Predicting the spin state of paramagnetic iron complexes by DFT calculation of proton NMR spectra

Many transition-metal complexes easily change their spin state S in response to external perturbations (spin crossover). Determining such states and their dynamics can play a central role in the understanding of useful properties such as molecular magnetism or catalytic behavior, but is often far from straightforward. In this work we demonstrate that, at a moderate computational cost, density functional calculations can predict the correct ground spin state of Fe(II) and Fe(III) complexes and can then be used to determine the 1H NMR spectra of all spin states. Since the spectral features are remarkably different according to the spin state, calculated 1H NMR resonances can be used to infer the correct spin state, along with supporting the structure elucidation of numerous paramagnetic complexes.