Intramolecular excimer formation and photoinduced electron-transfer process in bis-1,8-naphthalimide dyads depending...

The photophysical properties of bis-1,8-naphthalimide (NI-L-NI) dyads with different linkers ( L = -C 3H 6-, -C 4H 8-, -C 6H 12-, -C 8H 16-, and -C 9H 18-) as well as the reference NI derivative (NI-C 7H 15) were investigated in CH 3CN and H 2O/CH 3CN (v/v = 1:9). The normal fluorescence peak of (1)NI*-L-NI was observed at 379 nm together with a broad emission at longer wavelength both in aprotic CH 3CN and in H 2O/CH 3CN, which is assigned to an excimer, (1)(NI-L-NI)*. The excimer emission maximum was blue-shifted with increasing length of the linker. The photoinduced electron-transfer process of NI-L-NI was also investigated in both solvents by using nanosecond-laser flash photolysis. The T 1-T n absorption band for (3)NI*-L-NI was observed around 470 nm in both solvents. In H 2O/CH 3CN, NI-L-NI is solvated with H 2O in the ground state to exist as solvated NI-L-NI. In the excited triplet state, the NI radical anion (NI (*-)) was generated via the intramolecular quenching of (3)NI*-L-NI by another NI moiety. The solvated NI (*-)-L-NI may undergo the proton abstraction process to give NI(H) (*)-L-NI, which can be confirmed by the transient absorption band at 410 nm. This band was not observed in pure aprotic CH 3CN.