Solvent-Controlled Photoswitching of Azobenzene: An Excited State Shuttle

Abstract

The light-controlled excited state trans-cis isomerization process is a key to the development of conversion of light energy to mechanical motion at the molecular level. Considerable efforts have been made in tuning the isomerization process with electron donor and acceptor substituents by altering the excited state reaction coordinate. Here, we report a two novel push-pull series of para-diethylamino (DEA) and diphenylamino (DPA) substituted (E)-4′-((4-(diethylamino)phenyl)diazenyl)-N,N-diphenyl-[1,1′-biphenyl]-4-amine (1) and (E)-4′-((4-(diphenylamino)phenyl)diazenyl)-N,N-diphenyl-[1,1′-biphenyl]-4-amine (2). Compounds 1 and 2 undergo both photochemical and photophysical excited state deactivation pathways which can be controlled by varying the solvent polarity. These structural motifs of 1 and 2 would undergo torsional motions upon excitation to exhibit either trans→cis photoisomerization or to form a twisted intramolecular charge transfer state and both the process originates from the same excited state and competes with each other. Thus, alternations in the surrounding environment such as solvent polarity, solution viscosity, and protonation were employed to understand the preferential excited state deactivation pathway and thereby these systems could be employed as a new class of azobenzene-based luminescent photochromic molecules. For instance, in nonpolar solvent, toluene photoisomerization is preferred over TICT, but polar solvent, ethanol preferentially stabilizes the TICT state by virtue of N−C rotation which renders the energy barrier unfavourable for photoisomerization. The photostationary state of 1 in toluene is predominantly the Z isomer, whereas in ethanol E isomer is nearly two-fold higher than the Z isomer. These feature sets up a new approach towards the construction of multinary molecular switches and subsequent development in diverse fields.