Changes in energy of three types of hydrogen bonds upon excitation of aminocoumarins determined from absorption solvatochromic experiments

Abstract

Absorption spectra of 6-aminocoumarin (6AC) and 7-aminocoumarins (C120 and C151) were studied in polyfluorinated alcohols: (1,1,1,3,3,3-hexafluoroisopropanol (HFIP), 2,2,2-trifluoroethanol (TFE)), in water and in methanol, and compared to those taken in 1-chloro-n-alkanes. According to our results, the observed unusual blue-shift of a long-wavelength band in absorption spectra in strong protic solvents is direct evidence of significant weakening of a N⋯H–O hydrogen bond. The results obtained for the aminocoumarins in HFIP, which in contrast to aliphatic alcohols does not form hydrogen bonds of the acceptor type, prove that the decrease in the energy of the N⋯H–O hydrogen bond upon excitation to the lowest S₁-LE state is significantly greater than the increase in the energy of hydrogen bonds made by the oxygen atom of carbonyl group O⋯H–O. It is in contrast to theoretical calculations for C151 [Y. Liu, J. Ding, R. Liu, D. Shi and J. Sun, J. Photochem. Photobiol. A, 2009, 201, 203–207]. A comparison of the absorption spectra measured in DMSO and in 1-chloro-n-alkanes shows that the energy of two N–H⋯O hydrogen bonds considerably increases as a result of excitation. These results are consistent with those of the theoretical calculations [Y. Liu, J. Ding, R. Liu, D. Shi and J. Sun, J. Photochem. Photobiol. A, 2009, 201, 203–207; P. Zhou, P. Song, J. Liu, K. Han and G. He, Phys. Chem. Chem. Phys., 2009, 11, 9440–9449]. In this study we applied the procedure proposed by us in J. Photochem. Photobiol. A, 2006, 184, 250–264 for the determination of changes in hydrogen bond energy as a result of electronic excitation based on analysis of the absorption spectra of the probe studied in the solvents interacting with it exclusively nonspecifically and in those forming hydrogen bonds with it.