Effects of solvent, pH and beta-cyclodextrin on the photophysical properties of 4-hydroxy-3,5-dimethoxybenzaldehyde: intramolecular charge transfer associated with hydrogen bonding effect

The photophysical properties of 4-hydroxy-3,5-dimethoxybenzaldehyde (HDMB) in various solvents, pH and in aqueous beta-cyclodextrin (CD) have been investigated. In non-polar solvents, HDMB gives only one emission maxima; whereas, in polar solvents it shows a dual luminescence. The increase in Stokes shift with increase in polarity is much more for longer wavelength (LW) than for a shorter wavelength (SW) band. This behaviour indicates the formation of an intramolecular charge transfer (ICT) state through relaxation from the normal excited state. Especially in water, the ICT emission is further red shifted to 430 nm with the normal emission band at 330 nm and the relative fluorescence intensities between 330 nm and 430 nm emission bands are affected by the excitation wavelength. However, this excitation wavelength dependence is not large in aqueous beta-CD solutions. These results suggest that the ICT state in polar solvents/water is stabilized through exciplex formation by the hydrogen-bonding interaction between the carbonyl group and polar solvents/water. The ground and excited state pK(a) values for the neutral-monoanion equilibrium have been measured and discussed. HDMB forms a 1:1 inclusion complex with beta-CD. A mechanism is proposed to explain the inclusion process.