Component/Stimulus‐Dependent Multi‐Exciton Emission in Zr(IV)‐Based Organic Metal Halides Triggered by Supramolecular Assembly and Antimony Doping

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.