Polyimide and Imide Compound Exhibiting Bright Red Fluorescence with Very Large Stokes Shifts via Excited-State Intramolecular Proton Transfer II. Ultrafast Proton Transfer Dynamics in the Excited State

A novel polyimide (PI) and imide compound emitting prominent reddish-orange fluorescence under excitation by UV light were prepared based on 3-hydroxy­pyromellitic dianhydride (PHDA), and their fluorescence properties were examined. The steady-state fluorescence spectrum of a PI film displayed an emission band at 590 nm with a very large Stokes shift (ν = 10 448 cm^–1) via the excited-state intramolecular proton transfer (ESIPT), while the time-resolved fluorescence spectrum showed a rapid decay of the emission band of the enol form at around 400 nm within 15 ps. Transient absorption measurements showed an induced absorption and stimulated emission of the keto form with a time constant of ca. 3.0 ps, implying that ESIPT occurs on this time scale. Consequently, introduction of a hydroxy group into the pyromellitic moiety of PIs and imide compounds led to the long-wavelength ESIPT emission applicable to spectral converters having high thermal, mechanical, and environmental stabilities