Products Cited in Publications Worldwide The Multifaceted Utility of Hydrogen-Bonded Guanidinium Organosulfonate Host Frameworks

The Multifaceted Utility of Hydrogen-Bonded Guanidinium Organosulfonate Host Frameworks

Dillon, Alexandra

Abstract

Molecular frameworks have become central to solid-state chemistry, owing to the ability to tune their properties through careful design of their building blocks. Among these, crystalline hydrogen bonded frameworks (HBFs) stand out for their diversity and design, organized by hydrogen bonds between molecular constituents, often forming predictable topologies and architectures in the solid state. Guanidinium organosulfonate (GS) hydrogen bonded frameworks represent a robust class of HBFs, characterized by a two-dimensional sheet formed by charge-assisted hydrogen-bonds between guanidinium cations and organosulfonate anions. GS host frameworks also can encapsulate guest molecules spanning a wide range of shapes and sizes owing to their ability to access many framework architectures as well as the availability of a wide range of organosulfonates, enabling the design of new materials with engineered functions and properties. This thesis reports crystalline inclusion compounds based on two new aliphatic hosts – guanidinium cyclohexanemonosulfonate and guanidinium cyclohexylbenzenemonosulfonate – which exhibit five previously unobserved architectures despite over 700 known inclusion compounds realized. The aliphatic character of these simple hosts, combined with access to greater architectural diversity and adaptability, enables the host frameworks to accommodate a wide range of guests and promises to expand the utility of GS hosts. A particularly valuable and new application of GS frameworks is the structure determination and conformational analysis of guest molecules. The GS method was benchmarked against the 'molecular chaperone' method for structure determination using the same guest molecules, and the results demonstrated that the GS method generally outperformed. The frameworks were also employed to trap ahalopropiophenones and α-halocyclooctanones, which exist as liquids at room temperature, permitting determination of their molecular structure by single crystal X-ray diffraction. The large majority of encapsulated guest molecules adopted conformations expected from computational analysis, providing structural evidence to support the stereochemical outcomes of nucleophilic addition reactions. Additionally, GS hosts were used to coerce the assembly of donor-acceptor complexes. Spectroscopic studies of these v compounds revealed varying degrees of charge transfer in two different classes of donor-acceptor compounds, with the host acting as a donor in one case and an acceptor in the other. The results suggest potential for developing new charge-transfer complexes and optoelectronic materials through a combination of molecular and crystal design. Finally, a limited study on the microporosity of a chiral guanidinium binaphthyl host is discussed, further highlighting the diverse potential applications of GS frameworks.

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