混合稀土配合物白光材料：配体天线效应、异核设计与发光调控

White-Light-Emitting Mixed Lanthanide Complexes: Ligand Antenna Effect, Heteronuclear Design, and Luminescence Tuning

摘要: 混合稀土配合物白光材料因兼具稀土离子窄带发射、长荧光寿命和有机配体强光吸收等优势，成为固态照明与光学传感领域的研究热点。本文以“配体天线–异核设计–发光调控”三要素为框架，系统评述了该领域的最新进展。首先，阐明天线效应中配体三重态能级与稀土离子激发态能级的匹配原则，以及Eu³⁺/Tb³⁺间能量传递和浓度效应对发光色坐标的调控规律。其次，分类讨论离散型、掺杂型和MOF型异核稀土配合物的白光设计策略，指出掺杂型体系凭借连续可调的金属比例在色坐标精细调控方面优势突出，而稀土MOF则通过多组分协同实现高显色指数(CRI达88.7)的暖白光发射。再次，聚焦d-f异金属配合物的协同敏化机制，强调Zn²⁺/Cd²⁺配合物作为“干净”天线可有效避免d-d跃迁干扰，而Ir³⁺/Pt³⁺贵金属体系则通过MLCT态拓展激发窗口并提高量子产率(最高达59%)。随后，从配体功能化修饰、双配体协同和桥连工程三方面总结光谱工程策略，揭示辅助配体对能量传递路径的关键调控作用。在应用层面，评述了白光LED器件和比率温度传感(最大相对灵敏度7.94%∙K⁻¹)的代表性成果。最后，指出固态量子效率低、热稳定性不足和规模化合成困难等挑战，并对AIE配体结合、机器学习辅助筛选及柔性集成等未来方向进行展望。

Abstract: White-light-emitting mixed lanthanide complexes, combining the narrow-band emission and long luminescence lifetimes of lanthanide ions with the strong light-harvesting ability of organic ligands, have emerged as promising materials for solid-state lighting and optical sensing. This review systematically evaluates recent advances in this field within the framework of “ligand antenna-heteronuclear design-luminescence regulation.” We first elucidate the energy matching principle between ligand triplet states and lanthanide excited states in the antenna effect, as well as the roles of Eu³⁺/Tb³⁺ energy transfer and concentration effects in tuning emission chromaticity. Three categories of heteronuclear lanthanide complexes—discrete, doped, and MOF-based—are discussed, highlighting that doped systems enable precise color tuning through continuous metal-ratio adjustment, while lanthanide MOFs achieve warm white light with high color rendering index (CRI up to 88.7) via multicomponent synergy. The cooperative sensitization mechanism in d-f heterometallic complexes is then emphasized, where Zn²⁺/Cd²⁺ complexes serve as “clean” antennas avoiding d-d transition interference, and Ir³⁺/Pt³⁺ noble-metal systems extend excitation windows and enhance quantum yields (up to 59%) through MLCT states. Spectral engineering strategies are summarized from ligand functionalization, dual-ligand synergy, and bridging ligand design, revealing the critical role of ancillary ligands in modulating energy transfer pathways. Representative applications in white LEDs and ratiometric temperature sensing (maximum relative sensitivity 7.94%·K⁻¹) are reviewed. Finally, remaining challenges—low solid-state quantum efficiency, insufficient thermal stability, and scalable synthesis—are discussed, along with future directions including AIE ligand integration, machine-learning-assisted screening, and flexible device integration.