Spin Helicity in Chiral Lanthanide Chains

We report here the determination of the helical spin structure of three Ln-based chiral chains of the formula [Ln(Hnic)(nic)2(NO3)]n (Hnic = nicotinic acid; Ln = Tb, Dy, and Er) by means of cantilever torque magnetometry. While the Dy and Er derivatives are strongly axial (easy-axis and easy-plane anisotropy, respectively), the Tb derivative is characterized by a remarkable rhombicity. In agreement with these findings, alternating-current susceptibility reveals slow magnetic relaxation only in the Dy derivative. Dilution of Dy(III) ions in the diamagnetic Y-based analogue shows that the weak ferromagnetic intrachain interactions do not contribute significantly to the energy barrier for the reversal of magnetization, which is better described as a single-ion process. Single crystals of the two enantiomers of the Dy derivative have also been investigated using hard X-ray synchrotron radiation at the L-edge of the metal revealing optical activity although with negligible involvement of the 4f electrons of the Dy(III) ion.