Lanthanide luminescence efficiency in eight- and nine-coordinate complexes: Role of the radiative lifetime

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 τrad is experimentally estimated for 29 nine-coordinate EuIII complexes and 10 eight- and nine-coordinate YbIII complexes. The known dependence of τrad on refractive index is substantiated by comparing data for solid-state samples and solutions. Moreover, a clear dependence of τrad with the coordination environment is evidenced and in the case of EuIII, a comparison between τrad and the nephelauxetic effect generated by the ligands is attempted. Altogether, this extensive analysis points to the importance of having a handle on τrad when designing ligands for highly luminescent lanthanide-containing molecular edifices. This, in turn, should stimulate initiating theoretical considerations to unravel a reliable relationship between τrad and the electronic structure of the ligands.