Tuning the magnetic ground state of a tetranuclear nickel(II) molecular complex by high magnetic fields

Electron spin resonance and magnetization data in magnetic fields up to $55\phantom{\rule{0.3em}{0ex}}\mathrm{T}$ of a multicenter paramagnetic molecular complex $[{L}_{2}{\mathrm{Ni}}_{4}({\mathrm{N}}_{3}){({\mathrm{O}}_{2}\mathrm{C}\mathrm{Ada})}_{4}](\mathrm{Cl}{\mathrm{O}}_{4})$ are reported. In this compound, four Ni centers each having a spin $S=1$ are coupled in a single molecule via bridging ligands (including a ${\ensuremath{\mu}}_{4}$-azide) which provide paths for magnetic exchange. Analysis of the frequency and temperature dependence of the ESR signals yields the relevant parameters of the spin Hamiltonian, in particular the single ion anisotropy gap and the $g$ factor, which enables the calculation of the complex energy spectrum of the spin states in a magnetic field. The experimental results give compelling evidence for tuning the ground state of the molecule by magnetic field from a nonmagnetic state at small fields to a magnetic one in strong fields owing to the spin level crossing at a field of $\ensuremath{\sim}25\phantom{\rule{0.3em}{0ex}}\mathrm{T}$.