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. © 2019 American Chemical Society.

Lysova A.A.1, 2 , Samsonenko D.G.1, 2 , Dorovatovskii P.V. 3 , Lazarenko V.A. 3 , Khrustalev V.N. 4 , Kovalenko K.A.1, 2 , Dybtsev D.N.1, 2 , Fedin V.P.1, 2
American Chemical Society
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  • 1 Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, 630090, Russian Federation
  • 2 Novosibirsk State University, Novosibirsk, 630090, Russian Federation
  • 3 National Research Center 'Kurchatov Institute', Kurchatov Square 1, Moscow, 123182, Russian Federation
  • 4 Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklay Street 6, Moscow, 117198, Russian Federation
Ключевые слова
Adsorption; Benzene; Carbon dioxide; Carboxylation; Cesium compounds; Crystalline materials; Cyclohexane; Ethylene; Ethylene glycol; Organometallics; Single crystals; Urea; Wheels; X ray diffraction analysis; 1 ,2-propanediol; Adsorbate systems; Adsorption enthalpies; Adsorption selectivity; Complex compositions; Metal organic framework; Selectivity factors; Single crystal X-ray diffraction analysis; Zinc compounds; 1,2 butanediol; 1,2 pentanediol; 1,4 diazo[2.2.2.]bicyclooctane; alcohol derivative; benzene; carbon dioxide; carboxylic acid derivative; cesium; cyclohexane; ethylene glycol; glycerol; glycolic acid; lithium; metal organic framework; potassium; propylene glycol; sodium; thiophene 2,5 dicarboxylate; unclassified drug; zinc; adsorption; Article; binding affinity; chemical composition; chemical structure; deprotonation; enthalpy; liquid; luminescence; vapor; X ray diffraction
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