Ag~+-induced energy level splitting in Ln-MOFs achieves enhanced Eu~(3+)emission intensity  

作　　者：Xiaoyong Zhai Xijiao Mu Guoying Tan Lijuan Liang Yao Kou Pingru Su Chun-Hua Yan Yu Tang 

机构地区：[1]State Key Laboratory of Applied Organic Chemistry,Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province,College of Chemistry and Chemical Engineering,Lanzhou University,Lanzhou 730000,China [2]State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization,Baotou Research Institute of Rare Earths,Baotou 014030,China

出　　处：《Science China Chemistry》2025年第3期924-934,共11页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China (22221001,22131007,22401119);the Science and Technology Major Plan of Gansu Province (23ZDGA012,24JRRA435);the 111 Project (B20027);the Fundamental Research Funds for the Central Universities (lzujbky-2024-jdzx13)。

摘　　要：In lanthanide(Ln)complexes,the oversight of f-electrons and inner-shell relativistic interactions has constituted a critical gap,limiting a nuanced understanding and modulation of their luminescent properties.Addressing this issue,our study introduces a pioneering series of Ln-based metal-organic frameworks(Ln-MOFs),designated as Ln-TCPP,utilizing tetraphenylpyrazinederived ligand and Ln^(3+)ions(Ln=Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb and Lu)to modulate luminescence through advanced synthesis and theoretical analysis.We particularly emphasize the enhancement of Eu^(3+)luminescence in Ln-TCPP,where incorporating Ag^(+)ions to replace[(CH_(3))_(2)NH_(2)]^(+)within the Ln-MOFs plays a pivotal role.Theoretically,by employing timedependent density functional theory(TD-DFT)with full-electron relativistic effects,we demonstrate that Ag^(+)ions induce a splitting in the energy levels of Eu^(3+).This splitting effectively reduces the rate of non-radiative transitions,significantly amplifying Eu^(3+)emission intensity.Our findings not only fill a long-standing void in understanding the all-electron relativistic interaction between f-electrons in Ln-MOFs luminescence but also establish a new strategy for controlling and optimizing the luminescent efficacy of these materials for potential applications.

关 键 词：lanthanide metal-organic frameworks luminescence modulation relativistic interactions energy level splitting 

分 类 号：O641.4[理学—物理化学]