Field-mediated ring-expansion isomerization of cyclic hydrocarbons in ion-pair complexes: a computational study
M-mol-X insertion complexes (M=alkali, mol=molecule, X=halide) are highly polar systems that offer a wide array of potential applications spanning light-matter interactions, optics, energy storage, transmembrane ion-pair transport, and molecular interactions. In this thesis, we used ab initio methods to investigate the insertion complexes formed by seven- and nine-membered, cyclohexadiene-based, fused bicyclic molecules and their monocyclic tautomers confined in Na-I and Li-I counterion pairs. The stability, structural characteristics, charge distributions, and predicted infrared spectra of the complexes were analyzed. Notably, the influence of the counterions on the bicyclic ring-opening tautomerization processes were examined. Furthermore, we report upon an uncommon bond between carbon and iodine, which we hypothesize to be catalyzed by the presence of the cation in the insertion complexes. Overall, our findings provide valuable insights into the behavior of insertion complexes and their potential applications.
Networked Digital Library of Theses and Dissertations
University of Ontario Institute of Technology