WO2011020712A2

WO2011020712A2 - Oligothiophenes derivatives

Info

Publication number: WO2011020712A2
Application number: PCT/EP2010/061475
Authority: WO
Inventors: Jean-Yves Balandier; Florence Quist; Claire Amato; Serguei Sergueev; Yves Geerts; Jérôme CORNIL; Saïd BOUZAKRAOUI
Original assignee: Universite Libre De Bruxelles; Universite De Mons
Priority date: 2009-08-18
Filing date: 2010-08-06
Publication date: 2011-02-24
Also published as: WO2011020712A3

Abstract

The present invention is directed to new oligothiophene derivatives and their use as a semiconductor material in electronic devices. More specifically, the present invention relates to new 3,4-dicyanooligothiophenes derivatives, processes for manufacturing thereof, and to their use as organic n-type (electron-transporting) semiconductors, in particular, in field-effect transistors (FET).

Description

OLIGOTHIOPHENES DERIVATIVES

Technical field of the invention

[0001] The present invention is directed to new oligothiophene derivatives and their use as a semiconductor material in electronic devices. More specifically, the present invention relates to new 3, 4-dicyanooligothiophenes derivatives, processes for manufacturing thereof, and to their use as organic n-type (electron-transporting) semiconductors, in particular, in field-effect transistors

(FET) .

Background of the invention

[0002] Scientific community has shown increasing interest for linear conjugated systems (LCS) since the discovery in 1977 of conjugated polymers which have since then been intensively studied.

[0003] Current research focus on LCS concerns their use as semiconductors in a variety of devices such as field effect transistors (FETs) , light-emitting diodes (LED) and photovoltaic cells (PV) . The unique properties of these organic semiconductors make them more attractive than inorganic semiconductors for applications requiring large area coverage, structural flexibility, or solution processing.

[0004] In that context, organic semiconductor materials, and in particular conjugated/functionalized oligothiophenes have been intensively studied owing to their potential in molecular electronics as active layers in a variety of devices such as field effect transistors and light-emitting diodes. Organic semiconductor materials are also envisaged to have substantial cost and processing advantages over their silicon analogues if they can be deposited from solution, as this enables a fast, low temperature, and large-area fabrication route.

[0005] Many studies on oligothiophene derivatives have been reported in the literature to built p-type (hole- transporting) semiconductors which have shown highly promising electronic properties (high charge carrier mobility, low threshold voltage and high ON/OFF ratio) and impressive stability of the electronic devices under atmospheric conditions. However, organic n-type (electron- transporting) semiconductors have not extensively been studied yet because of their instability under ambient atmosphere (H₂O, O₂) . Such organic n-type or electron- transporting oligothiophenes would be, in particular, interesting for the fabrication of bipolar transistors or devices based on p-n heterojunctions, such as light- emitting diodes.

[0006] Organic semiconductor materials based on oligothiophenes have been described e.g. in US-Al- 2002/0072618, EP-Al-I 398 336, EP-A2-1 605 532 and in US- Al-2007/0078267. Cyano-substituted oligothiophenes have been described by A. Yassar et al . , in "Synthesis and electrical properties of cyano-substituted oligothiophenes towards n-type organic semiconductors" published in Optical Materials, Vol. 12 (1999), 379-382; and in "Cyano- substituted oligothiophenes: a new approach to n-type organic semiconductors" published in Adv. Funct. Mater., Vol. 12 (2002), No. 10, October, 699-708.

[0007] Without contesting advantages associated with the use of organic semiconductor materials described in the art, there is still a need for organic semiconductor or charge transport materials/compounds that possess higher electron affinity. Aims of the invention

[0008] It is an aim of the present invention to provide new organic materials/compounds suitable for use as semiconductor or charge transport material which possess high electron affinity.

[0009] Advantageously, materials/compounds according to the invention possess high charge carrier mobility and are easy to synthesize, while providing excellent processability (such as e.g. solution processing, continuous printing) and excellent stability under atmospheric/ambient conditions.

[0010] It is another aim of the present invention to provide new versatile processes for preparing the above- mentioned compounds that involve fewer reaction steps and/or provide higher overall yields, when compared to conventional processes.

[0011] Other aims of the invention will be immediately apparent to those skilled in the art from the following description. Summary of the invention

[0012] According to one aspect of the present invention, it is provided an oligothiophene derivative of the formula (I) or (II) :

(H)

wherein R¹; R²; R³ and R⁴ are the same or different from each other;

wherein each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

(a) hydrogen;

(b) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; and

(c) - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms;

wherein ni; n₂; mi and m₂ are the same or different from each other;

wherein n₂ is an integer ≥l;and

wherein ni; mi and m₂ are independently selected from the group consisting of 0 and integers ≥l;

with the proviso that if n₂=mi=m₂=l, R³ and R⁴ cannot simultaneously be selected to be hydrogen.

[0013] Preferably, in the oligothiophene derivative according to the invention, R¹⁼R² and/or R³=R⁴ _, more preferably R¹⁼R² and R³=R⁴ _.

[0014] Preferably, in the oligothiophene derivative according to the invention, mi=m_2.

[0015] Preferably, in the oligothiophene derivative according to the invention, each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

(a) hydrogen;

(b) linear or branched saturated hydrocarbon,

preferably with 1 to 8 carbon atoms, more preferably linear saturated hydrocarbon with 8 carbon atoms; and

(c) - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon, preferably with 1 to 8 carbon atoms, more preferably linear saturated hydrocarbon with 7 carbon atoms.

[0016] Preferably, in the oligothiophene derivative according to the invention, each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

- (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon, preferably with 1 to 8 carbon atoms, more preferably linear saturated hydrocarbon with 7 carbon atoms .

[0017] Preferably, in the oligothiophene derivative according to the invention, each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

(a) hydrogen;

(b) -C₈Hi₇; and

(c) -(C=O)-C₇H₁₅

[0018] Preferably, in the oligothiophene derivative according to the invention, each of R¹; R²; R³ and R⁴ are independently selected to be: -(C=O)-C₇Hi_5.

[0019] In a preferred aspect, the oligothiophene derivative according to the invention is according to formula (I), wherein R¹⁼R² and preferably n¹⁼θ; 1; 2; 3 or 4; more preferably ni=0; 1; 2 or 4.

[0020] In another preferred aspect, the oligothiophene according to the invention is according to formula (II), wherein R³=R⁴ and preferably n₂ ⁼l; 2; 3 or 4; more preferably n₂ ⁼l or 2.

[0021] Preferably, in the oligothiophene derivative according to the invention, mi=m₂, and preferably mi=m₂ ⁼ 1 or mi=m₂= 2. [0022] In a preferred aspect, the oligothiophene derivative according to the invention is selected from the group consisting of:

(E)

(G) wherein each of R¹; R²; R³ and R⁴ are preferably and independently selected from the group consisting of:

(a) hydrogen;

(b) -C₈Hi₇; and

(C) -(C=O)-C₇H₁₅

[0023] In a further preferred aspect, in the oligothiophene derivative according to the invention as described above, each of R¹; R²; R³ and R⁴ are independently selected to be: -(C=O)-C₇Hi₅.

[0024] In still another preferred aspect, the oligothiophene derivative according to the invention is selected from the group consisting of oligothiophenes according to formulas (A) , (C) , (E) and (F) as above- described.

[0025] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (1) :

(D

wherein R⁵ is selected from the group consisting of:

(a) halogen;

(b) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms;

(c) - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; (d) - (0(-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; and

(e) -Sn (X¹) (X²) (X³) ; wherein X¹; X²; X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 4 carbon atoms; more preferably selected from linear saturated hydrocarbon with 4 carbon atoms.

[0026] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (2) :

(2)

wherein :

(a) R⁶=R⁷=halogen or -Sn(X¹MX²MX³); wherein X¹; X²;

X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 4 carbon atoms; more preferably selected from linear saturated hydrocarbon with 4 carbon atoms; with the proviso that R⁶ and R⁷ cannot simultaneously be selected to be iodine or chlorine; or

(b) R⁶=halogen and R⁷ is selected from the group consisting of:

(bl) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms;

(b2) -(C=O)-R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; and

(b3) - (C (-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; or

(c) R⁶= -Sn (X¹) (X²) (X³) ; wherein X¹; X²; X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 4 carbon atoms; more preferably selected from linear saturated hydrocarbon with 4 carbon atoms; and R⁷ is selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably from linear saturated hydrocarbon with 8 carbon atoms.

[0027] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (3) :

( 3 )

wherein R⁸ is selected from the group consisting of:

(a) halogen;

(b) hydrogen;

(c) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms;

(d) - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; and

(e) - (0(-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms.

[0028] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (4) :

(4)

wherein R⁹ is selected from the group consisting of:

(a) halogen; and

(b) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms. [0029] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (5) :

(5)

wherein :

(a) R¹⁰=halogen and R¹¹ is selected from the group consisting of:

(al) hydrogen;

(a2) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms;

(a3) -(C=O)-R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; and

(a4) - (0(-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; or

(b) Rⁿ=halogen or -Sn (X¹) (X²) (X³) ; wherein X¹; X²; X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 4 carbon atoms; more preferably selected from linear saturated hydrocarbon with 4 carbon atoms; and R¹⁰ is selected from the group consisting of:

(b3) - (0(-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with

7 carbon atoms .

[0030] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (6) :

(6)

wherein :

R¹² is selected from the group consisting of:

(a) hydrogen; and (b) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms; and

R¹³=hydrogen or halogen.

[0031] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (7) :

wherein R¹⁴=R¹⁵=halogen .

[0032] According to still another aspect of the present invention, it is provided a process for the manufacture of an oligothiophene derivative as above- described, wherein the process comprises (or consists of) the step of subjecting a reaction mixture comprising a reaction medium and an intermediate product as described above to: (a) a Stille hetero coupling reaction between an aromatic stannane and an aromatic halide; or (b) a homo coupling reaction between aromatic halides, preferably catalyzed with palladium.

[0033] Preferably, in the method for the manufacture of an oligothiophene derivative according to the invention, the Stille hetero coupling reaction is performed between a 2- or 5-stannylthiophene and a 2- or 5- halogenothiophene; and/or the homo coupling reaction is performed between 2- or 5-halogenothiophenes .

[0034] In another aspect, the present invention is directed to a semiconductor or charge transport material, component or device comprising (or consisting of) at least one oligothiophene derivative as above-described. Preferably, the present invention is directed to a semiconductor material having high charge carrier mobility and/or high electron affinity and wherein the semiconductor material comprises (or consists of) at least one oligothiophene derivative as above-described.

[0035] According to another aspect, the present invention is directed to an electronic device comprising a semiconductor layer, wherein the semiconductor layer comprises (or consists of) at least one oligothiophene derivative as above-described. Preferably, the electronic device according to the invention is selected from the group consisting of optical devices, electrooptical devices, field effect transistors (FETs) , integrated circuit (IC), thin film transistors (TFTs), organic light- emitting devices (OLEDs), and any combinations thereof. More preferably, the electronic device according to the invention is a field effect transistor.

[0036] In another aspect, the present invention is directed to a semiconducting composition comprising (or consisting of) at least one oligothiophene derivative as above-described. Preferably, the semiconducting composition is an ink composition suitable for use in a continuous printing process, more preferably in an ink jet printing process .

[0037] According to still another aspect, the present invention is directed to process for printing an organic semiconductor onto a substrate, wherein the process comprises (or consists of) the step of depositing/printing a semiconducting composition as above-described.

[0038] In another aspect, the present invention is directed to the use of an oligothiophene derivative as above-described as a semiconductor or charge transport material. Preferably, an oligothiophene derivative according to the invention is used as a semiconductor in an electronic device selected from the group consisting of optical devices, electrooptical devices, field effect transistors (FETs), integrated circuit (IC), thin film transistors (TFTs) , organic light-emitting devices (OLEDs) , and any combinations thereof. More preferably, an oligothiophene derivative according to the invention is used as a semiconductor in a field effect transistor.

Detailed description of the invention

[0039] According to one aspect of the present invention, it is provided an oligothiophene derivative of the formula (I) or (II) :

(I)

(II) wherein R¹; R², R and R are the same or different from each other;

(a) hydrogen;

wherein ni; n2," mi and m2 are the same or different from each other;

wherein n2 is an integer ≥l;and

with the proviso that if n₂ ⁼mi=m2=l, R³ and R⁴ cannot simultaneously be selected to be hydrogen.

[0040] According to one aspect of the invention where R¹; R²; R³ and R⁴ are independently selected from the group consisting of linear or branched saturated hydrocarbon, and linear or branched unsaturated hydrocarbon, it is preferred that R¹; R²; R³ and R⁴ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹; R²; R³ and R⁴ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹; R²; R³ and R⁴ are selected to be -C₈Hi₇.

[0041] According to another aspect of the invention where R¹; R²; R³ and R⁴ are independently selected from the group consisting of - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁶ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁶ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁶ is selected to be -C₇Hi₅. [0042] Preferably, in the oligothiophene derivative according to the invention, each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

(a) hydrogen;

(b) linear or branched saturated hydrocarbon,

[0043] Preferably, in the oligothiophene derivative according to the invention, each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

[0044] According to a more preferred aspect, in the oligothiophene derivative according to the invention, each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

(a) hydrogen;

(b) -C₈Hi₇; and

(C) -(C=O)-C₇H₁₅

[0045] According to a still more preferred aspect, in the oligothiophene derivative according to the invention, each of R¹; R²; R³ and R⁴ are independently selected to be: -(C=O)-C₇Hi₅.

[0046] In another preferred aspect, in the oligothiophene derivative according to the invention, R¹⁼R² and/or R³=R⁴ _. More preferably R¹⁼R² and R³=R⁴ _. [0047] Preferably also, in the oligothiophene derivative according to the invention, mi=m2.

[0048] In one preferred aspect, the oligothiophene derivative according to the invention is according to formula (I), wherein R¹⁼R². According to this preferred aspect, n¹ is preferably selected to be 0; 1; 2; 3 or 4 ; more preferably ni is selected from the group of 0; 1; 2 or

4.

[0049] In another preferred aspect, the oligothiophene according to the invention is according to formula (II), wherein R³=R⁴. According to this preferred aspect, n² is preferably selected to be 1; 2; 3 or 4; more preferably n₂ is selected from the group of 1 or 2.

[0050] According to one aspect of the invention wherein the oligothiophene according to the invention is according to formula (II), it is preferred that mi=m₂. More preferably, mi=m₂ ⁼ 1 or mi=m₂ ⁼ 2.

[0051] In a preferred aspect of the present invention, the oligothiophene derivative is selected from the group consisting of:

(A)

(B)

(D )

(E )

( F)

(G) wherein R¹; R²; R³ and R⁴ have the same meanings as given above in Formula (I) and (II) . According to a preferred aspect, each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

(a) hydrogen;

(b) -C₈Hi₇; and

(c) -(C=O)-C₇H₁₅

[0052] In a further preferred aspect, in the oligothiophene derivative according to the invention as described above, each of R¹; R²; R³ and R⁴ are independently selected to be: -(C=O)-C₇Hi₅.

[0053] According to another preferred aspect, the oligothiophene derivative according to the invention is selected from the group consisting of oligothiophenes according to formulas (A) , (C) , (E) and (F) as above- described.

[0054] Preferred oligothiophene derivatives according to the invention which are according to formula (I) are for example the following:

(A4) (Bi; (B2)

(B3)

(El) (E2)

(E3) (E4)

(Gi:

(G2:

(G3)

(G4) [0055] Preferred oligothiophene derivatives according to the invention which are according to formula (II) are for example the following:

(F4 )

[0056] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (1) :

(D

wherein R⁵ is selected from the group consisting of:

(a) halogen;

(b) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms; (c) - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms;

(d) - (C (-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; and

(e) -Sn (X¹) (X²) (X³) ; wherein X¹; X² and X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 4 carbon atoms; more preferably selected from linear saturated hydrocarbon with 4 carbon atoms.

[0057] According to one preferred aspect of the invention where R is selected from the group consisting of halogens, it is preferred that halogen be selected from the group consisting of F, Cl, Br and I. More preferably, R is selected from the group of Br and I .

[0058] According to another preferred aspect of the invention where R⁵ is selected from the group consisting of linear or branched saturated hydrocarbon, and linear or branched unsaturated hydrocarbon, it is preferred that R⁵ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R⁵ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R⁵ is selected to be -C₈Hi₇.

[0059] According to another preferred aspect of the invention where R is selected from the group consisting of - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁶ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁶ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁶ is selected to be -C₇Hi₅.

[0060] According to another preferred aspect of the invention where R is selected from the group consisting of

- (C (-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁷ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁷ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁷ is selected to be -C₇Hi₅.

[0061] According to another preferred aspect of the invention where R is selected from the group consisting of -Sn (X¹) (X²) (X³) ; wherein X¹; X² and X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that X¹; X² and X³ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that X¹; X² and X³ be selected from hydrocarbon comprising from 1 to 10, preferably from 1 to 7, more preferably from 1 to 6, even more preferably from 1 to 4, most preferably about 4 carbon atoms. More preferably, X¹; X² and X³ are independently selected to be - C₄H₉. Preferably also, X¹= X² = X³.

[0062] In a preferred aspect of the intermediate product according to the invention, R⁵ is selected from the group of halogens and -Sn(X¹) (X²) (X³) .

[0063] Preferred intermediate products according to the invention which are according to formula (1) are for example the following:

( Ia) ( Ib) ( Ic) ( Id)

( Ie) ( if) [0064] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (2) :

(2:

wherein :

(a) R⁶=R⁷=halogen or -Sn(X¹MX²MX³); wherein X¹; X²;

(b) R⁶=halogen and R⁷ is selected from the group consisting of:

7 carbon atoms; or

[0065] According to one preferred aspect of the invention where R⁶ and/or R⁷ is selected from the group consisting of halogens, it is preferred that halogen be selected from the group consisting of F, Cl, Br and I. More preferably, R⁶ and/or R⁷ are selected from the group of Br and I .

[0066] According to another preferred aspect of the invention where R⁷ is selected from the group consisting of linear or branched saturated hydrocarbon, and linear or branched unsaturated hydrocarbon, it is preferred that R⁷ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R⁷ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R⁷ is selected to be -C₈Hi₇.

[0067] According to another preferred aspect of the invention where R⁷ is selected from the group consisting of - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁶ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁶ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁶ is selected to be -C7H15.

[0068] According to another preferred aspect of the invention where R⁷ is selected from the group consisting of - (C (-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁷ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁷ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁷ is selected to be -C7H15.

[0069] According to another preferred aspect of the invention where R⁶ and/or R⁷ are selected from the group consisting of -Sn (X¹) (X²) (X³) ; wherein X¹; X² and X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that X¹; X² and X³ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that X¹; X² and X³ be selected from hydrocarbon comprising from 1 to 10, preferably from 1 to 7, more preferably from 1 to 6, even more preferably from 1 to 4, most preferably about 4 carbon atoms. More preferably, X¹; X² and X³ are independently selected to be - C₄H₉. Preferably also, X¹= X² = X³.

[0070] In a preferred aspect of the intermediate product according to the invention, R⁶ and/or R⁷ are selected from the group of halogens and -Sn(X¹) (X²) (X³) .

[0071] Preferred intermediate products according to the invention which are according to formula (2) are for example the following:

(2a) (2b) (2c) (2d)

I (2e) [0072] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (3) :

(3)

wherein R⁸ is selected from the group consisting of:

(a) halogen;

(b) hydrogen;

(d) -(C=O)-R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; and

(e) - (C (-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms.

[0073] According to one preferred aspect of the invention where R⁸ is selected from the group consisting of halogens, it is preferred that halogen be selected from the group consisting of F, Cl, Br and I. More preferably, R is selected from the group of Br and I .

[0074] According to another preferred aspect of the invention where R⁸ is selected from the group consisting of linear or branched saturated hydrocarbon, and linear or branched unsaturated hydrocarbon, it is preferred that R⁸ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R⁸ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R⁸ is selected to be -CsHi₇.

[0075] According to another preferred aspect of the invention where R⁸ is selected from the group consisting of

- (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁶ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁶ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁶ is selected to be -C₇Hi₅.

[0076] According to another preferred aspect of the invention where R⁸ is selected from the group consisting of

- (C (-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁷ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁷ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁷ is selected to be -C₇Hi₅. [0077] In a preferred aspect of the intermediate product according to the invention, R⁸ is selected from the group of halogens.

[0078] Preferred intermediate products according to the invention which are according to formula (3) are for example the following:

C3a) (3b) (3c) (3d)

[0079] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (4) :

wherein R⁹ is selected from the group consisting of:

(a) halogen; and

(b) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms.

[0080] According to one preferred aspect of the invention where R⁹ is selected from the group consisting of halogens, it is preferred that halogen be selected from the group consisting of F, Cl, Br and I. More preferably, R⁹ is selected from the group of Br and I .

[0081] According to another preferred aspect of the invention where R⁹ is selected from the group consisting of linear or branched saturated hydrocarbon, and linear or branched unsaturated hydrocarbon, it is preferred that R⁹ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R⁹ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R⁹ is selected to be -CsHi₇.

[0082] In a preferred aspect of the intermediate product according to the invention, R⁹ is selected from the group of halogens.

[0083] Preferred intermediate products according to the invention which are according to formula (4) are for example the following:

( 4a) ( 4b) ( 4c)

[0084] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (5) :

wherein :

(a) R¹⁰=halogen and R¹¹ is selected from the group consisting of:

(al) hydrogen;

(a2) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms; (a3) -(C=O)-R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; and

(b) Rⁿ=halogen or -Sn (X¹) (X²) (X³) ; wherein X¹; X²; X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with

1 to 4 carbon atoms; more preferably selected from linear saturated hydrocarbon with 4 carbon atoms; and R¹⁰ is selected from the group consisting of:

(b3) - (C (-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms .

[0085] According to one preferred aspect of the invention where R¹⁰ and/or R¹¹ is selected from the group consisting of halogens, it is preferred that halogen be selected from the group consisting of F, Cl, Br and I. More preferably, R¹⁰ and/or R¹¹ is selected from the group of Br and I .

[0086] According to another preferred aspect of the invention where R¹⁰ and/or R¹¹ are selected from the group consisting of linear or branched saturated hydrocarbon, and linear or branched unsaturated hydrocarbon, it is preferred that R¹⁰ and/or R¹¹ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁰ and/or R¹¹ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁰ and/or R¹¹ are selected to be -C₈Hi₇.

[0087] According to another preferred aspect of the invention where R¹⁰ and/or R¹¹ are selected from the group consisting of - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁶ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁶ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁶ is selected to be -C₇Hi₅. [0088] According to another preferred aspect of the invention where R¹⁰ and/or R¹¹ are selected from the group consisting of - (C (-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that R¹⁷ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹⁷ be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹⁷ is selected to be -C₇Hi₅.

[0089] According to another preferred aspect of the invention where R¹¹ is selected from the group consisting of -Sn (X¹) (X²) (X³) ; wherein X¹; X² and X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, it is preferred that X¹; X² and X³ be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that X¹; X² and X³ be selected from hydrocarbon comprising from 1 to 10, preferably from 1 to 7, more preferably from 1 to 6, even more preferably from 1 to 4, most preferably about 4 carbon atoms. More preferably, X¹; X² and X³ are independently selected to be - C₄H₉. Preferably also, X¹= X² = X³.

[0090] Preferred intermediate products according to the invention which are according to formula (5) are for example the following:

(5b) (5e)

[0091] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (6) :

(6)

wherein :

R¹² is selected from the group consisting of:

(a) hydrogen; and

(b) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms; and

R¹³=hydrogen or halogen.

[0092] According to one preferred aspect of the invention where R¹³ is selected from the group consisting of halogens, it is preferred that halogen be selected from the group consisting of F, Cl, Br and I. More preferably, R¹³ is selected from the group of Br and I.

[0093] According to another preferred aspect of the invention where R¹² is selected from the group consisting of linear or branched saturated hydrocarbon, and linear or branched unsaturated hydrocarbon, it is preferred that R¹² be selected from linear or branched saturated hydrocarbon, more preferably from linear saturated hydrocarbon. According to this aspect of the invention, it is preferred that R¹² be selected from hydrocarbon comprising from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8, most preferably about 8 carbon atoms. More preferably, R¹² is selected to be -CsHi₇.

[0094] Preferred intermediate products according to the invention which are according to formula (6) are for example the following:

(6a) (6b)

[0095] According to another aspect, the present invention relates to an intermediate product for the manufacture of an oligothiophene derivative as above- described, wherein the intermediate is represented by the following formula (7) :

wherein R¹⁴=R¹⁵=halogen .

[0096] According to one preferred aspect of the invention, halogens are preferably selected from the group consisting of F, Cl, Br and I. More preferably, R¹⁴ and R¹⁵ are selected from the group of Br and I .

[0097] Preferred intermediate products according to the invention which are according to formula (7) are for example the following:

(7a)

[0098] According to still another aspect of the present invention, it is provided a process for the manufacture of an oligothiophene derivative as above- described, wherein the process comprises (or consists of) the step of subjecting a reaction mixture comprising a reaction medium and an intermediate product as described above to: (a) a Stille hetero coupling reaction between an aromatic stannane and an aromatic halide; or (b) a homo coupling reaction between aromatic halides, preferably catalyzed with palladium.

[0099] According to one preferred aspect of the process according to the present invention, wherein the process comprises (or consists of) the step of subjecting a reaction mixture comprising a reaction medium and an intermediate product as described above to a Stille hetero coupling reaction between an aromatic stannane and an aromatic halide, it is preferred that the Stille hetero coupling reaction is performed between a 2- or 5- stannylthiophene and a 2- or 5-halogenothiophene . More preferably, the Stille hetero coupling reaction is catalyzed with a palladium-based catalyst, even more preferably with Pd (PPh₃) ₄. According to still a preferred aspect, the Stille hetero coupling reaction is conducted in a reaction medium comprising (or consisting of) toluene or dimethylformamide (DMF) .

[0100] According to another preferred aspect of the process according to the present invention, wherein the process comprises (or consists of) the step of subjecting a reaction mixture comprising a reaction medium and an intermediate product as described above to a homo coupling reaction between aromatic halides, it is preferred that the homo coupling reaction is performed between 2- or 5- halogenothiophenes . More preferably, the homo coupling reaction is catalyzed with a palladium-based catalyst, even more preferably with Pd (OAc) ₂- According to still a preferred aspect, the homo coupling reaction is conducted in a reaction medium comprising (or consisting of) toluene and/or diisopropylethylamine .

[0101] Other reaction medium for use in the process according to the present invention include, but are not limited to, tetrahydrofuran, chloroform, dicholoromethane, 1, 2-dicholoroethane, chlorobenzene, xylene, heptanes, mesitylene, nitrobenzene, acetonitrile, cyanobenzene, and any mixtures thereof.

[0102] In the context of the present invention, it has been shown that the use of Grignard reagents (for use e.g. in a cross coupling of an aromatic Grignard reagents and an aromatic halide under Kumada conditions) is not compatible because of their reactivity with -CN groups.

[0103] The process according to the present invention is highly versatile and allows preparing a broad variety of oligothiophene derivatives according to a highly systematic approach.

[0104] In another aspect, the present invention is directed to a semiconductor or charge transport material, component or device comprising (or consisting of) at least one oligothiophene derivative as above-described. Preferably, the present invention is directed to a semiconductor material having high charge carrier mobility and/or high electron affinity and wherein the semiconductor material comprises (or consists of) at least one oligothiophene derivative as above-described.

[0105] In the context of the present invention, it has been surprisingly found that oligothiophene derivatives according to the invention have high charge carrier mobility and/or a high electron affinity. Without being bound by theory, it is believed that this is due to the strong electron-withdrawing effect of the dual -CN groups at the 3- and 4- position of the corresponding thiophene structures. Furthermore, it has been surprisingly discovered that the dual -CN groups allow improved intermolecular interactions in the solid state (via -CN- Hydrogen bond) .

[0106] According to another aspect, the present invention is directed to an electronic device comprising a semiconductor layer, wherein the semiconductor layer comprises (or consists of) at least one oligothiophene derivative as above-described. Preferably, the electronic device according to the invention is selected from the group consisting of optical devices, electrooptical devices, field effect transistors (FETs) , integrated circuit (IC), thin film transistors (TFTs), organic light- emitting devices (OLEDs), and any combinations thereof. More preferably, the electronic device according to the invention is a field effect transistor.

[0107] In another aspect, the present invention is directed to a semiconducting composition comprising (or consisting of) at least one oligothiophene derivative as above-described. Preferably, the semiconducting composition is an ink composition suitable for use in a continuous printing process, more preferably in an ink jet printing process .

[0108] In the context of the present invention, it has been surprisingly found that oligothiophene derivatives according to the invention exhibit excellent solubility in common organic solvents, which makes them suitable for the preparation of e.g. organic semiconductor inks which can be in turn be used in the manufacture of e.g. field-effect transistors by e.g. deposition solution. Without being bound by theory, it is believed that the strong (improved) solubility of some of the oligothiophene derivatives according to the invention is due to the presence of alkyl or keto-alkyl chains on their aromatic ring. [0109] According to still another aspect, the present invention is directed to process for printing an organic semiconductor onto a substrate, wherein the process comprises (or consists of) the step of depositing/printing a semiconducting composition as above-described.

[0110] In another aspect, the present invention is directed to the use of an oligothiophene derivative as above-described as a semiconductor or charge transport material. Preferably, an oligothiophene derivative according to the invention is used as a semiconductor in an electronic device selected from the group consisting of optical devices, electrooptical devices, field effect transistors (FETs), integrated circuit (IC), thin film transistors (TFTs), organic light-emitting devices (OLEDs), and any combinations thereof. More preferably, an oligothiophene derivative according to the invention is used as a semiconductor in a field effect transistor.

EXAMPLES

Example 1

[0111] Example of a homo coupling reaction performed between 2-halogenothiophenes . Detailed synthesis of 3, 3' , 4, 4' -tetracyano-2, 2' -bithiophene .

[0112] A mixture of 2-iodo-3, 4-dicyanothiophene (300.0 mg, 1.15 mmol) , palladium acetate (19 mg, 8.2.10-2 mmol) and diisopropylethylamine (149.2 mg, 198 μL, 1.15 mmol) under argon in toluene 10 mL was refluxed until the total consumption of 2-iodo-3, 4-dicyanothiophene

(monitoring by TLC, CH2CI2) (3 hours) . After cooling at room temperature, 5 mL of CH2CI2 was added and the solution obtained was filtered on silica gel (CH2CI2) to give a white solid (80 mg, 0.30 mmol, 52%).

1H-NMR (DMSO-d6) : 9.03 (s, 2H).

13 C-NMR (DMSO-d6) : 142.3, 141.0, 112.2, 112.0, 111.4. Example 2

[0113] Detailed synthesis of 5, 5' -dioctyl- 3, 3' , 4, 4' -tetracyano-2, 2' -bithiophene.

[0114] A mixture of 2-bromo-5-octyl-3, 4- dicyanothiophene (361.0 mg, 1.11 mmol), palladium acetate

(70 mg, 0.31 mmol) and diisopropylethylamine (143.4 mg, 190 μL, 1.11 mmol) under argon in toluene 15 mL was refluxed until the total consummation of 2-bromo-5-octyl-3, 4- dicyanothiophene (monitoring by TLC, CH₂CI₂) (2 hours) . After cooling at room temperature, the medium was purified by chromatography on silica gel (CH2CI2) to give a white solid (150 mg, 0.31 mmol, 56%).

¹H-NMR (CDCl₃) : 3.07 (t, 4H, J=7.59 Hz), 1.79 (m, 4H), 1.29 (m, 20H) 0.89 (t, 6H, J=6.95 Hz).

1³C-NMR (CDCl₃) : 160.4, 138.0, 111.7, 111.4, 111.1, 110.7, 31.7, 31.0, 30.0, 29.0, 29.0, 28.9, 22.6, 14.0.

Example 3

[0115] Detailed synthesis of 5, 5' -bis (heptyl-1, 3- dioxolan-2-yl) -3, 3' , 4, 4' -tetracyano-2, 2' -bithiophene .

[0116] A mixture of 2-bromo-5- (2-heptyl-l, 3- dioxolan-2-yl) -3, 4-dicyanothiophene (230.0 mg, 0.60 mmol), palladium acetate (60 mg, 0.27 mmol) and diisopropylethylamine (77.5 mg, 103 μL, 0.60 mmol) under argon in toluene 10 mL was refluxed until the total consummation of 2-bromo-5- (2-heptyl-l, 3-dioxolan-2-yl) -3, 4- dicyanothiophene (monitoring by TLC, CH2CI2) (2 hours) . After cooling at room temperature, the medium was purified by chromatography on silica gel (CH2CI2) to give a white solid (90 mg, 0.15 mmol, 49%).

¹H-NMR (CDCl₃) : 4.07 (m, 4H), 2.11 (m, 2H), 1.33 (m, 10H), 0.88 (t, 3H, J=6.95 Hz) .

1³C-NMR (CDCl₃) : 162.2, 138.8, 112.8, 111.4, 110.6, 110.0, 108.2, 66.0, 39.4, 31.7, 29.2, 29.1, 23.2, 22.6, 14.0.

Example 4

[0117] Detailed synthesis of 5, 5' -bis (octanoyl) - 3, 3' , 4, 4' -tetracyano-2, 2' -bithiophene.

[0118] 5' -bis (heptyl-1, 3-dioxolan-2-yl) -3, 3' , 4, 4' - tetracyano-2 , 2 ' -bithiophene (60 mg, 9.9.10-2 mmol) was dissolved in 10 mL of CH₂Cl₂. Then 1 g of amberlyst® A15 dry ion exchange resin was added and the medium was stirred overnight. The resin was removed by filtration and washed by 20 mL of CH₂Cl₂. The filtrate was concentrated and then purified by chromatography on silica gel (CH₂Cl₂) to afford a white solid (45 mg, 7.7.10-2 mmol, 88%).

¹H-NMR (CDCl₃): 3.13 (t, 4H, J=7.14 Hz), 1.81 (m, 4H), 1.35 (m, 16H), 0.89 (t, 6H, J=6.93 Hz).

¹³C-NMR (CDCl₃): 189.6, 153.0, 142.2, 115.0, 114.0, 110.7, 110.5, 40.9, 31.5, 29.0, 28.8, 23.7, 22.6, 14.0.

Example 5

[0119] Example of a Stille hetero coupling reaction performed between a 2, 5-bis (stannyl) thiophene and a 2- halogenothiophene . Detailed synthesis of 3, 4,3'', 4''- tetracyano-2, 2' :5' ,2' ' -terthiophene .

[0120] A mixture of 2, 5-bis (tributylstannyl) thiophene (0.265 g, 0.40 mmol), Pd(PPh₃)₄ (0.07 g, 0.06 mmol) and 2-bromo-3, 4-dicyanothiophene (0.161 g, 0.78 mmol) was heated overnight at 105⁰C in dry toluene (8 mL) . After cooling, the precipitate formed was isolated by filtration, washed by methanol and dried. A gold yellow solid (0.036 mg, 0.1 mmol, 26%) is obtained. ¹H-NMR (CDCl₃): 7.95 (s, 2H), 7.73 (s, 2H).

Example 6

[0121] Detailed synthesis of 5, 5' ' -dioctyl- 3, 4, 3'', 4'' -tetracyano-2,2' :5' ,2" -terthiophene .

[0122] A mixture of 2,5-bis (tributylstannyl) thiophene (0.172 g, 0.26 mmol) , Pd (PPh₃) ₄ (0.05 g, 0.04 mmol) and 2-bromo-5-octyl-3, 4-dicyanothiophene (0.166 g, 0.5 mmol) was heated overnight at 105⁰C in dry toluene (10 mL) under argon. After cooling, the medium was directly purified by chromatography on silica gel (CH2CI2) to afford a yellow orange solid (0.025 g, 0.044 mmol, 17%).

1H-NMR (CDCl₃): 7.63 (s, 2H), 3.02 (t, 4H, J=7.56 Hz), 1.76 (m, 4H), 1.34 (m, 20H), 0.89 (t, 6H, J=6.96 Hz).

¹³C-NMR (CDCl₃): 157.7, 143.4, 134.2, 112.6, 111.6, 111.0, 106.5, 31.7, 31.0, 29.9, 29.1, 29.0, 28.9, 22.6, 14.1.

Example 7

[0123] Detailed synthesis of 5, 5' ' -dioctanoyl- 3, 4, 3' ' , 4' ' -tetracyano-2,2' :5' ,2" -terthiophene.

[0124] A mixture of 2,5-bis (tributylstannyl) thiophene (0.219 g, 0.33 mmol), Pd(PPh₃)₄ (0.110 g, 0.09 mmol) and 2-bromo-5- (2-heptyl-l, 3-dioxolan-2-yl) -3, 4- dicyanothiophene (0.253 g, 0.66 mmol) was heated overnight at 105°C in dry toluene (10 mL) under argon. After cooling, the medium was directly purified by chromatography on silica gel (CH2CI2) to afford 45 mg of the corresponding protected terthiophene in presence of triphenylphospine oxide. This mixture was then solubilized in 10 mL of CH2CI2 and 1 g of amberlyst® A15 dry ion exchange resin was added and the medium was stirred overnight. The resin was removed by filtration and washed by 30 mL of CH₂Cl₂. The filtrate was evaporated to dryness and the solid residue was dispersed in methanol, filtered, washed by methanol and dried. A yellow orange solid (16 mg, 0.03 mmol, 10%) is obtained.

1H-NMR (CDCl₃): 7.85 (s, 2H, ) , 3.11 (t, 4H, J=7.21 Hz),

1.79 (m, 4H), 1.32 (m, 16H), 0.89 (t, 6H, J=6.85 Hz).

1³C-NMR (CDCl₃): 190.1, 149.5, 148.6, 134.9, 113.9, 11 111.3, 109.6, 40.7, 31.6, 29.0, 28.9, 23.9, 22.6, 14.1.

Example 8

[0125] Detailed synthesis Of 3' , 4' -dicyano-

2,2' :5' ,2" -terthiophene.

[0126] A mixture of 2, 5-dibromo-3, 4- dicyanothiophene (0.400 g, 1.37 mmol), Pd (PPh₃) ₄ (0.061 g, 0.053 mmol) and 2- (tributylstannyl) thiophene (1.023 g, 0.871 mL, 2.74 mmol) was heated at 8O⁰C in dry DMF (15 mL) under argon during 24 hours. After cooling, a saturated solution of NH4CI (40 mL) was added and the medium extracted by CH₂Cl₂. The organic layer was then washed by H2O. After drying over MgSO₄ the organic layer was concentrated under vacuum. Purification by column on silica gel eluting by CH₂Cl₂ afford 383 mg (1.28 mmol, 93%) of 3' , 4' -dicyano-2, 2' : 5' , 2' ' -terthiophene as a yellow solid. ¹H-NMR (CDCl₃) : 7.67 (dd, 2H, J=I.06 and 3.76 Hz) , 7.53

(dd, 2H, J=I.05 and 5.10 Hz) , 7.18 (dd, 2H, J=3.80 and 5.07 Hz) .

¹³C-NMR (CDCl₃) : 145.0, 131.2, 129.4, 128.7, 112.8, 106.5.

Example 9

[0127] Detailed synthesis of 5, 5"-dioctyl-3' , 4' - dicyano-2 , 2 ' : 5' , 2 ' ' -terthiophene .

[0128] A mixture of 2, 5-dibromo-3, 4- dicyanothiophene (0.250 g, 0.86 mmol) , Pd(PPh₃)₄ (0.150 g, 0.13 mmol) and 2-octyl-5-tributylstannylthiophene (1.455 g, 3.00 mmol) was heated at 80⁰C in dry DMF (20 mL) under argon during 5 hours. After cooling, a saturated solution of NH₄Cl (40 mL) was added and the medium extracted by CH₂Cl₂. The organic layer was then washed by H₂O. After drying over MgSO₄ the organic layer was concentrated under vacuum and the crude product was precipitated by addition of methanol. The dark yellow solid isolated by filtration was then purified by column on silica gel CH₂C1₂/Hexane 1/1 v/v. A yellow solid (0.270 g, 0.52 mmol, 60%) is obtained. ¹H-NMR (CDCl₃): 7.46 (d, 2H, J=3.75 Hz), 6.82 (d, 2H, J=3.75 Hz), 2.84 (t, 4H, J=7.54 Hz), 1.71 (m, 4H), 1.34 (m, 20H), 0.89 (t, 6H, J=6.92 Hz).

¹³C-NMR (CDCl₃): 151.1, 145.0, 128.8, 128.6, 125.8, 113.1, 105.2, 31.9, 31.4, 30.3, 29.2, 29.2, 29.1, 22.6, 14.1.

Example 10

[0129] Detailed synthesis of 5, 5"-dioctanoyl-3' , 4' - dicyano-2, 2' : 5' , 2' ' -terthiophene .

[0130] To a mixture of 3' , 4' -dicyano-2, 2' : 5' , 2' ' - terthiophene (101.5 mg, 0.34 mmol) and octanoyl chloride (165.9 mg, 0.175 mL, 1.02 mmol) in 50 mL of CH₂Cl₂, was added by portions AlCl₃ (266.7 mg, 2.00 mmol) at room temperature. The final mixture was stirred at reflux. After two days the starting compound was converted into 5- octanoyl-3' , 4' -dicyano-2, 2' : 5' , 2' ' - terthiophene (show by TLC) . To the medium was then added 1.1 mL of octanoyl chloride and 1.0 g of AICI₃ and the reaction was refluxed during 8 days. The reaction mixture was then poured into cold HCl (6M, 50 mL) . After extraction by CH₂Cl₂ (3 x 50 mL) , the combined organic layers were washed with brine (2 x 50 mL) and water (100 mL) . After drying over anhydrous MgSO₄, the desired product was purified by column on silica gel eluting with CH₂Cl₂. A yellow solid (103.0 mg, 0.19 mmol) was obtained in 55 % of yield.

1H-NMR (CDCl₃) : 7.72 (d, 2H, J=4.05 Hz), 7.70 (d, 2H, J=4.05 Hz), 2.91 (t, 4H, J=7.39 Hz), 1.76 (m, 4H), 1.35 (m, 16H), 0.89 (t, 6H, J=6.73 Hz).

¹³C-NMR (CDCl₃) : 192.9, 147.1, 144.7, 136.9, 132.1, 129.2, 112.1, 108.7, 39.5, 31.6, 29.2, 29.0, 24.5, 22.6, 14.1. Example 11

[0131] Detailed synthesis of 5-octanoyl-3' , 4' - dicyano-2 , 2 ' : 5' , 2 ' ' -terthiophene .

[0132] To a mixture of 3' , 4' -dicyano-2, 2' : 5' , 2" - terthiophene (128.0 mg, 0.43 mmol) and AlCl₃ (229.3 mg, 1.72 mmol) in 10 mL of CH2CI2 was added dropwise octanoyl chloride (139.9 mg, 0.15 mL, 0.86 mmol) diluted in 2 mL of CH2CI2 at room temperature. The final mixture was stirred for one week. The reaction mixture was then poured into cold HCl (6M, 50 mL) . After extraction by CH₂Cl₂ (3 x 50 mL) , the combined organic layers were washed with brine (2 x 50 mL) and water (100 mL) . After drying over anhydrous MgSθ4, the desired product was purified by column on silica gel eluting with CH₂C1₂/Hexane (1/1, v/v) . A yellow solid (56.0 mg, 0.13 mmol) was obtained in 31 % of yield.

¹H-NMR (CDCl₃) : 7.70 (m, 3H), 7.57 (dd, IH, J=I.05 and 5.09 Hz), 7.19 (dd, IH, J=3.82 and 5.07 Hz, H4), 2.91 (t, 2H, J=7.40 Hz), 1.75 (m, 2H), 1.35 (m, 8H), 0.89 (t, 3H, J=6.74 Hz) .

1³C-NMR (CDCl₃): 192.9, 146.6, 146.5, 143.2, 137.4, 132.1, 130.9, 130.0, 129.2, 128.9, 128.7, 112.5, 112.4, 108.3, 106.7, 39.4, 31.6, 29.2, 29.0, 24.5, 22.6, 14.1.

Example 12

[0133] Detailed synthesis of 3' , 4' -dicyano- 2,2' :5' ,2" -terthiophene-5, 5' ' -dicarbaldehyde .

[0134] 3' ,4'-dicyano-2,2' :5' , 2" -terthiophene (92.0 mg, 0.31 mmol) was solubilized under argon in 30 mL of dry THF. The solution was cooled to -8O⁰C and stirred during 10 min. Then 3.0 equivalents of LDA (1.8 M in solution in THF/n-heptane/ethylbenzene) were added dropwise. The mixture was then stirred for 10 min. Then dry DMF (113.3 mg, 120 μL, 1.55 mmol) was added in one time. The medium was stirred for 30 min. After adding a saturated solution of NH₄Cl (20 mL) , the solution was extracted by CH₂Cl₂. The organic layers were dried over MgSO₄. After filtration, the solvent was removed under vaccum. The solid residue was dispersed in hexane and filtrated. After several washes with MeOH and hexane, the product was obtained as a pure dark yellow solid (80.0 mg, 0.23 mmol, 75 %) .

1H-NMR (DMSO-d6) : 10.03 (s, 2H), 8.17 (d, 2H, J=4.04 Hz), 7.96 (d, 2H, J=4.04 Hz) .

Example 13

[0135] Detailed synthesis of 5, 5" -dibromo-3' , 4' - dicyano-2,2' :5' ,2" -terthiophene .

[0136] To a solution of 3' , 4' -dicyano-2, 2' : 5' , 2" - terthiophene (180.0 mg, 0.60 mmol) in 15 mL of CH₂CI₂ was added dropwise at room temperature 100 μL of bromine (300 mg, 1.88 mmol) . The medium was then stirring for lh30. The precipitate formed was isolated by filtration and washed by methanol and hexane. After drying, a yellow solid (265 mg, 0.58 mmol) was obtained in quantitative yield.

1H-NMR (DMSO-d6) : 7.53 (d, 2H, J=4.02 Hz), 7.29 (d, 2H, J=4.04 Hz) .

Example 14

[0137] Detailed synthesis of 3, 4,3'", 4'" - tetracyano-2,2' :5' ,2" :5" ,2" ' -quaterthiophene .

[0138] A mixture of 5' -bromo-3, 4-dicyano-2, 2' - bithiophene (146.0 mg, 0.49 mmol), palladium acetate (20 mg, 0.08 mmol) and diisopropylethylamine (70.0 mg, 90 μL, 0.54 mmol) under argon in toluene 8 mL was refluxed until the total consumption of the starting bithiophene (monitoring by TLC, CH2CI2) (2h) . Then the medium was filtrated and the filtrate was cooled at room temperature. The precipitate formed in the filtrate was then isolated by filtration. The quaterthiophene is obtained as an orange solid (22.0 mg, 0.05 mmol) in a 20% yield.

UV-Vis (nm) : λabs=416

Mp > 300⁰C

Example 15

[0139] Detailed synthesis of 5, 5' ' ' -dioctyl- 3, 4, 3'", 4" '-tetracyano-2,2' :5',2":5",2'"- quaterthiophene .

[0140] A mixture of 5' -iodo-5-octyl-3, 4-dicyano- 2, 2' -bithiophene (350.0 mg, 0.77 mmol), palladium acetate

(70 mg, 0.31 mmol) and diisopropylethylamine (99.5 mg, 132 μL, 0.77 mmol) under argon in toluene 20 mL was refluxed until the total consummation of 2- iodo-3,4- dicyanothiophene (monitoring by TLC, CH2CI2) (2 h 30) . After cooling at room temperature, the solvent was evaporated in vacuo. The residue was then solubilised in CH2CI2 and purification by chromatography on silica gel (CH2CI2) gave a shinning orange solid (199.0 mg, 0.30 mmol, 78%) .

[0141] The same procedure was performed starting from 5' -bromo-5-octyl-3, 4-dicyano-2 , 2 ' - bithiophene. In that case, the desired quaterthiophene was prepared in 51% of yield.

1H-NMR (CDCl₃) : 7.54 (d, 2H, J=3.97 Hz), 7.27 (d, 2H, J=3.97 Hz), 3.00 (t, 4H, J=7.54 Hz), 1.76 (m, 4H), 1.30 (m, 20H), 0.90 (t, 6H, J=6.97 Hz). ¹³C-NMR (CDCl₃): 156.7, 144.6, 138.9, 131.5, 129.2, 125.9, 112.9, 111.8, 110.7, 105.1, 31.7, 31.0, 29.8, 29.1, 28.9, 22.6, 14.1. Example 16

[0142] Detailed synthesis of 5, 5' ' ' -bis (heptyl-1, 3- dioxolan-2-yl) -3, 4, 3' ' ' , 4' ' ' -tetracyano- 2,2' :5' ,2" :5" ,2" ' -quaterthiophene .

[0143] A mixture of 5' -bromo-5- (2-heptyl-l, 3- dioxolan-2-yl) -3, 4-dicyano-2, 2 ' -bithiophene (321.0 mg, 0.69 mmol) , palladium acetate (110 mg, 0.49 mmol) and diisopropylethylamine (89.1 mg, 118 μL, 0.69 mmol) under argon in toluene 15 mL was refluxed until the total consumption of the starting bithiophene (monitoring by TLC, CH2CI2) (4 hours) . After cooling at room temperature, the solvent was evaporated in vacuo. The residue was then solubilised in CH2CI2 and purification by chromatography on silica gel (CH2CI2) gave a shinning orange solid (131.0 mg, 0.17 mmol, 49%) .

¹H-NMR (CDCl₃) : 7.58 (d, 2H, J=3.98 Hz), 7.28 (d, 2H, J=3.98 Hz), 4.08 (m, 8H), 2.09 (m, 4H), 1.33 (m, 20H), 0.88 (t, 3H, J=6.97 Hz) .

1³C-NMR (CDCl₃) : 157.6, 145.6, 139.2, 131.4, 129.5, 126.1, 112.7, 111.3, 109.4, 108.2, 106.9, 65.8, 39.5, 31.7, 29.3, 29.1, 23.3, 22.6, 14.0.

Example 17

[0144] Detailed synthesis of 5, 5' ' ' -bis (octanoyl) - 3,4,3' " ,4" '-tetracyano-2,2' :5',2" :5" ,2" '- quaterthiophene .

[0145] 5,5'" -bis (heptyl-1, 3-dioxolan-2-yl) - 3, 4, 3'", 4" '-tetracyano-2,2' :5',2":5",2'"- quaterthiophene (30.0 mg, 3.9.10-2 mmol) was dissolved in 10 mL of CH₂Cl₂. Then 1 g of amberlyst® A15 dry ion exchange resin was added and the medium was stirred overnight. The resin was removed by filtration and washed by 30 mL of CH₂Cl₂. The filtrate was concentrated and then purified by chromatography on silica gel (CH₂Cl₂) to afford a red solid (22 mg, 3.2.10-2 mmol, 81%).

¹H-NMR (CDCl₃): 7.75 (d, 2H, J=4.07 Hz), 7.38 (d, 2H, J=4.07 Hz), 3.1 (t, 4H, J=7.13 Hz), 1.78 (m, 4H), 1.35 (m, 16H), 0.90 (t, 6H, J=7.01 Hz). Example 18

[0146] Detailed synthesis of 3',4',3",4"- tetracyano-2,2' :5',2" : 5' ' , 2' ' ' -quaterthiophene .

[0147] A mixture of 5-bromo-3, 4-dicyano-2, 2' - bithiophene (80.0 mg, 0.27 mmol), palladium acetate (15 mg, 0.07 mmol) and diisopropylethylamine (34.8 mg, 46 μL, 0.27 mmol) under argon in toluene 7 mL was refluxed until the total consummation of the starting bithiophene (monitoring by TLC, CH₂Cl₂) (3h) . Then the medium was filtrated and the filtrate was cooled at room temperature. The precipitate formed in the filtrate was then isolated by filtration, dryed and purified on silica gel (CH₂Cl₂) . The quaterthiophene is obtained as an orange solid (16.0 mg, 0.04 mmol, 28%) . ¹H-NMR (CD₂Cl₂) : 7.78 (dd, 2H, J=I.16 et 3.80 Hz), 7.69 (dd, 2H, J=I.16 et 5.12 Hz) 7.25 (dd, 2H, J=3.80 et 5.12 Hz) .

Example 19

[0148] Detailed synthesis of 5, 5' ' ' -dioctyl- 3' ,4' ,3" ,4"-tetracyano-2,2' :5',2" :5",2'"- quaterthiophene .

[0149] A mixture of 5-bromo-5' -octyl-3, 4-dicyano- 2, 2' -bithiophene (75.0 mg, 0.18 mmol) , palladium acetate

(20 mg, 0.09 mmol) and diisopropylethylamine (24.0 mg, 32 μL, 0.18 mmol) under argon in toluene 7 mL was refluxed until the total consummation of starting bithiophene

(monitoring by TLC, CH₂Cl₂) (1 h 30) . After cooling at room temperature, the medium was directly purified by chromatography on silica gel (CH₂Cl₂) to afford the desired quaterthiophene as an orange solid (36.0 mg, 0.06 mmol, 60%) .

1H-NMR (CDCl₃): 7.60 (d, 2H, J=3.79 Hz), 6.88 (d, 2H, J=3.79 Hz), 2.88 (t, 4H, J=7.51 Hz), 1.73 (m, 4H), 1.35 (m, 20H), 0.89 (t, 6H, J=6.93 Hz).

¹³C-NMR (CDCl₃): 153.5, 149.4, 135.9, 130.3, 127.6, 126.4, 112.3, 112.0, 111.8, 105.8, 31.8, 31.4, 30.4, 29.2, 29.1, 29.0, 22.6, 14.1.

Example 20

[0150] Detailed synthesis of 5, 5' ' ' -dioctanoyl- 3', 4', 3", 4' '-tetracyano-2,2' :5',2":5",2'"- quaterthiophene .

[0151] A mixture of 5-bromo-5' -octanoyl-3, 4- dicyano-2, 2' -bithiophene (83.0 mg, 0.20 mmol) , palladium acetate (20 mg, 0.09 mmol) and diisopropylethylamine (25.9 mg, 34 μL, 0.20 mmol) under argon in toluene 6 mL was refluxed until the total consummation of starting bithiophene (monitoring by TLC, CH₂Cl₂) (lh30) . After cooling at room temperature, the medium was directly purified by chromatography on silica gel (CH₂Cl₂) to afford the desired quaterthiophene as an orange solid (36.0 mg, 0.05mmol, 53%) .

¹H-NMR (CDCl₃): 7.78 (d, 2H, J=4.06 Hz), 7.73 (d, 2H, J=4.06 Hz), 2.93 (t, 4H, J=7.31 Hz), 1.77 (m, 4H), 1.34 (m, 16H), 0.89 (t, 6H, J=6.85 Hz).

1³C-NMR (CDCl₃): 192.7, 148.2, 147.9, 137.4, 135.7, 132.0, 130.3, 113.2, 111.5, 111.2, 109.00, 39.6, 31.6, 29.2, 29.0, 24.4, 22.6, 14.1.

Example 21

[0152] Detailed synthesis of 5, 5' ' ' ' -dioctyl- 3" ,4' '-dicyano-2,2' :5',2":5",2'":5'",2""- quinquethiophene .

[0153] A mixture of 5, 5' ' -dibromo-3' , 4' -dicyano- 2,2' :5' , 2" -terthiophene (0.128 g, 0.28 mmol), Pd(PPh₃)₄ (0.060 g, 5.10-3 mmol) and 2-octyl-5- tributylstannylthiophene (0.477 g, 0.98 mmol) was heated at 80⁰C in dry DMF (20 mL) under argon during 4h30. After cooling, a saturated solution of NH₄Cl (30 mL) was added and the medium extracted by CH2CI2. The organic layer was then washed by H2O. After drying over MgSO₄ the organic layer was concentrated under vacuum and the crude product was precipitated by addition of methanol. The dark red solid isolated by filtration was then purified by column on silica gel (CH₂Cl₂). A red solid is obtained (0.128 g, 0.19 mmol, 67%) .

¹H-NMR (CDCl₃) : 7.55 (d, 2H, J=3.98 Hz), 7.10 (d, 2H, J=3.52 Hz), 7.09 (d, 2H, J=3.98 Hz), 6.73 (d, 2H, J=3.52

Hz), 2.81 (t, 4H, J=7.47 Hz), 1.69 (m, 4H), 1.33 (m, 20H),

0.89 (t, 6H, J=6.94 Hz) .

¹³C-NMR (CDCl₃): 147.8, 144.1, 142.2, 132.9, 129.4, 128.7,

125.3, 125.2, 123.8, 113.0, 105.5.

Example 22

[0154] Detailed synthesis of 5, 5' ' ' ' ' -dioctyl-

3, 4, 3'"", 4"" '-tetracyano-2,2' :5' ,2" :5" ,2" '

:5" ' ,2" " :5" " ,2" " ' -sexithiophene .

[0155] A mixture of 5-octyl-5' ' -bromo-3, 4-dicyano- 2, 2' :5' , 2' ' -terthiophene (140.0 mg, 0.29 mmol), palladium acetate (45 mg, 0.20 mmol) and diisopropylethylamine (37.5 mg, 50 μL, 0.29 mmol) under argon in toluene 8 mL was refluxed until the total consumption of starting bithiophene (monitoring by TLC, CH₂Cl₂) (4h30) . After cooling at room temperature, the medium was directly chromatographied on silica gel (CH₂Cl₂) to afford the desired sexithiophene as a red solid (13.0 mg, 0.016 mmol, 11%) . ¹H-NMR (CDCl₃): 7.53 (d, 2H, J=3.96 Hz), 7.19 (m, 4H), 7.14 (d, 2H, J=3.82 Hz), 2.99 (t, 4H, J=7.54 Hz), 1.75 (m, 4H), 1.34 (m, 20H), 0.89 (t, 6H, J=6.94 Hz). Example 23

[0156] Detailed synthesis of 3, 4-dicyanothiophene .

[0157] A mixture of 3, 4-dibromothiophene (2.00 g, 8.3 mmol) and copper (I) cyanide (CuCN) (2.24 g, 25 mmol) in dry DMF (5 mL) was stirred under reflux for 4 hours. After cooling, the dark solution thereby formed was added to a solution of FeC13 (8.50 g) in HCl 2M (15 mL) and maintained at 70⁰C for 45 minutes. After cooling at room temperature, this mixture was extracted three times with CH₂Cl₂. The organic layers were combined and washed successively with HCl 6M (2 times) , water, saturated NaHCO₃ solution and again water. The organic layer was dried over magnesium sulfate and then evapored to dryness. The crude solid produced was then purified by chromatography on silica gel (CH₂Cl₂) or sublimated (3.10-3 mbar, 140⁰C) to afford 800 mg of a white solid (72% yield) .

1H-NMR (CDCl₃): 8.07 (s, 2H).

1³C-NMR (CDC13) : 137.0, 113.0, 111.7. Example 24

[0158] Detailed synthesis of 2, 5-diiodo-3, 4- dicyanothiophene .

[0159] A solution of 3, 4-dicyanothiophene (0.40 g, 2.98 mmol) in dry THF (30 mL) under argon, was cooled at -

80°C and 2.2 equivalents of LDA (1.8 M in solution in THF/nheptane/ ethylbenzene) was added dropwise. After stirring this mixture for 15 min at -80⁰C, iodine (1.66 g,

6.56 mmol) in dry THF (10 mL) was slowly added. The medium was then stirred for 20 min at -80⁰C and allowed to warm to room temperature. The reaction was then quenched by adding

50 mL of a saturated aqueous solution of NH₄Cl. The mixture was extracted by CH2CI2 and the organic layer was dried over magnesium sulfate and then evaporated to dryness. The crude solid produced was then purified by chromatography on silica gel (CH2CI2) to give 2, 5-diiodo-3, 4-dicyanothiophene

(862 mg, 2.23 mmol) as a pale yellow solid (75% yield) .

¹³C-NMR (DMSO-d6) : 120.9, 112.6, 99.3.

Example 25

[0160] Detailed synthesis of 2-iodo-3,4- dicyanothiophene .

[0161] Method A: from 3, 4-dicyanothiophene :

[0162] A solution of 3, 4-dicyanothiophene (255.8 mg, 1.91 mmol) in dry THF (20 mL) under argon, was cooled at -8O⁰C and one equivalent of LDA (1.8 M in solution in THF/nheptane/ ethylbenzene) was slowly added (15 min). After stirring this mixture for 1 hour at - 8O⁰C, a solution of iodine (533.2 mg, 2.1 mmol) in dry THF (6 mL) was added in 15 minutes. The medium was then stirred for 1 hour at -8O⁰C and allowed to warm to room temperature. The mixture was filtered on silica gel to remove a black impurity (CH2CI2) . The filtrate was evaporated and the pale brown solid obtained was purified by chromatography on silica gel (CH₂Cl₂) to give 2-iodo-3, 4-dicyanothiophene (140.0 mg, 0.54 mmol, 35%) as a pale yellow solid. [0163] Method B: from 2, 5-diodo-3, 4- dicyanothiophene :

[0164] 2, 5-diodo-3, 4-dicyanothiophene (150 mg, 0.39 mmol) and Pd(PPh₃)₄ (10 mg, 8.6.10-3 mmol) were heating at 70⁰C in 10 mL of CH₃CN under argon for 10 min. Then NaBH₄

(12 mg, 0.32 mmol) was added in portions and the reaction was monitoring by TLC (CH2CI2) . After 10 min, the reaction was stopped by adding 30 mL of water. This mixture was extracted by CH2CI2 and the organic layer was dried over magnesium sulfate and then evaporated to dryness. The crude solid produced was then purified by chromatography on silica gel (CH₂Cl₂) to give 80 mg (0.31 mmol, 79%) of a pale yellow solid.

1H-NMR (DMSO-d6) : 8.86 (s, IH).

1³C-NMR (DMSO-d6) : 145.5, 119.3, 113.5, 111.9, 111.7, 96.8.

Example 2 6

[0165] Detailed synthesis of 2, 5-dibromo-3, 4- dicyanothiophene .

[0166] A solution of 3, 4-dicyanothiophene (2.19 g,

7.9 mmol) in dry THF (120 mL) under argon, was cooled at - 8O⁰C and 27.20 mL (49.0 mmol) of LDA (1.8 M in solution in THF/nheptane/ethylbenzene) was added dropwise. After stirring this mixture for 15 min at -8O⁰C, bromine (1.88 mL, 36.0 mmol) was slowly added. The medium was then stirred for 2 hours with a medium temperature between -8O⁰C and -50⁰C. The reaction was then quenched by adding 50 mL of a saturated aqueous solution of NH₄Cl. The mixture was extracted by CH₂Cl₂ and the organic layer was dried over magnesium sulfate and then evaporated to dryness. The crude solid produced was then purified by chromatography on silica gel (CH2CI2) to give 2, 5-dibromo-3, 4- dicyanothiophene (2.95 g, 10.1 mmol, 62%) as a white solid. ¹³C-NMR (DMSO-d6) : 126.4, 114.4, 111.3. Example 27

[0167] Detailed synthesis of 2-bromo-3,4- dicyanothiophene .

[0168] 2, 5-dibromo-3, 4-dicyanothiophene (500.0 mg, 1.71 mmol) and Pd (PPh₃) ₄ (200 mg, 0.17 mmol) were heated at

70⁰C in 40 mL of CH₃CN under argon for 10 min. Then NaBH₄

(65.0 mg, 1.71 mmol) was added in portions and the reaction was monitoring by TLC (CH₂CI₂) . After 45 min, the reaction was stopped by adding 30 mL of water. This mixture was extracted by CH₂Cl₂ and the organic layer was dried over magnesium sulfate and then evaporated to dryness. The crude solid produced was then purified by chromatography on silica gel (CH₂Cl₂) to give 259 mg (1.21 mmol, 71%) of a pale yellow solid.

1H-NMR (CDCl₃): 7.97 (s, IH).

¹³C-NMR (CDCl₃): 137.4, 125.9, 115.6, 113.2, 111.0, 110.9.

Example 28

[0169] Detailed synthesis of 2,5- bis (tributylstannyl) -3, 4-dicyanothiophene .

[0170] A solution of 3, 4-dicyanothiophene (406.0 mg, 3.03 mmol) in dry THF (50 mL) under argon, was cooled at -8O⁰C and three equivalents of LDA (1.8 M in solution in THF/nheptane/ethylbenzene) was slowly added (10 min) . The mixture was then stirred for 10 min at -8O⁰C and 1.81 mL of tributyltin chloride (2.17 g, 6.66 mmol) was added in 10 minutes. The medium was then stirred for 1 hour at -80⁰C. After adding a saturated solution of NH₄Cl (40 mL) , the solution was extracted by CH2CI2. The organic layers were dried over MgSO₄ and concentrated. The product was purified by fast chromatography on silica gel (CH₂Cl2/hexane 6/4 v/v) to give 1.71 g (2.40 mmol, 79 %.) of a colorless oil. ¹H-NMR (CDCl₃) : 1.56 (m, 12H), 1.33 (m, 24H), 0.90 (t, 18H, J=6.97 Hz) .

1³C-NMR (CDCl₃) : 159.5, 121.0, 114.9, 28.8, 27.1, 13.6, 11.4.

Example 28

[0171] Detailed synthesis of 2,5- bis (tributylstannyl) thiophene.

[0172] A procedure identical to that described in

Chem. Mater., 1996, 8(11), 2659-2666 was used. Starting from 10 mmol of 2, 5-dibromothiophene to obtain 9.7 mmol of 2, 5-bis (tributylstannyl) thiophene . A colorless liquid was obtained in a yield of 97%.

¹H-NMR (CDCl₃) : 7.36 (s, 2H) 1.56 (m, 12H), 1.36 (m, 12H),

1.11 (m, 12H), 0.90 (t, 18H, J=7.24 Hz).

¹³C-NMR (CDCl₃) : 141.7, 135.7, 29.0, 27.3, 13.7, 10.9.

Example 29

[0173] Detailed synthesis of 2- (tributylstannyl) -

3, 4-dicyanothiophene .

[0174] A solution of 3, 4-dicyanothiophene (1.00 g, 7.46 mmol) in dry THF (60 mL) under argon, was cooled at - 80°C and one equivalent of LDA (1.8 M in solution in THF/nheptane/ethylbenzene) was slowly added (10 min) . The mixture was then stirred for 10 min at -80⁰C and 2.02 mL of tributyltin chloride (2.43 g, 7.46 mmol) was added in 10 minutes. The medium was then stirred for 1 hour at -80⁰C. After adding a saturated solution of NH₄Cl (40 mL) , the solution was extracted by CH2CI2. The organic layers were dried over MgSO₄ and concentrated. The product was purified by fast chromatography on silica gel (CH2CI2) to give 2.64 g (6.24 mmol, 84 %) of a colorless oil.

¹H-NMR (CDCl₃) : 8.32 (s, IH), 1.57 (m, 6H), 1.33 (m, 12H),

0.89 (t, 9H, J=6.97 Hz) .

1¹³³CC--NNMMRR ((CCDDCCll₃₃)):: 115555..33,, 141.7, 119.3, 114.6, 114.2, 112.5, 28.7, 27.0, 13.5, 11.4.

Example 30

[0175] Detailed synthesis of 2-octyl-3,4- dibromothiophene .

[0176] A solution of 3, 4-dibromothiophene (8.75 g, 4 mL, 36 mmol) in dry THF (90 mL) under argon, was cooled at -8O⁰C and one equivalent of LDA (1.8 M in solution in THF/nheptane/ethylbenzene) was slowly added (10 min). The mixture was then stirred for 10 min. Then 6.55 mL of 1- iodooctane (8.65 g, 36 mmol) was added in one portion. The medium was then allowed to warm to room temperature overnight, protected from the light. After adding a saturated solution of NH₄Cl (20 mL) , the solution was extracted by hexane . The organic layers were dried over MgSO₄ and concentrated. The brown liquid residue was diluted in hexane and filtrated on silicagel (elution with hexane) . Fractions containing a mixture of monoalkyl, dialkylthiophene and starting 3, 4-dibromothiophene were collected. After removing the solvent under vacuum, the product was purified by kulgelrhor distillation to afford 7.95 g (22.4 mmol, 62 %) of 2-octyl-3, 4-dibromothiophene as a colorless liquid.

¹H-NMR (CDCl₃): 7.18 (s, IH), 2.81 (t, 2H, J=7.55 Hz), 1.65 (m, 2H), 1.28 (m, 10H), 0.89 (t, 3H, J=6.88 Hz).

1³C-NMR (CDCl₃): 141.3, 119.9, 112.9, 111.8, 31.8, 30.7,

30.1, 29.2 , 29.1, 29 .0, 22. 6, 14.1.

Example 31

[0177] Detailed synthesis of 2-octyl-3,4- dicyanothiophene .

NC CN

€k

[0178] A mixture of 2-octyl-3, 4-dibromothiophene

(10.55 g, 29.8 mmol) and copper (I) cyanide (CuCN) (8.00 g,

89.4 mmol) in dry DMF (35 mL) was stirred under reflux for

4 hours. After cooling, to the dark solution thereby formed was added to a solution of FeCl₃ (29.20 g) in HCl 2M (62 mL) and maintained at 70⁰C for 1 hour. After cooling at room temperature, this mixture was extracted several times with CH2CI2. The organic layers were combined and washed successively with HCl 6M (2 times) , water, saturated NaHCO₃ solution and again water. The organic layer was dried over magnesium sulfate and then evaporated to dryness. The crude product was then purified by chromatography on silica gel

(CH₂Cl₂/hexane 1/1 v/v) to afford 4.32 g (59% yield) of a yellow pale liquid.

¹H-NMR (CDCl₃) : 7.82 (s, IH), 3.02 (t, 2H, J=7.57 Hz), 1.74 (m, 2H), 1.30 (m, 10H), 0.88 (t, 3H, J=6.97 Hz) .

1¹³³CC--NNMMRR ((CCDDCCll₃₃)) :: 115599..66,, 113344..11,, 111122..22,, 1111:2.0, 111.8, 109.9, 31.7, 31.1, 29.7, 29.0, 28.8, 22.6, 14.0. Example 32

[0179] Detailed synthesis of 2-bromo-5-octyl-3, 4- dicyanothiophene .

[0180] A solution of 2-octyl-3, 4-dicyanothiophene (3.35 g, 13.6 mmol) in dry THF (90 mL) under argon, was cooled at -80⁰C and two equivalents of LDA (1.8 M in solution in THF/nheptane/ethylbenzene) was added dropwise. The mixture was then stirred for 10 min. Then 1.7 mL of bromine (5.31 g, 16.32 mmol) was added slowly added. The medium was then allowed to warm to -50⁰C (30 min) . After adding a saturated solution of NH₄Cl (20 mL) , the solution was extracted by CH₂Cl₂. The organic layers were dried over MgSO₄ and concentrated. The brown liquid residue was diluted in CH₂Cl₂ and purified by chromatography on silicagel (elution with CH₂Cl₂/hexane 1/1 v/v) to give a yellow liquid (4.23g, 13.0 mmol, 96 %) which crystallized in the fridge.

1H-NMR (CDCl₃): 2.98 (t, 2H, J=7.57 Hz), 1.71 (m, 2H), 1.27 (m, 10H), 0.88 (t, 3H, J=7.03 Hz).

¹³C-NMR (CDCl₃): 160.0, 122.1, 114.5, 111.3, 111.0, 109.9, 31.7, 30.9, 30.1, 29.0, 28.8, 22.6, 14.0. Example 33

[0181] Detailed synthesis of 2-tributylstannyl-5- octyl-3, 4-dicyanothiophene .

[0182] A solution of 2-octyl-3, 4-dicyanothiophene (911.0 mg, 3.7 mmol) in dry THF (50 mL) under argon, was cooled at -80⁰C and 1.2 equivalents of LDA (1.8 M in solution in THF/nheptane/ethylbenzene) was added dropwise. The mixture was then stirring for 10 min. Then 1.085 mL of tributyltin chloride (1.301 g, 4.0 mmol) was added slowly added. The medium was then allowed to warm to -50⁰C (30 min) . After adding a saturated solution of NH₄Cl (20 mL) , the solution was extracted by CH2CI2. The organic layers were dried over MgSO4 and concentrated. The brown liquid residue was diluted in 5 mL of CH2CI2 and purified by short chromatography on silicagel (elution with CH2CI2) to give a yellow liquid (1.934 g, 3.6 mmol, 97 %) .

¹H-NMR (CDCl₃): 3.00 (t, 2H, J=7.60 Hz), 1.73 (m, 2H), 1.57 (m, 6H), 1.32 (m, 22H), 0.91 (m, 12H, CHs). Example 34

[0183] Detailed synthesis of 2-octylthiophene .

[0184] A solution of thiophene (2.0 g, 1.90 mL, 23.8 mmol) in dry THF (30 mL) under argon, was cooled at - 8O⁰C and 1.1 equivalent of n-Buli (1.6 M in solution in hexane) was added dropwise. The mixture was then stirred for 15 min. Then 4.52 mL of 1-bromooctane (5.05 g, 26.2 mmol) was added in one time. The medium was then allowed to warm at room temperature and stirred overnight. After adding 20 mL of water, the solution was extracted by diethyl ether. The organic layers were dried over MgSO4 and the solvent removed in vacuum. Purification by Kugelrhor distillation (150⁰C, 30 Torr) afforded the desired alkyl thiophene as a colorless liquid (4.62g, 23.5 mmol) in quantitative yield.

¹H-NMR (CDCl₃) : 7.10 (dd, IH, J=I.14 and 5.13 Hz), 6.91 (dd, IH, J=3.21 and 5.13 Hz), 6.78 (dd, IH, J=I.14 and 3.21 Hz) , 2.82 (t, 2H, J=7.55 Hz) , 1.68 (m, 2H) , 1.28 (m, 10H) , 0.88 (t, 3H, J=6.89 Hz) .

Example 35

[0185] Detailed synthesis of 2-octyl-5- tributylstannyl thiophene.

Bu₃Sn ^^_s^^^CβHi7

[0186] A solution of 2-octylthiophene (4.62 g, 23.5 mmol) in dry THF (50 mL) under argon, was cooled at -80⁰C and 1.2 equivalent of LDA (1.8 M in solution in THF/nheptane/ethylbenzene) was added dropwise. The mixture was then stirring for 5 min. Then 6.59 mL of tributyltin chloride (7.91 g, 24.3 mmol) was slowly added. The medium was then stirred at -80⁰C for 1 hour. After adding 30 mL of water, the solution was extracted by diethyl ether. The organic layers were dried over MgSO₄ and the solvent removed in vaccum. Purification by Kugelrhor distillation (210⁰C, 35 Torr) afforded the desired compound as a colorless liquid (5.36 g, 11.0 mmol, 47%).

1H-NMR (CDCl₃): 6.97 (d, IH, J=3.15 Hz), 6.90 (d, IH, J=3.15 Hz), 2.85 (t, 2H, J=7.55 Hz), 1.60 (m, 8H), 1.32 (m, 16H), 1.06 (m, 6H), 0.89 (m, 12H).

Example 36

[0187] Detailed synthesis of 2-octanoyl-3, 4- dibromothiophene .

[0188] To a mixture of 3, 4-dibromothiophene (2.5 g,

1.131 mL, 10.3 mmol) and AlCl₃ (2.75 g, 20.6 mmol) in 15 mL of CH₂Cl₂ was added dropwise octanoyl chloride ( 1.68 g,

1.76 mL, 10.3 mmol) diluted in 5 mL of CH₂Cl₂ at room temperature. The final mixture was stirred for 30 min. The reaction monitored by TLC (CH₂Cl2/Hexane, 1/9, v/v) showed the complete conversion of the starting material into the target compound. The reaction mixture was then poured into cold HCl (6M, 50 mL) . After extraction by hexane (3 x 50 mL) , the combined organic layers were washed with brine (2 x 50 mL) and water (100 mL) . After drying over anhydrous MgSO4, the desired product was purified by column on silica gel eluting with CH2Cl2/Hexane (1/9, v/v) . A yellow solid (3.12 g, 8.5 mmol) was obtained in 82 % of yield.

¹H-NMR (CD₂Cl₂): 7.64 (s, IH), 3.03 (t, 2H, J=7.34 Hz), 1.71

(m, 2H), 1.35 (m, 8H), 0.89 (t, 3H, J=6.97 Hz).

1¹³³CC--NNMMRR ((CCDD₂₂CCll₂₂)):: 119922..33,, 140.3, 129.8, 117.3, 41.8, 32.3, 29.7, 24.6, 23.2, 14.4.

Example 37

[0189] Detailed synthesis of 2-octanoyl-3, 4- dicyanothiophene .

[0190] A mixture of 2-octanoyl-3, 4- dibromothithiophene (2.90 g, 7.89 mmol) and copper (I) cyanide (CuCN) (2.12 g, 23.67 mmol) in dry DMF (15 mL) was stirred under reflux for 4 hours. After cooling, the dark solution thereby formed was added to a solution of FeCl₃ (8.10 g) in HCl 2M (15 mL) and maintained at 70⁰C for 45 minutes. After cooling at room temperature, this mixture was extracted three times with CH₂Cl₂. The organic layers were then combined and washed successively with HCl 6M (2 times), water, saturated NaHCO₃ solution and again water. The organic layer was dried over magnesium sulfate and then evaporated to dryness. The crude solid produced was then purified by chromatography on silica gel (CH₂Cl₂/Hexane 1/1 v/v) to afford 827 mg (3.17 mmol, 40%) of a pale yellow solid.

¹H-NMR (CD₂Cl₂) : 8.24 (s, IH), 3.06 (t, 2H, J=7.34 Hz), 1.76 (m, 2H), 1.36 (m, 8H), 0.89 (t, 3H, J=6.97 Hz) .

¹³C-NMR (CD₂Cl₂) : 190.8, 152.0, 140.9, 115.7, 113 .6, 112.3, 112.0, 41.4, 32.2, 29.5, 29.4, 24.3, 23.1, 14.4.

Example 38

[0191] Detailed synthesis of 2- (2-heptyl-l, 3- dioxolan-2-yl) -3, 4-dicyanothiophene .

[0192] A mixture of 2-octanoyl-3, 4-dicyanothiophene (1.48 g, 5.68 mmol), ethylene glycol (2.22 mL, 2.47g, 39.76 mmol) and 300 mg of p-toluenesulfonic acid monohydrate in 80 mL of toluene was refluxed for 36 h with azeotropic removal of water (Dean-Stark) . After cooling, the medium is washed one by a saturated solution of sodium hydrogenocarbonate . The organic layer is then dried over MgSO₄ and the solvent is evaporated under vacuum. Purification by chromatography on silicagel (elution: CH₂Cl₂ with 2% of Et₃N) afforded 1.54 g of protected compound in mixture with starting material (ratio protected/starting compound: 80/20) as a colorless liquid which crystallized in the fridge.

¹H-NMR (CD₂Cl₂) : 7.94 (s, IH), 4.03 (m, 4H), 2.07 (m, 2H),

1.30 (m, 10H), 0.87 (t, 3H, J=6.97 Hz) .

¹ ¹³³CC--NNMMRR ((CCDD₂₂CCll₂₂)) :: 116611..44,, 113366..33,, 111144..11,, ] 112.7, 112.1, 109.I₁

108.8, 66.4, 40.1, 32.3, 29.9, 29.6, 23.9, 23.2, 14.4. Example 39

[0193] Detailed synthesis of 2-bromo-5- (2-heptyl-

1, 3-dioxolan-2-yl) -3, 4-dicyanothiophene .

[0194] A solution of 1.08 g of a mixture of 2- (2- heptyl-1, 3-dioxolan-2-yl) -3, 4-dicyanothiophene/2-octanoyl- 3, 4-dicyanothiophene (80:20) in dry THF (30 mL) under argon, was cooled at -80⁰C and 2.97 mL of LDA (1.8 M in solution in THF/n-heptane/ethylbenzene) was added dropwise. The mixture was then stirring for 10 min. Then 0.450 mL of bromine (1.39 g, 4.3 mmol) was added slowly added. The medium was then allowed to warm to -50⁰C (30 min) . After adding a saturated solution of NaCl (20 mL) , the solution was extracted by CH2CI2. The organic layers were dried over MgSO4 and concentrated. The brown liquid residue was diluted in 5 mL of CH2CI2 and purified chromatography on silicagel (elution with CH₂Cl₂) to give a yellow liquid which crystallized in the fridge (863 mg, 2.25 mmol) .

1H-NMR (CD₂Cl₂): 4.02 (m, 4H), 2.04 (m, 2H), 1.30 (m, 10H), 0.87 (t, 3H, J=6.97 Hz) .

¹³C-NMR (CD₂Cl₂): 161.9, 124.6, 116.8, 111.9, 111.3, 109.0, 108.8, 66.5, 39.8, 32.2, 29.8, 29.6, 23.8, 23.2, 14.4.

Example 40

[0195] Detailed synthesis of 5- (2-heptyl-l, 3- dioxolan-2-yl) -3, 4-dicyano-2 , 2 ' -bithiophene .

[0196] 2-bromo-5- (2-heptyl-l, 3-dioxolan-2-yl) -3, 4 dicyanothiophene (0.608 g, 1.59 mmol) and 2- (tributylstannyl) thiophene (1.184 g, 1.00 mL, 3.17 mmol) were solubilized in 15 mL of dry DMF under argon. To this solution was added 150 mg of Pd(PPh₃)₄ and the medium was warmed at 70-80⁰C for 3 hours. After cooling, 40 mL of saturated solution of ammonium chloride was added and the medium was extracted twice by CH2CI2. The combined organic phases were then washed twice by water and dried over magnesium sulfate. After filtration, the solvent was removed under vacuum. Purification by chromatography on silicagel eluting with CH₂Cl₂ (+2% Et₃N) afforded 536.9 mg (1.39 mmol, 87%) of desired bithiophene as a pale yellow waxy solid.

¹H-NMR (CDCl₃): 7.63 (dd, IH, J=I.09 Hz and 3.76 Hz), 7.51 (dd, IH, J=I.09 Hz and 5.10 Hz), 7.15 (dd, IH, J=3.76 Hz and 5.09 Hz), 4.07 (m, 4H), 2.09 (m, 2H), 1.31 (m, 10H), 0.87 (t, 3H, J=6.92 Hz) .

¹³C-NMR (CDCl₃): 157.2, 146.7, 131.4, 129.2, 128.6, 128.5, 112.8, 111.4, 109.1, 108.2, 106.7, 65.7, 39.5, 31.7, 29.3, 29.1, 23.3, 22.6, 14.0.

Example 41

[0197] Detailed synthesis of 5' -bromo-5- (2-heptyl-

1, 3-dioxolan-2-yl) -3, 4-dicyano-2, 2 ' -bithiophene .

[0198] To a solution of 5- (2-heptyl-l, 3-dioxolan-2- yl) -3, 4-dicyano-2 , 2 ' -bithiophene (600.0 mg, 1.55 mmol) in 30 mL of CH₂Cl₂, was added 250 μL of triethylamine (182.1 mg, 1.80 mmol). Then 191 μL of bromine (595.0 mg, 3.72 mmol) was added in one portion. The medium was stirred at room temperature for 2 hours (reaction monitoring by TLC using CH₂Cl₂ for elution) . The reaction medium was diluted in 60 mL of CH2CI2 and successively washed twice with sodium bisulfite (Na2S2<03) solution to remove the bromine excess and once with water. The organic layer was dried over magnesium sulfate, and concentrated under vacuum. A short filtration on silicagel (CH2CI2) afforded the desired brominated bithiophene as a yellow pale solid (464.0 mg, 1.00 mmol, 64%) .

¹H-NMR (CDCl₃) : 7.35 (d, IH, J=4.00 Hz), 7.11 (d, IH, J=4.00 Hz), 4.06 (m, 4H), 2.06 (m, 2H), 1.33 (m, 10H), 0.88 (t, 3H, J=7.00 Hz) .

¹³C-NMR (CDCl₃) : 157.6, 145.4, 132.7, 131.4, 128.8, 117.0, 112.5, 111.3, 109.2, 108.2, 107.07, 65.8, 39.5, 31.7, 29.3, 29.1, 23.3, 22.6, 14.0. Example 42

[0199] Detailed synthesis of 2-bromo-5- octanoylthiophene .

[0200] To a mixture of 2-bromothiophene (3.22 g, 1.912 mL, 19.8 mmol) and octanoyl chloride (3.21 g, 3.382 mL, 19.2 mmol) in 60 mL of CH₂Cl₂ was added by few portions

AlCl₃ (5.27 g, 39.5 mmol). The reaction monitored by TLC

(CH₂C1₂/Hexane, 1/1, v/v) showed the complete conversion of the starting material into the target compound after 30 minutes. The reaction mixture was then slowly poured into cold HCl (6M, 200 mL) . After extraction by CH₂Cl₂ (2 x 50 mL) , the combined organic layers were washed with HCl 6M (2 x 50 mL) and water (2 x 100 mL) . After drying over anhydrous MgSθ4, the desired product was purified by column on silica gel eluting with CH₂C1₂/Hexane (1/1, v/v) . A cream solid (3.91 g, 13.5 mmol) was obtained in 68 % of yield. ¹H-NMR (CDCl₃): 7.42 (d, IH, J=4.00 Hz), 7.08 (d, IH, J=4.00 Hz), 2.80 (t, 2H, J=7.44 Hz), 1.71 (m, 2H), 1.31 (m, 8H) , 0.88 (t, 3H, J=6.96 Hz) .

¹³C-NMR (CDCl₃): 192.4, 145.9, 131.7, 131.11, 122.2, 38.7, 31.6, 29.2, 29.0, 24.7, 22.6, 14.0.

Example 43

[0201] Detailed synthesis of 3,4-dicyano-

2,2' :5' , 2' ' -terthiophene.

[0202] 2-iodo-3, 4-dicyanothiophene (500.0 mg, 1.92 mmol) and Pd (PPh₃) ₄ (58.0 mg, 0.05 mmol) are dissolved in 15 mL of toluene. The solution is degazed under argon for 15 minutes. A suspension of 2, 2 ' -bithiophene-5, 5 ' -diboronic acid bis(pinacol) ester (402.4 mg, 0.96 mmol) in 5 mL of and a solution of K₂CO₃ in 5 mL of water are successively added. The reaction mixture is then stirred during two days at 75°C. After cooling at room temperature, the medium is extracted twice by 50 mL of CH₂Cl₂. The combined organic layers are washed by H2O. After drying over MgSO₄ the organic layer is concentrated under vacuum. Purification by column on silica gel eluting by CH₂Cl₂ affords 52 mg (0.18 mmol, 19%) of 3,4- dicyano-2, 2' : 5' , 2' ' -terthiophene as an orange solid.

1H-NMR (CD₂Cl₂): 7.87 (s, IH), 7.59 (d, IH, J=3.96 Hz), 7.37 (dd, IH, J=I.09 and 5.09 Hz), 7.33 (dd, IH, J=I.09 and 3.65 Hz), 7.24 (d, IH, J=3.96 Hz), 7.09 (dd, IH, J=3.65 and 5.09 Hz) .

1³C-NMR (CD₂Cl₂): 148.2, 141.6, 135.6, 134.2, 129.8, 129.6, 128.4, 126.4, 125.5, 124.8, 113.6, 113.0, 112.2, 105.7. Example 44

[0203] Detailed synthesis of 5-octyl-3, 4-dicyano-

2,2' :5' , 2' ' -terthiophene.

[0204] 5' -bromo-5-octyl-3, 4-dicyano-2,2' - bithiophene (163.0 mg, 0.40 mmol) , Pd (PPh₃) ₄ (60.0 mg, 0.05 mmol) and 2- (tributylstannyl) thiophene (224.0 g, 191 μL, 0.6 mmol) were mixed in 10 mL of dry toluene under argon. This mixture was then stirred at 105⁰C for 2 hours. After cooling, the medium was directly purified by chromatography on silicagel (CH2CI2) to afford the desired terthiophene (155.0 mg, 0.38 mmol, 94%) as a yellow solid.

¹H-NMR (CDCl₃): 7.50 (d, IH, J=3.95 Hz), 7.10 (d, IH, J=3.95), 7.02 (m, 2H), 2.99 (t, 2H, J=7.50 Hz), 1.75 (m, 2H), 1.34 (m, 10H), 0.89 (t, 3H, J=6.94 Hz).

¹³C-NMR (CDCl₃): 156.1, 145.3, 141.0, 135.7, 129.9, 129.0, 128.2, 126.1, 125.2, 124.5, 113.1, 111.9, 110.5, 104.4, 31.7, 31.0, 29.7, 29.1, 29.0, 28.9, 22.6, 14.1. Example 45

[0205] Detailed synthesis of 5-octyl-5' ' -bromo-3, 4- dicyano-2, 2' : 5' , 2' ' -terthiophene .

[0206] 5-octyl-3, 4-dicyano-2, 2' :5' ,2" -terthiophene (155.0 mg, 0.38 mmol) was dissolved into 20 mL of chloroform and N-bromosuccinimide (NBS) (101.5 mg, 0.57 mmol) was added in portions at room temperature. After stirring for 16 hours with light exclusion, the medium was washed twice with water. The organic layer was dried over magnesium sulfate and then concentrated under vacuum. Purification by column chromatography on silicagel (CH₂Cl₂/petroleum ether 6/4 v/v) afforded the desired brominated terthiophene (156.0 mg, 0.32 mmol, 84%) as a yellow solid.

1H-NMR (CDCl₃): 7.52 (d, IH, J=3.95 Hz), 7.31 (dd, IH, J=I.09 and 5.07 Hz), 7.27 (dd, IH, J=I.09 and 3.68 Hz), 7.17 (d, IH, J=3.95 Hz), 7.06 (dd, IH, J=3.68 and 5.07 Hz), 2.98 (t, 2H, J=7.62 Hz), 1.75 (m, 2H), 1.34 (m, 10H), 0.89 (t, 3H, J=6.69 Hz) .

1³C-NMR (CDCl₃): 156.4, 145.0, 139.8, 137.1, 131.0, 130.2, 129.0, 125.3, 124.8, 113.0, 112.9, 111.8, 110.5, 104.7, 31.7, 31.0, 29.8, 29.0, 28.9, 22.6, 14.1.

Example 46

[0207] Detailed synthesis of 3, 4-dicyano-2, 2' - bithiophene .

[0208] 2-bromo-3, 4-dicyanothiophene (500.9 mg, 2.35 mmol) and 2- (tributylstannyl) thiophene (1.754 g, 1.50 mL, 4.70 mmol) were solubilized in 20 mL of dry DMF under argon. To this solution was added 250 mg of Pd (PPh₃) ₄ and the medium was warmed at 70-80⁰C for 2 hours. After cooling, 50 mL of saturated solution of ammonium chloride was added and the medium was extracted twice by CH₂Cl₂. The combined organic phases were then washed twice by water and dried over magnesium sulfate. After filtration, the solvent was removed under vacuum. Purification by chromatography on silicagel eluting with CH₂Cl₂ afforded 394 mg (1.82 mmol, 77%) of 3, 4-dicyano-2, 2' -bithiophene as a yellow solid. ¹H-NMR (CDCl₃): 7.83 (s, IH), 7.68 (dd, IH, J=I.14 et 3.76 Hz), 7.54 (dd, IH, J=I.14 et 5.10 Hz) 7.18 (dd, IH, J=3.76 et 5.10 Hz) .

¹³C-NMR (CDCl₃): 148.7, 133.8, 131.1, 129.5, 128.9, 128.7, 113.7, 112.6, 111.9, 106.1.

Example 47

[0209] Detailed synthesis of 5-octyl-3, 4-dicyano-

2, 2' -bithiophene.

[0210] 2-bromo-5-octyl-3, 4-dicyanothiophene (800.0 mg, 2.46 mmol) and 2- (tributylstannyl) thiophene (1.832 g, 1.56 mL, 4.91 mmol) were solubilized in 28 mL of dry DMF under argon. To this solution was added 250 mg of Pd (PPh₃) ₄ and the medium was warmed at 70-80⁰C for 2 hours. After cooling, 50 mL of saturated solution of ammonium chloride was added and the medium was extracted twice by CH₂Cl₂. The combined organic phases were then washed twice by water and dried over magnesium sulfate. After filtration, the solvent was removed under vaccum. Purification by chromatography on silicagel eluting with CH₂Cl₂ afforded 750 mg (2.28 mmol, 93%) of 5-octyl-3, 4-dicyano-2, 2' -bithiophene as a white solid.

1H-NMR (CDCl₃): 7.61 (dd, IH, J=I.11 et 3.75 Hz), 7.48 (dd, IH, J=LIl et 5.10 Hz), 7.14 (dd, IH, J=3.75 et 5.10 Hz), 2.98 (t, 2H, J=I .11 Hz), 1.74 (m, 2H), 1.29 (m, 10H), 0.88 (t, 3H, J=7.00 Hz) .

¹³C-NMR (CDCl₃): 156.4, 145.6, 131.6, 128.8, 128.5, 128.2, 113.0, 111.9, 110.4, 104.9, 31.7, 31.0, 29.7, 29.0, 28.8, 22.6, 14.0. Example 4 8

[0211] Detailed synthesis of 5' -bromo-3, 4-dicyano-

2, 2' -bithiophene.

[0212] 3, 4-dicyano-2, 2' -bithiophene (152.3 mg, 0.70 mmol) was solubilized in 10 mL of CH2CI2. 78 μL of bromine

(244.0 mg, 0.75 mmol) was added dropwise. After stirring for 35 min at room temperature the reaction was completed.

The medium was washed by a solution of sodium bisulfite and by water. The organic layer was dried over magnesium sulfate. After filtration, the solvent was removed under vacuum and purification by chromatography on silicagel

(CH2CI2) afforded 5' -bromo-3, 4-dicyano-2, 2' -bithiophene as a pale yellow solid (162 mg, 0.55 mmol, 79%) .

1H-NMR (CDCl₃): 7.85 (s, IH), 7.41 (d, IH, J=4.01 Hz), 7.14 (d, IH, 4.01 Hz) .

¹³C-NMR (CDCl₃): 147.4, 133.9, 132.4, 131.5, 129.1, 117.4, 113.8, 112.4, 111.7, 106.4. Example 49

[0213] Detailed synthesis of 5' -octyl-3, 4-dicyano- 2, 2' -bithiophene.

[0214] A mixture of 2-bromo-3, 4-dicyanothiophene (0.418 g, 1.96 mmol), Pd(PPh₃)₄ (0.220 g, 0.19 mmol) and 2- octyl-5-tributylstannylthiophene (1.940 g, 4.00 mmol) was heated at 8O⁰C in dry DMF (20 mL) under argon during 4h30. After cooling, a saturated solution of NH₄Cl (40 mL) was added and the medium extracted by CH2CI2. The organic layer was then washed by H2O. After drying over MgSθ4, the organic layer was concentrated under vacuum and the residue was purified by column on silica gel (CH2Cl2/Hexane 7/3 v/v) to afford the desired bithiophene (520 mg, 1.58 mmol, 81%) as a white solid.

¹H-NMR (CDCl₃) : 7.76 (s, IH), 7.49 (d, IH, J=3.75 Hz), 6.83 (d, IH, J=3.75 Hz), 2.84 (t, 2H, J=7.56 Hz), 1.70 (m, 2H), 1.32 (m, 10H), 0.88 (t, 3H, J=6.94 Hz).

¹³C-NMR (CDCl₃) : 151.4, 149.3, 133.0, 128.9, 128.5, 125.8, 113.4, 112.9, 112.0, 109.5, 31.8, 31.4, 30.2, 29.2, 29.1, 29.0, 22.6, 14.1.

Example 50

[0215] Detailed synthesis of 5-bromo-5' -octyl-3, 4- dicyano-2, 2' -bithiophene .

[0216] A solution of 5' -octyl-3, 4-dicyano-2, 2' - bithiophene (335.0 mg, 1.02 mmol) in dry THF (30 mL) under argon, was cooled at -8O⁰C and 2 equivalents of LDA (1.8 M in solution in THF/nheptane/ethylbenzene) was added dropwise. The mixture was then stirred for 10 min. Then 78 μL of bromine (245.0 mg, 1.53 mmol) was added slowly added. The medium was then stirred for 2 hours at -8O⁰C. After adding a saturated solution of NH₄Cl (40 mL) , the solution was extracted by CH₂Cl₂. The organic layers were dried over MgSO4 and concentrated. The residue was then purified by column chromatography on silicagel (elution with CH₂C1₂/Hexane 7/3 v/v) to give a pale yellow solid (160.0 mg, 0.38 mmol, 38%) . ¹H-NMR (CDCl₃): 7.44 (d, IH, J=3.77 Hz), 6.83 (d, IH, J=3.77 Hz), 2.82 (t, 2H, J=7.54 Hz), 1.70 (m, 2H), 1.31 (m, 10H), 0.89 (t, 3H, J=6.96 Hz).

¹³C-NMR (CDCl₃): 152.1, 149.6, 129.1, 127.9, 125.9, 121.2, 115.9, 112.2, 111.2, 104.5, 31.8, 31.4, 30.2, 29.2, 29.1, 29.0, 22.6, 14.1.

Example 51

[0217] Detailed synthesis of 5-bromo-3, 4-dicyano- 2,2' -bithiophene.

[0218] 3, 4-dicyano-2, 2' -bithiophene (121.0 mg, 0.56 mmol) was solubilized under argon in 30 mL of dry THF. The solution was cooled to -80⁰C and stirred during 10 min. Then 1.1 equivalent of LDA (1.8 M in solution in THF/n- heptane/ethylbenzene) was added dropwise. The mixture was then stirred for 10 min. Then bromine (182.3 mg, 58 μL, 0.56 mmol) was slowly added. The medium was stirred for 30 min. After adding a saturated solution of NH4C1 (20 mL) , the solution was extracted by CH₂Cl₂. The organic layers were washed by a solution of sodium bisulfite (Na₂S₂O₃) and dried over MgSO₄. After filtration, the solvent was removed under vacuum. The residue was diluted in CH₂Cl₂ and purified by chromatography on silicagel (elution with CH₂Cl₂/hexane 1/1 v/v) to give a pale yellow solid (110.0 mg, 0.37 mmo1 , 67 % ) .

¹H-NMR (CDCl₃): 7.62 (dd, IH, J=LlO and 3.77 Hz), 7.55 (dd, IH, J=LlO and 5.09 Hz), 7.18 (dd, IH, J=3.77 and 5.09 Hz) .

1³C-NMR (CDCl₃): 149.0, 130.5, 129.9, 129.1, 128.8, 122.1, 116.1, 111.9, 111.1, 105.9. Example 52

[0219] Detailed synthesis of 5' -iodo-5-octyl-3, 4- dicyano-2, 2' -bithiophene .

[0220] 5-octyl-3, 4-dicyano-2, 2' -bithiophene (411.0 mg, 1.25 mmol) was solubilized under argon in 30 mL of dry THF. The solution was cooled to -80⁰C and stirred during 10 min. Then 1.1 equivalent of LDA (1.8 M in solution in THF/n-heptane/ethylbenzene) was added dropwise. The mixture was then stirred for 10 min. Then iodine (381.0 g, 1.50 mmol) in solution in 5 mL of dry THF was added slowly added. The medium was stirred for 30 min. After adding a saturated solution of NH₄Cl (20 mL) , the solution was extracted by CH₂Cl₂. The organic layers were washed by a solution of sodium bisulfite and dried over MgSO₄. After filtration, the solvent was removed under vacuum. The residue was diluted in CH₂Cl₂ and purified by chromatography on silicagel (elution with CH₂Cl₂/hexane 1/1 v/v) to give a pale yellow solid (374.0 mg, 0.82 mmol, 66 %) .

¹H-NMR (CDCl₃) : 7.29 (d, IH, J=3.92 Hz), 7.23 (d, IH, J=3.92 Hz), 2.98 (t, 2H, J=7.55 Hz), 1.73 (m, 2H), 1.30 (m, 10H), 0.89 (t, 3H, J=7.00 Hz) .

1³C-NMR (CDCl₃) : 156.8, 144.1, 138.2, 137.3, 129.5, 112.8, 111.7, 110.5, 105.3, 78.1, 31.7, 31.0, 29.8, 29.0, 28.9, 22.6, 14.1.

Example 53

[0221] Detailed synthesis of 5' -bromo-5-octyl-3, 4- dicyano-2, 2' -bithiophene .

[0222] 5-octyl-3, 4-dicyano-2,2' -bithiophene (106.5 mg, 0.32 mmol) was solubilized in 10 mL of chloroform. 51 μL of bromine (159.0 mg, 0.49 mmol) was added dropwise. After stirring for 15 min at room temperature the reaction was completed. The medium was washed by a solution of sodium bisulfite and by water. The organic layer was dried over magnesium sulfate. After filtration, the solvent was removed under vacuum to afford pure product as a pale yellow solid (101 mg, 0.25 mmol, 78%).

¹H-NMR (CDCl₃) : 7.34 (d, IH, J=4.00 Hz), 7.11 (d, IH, J=4.00 Hz), 2.98 (t, 2H, J=7.53 Hz), 1.74 (m, 2H), 1.29 (m, 10H), 0.89 (t, 3H, J=6.98 Hz) .

1³C-NMR (CDCl₃) : 156.7, 144.3, 132.9, 131.3, 128.5, 116.6, 112.8, 111.7, 110.5, 105.3, 31.7, 31.0, 29.8, 29.0, 28.9, 22.6, 14.1.

Example 54

[0223] Detailed synthesis of 5-bromo-5'octyl-3, 4- dicyano-2 , 2 ' -bithiophene .

[0224] 5-bromo-3, 4-dicyano-2, 2' -bithiophene (82.0 mg, 0.28 mmol) and 400 μL of octanoyl chloride (380.0 mg, 2.34 mmol) were solubilized in 15 mL of dry CH₂CI₂. After adding by portions 750 mg of AlCl₃ (5.62 mmol), the medium was refluxed for 3 days. After cooling, the reaction mixture was then poured into cold HCl (2M, 100 mL) . After extraction by CH2CI2 (3 x 50 mL) , the combined organic layers were washed with brine (2 x 50 mL) and water (100 mL) . After drying over anhydrous MgSθ4, the desired product was purified by column on silica gel eluting with CH2CI2. A yellow solid (102.0 mg, 0.24 mmol) was obtained in 86 % yield.

1H-NMR (CDCl₃) : 7.69 (d, IH, J=4.06 Hz), 7.64 (d, IH, J=4.06 Hz), 2.90 (t, 2H, J=7.31 Hz), 1.75 (m, 2H), 1.34 (m, 8H) , 0.88 (t, 3H, J=6.91 Hz) .

¹³C-NMR (CDCl₃) : 192.8, 147.4, 147.2, 136.5, 132.0, 129.1, 123.8, 116.7, 111.5, 110.8, 107.6, 39.4, 31.6, 29.2, 29.0, 24.5, 22.6, 14.1.

Claims

1. An oligothiophene derivative of the formula (I) or (II) :

(D

(H) wherein R¹; R², R and R are the same or different from each other;

(a) hydrogen;

(c: - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms;

wherein ni; n₂; mi and m2 are the same or different from each other;

wherein n₂ is an integer ≥l;and

2. The oligothiophene derivative according to claim 1 wherein R¹⁼R² and/or R³=R⁴ _; preferably R¹⁼R² and R³=R⁴ _.

3. The oligothiophene derivative according to any of claim 1 or 2, wherein mi=m₂.

4. The oligothiophene derivative according to any of the preceding claims, wherein each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

(a) hydrogen;

(b) linear or branched saturated hydrocarbon,

5. The oligothiophene derivative according to any of the preceding claims, wherein each of R¹; R²; R³ and R⁴ are independently selected from the group consisting of:

(a) hydrogen;

(b) -C₈Hi₇; and

(C) -(C=O)-C₇H₁₅ 6. The oligothiophene derivative according to claim 5, wherein said derivative is according to formula (I), and wherein R¹⁼R² and preferably n¹⁼θ; 1; 2; 3 or 4; more preferably ni=0; 1; 2 or 4.

7. The oligothiophene derivative according to claim 5, wherein said derivative is according to formula (II), and wherein R³=R⁴ and preferably n₂ ⁼l; 2; 3 or 4; more preferably n₂=l or 2.

8. The oligothiophene derivative according to claim 7, wherein mi=m₂, and preferably mi=m₂ ⁼ 1 or 2.

9. The oligothiophene derivative according to any of the preceding claims, which is selected from the group consisting of:

(E )

( F)

(a) hydrogen;

(b) -C₈H₁₇; and

(C) -(C=O)-C₇H₁₅

10. An intermediate product for the manufacture of an oligothiophene derivative according to any of the preceding claims, wherein said intermediate is represented by the following Formula (1) :

(D

wherein R⁵ is selected from the group consisting of:

(a) halogen;

(c) - (C=O) -R¹⁶; wherein R¹⁶ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms;

(d) - (0(-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with

1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; and

11. An intermediate product for the manufacture of an oligothiophene derivative according to any of claims 1 to 9, wherein said intermediate is represented by the following Formula (2) :

(2)

wherein :

(a) R⁶=R⁷=halogen or -Sn(X¹MX²MX³); wherein X¹; X²;

X³ are independently selected from linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with

1 to 4 carbon atoms; more preferably selected from linear saturated hydrocarbon with 4 carbon atoms; with the proviso that R⁶ and R⁷ cannot simultaneously be selected to be iodine or chlorine; or

(b) R⁶=halogen and R⁷ is selected from the group consisting of: (bl) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 8 carbon atoms;

(b3) - (0(-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms; or

12. An intermediate product for the manufacture of an oligothiophene derivative according to any of claims 1 to 9, wherein said intermediate is represented by the following Formula (3) :

( 3 )

wherein R is selected from the group consisting of:

(a) halogen;

(b) hydrogen;

13. An intermediate product for the manufacture of an oligothiophene derivative according to any of claims 1 to 9, wherein said intermediate is represented by the following Formula (4) :

(4)

wherein R⁹ is selected from the group consisting of:

(a) halogen; and

14. An intermediate product for the manufacture of an oligothiophene derivative according to any of claims 1 to 9, wherein said intermediate is represented by the following Formula (5) :

(5)

wherein:

(a) R¹⁰=halogen and R¹¹ is selected from the group consisting of:

(al) hydrogen;

(b3) - (0(-0-CH₂-CH₂-O-) ) -R¹⁷; wherein R¹⁷ is linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with 7 carbon atoms .

15. An intermediate product for the manufacture of an oligothiophene derivative according to any of claims 1 to 9, wherein said intermediate is represented by the following Formula (6) :

(6)

wherein :

R¹² is selected from the group consisting of: (a) hydrogen; and

(b) linear or branched saturated hydrocarbon; linear or branched unsaturated hydrocarbon, preferably with 1 to 8 carbon atoms; more preferably linear saturated hydrocarbon with

8 carbon atoms; and

R¹³=hydrogen or halogen.

16. An intermediate product for the manufacture of an oligothiophene derivative according to any of claims 1 to 9, wherein said intermediate is represented by the following Formula (7) :

(7)

wherein R¹⁴=R¹⁵=halogen .

17. A process for the manufacture of an oligothiophene derivative according to any of claims 1 to 9, wherein said process comprises the step of subjecting a reaction mixture comprising a reaction medium and an intermediate product according to any of claims 11 to 16 to: (a) a Stille hetero coupling reaction between an aromatic stannane and an aromatic halide; or (b) a homo coupling reaction between aromatic halides, preferably catalyzed with palladium.

18. The process according to claim 17, wherein said Stille hetero coupling reaction is performed between a 2- or 5-stannylthiophene and a 2- or 5- halogenothiophene; and/or said homo coupling reaction is performed between 2- or 5-halogenothiophenes .

19. A semiconductor or charge transport material, component or device comprising at least one oligothiophene derivative according to any of claims 1 to 9.

20. An electronic device comprising a semiconductor layer, wherein the semiconductor layer comprises at least one oligothiophene derivative according to any of claims 1 to 9.