The large paramagnetic shifts and short relaxation times resulting from the presence of ap aramagnetic centre complicate NMR data acquisition and interpretation in solution. As aresult, NMR analysis of paramagnetic complexes is limited in comparison to diamagnetic compounds and often relies on theoretical models.W er eport at oolbox of 1D (1 H, proton-coupled 13 C, selective 1 H-decoupling 13 C, steady-state NOE) and 2D (COSY,NOESY,HMQC) paramagnetic NMR methods that enables unprecedented structural characterisation and in some cases,p rovides more structural information than would be observable for ad iamagnetic analogue.W ed emonstrate the toolboxsb road versatility for fields from coordination chemistry and spin-crossover complexes to supramolecular chemistry through the characterisation of Co II and highspin Fe II mononuclear complexes as well as aC o 4 L 6 cage.

Bipyridine-and benzimidazole-based ligands for the self-assembly of Co4L6 cages were synthesised in short reaction times and high isolated yields directly from aryl halide precursors using a copper-free one-pot Sonogashira-type coupling. This one-pot method circumvents the often time-consuming and challenging ligand synthesis for the preparation and application of cages.

<div> <p>The large paramagnetic shifts and short relaxation times resulting from the presence of a paramagnetic centre complicate NMR data acquisition and interpretation in solution. In contrast to the large number of standard NMR methods for diamagnetic compounds, the number of paramagnetic NMR methods is limited and spectral assignment 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 for the straightforward structural characterisation of paramagnetic complexes in solution and demonstrate its general applicability for fields from coordination chemistry to spin‑crossover complexes and supramolecular chemistry through the characterisation of Co^II and high-spin Fe^II mononuclear complexes as well as a Co₄L₆ cage. The toolbox takes advantage of the reduced signal overlap, decreased instrument time and greater sensitivity from the presence of the paramagnetic centre while overcoming the loss of structural information from the wide chemical shift dispersion and broad signals. In some circumstances, more structural information was revealed in the COSY spectra than would be observable for a diamagnetic analogue; as well as the expected through-bond cross-peaks, through-space and exchange cross-peaks were also observed for mononuclear complexes with multiple ligand environments and fast ligand exchange. With this toolbox, the standard characterisation of paramagnetic complexes and cages is now possible using NMR spectroscopic methods. </p> </div> <br>

<div> <p>Bipyridine- and benzimidazole-based ligands for the self-assembly of Co₄L₆ cages were synthesised in short reaction times and high isolated yields directly from aryl halide precursors using a copper-free one-pot Sonogashira-type coupling. This one-pot method circumvents the often time-consuming and challenging ligand synthesis for the preparation and application of cages.</p> </div> <br>

<div> <p>Bipyridine- and benzimidazole-based ligands for the self-assembly of Co₄L₆ cages were synthesised in short reaction times and high isolated yields directly from aryl halide precursors using a copper-free one-pot Sonogashira-type coupling. This one-pot method circumvents the often time-consuming and challenging ligand synthesis for the preparation and application of cages.</p> </div> <br>