Novel cofacial ruthenium(II) porphyrin dimers and tetramers

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 H-1 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 (Delta E degrees' mV) of the oxidation steps were larger than 260 mV for all the porphyrin oligomers. The Sorer 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(IT) and Ru(III) cores in the near-IR region at around 1500 nm.