Polythiophene, alkyl-substituted

Thiophene polymers, in particular, alkyl-substituted polythiophenes (PTH), are some of the conducting polymers being most actively investigated at present. This fact is attributable to their high degree of processability, environmental stability [49, 50] and, in some cases, ability to exhibit reversible electrochrom-ism [51] and thermochromism [52]. Another important family of sulfur-... 

Order-disorder, or rod-to-coil , transitions in dilute solution have been reported for polydiacetylenes (2, 5-11), polysilylenes (12-15), and alkyl-substituted polythiophenes (16). The interpretation of the experimental observations has been the subject of considerable controversy with respect to whether the observations represent a single-polymer-molecule phenomenon or a many-chain aggregation or precipitation process (3-16). Our own experimental evidence (12, 13) and that of others (5-8, 10, 16) weigh heavily in favor of the single-chain interpretation. In our theoretical interpretation, we will assume that the order-disorder transitions observed in dilute pol-ysilylene solutions represent equilibrium, single-chain phenomena. 

Besides the oligomers based on thiophene units, polymers with similar backbones have become very represented in literature since the late nineties. Due to the fact that pure thiophene polymer chains without any substitutes show very poor solubility, mainly alkyl substituted polythiophenes are used. 

In this section, the structural studies of polythiophenes are reviewed the influence of structure on properties is considered in subsequent sections. The description of polythiophene structures include the alkyl-substituted thiophenes, such as poly(3-alkylthiophenes) (P3ATh s). 

The him morphology of electrochemically prepared polythiophene has been shown in numerous studies to be almost identical to that commonly observed for polypyrrole (described in Chapter 2). A nodular surface is observed for both unsubstituted and 3-alkyl substituted thiophenes.92 As with PPy, the electrochemical preparation of PTh at higher current densities produced rougher surface morphologies. The similarity in morphologies suggest a similar growth mechanism for electrochemically polymerized PPy and PTh. 

As with polyanilines, polythiophenes can either be prepared directly by electropolymerization, or by casting from solutions (for alkyl-substituted thiophenes). Most interest has focused on the latter because of their improved mechanical properties compared with those of electrochemically prepared films. The factors influencing the mechanical properties of PTh s are reviewed in this section. 

The interaction of CPs with different organic vapors is still a matter of discussion. Indeed, similar experiments performed with resistive CP-based sensors have reported that the change in electrical resistance occurring at alkyl-substituted polypyrroles and polythiophenes exposed to alcohols, esters, alkenes, and some aromatic... 

Fig. 3.2. The four possible conformational triads of alkyl substituted polythiophene, where R is the alkyl functionalizing group [20]. The HT-HT conformation has been found to stack the best. These triads can be monitored using NMR spectroscopy to determine the degree of regioregularity in a sample.

As in the cases of pyrrole and aniline polymers, both chemical and electrochemical procedures have been employed in the synthesis of polythiophene (PTH) and its derivatives. The thiophene polymers exhibit remarkable stability in air and water [119], The alkyl-substituted derivatives also exhibit a high degree of processability [120,121]. PTH has also been synthesized from bithiophane (the dimer) or terthiophene (the trimer). The resulting poly(2,2 -bithiophene) (PbTH) and polyterthiophene (PtTH) are more ordered than PTH and appear to have the same basic structure as the starting monomer [117,122],... 

There were however few exceptions—the most important being polythiophene and poly(p-phenylene vinylene). It was demonstrated [4,5] that in the case of polythiophene, the substitution of hydrogen in the 3 position of the thiophene ring, by an alkyl group longer than the propyl group, renders the polymer soluble in common solvents and the decrease of conductivity in the doped state, caused by the functionalization is rather minor. Since the initial work of Elsenbaumer [4,5] hundreds of papers devoted to soluble polythiophene derivatives have been published. 

The refractive index and the rugosity, i.e. the roughness of the sample, were studied by optical transmission in the transport region of unsubstituted and j8-alkyl substituted a6T [222]. The refractive index is n= 1.904 for a6T, n= 1.763 for diethyl-substituted 6T, and n= 1.688 for didecyl-substituted a6T, the rugosity of 6T is determined as 44.1 run which is much higher than in amorphous silicon with 16.9 nm. The latter is attributed to the large thickness of the film (1.4 pm) and to the microscopic molecular structure in the film. The differences of the refractive index can be simply explained by the lower density of the alkyl-substituted films. This is also a valid explanation for the lower refractive index of polythiophene and the higher one of amorphous Si. 

The phenomenon is found with many, but not all substituted polythiophenes. Studies of 3,3 -di-alkyl-substituted polythiophenes revealed no temperature-induced colour change [17]. But many other structures will give thermochromism and solvatochromism. Polythiophenes substituted both with alkoxy and alkyl side chains may show it both purely amorphous and partially crystalline polythiophenes show it short and long-chain polymers may show it both regular and irregular polymers show it (see Figure 15.1),... 

In most cases, stability and oxidation potential issues mean that polythiophenes are prepared, studied, and used in non-aqueous media, and the influence of the solvent can be significant. The extent of solvent swelling is determined by polymer-solvent interactions, which can be manipulated both by choice of solvent and introduction of substituents, here in the 3- and 4-positions. Electropolymerization of alkyl-substituted thiophenes provides good examples of the effects one can observe. EQCM (with PBD) measurements of potentiodynamic deposition from acetonitrile benzonitrile (4 1) of poly(didodecylterthiophene) (with the substituents in the 3, 4 - or 3,3"-positions) showed that film deposition occurred primarily during the reductive half-cycle, in the form of short chain oligomers of the... 

The theoretical simulations we have reviewed here are consistent with the changes in optical absorption observed experimentally when the degree of interchain order is improved in alkyl-substituted polythiophene derivatives [60,61]. The CMS spectrum of RR-P3HT exhibits a pronounced charge-induced... 

FET applications of thiophene-based materials have a two-decade history. Pioneering work was conducted by Koezuka and co-workers [33], The device utilized electrochemically synthesized polythiophene as the channel layer, its mobility being 10 cm V s . This work was followed by Garnier and co-workers [13], who used sexithiophene as the channel layer and recorded an enhanced mobility of 10 cm s . Akimichi et al. [14] made FET devices using alkyl-capped oligothiophenes and mentioned that the alkyl substitution not only improves the chemical stability of the oligothiophenes but also enhances the mobility. A similar substitution effect was also observed with other oligomers [34, 35]. 

Figure 16.38 Chemical structures of various alkyl-substituted polythiophenes...

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