title: What Makes Oxidized N-Acylanthranilamides Stable?
abstract: Oligoamides composed of anthranilic acid derivatives present a promising choice for mediating long-range charge transfer and controlling its directionality. Hole hopping, modulated by the anthranilamide (Aa) permanent dipoles, provides a plausible means for such rectified long-range charge transduction. All aliphatic and most aromatic amides, however, decompose upon oxidation, rendering them unacceptable for hole-hopping pathways. We, therefore, employ electrochemical and computational analysis to examine how to suppress oxidative degradation and stabilize the radical cations of N-acylated Aa derivatives. Our findings reveal two requirements for attaining long-lived radical cations of these aromatic amides: (1) keeping the reduction potentials for oxidizing the Aa residues under about 1.4 V vs SCE and (2) adding an electron-donating group para to the N-terminal amide of the aromatic ring, which prevents the electron spin density of the radical cation from extending over the C-terminal amide. These findings provide essential information for the design of hole-transfer amides.
authors: Department of Chemistry, University of California , Riverside, California 92521, United States.
authors: Eli M
authors: EM
authors: Espinoza
authors: Department of Bioengineering, University of California , Riverside, California 92521, United States.
authors: Jillian M
authors: JM
authors: Larsen
authors: Department of Chemistry, University of California , Riverside, California 92521, United States.|Department of Bioengineering, University of California , Riverside, California 92521, United States.|Department of Biochemistry, University of California , Riverside, California 92521, United States.|Materials Science and Engineering Program, University of California , Riverside, California 92521, United States.
authors: Valentine I
authors: VI
authors: Vullev
mesh_terms: D055664:Electrochemical Techniques; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008958:Models, Molecular; D010084:Oxidation-Reduction; D062367:ortho-Aminobenzoates / Q000737:chemistry*
chemical_list: D062367:ortho-Aminobenzoates; C000219:anthranilamide