Solid-state voltammetry and self-diffusion dynamics of a linear monotagged redox polymer:. omega. -ferrocenecarboxamido-. alpha. -methoxypoly(ethylene oxide)
- Univ. of North Carolina, Chapel Hill (USA)
The synthesized title labeled polymer, Fc-MePEG, MW = 2,590, analytically characterized as free of unlabeled PEO and of ferrocene monomer, dissolves LiClO{sub 4} electrolyte and in dry undiluted form is both a polymer electrolyte and an electroactive phase. The microelectrode solid-state voltammetrically measured, center-of-mass self-diffusion coefficient for Fc-MePEG in its polymer let, 1.3 {times} 10{sup {minus}8} cm{sup 2}/s at 62{degree}C, is 3.4 times smaller than that for ferrocene monomer dissolved in unlabeled (MW = 2,380) Me{sub 2}PEG. Electron hopping is estimated to contribute less than 10% to the diffusion rates of Fc-MePEG and of monomer dissolved at 40-50 mM concentrations in unlabeled Me{sub 2}PEG. At room temperature, where Fc-MePEG and Me{sub 2}PEG are waxy solids, D{sub Fc-MePEG} is 3.9 {times} 10{sup {minus}12} cm{sup 2}/s, 12 times smaller than that of monomer ferrocene, in Me{sub 2}PEG, and which corresponds to a diffusion pathlength of ca. 110-200 nm during the electrochemical experiment. Dissolved in CH{sub 3}CN or CH{sub 2}Cl{sub 2}, Fe-MePEG diffuses 8-10 times more slowly than ferrocene monomer which is consistent with transport as a random coiled sphere.
- DOE Contract Number:
- FG05-87ER13675
- OSTI ID:
- 6635982
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:10; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
COMPLEXES
DATA
DATA ANALYSIS
DIENES
DIFFUSION
DYNAMICS
EXPERIMENTAL DATA
FERROCENE
HYDROCARBONS
INFORMATION
IRON COMPLEXES
MEASURING INSTRUMENTS
MEASURING METHODS
MECHANICS
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
POLYMERS
SELF-DIFFUSION
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY