Lanthanide luminescence efficiency in eight- and nine-coordinate complexes: Role of the radiative lifetime
✍ Scribed by Jean-Claude G. Bünzli; Anne-Sophie Chauvin; Hwan Kyu Kim; Emmanuel Deiters; Svetlana V. Eliseeva
- Publisher
- Elsevier Science
- Year
- 2010
- Tongue
- English
- Weight
- 476 KB
- Volume
- 254
- Category
- Article
- ISSN
- 0010-8545
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✦ Synopsis
The photophysical parameters for the sensitization of metal-centred luminescence are analyzed in two series of complexes with tridentate and hexadentate ligands having N x O y chelating units. In particular, the radiative lifetime rad is experimentally estimated for 29 nine-coordinate Eu III complexes and 10 eight-and nine-coordinate Yb III complexes. The known dependence of rad on refractive index is substantiated by comparing data for solid-state samples and solutions. Moreover, a clear dependence of rad with the coordination environment is evidenced and in the case of Eu III , a comparison between rad and the nephelauxetic effect generated by the ligands is attempted. Altogether, this extensive analysis points to the importance of having a handle on rad when designing ligands for highly luminescent lanthanidecontaining molecular edifices. This, in turn, should stimulate initiating theoretical considerations to unravel a reliable relationship between rad and the electronic structure of the ligands.