Steady-state fluorescence and photo-isomerization study of 1-methyl-4'-(p-N,N dimethyl-amino styryl) pyridinium iodide

Photochemical and thermal trans/cis isomerization reactions are reported for 1-methyl-4'-(p-N,N dimethyl-amino styryl) pyridinium iodide, Cy, which is synthesized in the trans configuration. In a basic solution the trans form, Cytr, cannot isomerise directly to the cis form. Its protonated form, CytrH+, is active and reacts photochemically from trans to cis isomer, CycH+. The quantum yields Φtc and Φct are determined in water. Deprotonation process of CycH+ yields the cis isomer, Cyc, which can thermally revert to the stable trans form. The rate constant and the activated parameters of the thermal reaction are also determined. Due to irreversibility of the thermal reaction , a complete molecular reaction cycle is performed in one direction. To get more information on the spectral properties of protonated form, its absorption and fluorescence spectra were investigated in sixteen neat polar protic and aprotic solvents. Absorption energy correlates linearly with hydrogen bond acceptor ability of the solvent. Another linear correlation was found between fluorescence energy of CyH+ and free energy for transferring the proton to the surrounding solvent, ΔGto.