Charge percolation in redox-active thin membrane hybrids of mesoporous silica and poly(viologens).

This work reports the fabrication of redox-active films of oligomeric and molecular viologens and mesoporous silica via the infiltration method. Pore-ellipsometry and UV-vis confirm that low-molecular-weight poly(viologens) in solution are able to enter the mesoporous structure, in contrast to high-molecular weight polymers that adsorb only on top of the film. Cyclic voltammetry shows that viologens are able to reach the bottom of the pores and access the electrode/film interface. However, the number of viologen sites that can be accessed by cyclic voltammetry at 50 mV s-1 is only a tenth of the total viologen population determined by UV-vis and pore-ellipsometry. The effect is ascribed to the very small apparent diffusion coefficient for charge transport within the film (Dapp < 10-12 cm2 s-1). A theoretical model is put forward to describe charge transport via the electron-hopping mechanism for redox sites randomly adsorbed on the inner walls of the pores. Our model predicts that the threshold of charge percolation occurs for viologen surface coverages close to those observed in our experiments; therefore, the low fraction of electrochemically addressable viologens is ascribed to inefficient charge percolation via the electron-hopping mechanism.