Photochromic Radical Complexes That Show Heterolytic Bond Dissociation.

Photochromic materials have been widely used in various research fields because of their variety of photoswitching properties based on various molecular frameworks and bond breaking processes, such as homolysis and heterolysis. However, while a number of photochromic molecular frameworks have been reported so far, there are few reports on photochromic molecular frameworks that show both homolysis and heterolysis depending on the substituents with high durability. The biradicals and zwitterions generated by homolysis and heterolysis have different physical and chemical properties and different potential applications. Therefore, the rational photochromic molecular design to control the bond dissociation in the excited state on demand expands the versatility for photoswitch materials beyond the conventional photochromic molecular frameworks. In this study, we synthesized novel photochromic molecules based on the framework of a radical-dissociation-type photochromic molecule: phenoxyl-imidazolyl radical complex (PIC). While the conventional PIC shows the photoinduced homolysis, the substitution of a strong electron-donating moiety to the phenoxyl moiety enables the bond dissociation process to be switched from homolysis to heterolysis. This study gives a strategy for controlling the bond dissociation process of the excited state of photochromic systems, and the strategy enables us to develop further novel radical and zwitterionic photoswitches.