The influence of substituents in arene ring of aniline on dynamic, energetic and electrooptical non-equivalency of amino group NH-bonds in complexes with intermolecular H-bond of 1:1 and 1:2 composition

Infrared spectra of free and bound with different proton accepters in 1:1 and 1:2 complexes H-bonded molecules of 3,5-dichloroaniline, 3,5-dibromoaniline, 2,3,5,6-tetrafluoroaniline, 4-methoxytetrafluoroaniline, pentafluoroaniline, 4-nitro-aniline, 2,6-dichloro-4-nitroaniline, 4-nitrotetrafluoroaniline and 4-aminotetrafluoropyridine were studied in the region of stretching and deformational vibrations of amino group. Spectral characteristics of absorption bands of free and bound H-bonded molecules of substituted anilines in solutions were determined. With regard to dynamic and electrooptical non-equivalence of amino group NH-bonds in free and bound H-bonded molecules of anilines the solution of vibrational and electrooptical tasks was found. The valent angles gamma(HNH) and the dynamic and electrooptical characteristics of amino group NH-bonds were determined. Equilibrium constants monomer-complex were calculated for 1:1 H-bonded complexes. The influence of the position, number and individual properties of substituents on donor features in H-bond the geometrical, dynamic, electrooptical and energetic characteristics of amino group NH-bonds of anilines in complexes of different composition were investigated. It was shown that amino group NH-bonds in 1:1 and 1:2 complexes were non-equivalent dynamically, electrooptically and energetically. Non-equivalence of NH-bonds was mainly determined by the position, number and individual properties of substituents in aniline arene ring. The correlations between the spectral, geometrical, dynamic and electrooptical characteristics of amino group in 1:1 and 1:2 H-bonded complexes were stated.