Sparkle Model for AM1 Calculation of Lanthanide Complexes:  Improved Parameters for Europium

• Published in: Inorganic chemistry 2004-04, Vol.43 (7), p.2346-2354
• Main Authors: Rocha, Gerd B, Freire, Ricardo O, da Costa, Nivan B, de Sá, Gilberto F, Simas, Alfredo M
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic034882p

In the present work, we sought to improve our sparkle model for the calculation of lanthanide complexes, SMLC, in various ways:  (i) inclusion of the europium atomic mass, (ii) reparametrization of the model within AM1 from a new response function including all distances of the coordination polyhedron for tris(acetylacetonate)(1,10-phenanthroline) europium(III), (iii) implementation of the model in the software package MOPAC93r2, and (iv) inclusion of spherical Gaussian functions in the expression which computes the core−core repulsion energy. The parametrization results indicate that SMLC II is superior to the previous version of the model because Gaussian functions proved essential if one requires a better description of the geometries of the complexes. In order to validate our parametrization, we carried out calculations on 96 europium(III) complexes, selected from Cambridge Structural Database 2003, and compared our predicted ground state geometries with the experimental ones. Our results show that this new parametrization of the SMLC model, with the inclusion of spherical Gaussian functions in the core−core repulsion energy, is better capable of predicting the Eu−ligand distances than the previous version. The unsigned mean error for all interatomic distances Eu−L, in all 96 complexes, which, for the original SMLC is 0.3564 Å, is lowered to 0.1993 Å when the model was parametrized with the inclusion of two Gaussian functions. Our results also indicate that this model is more applicable to europium complexes with β-diketone ligands. As such, we conclude that this improved model can be considered a powerful tool for the study of lanthanide complexes and their applications, such as the modeling of light conversion molecular devices.