title: Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies.
abstract: 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.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Joan
authors.initials: J
authors.lastname: Gónzalez-Fabra
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.|Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016, Lisboa, Portugal.|Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, 1049-001, Lisboa, Portugal.
authors.forename: Nuno A G
authors.initials: NA
authors.lastname: Bandeira
authors.affiliation: Departement de Inorgánica, Universitat de Barcelona, Diagonal 645, 08028, Barcelona, Spain.
authors.forename: Verónica
authors.initials: V
authors.lastname: Velasco
authors.affiliation: Departement de Inorgánica, Universitat de Barcelona, Diagonal 645, 08028, Barcelona, Spain.
authors.forename: Leoní A
authors.initials: LA
authors.lastname: Barrios
authors.affiliation: Departement de Inorgánica, Universitat de Barcelona, Diagonal 645, 08028, Barcelona, Spain.
authors.forename: David
authors.initials: D
authors.lastname: Aguilà
authors.affiliation: Advanced Light Source, Berkeley Laboratory, 1 Cyclotron Road, Berkeley, California, 94720, USA.
authors.forename: Simon J
authors.initials: SJ
authors.lastname: Teat
authors.affiliation: Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC and Universidad de Zaragoza, Plaza San Francisco s/n, 50009, Zaragoza, Spain.
authors.forename: Olivier
authors.initials: O
authors.lastname: Roubeau
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.|Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
authors.forename: Carles
authors.initials: C
authors.lastname: Bo
authors.affiliation: Departement de Inorgánica, Universitat de Barcelona, Diagonal 645, 08028, Barcelona, Spain.
authors.forename: Guillem
authors.identifier: http://orcid.org/0000-0001-9821-3650
authors.initials: G
authors.lastname: Aromí
keywords: coordination chemistry; density functional calculations; functional molecules; lanthanides; supramolecular chemistry