Mononuclear and Polynuclear Copper(II) Complexes Derived from Pyridylalkylaminomethylphenol Polypodal Ligands
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- 作者：Jorge Manzur ; Hector Mora ; Andrs Vega ; Diego Venegas-Yazigi ; Miguel A. Novak ; Jos Ricardo Sabino ; Vernica Paredes-Garca ; Evgenia Spodine
- 刊名：Inorganic Chemistry
- 出版年：2009
- 出版时间：September 21, 2009
- 年：2009
- 卷：48
- 期：18
- 页码：8845-8855
- 全文大小：921K
- 年卷期：v.48,no.18(September 21, 2009)
- ISSN：1520-510X
文摘
Four mononuclear complexes [Cu(HL1)Cl]PF6·CH3OH (1), [Cu(HSL1)Cl]PF6·0.75H2O (2), [Cu(HL2)Cl]PF6·CH 3OH (3), [Cu(HSL2)Cl]PF6·1.5CH3OH (4), and two polynuclear complexes [Cu 2(SL2)2](PF6)2·2CH3OH (5) and {Cu[Cu(SL2)(Cl)]2}(PF6)2 (6) (HL1: 2-[(bis(2-pyridylmethyl)-amino)methyl]-4-methylphenol; HSL1: 2-[(bis(2-pyridylmethyl)amino) methyl]-4-methyl-6-(methyl-thio)phenol; HL2: 2-[(2-pyridylmethyl)(2′-pyridylethyl)-aminomethyl)]-4-methylphenol; HSL2: 2-[(2-pyridylmethyl)(2′-pyridylethyl)amino-methyl]-4-methyl-6-(methylthio)phenol were obtained and characterized. The crystal structures of the mononuclear complexes 1−4 show the copper centers in a square-base pyramidal environment with the phenolic oxygen coordinated at the axial position. Dinuclear complex 5 has two copper centers with different geometry and bridged by phenoxo oxygens; one of the copper atoms is square pyramidal while the other can be described with a highly distorted octahedral geometry with a long Cu−S distance (2.867 Å). Density functional theory calculations were used to obtain the reported structure of 6, since single crystals suitable for X-ray diffraction were not isolated. Magnetic studies done for 5 and 6 show an antiferromagnetic behavior for 5 (J = −134 cm −1) and a ferromagnetic behavior for 6 (J = +11.9 cm−1). Redox potentials for the mononuclear complexes were measured by cyclic voltammetry; the values show the effect of the chelating ring size (−213 mV and −142 mV for Cu-HL1 and Cu-HL2, respectively) and the presence of the thiomethyl substituent (−213 mV and −184 mV for Cu-HL1 and Cu-HSL1, respectively).