Abstract
The structural, electronic and magnetic properties of the MIL-47(Mn) metal-organic framework are investigated using first principles calculations. We find that the large-pore structure is the ground state of this material. We show that upon transition from the large-pore to the narrow-pore structure, the magnetic ground-state configuration changes from antiferromagnetic to ferromagnetic, consistent with the computed values of the intra-chain coupling constant. Furthermore, the antiferromagnetic and ferromagnetic configuration phases have intrinsically different electronic behavior: the former is semiconducting, the latter is a metal or half-metal. The change of electronic properties during breathing posits MIL-47(Mn) as a good candidate for sensing and other applications. Our calculated electronic band structure for MIL-47(Mn) presents a combination of flat dispersionless and strongly dispersive regions in the valence and conduction bands, indicative of quasi-1D electronic behavior. The spin coupling constants are obtained by mapping the total energies onto a spin Hamiltonian. The inter-chain coupling is found to be at least one order of magnitude smaller than the intra-chain coupling for both large and narrow pores. Interestingly, the intra-chain coupling changes sign and becomes five times stronger going from the large pore to the narrow pore structure. As such MIL-47(Mn) could provide unique opportunities for tunable low-dimensional magnetism in transition metal oxide systems.
Original language | English |
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Pages (from-to) | 4786-4794 |
Number of pages | 9 |
Journal | RSC Advances |
Volume | 10 |
Issue number | 8 |
DOIs | |
Publication status | Published - 28 Jan 2020 |
Keywords
- EXTENDING HIRSHFELD-I
- PHASE ADSORPTION
- SEPARATION
- CRYSTAL
- MIL-53
- CO2
- MN
- TRANSITION
- DIVERSITY
- CHEMISTRY