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Polymer chain diffusion within a hydrated polyelectrolyte complex, PEC, has been measured using an ultrathin film format prepared by the layer-by-layer method. Isotopically labeled self-exchange of deuterated poly(styrene sulfonate), dPSS, with undeuterated PSS of the same narrow molecular weight distribution permitted reliable estimates of whole-molecule diffusion coefficients, D. Narrow molecular weight distribution poly(diallyldimethylammonium), PDADMA, was used as the polycation for the PEC. Extensive pretreatment of starting films was undertaken to remove residual stress, anisotropy, and layering. PSS/PDADMA “multilayers,” PEMUs, thin enough to provide substantial exchange of polyelectrolyte, even with diffusion coefficients as low as 10–16 cm2 s–1, as a function of salt concentration and temperature were measured for this PEC, which has a glass-transition temperature, Tg, close to room temperature. Two molecular weights of dPSS, about 15 and 100 kDa, presumed to be below and above the entanglement molecular weight, respectively, both diffused faster at higher temperatures with respective activation energies, Ea, of about 21 and 53 kJ mol–1, the latter about the same as Ea for the place exchange between two pairs of PSS:PDADMA. Studies of the linear viscoelastic response of macroscopic PECs showed a difference of about 8 °C in the Tg of the two lengths of PSS complexed with the same PDADMA. Increasing concentrations of NaCl influenced D of 100 kDa PSS but not 15 kDa PSS at room temperature. D was faster in the region of the film near the solution interface, again attributed to a lower Tg caused by greater water content at this interface. 

Pinhole-free ultrathin films of polyelectrolyte complex assembled using layer-by-layer deposition were used to evaluate electron transfer from a redox species in solution to an electrode over the distance range 1 to 9 nm. Over this thickness, the polyelectrolytes employed wet the surface and the polymer molecules flatten to less than their equilibrium size in 3-dimensions. A decay constant β for current as a function of distance of about 0.3 nm-1 placed this system in the regime expected for multistep hopping versus a one-step tunneling event. Discreet hopping sites within the films were identified as ferrocyanide ions with an equilibrium concentration of 0.032 M and an average separation of 3.7 nm. The Butler-Volmer (BV) expression for electron transfer as a function of overpotential was modified by distributing the applied voltage evenly amongst the hopping sites. This modified BV expression fit both the distance dependence and the applied potential dependence well, wherein the only freely adjustable parameter was the electron transfer coefficient. The finding that β is simply the inverse of the hopping range is consistent with previous conclusions that electrons within conjugated molecule sites are delocalized, or, for non-conjugated systems, spread over more than one repeat unit by lattice distortions