The acid–base neutralization reaction of commercially available disodium 2,6-naphthalenedisulfonate (NDS, 2 equivalents) and the tetrahydrochloride salt of tetrakis(4-aminophenyl)methane (TAPM, 1 equivalent) in water gave a novel three-dimensional charge-assisted hydrogen-bonded framework (CAHOF, F-1). The framework F-1 was characterized by X-ray diffraction, TGA, elemental analysis, and 1H NMR spectroscopy. The framework was supported by hydrogen bonds between the sulfonate anions and the ammonium cations of NDS and protonated TAPM moieties, respectively. The CAHOF material functioned as a new type of catalytically active Brønsted acid in a series of reactions, including the ring opening of epoxides by water and alcohols. A Diels–Alder reaction between cyclopentadiene and methyl vinyl ketone was also catalyzed by F-1 in heptane. Depending on the polarity of the solvent mixture, the CAHOF F-1 could function as a purely heterogeneous catalyst or partly dissociate, providing some dissolved F-1 as the real catalyst. In all cases, the catalyst could easily be recovered and recycled.

A new self-assembled and self-healing class of metal free, recyclable, heterogeneous Brønsted acid catalysts has been developed by the protonation of aniline derivatives (tetrakis(4aminophenyl)methane, leuco-crystal violet, benzidine, and p-phenylenediamine) 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. Xray diffraction analysis of hydrated and dehydrated samples of F-1a and F-2 indicated that water of crystallization served as a crosslinking agent, diminishing the substrate induced "breathing" affinities of the frameworks.

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