Redox polymers that are both reducible and oxidizable can be
driven to disproportionate when sufficiently
large potential biases are applied across the polymer. Moreover,
if the polymer is ionic in its original form,
this disproportionation can be driven to occur without changes in the
net ionic content of the polymer (the
so-called ion-blocked case). In the first part of this paper we
provide a theoretical description of the steady-state redox gradients that are established in ion-blocked multivalent
redox polymers under voltage bias. In
the second part of the paper a similar treatment is developed for
ion-blocked redox polymer bilayers. The
bilayer systems considered are ones in which the oxidation reaction is
assumed to be sequestered entirely in
one of the polymer layers and the reduction entirely in the other.
The two types of polymer systems are
compared. Also, comparisons are made between the predicted
behavior under ion-blocked and non-ion-blocked conditions. Finally the potential advantages of bilayer
polymers in applications such as solid-state
electrochemically generated luminescence are discussed.
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