单核Ln到异核Ln-M超分子配合物的组装与发光性能  

Assembly and Luminescence of Mononuclear Ln to Heteronuclear Ln-M Supramolecular Complexes

作　　者：王政[1] 尹少云[1] 潘梅[1] 刘煜[1] 孙思思[1] 王海平[1] 范雅楠[1] 苏成勇[1] 

机构地区：[1]中山大学化学学院莱恩功能材料研究所,广州510275

出　　处：《应用化学》2017年第9期1017-1023,共7页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(21373276);广州市科技计划项目(201510010246,201504010031)资助~~

摘　　要：采用分步组装策略,利用3-位和4-位吡啶端基化的三脚配体,合成了分立的单核Ln(Ln=Tb/Sm/Yb)配合物,进一步通过吡啶端基的配位扩展,分别组装得到不同拓扑的Ln-M(M=Ag或Cd)三维金属-有机框架(MOF)结构。异核MOF保留了Ln配位中心的特征可见至近红外发光,并因配体能级结构和与稀土离子间的能量传递效率的改变,对配合物的发光性能产生调控。其中配合物2-Yb-Ag中,Yb的近红外发光与单核稀土配合物相比明显增强,荧光寿命从单核的4.3μs增加到6.7μs,而4-Tb-Cd则产生了配体发光与稀土中心发光的组合模式,其中来自Tb中心的荧光寿命从相应单核配合物中的2.91 ms缩短至0.62 ms。V/a stepwise assembly method, discrete mononuclear Ln （Ln = Tb/Sm/Yb ） complexes were synthesized from 3- or 4-pyridyl modified tripodal ligands, which were then assembled into three dimensional Ln-M （M = Ag or Cd） metal-organic frameworks （MOFs） with different topologies through the linkage of pyridyl ends. The heteronuclear MOFs sustain a characteristic emission of Ln3＋ coordination centers, but the energy levels of the ligands are lowered in the three-dimensional packing structures, which affects the energy transfer efficiency to lanthanide centers. As a result, a stronger near-infrared luminescence is obtained in 2-Yb-Ag compared with its mononuclear counterpart, and the decay lifetime increases from 4. 3 μs to 6. 7 μs. While 4-Tb-Cd simultaneously emits metal-centered and ligand-based emissions, in which the decay lifetime for Tb-centered emission shortens from 2. 91 ms to 0. 62 ms compared with the corresponding mononuclear complex.

关 键 词：稀土发光 金属-有机框架 异核配合物 

分 类 号：O641.3[理学—物理化学]