Due to their high thermal and environmental stability, polyimides (PIs) are one of the most attractive candidates for novel highly fluorescent polymers, though photophys. studies of PIs are challenging owing to their poor soly. in common solvents. To overcome these problems, we have synthesized and examd. a series of low mol. wt. model imide compds.: substituted N-cyclohexylphthalimides with alicyclic amino groups at the 3 or 4-positions of the benzene rings (x-NHPIs). Their photophys. properties were systematically investigated by steady-state UV/Visible absorption, fluorescence, and time-resolved fluorescence techniques. In soln., unsubstituted N-cyclohexylphthalimide (NHPI) showed almost no emission, while x-NHPIs exhibited enhanced fluorescence emission depending on the solvent polarity. Anal. of the solvatochromism of the x-NHPIs via Lippert-Mataga plots indicated the generation of large dipole moments in the excited singlet states originating from the intramol. charge-transfer (ICT) states. The significant difference in the fluorescence quantum yields (ﾎｦ) between the 3-substituted (3Pi and 3Pyr) and 4-substituted NHPIs (4Pi and 4Pyr) strongly suggests that the former form a twisted ICT (TICT) state, whereas the latter form a planar ICT (PICT) state when excited. 4-Substituted NHPIs also show high fluorescence yields in the cryst. state. A particularly large ﾎｦ value was obtained for the 4Pi crystal, which we explain by the large intermol. distances and the arrangement of mols. minimizing intermol. interactions as well as the small non-radiative deactivation rate. These facts clearly demonstrate that the introduction of an alicyclic amino group into NHPI at the 4-position enhances the fluorescence quantum yields significantly, which suggests a new pathway for the development of novel, highly fluorescent PIs. [on SciFinder(R)]
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