Subtle competition between ferromagnetic and antiferromagnetic order in a Mn(II)-free radical ferrimagnetic chain

Abstract

The macroscopic magnetic characterization of the Mn(II) nitronyl nitroxide free radical chain $[\mathrm{Mn}{(\mathrm{hfac})}_{2}(R)\text{\ensuremath{-}}3\mathrm{MLNN}]$ evidenced its transition from a one-dimensional behavior of ferrimagnetic chains to a three-dimensional ferromagnetic long-range order below $3\phantom{\rule{0.3em}{0ex}}\mathrm{K}$. Neutron-diffraction experiments, performed on a single crystal around the transition temperature, led to a different conclusion: the magnetic Bragg reflections detected below $3\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ correspond to a canted antiferromagnet, where the magnetic moments are mainly oriented along the chain axis. Surprisingly, in the context of other compounds in this family of magnets, the interchain coupling is antiferromagnetic. This state is shown to be very fragile, since a ferromagnetic interchain arrangement is recovered in a weak magnetic field. This peculiar behavior might be explained by the competition between dipolar interaction, shown to be responsible for the antiferromagnetic long-range order below $3\phantom{\rule{0.3em}{0ex}}\mathrm{K}$, and exchange interaction, the balance between these interactions being driven by the strong intrachain spin correlations. More generally, this study underlines the need, in this kind of molecular compounds, to go beyond macroscopic magnetization measurements.