Merohedral icosahedral M48 (M = CoII NiII) cage clusters supported by thiacalix4arene

摘要

Cage clusters are a discrete chemically and topologically diverse family of molecule-based functional materials. Presented here are two isostructural M48 (M = Co^II for >LSHU01, Ni^II for >LSHU02) cage clusters with a merohedral icosahedral cage structure featuring 12 M4-TC4A (H4TC4A, p-tert-butylthiacalix[4]arene) second building units as vertices and 18 asymmetric 5-(1H-tetrazol-1-yl)isophthalate ligands as faces. They are the highest-nuclearity cage compounds of Co^II and Ni^II. The activated Co48 cage exhibited high selectivity in the sorption of C3H8 over CH4 under ambient conditions. Frequency response experiments indicated that the extrinsic voids and matrix interface of the activated crystalline samples are primarily responsible for the observed gas adsorption performance.