Directed Templating and Synthesis of Low-Density Molecular Crystal Frameworks

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9908343WardThis project entitled Direct Templating and Synthesis of Low-Density Molecular Crystal Frameworks will explore materials design based on crystalline clathrates. The principal goals include the design and synthesis of host frameworks constructed from topologically complementary guanidinium (G) cations and sulfonate (S) moieties of various organodisulfonates by (i) using a diversified library of organodisulfonate pillars to generate new guanidinium organodisulfonate "porous" host frameworks; (ii) using the library to elicidiate molecular recognition factors that govern host-guest assembly and guest ordering; (iii) synthesizing GS clathrates based on organodisulfonate pillars equipped with various functionalities and shape; (iv) investigating the role of GS architectures in directing guest ordering; (v) synthesizing extended "multicomponent pillars" in which two monosulfonates projecting from opposing GS sheets are coupledby specific interactions such as hydrogen bonding or metal complexation; (vi) synthesizing multicomponent frameworks in which monosulfonate and disulfonate GS ribbon "modules" combine to form unique porous frameworks; (vi) exploring the inherent versatility of these modular materials to create a library of host frameworks that can be used for the synthesis of functionals materials and for crystallization-based separations protocols; (viii) extending these concepts to topologically similar structural homologs that replace organosulfonates with organophosphonates and guanidinium ions with other cations that have threefold symmetry.This project will advance the understanding of molecular recognition processes governing the assembly of low-density host frameworks and the inclusion of guest molecules. The aim is to be able to generate functional materials for potential applications in chemically selective and enatioselective separations, as well as materials with unique lattice architectures that may lead to novel optoelectronic and magnetic properties.