描述了由金属离子连接的卟啉二聚体的合成,并展示了两种新二聚体的 X 射线结构。如先前针对抗磁性金属离子所示,观察到各个亚基之间的强电子相互作用。通过 EPR 和 SQUID 测量研究了由钯 (II) 或铜 (II) 离子连接的铜 (II) 卟啉之间的反铁磁耦合。对于钯 (II) 连接的二聚体,通过 EPR 测量估计了非常小的反铁磁耦合(Ĵ<-1 厘米-1). 对于三核-铜 (II) 连接的二聚体,测量了铜 (II) 离子之间的大反铁磁耦合。在这种三核化合物中,连接铜 (II) 离子用作中继以增加两个铜 (II) 卟啉之间的相互作用。
Syntheses and Optical and Electrochemical Properties of Porphyrin Dimers Linked by Metal Ions
作者:Sébastien Richeter、Christophe Jeandon、Jean-Paul Gisselbrecht、Romain Ruppert、Henry J. Callot
DOI:10.1021/ja017531n
日期:2002.5.1
The preparation, isolation, and characterization of several new peripherally functionalized monomeric porphyrins and metalloporphyrins and of porphyrindimers are described. These dimers are obtained by linking with metal ions two monomeric porphyrins bearing at their periphery an enaminoketone chelate fully conjugated with the aromatic ring. Porphyrindimerslinked by metal ions display large interactions