A spectroscopic and photophysical study on molecular recognition via hydrogen-bonding and π—π stacking interactions

Spectroscopic and photophysical properties of a Kemp’s tricarboxylic acid derivative having an anthracene chromophore (I) upon recognition of 9-butyladenine (BA) in chloroform were studied in detail. Molecular recognition of BA by Ivia hydrogen-bonding and π—π stacking interactions were sensed successfully on the basis of absorption and fluorescence spectroscopies, by which the binding constant of the I:BA complex was determined to be 240 M−1. The fluorescence quantum yield and lifetime of I in the absence of BA were 0.24 and 5.6 ns, respectively, while those in the presence of an enough amount of BA increased to 0.35 and 13 ns, respectively. These values demonstrated that the nonradiative decay rate constant of I decreased from 13.6 × 107 to 5.0 × 107 s−1 upon binding with BA. Such changes in the photophysical properties of I before and after complexation with BA were discussed in terms of hydrogen-bonding and π—π stacking interactions between I and BA. In particular, intramolecular hydrogen-bonding between the amide and imide groups in I was shown to play important roles in determining the photophysical characteristics of I before complexation, while intermolecular hydrogen-bonding between I and BA governed the excited-state properties of the I:BA complex. The change in the hydrodynamic diameter of I before and after complexation with BA was also discussed on the basis of the results by fluorescence dynamic anisotropy measurements.