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

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      Publication Details (including relevant citation   information):

      Bunzli,J.C.G., Chauvin,A.S., Kim,H.K., Deiters,E., Eliseeva,S.V.   Coordination Chemistry Reviews 2010  254 (21-22) 2623-2633

      Abstract: 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

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