Component/Stimulus‐Dependent Multi‐Exciton Emission in Zr(IV)‐Based Organic Metal Halides Triggered by Supramolecular Assembly and Antimony Doping
Hui Peng, Wei Tian, Qilin Wei, Linghang Kong, Guang Dai, Jialong Zhao, Bingsuo Zou
Abstract
Abstract Recently, Sb 3+ ‐activated 0D Zr(IV)‐based metal halides have gained enormous attention for their unique optical properties. However, realizing efficient white emission and multiple reversible emissions in a single system remains a great challenge. Parallelly, the currently reported Sb 3+ ‐activated Zr(IV)‐based organic metal halides are mainly through aimless regulation of the type of A‐site organic cations, severely limiting their development. Herein, all‐inorganic Cs 2 ZrCl 6 :Sb 3+ is employed as the conformational model, three different compounds of Sb 3+ ‐doped [18‐crown‐6@A] 2 ZrCl 6 (A = K, Rb, Cs) are developed via supramolecular assembly. All compounds show efficient tunable white emission with luminous efficiency of 91.28% for [18‐crown‐6@K] 2 ZrCl 6 :Sb 3+ , 84.84% for [18‐crown‐6@Rb] 2 ZrCl 6 :Sb 3+ , and 78.63% for [18‐crown‐6@Cs] 2 ZrCl 6 :Sb 3+ , which shall stem from Sb 3+ ‐induced multi‐exciton emission in [SbCl 6 ] 3− octahedron. Particularly, the strong supramolecular interaction can enhance the structural rigidity and suppress nonradiative transitions, which is the dominated reason for [18‐crown‐6@A] 2 ZrCl 6 :Sb 3+ exhibits efficient emission. The component/excitation/temperature/moisture‐dependent multiple reversible PL switching characteristics are observed in Sb 3+ ‐doped [18‐crown‐6@A] 2 ZrCl 6 , which allows to demonstrate their applications in advanced optical anti‐counterfeiting and information encryption. Moreover, a single‐component white light‐emitting diode is also fabricated, which shows a high color rendering index of 96.1. Therefore, the work provides a feasible scheme for designing organic Zr(IV) halides with fascinating optical properties.