University of Bucharest, Faculty of Chemistry, Inorganic Chemistry Laboratory, Str. Dumbrava Rosie nr. 23, 020464-Bucharest, Romania.
Inorg Chem. 2011 Jul 4;50(13):5890-8. doi: 10.1021/ic2004276. Epub 2011 Jun 2.
A series of dinuclear [Ni(II)Ln(III)] Schiff-base complexes (using a Schiff-base dicompartmental ligand derived from o-vanillin [H(2)valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)]) with Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and a hydroxo-bridged tetranuclear [Ni(II)Yb(III)] are reported. The crystal structures have been solved for 10 dinuclear complexes revealing four arrangements for the dinuclear units, which are modulated by the coordinated solvent molecules and the nitrato-anion interactions. The magnetic behaviors have been investigated, and the nature of the Ni(II)-Ln(III) exchange interaction has been emphasized by comparison with the behavior of the related [Zn(II)Ln(III)] derivatives. This allowed for establishing that the interaction within these compounds is antiferromagnetic with the 4f ions of the beginning of the Ln series and turns ferromagnetic from Gd(III) toward the end of the series. AC susceptibility investigations clearly show the occurrence of slow relaxation processes of the magnetization close to 2 K for the dinuclear [Ni(II)Dy(III)] complex.
一系列双核[Ni(II)Ln(III)]希夫碱配合物(使用希夫碱双分隔配体,由邻香草醛[H(2)valpn = 1,3-丙二基双(2-亚氨基亚甲基-6-甲氧基苯酚)]衍生而来),其中 Ln = La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er 和一个偕羟桥连的四核[Ni(II)Yb(III)]。已经为 10 个双核配合物解决了晶体结构,揭示了双核单元的四种排列方式,这些排列方式由配位溶剂分子和硝酸根阴离子相互作用调节。已经研究了它们的磁行为,并通过与相关[Zn(II)Ln(III)]衍生物的行为进行比较,强调了 Ni(II)-Ln(III)交换相互作用的性质。这表明在这些化合物中,相互作用是反铁磁的,从 Ln 系列的起始端的 4f 离子开始,并且从 Gd(III)开始转向铁磁。交流磁化率研究清楚地表明,对于双核[Ni(II)Dy(III)]配合物,在接近 2 K 的温度下,磁化强度的缓慢弛豫过程发生。