The delicate forces that govern molecular organization in the solid state often frustrate attempts at de novo design of molecular crystals, and the prediction of crystal structure remains one of the foremost challenges in solid-state chemistry. Strategies that overcome this obstacle promise new materials with properties that can be manipulated through the versatility of organic synthesis. Low-density metal-organic frameworks (MOFs) and zeolite-like metal organic frameworks (ZMOFs), assembled through metal-based nodes and organic linkers, have proven particularly potent in this regard as they have expanded the utility of microporous solids. Using a design strategy based on molecular symmetry, metric matching and complementary hydrogen bonding, we have synthesized a zeolite-like hydrogen-bonded framework (ZHBF) through the self-assembly of two chemically distinct molecular tiles into hollow truncated octahedra, each held together by 72 hydrogen bonds and enclosing a volume of 2200 �3. These truncated octahedra assemble into a body-centered cubic microporous framework that mimics the sodalite topology of zeolite A. The peculiar characteristics of the molecular tiles precludes folding into other convex polyhedra, demonstrating that the realization of a particular solid-state architecture is often best achieved by frustration of all other possibilities. The ZHBF exhibits an extraordinary structural persistence as it encapsulates a wide range of molecular species, including transition metal complexes that thread through the framework as well as �ship-in-a-bottle� molecular clusters, confined within the truncated octahedra, which do not exist otherwise. The ZHBF is stable up to 160 oC as well, reflecting an unusual thermal stability for an organic hydrogen-bonded framework. The ZHBF suggests a new class of materials with properties that can be manipulated readily through modification of its organic components and encapsulation of functional guest molecules.

Organic zeolite-like hydrogen-bonded framework constructed from Archimedean principles

241st National Meeting (2011)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.