Controlling Diradical Character of Photogenerated Colored Isomers of Phenoxyl-Imidazolyl Radical Complexes
2022
Nishijima, Moe | Mutoh, Katsuya | Shimada, Rintaro | Sakamoto, Akira | Abe, Jiro
We propose a rational method for evaluating the diradical character of the photochromic phenoxyl-imidazolyl radical complex (PIC) derivatives based on their radical–radical coupling reaction rates. PIC consists of an imidazole ring, a phenoxyl ring, and a bridging unit that structurally connects them. The C–N bond formed between the imidazole and phenoxyl rings can be dissociated photochemically in a homolytic manner. The photochromism of PIC differs significantly from other photochromic molecules in that the transient colored open-ring isomer has a diradical character. The colored open-ring isomer returns promptly to the initial colorless closed-ring isomer by the intramolecular radical recombination reaction. By changing the aromaticity and substitution position of the bridging unit, it is possible to control the degree of contribution of the open-shell diradical and closed-shell quinoidal structures to the open-ring isomer. Systematic investigation of the photochromic reactions of several PIC derivatives revealed that the half-life of the open-ring isomers reflects the diradical character. Thus, the radical recombination reaction rate of the open-ring isomer of the PIC derivatives is an excellent parameter of the diradical character.
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