Satska Y. The influence of structure of chiral carboxylate coordination polymers on sorption of optically-active monoatomic alcohols.

The theses is devoted to investigation of the structure of chiral carboxylate polymers of Fe3+, Co2+, Ni2+, Cu2+, Zn2+, molecular compelxes of Со2+ with chiral carboxylate ligands, V4+ complex with β-cyclodextrine and their capacity to absorb enantiomers of 2-butanol from vapor phase (pure optical isomers) and from liquid racemic mixture, as well as their capacity to absorb enantiomers of 2-hexanol, 3-hexanol, 1-phenylathenol from the racemic mixtures. Chirality of all coordination polymers and molecular coordination compounds, studied in this work, was caused by the presence of asymmetric sites in the organic ligands. The structure of five new chiral coordination polymers and one binuclear molecular complex was determined by X-ray structure analysis. Despite the presence of "rigid" micropores in come compounds, in all cases interaction of alcohols with the coordination polymers according to the results of analysis of vapor phase sorption isotherms was not described as physical adsorption in microporous sorbents and was accompanied, most probably, by rearrangement of the crystal lattices of the coordination polymers. The ability to induce such rearrangement could be governed by the balance of sorption energy and polymeric framework rearrangement energy. It was shown that the size of pores accessible to the guest molecules in the coordination polymers, calculated by analysis of their crystal lattices, was not the main factor that determined sorption capacity of such system towards monoatomic alcohols. It was found that the structure of non-chiral ligands and the whole cavity of the coordination polymer determined, which enantiomer of 2-butanol was preferably absorbed by such compound. The ratio of sorption capacity of the coordination polymer in respect to different enantiomers of 2-butanol (enantioselectivity of sorption) from gas phase in the same conditions correlated with the highest value of enantiomeric excess, achieved at chromatographic separation of racemic mixture of this alcohol on the respective coordination polymers. The value of enantiomeric excess of the alcohol, which was achieved upon chromatographic separation of the racemic mixtures on the column filled with the coordination polymer, changed in antibate way with solvent's viscosity; this feature can be associated with the difference in diffusion rate of alcohols to the sorption sites in different solvents. The approaches to separation of the racemic mixtures of monoatomic alcohols using coordination polymer were developed. Such approaches can be used for isolation of pure optical isomers of such compounds. The conditions for full separation of the racemic mixture of 1-phenylethanol using coordination polymers as stationary phase for column chromatography were found.