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Bunzli, J.C.G.,Chauvin, A.S.,Kim, H.K.,Deiters, E.,Eliseeva, S.V. Elsevier Publishing Company 2010 Coordination Chemistry Reviews Vol. No.
The photophysical parameters for the sensitization of metal-centred luminescence are analyzed in two series of complexes with tridentate and hexadentate ligands having N<SUB>x</SUB>O<SUB>y</SUB> chelating units. In particular, the radiative lifetime τ<SUB>rad</SUB> is experimentally estimated for 29 nine-coordinate Eu<SUP>III</SUP> complexes and 10 eight- and nine-coordinate Yb<SUP>III</SUP> complexes. The known dependence of τ<SUB>rad</SUB> on refractive index is substantiated by comparing data for solid-state samples and solutions. Moreover, a clear dependence of τ<SUB>rad</SUB> with the coordination environment is evidenced and in the case of Eu<SUP>III</SUP>, a comparison between τ<SUB>rad</SUB> and the nephelauxetic effect generated by the ligands is attempted. Altogether, this extensive analysis points to the importance of having a handle on τ<SUB>rad</SUB> when designing ligands for highly luminescent lanthanide-containing molecular edifices. This, in turn, should stimulate initiating theoretical considerations to unravel a reliable relationship between τ<SUB>rad</SUB> and the electronic structure of the ligands.
엄유경,류정호,Jean-Claude G.Bunzli,백종범,김환규 한국고분자학회 2013 Macromolecular Research Vol.21 No.5
A series of novel lanthanide(III) complexes (Ln=Gd, Er, Yb) based on dendritic diphenylquinoxaline (DPQ) ligands was designed and synthesized with the aim of enhancing the luminescence intensity of Er3+ and Yb3+ions for photonic applications. The diphenyl-quinoxaline ligand was introduced as a photon antenna for efficient light harvesting and subsequent energy transfer onto the Ln3+ ions. The dendritic complexes showed strong near-IR emission at 981 (Yb3+) and 1,530 (Er3+) nm, which was sensitized through energy transfer from the excited states of the diphenyl-quinoxaline ligands. The near-IR emission intensity of the lanthanide ions in second-generation [Ln(G2-DPQ-COO)3(terpy)] complexes was significantly enhanced, due to the light-harvesting effect, with respect to [Ln(G1-DPQ-COO)3(terpy)]. However, increasing the size of the dendron in [Ln(G3-DPQ-COO)3(terpy)] was found to be detrimental to the emission efficiency. This may be attributed to the twisted structure of the dendritic ligand and suggests that conformational effects should be taken into consideration when designing ligands for photonic amplification.