Polypyrrole polarons

Conjugated polymers with a degenerate ground slate have a slightly different mechanism. As with polypyrrole, polarons and... 

Figure 3.72 Electronic structure diagrams for a polypyrrole chain containing (a) a polaron and (b) a bipolaron (c) The band structure obtained for highly oxidised (33 mol.0,, ) polypyrrole showing the presence of two broad bipolaron bands in the gap. After Bredas et al. (1984).

Hence the authors concluded that bipolarons are the major current carriers on the basis of the calculation showing them to be 0.49 eV more stable than two polarons, with polarons combining where possible to give bipolarons. This paper dominated the interpretation of experiments on polypyrrole for several years until in situ techniques became routinely applied,... 

This means that for a given polypyrrole chain if a unit cell (chosen as 6 monomer units on the basis of the observed maximum doping level of 2 charges per 6 monomer units) already has a polaron on it and a second charge is injected onto the same chain, it is more favourable to form a second polaron on another vacant unit cell than to force spin pairing to give a bipolaron. If, however, all the other unit cells are already occupied, then a bipolaron will be formed in the unit cell, rather than two polarons. 

Table 3.7 Polaron and bipolaron absorptions in polypyrrole (after Christensen and Hamnett, 1991) ...

On the basis of their results the authors concluded lhat the crossover from the neutral to oxidised form of polypyrrole, and vice versa, requires the number of spins to pass through a maximum, i.e. the creation and anihilation of bipolarons involves the passage through the polaron state. They expressed this as a two-step redox reaction ... 

However, while the evidence for the existence of polarons was extremely convincing, that for bipolarons was rather more problematical in that it was largely effectively negative in nature the absence of an absorption peak in the optical spectrum, the absence of a signal in epr studies on the decline of the observed signal. In essence, bipolarons had not been actually observed. This fact was remedied by the work of Christensen and Hamnett (1991) who employed ellipsometry and FTIR to study the growth and electrochemical cycling of polypyrrole in situ in aqueous solution. 

Aida and coworkers developed poly(pyrrole)-containing mesoporous silica films in both hexagonal and lamellar phases.34 The polypyrrole chains are highly constrained and insulated when incorporated within hexagonal mesoscopic channels and the possibility of the polarons recombining into bipolarons is significantly suppressed. In contrast, the two-dimensional lamellar phase affords spatial freedom for electron recombination. 

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. 

The case U = 0 is of special interest. In such a case, making one bipolaron from two polarons does not cost energy. The maximum spin concentration is i, which means that 50% of the boxes possess unpaired spins. This result can be explained as follows. Since (1) at the maximum spin concentration one has q = 1, and (2) placing one or two balls in the box is equivalent, there are four equiprobable cases (1) neutral site (no ball), (2) polaron up, (3) polaron down, and (4) bipolaron (two balls). Two among four of these states are magnetic, which gives for the spin concentration. The room-temperature data for polypyrrole and poly aniline can almost be fitted with U 0, which means that in these compounds polarons and bipolarons would be degenerate. 

Some conjugated polymers, such as polythiophene and polyaniline were synthesized already in the last century [8a,b], It is not surprising that, for example, polyaniline has played a major role in research directed toward synthetic metals because it possesses a relatively stable conducting state and it can be easily prepared by oxidation of aniline, even in laboratories without pronounced synthetic expertise (see section 2.6). It is often overlooked, however, that a representation of, for example, polypyrrole or polyaniline by the idealized structures 1 and 2 does not adequately describe reality, since various structural defects can occur (chart 1). Further, there is not just one polypyrrole, instead each sample made by electrochemical oxidation must be considered as a unique sample, the character of which depends intimately on the conditions of the experiment, such as the nature of the counterion or the current density applied (see section 2.5). Therefore, one would not at all argue against a practical synthesis, if the emphasis is on the active physical function and the commercial value of a material, even if this synthesis is quick and dirty . Care must be exercised, however, to reliably define the molecular structure before one proceeds to develop structure-property relationships and to define characteristic electronic features, such as effective conjugation length or polaron width. 

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