Structure-Directing Role of Hydrogen-Bonded Dimers of Phenylenediammonium Cations:  Supramolecular Assemblies of Octamolybdate-Based Organic−Inorganic Hybrids

Crystallization of three new organic/inorganic hybrid solids (1−3) based on octamolybdate under self-assembly conditions has demonstrated the structure-directing role of three hydrogen-bonded organic dimers (supramolecular synthons) in the construction of multidimensional networks. In acidified aqueous molybdate solution, isomeric phenylenediammonium ions form dimers through strong hydrogen-bonding and/or π−π interactions, which in turn dictate the supramolecular assemblies between themselves or with octamolybdate anions that eventually result in the growth of hybrid solids.