First thermal studies on visible-light-switchable negative T-type photochromes of a nitrile-rich series

Representatives of visible-light-switchable nitrile-rich negative T-type photochromes (NRP) were synthesized. The temperature effect on the thermal relaxation of the photoinduced form of NRP was studied for the first time. It was found that regardless the temperature the reverse thermal reaction in ethanol and 1,4-dioxane proceeded according to a first-order kinetic equation, while an unusual pseudo-zero order of the dark reaction was observed in acetonitrile. Using the obtained experimental data, the activation energy as well as the activation parameters, such as entropy and enthalpy of activation, were calculated for the first time for thermal relaxation of NRP photochromes. It was also shown that an initial form of NRP photochromes bearing a tricyanofuran acceptor was more temperature resistant than the initial form of photochromes with a tricyanopyrrole acceptor.