Emission spectra of polysilanes

We have examined the emission spectra of a variety of polysilanes as thin films and solutions. The solution fluorescence thermochromism provides evidence to support the rotational isomeric state model used to interpret the absorption spectrum. The structured character and low yield of phosphorescence in the alkyl polysilanes suggest that the triplet is the immediate precursor to photochemical scission. The change in character of both fluorescence and phosphorescence on going from phenyl to naphthyl in the aryl series indicates that the transitions in the naphthyl polymers are principally ..pi..-..pi... 31 refs., 10 figs., 2 tabs.