2026/03/16 by Sumit Sahu, Berk Delibas, Jahan M. Dawlaty · 1 voice
Chemistry · #Molecular Sensors and Ion Detection #Supramolecular Chemistry and Complexes #Electrochemical Analysis and Applications
paper · doi:10.1021/acs.jpclett.6c00561
openalex publication_date 2026/03/16 · openalex created_date 2026/03/17 · openalex updated_date 2026/07/22
measurements, supported by density functional theory calculations, show that encapsulated metal ions act as effective electron-withdrawing units that stabilize the carboxylate conjugate base. We show that the induced acidity change depends on metal-ion identity, charge, size complementarity with crown ether, and hydration energy. This study establishes a quantitative framework for defining Hammett-like parameters for metal ions and provides design principles and limitations for controlling acid-base chemistry using crown ether motifs. More broadly, it demonstrates a general supramolecular strategy for tuning reactivity via noncovalent electrostatic effects.