Permanent Porosity in the Room-Temperature Magnet and Magnonic Material V(TCNE) 2 .
Jesse G ParkDavid E JaramilloYueguang ShiHenry Z H JiangHuma YusufHiroyasu FurukawaEric D BlochDonley S CormodeJoel S MillerT David HarrisEzekiel Johnston-HalperinMichael E FlattéJeffrey R LongPublished in: ACS central science (2023)
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 ·0.95CH 2 Cl 2 , 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 m 2 /g). The porous structure of V(TCNE) 2 is accessible to the small gas molecules H 2 , N 2 , O 2 , CO 2 , ethane, and ethylene. While V(TCNE) 2 exhibits thermally activated electron transfer with O 2 , all the other studied gases engage in physisorption. The T * value of V(TCNE) 2 is slightly modulated upon adsorption of H 2 ( T * = 583 K) or CO 2 ( 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.