Conjugated polymers charge transfer processes

Abdou MSA, Orfino FP, Son S, Holdcroft S (1997) Interaction of oxygen with conjugated polymers charge transfer complex formation with poly(3-alkylthiophenes). J Am Chem Soc 119 4518-4524 Aldiss M (1989) Inherently conducting polymers processing, fabrication, applications, hmitations. Noyes Data Corporation, Park Ridge... 

The ruthenium oligothienylacetylide complexes 93 (Chart 5.30) [106] and the oligothienylferrocene complexes 94a and b were electrochemically polymerized [107]. The voltammetry of poly-94a and poly-94b films contains redox waves due to both the ferrocene and backbone redox couples. Low-energy absorption bands appear upon oxidation of both the Fe centers and the conjugated backbone in the UV-Vis-near-IR spectrum of the films, and these have been attributed to charge-transfer processes. The poor solubility of 94b prevents electropolymerization at room temperature however, polymer films can be prepared at elevated temperatures. Electropolymerization of 95, in which hexyl chains have been added to increase the monomer solubility, has also been reported [108]. 

Section 6.5 is dedicated to a theoretical characterization of the nature of the interfaces between a conjugated polymer and a metal as typically encountered within the architecture of an organic light-emitting diode. In the present case, we pay particular attention to the interface formed between model compounds of polythiophene and aluminum, which is a metal widely used as the LED cathode due to its high environmental stability. It is shown that covalent bonds are created between the conjugated backbone and the aluminum atoms, in contrast to the situation observed with calcium atoms for which charge transfer processes take place [35] the formation of these covalent bonds is accompanied by the appearance of new active vibrational modes, as seen from theoretical simulations of vibrational spectra. 

Bredas J-L, Beljonne D, Coropceanu V, Comil J (2004) Charge-transfer and energy-transfer processes in 7i-conjugated oligomers and polymers a molecular picture. Chem Rev 104 4971-5003... 

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