Photochromism of dihydroindolizines part X. Photo-responsive self-assembling organogelators based on photochromic dihydroindolizines and 11-aminoundecanoic acid (AUDA)

Multi-addressable photophysical properties of new synthesized photochromic materials based on photochromic dihydroindolizine system (DHI) covalently linked to N-acyl-11 aminoundecanoic acid (AUDA) or to its sodium salt or to its ester, through an amidic or urethane linkage have been studied. The DHI skeleton in these compounds is substituted in both the fluorene part (region A) or in the heterocyclic base (region B) with the gelling moieties. These molecules have been designed to respond to their environment. Interestingly, they are shown to act as efficient gelators for polar organic fluids, water and obviously they exhibit a thermosensitive answer as low molecular mass organogelators. In these fluids, the aggregative properties are totally suppressed upon conversion to neutral carboxylic species. The gels of these carboxylate sodium salts are shown to be markedly affected by light irradiation. Supramolecular gelating assemblies can be disrupted by the photoinduced ring opening of the DHI subunit, so that the macroscopic flowing property is recovered. Upon a further thermal treatment, the system is reversibly converted back to the supramolecular network. Controlled gelation could be achieved using temperature, light, or acidity as external stimuli. These new synthesized photochromic gels with their multi-addressable properties will find their applications as super photoresponsive materials. Developing and tuning of the photophysical properties of the synthesized compounds by the amide and urethane substituents in the 4-position of the fluorene and pyridazine regions have been achieved. The absorption maxima (λmax) and the half-lives (t1/2) of the colored betaines were detected in all cases using UV/VIS spectrophotometric measurements. Irradiation of DHI 12-20 in CH2Cl2 or in acetonitrile solutions at ambient temperature with polychromatic light leads to the formation of red to red-violet colored betaines 12′-20′. The kinetics of the bleaching process of betaines 12′-20′ to DHIs 12-20 were found to take place in the second range (96-218 s) and fit well the first order thermal back reaction. Some of these DHIs showed a photostability higher than that of the standard one. These interesting photophysical properties will help this family of compounds to find useful applications. Copyright © 2008 John Wiley & Sons, Ltd.