Azobenzenes immobilization on a solid support enables the usage of their trans-cis isomerization ability for preparation of functional materials. The behavior of azobenzenes in the interlayer space of α-zirconium phosphate (ZrP) upon the UV–Vis irradiation was investigated. Two experimental approaches were performed: (1) co-intercalation of benzylalkylammonium surfactants and azobenzene in the interlayers of ZrP (ZBCnA), and (2) intercalation of p-aminoazobenzene (ZpA). The materials were characterized with XRD, FTIR, UV–Vis, CHN analysis, and the molecular modeling. The molecules in ZBCnA samples were sparsely packed and held by weak hydrophobic interactions. Conversely, the molecules in ZpA sample were strongly H-bonded to the ZrP, well-ordered, and densely packed. These structural features determined the samples’ photoresponsive behavior. Low density of molecules in the ZBCnA samples, allowed the effective, fast, and reversible isomerization of azobenzene. Whereas the ZpA sample did not react to the UV irradiation because of the steric hindrance of tightly packed molecules.
Systems consisting of layered structures and photoactive molecules have been studied extensively. The structures of resulting complexes may be controlled by UV–Vis radiation, which subsequently affects their materials properties. This study describes a synthesis route for obtaining a photoresponsive kaolinite intercalation compound. The material was prepared by co-intercalating azobenzene and benzylalkylammonium chlorides into a methoxy form of kaolinite. The resultant materials possessed large basal spacing values in the range of 45–55 Å. The UV–Vis and Fourier-transform infrared spectroscopy analyses confirmed the reversible photoisomerization of azobenzene upon exposure to UV and Vis radiation. This phenomenon was significantly influenced by the type and amount of co-intercalated molecules. Upon multiple trans–cis conversions, the azobenzene partially evaporated. For the first time, a kaolinite-based material was prepared that exhibited photochromic behaviour upon UV and Vis irradiation.
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