Wang Shi-Cheng, Zhang Qiang-Sheng, Wang Zheng, Zheng Lin, Zhang Xiao-Dong, Fan Ya-Nan, Fu Peng-Yan, Xiong Xiao-Hong, Pan Mei
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510006, China.
College of Chemistry and Chemical Engineering, Key Laboratory of Chemical Additives for China National Light Industry, Shaanxi University of Science and Technology, Xi'an, 710021, China.
Angew Chem Int Ed Engl. 2022 Oct 24;61(43):e202211356. doi: 10.1002/anie.202211356. Epub 2022 Sep 20.
By designing a tetraphenylethylene (TPE)-based AIEgen-ligand with reduced symmetry, we obtained two alkaline-earth metal-based MOFs (LIFM-102 and LIFM-103) with dense packing structures and low porosity as proved by single-crystal X-ray diffraction and CO sorption data. Excitingly, the desolvated MOFs with rigid environment and reduced lattice free solvent exhibit high quantum yields (QY, 64.9 % and 79.4 %) and excellent two-photon excited photoluminescence (TPA cross-sections, 2946.6 GM and 2899.0 GM), while maintaining the external-stimuli-responsive properties suitable for anticounterfeit fields. The effect of ligand conformation was validated by comparing the structure and fluorescence properties of the samples before and after desolvation and further verified by theoretical calculations. This work expands the study on TPE-cored materials to symmetry-reduced ligand and might bring forward novel structures and excellent photoluminescent properties in the future.
通过设计一种对称性降低的基于四苯乙烯（TPE）的聚集诱导发光（AIE）配体，我们获得了两种基于碱土金属的金属有机框架材料（LIFM-102和LIFM-103），单晶X射线衍射和CO吸附数据证明它们具有紧密堆积结构和低孔隙率。令人兴奋的是，具有刚性环境和减少晶格自由溶剂的去溶剂化金属有机框架材料表现出高量子产率（QY，分别为64.9%和79.4%）和优异的双光子激发光致发光性能（双光子吸收截面，分别为2946.6 GM和2899.0 GM），同时保持了适用于防伪领域的外部刺激响应特性。通过比较去溶剂化前后样品的结构和荧光性质验证了配体构象的影响，并通过理论计算进一步证实。这项工作将基于TPE核心材料的研究扩展到对称性降低的配体，并可能在未来带来新颖的结构和优异的光致发光性能。
