Koval Iryna A, van der Schilden Karlijn, Schuitema Anna Maria, Gamez Patrick, Belle Catherine, Pierre Jean-Louis, Lüken Matthias, Krebs Bernt, Roubeau Olivier, Reedijk Jan
Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Inorg Chem. 2005 Jun 13;44(12):4372-82. doi: 10.1021/ic0501770.
The reaction of copper(II) perchlorate with the macrocyclic ligand [22]py4pz in the presence of base leads to formation of a dinuclear complex Cu(2)([22]py4pz)(mu-OH)(3)xH(2)O, in which two copper ions are bridged by a single mu-hydroxo bridge. Each copper ion is further surrounded by four nitrogen atoms of the ligand. The mu-hydroxo bridge mediates a strong antiferromagnetic coupling (2J = -691(35) cm(-1)) between the metal centers, leading to relatively sharp and well-resolved resonances in the (1)H NMR spectrum of the complex in solution. We herein report the crystal structure, the magnetic properties, and the full assignment of the hyperfine-shifted resonances in the NMR spectrum of the complex, as well as the determination of the exchange coupling constant in solution through temperature-dependent NMR studies.
在碱存在的情况下，高氯酸铜（II）与大环配体[22]py4pz反应生成双核配合物Cu(2)([22]py4pz)(μ-OH)(3)·xH(2)O，其中两个铜离子由一个单μ-羟基桥连接。每个铜离子还被配体的四个氮原子包围。μ-羟基桥介导了金属中心之间强烈的反铁磁耦合（2J = -691(35) cm(-1)），导致该配合物在溶液中的(1)H NMR谱中出现相对尖锐且分辨率良好的共振。我们在此报告该配合物的晶体结构、磁性、NMR谱中超精细位移共振的完全归属，以及通过变温NMR研究确定溶液中的交换耦合常数。
