Nitrides have potential for applications with highly inter¬est¬ing semi¬con¬duc¬¬ting, photocatalytic and mechanical properties, with a recent industry-led boom in search for efficient synthetic methods and full understanding of properties. The PhD project focusses on the synthesis, characterisation and reactivity study of of N-rich heterocycles and N-rich coor¬di¬nation compounds of light p-block elements as highly promising precursors of nitrides, and on the development of simple synthetic routes to such nitrides. A more fundamental understanding of reaction pathway to nitrides, and full (electronic, molecular, materials) characterisation is also urgently required. Investigations in this part of the project will be carried out in a collaborative fashion. The N-rich precur¬sors are important in their own right, as gas generants, propel¬lants, and ligands in metal-containing coordi¬nat¬ion polymers. Therefore, a selection of high pressure methods, neutron scattering, and thermal methods will be applied to investigate in a collaborative effort dense polymorphs, pressure-induced poly¬me¬ri-sation, hydrogen-bonding and nitride formation. Molecular properties (struc¬ture, polariza¬bi¬lity, delocali¬sat¬ion pathways relevant to layer isomorphs of heterocycles) will help predicting material properties. Thermochemical stability and reaction pathways to nitrides will be tested using ab initio calculations.
The project outcome are within the EPSRC portfolio of Energy storage, Materials for Energy applications and Synthetic coordination chemistry are: i) advanced synthetic methods for heavy-metal-free, hydrogen-bonded, energy-storing systems based on coordi¬nat¬ion compounds and polynitrogen ligands with tuneable nitrogen content and energy density; ii) predictive models underpinning thermal decompo¬sition mechanisms (GH); iii) efficient nitride synthesis.
Key papers: A Pathway to the Athermal Impact Initiation of Energetic Azides, A. A. L. Michalchuk, P. T. Fincham, P. Portius, C. R. Pulham, C. A. Morrison*, J. Phys. Chem. C, 2018, 199, 19395-19408. Labile Low-Valent Tin Azides: Syntheses, Structural Characterization, and Thermal Properties, R. Campbell, S. Konar, S. Hunter, C. R. Pulham, P. Portius*, Inorg. Chem. 2018, 57, 400-411. Desired key skills of suitable candidates are: understanding of and experience in preparative chemistry, willingness to collaborate in the computational and analytical chemistry aspects of the project, ability to present results in report and manuscript form and at conferences.