Unravelling self-assembled supramolecular constructs in catalysis with spectroscopic and computational methods

Supramolecular chemists have made tremendous advances in the design and synthesis of elaborate constructs that spontaneously organize from component molecules. Following these developments, researchers in homogeneous catalysis have sought to harness the internal environment of these constructs to improve the selectivity and efficacy of chemical transformations. The design and analysis of these supramolecular constructs present new challenges due to the added complexity of incorporating catalytic functionality with transition-metal complexes and substrates. In this thesis, we detail the use of combined spectroscopic and computational modeling approaches to study the self-assembly of these constructs as well as the structure of their internal environments. In chapter 1 we provide an overview of catalytically relevant supramolecular constructs and the computational tools employed to study them. In chapter 2, we investigate the effect of solvent and anion molecules on the substitution of pyridyl ligands at palladium metal centers to understand the elementary step of self-assembly by thermochemical NMR measurements supported by computational approaches. In chapter 3 we describe a robust approach to parameterize palladium-pyridyl interactions and then demonstrate the use of these parameters in molecular dynamics simulations enabled the topological prediction of self-assembled coordination constructs featuring one or more ditopic ligands. In chapter 4 we expanded on our molecular dynamics approach to include the intermediates of the self-assembly process where we identified how solvation entropy drives self-assembly. Lastly, in chapter 5 we used NMR spectroscopy and molecular dynamics simulations to identify catalytically relevant water-dependent structural conversion of hexameric undecyl-resorcin[4]arene hydrogen-bond capsules