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Leite ES Santana SR Hünenberger PH Freitas LC Longo RL 《Journal of molecular modeling》2007,13(9):1017-1025
The relative stabilities of the alkali [M ⊂ 222]+ cryptates (M = Na, K, Rb and Cs) in the gas phase and in solution (80:20 v/v methanol:water mixture) at 298 K, are computed
using a combination of ab initio quantum-chemical calculations (HF/6-31G and MP2/6-31+G*//HF/6-31+G*) and explicit-solvent
Monte Carlo free-energy simulations. The results suggest that the relative stabilities of the cryptates in solution are due
to a combination of steric effects (compression of large ions within the cryptand cavity), electronic effects (delocalization
of the ionic charge onto the cryptand atoms) and solvent effects (dominantly the ionic dessolvation penalty). Thus, the relative
stabilities in solution cannot be rationalized solely on the basis of a simple match or mismatch between the ionic radius
and the cryptand cavity size as has been suggested previously. For example, although the [K ⊂ 222]+ cryptate is found to be the most stable in solution, in agreement with experimental data, it is the [Na ⊂ 222]+ cryptate that is the most stable in the gas phase. The present results provide further support to the notion that the solvent
in which supramolecules are dissolved plays a key role in modulating molecular recognition processes.
Figure Alkali cryptates [M ⊂ 222]+ (M = Na, K, Rb and Cs) relative stabilities in gas and methanol:water solution: solvent effects
and molecular recognition
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献