Developing electrostatic catalysis for polymerization and synthesis

Polar effects on radical stability are traditionally attributed either to resonance effects or to dipole effects. The former involves donor-acceptor interactions between specific functional groups that are conjugated or hyperconjugated with one another; the latter involves through space electrostatic interactions between charged (or partially charge-separated) functional groups. Both types of effects are strongly directional. However, we have recently discovered a new type of polar effect that is in principle non-directional and requires no conjugation or permanent dipoles. When a localised anion is placed in the vicinity of a delocalised radical, the radical is strongly stabilized compared with its corresponding non-radical derivatives. The effect arises in the enhanced polarisability of delocalised radicals compared with their corresponding closed-shell counterparts. In this way the destabilising interaction between a remote negative charge and an unpaired electron is minimised and a greater overall stabilisation of the species through charge-nuclei attraction is achieved. We are now working towards harnessing both conventional and non-directional polar effects to develop electrostatic catalysis based on both external electric fields and acid/base groups whose charge can be manipulated via pH.

Selected recent publications

  • Gryn'ova G., Marshall D.L., Blanksby S.J., & Coote M.L. (2013) Switching Radical Stability By pH-Induced Orbital Conversion Nature Chem., 5, pp. 474-481.
  • Gryn’ova G., Coote M.L. (2013) Origin and scope of long-range stabilizing interactions and associated SOMO-HOMO conversion in distonic radical anions J. Am. Chem. Soc., 135, pp. 15392-15403.

Partnerships

The original research was carried out with funding from the ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, and our original theoretical findings were experimentally verified in the gas phase by Professor Stephen Blanksby, QUT. Synthetic applications are now being developed in collaboration with Professor Martin Banwell, while electromaterials applications are being developed through the ARC Centre of Excellence for Electromaterials Science.

Image gallery

Updated:  24 October 2017/Responsible Officer:  Director, RSC/Page Contact:  Web Admin, RSC