Liquid-crystalline ionic liquids as ordered reaction media for chemical and morphological control
Ionic liquids (ILs) are commonly defined as salts that have melting temperatures below 100 oC and they have been attracting a great deal of attention in recent years, particularly for their use as reaction media, where they have potential to contribute towards the development of greener chemical processes. Liquid-crystalline ionic liquids (LC-ILs) are an exciting class of material that combine the anisotropy of liquid crystals with the good solvent properties of ILs. However, in contrast to ILs, their use as reaction media is very underdeveloped, with few reports of this application in the literature.
During this project we plan to combine the excellent solvent properties of ILs with the order inherent in liquid crystals to investigate LC-ILs as ordered reaction media for chemical reactions and the synthesis of nanomaterials. We propose that the ordered environment in LC-ILs can be used to control the rate and/or stereochemical outcome of reactions that take place in an LC-IL when it is used as a solvent. We have preliminary results which give a strong indication that solvent ordering in LC-IL phases can indeed affect the stereochemical outcome and/or the kinetics of organic reactions taking place within the mesophase. This project will build on these initial results to investigate the generality of this effect, by probing a range of different substrates and reactions and by applying this concept in systems with real synthetic interest, where stereo/kinetic control is required. In addition to broadening the scope of this initial work, we will use a variety of theoretical methods (at York and through collaboration outside York) to understand the origins of the observed effects. We will also extend this methodology to investigate the potential for ordered LC-IL phases to be used to control the morphology of nanomaterials that are grown within LC-ILs to provide new tools for selective materials synthesis.
The student working on this project will receive training in synthetic and theoretical chemistry and in the characterisation of a range of materials phases. Experimental training will include techniques in synthetic organic, organofluorine and ionic liquid chemistry, variable-temperature, multinuclear NMR spectroscopy (including kinetic measurements), IR/ReactIR, MS, optical and electron microscopy. The student will also gain experience of various theoretical methodologies on a range of time and length scales (from single-molecule, gas-phase studies to large, long-time-scale MD simulations of condensed phases). The student will also be taught to evaluate the results of theoretical studies critically considering the limitations of the method being used.
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This project is part of a University of York Department of Chemistry competition for doctoral training grant funding from the Engineering and Physical Sciences Research Council (EPSRC) or Department of Chemistry Teaching Studentship. For UK students it would pay tuition fees and living costs in the form of a stipend. Students from other EU countries may be eligible to apply for this project on a fees only basis. Students from any country who are able to fully fund their own fees and living costs may also apply for this project.
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FTE Category A staff submitted: 47.06
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