Structural and magnetic properties of a complete halide series of Ni II complexes with a pyridine-containing 14-membered macrocycle

Abel Tamayo, Lluis Escriche, Carlos Lodeiro, Jordi Ribas-Ariño, Joan Ribas, Berta Covelo, Jaume Casabó

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)

Abstract

The complete halide series of NiII complexes containing the tetradentate macrocyclic ligand 3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca- 1(17),13,15-triene (L), was fully characterized by X-ray diffraction. The fluoro, chloro, and bromo complexes are dinuclear species with formula [{Ni(L)}2(μ-X)2]2+ (X = halide), whereas only mononuclear species with formula [Ni(Y)(solv)(L)]n+ (Y = halide or solvent molecule), were obtained with I. To date, the fluoro derivative is the first nonorganometallic coordination compound containing the Ni(μ-F) 2Ni core. The magnetic properties of these halo complexes have been studied. Intramolecular interactions were observed in the three dinuclear complexes, being antiferromagnetic in the fluoro derivative and ferromagnetic in both the chloro and bromo ones. The two iodo derivatives are paramagnetic species, as would be expected for mononuclear octahedral NiII complexes. Density functional theory calculations led us to relate the magnetic behaviors of these compounds to the values of the corresponding Ni-X-Ni i angle. The analysis of the singly occupied molecular orbitals gave a clear comprehension of the different magnetic exchange interactions found in these NiII complexes.

Original languageEnglish
Pages (from-to)7621-7627
Number of pages7
JournalInorganic Chemistry
Volume45
Issue number19
DOIs
Publication statusPublished - 18 Sep 2006

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