Uncovering the S=12 Kagome Ferromagnet within a Family of Metal–Organic Frameworks

Kagome networks of ferromagnetically or antiferromagnetically coupled magnetic moments represent important models in the pursuit of a diverse array of novel quantum and topological states of matter. Here, we explore a family of Cu 2+ -containing metal-organic frameworks (MOFs) bearing kagome layers pillared by ditopic organic linkers with the general formula Cu 3 (CO 3 ) 2 ( x ) 3 ·2ClO 4 (MOF- x ), where x is 1,2-bis(4-pyridyl)ethane ( bpe ), 1,2-bis(4-pyridyl)ethylene ( bpy ), or 4,4'-azopyridine ( azpy ). Despite more than a decade of investigation, the nature of the magnetic exchange interactions in these materials remained unclear, meaning that whether the underlying magnetic model is that of an kagome ferromagnet or antiferromagnet is unknown. Using single-crystal X-ray diffraction, we have developed a chemically intuitive crystal structure for this family of materials. Then, through a combination of magnetic susceptibility, powder neutron diffraction, and muon-spin spectroscopy measurements, we show that the magnetic ground state of this family consists of ferromagnetic kagome layers that are coupled antiferromagnetically via their extended organic pillaring linkers.