中性配体给电子取代基数目对Eu^(3+)配合物发光效率的调控  

Tuning Emission of Eu^(3+)Complexes by Increasing Electron-donating Unit Number on the Auxiliary Ligand

作　　者：韩淑雯 李洁 赵艳波 詹传郎 HAN Shuwen;LI Jie;ZHAO Yanbo;ZHAN Chuanlang(College of Chemistry and Environmental Science,Inner Mongolia Normal University,Hohhot 010022,China;Key Laboratory of Advanced Materials Chemistry and Devices(AMCDLab)of the Department of Education of Inner Mongolia Autonomous Region,Hohhot 010022,China)

机构地区：[1]内蒙古师范大学化学与环境科学学院,内蒙古呼和浩特010022 [2]先进材料化学与器件内蒙古自治区高等学校重点实验室,内蒙古呼和浩特010022

出　　处：《内蒙古师范大学学报（自然科学版）》2024年第6期621-629,共9页Journal of Inner Mongolia Normal University(Natural Science Edition)

基　　金：国家自然科学基金资助项目“手性稀土配合物圆偏振电致发光性能研究”(U23A20593),“非手性化合物的分子手性合成”(22171151);内蒙古自治区自然科学基金资助项目“AIEgen手性聚集体的构筑与圆偏振发光性能研究”(2021MS02004);内蒙古师范大学科研启动费和内蒙古自治区硕士研究生科学创新基金资助项目“Z-型异质结耦合Cu基光催化还原CO_(2)系统”(S20231072Z)。

摘　　要：稀土离子具有特殊的4f电子结构,与能级匹配的有机配体形成配合物后表现出良好的发光性能,但在溶液中大多数稀土配合物的荧光量子产率较低。以二苯甲酰甲烷和邻菲罗啉为配体合成三个Eu^(3+)配合物:Eu(DBM)3Phen、Eu(DBM)3 Bath、Eu(DBM)3Tmphen,发现随着中性配体邻菲罗啉上给电子取代基数目的增加,其T1态能级降低,由中性配体到中心稀土离子间的能量传递方式是由中性配体到阴离子配体再到稀土离子的方式,过渡到由中性配体直接到稀土离子的方式,因此获得了更高的荧光量子产率。三个稀土配合物在甲苯溶液中的荧光量子产率逐渐增加,分别为3.9%、6.1%、9.4%,在固态下的荧光量子产率也逐渐增加,分别为55.6%、61.2%和75.9%。Rare-earth ions have unique 4f electrons and may have enhanced photoluminescence when coordinated with energy-level-aligned ligands.However,most of rare earth complexes exhibit weak fluorescence in solutions.In the paper,dibenzoylmethane and 1,10⁃phenanthroline were selected as anion and auxiliary ligands and for synthesis of three Eu^(3+)complexes,e.g.Eu(DBM)3Phen,Eu(DBM)3Bath and Eu(DBM)3Tmphen.It was found that the energy levels of the T1 states of phenanthroline decreased with the increased number of the electron-donating units on phenanthroline,as the result,the energy transfer from phenanthroline to the central ion was tuned from an indirect mode(mediated by dibenzoylmethane)to a direct mode(directly from phenanthroline to the central ion),leading to gradually increasing the fluorescence quantum yields of the three rare earth complexes to 3.9%,6.1%,and 9.4%in toluene solution,respectively and also to 55.6%,61.2%,and 75.9%in solids,respectively.

关 键 词：稀土配合物 发光 能量转移 二苯甲酰甲烷 邻菲罗啉 

分 类 号：O641.4[理学—物理化学]