TY - JOUR

T1 - Tuning the Molecular and Cationic Affinity in a Series of Multifunctional Metal-Organic Frameworks Based on Dodecanuclear Zn(II) Carboxylate Wheels

AU - Lysova, Anna A.

AU - Samsonenko, Denis G.

AU - Dorovatovskii, Pavel V.

AU - Lazarenko, Vladimir A.

AU - Khrustalev, Victor N.

AU - Kovalenko, Konstantin A.

AU - Dybtsev, Danil N.

AU - Fedin, Vladimir P.

N1 - Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/10/30

Y1 - 2019/10/30

N2 - 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.

AB - 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.

KW - POROUS COORDINATION POLYMER

KW - ADSORPTIVE SEPARATION

KW - HOST-GUEST

KW - SELECTIVE SORPTION

KW - RATIONAL SYNTHESIS

KW - GAS-ADSORPTION

KW - CO2 ADSORPTION

KW - ETHANE

KW - MOF

KW - STORAGE

UR - http://www.scopus.com/inward/record.url?scp=85073834690&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b08322

DO - 10.1021/jacs.9b08322

M3 - Article

C2 - 31584810

AN - SCOPUS:85073834690

VL - 141

SP - 17260

EP - 17269

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 43

ER -