Commensurate CO2 Capture, and Shape Selectivity for HCCH over H2CCH2, in Zigzag Channels of a Robust CuI(CN)(L) Metal–Organic Framework

A novel copper­(I) metal–organic framework (MOF), {[CuI2(py-pzpypz)2(μ-CN)2]·MeCN}n (1·MeCN), with an unusual topology is shown to be robust, retaining crystallinity during desolvation to give 1, which has also been structurally characterized [py-pzpypz is 4-(4-pyridyl)-2,5-dipyrazylpyridine)]. Zigzag-shaped channels, which in 1·MeCN were occupied by disordered MeCN molecules, run along the c axis of 1, resulting in a significant solvent-accessible void space (9.6% of the unit cell volume). These tight zigzags, bordered by (CuICN)n chains, make 1 an ideal candidate for investigations into shape-based selectivity. MOF 1 shows a moderate enthalpy of adsorption for binding CO2 (−32 kJ mol–1 at moderate loadings), which results in a good selectivity for CO2 over N2 of 4.8:1 under real-world operating conditions of a 15:85 CO2/N2 mixture at 1 bar. Furthermore, 1 was investigated for shape-based selectivity of small hydrocarbons, revealing preferential uptake of linear acetylene gas over ethylene and methane, partially due to kinetic trapping of the guests with larger kinetic diameters.