Reversible Local Protonation‐Deprotonation: Tuning Stimuli‐Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti‐Counterfeiting and Encryption

• Published in: Angewandte Chemie International Edition Vol. 63; no. 46; pp. e202410416 - n/a
• Main Authors: Liu, Dan‐Yang, Xiong, Lin‐Yuan, Dong, Xi‐Yan, Han, Zhen, Liu, Hua‐Li, Zang, Shuang‐Quan
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 11.11.2024
• Edition: International ed. in English
• Subjects: Bromides; Cations; Chiral hybrid zinc halides; Circular dichroism; Circular polarization; Counterfeiting; Dichroism; Encryption; Halides; Information storage; Information storage and encryption; Luminescence; Metal halides; Optical properties; Protonation; Reversible local protonation-deprotonation; Stimuli; Stimuli-responsiveness; Structural distortions; Zinc; Chiral hybrid zinc halides; Reversible local protonation-deprotonation; stimuli-responsiveness; Structural distortions; Information storage and encryption
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202410416

Precise control over the organic composition is crucial for tailoring the distinctive structures and properties of hybrid metal halides. However, this approach is seldom utilized to develop materials that exhibit stimuli‐responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((R/S)‐C12H16N2)ZnBr4 ((R/S‐LH2)ZnBr4) and monoprotonated ((R/S)‐C12H15N2)2ZnBr4 ((R/S‐LH1)2ZnBr4), derived from the chiral organic amine (R/S)‐2,3,4,9‐Tetrahydro‐1H‐carbazol‐3‐amine ((R/S)‐C12H14N2). These compounds showcase luminescent properties; the zero‐dimensional biprotonated form emits green light at 505 nm, while the monoprotonated form, with a pseudo‐layered structure, displays red luminescence at 599 and 649 nm. Remarkably, the reversible local protonation‐deprotonation behavior of the organic cations allows for exposure to polar solvents and heating to induce reversible structural and luminescent transformations between the two forms. Theoretical calculations reveal that the lower energy barrier associated with the deprotonation process within the pyrrole ring is responsible for the local protonation‐deprotonation behavior observed. These enantiomorphic hybrid zinc bromides also exhibit switchable circular dichroism (CD) and CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting the halogen ions. Importantly, the unique stimuli‐responsive CPL characteristics position these hybrid zinc halides as promising candidates for applications in information storage, anti‐counterfeiting, and information encryption. Biprotonated (R/S‐LH2)ZnX4 and monoprotonated (R/S‐LH1)2ZnX4 (X=Cl, Br) were constructed from a single chiral organic cation. The reversible structural transformation induced by polar solvents and HBr/heat engenders chiroptical switching behaviors. The structural design strategy developed in this work elucidates the structure‐property mechanism underlying the structural transitions and the distortion‐related chirality transfer.