A Coordination Network Featuring Two Distinct Copper(II) Coordination Environments for Highly Selective Acetylene Adsorption

Chemistry. 2022 Sep 16;28(52):e202201188. doi: 10.1002/chem.202201188. Epub 2022 Jul 28.

Abstract

Single crystals of 2D coordination network {Cu2 L2 ⋅ (DMF)3 (H2 O)3 }n (1-DMF) were prepared by reaction of commercial reagents 3-formyl-4-hydroxybenzoic acid (H2 L) and Cu(NO3 )2 in dimethylformamide (DMF). The single-crystal structure shows two distinct Cu(II) coordination environments arising from the separate coordination of Cu(II) cations to the carboxylate and salicylaldehydato moieties on the linker, with 1D channels running through the structure. Flexibility is exhibited on solvent exchange with ethanol and tetrahydrofuran, while porosity and the unique overall connectivity of the structure are retained. The activated material exhibits type I gas sorption behaviour and a BET surface area of 950 m2 g-1 (N2 , 77 K). Notably, the framework adsorbs negligible quantities of CH4 compared with CO2 and the C2 Hn hydrocarbons. It exhibits exceptional selectivity for C2 H2 /CH4 and C2 H2 /C2 Hn , which has applicability in separation technologies for the isolation of C2 H2 .

Keywords: adsorption; copper; crystal engineering; metal-organic frameworks; microporous materials; supramolecular chemistry.