Machine Learning Quantitative Structure–Property Relationships as a Function of Ionic Liquid Cations for the Gas-Ionic Liquid Partition Coefficient of Hydrocarbons

Abstract

Ionic liquids (ILs) are known for their unique characteristics as solvents and electrolytes. Therefore, new ILs are being developed and adapted as innovative chemical environments for different applications in which their properties need to be understood on a molecular level. Computational data-driven methods provide means for understanding of properties at molecular level, and quantitative structure–property relationships (QSPRs) provide the framework for this. This framework is commonly used to study the properties of molecules in ILs as an environment. The opposite situation where the property is considered as a function of the ionic liquid does not exist. The aim of the present study was to supplement this perspective with new knowledge and to develop QSPRs that would allow the understanding of molecular interactions in ionic liquids based on the structure of the cationic moiety. A wide range of applications in electrochemistry, separation and extraction chemistry depends on the partitioning of solutes between the ionic liquid and the surrounding environment that is characterized by the gas-ionic liquid partition coefficient. To model this property as a function of the structure of a cationic counterpart, a series of ionic liquids was selected with a common bis-(trifluoromethylsulfonyl)-imide anion, [Tf2N]−, for benzene, hexane and cyclohexane. MLR, SVR and GPR machine learning approaches were used to derive data-driven models and their performance was compared. The cross-validation coefficients of determination in the range 0.71–0.93 along with other performance statistics indicated a strong accuracy of models for all data series and machine learning methods. The analysis and interpretation of descriptors revealed that generally higher lipophilicity and dispersion interaction capability, and lower polarity in the cations induces a higher partition coefficient for benzene, hexane, cyclohexane and hydrocarbons in general. The applicability domain analysis of models concluded that there were no highly influential outliers and the models are applicable to a wide selection of cation families with variable size, polarity and aliphatic or aromatic nature.

Chemical Accuracy Prediction of Molecular Solvation and Partition in Ionic Liquids with Educated Estimators

“…In total, our constructed dataset contains 1764 solvation and 1764 water-ILs transfer (partition) free energies involving 39 ILs formed by 37 ions and 120 solutes. Such a size of datasets is much larger than existing models with a similar goal 30 (e.g., ~252 data points in a solvation model published in 2021), 28 and our coverage of popular ILs compositions and solutes is also unprecedently diverse.…”