Realization of an excellent two-dimensional Heisenberg ferromagnetic system: the synthesis, structure, and thermodynamic properties of piperazinediium tetrabromocuprate

Abstract

As to the prototypical realization of the famous Mermin–Wagner theorem, two dimensional Heisenberg ferromagnets (2D HFMs) are expected to have no static order at finite temperatures [N. D. Mermin and H. Wagner, Phys. Rev. Lett., 1966, 17, 1133]. However, a perfect 2D HFM with negligible inter-layer exchange is still lacking, impeding studies of its novel properties. Here we report the synthesis, structure, and properties of a new metal–organic single crystal piperazinediium tetrabromocuprate ((C₄H₁₂N₂)CuBr₄, PTBC). The Cu²⁺ spins form perfect 2D layers which are well separated by organic ligands. Single crystal electron paramagnetic resonance (EPR) and magnetic susceptibility measurements reveal that PTBC is a highly isotropic Heisenberg ferromagnet with a strong intra-layer ferromagnetic exchange J/k_B = 31.34(6) K (H‖ab) and 36.54(17) K (H⊥ab). However, it does not order down to 2 K, indicating the negligible inter-layer exchange J′ and ultra-small R ratio (R = J′/J) below 6 × 10⁻²⁸. This is the smallest R ratio ever reported for a 2D HFM. These results imply that PTBC is by far the best realization of a 2D HFM system. Moreover, the typical single crystal size is as large as 20 mm × 20 mm × 3 mm, making it suitable for studying the magnetic dynamics of a 2D HFM by probes such as inelastic neutron scattering.