Use of a Wedge Scheme to Describe Intermolecular Proton-Coupled Electron Transfer through the H-bond Complex Formed Between a Phenylenediamine-Based Urea and 1,8-Naphthyridine
| Autor: | An T. Pham, Diane K. Smith, Mario Cedano, Bryan T. Tamashiro |
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| Rok vydání: | 2015 |
| Předmět: |
Chemistry
Hydrogen bond Stereochemistry Intermolecular force Photochemistry Surfaces Coatings and Films Electronic Optical and Magnetic Materials Solvent Electron transfer chemistry.chemical_compound General Energy Urea Physical and Theoretical Chemistry Cyclic voltammetry Proton-coupled electron transfer Voltammetry |
| Zdroj: | The Journal of Physical Chemistry C. 119:12865-12874 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/acs.jpcc.5b03357 |
| Popis: | Recently we introduced the “wedge scheme” as a convenient means to include H-bonded intermediates in an overall proton-coupled electron transfer (PCET) mechanism by showing that it can nicely explain the unusual solvent- and concentration-dependent voltammetry of a phenylenediamine-based urea, U(H)H. This compound undergoes an apparent 1 e– reversible oxidation in CH2Cl2 that actually corresponds to 2 e– oxidation of half of the ureas to the quinoidal cation accompanied by transfer of a H+ and deactivation of the other half of the ureas. The reversibility of the process is due to the second electron transfer and proton transfer proceeding through a H-bond complex between the oxidized urea and the dimethylamino group on another urea. In this study the effect of adding 1,8-naphthyridine, naph, which H-bonds to the U(H)H in its reduced state, is examined using cyclic voltammetry. Addition of naph causes both an increase in the current of the reversible U(H)H cyclic voltammetric wave as well as the appearance... |
| Databáze: | OpenAIRE |
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