The Harper Research Group
Our research is focussed on understanding how organic processes happen and what affects reaction outcomes. Particularly, this work encompasses examining how structural features in both the reagents themselves and the solvent used can change how a reaction proceeds. This knowledge can then be applied to a range of fields, including bioorganic, synthetic, analytical and environmental chemistry. Being particularly interdisciplinary, there is extensive opportunity for collaboration and projects are currently underway in catalysis, reaction kinetics, synthesis and molecular dynamics simulations.
Ionic liquid effects on organic reactions: understanding solvation, designing better solvents and getting the reaction outcomes you want!
Ionic liquids are salts that melt below 100 °C. They have the potential to replace volatile organic solvents but outcomes of reactions in ionic liquids are often different to those in traditional molecular solvents. The aim of this project is to understand the nature of solvation in these systems – the interactions between a solute and the ions of the ionic liquid – through analysis of reaction outcomes, measurements of solution properties (such as diffusion) and molecular dynamics simulations. The result would be to extend the understanding of these solvent effects we have developed and to use this knowledge to control reaction outcome.
The project would involve kinetic analyses using NMR spectroscopy to monitor the progress of reactions, along with synthetic organic and analytical chemistry. Importantly, it can be readily tailored to either the physical and analytical aspects, with the opportunity to focus on methods to measure interactions and molecular dynamics simulations, or the more synthetic aspects, by focussing on designing new ionic liquids, increasing reaction yield and optimising isolation. Either way, you will be designing solvents to get the reaction outcome you want!
This project is in collaboration with Dr Ron Haines & Prof. Stuart Prescott, UNSW; Prof.’s Anna Croft & Christof Jäger, University of Nottingham; Prof. Bill Price, Western Sydney University; Prof. Tam Greaves, RMIT University.)
Catalysis using N-heterocyclic carbenes: understanding structure-activity relationships
N-Heterocyclic carbenes, have significant roles in both organo- and organometallic catalysis, however some carbenes are effective for some processes but not for others; the origin of this is not well understood. This project aims to relate the tructure and chemical properties of carbenes to catalytic efficacy; particularly the effects of changing steric and electronic properties will be assessed. Along with making the precursors to the carbenes, this project involves the opportunity to utilise various characterisation techniques (such as measuring acidity of parent cations to generating electronic probes based on Pd and Se) along with evaluation of catalytic systems; the latter can vary from screening of catalysts to detailed kinetic analyses. The ultimate goal is to be able to rationally choose an NHC catalyst for a given process.
Non-planar aromatic hydrocarbons: different reactivity based on structure
Aromatic hydrocarbons are meant to be planar – right? Yet the synthesis of carbon nanotubes and related structures relies on the reactivity of curved aromatic systems. This project focuses on the different reactivities of these systems relative to 'normal' aromatics and how it might be controlled and exploited. It will predominantly involve synthesis and reactivity of systems, such as those shown below, with the opportunity for some kinetic studies to interpret the reactivity. Ultimately, understanding and exploiting these differences will allow the rational synthesis of these curved polyarenes.
This project is in collaboration with Prof. Larry Scott (Boston College).
Broader applications of physical organic chemistry
The understanding developed above can be applied broadly – from understanding lubrication mechanisms to develop new compounds for mechanical engineering throught to the preparation of samples to evaluate ancient climates. These projects focus on the ability to transfer understanding from one context to another and the skill sets required vary dramatically between projects. However, they all would suit someone with an interest in combining chemistry with an outside discipline as there will be opportunities to work closely with collaborators in different fields. Ultimately, these projects seek to expand the impact of the knowledge gained through our fundamental research.
This project is in collaboration with Drs Jeffrey Black, Jonathan Palmer, Chris Marjo and Prof. Chris Tierney, UNSW; Prof.’s Sergei Glavatskih and Mark Rutland, KTH, Stockholm.