Isatin N2-diphenylhydrazones: new easily synthesized Vis-Vis molecular photoswitches

Abstract

The photochromic properties of isatin N²-diphenylhydrazones as a new type of molecular switch were investigated. Interestingly, dimerization stabilizes the formation of only E-isomers in the synthesis, even without a Z-isomer presence in the mother liquor. The irradiation of E-isomers in solution at their absorption maxima leads to the formation of the corresponding Z-isomers. Although the shift in the absorption maximum is not large and photochemical quantum yields are lower compared to in commonly used photoswitches, the absorbance changes are sufficient for potential practical use of these compounds as On-Off switches when the readout wavelength is optimally selected. The process is reversible and switching cycles can be repeated many times in both directions. The determined thermodynamic parameters and calculated geometry of the transition state clearly indicate the inverse mechanism of the thermally initiated slow back Z–E isomerization. Due to the Vis-Vis character of molecular photoswitching and significant geometric changes during the switching process, isatin N²-diphenylhydrazones are eminently suitable for molecular switching in biological/biotechnological applications. Moreover, the interaction of isatin N²-diphenylhydrazones with strongly basic anions increases their functionality and creates a four-state On-Off switch in one molecule. This four-state switch includes the unique E–Z isomerization induced photochemical switching between two stable tautomeric forms of organic amide anions. Simple synthesis of these derivatives and their sufficiently sensitive response to external stimuli promote isatin N²-diphenylhydrazones as suitable candidates for both discussed photochemistry areas (molecular switching and actinometry).