A Paramagnetic NMR Spectroscopy Toolbox for the Characterisation of Paramagnetic/Spin‐Crossover Coordination Complexes and Metal–Organic Cages

Abstract The large paramagnetic shifts and short relaxation times resulting from the presence of a paramagnetic centre complicate NMR data acquisition and interpretation in solution. As a result, NMR analysis of paramagnetic complexes is limited in comparison to diamagnetic compounds and often relies on theoretical models. We report a toolbox of 1D (1H, proton‐coupled 13C, selective 1H‐decoupling 13C, steady‐state NOE) and 2D (COSY, NOESY, HMQC) paramagnetic NMR methods that enables unprecedented structural characterisation and in some cases, provides more structural information than would be observable for a diamagnetic analogue. We demonstrate the toolbox's broad versatility for fields from coordination chemistry and spin‐crossover complexes to supramolecular chemistry through the characterisation of CoII and high‐spin FeII mononuclear complexes as well as a Co4L6 cage.