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Beyond the Hammett Effect: Using Strain to Alter the Landscape of Electrochemical Potentials
- Source :
- Chemphyschem : a European journal of chemical physics and physical chemistry. 18(16)
- Publication Year :
- 2017
-
Abstract
- The substitution of sterically bulky groups at precise locations along the periphery of fused-ring aromatic systems is demonstrated to increase electrochemical oxidation potentials by preventing relaxation events in the oxidized state. Phenothiazines, which undergo significant geometric relaxation upon oxidation, are used as fused-ring models to showcase that electron-donating methyl groups, which would generally be expected to lower oxidation potential, can lead to increased oxidation potentials when used as the steric drivers. Reduction events remain inaccessible through this molecular design route, a critical characteristic for electrochemical systems where high oxidation potentials are required and in which reductive decomposition must be prevented, as in high-voltage lithium-ion batteries. This study reveals a new avenue to alter the redox characteristics of fused-ring systems that find wide use as electroactive elements across a number of developing technologies.
- Subjects :
- Steric effects
Strain (chemistry)
Chemistry
Relaxation (NMR)
02 engineering and technology
010402 general chemistry
021001 nanoscience & nanotechnology
Electrochemistry
Photochemistry
01 natural sciences
Redox
Atomic and Molecular Physics, and Optics
0104 chemical sciences
Organic chemistry
Reductive decomposition
Physical and Theoretical Chemistry
0210 nano-technology
Subjects
Details
- ISSN :
- 14397641
- Volume :
- 18
- Issue :
- 16
- Database :
- OpenAIRE
- Journal :
- Chemphyschem : a European journal of chemical physics and physical chemistry
- Accession number :
- edsair.doi.dedup.....4590b368101c939838fd8b62f684e564