Reversible Luminescent Switching Induced by Heat/Water Treatment in a Zero-Dimensional Hybrid Antimony(Ⅲ) Chloride

Recently zero-dimensional (0-D) inorganic-organic metal halides (IOMHs) have become a promising class of optoelectronic materials. Herein, we report a new photoluminescent (PL) 0-D antimony(III)-based IOMH single crystal, namely [H₂BPZ][SbCl₅]·H₂O (BPZ = benzylpiperazine). Photophysical characterizations indicate that [H₂BPZ][SbCl₅]·H₂O exhibits singlet/triplet dual-band emission. Density functional theory (DFT) calculations suggest that [H₂BPZ][SbCl₅]·H₂O has the large energy difference between singlet and triplet states, which might induce the dual emission in this compound. Temperature-dependent PL spectra analyses suggest the soft lattice and strong electron-phonon coupling in this compound. Thermogravimetric analysis shows that the water molecules in the lattice of the title crystal could be removed by thermal treatment, giving rise to a dehydrated phase of [H₂BPZ][SbCl₅]. Interestingly, such structural transformation is accompanied by a reversible PL emission transition between red light (630 nm, dehydrated phase) and yellow light (595 nm, water-containing phase). When being exposed to an environment with 77% relative humidity, the emission color of the dehydrated phase was able to change from red to yellow within 20 s, and the red emission could be restored after reheating. The red to yellow emission switching could be achieved in acetone with water concentration as low as 0.2 vol%. The reversible PL transition phenomenon makes [H₂BPZ][SbCl₅]·H₂O a potential material for luminescent water-sensing.