Photochromic heteroarylethenes with fast thermal isomerization kinetics

Abstract

Stilbenes (diphenylethenes) are fully examined organic chromophores for very diverse applications. However, these molecules might show poor stability under irradiation because several simultaneous reactions (oxidative photocyclization and dimerization) can take place during the photochemical isomerization of their C=C bond. In this context, heteroarylethenes emerge as powerful counterparts thanks to their improved stability. In addition, the chosen heterocycles and their functionalization allows to fine tune and increase the speed at which the thermal back reaction occurs, broadening the scope of application of the resulting chromophores. Here we report on the thermal Z-to-E isomerization kinetics of a series of rationally designed heteroarylethenes and how the chemical architecture of the chromophore modulates the speed of the process. Specifically, the metastable Z isomers display relaxation times covering a wide time window, from a few hours to hundreds of microseconds. In fact, one of the studied dyes is the fastest heteroarylethene known to date. It should be also noticed that the described heteroarylethenes exhibit great photochemical stability, it being possible to switch them back and forth many times without degradation.