Intramolecular photoinduced electron transfer of fluorescent probes based on 1,8-naphthalimide and aniline derivatives

The effect of conformation and electronic structure of fluorescent probes based on 1,8-naphthalimide and aniline derivatives (4-methoxyaniline and N,N-dimethyl-p-phenylenediamine) on the intramolecular photoinduced electron transfer (PET) was investigated by density functional theory calculations (B3LYP/6-31G (d, p)). We established restricted rotation around spacer bonds of the model compounds and their protonated and oxidized forms do not block the convergence of the nitrogen atoms involved in the electron transfer at a distance of ~3Å, which is adequately for PET. Computed values of protonation free energy for the gas-phase (ΔG298 r) show that the investigated fluorescent probes are predominantly protonated on the nitrogen atoms of the donor moiety. Electron population and localization of the frontier orbitals (LUMO, HOMO, HOMO-1) on the donor and acceptor moieties are transformed under protonation and one-electron oxidation of fluorescent probes. The results show that appearance or disappearance of the PET can be predicted by the energy difference between the frontier orbitals and the nature of their location of donor and acceptor moieties, which is in agreement with the PET theory and observed experimental data.