Selected Papers : Different Photochromic Rates of Azopyridine Derivatives in New Dual Photoisomeric Cobaloxime Complex Crystals

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<jats:title>Abstract</jats:title> <jats:p>Two cobaloxime complexes, namely (3-cyanopropyl)(3-phenylazopyridine)cobaloxime and (3-cyanopropyl)(4-phenylazopyridine)cobaloxime, were synthesized as new dual photoisomeric complexes for controlling the reactivity of trans–cis photoisomerization of phenylazopyridine derivatives in the solid state. The phenylazopyridine moieties of the crystals were transformed from the trans to the cis-form on exposure to UV light. In contrast, the 3-cyanopropyl groups of the crystals were isomerized to 1-cyanopropyl groups on irradiation with visible light. Moreover, the 3–1 photoisomerization of the 3-cyanopropyl group occurred with retention of the single-crystal form. The rates of the trans–cis transformations of the phenylazopyridine moieties of the crystals before the 3–1 phototransformation were compared with those after the phototransformation in the solid state. For the two crystals, the rates of the trans–cis phototransformations significantly increased after 3–1 photoisomerization. The crystal structures before and after 3–1 photoisomerization were analyzed. The free space around the phenylazopyridine moieties expanded as a result of 3–1 photoisomerization. It is clear that the reaction rates of the trans–cis transformations of the phenylazopyridine moieties on exposure to UV light can be modified by introducing another photoreactive group that is photoisomerized by visible light.</jats:p>

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