Synthesis, characterization and photophysical properties of benzidine-based compounds

The N-alkylation of the 3,3′-diaminobenzidine with innocent substituents leads to unusual properties. The emission of the benzidine core can be fine-tuned by subtle modifications, and the N-substitution with benzylic groups results in photoinduced exciplexes with distinct and increased emission. This compound constitutes the first example of intramolecular exciplex containing benzidine unit. We also show that these photoinduced processes could be modulated by proton input, and that the diprotonation of the benzidine core disrupted the intramolecular communication in the excited states with a concomitant inhibition of the ligand-centred fluorescence. Furthermore, upon photo-irradiation at 254 nm, semiquinone imine and quinone diimine systems are produced in CH2Cl2 of which the photolysis generates Cl radicals, which rapidly oxidize the tetraamine compounds.

Graphical abstractDownload full-size imageEmission of the benzidine core can be fine-tuned by subtle modifications and, interestingly, N-benzylation results in photoinduced exciplex. These photoinduced processes could be modulated by proton input.