B.Sc. Adelaide 1995, B.Sc. (Hons) Australian National University 1996, Ph.D. Australian National University 2000.
Associate Professor, Director of Teaching (School of Chemistry), Director of Talented Students Programme (Faculty of Science)
Phone: (02) 9385 4692
Fax: (02) 9385 6141
Room 223, Dalton Building
UNSW, Kensington 2052
Research Group Website
Born 1974. Undergraduate work carried out at the University of Adelaide (B.Sc. 1995) and in The Faculties, Australian National University (B.Sc.(Hons) 1996). Shell Australia Postgraduate Scholar, Research School of Chemistry, Australian National University (Ph.D. 2000). C. J. Martin Postdoctoral Fellow, University Chemical Laboratory, Cambridge (2000-2002). Associate Lecturer, The Open University in East Anglia (2001). Appointed Lecturer (2002-2006) Senior Lecturer (2007-2015) and Associate Professor (2016-). SSP at Boston College (2009).
Our research is focussed on understanding how organic processes happen and what affects reaction outcomes. Particularly this 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 this is currently underway in the areas of catalysis, reaction kinetics, synthesis and molecular dynamics simulations.
The major areas of research are:
Ionic liquid effects on organic reactions: getting the reaction outcomes you want
(in collaboration with Dr Anna Croft, University of Nottingham, UK; Dr Ron Haines, University of New South Wales; and Dr James Hook, Mark Wainwright Analytical Centre)
Ionic liquids are salts that melt below 100°C. They have potential as replacements for volatile organic solvents but outcomes of reactions in ionic liquids are often unexpectedly different to those in traditional molecular solvents. The focus of this project is to extend the understanding of ionic liquid solvent effects we have already developed and to use this knowledge to demonstrate that ionic liquids can be used to control reaction outcome. The project involves using NMR spectroscopy to monitor reactions and kinetic analyses of these results, along with synthetic organic and analytical chemistry. The project has both physical and analytical aspects, with the opportunity to develop new methods for following reaction progress and undertake molecular dynamics simulations, along with more synthetic aspects, focussing on increasing reaction yield and optimising isolation. That is, the aim is to get the reaction outcome you want!
Solvent-solute interactions in ionic liquids: can we design better solvents?
(in collaboration with Drs Leigh Aldous and Ron Haines, University of New South Wales; and Dr Anna Croft, University of Nottingham, UK)
We have previously made use of molecular dynamics simulations to understand interactions between a solute and the components of an ionic liquid; this can be used to explain why benzene is so soluble in ionic liquids and why certain reactions proceed faster on moving to ionic solvents. This project aims to extend this and to model - both with simple compounds and simulations – which ionic liquid would be better solvents for a given solute. In order to do this both physical measurements of solubility and molecular dynamics are being undertaken to highlight key solute-solvent interactions. The outcome would be a better understanding of what interactions are required to confer good solubility giving us the opportunity to 'design' appropriate properties into ionic liquids – and these could then be made and used!
Catalysis using N-heterocyclic carbenes: understanding structure/activity relationships
(in collaboration with Assoc. Prof. Marcus Cole, University of New South Wales)
N-Heterocyclic carbenes, have significant roles in 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 structure and chemical properties of carbenes to catalytic efficacy, along with observing any solvent effects – this requires a series of chosen carbenes that vary in one way only (steric bulk, electronics, heteroatoms). Along with making the precursors to the carbenes, this project involves the opportunity to utilise various characterisation techniques and to undertake evaluation of catalytic systems; the latter can vary from simple screening of catalysts through 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
(in collaboration with Prof. Lawrence Scott, Boston College, USA)
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 predominantly involves synthesis and reactivity of systems, such as those shown below, along 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.
For more information on all of these research projects and where they sit in the ongoing scheme of the research group, please see the Harper Group Site.
- Keaveney, S. T.*; Haines, R. S.; Harper, J. B.: "Ionic liquid solvents: the importance of microscopic interactions in predicting organic reaction outcomes", Pure and Applied Chemistry, accepted 25th November 2016.
- Keaveney, S. T.; Greaves, T. L.; Kennedy, D. F.; Harper, J. B.*: "Understanding the Effect of Solvent Structure on Organic Reaction Outcomes when Using Ionic Liquid / Acetonitrile Mixtures ", Journal of Physical Chemistry B, in press, accepted 18th November 2016.
- Keaveney, S. T.Keaveney, S. T.; Schaffarczyk McHale, K. S.; Stranger, J. W.; Ganbold, B.; Prices, W. S.; Harper, J. B.*: "NMR diffusion measurements as a simple method to examine solvent – solvent and solvent – solute interactions in mixtures of the ionic liquid [Bmim][N(SO2CF3)2] and acetonitrile", ChemPhysChem, in press (accepted 27th September 2016).
- Keaveney, S. T.; Haines, R. S.; Harper, J. B.*: "Reactions in Ionic Liquids" in Encyclopedia of Physical Organic Chemistry, Volume 2 (Volume editor U. Wille), accepted July 2014. [Invited Article]
- Butler, B. J.; Harper, J. B.*: "The effect of the structure of the cation of an ionic liquid on the rate of reaction at a phosphorus centre ", Journal of Physical Organic Chemistry, 2016, 29, 700-708.
- Gondosiswanto, R.; Gunawan, C. A.; Hibbert, D. B.; Harper, J. B.; Zhao, C.*: "Microcontact Printing of Thiol-Functionalized Ionic Liquids Microarrays for “Membrane-less” and “Spill-less” Gas Sensors" ACS Applied Materials & Interfaces, 2016, 8, 31368-31374.
- Mallo, N.; Brown, P. T.; Iranmanesh, H.; MacDonald, T. S. C.; Teusner, M. J.; Harper, J. B.; Ball, G. E.; Beves, J. E.*: "Photochromic Switching Behaviour of Donor-Acceptor Stenhouse Adducts in Organic Solvents" Chemical Communications, 2016, 52, 13576-13579.
- Francis, D. V.; Harper, J. B.; Read, R. W.*: "Titration Characteristics of Fluorous 1,2,3-Triazol-4-ylmethyl Ethers, Bis(1,2,3-Triazol-4-ylmethyl) Ethers and Bis(1,2,3-Triazol-4-ylmethyl)Amines" Journal of Fluorine Chemistry, 2016, 192, 86-97.
- George, S. R. D.; Scott, L. T.; Harper, J. B.*: "Synthesis of 1-substituted fluorenones", Polycyclic Aromatic Compounds, 2016, 36, 697-715.
- Schaffarczyk McHale, K. S.; Hawker, R. R.; Harper, J. B.*: "Nitrogen versus phosphorus nucleophiles – how changing the nucleophilic heteroatom affects ionic liquid solvent effects in bimolecular nucleophilic substitution processes", New Journal of Chemistry, 2016, 40, 7437-7445
- Blümel, M.; Crocker, R.; Harper, J. B.; Enders, D.; Nguyen, T. V.*: "N-Heterocyclic Olefins as Efficient Phase-Transfer Catalysts for Base-Promoted Alkylation Reactions", Chemical Communications, 2016, 52, 7958-7961.
- Hawker, R. R.; Panchompoo, J.; Aldous, L.; Harper, J. B.*: "Novel chloroimidazolium-based ionic liquids: synthesis, characterisation and behaviour as solvents to control reaction outcome", ChemPlusChem, 2016, 81, 574-583.
- Butler, B. J.; Thomas, D. S.; Hook, J. M.; Harper, J. B.*: "NMR spectroscopy to follow reaction progress in ionic liquids", Magnetic Resonance in Chemistry, 2016, 54, 423-428.
- Keaveney, S. T.; White, B. P.; Haines, R. S.; Harper, J. B.*: "The effects of an ionic liquid on unimolecular substitution processes: the importance of the extent of transition state solvation", Organic and Biomolecular Chemistry, 2016, 14, 2572-2580.
- Francis, D. V.; Harper, J. B.; Gioia, S.; Lamb, R. N.; Read, R. W.*: "Defining Surface Properties of Fluorous 1H-1,2,3-Bistriazoles", Journal of Fluorine Chemistry, 2016, 183, 36-43.
- George, S. R. D.; Elton, T. E.; Harper, J. B.*: "Electronic effects on the substitution reactions of benzhydrols and fluorenyl alcohols. Determination of mechanism and effects of antiaromaticity", Organic and Biomolecular Chemistry, 2015, 13, 10745-10750.
- George, S. R. D.; Frith, T. D. H.; Thomas, D. S.; Harper, J. B.*: "Putting corannulene in its place. Reactivity studies comparing corannulene with other aromatic hydrocarbons", Organic and Biomolecular Chemistry, 2015, 13, 9035-9041.
- Keaveney, S. T.; Haines, R. S.; Harper, J. B.*: "Ionic liquid effects on a multistep process. Increased product formation due to enhancement of all steps", Organic and Biomolecular Chemistry, 2015, 13, 8925-8936.
- Keaveney, S. T.; Harper, J. B.*; Croft, A. K.*: "Computational approaches to understanding reaction outcomes of organic processes in ionic liquids", RSC Advances, 2015, 5, 35709-35729.
- Yau, H. M.; Haines, R. S.*; Harper, J. B.*: "A robust, 'one-pot' method for acquiring kinetic data for Hammett plots used to demonstrate transmission of substituent effects in reactions of aromatic ethyl esters", Journal of Chemical Education, 2015, 92, 538-542.
- Keaveney, S. T.; Haines, R. S.; Harper, J. B.*: "Developing principles for predicting ionic liquid effects on reaction outcome. The importance of the anion in controlling microscopic interactions", Organic and Biomolecular Chemistry, 2015, 13, 3771-3780.
- Hart, W. E. S.; Harper, J. B.*; Aldous, L.*: "The effect of changing the components of an ionic liquid upon the solubility of lignin", Green Chemistry, 2015, 17, 214-218.
- Butler, B. J.; Harper, J. B.*: "The effect of an ionic liquid on the rate of reaction at a phosphorus centre", New Journal of Chemistry, 2015, 39, 213-219.
- Francis, D. V.; Harper, J. B.; Read, R. W.*: "Fluorous 1,2,3-Triazol-4-ylmethyl Amines and Amine Derivatives for Novel Surfactant Applications", Australian Journal of Chemistry, 2015, 68, 57-68.
- Keaveney, S.T.; Francis, D. V.; Cao, W.; Haines, R. S.; Harper, J. B.*: "The effect of modifying the anion of an ionic liquid on the outcome of an SN2 process", Australian Journal of Chemistry, 2015, 68, 31-35.