稀土配位化学在光功能材料中的应用：从配体设计到荧光传感与信息加密

Application of Rare Earth Coordination Chemistry in Photo-Functional Materials: from Ligand Design to Fluorescence Sensing and Information Encryption

摘要: 稀土离子凭借其独特的4f电子构型和屏蔽的f-f跃迁，展现出窄带发射、长寿命发光和丰富的能级结构等优异光物理性质，成为构建高性能光功能材料的理想光学中心。然而，稀土离子固有的弱吸收能力严重限制了其直接激发效率，这一缺陷通过“天线效应”——由精心设计的有机配体作为高效光捕获单元——得到了有效克服。本文系统综述了稀土配位光功能材料的研究进展，从配体工程的基本原理出发，深入探讨了单核配合物、多核簇合物、配位聚合物、金属有机框架(MOFs)、共价有机框架(COFs)及超分子组装体等不同材料体系的结构–性能关系与演进逻辑。在此基础上，重点介绍了这些材料在荧光传感领域的最新应用，涵盖抗生素检测、生物标志物识别、金属离子传感等前沿方向，并通过总结性表格对各传感体系的检测限、选择性、适用场景和局限性进行了横向比较与批判性评述。进一步地，本文综述了稀土材料在多维度信息加密中的独特优势，包括动态响应加密、时间维度编码及物理不可克隆函数等高级防伪策略。此外，本文系统介绍了机器学习辅助稀土发光材料设计的新范式，从数据驱动预测、图神经网络建模到逆向设计优化，展示了人工智能技术在加速材料发现与性能优化中的巨大潜力。最后，本文展望了该领域面临的挑战与未来发展方向，强调了能量转移动力学的原子级解析、水性稳定体系的构建、生物正交探针开发以及“设计–合成–表征–反馈”闭环研发平台建设等具体可操作的研究路径，旨在为新一代稀土分子光子材料的设计与应用提供系统性参考。

Abstract: Rare earth (RE) ions, characterized by their unique 4f electronic configurations and shielded f-f transitions, exhibit exceptional photophysical properties including narrow‑band emission, long‑lived luminescence, and rich energy‑level structures, making them ideal optical centers for constructing high‑performance photofunctional materials. However, the intrinsically weak absorption capacity of RE ions severely limits their direct excitation efficiency—a drawback that has been effectively overcome through the “antenna effect,” in which judiciously designed organic ligands serve as efficient light‑harvesting units. This review provides a systematic overview of the research progress in RE coordination‑based photofunctional materials, starting from the fundamental principles of ligand engineering and delving into the structure-property relationships and evolutionary logic across diverse material systems, including mononuclear complexes, polynuclear clusters, coordination polymers, metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and supramolecular assemblies. On this basis, the review highlights the latest applications of these materials in fluorescence sensing, covering antibiotic detection, biomarker recognition, and metal ion sensing. A comprehensive summary table is provided for critical comparison of key performance metrics (detection limits, selectivity, applicable scenarios, and limitations) across different sensing systems, accompanied by critical commentary. Furthermore, this review discusses the unique advantages of RE materials in multidimensional information encryption, including dynamic responsive encryption, time‑domain coding, and physically unclonable functions (PUFs) for advanced anti‑counterfeiting. In addition, we systematically introduce the emerging paradigm of machine learning‑assisted design of RE luminescent materials, covering data‑driven prediction, graph neural network modeling, and inverse design optimization, demonstrating the great potential of artificial intelligence in accelerating materials discovery and performance optimization. Finally, the challenges and future directions are discussed, with emphasis on specific actionable research pathways such as atomic‑scale elucidation of energy transfer dynamics, construction of water‑stable systems, development of bioorthogonal probes, and establishment of closed‑loop “design-synthesis-characterization-feedback” platforms. This review aims to provide a systematic reference for the design and application of next‑generation RE molecular photonic materials.