitions at ultrahigh T c values of 463 K and 495 K, respectively. This finding provides important clues to judiciously tuning the intermolecular interactions in hybrid crystals for developing high- T c ferroic materials.