The Chemistry of Energetic Coordination Compounds

About the Project

This PhD project aims at fundamental research into the discovery of novel energetic materials. Results will inform solutions to challenges posed by current requirements to remove heavy metals and perchlorate from energetic materials such as propellants, explosives and pyrotechnics.

The open-ended postgraduate research involves the chemical synthesis, crystallisation and reactivity studies of nitrogen-rich compounds (e.g. azides, tetrazoles) and nitrated N-heterocyclic (e.g. polynitroazoles) precursors, which are then used, for instance, as explosophoric group transfer reagents to form metal-based energetic coordination compounds, or to investigate mixed and co-crystals. Methods typical in organic chemistry such as N-heterocyclic ring formation and nitrations, coordination chemistry and crystallisation (autoclaves, co-crystallisation, seeding, polymorphism) will be employed. Compound and material characterisation will be achieved by state-of-the-art techniques such as infrared and NMR spectroscopies, crystallographic methods, mass spectrometry, thermal analysis, sensitivity testing etc. The properties of novel molecules (geometric & electronic structure, electric moments, frequency-dependent polarizability, vibrational partition functions etc.) and thermochemical stability will also be explored computationally using density functional theory, including reaction-coordinate methods to check against low-energy decomposition pathways that could impede chemical synthesis efforts.

Typically, the chemical potential of high energy density materials is released by a stimulus (initiation) that overcomes a reaction barrier to rapidly generate large amounts of expanding hot gas that can be used to perform work. In this context, the project is part of a wider collaboration with groups at Birmingham (A Michalchuk & P Portius, theory & synthesis) and Edinburgh (C Morrison & C Pulham, theory & crystallography) contributes to developing theories that help solve two of the most intriguing problems in energetic materials – predicting the sensitivity to initiation of a material based on its structure and morphology, and predicting crystal structure based on molecular structure. This effort will produce much-needed deep insight into molecular design and how to achieve optimal balance between energy density and sensitivity.

The School of Chemistry at Birmingham is a large and vibrant first-class academic hub to be doing chemistry. Many opportunities for collaboration exist within the school and related disciplines at the university. Newly built laboratory space (the Molecular Sciences Building) in combination with excellent in-hause analytical facilities provide an ideal environment for the required experimental work. The project is supervised by a chemist with high reputation who has long-standing experience in the field of energetic materials synthesis, discovery and characterisation. Opportunities exist for involvement in industrial projects, and for access to national research facilities. The successful candidate will play a crucial role in the synthetic and analytical work and interact closely with the theory research group. This setting provides an environment conducive to developing into a professional research scientist with multi-disciplinary skills and experience.

Funding notes:

Candidates must have a completed a Master of Chemistry (2.1 or higher, MSci, MChem) at the start of the project.

References

Some relevant recent papers related to the project:
W. Greenwood, C. C. Robertson and P. Portius, Cryst. Growth Des. 2025 Vol. 25 Issue 19 Pages 7966–7975
B. Westwater, H. J. Lloyd, I. J. Vitorica-Yrezabal, A. Fong, P. McMaster, M. Sloan, et al. Dalton Transactions 2020, 49, 14975–14984.
A. A. L. Michalchuk, P. T. Fincham, P. Portius, C. R. Pulham and C. A. Morrison, J. Phys. Chem. C 2018, 122,19395-19408.
P. Portius, B. Peerless, M. Davis and R. Campbell, Inorg. Chem. 2016, 55, 8976-8984