Design principles for efficient metal-oxo catalysts revealed by x-rays

Metal-oxo species are essential intermediates in a number of bioinorganic reactions, with the most prominent example being photosynthetic water oxidation.

Their activity inspires the search for synthetic metal-oxo catalysts for key chemical reactions to address societal challenges in renewable energy storage and sustainable synthesis. For many reactions computational design has become an important tool to identify new catalyst candidates.

However, a number of obstacles must be overcome to realize its potential for metal-oxo catalysts: elimination of mechanistic uncertainties, filling of a sparse data space, and proper handling of multiple electronic states.

This proposal aims to remove these obstacles through a combination of advanced x-ray spectroscopy and multiconfigurational wavefunction calculations.

The ab initio method shows excellent accuracy and is a powerful predictive tool for assigning electronic structure from spectroscopic signals.

This will be used to remove mechanistic uncertainty, with the identity of the reactive species in plant photosynthesis as the main example.

Further, the project will establish reliable correlations between reactivity and experimental data, and propose a new route to reveal the role of valence-excited states for reactivity.

Finally, these newly discovered principles will be used to propose novel metal-oxo complexes with tuned reactivity, designed from both synthetic and fully computational platforms.