Diffusion-cooperative Model for Charge Transport by Redox-active Non-conjugated Polymers

Charge transport processes in non-conjugated 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-1s-1) and populated site density (> 1 mol/L).