Thiophene oligomer

The XPS Cls and S2p core-level lineshapes for the thiophene oligomers, thiophene polymers and alkyl-substituted thiophene polymers are well documented in the literature [117,123—126]. Table 3.4 summarizes the Cl s, S2p BE values, their linewidths (full width at half maximum, FWHM) and the S/C atomic ratios for several thiophene oligomers and polymers [117]. In general, the a and p carbons in thiophene polymers with a BE separation of only 0.34 eV cannot be resolved from the main Cls component. Two other minor Cls components located at above 2.6 eV and 5.2 eV above the main peak have been assigned to the shake-up structures. The S2p core-level spectrum is curve-fitted with two components with BEs at about 163.8 and 165.5 eV, corresponding to the respective spin-orbit split doublets (S2p3/2 and S2pi/2). An n transition shake-up structure is also discernible at... 

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 most widely accepted mechanism for the anodic polymerization of pyrroles and thiophenes involves the coupling of radical cations produced at the electrode (Scheme l).5 The oligomers so produced, which are more easily oxidized than the monomer, are rapidly oxidized and couple with each other and with monomer radical cations. Coupling occurs predominantly at the a-positions (i.e., 2- and 5-position),5 and so pyrroles and thiophenes with substituents in either of these positions do not undergo anodic polymerization. The reaction is stoichiometric in that two... 

Two years later, the same research group published an alternative to the solvent-free method, since this method cannot be applied to the synthesis of insoluble thiophene oligomers such as sexithiophene [43]. Obviously, their insolubility prevents separation of the AI2O3 solid support. The effectiveness of PdCl2(dppf)/KF in solution phase was tested in the synthesis of soluble quinquethiophene from diiodoterthiophene and 2-thi-... 

In general the mechanism of polymerisation for thiophene appears to be similar to that of pyrrole (Section 4.11.2), occurring via a radical coupling mechanism [423] giving mainly a-a linkages [293,400,405], and involves oligomer as well as monomer radicals, with evidence to suggest that the polymerisation reaction occurs at a lower... 

The use of organic polymers as conductors and semiconductors in the electronics industry has led to a huge research effort in poly(thiophenes), with a focus on the modification of their electronic properties so that they can behave as both hole and electron conductors. Casado and co-workers [60] have performed combined experimental and theoretical research using Raman spectroscopy on a variety of fluorinated molecules based on oligomers of thiophene, an example of one is shown in Figure 7. 

Figure 8 Comparison of experimental and predicted Raman spectrum for thiophene-phosphole oligomer. Reprinted from Casado et al. [61], Figure 4, with permission from Elsevier. Copyright (2005).

Redox molecules are particularly interesting for an electrochemical approach, because they offer addressable (functional) energy states in an electrochemically accessible potential window, which can be tuned upon polarization between oxidized and reduced states. The difference in the junction conductance of the oxidized and the reduced forms of redox molecules may span several orders of magnitude. Examples of functional molecules used in these studies include porphyrins [31,153], viologens [33, 34,110,114,154,155], aniline and thiophene oligomers [113, 146, 156, 157], metal-organic terpyridine complexes [46, 158-163], carotenes [164], nitro derivatives of OPE (OPV) [165, 166], ferrocene [150, 167, 168], perylene tetracarboxylic bisimide [141, 169, 170], tetrathia-fulvalenes [155], fullerene derivatives [171], redox-active proteins [109, 172-174], and hydroxyquinones [175]. 

The thiophene ring is a common building block for novel oligomeric and polymeric materials. The synthesis of monodisperse thiophene oligomers continues to be widely studied and the preparation of one class of oligomers, oligothienylenevinylenes <00CEJ1698,... 

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