Study on intramolecular charge transfer fluorescence properties of trans-4-[4′-(N,N′-dimethylamino)styryl]pyridine: Effect of solvent and pH

Abstract

Photophysical characterization of a molecule, trans-4-[4′-(N,N′-dimethylamino)styryl]pyridine (4-DMASP) containing donor and acceptor moieties has been done experimentally as well as theoretically. Upon single excitation a charge-transfer state with high dipole moment is formed through rapid relaxation of a locally excited (LE) state in polar medium. A complete charge transfer process occurs as a result of twisting of donor group with respect to the acceptor part of the molecule resulting in the highly stabilized twisted state in polar medium giving fluorescence from LE state as well as from twisted state. However, in a nonpolar solvent emission occurs explicitly from a LE state. Hydrogen bond donor ability of solvents rather than dipolar interactions contributes more to the stability of ground state. However, dipolar interactions have greater contribution towards the stability of an excited state. All such interactions have higher contribution towards the stability of excited state than that of ground state. Very low fluorescence quantum yield in water is because of high rate of nonradiative processes as a result of high degree of stabilization of charge transfer state thereby making closer proximity of this state to triplet as well as ground charge transfer states. Monocation of 4-DMASP formed due to the protonation of pyridine nitrogen atom is more stable than neutral and dication species at ground as well as excited states because of greater extent of flow of charge from donor to acceptor part in monocation. Basicity of pyridine nitrogen atom being greater at excited state than that in ground state results in higher extent of pulling of charge from donor to acceptor part of monocation at excited state. Theoretical calculations suggest donor twisting as a possible path for creation of a charge transfer state rather than acceptor twisting. Excited state dipole moment value obtained from theoretical calculation corroborates well with the value determined experimentally. Theoretical calculation suggests no cis–trans photoisomerization in the ground state as well as excited state at room temperature.