Sulfur-bridged polycyclic aromatic compounds

When polycyclic aromatic hydrocarbons are heattreated with an excess amount of sulfur in evacuated closed tubing, they react with sulfur, liberating hydrogen sulfide; after removing unreacted sulfur, dark-colored compounds in the form of an amorphous solid are obtained. These compounds possess semiconductive properties; the electrical resistivity is greatly reduced from that of the original hydrocarbons. The ESR absorption of these compounds is characterized by the large g-value, which is due to sulfur-centered unpaired electrons.From these findings, with the results of chemical analysis, we can assume that the polycyclic aromatic nuclei crosslink with each other through the sulfur-bridges, which are good electron transport paths, and yield the aromaticity of the molecule. The sulfur-bridged polycyclic aromatic hydrocarbons can be considered as the structural model of chars and cokes. The ESR studies of a violanthrene-sulfur compound were carried out during its heat-treatment up to 1000°C.