A selenophene-incorporated metal–organic framework for enhanced CO₂ uptake and adsorption selectivity

A new metal–organic coordination polymer [Zn₂(sedc)₂(dabco)] (1se; sedc²⁻ = selepophene-2, 5-dicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane) was synthesized and characterized by single-crystal X-ray diffraction analysis. This MOF is based on {Zn₂(OOCR)₄N₂} paddle wheels and is isoreticular to the family of [Zn₂(bdc)₂(dabco)] derivatives (1b; bdc²⁻ = 1,4-benzenedicarboxylate) with pcu topology. The gas adsorption measurements revealed that 1se shows a 15% higher CO₂ volumetric uptake at 273 K and 28% higher CO₂ uptake at 298 K (both at 1 bar) compared to the prototypic framework 1b. Methane and nitrogen adsorption at 273 K was also investigated, and IAST calculations demonstrated a pronounced increase in CO₂/CH₄ and CO₂/N₂ selectivity for 1se, compared with 1b. For example, the selectivity factor for the equimolar CO₂/CH₄ gas mixture at 1 bar = 15.1 for 1se and 11.9 for 1b. The obtained results show a remarkable effect of the presence of selenium atom on the carbon dioxide affinity in the isoreticular metal–organic frameworks with very similar geometry and porosity.