Protolytic dissociation of cyanoanilines in the ground and excited state in water and methanol solutions

The effect of cyano substituents on the photoacidity of mono- and dicyanoanilines has been investigated. It was demonstrated that the cyano substitution increases significantly the acidity of aniline derivatives in the excited state in comparison to the ground state. 3,5-Dicyanoaniline is the strongest acid in the lowest excited singlet state, while 4-cyanoaniline is the weakest one. The derivatives of aniline with two cyano groups in o,o'-position show different properties from those characteristic for aniline and other investigated cyanoanilines. In the methanol solution with sodium methanolate the anions of 2,6-dicyano-3,5-dimethylaniline and 2,6-dicyano-3,5-diphenylaniline appear already in the ground state.The electronic ground and excited state charge distributions and dipole moments of all investigated cyanoanilines have been evaluated by ab initio calculations using the GAMESS program. (c) 2008 Elsevier B.V. All rights reserved.