Characterization and Structure⁻Property Relationships of Organic⁻Inorganic Hybrid Composites Based on Aluminum⁻Magnesium Hydroxycarbonate and Azo Chromophore.

In this study, novel organic⁻inorganic composites were prepared by the complexation of dicarboxylic azo dye (AD) with aluminum⁻magnesium hydroxycarbonate (AlMg⁻LH). This procedure provides an effective method for the stabilization of dicarboxylic organic chromophores on an AlMg-LH host. The structures of the hybrid composites were examined by X-ray diffraction (XRD), secondary ion mass spectrometry (TOF-SIMS), 27-Al solid-state nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA) and scanning transmission electron microscopy (STEM). The TOF-SIMS method was applied to investigate the metal⁻dye interactions and to monitor the thermal stability of the organic⁻inorganic complexes. Secondary ion mass spectrometry confirmed the presence of a characteristic peak for C18H10O₅N₂Mg₂2+, indicating that both carboxylic groups interacted with AlMg-LH by forming complexes with two Mg2+ ions. Modification with hybrid pigments affected the crystal structure of the AlMg-LH mineral, as shown by the appearance of new peaks on the X-ray diffraction patterns. Adsorption of the dicarboxylic chromophore not only led to significantly enhanced solvent resistance but also improved the thermal and photostability of the hybrid pigments. We propose a possible arrangement of the azo dye in the inorganic matrix, as well as the presumed mechanism of stabilization.