Influence of geometry on the emitting properties of 2,3-naphthalimides

Abstract

The luminescence properties of 2,3-naphthalimides have been studied using picosecond and nanosecond spectroscopies. In acetonitrile solution N-phenyl-2,3-naphthalimid(e3 ) is found to emit dual fluorescence with emission maxima at 385 and 490 nm, respectively. The short-wavelength emission corresponds to the known fluorescence of the naphthalimides and is demonstrated for 3 to originate from a molecular conformation in which the phenyl substituent and the naphthalimide skeleton are orthogonal to each other. The long-wavelength emission is assumed to originate from a singlet excited state formed by a ca. 90° rotation of the phenyl group so that the two moieties are coplanar. Only a small dipole moment change is found between this excited state and the ground state. Only short-wavelength emission is observed with a lifetime in the nanosecond range as in the case of 1 and 2 when phenyl rotation is blocked with a bulky ortho tert-butyl group (compound 4). Increasing the viscosity of a glycerol/ethanol medium enhances both the efficiency and the lifetime of the short-wavelength emission of 3. It appears that at 77 K the emission originates directly from the Franck-Condon state. At room temperature, the other two emitting species are shown to arise from the Franck-Condon state by competitive intramolecular geometrical relaxation processes. Structures 5 and 6 are tentatively put forward to explain the formation of naphthazepinedione 8 by a 2 \pi + 2 \pi photochemical cycloaddition reaction