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 pi-pi interactions, which in turn dictate the supramolecular assemblies between themselves or with octamolybdate anions that eventually result in the growth of hybrid solids.