The effect of intermolecular interactions on photoluminescence of a porphyrin side-chain polymer

Photoluminescence properties and exciton decay dynamics in a porphyrin side-chain polymer, polyporphyrin acrylate- acrylonitrile (abbreviated p(por)A-AN), have been investigated by femtosecond time-resolved photoluminescence spectroscopy. All the luminescences of p(por)A-AN films are due to the emissive decay of the photoexcited singlet excitons in the porphyrins. The luminescence efficiencies and lifetimes are increased for samples from pure films to dilute blend films. However, they are increased as the intrachain concentration of the porphyrin sidechain groups is decreased. The intrachain rotation motions of porphyrin sidechain groups result in the initial ultrafast luminescence decays, which are much faster than those due to the interchain interactions. All the samples show no significant red-shift and broadening of the transient luminescence spectra. The interchain and intrachain nonradiative exciton relaxation processes may play an important role in the luminescence dynamics in the p(por)A-AN films. The possible origin of different intrachain and interchain dynamic behaviours in p(por)A-AN films is discussed.