单核Ln到异核Ln-M超分子配合物的组装与发光性能

doi:10.11944/j.issn.1000-0518.2017.09.170144

摘要/Abstract

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4.3 μs增加到6.7 μs,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。

关键词: 稀土发光, 金属-有机框架, 异核配合物

Abstract:

Via 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.

Key words: lanthanide emission, metal-organic framework, heteronuclear complex

王政, 尹少云, 潘梅, 刘煜, 孙思思, 王海平, 范雅楠, 苏成勇. 单核Ln到异核Ln-M超分子配合物的组装与发光性能[J]. 应用化学, 2017, 34(9): 1017-1023.

WANG Zheng, YIN Shaoyun, PAN Mei, LIU Yu, SUN Sisi, WANG Haiping, FAN Ya'nan, SU Chengyong. Assembly and Luminescence of Mononuclear Ln to Heteronuclear Ln-M Supramolecular Complexes[J]. Chinese Journal of Applied Chemistry, 2017, 34(9): 1017-1023.

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