Funatsu Kenji, Imamura Taira, Ichimura Akio, Sasaki Yoichi
Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan, and Department of Chemistry, Faculty of Science, Osaka City University, Osaka 558-0022, Japan.
Inorg Chem. 1998 Sep 21;37(19):4986-4995. doi: 10.1021/ic971361r.
A series of cofacially arranged ruthenium(II) porphyrin dimers 1-5 having a variety of axial ligands such as CO, pyridine, and 4-cyanopyridine, were synthesized. Porphyrin tetramers, 6 and 7, which have pyridylporphyrin ligands at the axial positions of the parent cofacial ruthenium(II) dimers, were also prepared. These porphyrin dimers and tetramers were characterized by (1)H NMR spectroscopy, ESI (electrospray ionization)-mass spectroscopy, and elemental analysis. The ruthenium porphyrin dimers and tetramers exhibited characteristic electrochemical and spectroscopic properties caused by interactions between the porphyrin subunits. Stepwise oxidations of the porphyrin rings or the ruthenium ions in the cofacial dimer skeltons were observed in the cyclic voltammograms. The potential differences (DeltaE degrees ' mV) of the oxidation steps were larger than 260 mV for all the porphyrin oligomers. The Soret bands of the cofacial dimers were significantly broadened by excitonic interactions between the two porphyrin subunits. Furthermore, the mixed-valence states of 3-7 showed specific intervalence charge-transfer (IT) bands between the Ru(II) and Ru(III) cores in the near-IR region at around 1500 nm.
