Integrating redox-response in crown ethers by disulfide incorporation: a computational approach

• Published in: Structural chemistry Vol. 32; no. 5; pp. 1833 - 1842
• Main Authors: Jayasree, Elambalassery G., Sukumar, Chinthu
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.10.2021; Springer Nature B.V
• Subjects: Alkali metals; Chemistry; Chemistry and Materials Science; Computer Applications in Chemistry; Crown ethers; Electron affinity; Original Research; Physical Chemistry; Redox reactions; Supramolecular compounds; Theoretical and Computational Chemistry; Vapor phases; Thiacrown ether; Thiacalixarene; AEA; Binding energy; Disulfide; Conformational analysis
• ISSN: 1040-0400; 1572-9001
• DOI: 10.1007/s11224-021-01761-7

Reducing properties are investigated for the minimum energy conformers of selected thiacrown systems with redox-responsive disulfide linkage. The adiabatic electron affinity values of the investigated host systems in the gas phase lie in a range that makes them capable to undergo reversible redox reactions. In water, these show a high propensity to get reduced. Their binding energy with different alkali metal ions (Li + , Na + , and K + ) is also determined under gas and aqueous phase conditions. The computational analysis reveals the weak metal binding interactions of disulfide systems than the parent thiacrown ethers. Such weak interaction energies in host-guest complexes indicate the possibility of reversible complexation-decomplexation. This assumably assists the fast release of guest molecules from the disulfide systems in response to the redox stimuli. Possibilities of incorporating such disulfide incorporated moieties in thiacalixarenes are also discussed. The results discussed in the present work are valuable for further development in the practical applications of crown ether–based host materials.