Hybrid Chloroantimonates(III): Thermally Induced Triple-Mode Reversible Luminescent Switching and Laser-Printable Rewritable Luminescent Paper.

Two hybrid chloroantimonates(III), [Bzmim]3 SbCl6 (1, Bzmim=1-benzyl-3-methylimidazolium, Tm1 =410 K) and [Bzmim]2 SbCl5 (2, Tm2 =348 K) are presented. 1 exhibits green emission (quantum efficiency of 87.5 %); 2 exhibits blue and red emissions under the irradiation of 310 and 396 nm light, respectively. Using different cooling methods, crystalline 1 and IL@2 (IL=ionic liquid of [Bzmim]Cl) could be generated from the molten 1. Reversible structural and PL transformation triggered by moisture or heat was observed between 1 and IL@2. Such PL switching, combined with the crystallization-induced PL properties of 1 and 2, resulted in the firstly reported triple-mode reversible PL switching, that is, on-off (T>Tm1 ), color switching (T<Tm2 ), and on-off-on (Tm2 <T<Tm1 ). Furthermore, ink- and mask-free laser-printable rewritable PL paper was achieved. This study demonstrates the promise of dynamic insertion/extraction of ILs in hybrid chloroantimonates for anti-counterfeiting and rewritable PL paper.