Tunable Electrochemical Entropy through Solvent Ordering by a Supramolecular Host

[Image: see text] An aqueous electrochemically controlled host–guest encapsulation system demonstrates a large and synthetically tunable redox entropy change. Electrochemical entropy is the basis for thermally regenerative electrochemical cycles (TRECs), which utilize reversible electrochemical processes with large molar entropy changes for thermogalvanic waste-heat harvesting and electrochemical cooling, among other potential applications. A supramolecular host–guest system demonstrates a molar entropy change of 4 times that of the state-of-the-art aqueous TREC electrolyte potassium ferricyanide. Upon encapsulation of a guest, water molecules that structurally resemble amorphous ice are displaced from the host cavity, leveraging a change in the degrees of freedom and ordering of the solvent rather than the solvation of the redox-active species to increase entropy. The synthetic tunability of the host allows rational optimization of the system’s ΔS, showing a range of −51 to −101 cal mol(–1) K(–1) (−2.2 to −4.4 mV K(–1)) depending on ligand and metal vertex modifications, demonstrating the potential for rational design of high-entropy electrolytes and a new strategy to overcome theoretical limits on ion solvation reorganization entropy.