Fu Peng-Yan, Yi Shao-Zhe, Wang Zhong-Hao, Zhuang Jia-Yi, Zhang Qiang-Sheng, Mo Jun-Ting, Wang Shi-Cheng, Zheng Hao, Pan Mei, Su Cheng-Yong
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510006, China.
Angew Chem Int Ed Engl. 2023 Sep 11;62(37):e202309172. doi: 10.1002/anie.202309172. Epub 2023 Aug 4.
The multiple metastable excited states provided by excited-state intramolecular proton transfer (ESIPT) molecules are beneficial to bring temperature-dependent and color-tunable long persistent luminescence (LPL). Meanwhile, ESIPT molecules are intrinsically suitable to be modulated as D-π-A structure to obtain both one/two-photon excitation and LPL emission simultaneously. Herein, we report the rational design of a dynamic Cd coordination polymer (LIFM-106) from ESIPT ligand to achieve the above goals. By comparing LIFM-106 with the counterparts, we established a temperature-regulated competitive relationship between singlet excimer and triplet LPL emission. The optimization of ligand aggregation mode effectively boost the competitiveness of the latter. In result, LIFM-106 shows outstanding one/two-photon excited LPL performance with wide temperature range (100-380 K) and tunable color (green to red). The multichannel radiation process was further elucidated by transient absorption and theoretical calculations, benefiting for the application in anti-counterfeiting systems.
激发态分子内质子转移（ESIPT）分子提供的多个亚稳态激发态有利于产生温度依赖性和颜色可调的长余辉发光（LPL）。同时，ESIPT分子本质上适合被调制为D-π-A结构，以同时获得单光子/双光子激发和LPL发射。在此，我们报道了一种由ESIPT配体合理设计的动态镉配位聚合物（LIFM-106），以实现上述目标。通过将LIFM-106与其对应物进行比较，我们建立了单重态激基缔合物和三重态LPL发射之间的温度调节竞争关系。配体聚集模式的优化有效地提高了后者的竞争力。结果，LIFM-106在宽温度范围（100 - 380 K）和可调颜色（绿色到红色）下表现出出色的单光子/双光子激发LPL性能。通过瞬态吸收和理论计算进一步阐明了多通道辐射过程，这有利于其在防伪系统中的应用。
