RESUMO
Cage clusters are a discrete chemically and topologically diverse family of molecule-based functional materials. Presented here are two isostructural M48 (M = CoII for LSHU01, NiII 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 CoII and NiII. 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.
RESUMO
A 2D layered structure {[Co4(TC4A)Cl](L)2][(CH3CH2)4N]}n (+solvent)(1) has been solvothermally synthesized by assembly of Co4-TC4A (H4TC4A = p-tert-butylthiacalix[4]arene) subunits and L (H2L = 4-(1H-tetrazol-5-yl)benzoic acid) ligands. The layers arranged in an edge-to-edge (AAAA) manner, which represented the only example of 2D porous coordination polymers (PCPs) with 1D uniform channels of metal-thiacalix[4]arene. The activated PCP 1 exhibited high selectivity for C3H8/C2H6, C3H6/C2H4, and C3H8/C2H4, which makes it a competitive porous material for C3/C2 alkane and/or olefin separations. Frequency response investigations for C3H8 and C2H6 indicated that the 1D channels and inter-layer voids of the activated crystalline samples are primarily responsible for the observed gas adsorption and separation performances.
