Pressure dependence of the magnetic anisotropy in the single-molecule magnetMn4O3Br(OAc)3(dbm)3

The anisotropy splitting in the ground state of the single-molecule magnet ${\mathrm{Mn}}_{4}{\mathrm{O}}_{3}\mathrm{Br}{(\mathrm{O}\mathrm{Ac})}_{3}{(\mathrm{dbm})}_{3}$ is studied by inelastic neutron scattering as a function of hydrostatic pressure. This allows a tuning of the anisotropy and thus the energy barrier for slow magnetization relaxation at low temperatures. The value of the negative axial anisotropy parameter ${D}_{\text{cluster}}$ changes from $\ensuremath{-}0.0627(1)\phantom{\rule{0.3em}{0ex}}\mathrm{meV}$ at ambient to $\ensuremath{-}0.0603(3)\phantom{\rule{0.3em}{0ex}}\mathrm{meV}$ at $12\phantom{\rule{0.3em}{0ex}}\mathrm{kbar}$ pressure, and in the same pressure range the height of the energy barrier between up and down spins is reduced from $1.260(5)\phantom{\rule{0.3em}{0ex}}\mathrm{meV}\phantom{\rule{0.5em}{0ex}}\text{to}\phantom{\rule{0.5em}{0ex}}1.213(9)\phantom{\rule{0.3em}{0ex}}\mathrm{meV}$. Since the $\mathrm{Mn}\mathrm{Br}$ bond is significantly softer and thus more compressible than the $\mathrm{Mn}\mathrm{O}$ bonds, pressure induces a tilt of the single ion ${\mathrm{Mn}}^{3+}$ anisotropy axes, resulting in the net reduction of the axial cluster anisotropy.