Interest in the magnetic properties of polymetallic clusters of Ni II began with the development of magneto-structural correlations of [Ni2] dimers 1 and [Ni4] cubanes 2 that revealed a dependence of the sign and magnitude of the exchange interaction on both the Ni-X-Ni bridging angle and the anisotropy of the Ni II ion. The large axial zero-field splitting displayed by the latter in certain geometries also lends itself to the construction of both single-molecule magnets (SMMs) and single-ion magnets (SIMs) displaying slow relaxation of the magnetisation. Indeed, recent studies of Ni II SIMs at both ambient and high pressure have revealed how magnetic anisotropy is extremely susceptible to even small structural distortions, in turn highlighting target geometries and directing the synthetic methodologies required to engineer molecules possessing giant magneto-anisotropies. Flexible N,O-bridging ligands have proved particularly successful in the construction of polymetallic clusters of Ni II displaying a variety of topologies and nuclearities, including supertetrahedra, 9 wheels, 10 planar discs and icosahedra. The pro-ligand (3,5-dimethyl-1H-pyrazol-1-yl)methanol (HL 1 ) belongs in this family, having been employed to make both mono-and tetranuclear clusters of Ni II . Here, we expand this chemistry to include the synthesis, structure and characterisation of [Ni14(HL 2 )12(HCOO)14Cl14(MeOH)(H2O)]•4Me2CO (1•4Me2CO, HL 2 = 3,5-dimethylpyrazole), an aesthetically pleasing wheel formed serendipitously via the in-situ transformation of HL 1 to HL .