Spectroscopic properties of aromatic dicarboximides. Part 1.-N-H and N-methyl-substituted naphthalimides

Véronique Wintgens, Pierre Valat, Jean Kossanyi, Làszlo Biczok, Attila Demeter, Tibor Bérces

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The photophysical properties of the N-H and N-methyl derivatives of 1,2-, 2,3- and 1,8-naphthalimides have been studied. The shift of the fluorescence emission position as a function of the solvent polarity indicates only a weak variation of dipole moment for the excited state compared with the corresponding value in the ground state (5.7 D for 2b, 2.8 D for 3b and <2 D for 4b, 1 D ≈ 3.335 64 × 10-30 C m, and 2b, 3b and 4b are N-methyl-1,2- naphthalimide, N-methyl-2,3-napthalimide and N-methyl-1,8-naphthalimide). However, important modifications of the photophysical properties are observed which depend on the relative position of the dicarboximide moiety on the naphthalene ring: the intersystem crossing rate constant of 4b increases dramatically by three orders of magnitude compared with that of 2b; simultaneously, the fluorescence quantum yield decreases from 0.77 to 0.03, although the corresponding rate constant, kf, increases. This difference is found to arise from the energy gap between the lowest 1(π, π*) singlet excited state and the upper 3(n,π*) triplet state, which is of the order of 9 kcal mol-1 for 2b and less than 2 kcal mol-1 for 4b in acetonitrile solution. Protic solvents increase the energy difference between the n,π* and π,π* states thus decreasing the mixing of the two levels; as a consequence, the lifetime of 4b is increased, i.e. from <60 ps in hexane to 2.1 ns in trifluoroethanol. A triplet-triplet annihilation process occurs with the N-methyl derivatives 3b and 4b which leads to a monomer delayed fluorescence with the former, and mainly to a delayed excimer emission with the latter.

Original languageEnglish
Pages (from-to)411-421
Number of pages11
JournalJournal of the Chemical Society, Faraday Transactions
Issue number3
Publication statusPublished - Dec 1 1994


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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