Optical and Conductive Properties of Pyrazine-Bridged Iron, Ruthenium and Osmium Octaethylporphyrin Coordination Polymers

摘要

The optical and conductive properties of neutral and partially oxidized pyrazine-bridged polymers of iron, ruthenium, and osmium octaethylporphyyrin are reported. Analogies between these systems and the Creutz-Taube mixed valence dimers are drawn. Analysis of the infrared spectra of the neutral polymers establishes a lower limit for the polymer chain lengths. Examination of a broad transition that develops in the infrared upon partial oxidation of these polymers offers insight into the degree of delocalization of the conduction electrons, which is found to increase on descending the iron triad. Varying the degree of oxidation affects both the features of this broad transition and the d.c. conductivities.