Quantifying Solvophobic Effects in Organic Solvents Using a Hydrocarbon Molecular Balance

Area of Science:

• Physical Chemistry
• Organic Chemistry
• Computational Chemistry

Background:

• Solvophobic effects significantly influence molecular interactions and reaction outcomes in organic solvents.
• Accurate quantification of solvophobic effects is crucial for predicting and controlling chemical processes.
• Cohesive energy density (ced) has been proposed as a descriptor for these effects.

Purpose of the Study:

• To evaluate cohesive energy density (ced) as a quantitative descriptor for solvophobic effects in organic solvents.
• To measure the Gibbs free energy of transfer (ΔG) for rigid Z- and E-2,2'-diethynyl-9,9'-bifluorenylidene to assess solvent effects.

Main Methods:

• Experimental measurement of ΔG for Z- and E-2,2'-diethynyl-9,9'-bifluorenylidene in various organic solvents.
• Correlation analysis between solvent-dependent ΔG changes and the cohesive energy density (ced) of the solvents.
• B3LYP-D3/def2TZVP computational modeling to support experimental findings.

Main Results:

• Solvent-dependent changes in ΔG were predominantly driven by solvophobic effects.
• A strong positive correlation was observed between ΔG and the cohesive energy density (ced) of the solvents.
• Experimental results were consistent with computational predictions.

Conclusions:

• Cohesive energy density (ced) serves as a reliable quantitative descriptor for solvophobic effects in organic solvents.
• The study reinforces the utility of ced in understanding and predicting solvent-mediated molecular behavior.
• The findings provide valuable insights for solvent selection in chemical synthesis and material science.