Anion Regulates scu Topological Porous Coordination Polymers into the Acetylene Trap

The development of efficient porous absorbents with high uptake and selectivity remains a great challenge, especially for the recovery of acetylene (C₂H₂) from its carbon dioxide (CO₂)-containing mixtures. Here, we propose and report an anion-planting strategy for regulating the scu topological porous coordination polymers (PCPs) into the C₂H₂ trap. The three electronegative anions SiF₆^2-, TiF₆^2-, and ZrF₆^2-, in addition to the ligand of 3,5-di(1H-imidazol-1-yl)benzoic acid (HL) and Cu²⁺ ion, were employed to construct highly porous PCPs (NTU-60, NTU-61, and NTU-62) with varied window aperture. Especially, due to a matching distance (d_F-F) of 5.7 Å along the c-axis, the limited space that can be assigned as a single C₂H₂ trap enables NTU-61 to show optimal ability for C₂H₂ (van der Waals (vdW) parameters of the two H atoms: ∼5.72 Å) recognition, validated by Grand Canonical Monte Carlo (GCMC) calculations and Raman spectra. These characteristics allow the NTU-series to show higher C₂H₂ uptake, as well as excellent C₂H₂/CO₂ separation performance under dynamic conditions. The molecular insight and strategy here not only permit balanced adsorption and separation in a single domain but also exhibit an opportunity to develop advanced adsorbents in nearly all frameworks with lattice or coordinated ions, which may act as the platforms for various selective guest trappings with on-demand time and/or spatial resolution.