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Details of Grant 

EPSRC Reference: GR/M96827/01
Title: EXTENDED REDOX-ACTIVE CUMULENES: SYNTHESIS, PROPERTIES AND REACTIVITY
Principal Investigator: Bryce, Professor M
Other Investigators:
Researcher Co-Investigators:
Project Partners:
University of Massachusetts, Amherst
Department: Chemistry
Organisation: Durham, University of
Scheme: Standard Research (Pre-FEC)
Starts: 01 June 2000 Ends: 31 October 2003 Value (£): 153,153
EPSRC Research Topic Classifications:
Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:
Electronics No relevance to Underpinning Sectors
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Panel History:  
Summary on Grant Application Form
The aim of this project is a systematic study of the chemistry of novel C4-C8 cumulenes capped with redox-active substituents. Their synthesis, characterisation, reactivity and physical properties will be explored in detail, as the neutral and cationic species. Terminal TTF and Fc groups are expected to have profound effects on the stability and properties of these molecules. We will also investigate the stabilisation of cumulenes by encapsulation within a dendritic microenvironment. Cumulenes offer the very attractive features of rigidity and directionality, and we will explore how the stability and the electronic and structural properties depend on the length of the cumulene unit, including a comparison of odd and even cumulenes. UV-Vis spectroscopy, solution electrochemical techniques, spectroelectrochemistry and single crystal X-ray analysis should shed light on this important issue. We plan to generate cation radical and multi-cationic species by reversible electrochemical oxidation of the TTF and ferrocenyl substituents and probe the extent to which these radicals are delocalised by EPR spectroscopy, including SEEPR (Simultaneous Electrochemistry and EPR) techniques (in collaboration with Professor V Rotello, U Mass, Amherst). New reactions of these electron-rich cumulenes, eg cycloadditions and reactions with electrophiles will be explored with the prospects of obtaining some very unusual compounds.
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