Tuning lanthanide luminescence from bipyridine-bis(oxazoline/thiazoline)tetradentate ligands  

作　　者：Hao Jiang Yuan-Yuan He Hai-Chao Liang Meng-Jia Shang Han-Han Lu Chun-Hua Liu Yin-Shan Meng Tao Liu Yuan-Yuan Zhu 

机构地区：[1]State Key Laboratory of Fine Chemicals,Dalian University of Technology,2 Linggong Road,Dalian,116024,China [2]School of Chemistry and Chemical Engineering,Hefei University of Technology and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering,Hefei,230009,China

出　　处：《Chinese Journal of Structural Chemistry》2024年第9期46-51,共6页结构化学(英文)

基　　金：supported by the National Natural Science Foundation of China(Nos.22371063,22222103,22173015,22025101,and 91961114);the State Key Laboratory of Fine Chemicals at Dalian University of Technology(KF 1607);the Fundamental Research Funds for the Central Universities of China(PA2021GDSK0063,DUT22LAB606).

摘　　要：Organic ligands play a pivotal role in lanthanide luminescence by acting as sensitizers for energy absorption and transfer,a phenomenon known as the fluorescence antenna effect.Herein,we introduce two tetradentate nitrogen ligands renowned for their efficient sensitization of lanthanide luminescence,with their luminous efficacy finely adjustable through subtle modifications to their structure.Through the synthesis of four Eu(Ⅲ)/Tb(Ⅲ)mono-nuclear complexes via the complexation of ligands 6,6'-bis(4,5-dihydrooxazol-2-yl)-2,2'-bipyridine(bpybox,L^(1))and 6,6'-bis(4,5-dihydrothiazol-2-yl)-2,2'-bipyridine(thio-bpybox,L^(2))with europium/terbium trifluorosulfonate,structural analysis reveals that the lanthanide ion coordinates with eight nitrogen atoms from two ligands and one oxygen atom from trifluorosulfonate.Among them,two Eu(Ⅲ)complexes([Eu(L^(1))_(2)(SO_(3)CF_(3))](SO_(3)CF_(3))_(2) EuL^(1) and[Eu(L^(2))_(2)(SO_(3)CF_(3))](SO_(3)CF_(3))_(2) EuL^(2))and one Tb(Ⅲ)complex([Tb(L^(1))_(2)(SO_(3)CF_(3))](SO_(3)CF_(3))_(2) TbL^(1))exhibit lumi-nosity,displaying characteristic lanthanide metal ion luminescence characterized by high fluorescence quantum yields and prolonged excited state lifetimes.In contrast,TbL^(2)([Tb(L^(2))_(2)(SO_(3)CF_(3))](SO_(3)CF_(3))_(2))is non-luminous,with the sole structural distinction being the substitution of oxygen atoms with sulfur atoms within the ligand.This minor alteration significantly impacts the triplet(^(3)T)state energy level of the ligands,thereby influencing their sensitizing effect on Tb(Ⅲ)luminescence.These findings underscore the remarkable efficiency of bpybox-type ligands as sensitizers for Ln(Ⅲ)luminescence,with their structural versatility enabling effective modula-tion of luminous capacities and efficiency.

关 键 词：LANTHANIDE Luminescence Antenna effect EUROPIUM TERBIUM 

分 类 号：O62[理学—有机化学]