Thermodynamic stability of heterodimetallic [LnLn] complexes: synthesis and DFT studies

The solid-state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL)(3)(NO3)(py)(H2O)] (1), (Hpy)[CeEr(HL)(3)(NO3)(py)(H2O)] (2), (Hpy)[CeGd(HL)(3)(NO3)(py)(H2O)] (3), (Hpy)[PrSm(HL)(3)(NO3)(py)(H2O)] (4), and (Hpy)(2)[LaYb(HL)(3)(NO3)(H2O)](NO3) (5), in which H3L is 6-(3-oxo...

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Detalles Bibliográficos
Autores: González Fabra, Joan, Bandeira, Nuno A. G., Velasco Amigó, Verónica, Barrios Moreno, Leoní Alejandra, Aguilà Avilés, David, Teat, Simon J., Roubeau, Olivier, Bo, Carles, Aromí Bedmar, Guillem
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/153720
Acceso en línea:https://hdl.handle.net/2445/153720
Access Level:acceso abierto
Palabra clave:Teoria del funcional de densitat
Química supramolecular
Compostos de coordinació
Density functionals
Supramolecular chemistry
Coordination compounds
Descripción
Sumario:The solid-state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL)(3)(NO3)(py)(H2O)] (1), (Hpy)[CeEr(HL)(3)(NO3)(py)(H2O)] (2), (Hpy)[CeGd(HL)(3)(NO3)(py)(H2O)] (3), (Hpy)[PrSm(HL)(3)(NO3)(py)(H2O)] (4), and (Hpy)(2)[LaYb(HL)(3)(NO3)(H2O)](NO3) (5), in which H3L is 6-(3-oxo-3-(2-hydroxyphenyl)propionyl)pyridine-2-carboxylic acid and py is pyridine, were analyzed experimentally and by using DFT calculations. Complexes 3, 4, and 5 are described here for the first time, and were analyzed by using single-crystal X-ray diffraction and mass spectrometry. The theoretical study was also extended to the [LaCe] and [LaLu] analogues. The results are consistent with a remarkable selectivity of the metal distribution within the molecule in the solid state, enhanced by the size difference between the different ions. This selectivity was reduced in solution, particularly for ions with the most similar radii. This unique entry into 4f-4f heterometallic chemistry establishes for the first time the difference between the selectivity in solution and that in the solid state, as a result of changes to the coordination that follow the dissociation of terminal ligands upon dissolution of the complexes.

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