A coronene-based semiconducting two-dimensional metal-organic framework with ferromagnetic behavior

Metal–organic frameworks (MOFs) have so far been highlighted for their potential roles in catalysis, gas storage and separation. However, the realization of high electrical conductivity (>10 −3 S cm −1 ) and magnetic ordering in MOFs will afford them new functions for spintronics, which remains relatively unexplored. Here, we demonstrate the synthesis of a two-dimensional MOF by solvothermal methods using perthiolated coronene as a ligand and planar iron-bis(dithiolene) as linkages enabling a full π-d conjugation. This 2D MOF exhibits a high electrical conductivity of ~10 S cm −1 at 300 K, which decreases upon cooling, suggesting a typical semiconductor nature. Magnetization and 57 Fe Mössbauer experiments reveal the evolution of ferromagnetism within nanoscale magnetic clusters below 20 K, thus evidencing exchange interactions between the intermediate spin S = 3/2 iron(III) centers via the delocalized π electrons. Our results illustrate that conjugated 2D MOFs have potential as ferromagnetic semiconductors for application in spintronics. Endowing metal–organic frameworks with both high electrical conductivity and magnetic ordering could make such materials useful for spintronics. Here the authors design a layer-stacking coronene-based 2D MOF that exhibits a semiconducting feature with an electrical conductivity of ~10 S cm −1 at 300 K, as well as ferromagnetism below ~20 K.