Inorganic Electrochemistry |
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Sandy Delf
Investigations into solvent and electrolyte effects on the electronic structure of derivitised 2,2´-bipyridine ligands and complexes.
My Project
Previous work in the Inorganic Electrochemistry group has inverstigated ligands of the form n,n´-X,X´-bpy (bpy = 2,2´-bipyridine) and their transition metal coordination complexes (X=NO2, MeOCO2, EtOCO2, Br, Cl, ph, Me and NH2, n = 3, 4 and 5). Electrochemical and spectroelectrochemical studies have shown similar results for most derivatives in that they undergo two, reversible one electron reductions. The first of these is located in a molecular orbital spread over both X-py rings and the second in the spin pairing process (Fig. 1). The NO2 derivatives are of particular interest as they give two, reversible one electron reductions. The molecular orbitals for these processes are spread over both NO2 rings for the 3,3´ and 5,5´ derivatives. However, for the 4,4´ derivative, each reduction is an electron entering an orbital based on one single NO2-py ring.
![Fig. 1 - Cyclic voltammetry of 5,5´-(NO2)2-bpy vs. Ag/AgCl in 0.1 M [TBA][BF4]/DMF at 293 K](./../people/images/sandy1.gif "Fig. 1 - Cyclic voltammetry of 5,5´-(NO2)2-bpy vs. Ag/AgCl in 0.1 M [TBA][BF4]/DMF at 293 K")
Fig. 1 - Cyclic voltammetry of 5,5´-(MeO2C)2-bpy vs. Ag/AgCl in 0.1 M [nBu4][BF4]/DMF at 293 K
The aim of my project is to study n,n´-(CN)2-bpy (n=3, 4 and 5) derivatives and thus determine whether the cyano group induces behaviour like the MeOCO2 and EtOCO2 derivatives or like the NO2 deivative. I am also investigating solvent effects on these ligands and complexes.
Fig. 2 - 5,5´-(CN)2-bpy
Initial results are suggestion that 5,5´-(CN)2-bpy (Fig. 2) exhibits behaviour part-way between MeOCO2 and NO2. It has two, fully reversible one electron reductions at potentials similar to those of 5,5´-(MeOCO2)2-bpy (Fig. 3). However, EPR spectroelectrochemistry results show coupling to two pairs of equivalent nitrogens (i.e. the CN and ring nitrogens). Thus, the reduction electrons are entering an orbital which is spread over both CN-py rings and there is considerable electron density on the CN group.
![Fig. 3 - Cyclic voltammetry of 5,5´-(CN)2-bpy vs. Ag/AgCl in 0.1 M [TBA][BF4]/DMF at 293 K](./../people/images/sandy3.gif "Fig. 3 - Cyclic voltammetry of 5,5´-(CN)2-bpy vs. Ag/AgCl in 0.1 M [TBA][BF4]/DMF at 293 K")
Fig. 3 - Cyclic voltammetry of 5,5´-(CN)2-bpy vs. Ag/AgCl in 0.1 M [nBu4][BF4]/DMF at 293 K
About Me
I was born in the Brittish Overseas Territory of Gibraltar. After spending a year plying the sea lanes between Gibraltar and Tangier in Morocco on my father’s car ferry, we moved back to Scotland. I was brought up in the equally nautical ferry port of Stranraer in Dumfries and Galloway.
I started my journey into the world of chemistry at Stranraer Academy under the tutelage of Malcolm McNeil. I then came to the University of Edinburgh to do my Masters degree in chemistry which I graduated from in 2006
In the short break between the end of my degree and starting my Ph.D I spent a month travelling around New Zealand, throwing myself out of perfectly good planes and the like. Outside the lab I spend my time practising Kendo (Japanese fencing or "the way of the sword"). I also have a keen interest in history, particularly military history and can often be found reading books on everything from ancient Egypt to WW2
Salma Al-Musharafy - Rakesh Barik - Sandy Delf - Calum Findlay - Lucy Moorcraft - Paul Murray - Lesley Yellowlees
School of Chemistry, Joseph Black Building
King`s Buildings, West Mains Road
Edinburgh, EH9 3JJ
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