Tuning the Molecular and Cationic Affinity in a Series of Multifunctional Metal–Organic Frameworks Based on Dodecanuclear Zn(II) Carboxylate Wheels

A series of new zinc(II)-thiophene-2,5-dicarboxylate (tdc) MOFs based on novel dodecanuclear wheel-shaped building blocks has been synthesized in almost quantative yields. Single-crystal X-ray diffraction analyses reveal 3D porous frameworks with a complex composition [Zn₁₂(tdc)₆(glycolate)₆(dabco)₃] where glycolate is a deprotonated polyatomic alcohol (ethylene glycol, EgO₂, 1; 1,2-propanediol, PrO₂, 2; 1,2-butanediol, BuO₂, 3; 1,2-pentanediol, PeO₂, 4; glycerol, GlO₂, 5) and dabco is 1,4-diazo[2.2.2.]bicyclooctane. All compounds 1-5 are isostructural except for pendant groups of the diols decorating the surface of channels. The adsorption of small gases (N₂, CO₂, CH₄, C₂H₂, C₂H₄, C₂H₆) and larger hydrocarbons (benzene, cyclohexane) both in liquid and vapor phases was thoroughly investigated for all compounds. The zero-coverage adsorption enthalpies, Henry constants, and selectivity factors by various models are calculated and discussed. The versatile adsorption functionality of the title series results from the variable nature of the diol and could be tailored for a specific adsorbate system. For example, 1 shows excellent selectivity of benzene over cyclohexane (20:1 for vapors, 92:1 for liquid phase), while 4 demonstrates unprecedented adsorption preference of cyclohexane over benzene (selectivity up to 5:1). The compound 5 demonstrates great adsorption selectivity for CO₂/N₂ (up to 75.1), CO₂/CH₄ (up to 7.7), C₂H₂/CH₄ (up to 14.2), and C₂H₄/CH₄ (up to 9.4). Also, due to polar nature of the pores, 5 features size-selective sorption of alkaline metal cations in order Li⁺ > Na⁺ > K⁺ > Cs⁺ as well as a notable luminescent response for cesium(I) ions and urea.