4.6 Article

Pressure effect on the magnetism and crystal structure of magnetoelectric metal-organic framework [CH3NH3][Co(HCOO)3]

Journal

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 25, Issue 48, Pages 32863-32867

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d3cp02311g

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This study investigates the spin-driven magnetoelectric effects of the perovskite-like metal-organic framework [CH3NH3][Co(HCOO)(3)]. The magnetic properties and crystal structure of [CH3NH3][Co(HCOO)(3)] under high pressure are studied. It is found that high pressure can alter the crystal structure and magnetic properties of perovskite type MOF materials.
[CH3NH3][Co(HCOO)(3)] is the first perovskite-like metal-organic framework exhibiting spin-driven magnetoelectric effects. However, the high-pressure tuning effects on the magnetic properties and crystal structure of [CH3NH3][Co(HCOO)(3)] have not been studied. In this work, alongside ac magnetic susceptibility measurements, we investigate the magnetic transition temperature evolution under high pressure. Upon increasing the pressure from atmospheric pressure to 0.5 GPa, T-N (15.2 K) remains almost unchanged. Continuing to compress the sample results in T-N gradually decreasing to 14.8 K at 1.5 GPa. This may be due to pressure induced changes in the bond distance and bond angle of the O-C-O superexchange pathway. In addition, by using high pressure powder X-ray diffraction and Raman spectroscopy, we conducted in-depth research on the pressure dependence of the lattice parameters and Raman modes of [CH3NH3][Co(HCOO)(3)]. The increase in pressure gives rise to a phase transition from the orthorhombic Pnma to a monoclinic phase at approximately 6.13 GPa. Our study indicates that high pressure can profoundly alter the crystal structure and magnetic properties of perovskite type MOF materials, which could inspire new endeavors in exploring novel phenomena in compressed metal-organic frameworks.

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