Tautomerism of acridin-9-amines substituted at the exocyclic nitrogen atom: spectroscopic investigations and theoretical studies

In the ground electronic state, the first two (1 and 2) of the compounds investigated--9-(methoxyamino)acridine (1), 9-hydrazinoacridine (2), N-(2-chloroethyl)acridin-9-amine (3) and N-(5-methylpyridin-2-yl)acridin-9-amine (4)--exist principally in the imino tautomeric form, while the other two (3 and 4) can coexist as amino and imino tautomers in solvents of various polarities and abilities to enter into specific interactions. These features of the molecules are reflected in the experimental absorption spectra and the predicted thermodynamic and spectral data. The predicted thermodynamic characteristics suggest that in the S1 state, the imino tautomers of 1, 2 and 4 and the amino tautomer of 3 are more stable than their tautomeric counterparts. However, the predicted rates of intersystem crossing suggest that the imino tautomers of 1-3 and the amino tautomer of 4 lose excitation energy very rapidly, so that only their counterpart tautomers in fact emit radiation. This explains why 1 and 2 do not fluoresce and why the amino form of 3 and the imino form of 4 are the emitters. 3 and 4 thus represent acridin-9-amines whose imino forms are preferred in the ground state, but whose respective amino and imino forms are preferred in the excited state. Because 3 and 4 are capable of tautomeric transformations in the ground and excited states, and also enter into specific interactions with solvents, these compounds could be potent spectral indicators or probes of environmental properties.