Wang Shi-Cheng, Zhang Qiang-Sheng, Wang Zheng, Guan Shao-Qi, Zhang Xiao-Dong, Xiong Xiao-Hong, Pan Mei
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, IGCME, GBRCE for Functional Molecular Engineering, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510006, China.
Key Laboratory of Advanced Materials of Tropical Island Resources, Ministry of Education, School of Chemistry and Chemical Engineering, Hainan University, Haikou, 570228, China.
Angew Chem Int Ed Engl. 2023 Dec 21;62(52):e202315382. doi: 10.1002/anie.202315382. Epub 2023 Nov 23.
By synergistically employing four key strategies: (I) introducing tetraphenylethylene groups as the central core unit with aggregation-induced emission (AIE) properties, (II) optimizing the π-conjugated length by extending the building block branches, (III) incorporating flexible groups containing ethylenic bonds, and (IV) applying crystal engineering to attain dense stacking mode and highly twisty conformation, we successfully synthesized a series of hydrogen-bonded organic frameworks (HOFs) exhibiting exceptional one/two-photon excited fluorescence. Notably, when utilizing the fluorescently superior building block L2, HOF-LIFM-7 and HOF-LIFM-8 exhibiting high quantum yields (QY) of 82.1 % and 77.1 %, and ultrahigh two-photon absorption (TPA) cross-sections of 148959.5 GM and 123901.1 GM were achieved. These materials were successfully employed in one and two-photon excited lysosome-targeting cellular imaging. It is believed that this strategy, combining building block optimization and crystal engineering, holds significant potential for guiding the development of outstanding fluorescent HOF materials.
（I）引入具有聚集诱导发光（AIE）特性的四苯基乙烯基团作为中心核心单元；（II）通过延长构建模块分支来优化π共轭长度；（III）引入含有烯键的柔性基团；以及（IV）应用晶体工程以实现密集堆积模式和高度扭曲的构象，我们成功合成了一系列表现出优异单光子/双光子激发荧光的氢键有机框架（HOF）。值得注意的是，当使用荧光性能优异的构建模块L2时，实现了HOF-LIFM-7和HOF-LIFM-8，其量子产率（QY）分别高达82.1%和77.1%，双光子吸收（TPA）截面分别高达148959.5 GM和121901.1 GM。这些材料成功应用于单光子和双光子激发的溶酶体靶向细胞成像。相信这种结合构建模块优化和晶体工程的策略在指导开发优异荧光HOF材料方面具有巨大潜力。
