Electrochemical and resonance Raman spectroscopic characterization of polyaniline and polyaniline-metalloporphyrin electrode films

Journal Article · Wed Aug 12 04:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00263a009· OSTI ID:5418747

Macor, K A; Su, Y O; Miller, L A; Spiro, T G

Characteristics of electropolymerized aniline and metallotetrakis(2-aminophenyl)porphine (metallo-2-TAPP) films are described. Aniline polymerized from methylene chloride solution by oxidative cycling at a platinum electrode shows characteristic two-wave or one-wave cycle voltammograms when scanned in pH 1 aqueous solution, depending on the positive potential sweep limit. Similar CV's are produced when the solution contains metallo-TAPP's, except that additional waves associated with metalloporphyrin redox processes are superimposed. The absorption spectra of the films formed on transparent SnO/sub 2/ electrodes showed characteristic metalloporphyrin Soret absorption bands, with red shifts relative to the solution spectra, due to axial coordination and/or excitonic effects. Raman spectra are reported for films polymerized from aniline, aniline-/sup 15/N, aniline-N,N-d/sub 2/, and aniline-d/sub 5/. The replacement of strong aniline bands at 1000 and 1029 cm/sup -1/ with bands in the films at 1190 and 1200 cm/sup -1/ is diagnostic for para-substituted aniline units in the polymer. The films show a strong /sup 15/N-sensitive band at 1525 cm/sup -1/, which is absent in aniline but present in p-phenylenediamine. Thus the electrochemical and spectroscopic characteristics of the TAPP films are fully consistent with unmodified porphyrin units contained within a polyaniline polymer. Porphyrin radical cation formation is insufficient to induce polymerization if the potential is lower than that required for aniline oxidation. Films containing Mn(2-TAPP) show a Mn/sup 3+/2+/ wave at approx.-0.2 V, negative of the polyaniline redox waves, when the electrode is in contact with nonaqueous or aqueous electrolyte. The metalloporphyrin redox process does not require electronic conduction through the polyaniline framework. 21 references. 8 figures.

• Research Organization: Princeton Univ., NJ
• DOE Contract Number: AC02-81ER10861
• OSTI ID: 5418747
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:16; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMINES
ANILINE
AROMATICS
CARBOXYLIC ACIDS
CHALCOGENIDES
CHEMISTRY
DATA
ELECTROCHEMISTRY
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POLYMERS
PORPHYRINS
RAMAN SPECTRA
SPECTRA
TIN COMPOUNDS
TIN OXIDES