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The synthesis and characterization of benz-1,4-dioxane crown ethers (CEs) and some of its homologues are described and analyzed. The effect of added C-atom within the CE ring (increasing the hydrophobicity of the CE ring by increasing the number of CH2-units) on the Li+ and Mg2+ complexation within a liquid-liquid extraction (LLE) is investigated and thermodynamically analyzed. The complex stability constant K, the change of entropy ΔS and enthalpy ΔH, and the Gibbs energy ΔG are determined.doi:10.1039/d2cp01076c pmid:35506443 fatcat:2jr7s6dwuffe7clrupavivbb6y