Maximising f-element oxidation states

The applicant is a rising early-career scientist with an international reputation in frontier rare earth and actinide science. This StG project melds synthesis and electrochemistry with computational and spectroscopic methods to afford a transformative advancement in electronic structure and oxidation state control in f-elements. By advancing our understanding of the design principles which influence the properties of these complexes, we propose to maximise their stability and expand beyond the current approaches to isolate molecular lanthanide species in unprecedented high oxidation states.We target high oxidation state lanthanide (Ln), actinide (An), and transuranium f-element complexes beyond the current state-of-the-art by expanding to novel ligand platforms which address all key aspects to maximize the thermodynamic, and hence electrochemical, stability of these powerful oxidisers. We will show that the range limit of tetravalent Ln ions available to solution chemistry has not been reached.By accessing high oxidation states we will isolate multiply bonded motifs to Ln(IV) beyond Ce for the first time, including iconic organometallic linkages which offer unique spectroscopic (EPR and NMR) handles with which to probe the bonding in these systems. This will be extended to actinide and transuranium elements, affording unprecedented opportunities to gain insight into orbital energy vs spatial overlap components in bonding, and probe the relative magnitudes of inter-electronic repulsion, spin-orbit coupling, and crystal field effects in f-elements.An StG will provide resources required to bring this ambitious project to fruition. We will address the rarity of high oxidation state 4f-elements and define the chemical properties that can be leveraged to control their electronic structures. This addresses the Quantum Flagship, a key Horizon 2020 priority area, and will train a cohort of interdisciplinary scientists essential for the scientific goals of the EU.