Function from structure: Design, synthesis, and physicochemical characterization of flexible metal-sulfonate materials

The design, synthesis, and physicochemical characterization of flexible metal-sulfonate materials is presented with a particular emphasis on the functional properties rationalized in terms of structure. Specifically, a new series of heterobimetallic luminescent porous lanthanide metal organic frameworks exhibiting both rigid and flexible morphologies are presented along with applications towards the development of solid state sensors. The surface area and pore volume of the synthesized materials are analyzed using a newly constructed manometric instrument for the fast and rapid collection of isothermal adsorption data. The flexibility (i.e., coordinative adaptability) of porous metal organic frameworks formed via barium-sulfonate coordination is explored in detail through the crystal-to-crystal transformation of a porous hydrated three-dimensional barium-sulfonate pseudo-polymorphic framework. This material introduces a new functional methodology for real world applications via the unique ability to mechanically trap freely diffusing gas through barium-sulfonate coordinative adaptability. Finally, the rationalization and mechanism of formation for a new low molecular weight supramolecular hydrogel is presented in terms of the sodium-sulfonate coordination and structural features obtained from single crystal X-ray diffraction; the first complete crystal structure of a hydrogel interacting with water.