Effect of Cis-Backbone on Optical Properties of Polyphenylacetylene
By controlling the temperature of chemical reaction, we synthesized four polyphenylacetylene samples, in which the percentages of cis configurations were determined to be 65, 75, 85 and 100%, respectively. Ultraviolet-visible and fluorescence studies show that the cis-configured backbones have posed significant effects on the optical absorption and fluorescence of the polyphenylacetylenes. Upon the 325-nm excitation, the dilute solutions of these cis-polyphenylacetylenes give off weak fluorescence with their peak located at about 390 nm, but the concentrated solutions of the polymer can give off strong orange-red fluorescence with their peak located at about 600 nm. With Hückel tight binding theory, both the E-k dispersion relations and the density of states were calculated for cis-polyphenylacetylene. Our results suggest that the blue photoluminescence of polyacetylenes origins from the backbone enhanced -conjugation of the phenyl chromophors in the polymer, and that intermolecular interactions can occur in the excited complex of the polymer.
Yuan Ming Huang
B. G. Zhai and Y. M. Huang, "Effect of Cis-Backbone on Optical Properties of Polyphenylacetylene ", Key Engineering Materials, Vols. 428-429, pp. 483-486, 2010