Tuning Magnetism of Metal-Organic Framework by Different Types of Pressure

The properties of metal-organic frameworks (MOFs) are expected to be sensitive to external pressures because of their inherently flexible structures. Although pressure-driven structural transitions have been intensively studied, the influence of pressure on magnetism has been less exploited for MOFs. Especially, the efficiency of applied pressure may strongly depend on the pressure-transmitting medium (PTM) which may have a complex interaction with MOFs. Here, we report the distinctive effects of different types of pressure, including isotropic hydrostatic pressure, quasi-hydrostatic pressure, and uniaxial pressure, on the anisotropic magnetism of the perovskite MOF, [CH3NH3][Co(COOH)3]. It is found that the hydrostatic pressure has the minimal effect whereas the uniaxial pressure has the highest efficiency in tuning magnetization and magnetic anisotropy of the MOF. First-principles calculations reveal that the applied low pressures (less than 11 kbar) do not induce notable lattice distortion in the framework or the superexchange path. Instead, the modulation of hydrogen bonds is identified as a critical factor for pressure tuning of magnetization and anisotropy. These findings underscore the potential applications of directional pressure in precisely controlling the magnetic and electronic properties of MOFs.