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Electro-oxidative polymerization and spectroscopic characterization of novel amide polymers using diphenylamine coupling

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/1.1838694· OSTI ID:653522
; ;  [1]
  1. Auburn Univ., AL (United States). Dept. of Chemistry

The authors have electropolymerized 1,1{prime}-bis[[p-phenylamino(phenyl)]amido-]ferrocene from CH{sub 3}CN, tetrahydrofuran (THF), and CH{sub 2}Cl{sub 2} to form an alternating main chain polymer of diphenylbenzidine and ferrocene. As a comparison, the authors have electropolymerized 1,4 bis[[p-phenylamino(phenyl)]amido-]benzene which lacks the electrochemical response of the ferrocene group. In nonaqueous solvents, the diphenylbenzidine group shows two reversible le{sup {minus}} oxidations. The second le{sup {minus}} oxidation of the diphenylbenzidine overlaps with the le{sup {minus}} oxidation of the ferrocene group at 0.88 V vs. Ag/AgCl in CH{sub 2}Cl{sub 2}. The electrochemistry of the polymer film in aqueous acid shows two le{sup {minus}} waves consistent with oxidation of the diphenylbenzidine group to the cation and then the dication. The spectroelectrochemistry of both polymer films show broad, low-energy, near-IR bands in aprotic solvents such as CH{sub 2}Cl{sub 2}, THF, and CH{sub 3}CN and aqueous solutions with pH < 3. The authors assign these bands to intermolecular {pi} stacking of the protonated diphenylbenzidinium cations. The electrochemistry of both materials is chemically reversible and forms the basis for electrochromic and redox applications.

Sponsoring Organization:
USDOE, Washington, DC (United States)
OSTI ID:
653522
Journal Information:
Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 8 Vol. 145; ISSN JESOAN; ISSN 0013-4651
Country of Publication:
United States
Language:
English

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