Permanent Porosity in the Room-Temperature Magnet and Magnonic Material V(TCNE)₂

Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)₂ (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)₆ with TCNE yields V(TCNE)₂·0.95CH₂Cl₂, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)₂, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m²/g). The porous structure of V(TCNE)₂ is accessible to the small gas molecules H₂, N₂, O₂, CO₂, ethane, and ethylene. While V(TCNE)₂ exhibits thermally activated electron transfer with O₂, all the other studied gases engage in physisorption. The T* value of V(TCNE)₂ is slightly modulated upon adsorption of H₂ (T* = 583 K) or CO₂ (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.