Date of Award
Summer 2016
Document Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
First Advisor
Ryan, Michael D.
Second Advisor
Timerghazin, Qadir
Third Advisor
Rathore, Rajendra
Abstract
Room temperature ionic liquids (RTIL) have been very attractive as replacements for molecular solvents (MS) in many areas in chemistry. The use of the RTIL in mixture with MS as reaction media will reduce the cost and viscosity of RTILs. The formation of RTIL nano-domains (nano-structures) in the mixture may lead to partitioning of solutes between the MS and the RTIL phase, where the properties and reactivity would be more like those in pure ionic liquids. In the present work, analytical approaches have been employed to probe the presence and effects of RTIL nano-domains on redox processes in the mixture. A focus was on substrates that undergo multi-electron reductions/oxidations, such as: dinitrobenzene, fullerene and metalloporphyrins. Throughout our investigation, there was strong evidence of the presence of RTIL and MS domains in the mixture system. Correlation of the potential shifts with acceptor properties of the mixture enabled to evaluate the extent of ion paring interactions within the molecular and RTIL domains. Influence of RTIL domains on the transport properties of the solution was evaluated versus the change in the viscosity of the mixture. The impact of RTIL domains on the electronic structures of redox products was examined using several spectroscopic methods, including UV-visible, infrared and NMR spectroscopy. Computational tools such as chemometrics, voltammetric simulations and DFT calculations were used to complement the experimental analysis.