Self-Enhancement of Rotating Magnetocaloric Effect in Anisotropic Two-Dimensional (2D) Cyanido-Bridged Mn<sup>II</sup>–Nb<sup>IV</sup> Molecular Ferrimagnet

The rotating magnetocaloric effect (RMCE) is a new issue in the field of magnetic refrigeration. We have explored this subject on the two-dimensional (2D) enantiopure {[Mn<sup>II</sup>(R-mpm)<sub>2</sub>]<sub>2</sub>[Nb<sup>IV</sup>(CN)<sub>8</sub>]}·4H<sub>2</sub>O (where mpm = α-methyl-2-pyridinemethanol) coordination ferrimagnet. In this study, the magnetic and magnetocaloric properties of single crystals were investigated along the <i>bc</i>//<i>H</i> easy plane and the <i>a</i>*//<i>H</i> hard axis. The observed small easy plane anisotropy is due to the dipole–dipole interactions. For fields higher than 0.5 T, no significant difference in the magnetocaloric effect between both geometries was noticed. The maximal magnetic entropy change for conventional effect was observed at 32 K and the magnetic field change μ<sub>0</sub>Δ<i>H</i> = 5.0 T attaining the value of ∼5 J mol<sup>–1</sup> K<sup>–1</sup>. The obtained maximal value of −Δ<i>S</i><sub>m</sub> is comparable to previously reported results for polycrystalline octacyanidoniobate-based bimetallic coordination polymers. A substantial anisotropy of magnetocaloric effect between the easy plane and hard axis appears in low fields. This includes the presence of inverse magnetocaloric effect only for the <i>a</i>*//<i>H</i> direction. The difference between both geometries was used to study the rotating magnetocaloric effect. We show that the inverse part of magnetocaloric effect can be used to enhance the rotating magnetic entropy change up to 51%. This finding is of key importance for searching efficient materials for RMCE.