Beyond the Hammett Effect: Using Strain to Alter the Landscape of Electrochemical Potentials

Matthew D. Casselman, Corrine F. Elliott, Subrahmanyam Modekrutti, Peter L. Zhang, Sean R. Parkin, Chad Risko, Susan A. Odom

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

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.

Original languageEnglish
Pages (from-to)2142-2146
Number of pages5
JournalChemPhysChem
Volume18
Issue number16
DOIs
StatePublished - Aug 18 2017

Bibliographical note

Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

  • conjugation
  • electronic structure
  • redox chemistry
  • strained molecules
  • substituent effects

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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