Isatin phenylhydrazones: anion enhanced photochromic behaviour

Abstract

The photochemical properties of two basic easily synthesized isatin N²-phenylhydrazones were investigated. Contrary to the corresponding isatin N²-diphenylhydrazones, only Z-isomers were isolated from the reaction mixtures during the synthesis due to their stabilization by intramolecular hydrogen bonding. Although the presence of the CN double bond creates conditions for the formation of a simple on–off photoswitch, the low photochemical quantum yield and particularly the low switching amplitude in absorbance hamper their photochromic applications. However, the addition of strongly basic anions to phenylhydrazone solutions leads to isatin NH group deprotonation and creates a new diazene T-type Vis–Vis photochromic system with sufficiently separated absorption maxima. Interestingly, although the thermally stable A-form is also photostable in ambient light, its irradiation with a stronger LED source leads to thermally unstable B-form formation which rapidly isomerizes back to the corresponding A-form. The process is reversible and switching cycles can be repeated in both directions. The important advantages of this two-component organic chromophore–inorganic anion photochromic system are its easy synthesis, easy handling due to its insensitivity to room light, easy further structural modification and reversibility. The corresponding photochemical quantum yield, however, remains relatively low (Φ ∼ 0.001). The theoretically calculated properties are in agreement with the obtained experimental results and support the proposed reaction mechanism.