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Synthetic Control to Achieve Lanthanide(III)/Pyrimidine-4,6-dicarboxylate Compounds by Preventing Oxalate Formation: Structural, Magnetic, and Luminescent Properties

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journal contribution
posted on 16.07.2012 by Javier Cepeda, Rolindes Balda, Garikoitz Beobide, Oscar Castillo, Joaquín Fernández, Antonio Luque, Sonia Pérez-Yáñez, Pascual Román
Control over the synthetic conditions in many metal/diazinedicarboxylato systems is crucial to prevent oxalate formation, since dicarboxylato ligands easily undergo degradation in the presence of metal salts. We report here an efficient route to obtain oxalato-free compounds for the lanthanide/pyrimidine-4,6-dicarboxylato (pmdc) system on the basis of the reaction temperature and nonacidic pH or oxygen free atmosphere. Two different crystal architectures have been obtained: {[Ln­(μ-pmdc)1.5(H2O)3xH2O}n (1-Ln) and {[Ln24-pmdc)2(μ-pmdc)­(H2O)2]·H2O}n (2-Ln) with Ln­(III) = La–Yb, except Pm. Both crystal structures are built from distorted two-dimensional honeycomb networks based on the recurrent double chelating mode established by the pmdc. In compounds 1-Ln, the tricapped trigonal prismatic coordination environment of the lanthanides is completed by three water molecules, precluding a further increase in the dimensionality. Crystallization water molecules are arranged in the interlamellar space, giving rise to highly flexible supramolecular clusters that are responsible for the modulation found in compound 1-Gd. Two of the coordinated water molecules are replaced by nonchelating carboxylate oxygen atoms of pmdc ligands in compounds 2-Ln, joining the metal–organic layers together and thus providing a compact three-dimensional network. The crystal structure of the compounds is governed by the competition between two opposing factors: the ionic size and the reaction temperature. The lanthanide contraction rejects the sterically hindered coordination geometries whereas high-temperature entropy driven desolvation pathway favors the release of solvent molecules leading to more compact frameworks. The characteristic luminescence of the Nd, Eu, and Tb centers is improved when moving from 1-Ln to 2-Ln compounds as a consequence of the decrease of the O–H oscillators. The magnetic properties of the compounds are dominated by the spin–orbit coupling and the ligand field perturbation, the exchange coupling being almost negligible.