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

Abstract

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–on^I–on^II 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.

Keywords

information encryption / Sb³⁺-doping / Sn(IV)-based metal halides / structural modulation / triple-mode

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