Merohedral icosahedral M48 (M = CoII, NiII) cage clusters supported by thiacalix[4]arene

摘要

Cage clusters are a discrete chemically and topologically diverse family of molecule-based functional materials. Presented here are two isostructural M _(48) (M = Co ~(II) for LSHU01 , Ni ~(II) for LSHU02 ) cage clusters with a merohedral icosahedral cage structure featuring 12 M _(4) -TC4A (H _(4) TC4A, p-tert -butylthiacalix[4]arene) second building units as vertices and 18 asymmetric 5-(1 H -tetrazol-1-yl)isophthalate ligands as faces. They are the highest-nuclearity cage compounds of Co ~(II) and Ni ~(II) . The activated Co _(48) cage exhibited high selectivity in the sorption of C _(3) H _(8) over CH _(4) 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.