Photoinduced Intramolecular Electron Transfer in Phenylene Ethynylene Naphthalimide Oligomers.

This paper reports a photophysical investigation of a series of phenylene ethynylene oligomers (OPE) that are end-substituted with a 1,8-naphthalene imide (NI) acceptor. The NI acceptor is attached to the terminus of the OPEs an ethynylene (-C≡C-) unit that is linked at the 4-position of the NI unit. A series of three oligomers is investigated, OPE1-NI, OPE3-NI, and OPE5-NI, which contain 1, 3, and 5 phenylene ethynylene repeat units, respectively. The properties of the OPEn-NI series are compared to a corresponding set of unsubstituted OPEs, OPE3 and OPE5, which contain 3 and 5 phenylene ethynylene repeats, respectively. The photophysics of all the compounds are interrogated using a variety of techniques including steady-state absorption, steady-state fluorescence, two-photon absorption, time-resolved fluorescence, and transient absorption spectroscopy on femtosecond-to-microsecond time scales. The effect of solvent polarity on the properties of the oligomers is examined. The results show that the NI-substituted oligomers feature a lowest charge transfer (CT) excited state, where the OPE segment acts as the donor and the NI moiety is the acceptor (OPE-NI). The absorption spectra in one-photon and two-photon exhibit a clear manifold of absorption features that can be attributed to direct CT absorption. In moderately polar solvents, the emission is dominated by a broad, solvatochromic band that is due to radiative decay from the CT excited state. Ultrafast transient absorption provides evidence for initial population of a locally excited state (LE) which in moderately polar solvents rapidly (∼1 ps) evolves into the CT excited state. The structure, spectroscopy, and dynamics of the CT state are qualitatively similar for OPE3-NI and OPE5-NI, suggesting that delocalization in the OPE segment does not have much effect on the structure or energetics of the CT excited state.