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On the relative stabilities of the alkali cations 222 cryptates in the gas phase and in water-methanol solution

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Abstract

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.

Alkali cryptates [M ⊂ 222]+ (M = Na, K, Rb and Cs) relative stabilities in gas and methanol:water solution: solvent effects and molecular recognition

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Acknowledgements

This work was partially supported by FAPESP, CAPES, CNPq, PADCT and CENAPAD-SP. ESL thanks FAPESP for the award of a fellowship.

Author information

Authors and Affiliations

  1. Departamento de Química Fundamental, Universidade Federal de Pernambuco, 50740-540, Recife, PE, Brazil

    Elisa S. Leite, Sidney R. Santana & Ricardo L. Longo

  2. Departamento de Química, Universidade Federal de São Carlos, CP-676, 13565-905, São Carlos, SP, Brazil

    Elisa S. Leite & Luiz C. G. Freitas

  3. Laboratory of Physical Chemistry, ETH, 8093, Zurich, Switzerland

    Philippe H. Hünenberger

Authors
  1. Elisa S. Leite
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  2. Sidney R. Santana
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  3. Philippe H. Hünenberger
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  4. Luiz C. G. Freitas
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  5. Ricardo L. Longo
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Corresponding author

Correspondence to Ricardo L. Longo.

Electronic Supplementary Material

The Supplementary Material contains the Cartesian coordinates of the optimized structures as well as their corresponding pictures with the atom labels.

Figure S1

Structure of the [Na ⊂ 222]+ endo cryptate optimized with the HF/6-31+G* and HF/6-311++G** methods, together with the corresponding atom-labeling scheme (see coordinates in Table S2 and Table S8). (DOC 101 kb)

Figure S2

Structure of the [K ⊂ 222]+ endo cryptate optimized with the HF/6-31+G* method, together with the corresponding atom-labeling scheme (see coordinates in Table S3). (DOC 99.5 kb)

Figure S3

Structure of the [K ⊂ 222]+ endo cryptate optimized with the HF/6-31+G*/ LanL2DZ method, together with the corresponding atom-labeling scheme (see coordinates in Table S4). (DOC 92.5 kb)

Figure S4

Structure of the [Rb ⊂ 222]+ endo cryptate optimized with the HF/6-31+G*/LanL2DZ method, together with the corresponding atom-labeling scheme (see coordinates in Table S5). (DOC 94 KB)

Figure S5

Structure of the [Cs ⊂ 222]+ endo cryptate optimized with the HF/6-31+G*/LanL2DZ method, together with the corresponding atom-labeling scheme (see coordinates in Table S6). (DOC 95.5 kb)

Figure S6

Structure of the [Cs ⊂ 222]+ exo cryptate optimized with the HF/6-31+G*/LanL2DZ method, together with the corresponding atom-labeling scheme (see coordinates in Table S7). (DOC 93 kb)

Table S1

Partial atomic charges (in |e|) used in the explicit-solvent MC simulations of the [M ⊂ 222]+ cryptates. The charges were derived from a CHELPG analysis based on the optimized structures (at the same level of theory as the optimization for [Na ⊂ 222]+ and [K ⊂ 222]+, or at the HF/6-31G level with an SDD pseudopotential [27] for the Rb and Cs atoms in [Rb ⊂ 222]+ and [Cs ⊂ 222]+). See Figures S1, S2, S3 and S4 for the atom-labeling scheme. (DOC 42.5 kb)

Table S2

Cartesian coordinates of the [Na ⊂ 222]+ endo cryptate optimized with the HF/6-31+G* method (energy -1422.3664973 E h; MP2 energy -1426.152491 E h). See Fig. S1 for the structure and atom-labeling scheme. (DOC 42.5 kb)

Table S3

Cartesian coordinates of the [K ⊂ 222]+ endo cryptate optimized with the HF/6-31+G* method (energy -1859.6493126 E h; MP2 energy -1863.4713692 E h). See Fig. S2 for the structure and atom-labeling scheme. (DOC 42 kb)

Table S4

Cartesian coordinates of the [K ⊂ 222]+ endo cryptate optimized with the HF/6-31+G*/LanL2DZ method (energy -1288.3847267 E h; MP2 energy -1292.2569353 E h). See Fig. S3 for the structure atom labeling scheme. (DOC 42 kb)

Table S5

Cartesian coordinates of the [Rb ⊂ 222]+ endo cryptate optimized with the HF/6-31+G*/LanL2DZ method (energy -1284.0926095 E h; MP2 energy -1287.9527188 E h). See Fig. S4 for the structure and atom-labeling scheme. (DOC 42 kb)

Table S6

Cartesian coordinates of the [Cs ⊂ 222]+ endo cryptate (based on the crystallographic structure) optimized with the HF/6-31+G*/LanL2DZ method (energy -1280.1065032 E h; MP2 energy -1283.9468867 E h). See Fig. S5 for the structure and atom-labeling scheme. (DOC 41.5 kb)

Table S7

Cartesian coordinates of the [Cs ⊂ 222]+ exo cryptate optimized with the HF/6-31+G*/LanL2DZ method (energy -1280.0946488 E h; MP2 energy -1283.9294974 E h). See Fig. S6 for the structure and atom-labeling scheme. (DOC 41.5 kb)

Table S8

Cartesian coordinates of the [Na ⊂ 222]+ endo cryptate optimized with the HF/6-311++G** method (energy -1422.6813206 E h). See Fig. S1 for the structure and atom-labeling scheme. (DOC 43.5 kb)

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Leite, E.S., Santana, S.R., Hünenberger, P.H. et al. On the relative stabilities of the alkali cations 222 cryptates in the gas phase and in water-methanol solution. J Mol Model 13, 1017–1025 (2007). https://doi.org/10.1007/s00894-007-0213-8

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