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 Co^II and high-spin Fe^II mononuclear complexes as well as a Co₄L₆ cage.