Zhang Zhizhuan, Lin Yangpeng, Jin Jiance, Gong Liaokuo, Peng Yingchen, Song Ying, Shen Nannan, Wang Zeping, Du Kezhao, Huang Xiaoying
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
College of Chemistry and Materials Science, Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, Fuzhou, Fujian, 350007, P. R. China.
Angew Chem Int Ed Engl. 2021 Oct 18;60(43):23373-23379. doi: 10.1002/anie.202110088. Epub 2021 Sep 24.
Herein, a new mechanism, namely, crystalline phase recognition (CPR), is proposed for the single-crystal-to-single-crystal (SCSC) transition of metal halides. Chiral β-[Bmmim] SbCl (Bmmim=1-butyl-2,3-methylimidazolium) can recognize achiral α-[Bmmim] SbCl on the basis of a key-lock feature through intercontact of their single crystals, resulting in a domino phase transition (DPT). The concomitant photoluminescence (PL) switching enables observation of the DPT in situ. The liquid eutectic interface, stress-strain transfer, and feasible thermodynamics are key issues for the CPR. DFT calculations and PL measurements revealed that the optical absorption and emission of the isomers mainly originate from [SbCl ] anions. The structural effects (e.g., supramolecular interactions and [SbCl ] distortion) on the optical emission are clarified. As a novel type of stimuli response, the CPR-induced DPT and luminescence switching exhibit potential for application in advanced time-resolved information encryption.
在此,我们提出了一种新机制,即晶相识别(CPR),用于金属卤化物的单晶到单晶(SCSC)转变。手性β-[Bmmim]SbCl(Bmmim = 1-丁基-2,3-二甲基咪唑鎓)可以基于其单晶之间的相互接触,通过锁钥特性识别非手性α-[Bmmim]SbCl,从而导致多米诺相变(DPT)。伴随的光致发光(PL)切换使得能够原位观察DPT。液-共晶界面、应力-应变传递和可行的热力学是CPR的关键问题。密度泛函理论(DFT)计算和PL测量表明,异构体的光吸收和发射主要源于[SbCl]阴离子。阐明了结构效应(例如超分子相互作用和[SbCl]畸变)对光发射的影响。作为一种新型的刺激响应,CPR诱导的DPT和发光切换在先进的时间分辨信息加密中具有应用潜力。