Polythiophenes oligomers

Figure 9.4. Molecular orbital interpretation of polaron- and bipolaron-like charge state formation in polythiophene oligomers.

Polythiophene can be synthesized by electrochemical polymerization or chemical oxidation of the monomer. A large number of substituted polythiophenes have been prepared, with the properties of the polymer depending on the nature of the substituent group. Oligomers of polythiophene such as (a-sexithienyl thiophene) can be prepared by oxidative linking of smaller thiophene units (33). These oligomers can be sublimed in vacuum to create polymer thin films for use in organic-based transistors. 

The polaron is characterized by the reversal of bond alternation, which, in the case of polythiophene, extends over five monomer units [30-32], and the appearance of two localized stales in the band gap ). These states have been indeed observed by UV-V1S absorption of both oligomers and polymers, in solution [33— 40] and in the solid state [41-45]. 

Several n-conjugated polymers and oligomers (polyacetylene, several polythiophenes, Ooct-OPV5 oligomers, and phthalocyanines) have been used for the active layer of the transistors. 

Many other air-stable conducting polymers followed (Fig. 12.10) polypyrrole, polythiophene, polyaniline (which had been known since the nineteenth century as "aniline black"), and so on (Table 12.4). These polymers are semiconducting, not metallic, when "doped" with electron donors or acceptors the individual conjugated chains have finite length, so the conductivity is limited by chain-to-chain hopping. Also, if the individual strands exceed four or so oligomers, the conjugation tends to decrease, as the strand tends to adopt a screw-type distortion. The transport within each strand is attributed to polarons and bipolarons. 

Figure 14 shows the unpolarized absorption spectra of films of polythiophene [124] and its hexamer a-sexithienyl [125]. The hexamer solution spectrum is at almost the same energy. As in Fig. 12a, the oligomer shows structure on its rising edge, and the polymer spectrum is structureless. But in Fig. 14 the absorption thresholds differ by = 0.2 eV only one would then say that conjugation extends in PT over only about six monomers. One could show similar data for many other CPs. 

In fact, an exciton approach was applied to carotenoids many years ago [209]. This approach was revived recently and applied to polythiophene solutions and oligomers [210]. The experimental spectroscopic results are easily accounted for, so this type of work should be continued, especially if excitons turn out to be quite strongly bound in other polymers of practical interest, such as PPV. It will also be needed to understand the vibronic interactions apparent in some spectra. 

Toward an understanding of the conduction properties of polythiophenes (26) and polypyrroles (25) a large number of soluble oligomers has been prepared. Oligothiophenes, indeed, represent the most common model compounds for electrically conducting polymers [149]. Thereby, lower oligomers... 

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