Coordination-driven self-assembly: solids with bidirectional porosity

Coordination-driven self-assembly reactions have been used in the preparation of a variety of discrete supramolecular species, some of which have shown promise as synthetic receptors. Many highly ordered coordination polymers and porous networks have been prepared in a similar fashion. While a few of these solids are capable of the uptake of small organic molecules in the resultant molecular channels, the formation of truly porous structures has frequently been thwarted by lattice interpenetration. A strategy for the formation of porous solids that may circumvent this problem is based on the covalent construction of nanoscale macrocycles which, when eclipsed in the solid state, may lead to porous, tubular assemblies. We have incorporated these concepts toward the realization of a bidirectionally porous solid. The metal-directed, self-assembly of a conjugated, macrocyclic ligand provides a discrete, supramolecular entity in solution and the solid state. X-ray crystallographic analysis establishes that this assembly packs such that bidirectional channels are realized, and the incorporation of only ClCH2CH2Cl into the crystal lattice demonstrates that these channels are potentially suitable for the selective uptake of small organic guests.