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Calum Findlay

Synthesis of and electrochemical and spectroelectrochemical studies on novel nitrated 2,2´;6´,2´´-terpyridine derivatives and their transition metal complexes.

My Project

I am currently pursuing electrochemical and spectroelectrochemical characterisations of substituted 2,2’:6’,2’’-terpyridine ligands and their complexes, which represents a new direction for the Yellowlees group, as previous work has focussed on bipyridine ligands and complexes.

I have synthesised 4,4´,4´´-trinitro-2,2´:6´,2´´-terpyridine (Fig. 1, left) and subjected it to cyclic voltametry in various solvents yielding results which indicate three reversible reductions between 0 and -1 Volts (Fig. 1, right).

Fig. 1 - 4,4´,4´´-trinitro-2,2´:6´,2´´-terpyridine (left) and Cyclic voltammetry of 4,4´,4´´-trinitro-2,2´:6´,2´´-terpyridine vs. Ag/AgCl in 0.3 M TBABF₄/THF at 293 K (right)

Analysis of these results show that the position of the reductions is solvent dependent and there is direct relation between solvent acceptor number and half wave potential. (Fig. 2).

Fig. 2 - Halfwave Potential of Three Reductions of 4,4´,4´´-trinitro-2,2´;6´,2´´-terpyridine against Acceptor Number

In situ reduction in an X band EPR spectrometer has so far been carried out only in DMF and initial results suggest two distinct paramagnetic species within the potential range of the three reversible reductions. (Fig. 3) The hypothesis at the moment is that the first unpaired electron goes into a LUMO located on the central nitro group, followed by a second electron which pairs with this, followed by a third which is unpaired and more delocalised than the first.

Fig. 3 - EPR spectra for [4,4´,4´´-trinitro-2,2´:6´,2´´-terpyridine]^1- and [4,4´,4´´-trinitro-2,2´:6´,2´´-terpyridine]^2- generated in-stu at -0.90 V and -1.0V respectively at 233 K in 0.1 M [ⁿBu₄N][BF₄]

Further work will include simulations of these spectra in combination with DFT calculations to determine the location of the unpaired electrons, a crystal structure of the ligand, followed by synthesis of the Fe, Pt and Ru homoleptic and heteroleptic complexes.

About Me

I was born in the West Highlands of Scotland and brought up there and in East Lothian. After leaving school I went on to study Painting and Sculpture at Gray’s School of Art in Aberdeen and subsequently worked in theatre production and writing with an Edinburgh based theatre company. Upon marrying a South African I moved to Johannesburg in 2002 and began studying Chemistry at undergraduate level with the University of South Africa, and then began teaching science in a Johannesburg secondary school. When our first child arrived we returned to Scotland and I finished my degree with the Open University. I now have three children – the oldest has just started school, so there is not much time for hobbies.

When I get the chance I go sailing

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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