TY - JOUR
T1 - Diffusion-Cooperative Model for Charge Transport by Redox-Active Nonconjugated Polymers
AU - Sato, Kan
AU - Ichinoi, Rieka
AU - Mizukami, Ryusuke
AU - Serikawa, Takuma
AU - Sasaki, Yusuke
AU - Lutkenhaus, Jodie
AU - Nishide, Hiroyuki
AU - Oyaizu, Kenichi
N1 - Funding Information:
This work was partially supported by Grants-in-Aid for Scientific Research (Nos. 24225003, 16K14010, and 17H03072) and the Leading Graduate Program in Science and Engineering, Waseda University, from MEXT, Japan. The research was also partially supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award No. DE-SC0014006 (JLL). K.S. acknowledges the JSPS Fellowship from MEXT, Japan.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2018/1/24
Y1 - 2018/1/24
N2 - Charge transport processes in nonconjugated redox-active polymers with electrolytes were studied using a diffusion-cooperative model. For the first time, we quantitatively rationalized that the limited Brownian motion of the redox centers bound to the polymers resulted in the 103-4-fold decline of the bimolecular and heterogeneous charge transfer rate constants, which had been unexplained for half a century. As a next-generation design, a redox-active supramolecular system with high physical mobility was proposed to achieve the rate constant as high as in free solution system (>107 M-1 s-1) and populated site density (>1 mol/L).
AB - Charge transport processes in nonconjugated redox-active polymers with electrolytes were studied using a diffusion-cooperative model. For the first time, we quantitatively rationalized that the limited Brownian motion of the redox centers bound to the polymers resulted in the 103-4-fold decline of the bimolecular and heterogeneous charge transfer rate constants, which had been unexplained for half a century. As a next-generation design, a redox-active supramolecular system with high physical mobility was proposed to achieve the rate constant as high as in free solution system (>107 M-1 s-1) and populated site density (>1 mol/L).
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U2 - 10.1021/jacs.7b11272
DO - 10.1021/jacs.7b11272
M3 - Article
C2 - 29276830
AN - SCOPUS:85041178648
SN - 0002-7863
VL - 140
SP - 1049
EP - 1056
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -