Details of Grant 

EPSRC Reference:	EP/E010695/1
Title:	Stable Phosphorus Centred Radicals and Odd Electron Bonds
Principal Investigator:	Kilian, Dr P
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Chemistry
Organisation:	University of St Andrews
Scheme:	First Grant Scheme
Starts:	08 January 2007	Ends:	07 January 2009	Value (£):	165,142
EPSRC Research Topic Classifications:	Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:	Chemicals
Related Grants:
Panel History:
Summary on Grant Application Form
Free radicals with suitable geometrical and electronic structures can be stable. Stable radicals are central to techniques such as spin labelling, ESR imaging and Dynamic Nuclear Polarization (DNP, NMR enhancement technique). The pursuit of new generations of functional molecular-based materials generates tremendous interest in the electronic and magnetic properties of stable radical materials. The aim of our proposed research is to make new stable phosphorus centred radicals, which will afford significant advantages over those used currently. Central to this proposal is the idea of utilizing tight geometric constraints of rigid systems to gain the desirable stability. Two distinct classes of molecules will be studied for the generation of stable radicals. Firstly, molecules containing highly coordinated phosphorus atom encapsulated in the macrocycle, such as porphyrin, will be synthesized and their ability to form hypervalent radicals will be tested. Kinetic and thermodynamic stabilization will be provided via extensive spin delocalization and substituent electronic effects. Secondly, open-shell systems containing odd-electron P-P bonds will be synthesized. Rigid aromatic backbones (substituted in a special way to serve as clamping framework) in combination with electronic effects will provide support for these odd electron bonds, a rare phenomena attracting much interest at the moment. A great deal of adventure is associated with this proposal, we will attempt the preparation of unknown hypercoordinated radicals R5P-. We will also pioneer preparation of systems with fundamentally new types of odd electron bonds, which will be constructed from a wider variety of phosphorus environments than ever before. At the end of this project we anticipate having one or more new bottleable molecular free radical species and also one or more clamping-framework stabilised odd-electron bonded species. This project is the foundation of what we believe will become an important avenue of our research.
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Organisation Website:	http://www.st-and.ac.uk