2-(Hydroxyimino)aldehydes: Photo- and Physicochemical Properties of a Versatile Functional Group for Monomer Design

In the context of our research on stimuli-responsive polymers bearing the 2-(hydroxyimino)aldehyde (HIA) group, we have explored the photochemical behavior and physicochemical properties of a number of HIAs. Interpretation of the experimental data is supported by quantum mechanical calculations. HIAs are expected to undergo photoisomerization, chelate metal ions, yield hydrogen-bonded dimers or oligomers, exhibit relatively low pK_a s, and form >C=NO^. radicals through OH hydrogen abstraction or oxidation of the oximate ion. Besides the well-established E/Z oxime photoisomerism, we observed a Norrish-Yang cyclization resulting in cyclobutanol oximes, to our knowledge not previously described in the literature. The acidity, bond dissociation enthalpies, and electrochemical properties of the HIAs are compared with literature data of simple oximes. The results are discussed in relation to the many potential applications for HIAs, with emphasis on the synthesis of novel HIA-containing responsive polymers.