On the angular dependence of the optical polarization anisotropy in ladder-type polymers

Two ladder-type polymers have been examined using polarized optical absorption and fluorescence spectroscopy in solution and solid state. The fluorescence anisotropy excitation spectra of ladder-type methyl-substituted poly(para-phenylene) and poly(naphthylene-phenylene) follow their absorption profiles, contrary to the typical behavior in other conjugated polymers, which show excitation wavelength dependent anisotropy until the onset of the typical red edge effect. Using Raman microscopy and linear dichroism of aligned stretched polyethylene films containing the ladder polymer, it has been found that the orientation of the absorption transition dipole moment is dependent on the conjugation length. The transition dipole of the shorter conjugation lengths of the distribution is localized approximately 7 degrees off axis, and that of the longer conjugation lengths is delocalized along the chain.