Novel organosynthetic routes to polythiophene and its derivatives

doi:10.1016/0379-6779(88)90243-3

Synthetic Metals

Volume 26, Issue 3, 11 November 1988, Pages 267-279

https://doi.org/10.1016/0379-6779(88)90243-3 Get rights and content

Abstract

Polythiophene and its 3-alkyl derivatives have been synthesized by novel organosynthetic techniques. The organochemical syntheses were carried out by dehydrohalogenation of 2-halogenothiophene (or its 3-alkyl derivatives) or by dehydrogenation of thiophene (or its 3-alkyl derivatives). Copolymers can also be obtained from a solution involving two (or more) kinds of thiophene monomer species. The resulting polythiophene and its derivatives have well-defined chemical and electronic structure and molecular weights as large as 2.5 × 10⁵.

The poly(3-alkylthiophenes) with long alkyl side groups, typically poly(3-hexylthiophene), are readily soluble in common organic solvents and can subsequently be processed into uniform films from their solution. These solution-cast films, furthermore, can be easily stretched up to a stretching ratio of about five. The stretched films exhibit excellent conductivity (as high as 200 S/cm) after doping. The effect of the copolymerization between two thiophene monomers is also discussed.

References (30)

R.L Elsenbaumer et al.
Synth. Met.
(1986)
G Tourillon et al.
J. Electroanal. Chem.
(1982)
S Hotta
Synth. Met.
(1987)
K Kaeriyama et al.
Synth. Met.
(1987)
S Hotta et al.
Synth. Met.
(1984/1985)
S Hotta et al.
Synth. Met.
(1985)
O Inganäs et al.
Synth. Met.
(1988)
S Hotta et al.
Synth. Met.
(1987)
H Shirakawa et al.
J. Chem. Soc. Chem. Commun.
(1977)

D.M Ivory et al.

J. Chem. Phys.

(1979)

A.F Diaz et al.

J. Chem. Soc. Chem. Commun.

(1979)

T Yamamoto et al.

J. Polym. Sci. Polym. Lett. Ed.

(1980)

K Yoshino et al.

Polym. Commun.

(1987)

M Sato et al.

J. Chem. Soc. Chem. Commun.

(1986)

Cited by (118)

Mechanical properties of conjugated polymers
2022, Conjugated Polymers for Next-Generation Applications, Volume 1: Synthesis, Properties and Optoelectrochemical Devices
A balance of mechanical integrity, stiffness, flexibility, and materials performance is one of the most important tasks to be undertaken while designing the conjugated polymer (CP)-based optoelectronic devices. The deformation behavior of such materials in different length scales (molecular, mesoscopic, and macroscopic levels) can be optimized by controlling the synthetic parameters, processing conditions and blending with other polymers and inorganic substances. Thus, detailed understanding of structure–mechanical–property correlations of polymers that can be assessed by various ways including the use of in situ techniques is crucial part of novel materials designs. This chapter addresses first the morphology–property relationship particularly taking into account the essence of microstructural construction of polymeric materials. The hierarchical morphological diversity is highlighted with typical examples chosen from selected classes of CPs and their derivatives. Different methods of mechanical properties characterization are briefly introduced. The various factors influencing the mechanical deformation behavior of CPs with special emphasis on molecular, temperature, regioregularity, and various architectural parameters have been discussed. Finally, an outlook emphasizing the need to explore in situ imaging techniques for the simultaneous elucidation of structure and deformation mechanisms of CPs have been highlighted.
An ester functionalized wide bandgap polythiophene for organic field-effect transistors
2021, Synthetic Metals
Citation Excerpt :
To alleviate this problem, the ionization potential of the materials must be increased. This can be achieved in a variety of ways including, (i) increasing the π overlap through fused ring systems such as fluorene, thieno[3,2-b]thiophene, and naphthalene units [22,23], (ii) developing donor-acceptor molecular architectures [22], and (iii) attaching electron-withdrawing units on the thiophenes [17,21,24,25]. The thiophene's functionalization at 3-position has been used for many years to tune the electronic properties of thiophene-based polymers.
Amongst organic semiconducting polymers, polythiophenes are an attractive class due to relatively easy synthesis and good optical and electronic properties. Herein, we report wide-bandgap polythiophene constructed by copolymerization of ester-functionalized bithiophene and thiophene vinylene thiophene monomers. The novel polymer, poly (E)-di(nonadecan-9-yl) 5-(2-(thiophen-2-yl)vinyl)-[2,2':5',2''-terthiophene]-3',4''-dicarboxylate (PDCTVT) exhibited moderate hole mobilities in bottom-gate/top-contact organic field-effect transistors up to 2.18 × 10^-2 cm² V^-1 s^-1 with higher on-to-off ratio ~10⁵.
Synthesis and utility of 3-silylthiophenes having perfluoroalkyl groups
2017, Tetrahedron Letters
Citation Excerpt :
The treatment of 3-silylthiophenes 1 or 3 with NBS afforded 2-bromo-3-silylthiophenes,18 and then the treatment of 1 or 3 with n-butyllithium followed by an addition of trimethyltin chloride gave 4-silyl-2-stannylthiophenes.19 The still coupling of the resulting thienyl bromides with thienylstannanes provided the corresponding 2,5′-bithiophenes 9 in good yields.19 On the other hand, self-coupling of thienyllithium derived from the reaction of 1 or 3 with n-butyllithium in the presence of Cu catalyst yielded 5,5′-bithiophenes 10.20
The synthesis of a novel class of 3-silyl substituted thiophenes possessing perfluoroalkyl groups on the silicon atom was investigated. The treatment of 3-bromothiophene with n-butyllithium followed by the reaction with halosilanes proceeded to afford the corresponding 3-silyl substituted thiophenes 1 in good yields. The chemical polymerization of the resulting 1 did not work well. However, the electropolymerization of 3-silylthiophenes 1a and 1b provided the corresponding polymers 5a and 5b with head-to-tail regioregularity. The cyclic voltammogram of the resulting polymers 5a and 5b indicated both n- and p-doping properties.
An in depth study of solvent effects on yield and average molecular weight in poly(3-hexylthiophene)
2017, Polymer
Citation Excerpt :
The two most commonly used analysis methods included gel permeation chromatography (GPC), which is known to overestimate chain lengths for P3HT, and matrix assisted laser desorption ionization mass spectrometry (MALDI-MS), which can underestimate chain lengths due to more facile ionization of shorter chains [19]. This paper presents a comprehensive study of the influence of solvent choice on yield, polymer chain lengths and polydispersity under identical reaction conditions using five common solvents for poly(3-hexylthiophene) synthesis, namely chloroform [20–22], acetonitrile [23,24], dichloromethane [23], nitrobenzene [25], and nitromethane [17,18]. Analysis of molecular weight and polydispersity was carried out using MALDI-MS on all samples.
Poly(3-hexylthiophene) was synthesized by chemical oxidation using FeCl₃ in chloroform, dichloromethane, acetonitrile, nitromethane, nitrobenzene and mixtures of these solvents. Comparative reactions for 1 day at room temperature were carried out to investigate solvent effects. Polymer samples and the remaining reaction solutions were analyzed by MALDI-MS and LDI-MS to determine M_w and reaction completeness, respectively. Solubilities of FeCl₃, FeCl₂, and P3HT in each pure solvent were measured and correlated to the results. Open circuit potentials of FeCl₃ and mixtures of FeCl₃ and FeCl₂ in pure solvents were measured and compared to the experimentally determined oxidation potential of 3-hexylthiophene. An optimized solvent system for reproducible synthesis of high M_w P3HT with quantitative yields is proposed based on MS analysis results.
Review on recent advances in polythiophene based photovoltaic devices
2016, Renewable and Sustainable Energy Reviews
Citation Excerpt :
Due to several unsuitable properties of pure polythiophene, thiophene monomer was functionalized with different groups to get desired properties in the final polymer. Introduction of an alkyl group into the β-position of thiophene ring and subsequent polymerization of this monomer considered as a milestone in the development of polythiophene derivatives [44]. This new polymer, poly(3-alkylthiophene) was found to be processable into film, was possible to characterize fully and also offered reasonable conductivity after p-type doping [20].
Discovery of conducting polymer introduced us to the total polymeric solar cells (PSC). During the last decade, power conversion efficiency (PCE) of these solar cells has increased from 1% to 11.5% (with the bulk heterojunction concept). Though they are still behind their inorganic counterparts in terms of efficiency, these solar cells have several advantages, such as scalability, it is printable, we can get flexible solar panels and low cost, etc. This comparatively lower efficiency is the key driving force behind the ongoing research and development on organic photovoltaics. Functionalized polythiophenes are the most studied donors and hole transporting materials in this technology (total polymer and polymer based hybrid solar cells). Like all other conducting polymers, pure polythiophene (un-substituted) is difficult to process, but its processability can be improved through the addition of functional moieties, mostly alkyl side chains. These modified polyalkylthiophenes are relatively stable, processable and have excellent optical and electrical properties. For examples, poly (3,4-ethylenedioxythiophene) doped with poly (styrenesulfonate) (PEDOT:PSS) and poly (3-hexylthiophene) (P3HT) are the most investigated materials. Here, in this review article, we have summarized some of the important modification techniques of thiophene monomer to get the desired polymers, its features and recent uses in the polymer based solar cells.
Easy preparation and characterization of conducting polymer-low molecular weight organogel system
2015, Polymer
Novel organogel system was successfully prepared from organically dispersed polyaniline (PANI) and a low molecular weight organogel system. Organogelator, consisting of cholesteryl hydrogen succinate (CHS) and 1,10-diaminodecane, and organically well-dispersible PANI were synthesized. PANI-containing toluene gels showed thermal reversibility and thixotropic behavior. Viscoelastic measurements demonstrated that PANI-containing toluene gels show rapid and repeated thixotropic behavior. A ballpoint pen refill was packed with PANI-containing toluene gel just like a gel ink, lines similar to the ones produced by ballpoint pen were successfully produced. In addition, PANI-organogelator composites of arbitrary shape were easily prepared by means of toluene evaporation from toluene gel. “Dried” PANI composites showed electrical conductivity. Compared with the neat PANI, the electrical conductivity of the PANI-organogelator composite is hardly affected by about 10 weight% of organogelator in the composite.

View all citing articles on Scopus

View full text

Novel organosynthetic routes to polythiophene and its derivatives

Abstract

Synth. Met.

J. Electroanal. Chem.

Synth. Met.

Synth. Met.

Synth. Met.

Synth. Met.

Synth. Met.

Synth. Met.

J. Chem. Soc. Chem. Commun.

J. Chem. Phys.

J. Chem. Soc. Chem. Commun.

J. Polym. Sci. Polym. Lett. Ed.

Polym. Commun.

J. Chem. Soc. Chem. Commun.