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Redox Control of the Binding Modes of an Organic Receptor
- Publication Year :
- 2015
- Publisher :
- American Chemical Society, 2015.
-
Abstract
- The modulation of noncovalent bonding interactions by redox processes is a central theme in the fundamental understanding of biological systems as well as being ripe for exploitation in supramolecular science. In the context of host-guest systems, we demonstrate in this article how the formation of inclusion complexes can be controlled by manipulating the redox potential of a cyclophane. The four-electron reduction of cyclobis(paraquat-p-phenylene) to its neutral form results in altering its binding properties while heralding a significant change in its stereoelectronic behavior. Quantum mechanics calculations provide the energetics for the formation of the inclusion complexes between the cyclophane in its various redox states with a variety of guest molecules, ranging from electron-poor to electron-rich. The electron-donating properties displayed by the cyclophane were investigated by probing the interaction of this host with electron-poor guests, and the formation of inclusion complexes was confirmed by single-crystal X-ray diffraction analysis. The dramatic change in the binding mode depending on the redox state of the cyclophane leads to (i) aromatic donor-acceptor interactions in its fully oxidized form and (ii) van der Waals interactions when the cyclophane is fully reduced. These findings lay the foundation for the potential use of this class of cyclophane in various arenas, all the way from molecular electronics to catalysis, by virtue of its electronic properties. The extension of the concept presented herein into the realm of mechanically interlocked molecules will lead to the investigation of novel structures with redox control being expressed over the relative geometries of their components.
- Subjects :
- Models, Molecular
Paraquat
Stereochemistry
Radical
Supramolecular chemistry
Context (language use)
macromolecular substances
Crystallography, X-Ray
Biochemistry
Redox
Catalysis
chemistry.chemical_compound
Electron transfer
Colloid and Surface Chemistry
Piperidines
Computational chemistry
mechanically interlocked molecules, radical chemistry, template directed synthesis, electron-transfer, donor-acceptor, supramolecular assemblies
Ethers, Cyclic
Molecule
radical chemistry
Binding site
mechanically interlocked molecules
Binding Sites
Molecular Structure
General Chemistry
electron-transfer
chemistry
donor-acceptor
Quantum Theory
Oxidation-Reduction
template directed synthesis
Cyclophane
supramolecular assemblies
Subjects
Details
- Language :
- English
- Database :
- OpenAIRE
- Accession number :
- edsair.doi.dedup.....af8dae133829d2b41d0327a24802c5f9