Lanthanide luminescence efficiency in eight- and nine-coordinate complexes: Role of the radiative lifetime
Lanthanide luminescence efficiency in eight- and nine-coordinate complexes: Role of the radiative lifetime
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DOI：
10.1016/j.ccr.2010.04.002
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发表时间：
2010-11-01
影响因子：
20.6
通讯作者：
Eliseeva, Svetlana V.
中科院分区：
文献类型：
--
作者：
Buenzli, Jean-Claude G.;Chauvin, Anne-Sophie;Eliseeva, Svetlana V.
本文分析了具有NxOy螯合单元的三齿和六齿配合物对金属中心发光敏化的光物理参数。特别是，实验估计了29个九坐标Eu-III配合物和10个八坐标和九坐标Yb-III配合物的辐射寿命tau（rad）。已知的tau（rad）对折射率的依赖是通过比较固体样品和溶液的数据来证实的。此外，证明了tau（rad）与配位环境的明显依赖性，并且在Eu-III的情况下，试图比较tau（rad）与配体产生的非相干效应。总之，这一广泛的分析指出，在为高发光含镧的分子结构设计配体时，掌握tau（rad）的重要性。反过来，这应该激发开始的理论考虑，以揭示tau（rad）和配体的电子结构之间的可靠关系。(C) 2010 Elsevier B.V.版权所有
The photophysical parameters for the sensitization of metal-centred luminescence are analyzed in two series of complexes with tridentate and hexadentate ligands having NxOy chelating units. In particular, the radiative lifetime tau(rad) is experimentally estimated for 29 nine-coordinate Eu-III complexes and 10 eight- and nine-coordinate Yb-III complexes. The known dependence of tau(rad) on refractive index is sub-stantiated by comparing data for solid-state samples and solutions. Moreover, a clear dependence of tau(rad) with the coordination environment is evidenced and in the case of Eu-III, a comparison between tau(rad) and the nephelauxetic effect generated by the ligands is attempted. Altogether, this extensive analysis points to the importance of having a handle on tau(rad) when designing ligands for highly luminescent lanthanide-containing molecular edifices. This, in turn, should stimulate initiating theoretical considerations to unravel a reliable relationship between tau(rad) and the electronic structure of the ligands. (C) 2010 Elsevier B.V. All rights reserved.