I. Functionalization and Investigation of Highly Efficient Hosts for Use in Macromolecular Self-Assemblies and II. The Design and Synthesis of ROMP Imidazolium Systems for Use as Mechanical Actuators

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Virginia Tech


Recent advancements in supramolecular chemistry have given a wealth of strongly binding host-guest combinations. However, the deployment of these systems into meaningful constructs has been hindered due to difficulty of synthesis or to the lack of functionality in one or both components. Systems caught in this trap were the pyridyl cryptands of dibenzo-30-crown-10 and bis(m-phenylene)-32-crown-10 paired with paraquat. Exceptionally high association constants in the range of 105 to 106 have been observed for these systems, but their applications have been hindered.

Easing the implementation of pyridyl cryptands based on dibenzo-30-crown-10 was made a priority. An efficient method for the synthesis of pyridyl cryptands based on dibenzo-30-crown-10 and bis(m-phenylene)-32-crown-10 made use of the salt pyridinium bis(trifluoromethane)sulfonamide (TFSI) as a template. Optimization of the pyridinium TFSI template allowed for cyclization yields as high as 89%, as well as without the use of a syringe pump. Addressing the concern of functionality, for pyridyl cryptands, chelidamic acid was targeted as a way to build in functionality. Using a chelidamic isopropyl ester, 20 new chelidamic precursors of varying functionality were synthesized. The chelidamic derivatives fell into six groups: potential covalent monomers, initiators, chain terminators, leaving groups, aryl halides and host-guest monomers.

In an attempt to boost the association constants of pyridyl cryptands based on dibenzo-30-crown-10 with paraquat, alterations to the paraquat guest were explored. It was found that the association constants could be increased by nearly an order of magnitude. Tweaks to the paraquat included changing the counterion to TFSI, methyl groups to benzyl and allowing for access to more nonpolar solvents that were previously inaccessible, such as solvent change from DCM to acetone.

Two new biscryptands and two new bisparaquat TFSI monomers were synthesized. Using these monomers supramolecular polymers were synthesized and characterized. Fibers of these polymers drawn from concentrated solutions were found to be flexible and one such polymer solution was found to have an upper log / log specific viscosity–concentration slope of 3.55, which is the theoretical maximum. Additionally, a biscryptand was used to produce a chain extended polymer.

Using a fundamental understanding of host-guest chemistry, work was conducted on the synthesis of norbornene monomers and polymers with pendant imidazolium tethered by ethyleneoxy linkages to aid in the stabilization of the imidazolium cation. Through the use of ethyleneoxy linkages, the free anion content and conductivity was increased. Imidazolium monomer and polymer conductivities ranged up to nearly 10-4 S/cm. Furthermore, it was determined that as long as the ethyleneoxy spacer between the norbornene and imidazolium was two units or greater, similar properties were obtained for both the monomer and corresponding polymer. Expanding the work further, the imidazolium monomers were incorporated as a soft segment into a triblock copolymer to produce a single direction mechanical actuator.



host/guest, ionomer, polymer, imidazolium, paraquat, cryptand, pseudorotaxane