Realizing efficient emission and triple‐mode photoluminescence switching in air‐stable tin(IV)‐based metal halides via antimony doping and rational structural modulation

• Published in: Aggregate (Hoboken) Vol. 5; no. 1
• Main Authors: He, Xuefei, Peng, Hui, Wei, Qilin, Zhou, Zhijie, Zhang, Guolun, Du, Zhentao, Zhao, Jialong, Zou, Bingsuo
• Format: Journal Article
• Language: English
• Published: Guangzhou John Wiley & Sons, Inc 01-02-2024; Wiley
• Subjects: Charged particles; Composite materials; Crystal structure; Efficiency; information encryption; Lead; Ligands; Optical properties; Sb3+‐doping; Sn(IV)‐based metal halides; Spectrum analysis; structural modulation; Toxicity; triple‐mode
• ISSN: 2692-4560; 2766-8541; 2692-4560
• DOI: 10.1002/agt2.407

Recently, many lead‐free metal halides with diverse structures and highly efficient emission have been reported. However, their poor stability and single‐mode emission color severely limit their applications. Herein, three homologous Sb3+‐doped zero‐dimensional (0D) air‐stable Sn(IV)‐based metal halides with different crystal structures were developed by inserting a single organic ligand into SnCl4 lattice, which brings different optical properties. Under photoexcitation, (C25H22P)SnCl5@Sb·CH4O (Sb3+−1) does not emit light, (C25H22P)2SnCl6@Sb‐α (Sb3+−2α) shines bright yellow emission with a photoluminescence quantum yield (PLQY) of 92%, and (C25H22P)2SnCl6@Sb‐β (Sb3+−2β) exhibits intense red emission with a PLQY of 78%. The above three compounds show quite different optical properties should be due to their different crystal structures and the lattice distortions. Particularly, Sb3+−1 can be successfully converted into Sb3+−2α under the treatment of C25H22PCl solution, accompanied by a transition from nonemission to efficient yellow emission, serving as a “turn‐on” photoluminescence (PL) switching. Parallelly, a reversible structure conversion between Sb3+−2α and Sb3+−2β was witnessed after dichloromethane or volatilization treatment, accompanied by yellow and red emission switching. Thereby, a triple‐mode tunable PL switching of off–onI–onII can be constructed in Sb3+‐doped Sn(IV)‐based compounds. Finally, we demonstrated the as‐synthesized compounds in fluorescent anticounterfeiting, information encryption, and optical logic gates.
Three homologous compounds of Sb3+‐doped zero‐dimensional Sn(IV)‐based metal halides with different crystal structures were synthesized, and they show different optical properties. Particularly, the nonemitting Sb3+−1 can be converted into yellow‐emitting Sb3+−2α, and further turn into red‐emitting Sb3+−2β under the treatment of C25H22PCl and CH2Cl2 solution, respectively. Thus, a triple‐mode PL switching of off–onI–onII was constructed in Sb3+‐doped Sn(IV)‐based metal halides.