The great potential of supramolecular materials is the possible discovery of properties that are characteristic of molecular clusters and not of individual molecules. Simple changes in the chemistry of building blocks in such clusters enhance further our ability to target specific properties in supramolecular materials. Designing for polar order in organic systems has long been a goal in materials chemistry because of its implications in surface properties, nonlinear optics, piezo-, ferro-, and pyroelectricity. The approaches to polar organic materials include the poling of host ± guest systems [1] self-assembled host ± guest systems, [2] the poling of polymer films, [3] Langmuir ± Blodgett film multilayers, [4±6]