Jean-Claude Bunzli - Role of Inner- and Outer-Sphere Bonding in the Sensitization of Eu(III)-Luminescence Deciphered by Combined Analysis of Experimental Electron Density Distribution Function and Photophysical Data

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  Puntus,L.N., Lyssenko,K.A., Antipin,M.Y., Bunzli,J.C.G.   Inorganic Chemistry 2008 47  (23) 11095-11107

  Abstract: A series of lanthanide adducts with   different amounts of 1,10-phenanthroline, chloride ions, and   water molecules in the inner and outer coordination spheres are   investigated with the aim of relating the chemical bonding   pattern in the crystals to the luminescence properties of the Eu   ion: [LnCl(1)Phen(2)(H(2)O)(3)]Cl(2)(H(2)O) (Ln = Eu, 1Eu; Gd,   1Gd; Tb, 1Tb), [EuCl(2)Phen(2)(H(2)O)(2)]Cl(1)(H(2)O) (2), and   [EuCl(2)Phen(1)(H(2)O)(4)]Cl(1)(H(2)O) (3). The influence of   inner-versus outer-sphere ligands on the Ln-X bond lengths and   angles in the structure is examined. A detailed topological   analysis of the electron density function derived from the X-ray   diffraction data for 1Gd is performed within the frame of the   "atoms in molecule" theory for the first time for a lanthanide   complex.,The chemical bonding pattern is interpreted in terms of   net atomic charges, bond energies, and electron transfers from   the ligands to the metal ion. A noteworthy finding is that the   energy of extended noncovalent interactions occurring in the   second coordination sphere (H-bonding and T-stacking   interactions) is comparable to that of Ln-ligand bonds. The   luminescence properties of the three Eu adducts are interpreted   with the results of electron density distribution function   topology. An intraligand charge transfer state is identified, and   its contribution in the ligand-to-europium energy transfer   process is analyzed. The outcome of this study is that specific   interionic interactions which are usually not considered in   theoretical calculations or in the interpretation of luminescence   properties play an important role in the sensitization of the Eu   luminescence

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