3 years ago

Diffusion-Cooperative Model for Charge Transport by Redox-Active Nonconjugated Polymers

Model for Charge Transport by
Redox-Active Nonconjugated Polymers
Kenichi Oyaizu, Jodie Lutkenhaus, Takuma Serikawa, Ryusuke Mizukami, Rieka Ichinoi, Yusuke Sasaki, Kan Sato, Hiroyuki Nishide
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).

Publisher URL: http://dx.doi.org/10.1021/jacs.7b11272

DOI: 10.1021/jacs.7b11272

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