Li Si, Dong Xi-Yan, Qi Kong-Sheng, Zang Shuang-Quan, Mak Thomas C W
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, China.
J Am Chem Soc. 2021 Dec 15;143(49):20574-20578. doi: 10.1021/jacs.1c09245. Epub 2021 Dec 2.
Four pairs of defective crystals exhibiting full-color emission and circularly polarized luminescence (CPL) with high luminescence dissymmetry factor () values (∼3 × 10) were successfully obtained by doping dye molecules into the chiral crystalline metal cluster-based matrixes. The dye molecules function as defect inducers and confer fluorescence on the crystals. Studies reveal that electrostatic interactions provide the main impetus in generating defective crystals, and the restricted effect of chiral space and the weak interactions in defect crystal enable the efficient chiral transfer from the intrinsically chiral host silver(I) clusters to achiral luminescent dopants and finally induce them to emit bright CPL. This defect engineering strategy opens a new way to versatile functions for crystalline cluster-based materials.
通过将染料分子掺杂到手性晶体金属簇基基质中，成功获得了四对具有全色发射和圆偏振发光（CPL）且发光不对称因子（）值较高（约3×10）的缺陷晶体。染料分子作为缺陷诱导剂，赋予晶体荧光特性。研究表明，静电相互作用是产生缺陷晶体的主要推动力，手性空间的限制作用以及缺陷晶体中的弱相互作用能够实现从本质上手性的主体银（I）簇到手性发光掺杂剂的有效手性转移，最终诱导它们发出明亮的CPL。这种缺陷工程策略为基于晶体簇的材料实现多功能开辟了一条新途径。
