This paper describes a study of excited-state properties of naphthalmide (NI) and four 4-substituted derivatives: 4-chloronaphthalimide (Cl-NI), 4-methylthionaphthalmide (MeS-NI), 4-nitronaphthalimide (O(2)N-NI), and 4-(N,N-dimethylaminonaphthalimide (Me(2)N-NI). Steady-state absorption and fluorescence spectra were collected in solvents of varying polarity to determine the excited-state character of NI derivatives. Furthermore. the excited-state dynamics were studied Using femtosecond transient absorption spectroscopy. The experimental findings were compared to calculated data obtained using time-dependent density functional (TD-DFT) methods. We found that light absorption by all NI derivatives leads to the production of the second excited state (S(2)), which was found to have a n,pi* character. Within similar to 40 ps, the S(2) state undergoes internal conversion to produce the S(1) state. The S(1) state is relatively long-lived (similar to 4 ns) and has charge-transfer character in NI derivatives with electron-withdrawing and electron-donating groups (MeS-NI, O(2)N-Ni, and Me(2)N-NI). In the case of NI and Cl-NI, the S(1) state has a pi,pi* character and undergoes intersystem crossing to produce the T(1) state within 400 ps.
Kucheryavy, Pavel; Li, Guifeng; Vyas, Shubham; Hadad, Christopher; and Glusac, Ksenija D., "Electronic Properties Of 4-substituted Naphthalimides" (2009). Chemistry Faculty Publications. 160.
Journal Of Physical Chemistry A