Cooperative polar ordering of acentric guest molecules in topologically controlled host frameworks

Acentric organic guest molecules exhibit polar ordering in a crystalline 'brick-like' orthorhombic host framework constructed from guanidinium (G) ions and 4,4'-biphenyldisulfonate ions, the latter connecting hydrogen-bonded sheets of the G ions and sulfonate (S) residues to create lamellar porous host galleries occupied by the guests. The single-crystal structures of the inclusion compounds suggest that polar ordering is governed by cooperative host-guest interactions during assembly of the pillared lamellae, resulting in guest dipole alignment orthogonal to the GS sheets.