Creation of a Field-Induced Co(II) Single-Ion Magnet by Doping into a Zn(II) Diamagnetic Metal-Organic Framework

The combination of single-ion magnets (SIMs) and metal-organic frameworks (MOFs) is expected to produce new quantum materials. The principal issue to be solved in this regard is the development of new strategies for the synthesis of SIM-MOFs. This work demonstrates a new simple strategy for the synthesis of SIM-MOFs where a diamagnetic MOF is used as the framework into which the SIM sites are doped. 1, 0.5, and 0.2 mol% of the Co(II) ions are doped into the Zn(II) sites of [CH₆ N₃ ][Zn^II (HCOO)₃ ]. The doped Co(II) sites in the MOFs perform as SIM with a positive D term of zero-field splitting. The longest magnetic relaxation time is 150 ms (0.2 mol% Co) at 1.8 K under a static field of 0.1 T. Temperature dependency of the relaxation time suggests suppressing magnetic relaxation by reduction of spin-spin interaction upon doping in the rigid framework. Thus, this work represents a proof of concept for the creation of a single-ion doped magnet in the MOF. This simple synthetic strategy will be widely applied for the creation of quantum magnetic materials.