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通过电子 - 振动解耦提高溶剂化铕(III)的发光效率:一种非常规的聚集诱导发光体系。

Enhancing Luminescence Efficiency of Solvated Europium(III) via Electronic-Vibrational Decoupling: An Unconventional Aggregation-Induced Emission System.

作者信息

Wang Yifan, Wang Jinjin, Zhang Siwei, Tang Natalie Y Baona, Ou Xinwen, Jiang Jinhui, Ma Fulong, Alam Parvej, Qiu Zijie, Wang Wen-Jin, Zhao Zheng, Lam Jacky W Y, Tang Ben Zhong

机构信息

Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Division of Life Science and State Key Laboratory of Molecular Neuroscience, The Hong Kong University of Science and Technology, Kowloon 999077, Hong Kong, China.

The Second Affiliated Hospital, School of Medicine, The Chinese University of Hong Kong, Shenzhen & Longgang District People's Hospital of Shenzhen, Shenzhen 518172, Guangdong, China.

出版信息

ACS Nano. 2025 Jul 15;19(27):25042-25051. doi: 10.1021/acsnano.5c04432. Epub 2025 Jun 30.

DOI:10.1021/acsnano.5c04432
PMID:40587592
Abstract

Europium(III) (Eu) ions are renowned for their exceptional photophysical properties, making them invaluable in applications such as energy-efficient lighting, display technologies, and advanced laser systems. However, transitioning Eu from solid-state matrices to solution-based environments typically results in a significant decline in luminescence efficiency due to strong vibrational coupling and dynamic coordination interactions with solvents. These issues have hindered the broader application of rare earth ions in solution-based technologies such as biological imaging probes and optical sensors. Herein, we report an innovative electronic-vibrational decoupling (EVD) strategy aimed at minimizing nonradiative decay pathways in rare earth ions. Through systematic modulation of the solvent environment─including replacing water with ,-dimethylformamide (DMF), tuning temperature, and employing deuterated solvents─we demonstrate that the photoluminescence quantum yield (Φ) of Eu solutions can be enhanced dramatically from around 2% in HO to over 80% in deuterated DMF. The suppression of nonradiative decay pathways is corroborated by significant increases in emission intensity, prolonged luminescence lifetimes, and marked shifts in the / intensity ratio, an established indicator of coordination symmetry. Furthermore, our study reveals that the unconventional aggregation-induced emission (AIE) phenomenon in Eu solvents is governed by EVD rather than by restrictions of the intramolecular motion (RIM) mechanism found in organic systems. This work highlights the interplay between solvent vibrations and rare earth photophysics, establishing a robust framework for developing high-performance, solution-based rare earth luminescent materials.

摘要

铕(III)(Eu)离子因其卓越的光物理性质而闻名,这使其在诸如节能照明、显示技术和先进激光系统等应用中具有极高价值。然而,将Eu从固态基质转移到基于溶液的环境中时,由于与溶剂的强烈振动耦合和动态配位相互作用,通常会导致发光效率显著下降。这些问题阻碍了稀土离子在基于溶液的技术(如生物成像探针和光学传感器)中的更广泛应用。在此,我们报告了一种创新的电子 - 振动解耦(EVD)策略,旨在最小化稀土离子中的非辐射衰变途径。通过对溶剂环境的系统调节 ── 包括用N,N - 二甲基甲酰胺(DMF)代替水、调节温度以及使用氘代溶剂 ── 我们证明Eu溶液的光致发光量子产率(Φ)可以从水中的约2%显著提高到氘代DMF中的80%以上。发射强度的显著增加、发光寿命的延长以及/强度比(配位对称性的既定指标)的明显变化证实了非辐射衰变途径的抑制。此外,我们的研究表明,Eu溶剂中非常规的聚集诱导发光(AIE)现象是由EVD而非有机体系中发现的分子内运动受限(RIM)机制所控制。这项工作突出了溶剂振动与稀土光物理之间的相互作用,为开发高性能、基于溶液的稀土发光材料建立了一个强大的框架。

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