Assessment of the Macrocyclic Effect for the Complexation of Crown-Ethers with Alkali Cations Using the Substructural Molecular Fragments Method

• Published in: Journal of Chemical Information and Computer Sciences Vol. 42; no. 4; pp. 812 - 829
• Main Authors: Varnek, A, Wipff, G, Solov'e, V. P, Solotnov, A. F
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 01.07.2002
• ISSN: 0095-2338; 1549-960X; 1520-5142
• DOI: 10.1021/ci010318q

The Substructural Molecular Fragments method (Solov'ev, V. P.; Varnek, A. A.; Wipff, G. J. Chem. Inf. Comput. Sci. 2000, 40, 847−858) was applied to assess stability constants (logK) of the complexes of crown-ethers, polyethers, and glymes with Na+, K+, and Cs+ in methanol. One hundred forty-seven computational models including different fragment sets coupled with linear or nonlinear fitting equations were applied for the data sets containing 69 (Na+), 123 (K+), and 31 (Cs+) compounds. To account for the “macrocyclic effect” for crown-ethers, an additional “cyclicity”descriptor was used. “Predicted” stability constants both for macrocyclic compounds and for their open-chain analogues are in good agreement with the experimental data reported earlier and with those studied experimentally in this work. The macrocyclic effect as a function of cation and ligand is quantitatively estimated for all studied crown-ethers.