SOLID-STATE ELECTROCHEMICALLY GENERATED LUMINESCENCE BASED ON SERIAL FROZEN CONCENTRATION GRADIENTS OF RU-III II AND RU-II/I COUPLES IN A MOLTEN RUTHENIUM 2,2'-BIPYRIDINE COMPLEX/
Km. Maness et al., SOLID-STATE ELECTROCHEMICALLY GENERATED LUMINESCENCE BASED ON SERIAL FROZEN CONCENTRATION GRADIENTS OF RU-III II AND RU-II/I COUPLES IN A MOLTEN RUTHENIUM 2,2'-BIPYRIDINE COMPLEX/, Journal of the American Chemical Society, 119(17), 1997, pp. 3987-3993
The attachment of two polyethylene glycol tails (n = 7, MW = 350) to r
uthenium tris(bipyridine) via ester links on the 4,4'-positions of one
of the bipyridine ligands yields a highly viscous (eta approximate to
10(7) cP) molten salt (abbreviated [Ru(bpy)(2)(bpy(CO(2)MePEG350)(2))
](ClO4)(2)) that glasses at ca. -5 degrees C. At room temperature, the
ionic conductivity of the melt is sufficiently high that application
of 2.4 V across the fingers of a Pt interdigitated electrode array (ID
A) coated with the melt leads to the electrolytic development of seria
l concentration gradient microstructures of Ru-III/II and Ru-II/I stat
es. At the intersection of the two concentration gradients, in the int
erior of the coating, reaction between the Ru-III and Ru-I states lead
s to ECL emission with an efficiency of 0.2% photons/electron. Cooling
a concentration gradient-containing film to -20 degrees C under volta
ge bias, so as to preserve the gradient microstructure, yields a film
that has an emission efficiency of 0.1%, a current and light emission
response that rapidly changes with the applied voltage bias, and a dio
de-like current-voltage profile with a ca. 100 rectification ratio.