Structural and Magnetic Properties of a Complete Halide Series of NiII Complexes with a Pyridine-Containing 14-Membered Macrocycle

详细信息    查看全文

• 作者：Abel Tamayo ; Lluis Escriche ; Carlos Lodeiro ; Jordi Ribas-Ariñ ; o ; Joan Ribas ; Berta Covelo ; Jaume Casab&oacute
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：September 18, 2006
• 年：2006
• 卷：45
• 期：19
• 页码：7621 - 7627
• 全文大小：152K
• 年卷期：v.45,no.19(September 18, 2006)
• ISSN：1520-510X

文摘

The complete halide series of Ni^II 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(ges/entities/mgr.gif">-X)₂]²⁺ (X = halide), whereas only mononuclearspecies with formula [Ni(Y)(solv)(L)]ⁿ⁺ (Y = halide or solvent molecule), were obtained with I. To date, the fluoroderivative is the first nonorganometallic coordination compound containing the Ni(ges/entities/mgr.gif">-F)₂Ni core. The magnetic propertiesof these halo complexes have been studied. Intramolecular interactions were observed in the three dinuclearcomplexes, 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 Ni^II complexes.Density functional theory calculations led us to relate the magnetic behaviors of these compounds to the values ofthe corresponding Ni-X-Niⁱ angle. The analysis of the singly occupied molecular orbitals gave a clear comprehensionof the different magnetic exchange interactions found in these Ni^II complexes.