Wang Hai-Ling, Li Yun-Lan, Zou Hua-Hong, Liang Fu-Pei, Zhu Zhong-Hong
School of Chemistry and Chemical Engineering, Guangxi Key Laboratory of Electrochemical Energy Materials, Guangxi University, Nanning, 530004, P. R. China.
School of Chemistry and Pharmaceutical Sciences, State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Guangxi Normal University, Guilin, 541004, P. R. China.
Adv Mater. 2025 Jul;37(29):e2502742. doi: 10.1002/adma.202502742. Epub 2025 May 8.
In this work, dynamic molecular rotors are used to construct smart lanthanide metal-organic frameworks (Ln-MOFs) emitters with adaptive antenna effects for the first time. The movement or distortion of the molecular rotors can be easily regulated by temperature changes, thereby inducing a dynamically changing antenna effect that can automatically match different lanthanide ions, achieving cyclic multicolor luminescence switching behavior and extremely complex multiple encryption anti-counterfeiting technology. In addition, by regulating the doping ratios of Gd(III) and Tb(III) with Eu(III) within the Ln-MOFs, differentiated energy transfer pathways are discovered, and red light emission very close to the BT.2020 color gamut standard is obtained. GdEu-MOF containing only 1% Eu(III) can show bright red luminescence, and in the range of 1-9% Eu(III) content, the characteristic emission intensity of Eu(III) ions and the content show an excellent linear relationship with a slope k as high as 2299. This can be used to identify the content of Eu(III) ions impurities in gadolinium salts from different manufacturers. Eu/Tb-MOF showed highly sensitive and visualized smart photoresponse behaviors to specific antibiotics and amino acids, respectively, with detection limits of 3.2/2.7 nM (tetracycline), 1.7/15.5 nM (oxytetracycline), 0.13/0.97 nM (aspartic acid), and 0.26/1.16 nM (glutamic acid).
在这项工作中，首次使用动态分子转子构建具有自适应天线效应的智能镧系金属有机框架（Ln-MOFs）发光体。分子转子的移动或变形可通过温度变化轻松调节，从而引发动态变化的天线效应，该效应可自动匹配不同的镧系离子，实现循环多色发光切换行为以及极其复杂的多重加密防伪技术。此外，通过调节Ln-MOFs中Gd(III)和Tb(III)与Eu(III)的掺杂比例，发现了不同的能量转移途径，并获得了非常接近BT.2020色域标准的红光发射。仅含1% Eu(III)的GdEu-MOF可呈现明亮的红色发光，在Eu(III)含量为1-9%的范围内，Eu(III)离子的特征发射强度与含量呈现出优异的线性关系，斜率k高达2299。这可用于鉴定不同厂家钆盐中Eu(III)离子杂质的含量。Eu/Tb-MOF分别对特定抗生素和氨基酸表现出高度灵敏且可视化的智能光响应行为，检测限分别为3.2/2.7 nM（四环素）、1.7/15.5 nM（土霉素）、0.13/0.97 nM（天冬氨酸）和0.26/1.16 nM（谷氨酸）。
