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Synthesis and redox characterization of phosphazene terpolymers with pendant ferrocene groups

Publication ,  Journal Article
Kraiter, DC; Wisian-Neilson, P; Zhang, C; Crumbliss, AL
Published in: Macromolecules
May 8, 2012

The synthesis, characterization, and electrochemistry of a series of five ferrocene-containing phosphazene terpolymers derived from the poly(alkyl/arylphosphazene) random copolymer, [(Ph)(Me)PN] 0.6[Me 2PN] 0.4, 5, are described. The new terpolymers, 6 {[(Ph)(Me)PN] 0.6[Me 2PN] 0.4} x{[(Ph) {FcCH(OH)CH 2}PN] 0.6[(Me){FcCH(OH)CH 2}PN] 0.4} y, where Fc = (Ε 5-C 5H 5)Fe(Ε 5-C 5H 4) (6a, x = 0.50, y = 0.50; 6b, x = 0.60, y = 0.40; 6c, x = 0.65, y = 0.35; 6d, x = 0.70, y = 0.30; and 6e, x = 0.85, y = 0.15), were prepared by deprotonation-substitution reactions and were characterized by NMR spectroscopy, elemental analyses, gel permeation chromatography, and thermal analysis. The redox properties are described by electrochemistry performed in dichloromethane solutions and evaporatively cast films. In solution, cyclic voltammograms of these polymers display a one-electron reversible (ΔE p ca. 60 mV) wave in the range of 433-492 mV (vs Ag/AgCl) combined with adsorption, depending on the degree of substitution with Fc groups. The adsorption of the oxidized polymer on a Pt electrode was established using double potential step chronocoulometry. A mechanism for electron diffusion is discussed in terms of physical diffusion and electron hopping. The apparent electron diffusion coefficient was calculated from a combination method of chronocoulometry and rotating disk voltammetry. The observed diffusion coefficients are larger than those of corresponding polymers that contain a larger number of phenyl side groups and are largely independent of the degree of Fc substitution. A second, less intense wave about 220-250 mV more positive than the main wave was also observed and attributed to the internal oxidation of a secondary alcohol to a ketone group. Reversible electrochemical behavior of surface bound species is also observed for the ferrocene/ferricenium couple in evaporatively cast films of the phosphazene polymers. Cyclic voltammetry and chronoamperometry were used to determine the electrochemical characteristics and charge transport quantities (and CD 01/2) of the terpolymer films. These quantities vary with the degree of substitution with Fc groups of the phosphazene terpolymers. © 2012 American Chemical Society.

Duke Scholars

Published In

Macromolecules

DOI

ISSN

0024-9297

Publication Date

May 8, 2012

Volume

45

Issue

9

Start / End Page

3658 / 3668

Related Subject Headings

  • Polymers
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
 

Citation

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Kraiter, D. C., Wisian-Neilson, P., Zhang, C., & Crumbliss, A. L. (2012). Synthesis and redox characterization of phosphazene terpolymers with pendant ferrocene groups. Macromolecules, 45(9), 3658–3668. https://doi.org/10.1021/ma300336e
Kraiter, D. C., P. Wisian-Neilson, C. Zhang, and A. L. Crumbliss. “Synthesis and redox characterization of phosphazene terpolymers with pendant ferrocene groups.” Macromolecules 45, no. 9 (May 8, 2012): 3658–68. https://doi.org/10.1021/ma300336e.
Kraiter DC, Wisian-Neilson P, Zhang C, Crumbliss AL. Synthesis and redox characterization of phosphazene terpolymers with pendant ferrocene groups. Macromolecules. 2012 May 8;45(9):3658–68.
Kraiter, D. C., et al. “Synthesis and redox characterization of phosphazene terpolymers with pendant ferrocene groups.” Macromolecules, vol. 45, no. 9, May 2012, pp. 3658–68. Scopus, doi:10.1021/ma300336e.
Kraiter DC, Wisian-Neilson P, Zhang C, Crumbliss AL. Synthesis and redox characterization of phosphazene terpolymers with pendant ferrocene groups. Macromolecules. 2012 May 8;45(9):3658–3668.
Journal cover image

Published In

Macromolecules

DOI

ISSN

0024-9297

Publication Date

May 8, 2012

Volume

45

Issue

9

Start / End Page

3658 / 3668

Related Subject Headings

  • Polymers
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences