Inhibition by Water during Heterogeneous Bronsted Acid Catalysis by Three-Dimensional Crystalline Organic Salts

A new self-assembled and self-healing class of metal free, recyclable, heterogeneous Bronsted acid catalysts has been developed by the protonation of aniline derivatives (tetrakis(4-aminophenyl)methane, leuco-crystal violet, benzidine, and p-phenyl-enediamine) with aromatic sulfonic acids (tetrakis(phenyl-4-sulfonic acid)methane, and 2,6-naphthalenedisulfonic acid). As a result, five three-dimensional crystalline organic salts (F-1a, F-1b, F-1c, F-2, and F-3) were obtained, linked by hydrogen bonds and additionally stabilized by the opposite charges of the components. Frameworks F-2 and F-3 were prepared for the first time and characterized by elemental analysis, X-ray structural analysis (for F-2), thermogravimetry, SEM, and FTIR spectroscopy. The catalytic activities of crystalline organic salts F-1-3 have been explored in industrially important epoxide ring-opening and acetal formation reactions. The presence of encapsulated water inside frameworks F-1a and F-2 had an inhibitory effect on the performance of the catalysts. X-ray diffraction analysis of hydrated and dehydrated samples of F-1a and F-2 indicated that water of crystallization served as a cross-linking agent, diminishing the substrate induced "breathing" affinities of the frameworks.