Triplet excitons in acyl- and alkyl-substituted polycarbazolyldiacetylenes: a spectroscopical and photophysical study

Absorption, photoluminescence, and photoinduced absorption (PIA) spectra of films of red phase polycarbazolyldiacetylenes (polyCzDAs) carrying selected acyl (polyDPCHD) or alkyl (polyDCHD-HS) groups are reported. The absorption spectrum of polyDCHD-HS, which is almost independent of the temperature down to 20 K, shows an excitonic absorption followed by an inhomogeneously broadened vibronic progression. Very different is instead the case of polyDPCHD whose thin films show a very sharp excitonic transition and a vibronic progression with a lower electron-phonon coupling with respect to that of polyDCHD-HS. These peculiar characteristics allow the detection of additional features in the spectra, which are assigned on the basis of quantum chemical calculations to string modes of the backbone. As far as thick films of polyDPCHD are concerned, broad electronic spectra are observed. Raman spectroscopy studies suggest that this broadening is due to the presence of two forms of the polymer. Unlike other polydiacetylenes including polyDCHD-HS films, polyDPCHD films are also strongly luminescent, thus suggesting a different ordering of the dipole forbidden and allowed states. For these materials, the photoinduced absorption spectra are dominated by triplet excitons. Effects of different forms in acyl substituted polymers are observed also in the PIA spectra. The rise and decay of the triplet signal for polyDCHD-HS are accounted for through a dynamical model, which includes saturation effects in the monomolecular decay regime. A more complex kinetics is instead observed for polyDPCHD. From the study of the kinetics of the PIA spectra both the triplet generation efficiency and the density of traps are evaluated.