Rate-Tunable Stepwise Two-Photon-Gated Photoresponsive Systems Employing a Synergetic Interaction between Transient Biradical Units.

The cooperative interaction between photons and molecules, recently termed as the "photosynergetic" effect, is crucial to develop advanced photofunctional materials beyond a one-photon reaction of a single chromophore. The two-photon absorption is one of the attractive processes for the efficient utilization of photons. Especially, the nonlinear response of the two-photon absorption process is of interest not only to realize temporal and spatial control of reactions but also to develop the rewritable optical memory media and smart optical devices responding to the intensity of light. The stepwise two-photon-induced photochromism, which involves a short-lived transient species as an intermediate state, is one of the advanced photoresponsive compounds. The key feature of the stepwise two-photon-induced photochromism is an effective electronic interaction between the photogenerated transient chromophores. Here, we designed bis(phenoxyl-imidazolyl radical complex) (bisPIC) derivatives, which are composed of a couple of photochromic units and absorb two photons in a stepwise manner. The stepwise photochromic properties were investigated in detail by using double pulse laser flash photolysis and time-resolved Fourier transform infrared (TR-FTIR) spectroscopy. The one-photon reaction leads to the generation of a short-lived biradical species, which absorbs an additional photon and generates two electronically coupled biradical units, resulting in the formation of the long-lived quinoid species. The short-lived biradical species and the long-lived quinoid species of each bisPIC derivatives show the significantly different absorption spectra and rates of the thermal back reactions. These results indicate the colors and the lifetimes of the transient species can be systematically changed by switching the wavelength and intensity of the excitation light. The development of an excitation light threshold system based on the fast-switchable photochromic compounds will give important insights not only for the development of functional photoresponsive materials but also for the fundamental research using the cooperative excitation and interaction between photochromophores.