Issue 96, 2016, Issue in Progress

Sorption discrimination between secondary alcohol enantiomers by chiral alkyl-dicarboxylate MOFs

Abstract

The 3D coordination polymer [Co2(H2O)(cpda)2(py)4·py]n (cpdaH2 is trans-(S,S)-1,2-cyclopropane dicarboxylic acid, py = pyridine) crystallizes from pyridine as 1·5py (one py is not coordinated) and was characterized by X-ray single crystal diffraction. Desolvation of 1·5py was accomplished with decoordination of pyridine and transformation of the CoII octahedral coordination into tetrahedral, as confirmed by electronic spectroscopy. Sorption of individual optical isomers – (S)-2-butanol and (R)-2-butanol – from the gas phase at 303 K by desolvated 1 was studied, and for comparison sorption of these substrates by the chiral MOFs [Zn2(camph)2(bipy)]n (2) and [Zn2(camph)2(dpe)]n (3) was examined (camphH2 is (1R,3S)-camphoric acid, bipy is 4,4′-bipyridine, dpe is trans-1,2-di(4-pyridyl)ethylene). Chiral sites in 1–3 contain only one polar group (carboxylate) in close proximity to the asymmetric C atom, while the other groups contain only C–H or C–C bonds. In the cases of 1 or 2 the absorption isotherms grew abruptly at certain pressure values P, and these values were different for the (R) or (S) isomers' sorptions. Such differential growth can be accounted for through the polymeric framework's rearrangement induced by interaction with 2-butanol, the difference in P values for (R) and (S) isomers being an indication of different interaction energies for these isomers with the MOF. There was no significant difference between the values of total sorption capacity of 1 for the two enantiomers of 2-butanol at pressures close to the saturation vapor pressure. In contrast, the sorption capacity of 3 was higher for (R)-2-butanol than for (S)-2-butanol over the whole pressure range.

Graphical abstract: Sorption discrimination between secondary alcohol enantiomers by chiral alkyl-dicarboxylate MOFs

Supplementary files

Article information

Article type
Paper
Submitted
11 Apr 2016
Accepted
20 Sep 2016
First published
20 Sep 2016

RSC Adv., 2016,6, 93707-93714

Sorption discrimination between secondary alcohol enantiomers by chiral alkyl-dicarboxylate MOFs

Y. A. Satska, E. A. Mikhalyova, Z. V. Chernenko, S. V. Kolotilov, M. Zeller, I. V. Komarov, A. V. Tymtsunik, A. Tolmachev, K. S. Gavrilenko and A. W. Addison, RSC Adv., 2016, 6, 93707 DOI: 10.1039/C6RA09353A

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