Magneto-structural correlations of cyclo-tetravanadates functionalized with mixed-ligand copper(ii) complexes

Autor: Amalia García-García, Eduardo Sánchez-Lara, Javier Cepeda, Enrique González-Vergara, Antonio Rodríguez-Diéguez
Rok vydání: 2021
Předmět:
Zdroj: New Journal of Chemistry. 45:5081-5092
ISSN: 1369-9261
1144-0546
DOI: 10.1039/d0nj06004f
Popis: Tetravanadate [V4O12]4− anion, one of the cyclic polyoxovanadates formed by the condensation of VO4 units, was used as the bidentate bridging ligand to design bimetallic materials from its functionalization with copper(II) complexes based on α-amino acids and typical aromatic ligands. The complexes {[Cu(Orn)(phen)]2[μ2-V4O12]}·6H2O (1), {[Cu(Lys)(bipy)]4[μ2-V4O12]·14H2O}n (2) and {[Cu(Gly)(phen)]2[μ2-V4O12]} [Cu(Gly)(phen)(H2O)]2·10H2O (3) (Orn = ornithine, phen = 1,10-phenanthroline, Lys = lysine, bipy = 2,2′-bipyridine, Gly = glycine) were prepared under non-hydrothermal conditions. These compounds were obtained at basic pH values (close to 9), which facilitated the formation of tetravanadate anion (from the precursor NH4VO3) and its stabilization with the metal complexes. All compounds crystallized in the triclinic system and showed an interesting structural and magnetic diversity, despite the fact that the components that form them are very similar. Although in compounds 1 and 3 the copper atoms are separated by the inorganic [V4O12]4− anion by about 10 A, the magnetic properties suggest antiferromagnetic interactions, which are explained through the intermolecular Cu⋯Cu interactions and the magnetic exchange pathways between the COO− groups and the magnetic centres. The most striking feature of compound 2 was the formation of a 1D polymeric chain constructed with [V4O12]4− units separated by [Cu(Lys)(bipy]24+ dinuclear bridges. The intramolecular Cu⋯Cu separation in this compound was 5.2 A, and the magnetic properties suggest a canted antiferromagnetic ordering at low applied magnetic fields.
Databáze: OpenAIRE