Fast Photochromism Involving Thermally-Activated Valence Isomerization of Phenoxyl-Imidazolyl Radical Complex Derivatives.

Open-shell biradicals have received considerable attention in material science because of their high two-photon absorption cross sections and broad and high absorptive features over the visible region. However, the instability of the biradical caused by the open-shell nature was one of the drawbacks; therefore, novel radical compounds which can suppress unwanted reactions by tuning the open-shell features are desired to expand the versatility of the radical compounds. Here, we report a novel radical-dissociation-type photochromic compound whose photochromic reaction involves a valence isomerization from the open-shell biradical to closed-shell quinoidal forms by using a phenoxyl-imidazolyl radical complex framework. The valence isomerization from the biradical to quinoid forms effectively tunes the open-shell feature in time and drastically changes the spectral features, which were revealed by time-resolved Fourier transform infrared spectroscopy. This novel fast photochromic property not only is important for fundamental spin chemistry but also expands the versatility of the radical compounds for novel advanced photofunctional materials.