Doping heterocyclic polymers

The occurrence of bipolaronic states in the polymer chains promotes optical absorption prior to the n-n gap transitions. In fact, referring to the example (9.30) of the band structure of doped heterocyclic polymers, transitions may occur from the valence band to the bipolaronic levels. These intergap transitions are revealed by changes in the optical absorptions, as shown by Fig. 9.8 which illustrates the typical case of the spectral evolution of polydithienothiophene upon electrochemical doping (Danieli et al., 1985). 

Once deposited as conductive films, the heterocyclic polymers can be repeatedly cycled from the undoped to the doped forms (and vice versa) in electrochemical cells substantially similar to those used for the electropolymerisation reactions. 

For example, the p-doping process of a typical heterocyclic polymer, say polypyrrole, can be reversibly driven in an electrochemical cell by polarising the polymer electrode vs a counterelectrode (say Li) in a suitable electrolyte (say LiC104-PC). Under these circumstances the p-doping redox reaction (9.15) can be described by the scheme ... 

Also the case of polyaniline is somewhat different from that of heterocyclic polymers. It has been proposed (MacDiarmid and Maxfield, 1987) that the doping process does not induce changes in the number of electrons associated with the polymer chain but that the high conductivity of the emeraldine salt polymers is related to a highly symmetrical 7r-delocalized structure. 

Considerable attention is presently devoted to heterocyclic polymers, such as polypyrrole, polythiophene and their derivatives. The kinetics of the electrochemical doping processes of these polymers has been extensively studied in electrochemical cells using non-aqueous electrolytes. 

Brown et al. 3S2) have recently emphasised the role of defect structures in heterocyclic polymers. They point out that the reported doped conductivities of these polymers may vary by as much as six orders of magnitude depending on the preparation procedure. They have applied the laser desorption method, discussed earlier for polyphenylene, to a range of polyheterocycles. Unlike polyphenylene, there was evidence for incomplete desorption and rearrangement of evaporated molecules. The results show that polymers prepared by Grignard coupling vary in their extent of bromination, the nature of the terminal species and the extent of formation of cyclic, polynuclear contaminants. 

Polypyrrole is one of a series of heterocyclic polymers which has attracted much attention due to its characteristic electric and electronic properties. However, there are some problems relating to the physical and material properties associated with its structure. The fundamental structural formulae shown in Fig. 16.5 have been generally proposed for the structures of dedoped and doped polypyrroles, where the aromatic form corresponds to the dedoped state and the quinoid form corresponds to the doped state [9-11]. However, the actual structure appears to be more complicated. At present the exact structure is not known because the polymer is amorphous and insoluble. Consequently, various structures have been proposed for polypyrrole [10]. 

Table 12-3c Comparative nonlinearities, x xxxx(P ) S-heterocycle polymers studied in present report at identical doping (ca. 2.0% with BF ) and concentration (20 mM) in DMF. After Reference [293b-c]. ...

Polyheterocycles. Heterocychc monomers such as pyrrole and thiophene form hiUy conjugated polymers (4) with the potential for doped conductivity when polymerization occurs in the 2, 5 positions as shown in equation 6. The heterocycle monomers can be polymerized by an oxidative coupling mechanism, which can be initiated by either chemical or electrochemical means. Similar methods have been used to synthesize poly(p-phenylenes). 

Polyfarylene vinylene)s form an important class of conducting polymers. Two representative examples of this class of materials will be discussed in some detail here. There are poly(l,4-phenylene vinylcne) (PPV) 1, poly(l,4-thienylene viny-lenc) (PTV) 2 and their derivatives. The polymers are conceptually similar PTV may be considered as a heterocyclic analog of PPV, but has a considerably lowci band gap and exhibits higher conductivities in both its doped and undoped stales. The semiconducting properties of PPV have been shown to be useful in the manufacture of electroluminescent devices, whereas the potential utility of PTV has yet to be fully exploited. This account will provide a review of synthetic approaches to arylene vinylene derivatives and will give details an how the structure of the materials relate to their performance in real devices. 

The degeneracy of the ground state of polyacetylene influences its charge distribution. In fact, upon doping the charges, which in other polymers, such as the heterocyclics, would pair to form bipolarons, are here readily separated to form two positively charged solitons ... 

The field of organic conductors has been extensively reviewed (B-77MI1300, 78ANY25, B-78MI11300, 78MI11302, 79ACR79) and no attempt is made here to describe the synthesis and properties of known materials. Molecular conductors of the doped polymer type have been excluded since these are neither intrinsic conductors nor heterocyclic. A review of the principal requirements for the molecular and crystal structures as currently understood is presented as an introduction to the field of organic conductors. 

Using physical organic chemical rationalizations, we were able to modify the electronic structure of a poly(heterocycle). The result was poly(isothianaphthene) a polymer which is already a semiconductor in the neutral (undoped) state. In the fully doped state, PITN is a transparent conducting polymer. 

Depending on their structure, the polymers containing heterocycles have various applications. For example, poly(furfuryl alcohol) is used in composite materials with fillers such as sand and concrete, in copolymers with formaldehyde, etc. Some of the polymers from this group have special properties such as good electrical conductivity (after appropriate doping). Among these polymers are poly(thiophene-2,5-diyl) and particularly polypyrrole, CAS 109-97-7, (usually in carbon black doped with an organic acid anion). The structure of this polymer is shown below ... 

Polypyrrole Apolymer of pyrrole, afive-membered heterocyclic substance with one nitrogen and four carbon atoms and with two double bonds. The polymer can be prepared via electrochemical polymerization. Polymers thus prepared are doped by electrolyte anion and are electrically conductive. Polypyrrole is used in lightweight secondary batteries, as electromagnetic interference shielding, anodic coatings, photoconductors, solar cells, and transistors. 

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