The electronic conductivity and electrogenerated
chemiluminescence (ECL) of thin, electropolymerized
films of the fixed-site redox polymer
poly[Ru(vbpy)3](PF6)2
(vbpy = 4-vinyl-4‘-methyl-2,2‘-bipyridine) on Pt
interdigitated array electrodes were examined for both solvent-swollen
and dry films. In both cases emission arose
from *Ru2+ produced via the electron-transfer reaction
between Ru3+ and Ru1+ states within the
film (Ru = Ru(vbpy)3). Dry films contained fixed concentration
gradients of Ru3+, Ru2+, and
Ru1+ states which were first introduced
in an acetonitrile-swollen film via the constant potential oxidation
and reduction of Ru2+ at opposing IDA
fingers.
The gradients were then immbolized by drying and cooling the film
while retaining the inter-electrode bias (2.6 V).
The resulting dried and cooled films responded rapidly to changes
in voltage bias and exhibited diode-like
characteristics, conducting and emitting light at biases ≥2.6 V and
undergoing a reverse bias breakdown current,
unassociated with light emission, at ca. −5.5 V. At 0 °C the
optimum quantum efficiency of solid-state ECL emission
(φECL) was similar to that in solvent-swollen films:
0.0003 photon/electron. In contrast to the dry films,
solvent-swollen films were slow to respond to changes in voltage bias and did
not exhibit diode-like behavior.
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