WO2012156500A1

WO2012156500A1 - Semiconducting compound for gas sensing

Info

Publication number: WO2012156500A1
Application number: PCT/EP2012/059238
Authority: WO
Inventors: Jean-Yves Balandier; Claude NIEBEL; Yves Henri GEERTS
Original assignee: Université Libre de Bruxelles
Priority date: 2011-05-18
Filing date: 2012-05-18
Publication date: 2012-11-22

Abstract

A compound of general formula (I), as well as organic field effect transistors and gas sensors comprising the same.

Description

Semiconducting Compound for Gas Sensing

Technical field of the invention

The present invention relates to the field of semiconducting organic compounds for use in gas sensing applications. Background of the invention

Organic semiconductor molecules have been used in various electronic components, including organic light emitting diodes, organic solar cells and organic field effect transistors. In particular, organic semi-conductors have been used for the fabrication of field effect sensors.

For instance, F. Naso et al (nature materials, vol. 7, May 2008, 412-417) disclose a chiral bilayer organic thin-film transistor gas sensor. It comprises a first active layer composed of an alkoxyphenylene-thiophene oligomer wherein the two alkyl chains are octyl chains (PTO), and an outermost active layer composed of a phenylene-thiophene oligomer with built-in enantioselective properties (either a phenylene-thiophene oligomer wherein the two side chains comprise D-glucose moieties (PTG) or an alkoxyphenylene-thiophene oligomer wherein the two alkyl chains are hexyl chains terminated by L-phenylalanine moieties (PTA)), enabling differential detection of optical isomers. The bilayer was composed of ten Langmuir- Schafer transfers of PTO and five of PTA or PTG.

Although this device enabled the differential detection of optical isomers, the quantity of non-semiconductive material (in the form of the enantioselective side- chains) present in the outermost active layer of the sensor is relatively large. This is likely to have a negative effect on the electrical properties of the device. In other words, the large quantity of PTA or PTG (roughly 50 % of the quantity of PTO) whose large side-chains have no semiconducting properties, are likely to have a negative impact on the electrical properties of the device. Furthermore, this relatively large quantity of selective molecules (PTA or PTG), which are difficult to synthesize in good yield, represents an economical disadvantage and a potential waste of material.

There is therefore a need in the art for devices and compounds permitting the sensing of an analyte within a gaseous phase while diluting as less as possible the electronic properties of the active layer(s). Amongst said electronic properties, notable are the charge mobility and the threshold voltage.

Summary of the invention It is an object of the present invention to provide good apparatus or methods for the detection of an analyte within a gaseous phase.

It is an advantage of embodiments of the present invention that a relatively low amount of sensing molecules are necessary.

It is an advantage of embodiments of the present invention that the sensing of an analyte within the gaseous phase with good sensitivity is made possible.

It is an advantage of embodiments of the present invention that the sensing of an analyte within the gaseous phase with good selectivity is made possible

It is an advantage of embodiments of the present invention that sensing molecules automatically placing themselves at the grain boundaries of a polycrystalline semiconducting layer are provided.

It is a further advantage of embodiments of the present invention that a single active layer is sufficient where two layers were necessary in the prior art. This means that processing is made easier. It is also possible to print this layer.

The above objective is accomplished by a compound and device according to the present invention.

In a first aspect, the present invention relates to a compound of general formula (F)

Wherein Ar is selected from the group consisting of pyrenyl derivatives, pyrrolyl derivatives, carbazolyl derivatives, naphthalenyl derivatives, naphtha[1 ,8- bc:5,4-0'c]dithiophenyl derivatives, benzodithiophenyl derivatives, anthrathiophenyl derivatives, thiazolyl derivatives, thiazolothiazolyl derivatives, thiadiazolyl derivatives, thienoacenyl derivatives, tetrathiafulvalenyl derivatives, thiophenyl derivatives, thieno[3,2-0]thiophenyl derivatives, and thieno[2,3-0]thiophenyl derivatives,

wherein Y is a substituent other than hydrogen, preferably selected from the group consisting of -C(OH)RR\ -COR (e.g. -CHO), -X, -R, -SnR₃, -B(OR)(OR'), -BF₃ ^~, -CH₂-IMRR', -CH₂OR⁵, -CH₂-0-COR, -CH₂-0-CO-OR, -C(OR")RR', -C(RR')0-CO- OR", -COOR (e.g. -COOH), -CONHR, -CH₂NR⁶R⁷, -CH=N-Ar', -N=CH-Ph, and -CH₂- NH-Ar',

wherein R⁵ is selected from the group consisting of H, d-₂o alkyl groups and hydroxyl protecting groups, wherein R⁶ is hydrogen when R⁷ is an amine protecting group and otherwhise R⁶ and R⁷ form together an amine protective group such as a phthalimide group, wherein R, R' and R" are independently selected from the list consisting of H, d-20 alkyl groups, or R and R' may be taken together to form a ring, which may be a five- to seven-member ring, which may be non-aromatic, which may be part of a polynuclear condensed ring system, and which may be substituted,

wherein X is selected from the list consisting of CI, Br, I, F and pseudohalogens,

-Ar' has for general formula (I)

Wherein R², R³ and R⁴ are independently selected from the list consisting of - CN, -OR⁸, -SiR⁸ ₃, -halogen, -R⁸, -S-R⁸, -N0₂, wherein R⁸ is selected from the group consisting of H and d-20 alkyl groups. For instance, R², R³ and R⁴ may be independently selected from H, -CN and -OR⁸ (wherein R⁸ is e.g. -CH₃).

Compound (F) is an asymm mmetric

organic semiconducting compound (E)

Compound (F) has the advantage to 1 ) have sufficient structural similarity with compound (E) for having a tendency to integrate its crystal lattice, and 2) to be sufficiently different from compound (E), to disrupt to create defects in the crystal lattice of (E) and to have the tendency to be integrated at the boundaries of the crystals more than in the core of the crystal. As a result, when comprised together with a compound (E) in an organic polycrystalline semiconducting material, (F) has a tendency to be present at the grain boundaries of the organic polycrystalline semiconducting material, i.e. at the area limiting charge transport. This solves the problem of improving the sensibility of the device. This problem is solved with an economy of sensing molecules (F) since these molecules are preferably incorporated where they are the most efficient, i.e. at the grain boundaries. This also solves the problem of how to improve sensibility while not diluting the electrical properties of the active layer. When used together, compounds (E) and (F) may synergistically interact to form an organic polycrystalline semiconducting material with the sensing molecules (F) being preferentially present at the grain boundaries.

If Y is -B OR)(OR'), the following are non-limitative examples:

Preferably, the Y may be selected from -CH₂-NRR', -CONHR, -CH₂NH-CO- OR, -CH=N-Ar', and -CH₂-NH-Ar'. This is advantageous because these groups have a good affinity with sulphur and therefore also with tetrahydrothiophene which is present as an odorant in natural gas.

X is preferably Br.

In an embodiment of the first aspect, Ar may be selected from the list consisting of

, wherein the dotted line indicates the location of the connection of the Ar group within the compound (F),

Wherein R and R' are independently selected from H and d-20 alkyl groups, Wherein is 0, 1 or 2, wherein n₂ is from 1 to 3, and wherein n₃ is 0 or 1.

In another embodiment of the first aspect, said compound (F) may have the general formula I I a)

This is advantageous since the corresponding symmetric organic semiconductin compound (lis)

is a semiconductor having a good charge mobility. In an embodiment of the first aspect he compound may be selected from the list consisting of:

wherein R¹ is selected from hydrogen atom and d-^ linear alkyl groups,

wherein R², R³, R⁴ are as defined above,

wherein R⁵ is selected from -CH₃, -(CO)-0-C(CH₃)₃, and -(CO)-CH₃), and

wherein R⁶ is selected from d-20, preferably C₆.₁₂ linear alkyl groups.

In a second aspect, the present invention relates to a compound of general

(E)

wherein Ar is selected from pyrenyl derivatives, pyrrolyl derivatives, carbazolyl derivatives, naphthalenyl derivatives, naphtha[1 ,8-oc:5,4-o'c]dithiophenyl derivatives, benzodithiophenyl derivatives, anthrathiophenyl derivatives, thiazolyl derivatives, thiazolothiazolyl derivatives, thiadiazolyl derivatives, thienoacenyl derivatives, tetrathiafulvalenyl derivatives, thiophenyl derivatives, thieno[3,2-0]thiophenyl derivatives, and thieno[2,3-0]thiophenyl derivatives, with the proviso that Ar is not the unsubstituted thiophenyl group. Compound (E) is a) an intermediate in the synthesis of compound (F) and b) a good symmetric organic semiconducting compound for use in an analyte detector. When used together, compounds (E) and (F) have a synergetic effect.

In a third aspect, the present invention relates to a method for synthesizing a compound according to the first aspect, said method comprising the steps of:

a) Forming a compound according to formula (E)

by either

a1 ) reacting a compound according to formula (A)

Ar- X _(A)

ing to formula (B)

(B)

in presence of a Pd catalyst or a Ni catalyst (route A), or

a2) reacting a compound according to formula (C)

Ar-M (C)

wi ing to formula (D)

(D)

in presence of a Pd catalyst or a Ni catalyst (route B), and

b) forming a compound according to formula (F)

by lithiating said compound according to formula (E) with a lithiation agent, followed by reaction of the lithiated derivative of compound (D) with an excess of a functionalization agent Y', wherein X is selected from I, Br, CI, F and pseudohalogens (for Stille or Suzuki couplings), and wherein M is selected from -B(OR)(OR'), -BF₃ ^", - SnR₃, -ZnX' and -MgX', wherein X' is selected from the group consisting of Br, I and CI wherein R and R' are independently selected from the list consisting of H, C_{1 -2}o alkyl groups or R and R' may be taken together to form a non-aromatic ring, which may be a five- to seven-member ring, which may be part of a polynuclear condensed ring system optionally comprising one or more aromatic rings, and which may be substituted. For -B(OR)(OR'), the following are non-limitative examples:

The following table provides a non-limitating list of examplary functionalization agents Y' known to the person skilled in the art for obtaining the target function via the lithiation reaction.

Functionalization agents Target functions

R-CHO -CH(OH)R

(aldehyde) (secondary alcohol)

R-CO-R" -C(OH)RR"

(ketone) (tertiary alcohols)

-CHO

Dimethylformamide (DMF)

(aldehyde)

-COOH

C0₂

(carboxylic acid)

R-COCI (acid chloride)

-CO-R

or

(ketone)

R-CO-NR'₂ (amide)

-X

for example: CBr₄, l₂ , Br_2, Cl₂

(halogen)

R-X -R

(halogenated alkyl chains) Alkyl chains

for example: -SnR₃ CI-SnMe₃, CI-SnBu₃ (stannyl derivatives) for example: -B(OR)₂ 2-isopropoxy-4,4,5,5-tetramethyl-1 ,3,2- (boronate, trifluoroborate or boronic dioxoborolane derivatives)

In a fourth aspect, the present invention relates to a semiconducting device and preferably to an organic or hybrid organic/inorganic semiconducting device. In an embodiment, the semiconducting device may be a field effect transistor. The semiconducting device of the present invention preferably comprises an organic polycrystalline semiconducting material. This material preferably comprises:

a. From 98.00 to 99.95 mol%, preferably from 99.00 to 99.95 mol%, most preferably from 99.50 to 99.95 mol% of a symmetric organic semiconducting compound, and

b. From 0.05 to 2.00 mol%, preferably from 0.05 to 1.00 mol%, most preferably from 0.05 to 0.50 mol% of an asymmetric derivative of said symmetric organic semiconducting compound wherein the structural formula of said asymmetric derivative is the structural formula of said symmetric organic semiconducting compound wherein one or more hydrogen atoms have been replaced by a corresponding number of substituents.

This relatively low amount of asymmetric derivative is sufficient for sensitive analyte detection due to its tendency to be incorporated at the grain boundaries of the polycrystalline semiconducting material, where it is most efficient in influencing the electrical characteristics of the field effect transistor. The use of a single layer fulfilling both functions of transporting the charges and detecting the analyte is advantageous as it is easier to process and more economical than the use of a bilayer according to the prior art. In an embodiment of the fourth aspect, at least one of said substituents on said asymmetric derivative may be a polar substituent. This is advantageous for detecting polar analytes.

In an embodiment of the fourth aspect, at least one substituent on said asymmetric derivative may be selected from the group consisting of -C(OH)RR', - COR, -X, -R, -SnR³, -B(OR)(OR'), -BF₃ ^", -CH₂-NRR', -CH₂OR⁵, -CH₂-0-COR, -CH₂-0- CO-OR, -C(OR")RR\ -C(RR')0-CO-OR", -COOR, -CONHR, -CH₂NH-CO-OR, - CH=N-Ar', and -CH₂-NH-Ar',

wherein R, R' and R" are independently selected from the list consisting of H and d-20 alkyl groups,

wherein R⁵ is selected from the group consisting of H, d-20 alkyl groups, - C(0)-0-R (e.g. -C(0)-0-C(CH₃)₃), and C(0)R.(e.g. C(0)CH₃).

In an embodiment of the fourth aspect, said symmetric organic semiconducting compound may be according to any embodiment of the second aspect of the present invention.

In an embodiment of the fourth aspect, said asymmetric derivative of said organic semiconducting compound may be according to any embodiment of the first aspect of the present invention.

Preferably, said symmetric organic semiconducting compound may be according to any embodiment of the second aspect of the present invention and said asymmetric derivative of said organic semiconducting compound may be according to any embodiment of the first aspect of the present invention.

In an embodiment of the fourth aspect, said symmetric organic semiconducting compo formula:

Wherein R¹⁰ is a d-20 alkyl group.

In an embodiment of the fourth aspect, said asymmetric derivative of said organic semiconducting compound may be according to the following formula:

wherein R¹⁰ is as defined above, wherein Y' is a substituent other than hydrogen, preferably selected from the group consisting of -C(OH)RR\ -COR (e.g. -CHO), -X, -R, -SnR₃, -B(OR)(OR'), -BF₃ ^~, -CH₂-NRR', -CH₂OR⁵, -CH₂-0-COR, -CH₂-0-CO-OR, -C(OR")RR', -C(RR')0-CO- OR", -COOR (e.g. -COOH), -CONHR, -CH₂NR⁶R⁷, -CH=N-Ar', -N=CH-Ph, COAr' and -CH₂-NH-Ar',

wherein R⁵ is selected from the group consisting of H, d-₂₀ alkyl groups and hydroxyl protecting groups,

wherein R⁶ is hydrogen when R⁷ is an amine protecting group and otherwhise R⁶ and R⁷ form together an amine protective group such as a phthalimide group, wherein R, R' and R" are independently selected from the list consisting of H,

C1 -20 alkyl groups, or R and R' may be taken together to form a ring, which may be a five- to seven-member ring, which may be non-aromatic, which may be part of a polynuclear condensed ring system, and which may be substituted,

w r general formula (I)

Wherein R², R³ and R⁴ are independently selected from the list consisting of - CN, -OR⁸, -SiR⁸ ₃, -halogen, -R⁸, -S-R⁸, -N0₂, wherein R⁸ is selected from the group consisting of H and d-₂₀ alkyl groups. For instance, R², R³ and R⁴ may be independently selected from H, -CN and -OR⁸ (wherein R⁸ is e.g. -CH₃). As another example, R⁴ may be a halogen (such as e.g. CI) while R² and R³ are hydrogen.

In an embodiment of the fourth aspect, said asymmetric substituted derivative may be essentially located at the grain boundaries of said organic polycrystalline semiconducting material. This is advantageous as it is there that it is most efficient in influencing the electrical characteristics of the field effect transistor.

In a fifth aspect, the present invention relates to a device for detecting analyte within a gaseous phase, said device comprising: a. one or more field effect transistors according to any embodiment of the third aspect electrically connected to said input,

b. means for connecting electrically said one or more field effect transistors to a power supply,

c. means for connecting said one or more field effect transistors to signal processing means.

In an embodiment of the fifth aspect, the signal processing means may comprise signalling means and or analyzing means. The signalling means can for instance be an alarm set to go off when the electrical potential of a transistor goes outside of a predefined range, thereby indicating the presence of the analyte. It can also for instance be a display indicating an electrical parameter of the device such as the electrical potential of a transistor. Analyzing means can for instance be means for determining from a measured electrical parameter (e.g. the electrtical potential) of e.g. at least two field effect transistors, the nature and optionally the amount of analyte present within said gaseous phase.

In an embodiment of the fifth aspect, said analyte may be any kind of compound susceptible to be found within a gaseous phase either as a gas molecule, as a vapor or as an aerosol. In an embodiment, the analyte can also constitute the gaseous phase. The analyte can for instance be selected from the list consisting of nitric oxide, ether, thioethers, alcohols (e.g. ethanol or octanol), amine , thioesters and esters such as allyl propionate In an embodiment of the fifth aspect, said analyte may be a compound according to formula (G)

R-S-R" (G)

wherein R and R' are independently selected from the list consisting of H, C_1-5 linear alkyl, C₃-₅ branched alkyl or R and R' form together a saturated 5 or 6- membered ring. Preferably, (G) is tetrahydrothiophene. This is advantageous because this compound is used as an odorant in natural gas.

In an embodiment of the fifth aspect, said gaseous phase may be natural gas.

This is advantageous because natural gas is a widespread gas used in households and its detection is important due to its suffocating and explosive hazards. In an embodiment of the fifth aspect, the number of field effect transistors can be from 1 to 100 (or even more).

In an embodiment of the fifth aspect where more than one field effect transistors are present, at least two of said field effect transistors may differ by the nature of the asymmetric substituted derivative of said symmetric organic semiconducting compound and/or by the amount (in weight %) of said asymmetric substituted derivative of said symmetric organic semiconducting compound. In a sixth aspect, the present invention relates to the use of a compound according to anyone of the first or the second aspect for detecting an analyte within a gaseous phase.

Particular and preferred aspects of the invention are set out in the accompanying independent and dependent claims. Features from the dependent claims may be combined with features of the independent claims and with features of other dependent claims as appropriate and not merely as explicitly set out in the claims.

Although there has been constant improvement, change and evolution of devices in this field, the present concepts are believed to represent substantial new and novel improvements, including departures from prior practices, resulting in the provision of more efficient, stable and reliable devices of this nature.

The above and other characteristics, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. This description is given for the sake of example only, without limiting the scope of the invention. The reference figures quoted below refer to the attached drawings. Brief description of the drawings

Fig. 1 is a diagrammatic illustration of a device according to an embodiment of the fifth aspect of the present invention.

Fig. 2 is a diagrammatic illustration of a transistor according to an embodiment of the fourth aspect of the present invention. In the different figures, the same reference signs refer to the same or analogous elements.

Description of illustrative embodiments

The present invention will be described with respect to particular embodiments and with reference to certain drawings but the invention is not limited thereto but only by the claims. The drawings described are only schematic and are non-limiting. In the drawings, the size of some of the elements may be exaggerated and not drawn on scale for illustrative purposes. The dimensions and the relative dimensions do not correspond to actual reductions to practice of the invention.

Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequence, either temporally, spatially, in ranking or in any other manner. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.

Moreover, the terms top, bottom, over, under and the like in the description and the claims are used for descriptive purposes and not necessarily for describing relative positions. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other orientations than described or illustrated herein.

It is to be noticed that the term "comprising", used in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It is thus to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression "a device comprising means A and B' is not limited to devices consisting only of components A and B. It means that with respect to this embodiment of the present invention, the only relevant components of the device are A and B.

When the term "comprising" is used anywhere in the present application, and unless provided otherwise, an embodiment where the term "consisting" is replacing the term "comprising" is also considered an embodiment of the present invention. Reference throughout this specification to "one embodiment' or "an embodiment means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment or "in an embodiment in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments.

Similarly it should be appreciated that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.

Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination.

Furthermore, some of the embodiments are described herein as a method or combination of elements of a method that can be implemented by a processor of a computer system or by other means of carrying out the function. Thus, a processor with the necessary instructions for carrying out such a method or element of a method forms a means for carrying out the method or element of a method. Furthermore, an element described herein of an apparatus embodiment is an example of a means for carrying out the function performed by the element for the purpose of carrying out the invention.

In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In other instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.

The following terms are provided solely to aid in the understanding of the invention.

As used herein and unless provided otherwise, the term "C_/-„ alkyt' designates any saturated radical consisting only of hydrogen atoms and from 1 to n carbon atoms. It encompasses linear alkyls, branched alkyls (e.g. C₃-₂o branched radicals), and cycloalkyls (e.g. C₄-2₀ cycloalkyls).

As used herein and unless provided otherwise, the term "pseudohalogen" designates a group that has chemical reactivity similar to that of a halogen group in a Susuki or Stille couplings. Examples of pseudohalogen groups include triflate (-0- S(0)₂-CF₃) and methanesulfonate (-0-S(0)₂-CH₃) amongst others.

As used herein and unless provided otherwise, the term "derivative" when relating to a radical or molecule designates said radical or molecule as well as radicals or molecules obtained by the substitution of one or more hydrogen atoms of this radical or molecule by a corresponding number of substituents. The substituents can be any substituents. For instance, they can be selected from the list consisting of alkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group and phosphine oxide group, and adjacent substituents may form a ring. Other examples of substituents are Y groups as defined in the first aspect of the present invention. Preferably, only one or two hydrogen atoms of the radical is substituted with a substituent. For instance, the term "pyrenyl derivative" encompasses the following radicals:

wherein R¹ to R⁹ could be any sbstituents. For instance, R¹ to R⁹ could be independently selected from hydrogen and the examples of substituents given above, and the R¹ to Rⁿ may form a ring with adjacent substituents. As used herein and unless provided otherwise, the term "protecting group" when relating to a chemical function, refers to a chemical group that can be reversibly introduced in a molecule in order to masks said chemical function, thereby protecting said chemical function from reaction in the next step(s) of a reaction scheme.

Examples of "hydroxyl protecting groups" comprise but are not limited to -

C(CH₃)₃), -C(0)-0-C(CH₃)₃, -CH₂-0-CH₃, ^{0 0} (tetrahydropyranyl ether), - CH-C=CH₂, -CH₂-Ph, -Si(CH₃)₂-C(CH₃)₃, -Si(ph)(ph)(C(CH₃)₃), C(0)-ph and -C(0)R (e.g. -C(0)CH₃ or C(0)C(CH₃)₃).

Exam les of "amino protecting groups" comprise but are not limited to -

, ,-C(0)-0-C(CH₃)₃, -C(0)-0-CH₂-

Ph, -C(0)CH₃, -C(0)CF₃, -CH₂-Ph, -C(Ph)₃.

As used herein and unless provided otherwise, the term "symmetric organic semiconducting compound' relates to an organic semiconducting compound that has at least one centre of symmetry or one axis of symmetry other than the plan comprising tion of said compound. For instance, the following

compound

and compound (E) are such compounds by virtue of a centre of symmetry present in the middle of the bond fusing both thiophene units. Other examples of symmetric organic semiconducting compounds are compound

and compound

by virtue of a centre of symmetry present in the middle of the bond fusing both thiophene units. Y' and R¹⁰ are as defined above,

As used herein and unless provided otherwise, the term "asymmetric organic semiconducting compound" relates to an organic semiconducting compound having no centre of symmetry or axis of symmetry other than the plan comprising the all- planar representation of said compound. For instance, compound (F)

is such a compound by virtue of the substituent Y.

Another example of asymmetric organic semiconducting compound is

compound

wherein Y' and R¹⁰ are as defined above, by virtue of the substitutent Y'.

As used herein and unless provided otherwise, the term "Uthiation agent relates to a compound comprising at least a Lithium atom in its structure and suitable for introducing a lithium atom on an aromatic group (and therefore at the Y position of compound (E)). Examples of such compounds are lithium metal, phenyllithium, lithium diisopropylamide, lithium bis(trimethylsilyl) amide, n-butyllithium, sec-butyllithium, and tert-butyllithium. N-butyllithium is prefered. The invention will now be described by a detailed description of several embodiments of the invention. It is clear that other embodiments of the invention can be configured according to the knowledge of persons skilled in the art without departing from the true spirit or technical teaching of the invention, the invention being limited only by the terms of the appended claims.

Reference will be made to transistors. These are three-terminal devices having a first main electrode such as a drain, a second main electrode such as a source and a control electrode such as a gate for controlling the flow of electrical charges between the first and second main electrodes.

Fig. 1 shows a device (2) for detecting an analyte (3) within a gaseous phase (4), said device comprising a substrate bearing: four field effect transistors (1 ) connected via connecting means (8) to a power supply (5) on one hand and to signaling means (6) on another hand. When put under electrical tension (preferably at its threshold voltage), the device will react to the presence of an analyte interacting with the asymmetric organic semiconducting compound by changing said threshold voltage. This change can trigger the signaling means (6) by e.g. setting off an alarm.

Fig. 2 shows a field effect transistor (1 ) comprising a gate (1 1 ), a dielectric

(12), and an organic polycrystalline semiconducting material (9). An enlarged portion of the organic polycrystalline semiconducting material (9) is shown on the right side of said field effect transistor (1 ). It shows inter-grains regions (10) delimited by grain boundaries.

General synthetic pathway

OR

M - SnH, ZnX ; MgX

OR

Wherein Ar and Y are as defined in the first aspect of the present invention.

Wherein M, X and X' are as defined in the third aspect of the present invention. The following are examples of how the person skilled in the art would introduce some of the functions Y:

Primary and secondary alcohols of the formula -C(OH)RR', aldehyde of the formula - CHO, carboxylic acid of the formula -COOH, ketones of the formula -CO-R, halogens of the formula -X, alkyl groups of the formula -R, stannyl groups of the formula - SnR₃, boronic and boronate groups of the formula B(OR)(OR') can all be synthesized via lithiation.

-BF₃ ^" can be synthesized by reacting boronic acid with K[HF₂] to obtain -BF₃ ^"K⁺.

Primary alcohols of formula -CH₂-OH and amines of the formula -CH₂-NRR' can both be synthesized from an aldehyde.

Ethers of the formula -CH₂OR, esters of the formula -CH₂-0-COR, carbonates of the formula -CH₂0-CO-OR can all be synthesized from a primary alcohol.

Esters of the formula -COOR, amides of the formula -CONHR can all be synthesized from a carboxylic acid.

Carbamates of the formula -CH₂NH-CO-OR can be synthesized from a primary amine.

Synthesis of compound (E) Compound type (E) can be synthesized through i) three synthetic routes by palladium catalyzed Stille (M = -SnR₃), Suzuki (M = -B(OR)(OR') or -BF3^") or organozinc (M = - ZnX') couplings and ii) one synthetic route by Nickel catalyzed (M = -MgX') Kumada coupling. Route A:

Example 1 : General procedure of a Stille coupling:

A mixture of a conjugated π-system (Ar) halogenated derivative (A), a palladium catalyst (e.g. Pd(PPh₃)₄) and a distannyl thieno[3,2-0]thiophene derivative (B) (M = - SnR₃) in an organic solvent (e.g. toluene) is refluxed until the total consumption of Ar- X (e.g. Ar-Br). The desired product (E) is purified using common purification techniques (column chromatography, recrystallisation,...). Example 2: General procedure of a Suzuki coupling:

To a mixture of a conjugated π-system (Ar) halogenated derivative (A), a palladium catalyst (e.g. Pd(PPh₃)₄) and a diboronate (or diboronic) thieno[3,2-0]thiophene derivative (B) (M = -B(OR)(OR') or -BF₃ ^~) in an organic solvent (e.g. toluene), few drops of a phase transfer catalyst (e.g. aliquat 336) and a 2M aqueous solution of an inorganic base (e.g. K₂C0₃, Na₂C0₃ or Cs₂C0₃) are added. The mixture is then refluxed until the total consumption of Ar-X. The desired product (E) is purified using common purification techniques (column chromatography, recrystallisation,...).

Example 3: General procedure of an organozinc coupling:

To a solution of thieno[3,2-0]thiophene or 2,5-dihalothieno[3,2-0]thiophene in an organic solvent (e.g. THF) at -80 °C under an inert gas (e.g. nitrogen or argon) are added dropwise 2.2 equivalents of a lithiated organic base (e.g. n-BuLi) and then 2.2 equivalents of a solution of ZnCI₂ is added. To the mixture is then added a palladium catalyst (e.g. Pd(PPh₃)₄) and 2.2 equivalents of a halogenated conjugated π-system (Ar) derivative (A) and the mixture is stirred for 24 hours. The reaction is quenched by adding water. The mixture is extracted with an organic solvent (e.g. CH₂CI₂) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 4: General procedure of a Kumada coupling:

To 2.2 equivalents of magnesium at room temperature under an inert gas (e.g.

nitrogen or argon) is added a solution of 2,5-dihalothieno[3,2-0]thiophene in an organic solvent (e.g. THF) and few drops of a solution of MgBr₂ and the mixture is refluxed for 30 minutes. To the mixture is then added a nickel catalyst (e.g. NidpppCI₂) and 2.2 equivalents of a halogenated conjugated π-system (Ar) derivative (A) and the mixture is stirred for 24 hours. The reaction is quenched by adding water. The mixture is extracted with an organic solvent (common example: CH₂CI₂) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Route B: Example 5: General procedure of a Stille coupling:

A mixture of a conjugated π-system (Ar) stannyl derivative (C) (M = -SnR₃), a palladium catalyst (e.g. Pd(PPh₃)₄) and 2,5-dihalothieno[3,2-0]thiophene (D) in an organic solvent (e.g. toluene) is refluxed until the total consumption of (D). The desired product (E) is purified using common purification techniques (column chromatography, recrystallisation,...). Example 6: General procedure of a Suzuki coupling:

To a mixture of a conjugated π-system (Ar) boronate (or boronic) derivative (C) (M = B(OR)(OR") or BF₃ ^"), a palladium catalyst (e.g. Pd(PPh₃)₄) and a 2,5-dihalothieno[3,2- bjthiophene (D) in an organic solvent (e.g. toluene), a few drops of a phase transfer catalyst (e.g. aliquat 336) and a 2M aqueous solution of an inorganic base (common base : K₂C0₃, Na₂C0₃ or Cs₂C0₃) are added. The mixture is then refluxed until the total consumption of (D). The desired product (E) is purified using common purification techniques (column chromatography, recrystallisation, ...). Example 7: General procedure of an organozinc coupling:

To a solution of 2.2 equivalents of a halogenated conjugated π-system (Ar) derivative in an organic solvent (e.g. THF) at -80 °C under an inert gas (e.g. nitrogen or argon) is added dropwise 2.2 equivalents of a lithiated organic base (e.g. n-BuLi) and then a solution of ZnCI₂ is added. To the mixture is then added a palladium catalyst (e.g. Pd(PPh₃)₄) and 2,5-dihalothieno[3,2-£>]thiophene (D) and the mixture is stirred for 24 hours. The reaction is quenched by adding water. The mixture is extracted with an organic solvent (e.g. CH₂CI₂) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography,

recrystallisation, ...).

Example 8: General procedure of a Kumada coupling:

To 2.2 equivalents of magnesium at room temperature under an inert gas (e.g.

nitrogen or argon) is added 2.2 equivalents of a solution of a halogenated conjugated TT-system (Ar) derivative in an organic solvent (e.g. THF) and few drops of a solution of MgBr₂ and the mixture is refluxed for 30 minutes. To the mixture is then added a nickel catalyst (e.g. NidpppCI₂) and 2,5-dihalothieno[3,2-0]thiophene (D) and the mixture is stirred for 24 hours. The reaction is quenched by adding water. The mixture is extracted with an organic solvent (common example: CH₂CI₂) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 9: Synthesis of compound (F)

Example 9a: Functionalization of (E) via lithiation

To a suspension of thieno[3,2-0]thiophene derivative (E) (1 eq) in dry THF, at -30 under argon, is added dropwise n-BuLi (2.5 eq, 2.5M solution in hexane). The cooling bath is then removed and the mixture is stirred at room temperature for 25 min. After cooling to -60 ^<€, an excess of the desired functionalization agent Y' is added in one portion and the mixture is stirred until the complete consumption of the starting compound (E). The reaction is quenched by adding water. The mixture is extracted with an organic solvent (common example: CH₂CI₂) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column

chromatography, recrystallisation, ...).

Example 10: Functionalization synthesized from -CHO

For the synthesis of a primary alcohol: see synthetic procedure of compound 5 (example 19)

Example 10a: Synthesis of a primary amine derivatives:

To a solution of thieno[3,2-0]thiophene aldehyde derivative (F) (1 eq) in a saturated solution of NH₄OAc in organic solvent(s) (e.g. EtOH, CHCI₃/EtOH,...) is added a soft reductive agent (3 eq, e.g. NaCNBH₃) and an excess of aqueous NH₃ (e.g. -150 eq). The reaction mixture is stirred under reflux until the total consumption of the starting aldehyde and the subsequent reduction of the imine intermediate. The mixture is then cooled down to room temperature, poured into ice/water and extracted with an organic solvent (e.g. CH₂CI₂). The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 10b: Synthesis of a secondary or a tertiary amine derivatives:

To a solution of thieno[3,2-0]thiophene aldehyde derivative F (1 eq) in a dry organic solvent (e.g. CH₂CI₂, THF,...) is added under argon a soft reductive agent (3 eq, e.g. NaCNBH₃) and the desired primary (if the synthesis of a secondary amine derivative is desired) or secondary amine (if the synthesis of a tertiary amine derivative is desired (1.2 eq). The reaction mixture is stirred under reflux until the total consumption of the starting aldehyde and the subsequent reduction of the imine intermediate. The mixture is then cooled down to room temperature, poured into ice/water and extracted with an organic solvent (common example: CH₂CI₂). The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 11 : Functionalization synthesized from -CH₂-OH

For the synthesis of ether, ester and carbonate derivatives starting from compound 5: see example 20.

Example 11a: Synthesis of halogenated derivatives, example of -CH₂-Br:

PBr₃ (4 eq) is added dropwise to a stirred solution of thieno[3,2-0]thiophene hydroxy derivative 5 (see example 19) (1 eq) in a dry organic solvent (e.g. CH₂CI₂) at 0°C. The reaction mixture is stirred at room temperature until the complete consumption of the starting compound 5. The reaction is then quenched by adding water. The mixture is extracted with an organic solvent (common example: CH₂CI₂) and the combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 12: Functionalization synthesized from -COOH Example 12a: Synthesis of an ester -COOR: To a solution of a thieno[3,2-0]thiophene carboxylic acid derivative (1 eq) in a dry organic solvent (e.g. CH₂CI₂, THF,...), the desired alcohol (1 .5 eq) and N,N- dimethylaminopyridine (0.8 eq) are added under argon. The reaction mixture is then cooled to 0°C before the addition of dicyclohexylcarbodiimide (1.1 eq). The resulting precipitate is filtered off and washed with an organic solvent (e.g. CH₂CI₂). The filtrate is washed with 0.5 M aq. HCI and saturated aqueous NaHC0₃. The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column

chromatography, recrystallisation, ...).

Example 12b: Synthesis of amide -CONHR:

To a solution of thieno[3,2-0]thiophene carboxylic acid derivative (1 eq) in a dry organic solvent (e.g. CH₂CI₂, THF,...) is added under argon the desired primary amine (1 .5 eq) and N,N-dimethylaminopyridine (0.8 eq). The reaction mixture is then cooled to 0°C before the addition of dicyclohexylcarbodiimide (1 .1 eq). The resulting precipitate is filtered off and washed with an organic solvent (e.g. CH₂CI₂). The filtrate is washed with 0.5 M aq. HCI and saturated aq. NaHC0₃. The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column

chromatography, recrystallisation, ...).

Example 13: Functionalization synthesized from -CH₂NRR' (primary amine R = R' = H) Example 13a: Synthesis of a carbamate:

To a solution under argon of a thieno[3,2-0]thiophen-3-yl)methanol derivative in a dry organic solvent (e.g. THF), is added 4-Dimethylaminopyridine (DMAP) and an anhydride derivative (e.g. Di-tert-butyl dicarbonate (Boc₂0)). The mixture is then stirred overnight at room temperature and then extracted with an organic solvent (for example Diethyl ether, CH₂CI₂ or Ethyl acetate). The combined organic phases are washed with water and collected, dried over magnesium sulfate, filtered and the solvents are removed under vacuum. The residue is purified using common purification techniques (column chromatography, recrystallisation ...). The following series of examples relates to a synthetic pathway (Route B) toward various 2,5-bis(thiophen-2-yl)thieno[3,2-b]thiophene derivatives.

Example 14: Synthesis of starting materials (A) and (B)

a. Synthesis of (A)

General procedure:

To a solution of 2-alkylthiophene (1 eq) in dry THF at -80 °C under argon, was added dropwise n-BuLi (1 .2 eq, 2.5M solution in hexane). The mixture was stirred for 10 min at -80 °C and 30 min at -60 °C. After cooling to -80 °C, 2-isopropoxy-4,4,5,5- tetramethyl-1 ,3,2-dioxoborolane (1.1 eq) was added in one portion and the mixture was stirred for 1 hour at -80 °C and then overnight at room temperature. The reaction was quenched by adding water and the mixture was then extracted three times with diethyl ether. The combined organic phases were dried over MgS0₄, filtered and the solvents were removed under vacuum. The crude product was used without any purification.

Example 13a (R¹ = C₄H₉): synthesis of 4,4,5,5-tetramethyl-2-(5-butylthiophen-2- yl)-1 ,3,2-dioxoborolane Product

7.80 g

5.35 g 18.3 mL 7.95 g

60 8.6 mL 78%

38.1 mmol 45.7 mmol 29.9 mmol

41 .9 mmol

¹ H NMR (300 MHz, CDCI₃, 25 °C) 5 7.47 (d, J = 3.4 Hz, 1 H), 6.86 (d, J = 3.4 Hz, 1 H), 2.86 (t, J = 7.6 Hz, 2H), 1 .73 - 1 .60 (m, 2H), 1 .46 - 1 .28 (m, 14H), 0.92 (t, J = 7.3 Hz, 3H).

Example 13b (R¹ = C₆H₁₃): synthesis of 4,4,5,5-tetramethyl-2-(5-hexylthiophen-2- yl)-1 ,3,2-dioxoborolane

7.80 g

6.42 g 18.3 mL 10.82 g

60 8.6 mL 97%

38.1 mmol 45.7 mmol 36.8 mmol

41 .9 mmol

¹ H NMR (300 MHz, CDCI₃, 25 °C) δ 7.47 (d, J = 3.4 Hz, 1 H), 6.86 (d, J = 3.4 Hz, 1 H), 2.85 (t, J = 7.6 Hz, 2H), 1 .67 (m, 2H), 1 .42 - 1 .27 (m, 18H), 0.88 (t, J = 6.6 Hz, 3H). Example 13c (R¹ = C₈H₁₇): synthesis of 4,4,5,5-tetramethyl-2-(5-octylthiophen-2- yl)-1 ,3,2-dioxoborolane

22.55 g

21 .63 g 52.9 mL 35.3 g

250 24.7 mL 99

110.2 mmol 132.2 mmol 109.5 mmol

121 .2 mmol

¹ H NMR (300 MHz, CDCI₃, 25 °C) 5 7.47 (d, J = 3.4 Hz, 1 H), 6.86 (d, J = 3.4 Hz, 1 H), 2.85 (t, J = 7.6 Hz, 2H), 1 .68 (m, 2H), 1 .43 - 1 .18 (m, 22H), 0.88 (t, J = 6.7 Hz, 3H). Example 13d (R¹ = Ci₂H₂₅): synthesis of 4,4,5,5-tetramethyl-2-(5- dodecylthiophen-2-yl)-1 ,3,2-dioxoborolane

2.43 g

3.00 g 5.7 mL 3.72 g

50 2.66 mL 82

11.9 mmol 14.3 mmol 9.8 mmol

121. 2 mmol

¹ H NMR (300 MHz, CDCI₃, 25 °C) 5 7.47 (d, J = 3.4 Hz, 1 H), 6.86 (d, J = 3.4 Hz, 1 H), 2.85 (t, J = 7.6 Hz, 2H), 1 .76 - 1 .61 (m, 2H), 1.30 (m, 30H), 0.89 (t, J = 6.6 Hz, 3H).

b. Synthesis of (B)

(B) is commercially available.

Example14: Synthesis of compounds (1)

General procedure:

To a mixture of thiophen-2-yl boronic derivative (2.5-3.0 eq), 2,5-dibromothieno[3,2- £>]thiophene (1 eq) and Pd(PPh₃)₄ (10% molar) in dry toluene under argon, were added few drops of aliquat 336 and 2M K₂C0₃aq solution. The mixture was then refluxed for 24 hours. After cooling to room temperature, MeOH (100 mL) was added and the precipitate formed was isolated by filtration and washed with water and methanol. The solid residue was then purified by column chromatography on silicagel eluting with chloroform.

Example 14a (R¹ = H): synthesis of 2,5-bis(thiophen-2-yl)thieno[3,2-/3]thiophene

208 mg 115 mg

676 mg 525 mg

15 1.25 0.18 0.38 22% 5.28 mmol 1.76 mmol

mmol mmol

[a] thiophen-2-ylboronic acid (commercially available)

¹ H NMR (300 MHz, CD₂CI₂, 25 °C) 5 7.33 (s, 2H), 7.29 (dd, J = 5.1 , 1 .2 Hz, 2H), 7.24 (dd, J = 3.6, 1 .2 Hz, 2H), 7.06 (dd, J = 5.1 , 3.6 Hz, 2H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 138.99, 138.57, 137.75, 128.07, 124.94, 124.07, 1 15.94. Mp = 254-256°C. R CHCI₃) = 0.89. C₁₄H₈S₄: MALDI-HRMS: (M⁺ ): calc : 303.9509; found: 303.9515.

Example 14b (R¹ = CH₃): synthesis of 2,5-bis(5-methylthiophen-2-yl)thieno[3,2- b]thiophene

1.52 g 374 mg 319 mg

503 mg

6.76 mmol 0.32 0.96 57%

1.69 mmol

1.62 mL mmol mmol

[a] 4,4,5,5-tetramethyl-2-(5-methylthiophen-2-yl)-1 ,3,2-dioxoborolane (commercially available)

¹ H NMR (CDCI₃, 300 MHz, 25 °C) 7.18 (s, 2H), 6.99 (d, J = 3.5 Hz, 2H), 6.70 - 6.65 (m, 2H), 2.49 (s, 6H). ¹³C NMR (75 MHz, CDCI₃, 25 °C) δ 139.75, 139.13, 138.13, 135.47, 126.19, 123.86, 1 15.19, 15.56. Mp = 226-229 °C. R,(CH₂CI₂) = 0.95

Example 14c (R¹ = C₄H₉): synthesis of 2,5-bis(5-butylthiophen-2-yl)thieno[3,2- b]thiophene

1.55 g 992 mg

5.35 g 2.00 g

60 1.34 2.38 35% 20.1 mmol 6.71 mmol

mmol mmol

[a] 4,4,5,5-tetramethyl-2-(5-butylthiophen-2-yl)-1 ,3,2-dioxoborolane

1 H NMR (CDCI₃, 300 MHz, 25 °C) 7.19 (s, 2H), 7.00 (d, J = 3.5 Hz, 2H), 6.69 (d, J = 3.5 Hz, 2H), 2.81 (t, J = 7.6 Hz, 4H), 1 .68 (m, 4H), 1.42 (m, 4H), 0.95 (t, J = 7.3 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 145.93, 139.22, 138.13, 135.17, 125.00, 123.63, 1 15.15, 33.84, 30.04, 22.32, 13.96. R,(CH₂CI₂) = 0.94

Example 14d (R¹ = C₆H₁₃): synthesis of 2,5-bis(5-hexylthiophen-2-yl)thieno b]thiophene

1.55 g 2.43 g

5.91 g 2.00 g

60 1.34 4.32 64% 20.1 mmol 6.71 mmol

mmol mmol

[a] 4,4,5,5-tetramethyl-2-(5-hexylthiophen-2-yl)-1 ,3,2-dioxoborolane

¹ H NMR (CDCI₃, 300 MHz, 25 °C) 7.19 (s, 2H), 7.00 (d, J = 3.5 Hz, 2H), 6.69 (d, J = 3.5 Hz, 2H), 2.80 (t, J = 7.5 Hz, 4H), 1 .76 - 1 .61 (m, 4H), 1 .46 - 1 .24 (m, 12H), 0.90 (t, J = 6.7 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 145.99, 139.22, 138.13, 135.16, 124.99, 123.63, 1 15.15, 31 .72, 30.36, 28.92, 22.73, 14.24. Mp = 189-192°C. R,(CH₂CI₂) = 0.94

Example 14e (R¹ = C₈H₁₇): synthesis of 2,5-bis(5-octylthiophen-2-yl)thieno[3,2- b]thiophene

3.00 g 8.27 g

17.37 g 6.43 g

75 15 2.60 15.6 72 53.9 mmol 21.56 mmol

mmol mmol

[a] 4,4,5,5-tetramethyl-2-(5-octylthiophen-2-yl)-1 ,3,2-dioxoborolane

¹ H NMR (CDCI₃, 300 MHz, 25 °C) 7.19 (s, 2H), 7.00 (d, J = 3.5 Hz, 2H), 6.69 (d, J = 3.6 Hz, 2H), 2.80 (t, J = 7.3 Hz, 4H), 1.69 (m, 4H), 1 .28 (m, 20H), 0.89 (t, J = 6.6 Hz, 6H). ¹³C NMR (CDCI₃, 75 MHz, 25 °C) 146.00, 139.22, 138.13, 135.16, 124.99, 123.63, 1 15.15, 32.02, 31 .76, 30.36, 29.48, 29.37, 29.25, 22.82, 14.26. Mp = 182- 185°C. C30H40S4: EI-HRMS: (M⁺ ): calc: 528.2013; found: 528.2023. R^CHCI₃) = 0.89

Example 14f (R¹ = Ci₂H₂₅): synthesis of 2,5-bis(5-dodecylthiophen-2- yl)thieno[3,2-fo]thiophene Pd(PPh₃)₄ Product

[a] (mL)

0.54 g 1.45 g

3.70 g 1.17 g

50 2.80 0.47 2.26 59

9.78 mmol 3.91 mmol

mmol mmol

[a] 4,4,5,5-tetramethyl-2-(5-dodecylthiophen-2-yl)-1 ,3,2-dioxoborolane

¹ H NMR (CDCI₃, 300 MHz, 40°C) 7.19 (s, 2H), 7.00 (d, J = 3.5 Hz, 2H), 6.69 (d, J = 3.5 Hz, 2H), 2.79 (t, J = 7.6 Hz, 4H), 1 .67 (m, 4H), 1.26 (s, 36H), 0.88 (t, J = 6.5 Hz, 6H). ¹³C NMR: solubility is too low. Mp = 166-172°C. R^CHCIs) = 0.91 . C38H56S4: MALDI-HRMS: (M⁺ ): calc. : 640.3265; found: 640.3284.

Example 15: Synthesis of compounds (2)

General procedure:

To a suspension of 2,5-bis(thiophen-2-yl)thieno[3,2-0]thiophene derivative (1 eq) in dry THF, at -30 under argon, was added dropwise n-BuLi (2.5 eq, 2.5M solution in hexane). The cooling bath was then removed and the mixture was stirred at room temperature for 25 min. After cooling to -60 °C, an excess of dry DMF was added in one portion and the mixture was stirred for additionnal 15 min at -60 °C and the reaction was quenched by adding 30 mL of water. The mixture was extracted with CH₂CI₂ and the combined organic phases were dried over MgS0₄, filtered and the solvents were removed under vacuum. The crude residue was purified by column chromatography on silicagel to give the desired carboxaldehyde product.

Example 15a (R¹ = C₈H₁₇): synthesis of 2,5-Bis(5-octylthiophen-2-yl)thieno b]thiophene-3-carboxaldehyde

111 mg

200 mg 0.38 mL 149 mg

8 0.12 mL 71 0.38 mmol 0.95 mmol 0.27 mmol

1.52 mmol

¹ H NMR (CDCI₃, 300 MHz, 25 °C) 10.23 (s, 1 H), 7.21 (s, 1 H), 7.16 (d, J = 3.6 Hz, 1 H), 7.08 (d, J = 3.6 Hz, 1 H), 6.84 (d, J = 3.6 Hz, 1 H), 6.71 (d, J = 3.6 Hz, 1 H), 2.83 (m, 4H, CH₂-C₇H₁₅), 1.70 (m, 4H), 1.29 (m, 20H), 0.89 (m, 6H). ¹³C NMR (CDCI₃, 75 MHz, 25°C) 184.35, 151 .00, 150.01 , 146.83, 142.54, 136.38, 136.33, 134.96, 130.83, 129.75, 129.42, 125.97, 125.41 , 124.53, 1 13.92, 32.25, 31.98, 31.92, 30.66, 30.61 , 29.72, 29.68, 29.61 , 29.59, 29.50, 23.05, 14.50. Mp = 49-52 °C.

R toluene/petroleum ether 4/6 v/v)=0.46. C31 H40OS4: EI-HRMS: (M⁺ ): calc: 556.1962; found: 556.1971.

Example 15b (R¹ = Ci₂H₂₅): synthesis of 2,5-Bis(5-dodecylthiophen-2- yl)thieno[3,2-/3]thiophene-3-carboxaldehyde

228 mg

500 mg 0.78 mL 240 mg

30 0.24 mL 46 0.78 mmol 1.95 mmol 0.36 mmol

3.12 mmol

1 H NMR (CDCI₃, 300 MHz, 25 °C) δ 10.23 (s, 1 H), 7.21 (s, 1 H), 7.16 (d, J = 3.6 Hz, 1 H), 7.08 (d, J = 3.5 Hz, 1 H), 6.84 (d, J = 3.5 Hz, 1 H), 6.71 (d, J = 3.5 Hz, 1 H), 2.83 (m, 4H), 1 .71 (m, 4H), 1 .27 (s, 36H), 0.88 (t, J = 6.6 Hz, 6H). ¹³C NMR (CDCI₃, 75 MHz, 25 ^<€) δ 184.1 1 , 150.76, 149.77, 146.59, 142.31 , 136.14, 134.73, 130.59, 129.51 , 129.18, 125.73, 125.17, 124.29, 1 13.68, 32.08, 31.73, 31 .68, 30.42, 30.37, 29.80, 29.69, 29.51 , 29.24, 22.85, 14.28. Mp = 62-64 °C. R,(CH₂CI₂/petroleum ether) = 0.63. C₃₉H5₆OS₄: MALDI-HRMS: (M⁺ ): calc: 668.3214; found: 668.3221 .

Example 16: Synthesis of compounds (3)

General procedure:

A mixture of 2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophene-3-carboxaldehyde (1 eq) and p- or m-R-phenylamine (3 eq) in dry toluene was refluxed overnight under argon, in presence of 2 g of molecular sieves (4A). After cooling to room temperature, the molecular sieves were removed by filtration and the filtrate was concentrated under vacuum. The residue was then purified by chromatography on silica gel with 2% of Et₃N in the eluent.

Example 16a (R² = R³ = R⁴ = H): Synthesis of Af-((2,5-bis(5-octylthiophen-2- yl)thieno[3,2-/3]thiophen-3-yl)methylene)aniline

toluene eluent used for Yield

R-CHO^[a] Aniline Product

(mL) chromatography' (%)

84 mg

155 mg CH₂CI₂/petroleum ether 4/6 158 mg

0.90

0.28 v/v 0.25 89 mmol

mmol R_f = 0.87 mmol

83 μΙ_

[a] R-CHO = 2,5-bis(5-octylthiophen-2-yl)thieno[3,2-o]thiophene-3-carboxaldehyde

[b] 2% of Et₃N was added to the eluent

¹ H NMR (300 MHz, CDCI₃, 25 °C) δ 8.87 (s, 1 H), 7.42 (m, 2H), 7.35 - 7.25 (m, 4H), 7.10 (m, 2H), 6.81 (d, J = 3.6 Hz, 1 H), 6.71 (d, J = 3.6 Hz, 1 H), 2.83 (m, 4H), 1 .78 - 1 .64 (m, 4H), 1 .32 (m, 20H), 0.89 (t, J = 6.5 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25 °C) δ 152.20, 151 .78, 149.28, 146.10, 142.37, 142.20, 136.57, 136.22, 135.34, 132.01 , 129.30, 128.40, 128.02, 126.27, 125.34, 125.06, 123.89, 121 .41 , 1 14.08, 32.01 , 31 .75, 31 .72, 30.39, 29.49, 29.46, 29.37, 29.31 , 29.27, 22.82, 14.26. Mp = 63-65 °C. C₃₇H₄₅NS₄: MALDI-HRMS: (M⁺ ): calc : 631 .2435; found: 631 .2453. Example 16b (R² = CN; R³ = R⁴ = H): synthesis of 4-((2,5-bis(5-octylthiophen-2- yl)thieno[3,2-fo]thiophen-3 yl)methyleneamino)benzonitrile

R- 4- toluene eluent used for Yield

Product

CHO^[a] aminobenzonitrile (mL) chromatography' (%)

161 mg CH₂CI₂/Petroleum 183 mg

103 mg

0.29 ether 4/6 v/v 0.28 97

0.87 mmol

mmol R_f = 0.37 mmol

[b] 2% of Et₃N was added to the eluent

¹ H NMR (300 MHz, CDCI₃, 25 °C) δ 8.81 (s, 1 H), 7.70 (d, J = 8.6 Hz, 2H), 7.32 (d, J = 8.6 Hz, 2H), 7.25 (s, 1 H), 7.10 (d, J = 3.6 Hz, 2H), 6.82 (d, J = 3.6 Hz, 1 H), 6.72 (d, J = 3.6 Hz, 1 H), 2.83 (m, 4H), 1 .71 (m, 4H), 1 .28 (m, 20H), 0.88 (t, J = 5.8 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25 °C) δ 155.70, 154.22, 149.90, 146.41 , 144.47, 142.41 , 136.41 , 136.26, 135.05, 133.49, 131 .54, 128.38, 127.81 , 125.54, 125.12, 124.06, 122.12, 1 19.24, 1 14.08, 109.27, 32.01 , 32.00, 31 .75, 31 .72, 30.41 , 30.39, 29.48, 29.45, 29.37, 29.30, 29.26, 22.81 , 14.26. Mp = 69-71 "C. R, (CH₂CI₂/Petroleum ether 4/6 v/v) = 0.37. C₃8H44N₂S₄: MALDI-HRMS: (M⁺ ): calc : 656.2387; found: 656.2381 .

Example 16c (R² = OMe; R³ = R⁴ = H): synthesis of Af-((2,5-bis(5-octylthiophen-2- yl)thieno[3,2-/7]thiophen-3-yl)methylene)-4-methoxyaniline

R- 4- toluene eluent used for Yield

Product

CHO^[a] methoxyaniline (mL) chromatography' (%)

170 mg CH₂CI₂/petroleum ether 181 mg

111 mg

0.31 4/6 v/v 0.28 87

0.90 mmol

mmol R_f = 0.64 mmol

[b] 2% of Et₃N was added to the eluent

1 H NMR (300 MHz, CDCI₃, 25 °C) δ 8.89 (s, 1 H), 7.33 (d, J = 8.9 Hz, 2H), 7.24 (s, 1 H), 7.10, (d, 3.6 Hz, 1 H), 7.09 (d, J = 3.6 Hz, 1 H), 6.95 (d, J = 8.9 Hz, 2H), 6.81 (d, J = 3.6 Hz, 1 H), 6.71 (d, J = 3.6 Hz, 1 H), 3.85 (s, 3H), 2.83 (m, 4H), 1 .71 (m, 4H), 1 .31 (m, 20H), 0.89 (t, J = 6.7 Hz, 6H).¹³C NMR (75 MHz, CDCI₃, 25 °C) δ 158.63, 150.1 1 , 149.10, 146.05, 144.65, 142.12, 141 .43, 136.57, 136.17, 135.41 , 132.23, 128.63, 127.87, 125.30, 125.05, 123.84, 122.73, 1 14.55, 1 14.12, 55.69, 32.02, 31 .76, 31 .73, 30.40, 29.49, 29.47, 29.38, 29.32, 29.27, 22.82, 14.27. Mp = 82-84 °C.

MALDI-HRMS: (M⁺ ): calc : 661 .2541 ; found: 661 .2535.

Example 16d (R² = R⁴ = H; R³ = CN): synthesis of 3-((2,5-bis(5-octylthiophen-2- yl)thieno[3,2-/7]thiophen-3-yl)methyleneamino)benzonitrile

R- 3- toluene eluent used for Yield

Product

CHO^[a] aminobenzonitrile (mL) chromatography' (%)

154 mg CH₂CI₂/petroleum 169 mg

106 mg

0.28 ether 4/6 v/v 0.26 93

0.90 mmol

mmol R_f = 0.45 mmol

[b] 2% of Et₃N was added to the eluent ¹ H NMR (300 MHz, CDCI₃, 25 °C) δ 8.83 (s, 1 H), 7.59 - 7.48 (m, 4H), 7.25 (s, 1 H), 7.10 (d, J = 3.6 Hz, 2H), 6.83 (d, J = 3.6 Hz, 1 H), 6.72 (d, J = 3.6 Hz, 1 H), 2.83 (m, 4H), 1 .71 (m, 4H), 1.49 - 1 .19 (m, 20H), 0.89 (t, J = 6.8 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 153.95, 152.45, 149.85, 146.35, 144.13, 142.36, 136.39, 136.27, 135.09, 131 .55, 130.22, 129.49, 128.36, 127.80, 126.19, 125.54, 125.12, 124.73, 124.03, 1 18.81 , 1 14.07, 1 13.36, 32.01 , 31 .75, 31 .72, 30.42, 30.39, 29.49, 29.45, 29.37, 29.32, 29.27, 22.81 , 14.26. Mp = 89-92°C. C₃8H44N₂S₄: MALDI-HRMS: (M⁺ ): calc: 656.2387; found: 656.2394. Example 16e (R² = R⁴ = H; R³ = OCH₃) synthesis of

A^((2,5-bis(5-octylthiophen-2-yl)thieno[3,2 ]thiophen-3-yl)methylene)-3- methoxyaniline

R- 3- toluene eluent used for Yield

,_H Product

CHCr¹ methoxyaniline (mL) chromatography¹"¹ (%)

165 mg 111 mg CH₂CI₂/petroleum ether 110 mg

0.30 0.90 mmol 20 4/6 v/v 0.17 57 mmol 101 R_f = 0.66 mmol

[b] 2% of Et₃N was added to the eluent

1 H NMR (300 MHz, CDCI₃, 25 °C) 5 8.86 (s, 1 H), 7.31 (m, 1 H), 7.25 (s, 1 H), 7.09 (m, 2H), 6.85 (m, 4H), 6.71 (d, J = 3.6 Hz, 1 H), 3.87 (s, 3H), 2.82 (m, 4H), 1.71 (m, 4H), 1 .29 (m, 20H), 0.89 (t, J = 6.6 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25 °C) δ 160.51 , 153.27, 152.44, 149.34, 146.13, 142.56, 142.20, 136.54, 136.23, 135.32, 131 .96, 130.03, 128.30, 128.06, 125.37, 125.07, 123.92, 1 14.1 1 , 1 13.37, 1 12.05, 107.28, 55.57, 32.02, 31 .76, 31 .72, 30.40, 29.49, 29.46, 29.37, 29.32, 29.27, 22.82, 14.26. Mp = 62-64 °C. C38H47NOS4: MALDI-HRMS: (M⁺ ): calc: 661 .2541 ; found: 661 .2549.

Example 17 and 18: Synthesis of compounds (4)

Example 17 (R² = R³ = H; R⁴ = OMe or CN)

General procedure:

A mixture of 2,5-bis(5-octylthiophen-2-yl)thieno[3,2-ib]thiophene-3-carboxaldehyde (1 eq) and o-R-phenylamine (3 eq) in 20 mL of dry toluene was refluxed overnight under argon, in presence of 2 g of molecular sieves (4A). After cooling to room temperature, the molecular sieves were removed by filtration and the filtrate was concentrated under vacuum. The residue was then dissolved in 20 mL of dry THF and an excess of LiBH₄ (30 eq, 2.0 M in THF solution) was added and the mixture was refluxed for 20 hours, under argon. After cooling to room temperature, 100 mL of diethyl ether was added and the mixture was washed with water. The organic layer was collected, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silicagel.

Example 17a (R² = R³ = H; R⁴ = OCH₃): synthesis of Af-((2,5-bis(5-octylthiophen- 2-yl)thieno[3,2-/7]thiophen-3-yl)methyl)-2-methoxyaniline

Synthesis of the imine Synthesis of the amine

intermediate

R- 2- eluent used for Yield¹"¹

LiBH₄ Product

CHO^[a] methoxyaniline chromatography (%)

154 8.4

111 mg CH₂CI₂/petroleum ether 132 mg mg mmol

0.90 mmol 4/6 v/v 0.20 71

0.28 4.2

102 μί R_f = 0.73 mmol mmol mL

[a] R-CHO = 2,5-bis(5-octy thiophen-2-yl)thieno[3,2-0]thiophene-3-carboxaldehyde

[b] Yield calculated on the two steps (condensation + reduction)

¹ H NMR (300 MHz, CDCI₃, 25 °C) 5 7.18 (s, 1 H), 7.01 (d, J = 3.6 Hz, 1 H), 6.97 (d, J = 3.5 Hz, 1 H), 6.88 - 6.58 (m, 6H), 4.76 (s, 1 H), 4.57 (s, 2H), 3.87 (s, 3H), 2.80 (m, 4H), 1 .69 (m, 4H), 1 .29 (s, 20H), 0.89 (t, J = 6.0 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25 °C) δ 147.42, 147.24, 145.91 , 139.93, 138.82, 138.18, 136.88, 135.26, 133.38, 133.25, 128.37, 126.39, 124.91 , 123.67, 121 .45, 1 17.40, 1 14.82, 1 10.53, 109.86, 55.79, 42.80, 32.01 , 31 .75, 30.33, 29.47, 29.37, 29.31 , 29.24, 22.81 , 14.26. Mp = 80-82 °C. C₃₈H₄₉NOS₄: MALDI-HRMS: (M⁺ ): calc : 663.2697; found: 663.2708. Example 17b (R² = R³ = H; R⁴ = CN): synthesis of 2-((2,5-bis(5-octylthiophen-2- yl)thieno[3,2-/7]thiophen-3-yl)methylamino)benzonitrile

Synthesis of the imine

Synthesis of the amine

intermediate

R- 2- eluent used for Yield^{l J}

LiBH₄ Product

CHO^[a] aminobenzonitrile chromatography (%)

157

8.4 CH₂CI₂/petroleum

mg 103 mg 105 mg

mmol ether 1/1 v/v 57 0.28 0.87 mmol 0.16 mmol

4.2 mL R_f = 0.64

mmol

[a] R-CHO = 2,5-bis(5-octylthiophen-2-yl)thieno[3,2-ib]thiophene-3-carboxaldehyde

[b] Yield calculated on the two steps (condensation + reduction)

1 H NMR (300 MHz, CDCI₃, 25 °C) 5 7.42 (dd, J = 7.7, 1.5 Hz, 1 H), 7.30 (m, 1 H), 7.16 (s, 1 H), 6.99 (dd, J = 3.5, 1 .1 Hz, 2H), 6.78 (d, J = 3.6 Hz, 1 H), 6.74 - 6.64 (m, 2H), 6.59 (d, J = 8.5 Hz, 1 H), 5.10 (t, J = 5.2 Hz, 1 H), 4.67 (d, J = 5.4 Hz, 2H), 2.80 (m, 4H), 1 .69 (m, 4H), 1 .28 (s, 20H), 0.88 (t, J = 6.8, 6H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 149.85, 147.93, 146.23, 140.18, 137.85, 137.31 , 134.85, 134.42, 133.80, 132.95, 132.72, 126.78, 126.69, 125.02, 124.03, 1 17.83, 1 17.61 , 1 14.80, 1 1 1 .14, 96.56, 42.17, 32.00, 31 .73, 30.34, 29.46, 29.36, 29.30, 29.23, 22.80, 14.25. Mp = 99- 101 °C. C₃8H46N₂S₄: MALDI-HRMS: (M⁺ ): calc: 658.2544; found: 658.2567.

Example 18 (R² = R³ = H, CN or OMe; R⁴ = H)

General procedure A:

The imine derivative (1 eq) was dissolved in 15 mL of a 2/1 (v/v) mixture of dry toluene and absolute ethanol. An excess of NaBH₄ (20 eq) was added and the mixture was refluxed overnight, under argon. After cooling to room temperature, 100 mL of diethyl ether was added and the mixture was washed with water. The organic layer was collected, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silicagel.

General procedure B:

The imine derivative (1 eq) was dissolved in 20 mL of dry THF and an excess of LiBH₄ (30 eq, 2.0 M in THF solution) was added and the mixture was refluxed for 20 hours, under argon. After cooling to room temperature, 100 mL of diethyl ether was added and the mixture was washed with water. The organic layer was collected, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silicagel.

Example 18a (R² = CN; R³ = R⁴ = H); General procedure A was used. Synthesis of 4-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-/3]thiophen-3- yl)methylamino)benzonitrile

Yield imine^laJ NaBH₄ eluent used for chromatography Product

(%)

105 mg 121 mg CH₂CI₂ 98 mg

94

0.16 mmol 3.20 mmol R_f = 0.80 0.15 mmol

[a] imine = 4-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3- yl)methyleneamino)benzonitrile

¹ H NMR (300 MHz, CDCI₃, 25 °C) δ 7.42 (d, J = 8.8 Hz, 2H), 7.19 (s, 1 H), 6.98 (d, J = 3.5 Hz, 1 H), 6.97 (d, J = 3.5 Hz, 1 H), 6.78 (d, J = 3.6 Hz, 1 H), 6.68 (d, J = 3.6 Hz, 1 H), 6.61 (d, J = 8.9 Hz, 2H), 4.60 (bs, 3H), 2.80 (m, 4H), 1 .75 - 1.62 (m, 4H), 1 .28 (m, 20H), 0.88 (t, J = 6.6 Hz, 6H). ¹³C NMR (300 MHz, CDCI₃, 25 °C) δ 150.95, 148.01 , 146.36, 139.96, 137.90, 137.32, 134.77, 134.28, 133.87, 132.58, 126.74, 126.37, 125.04, 123.92, 120.35, 1 14.95, 1 12.77, 100.04, 41 .99, 32.00, 31 .73, 30.34, 29.45, 29.36, 29.29, 29.23, 22.80, 14.25. Mp = 84-87°C. Css^eN^: MALDI-HRMS: (M⁺ ): calc: 658.2544; found: 658.2558. Example 18b (R² = R⁴ = H; R³ = CN); General procedure A was used. Synthesis of 3-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-/3]thiophen-3- yl)methylamino)benzonitrile

Yield imine'^aJ NaBH₄ eluent used for chromatography Product

115 mg 136 mg CH₂CI₂/petroleum ether 4/6 v/v 85 mg

0.18 mmol 3.60 mmol R_f = 0.40 0.13 mmol

[a] imine = 3-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3- yl)methyleneamino)benzonitrile ¹ H NMR (300 MHz, CDCI₃, 25 °C) δ 7.24 - 7.16 (m, 2H), 7.02 - 6.95 (m, 3H), 6.87 - 6.76 (m, 3H), 6.68 (d, J = 3.6 Hz, 1 H), 4.56 (d, J = 5.3 Hz, 2H), 4.35 (t, J = 5.2 Hz, 1 H), 2.80 (m, 4H), 1.79 - 1 .60 (m, 4H), 1.35 (m, 20H), 0.88 (t, J = 6.7 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 148.10, 147.99, 146.28, 139.95, 137.98, 137.30, 134.88, 134.10, 132.64, 130.09, 126.80, 126.78, 125.03, 123.89, 121 .75, 1 19.46, 1 17.55, 1 15.58, 1 14.95, 1 13.16, 42.39, 32.01 , 31 .74, 30.34, 29.46, 29.36, 29.31 , 29.24, 22.81 , 14.26. Mp = 129-131 °C.

MALDI-HRMS: (M⁺ ): calc: 658.2544; found: 658.2556. Example 18c (R² = R³ = R⁴ = H); General procedure B was used. Synthesis of Λί- ((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-/3]thiophen-3-yl)methyl)aniline

Yield imine'^aJ LiBH₄ eluent used for chromatography Product

105 mg 5.10 mmol CH₂CI₂/petroleum ether 4/6 v/v 85 mg

0.17 mmol 2.55 mL R_f = 0.79 0.13 mmol

[a] imine = /V-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3- yl)methylene)aniline

¹ H NMR (300 MHz, CDCI₃, 25 °C) δ 7.23 - 7.13 (m, 3H), 6.99 (dd, J = 9.1 , 3.6 Hz, 2H), 6.80 - 6.64 (m, 5H), 4.56 (bs, 2H), 4.09 (s, 1 H), 2.81 (m, 4H), 1 .69 (m, 4H), 1 .35 (m, 20H), 0.89 (t, J = 6.7 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 148.08, 147.50, 145.98, 139.96, 138.60, 136.94, 135.15, 133.45, 133.14, 129.37, 128.09, 126.41 , 124.96, 124.92, 123.71 , 118.29, 1 14.82, 1 13.32, 42.96, 32.01 , 31 .74, 31 .73, 30.33, 29.47, 29.37, 29.31 , 29.24, 22.81 , 14.26. Mp = 60-62°C. C37H47NS4: MALDI-HRMS: (M⁺ ): calc : 633.2591 ; found: 633.2582.

Example 18d (R² = OMe; R³ = R⁴ = H); General procedure B was used. Synthesis of Ai-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-/3]thiophen-3-yl)methyl)-4- methoxyaniline

Yield imine'^aJ LiBH₄ eluent used for chromatography Product

120 mg 5.44 mmol CH₂CI₂/petroleum ether 4/6 v/v 93 mg

0.18 mmol 2.72 mL R_f = 0.39 0.14 mmol [a] imine = N-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3-yl)methylene)-4- methoxyaniline

¹H NMR (300 MHz, CDCI₃, 25 °C) δ 7.17 (s, 1H), 6.98 (m, 2H), 6.77 (m, 3H), 6.68 - 6.60 (m, 3H), 4.52 (s, 2H), 3.87 (s, 1H), 3.73 (s, 3H), 2.80 (m, 4H), 1.77 - 1.59 (m, 4H), 1.28 (m, 20H), 0.88 (t, J = 6.6 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25 °C) δ 152.76, 147.44, 145.96, 142.32, 140.04, 138.64, 136.89, 135.22, 133.25, 133.12, 128.56, 126.36, 124.96, 124.90, 123.68, 115.00, 114.78, 114.64, 55.90, 43.94, 32.01, 31.76, 31.74, 30.34, 29.47, 29.37, 29.31, 29.24, 22.82, 14.26. Mp = 75-77^t€. C38H49NOS4: MALDI-HRMS: (M⁺): calc: 663.2697; found: 663.2681.

Example 18e (R² = R⁴ = H; R³ = OCH₃); General procedure B was used. Synthesis of Ai-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-/3]thiophen-3-yl)methyl)-3- methoxyaniline

Yield imine^laJ LiBH₄ eluent used for chromatography Product 75 mg 3.40 mmol CH₂CI₂/petroleum ether 4/6 v/v 61 mg

82

0.11 mmol 1.70 mL R_f=0.57 0.09 mmol

[a] imine = /V-((2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3-yl)methylene)-3- methoxyaniline

¹H NMR (300 MHz, CDCI₃, 25 °C) 57.18 (s, 1H), 7.08 (m, 1H), 6.98 (m, 2H), 6.75 (d, J = 3.6 Hz, 1H), 6.67 (d, J= 3.6 Hz, 1H), 6.30 (m, 2H), 6.22 (m, 1H), 4.55 (s, 2H), 4.13 (s, 1H), 3.73 (s, 3H), 2.80 (m, 4H), 1.77- 1.59 (m, 4H), 1.31 (m, 20H), 0.89 (t, J=6.6 Hz, 6H).¹³C NMR (75 MHz, CDCI₃, 25°C) δ 160.90, 149.45, 147.56, 146.03, 139.96, 138.62, 136.98, 135.14, 133.54, 133.07, 130.12, 127.94, 126.46, 124.98, 124.95, 123.75, 114.86, 106.41, 103.62, 99.19, 55.21, 42.89, 32.01, 31.76, 31.74, 30.33, 29.47, 29.37, 29.31, 29.24, 22.81, 14.26. Mp = 61-63°C. C38H49NOS4: MALDI-HRMS: (M⁺): calc: 663.2697; found: 663.2704. Example 19: Synthesis of compound (5)

Example 19a (R¹ = C₈H₁₇): Synthesis of (2,5-Bis(5-octylthiophen-2-yl)thieno[3,2- b]thiophen-3-yl)methanol

To a solution of 2,5-bis(5-octylthiophen-2-yl)thieno[3,2-ib]thiophene-3-carboxaldehyde (109.8 mg, 0.20 mmol) in a mixture of dry toluene and absolute ethanol (1/1 v/v) was added in one portion NaBH₄ (45.1 mg, 1.19 mmol) at room temperature. The mixture was then stirred for 15 min and 50 ml_ of water were added. The mixture was extracted with toluene (2 x 50 ml_). The combined organic phases were washed with water, dried over MgS0₄, filtered. The solvents were removed to provide pure (2,5- bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3-yl)methanol (1 12 mg, 0.20 mmol) as a yellow solid in quantitative yield.

¹ H NMR (CDCI₃, 300 MHz, 25 °C) 7.20 (s, 1 H), 7.03 (d, J = 3.5 Hz, 1 H), 6.97 (d, J = 3.6 Hz, 1 H), 6.75 (d, J = 3.5 Hz, 1 H), 6.70 (d, J = 3.6 Hz, 1 H), 4.95 (d, J = 5.8 Hz, 2H), 2.80 (m, 4H), 1 .84 (t, J = 5.9 Hz, 1 H), 1 .69 (m, 4H), 1 .29 (m, 20H), 0.89 (t, J=6.6 Hz, 6H). ¹³C NMR (CDCI₃, 75 MHz, 25 °C) 147.63, 146.10, 139.86, 138.59, 137.14, 135.14, 133.88, 132.95, 129.34, 126.48, 125.03, 124.99, 123.76, 1 14.93, 59.36,

32.02, 31 .76, 30.37, 30.34, 29.48, 29.37, 29.30, 29.26, 22.82, 14.26. Mp = 92-96 °C. C31 H42OS4: MALDI-HRMS: (M⁺ ): calc: 558.21 19; found: 558.2101

Example 20: Synthesis of compounds (6)

Example 20a (R¹ = C₈H₁₇; R⁵ = CH₃): synthesis of 3-(Methoxymethyl)-2,5-bis(5- octylthiophen-2-yl)thieno[3,2-/3]thiophene

To a solution of (2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3-yl)methanol (179 mg, 0.32 mmol) in 10 ml_ of dry THF, was added NaH (16 mg, 0.64 mmol) under argon and at 0°C. The mixture was stirred for 15 min at 0°C and Mel (182 mg, 1 .28 mmol, 80 μΙ_) was added in one portion. The mixture was stirred for 2.5 hours and then 50 ml_ of diethyl ether was added. The mixture was washed with water and the organic phase was collected, dried over magnesium sulfate, filtered and solvents were removed under vacuum. The residue was purified by column chromatography on silicagel using CH₂CI₂/petroleum ether 4/6 v/v as eluent. Yield=88%. ¹ H NMR (300 MHz, CDCI₃, 25 °C) 5 7.19 (s, 1 H), 7.03 (d, J = 3.5 Hz, 1 H), 6.96 (d, J = 3.5 Hz, 1 H), 6.76 (d, J = 3.5 Hz, 1 H), 6.69 (d, J = 3.5 Hz, 1 H), 4.71 (s, 2H), 3.45 (s, 3H), 2.81 (m, 4H), 1 .68 (m, 4H), 1.32 (m, 20H), 0.89 (t, J = 5.9 Hz, 6H). ¹³C NMR (75 MHz, CDCI_3, 25 °C) «5 147.51 , 145.96, 139.85, 138.77, 136.94, 135.27, 134.36, 133.17, 127.39, 126.44, 125.00, 124.91 , 123.65, 1 14.80, 68.41 , 58.65, 32.02, 31 .76, 30.36, 30.34, 29.48, 29.38, 29.32, 29.26, 22.82, 14.26. Mp = 68-69°C. R,(CH₂CI₂/petroleum ether 4/6 v/v) = 0.71. C32H44OS4: MALDI-HRMS: (M⁺ ): calc: 572.2275; found: 572.2266. Example 20b (R¹ = C₈H₁₇; R⁵ = (CO)-0-C(CH₃)₃ (Boc)): synthesis of (2,5-Bis(5- octylthiophen-2-yl)thieno[3,2-/3]thiophen-3-yl)methyl-iert-butyl carbonate

To a solution under argon of (2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3- yl)methanol (150 mg, 0.27 mmol) in 10 mL of dry THF, was added DMAP (33 mg, 0.27 mmol) and Boc₂0 (1 18 mg, 0.54 mmol). The mixture was then stirred overnight at room temperature. 50 mL of diethyl ether was added. The mixture was washed with water and the organic phase was collected, dried over magnesium sulfate, filtered and the solvents were removed under vacuum. The residue was purified by column chromatography on silicagel using CH₂CI₂/petroleum ether 4/6 v/v as eluent.

Yield=96%.

1 H NMR (300 MHz, CDCI₃, 25 °C) 5 7.19 (s, 1 H), 7.03 (d, J = 3.5 Hz, 1 H), 7.01 (d, J = 3.6 Hz, 1 H), 6.76 (d, J = 3.5 Hz, 1 H), 6.70 (d, J = 3.5 Hz, 1 H), 5.32 (s, 2H), 2.81 (m, 4H), 1 .68 (m, 4H), 1 .52 (s, 9H), 1 .31 (m, 20H), 0.89 (t, J = 6.0 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 153.58, 148.05, 146.13, 139.80, 138.88, 137.19, 136.60, 135.07, 132.46, 126.95, 125.08, 125.00, 124.30, 123.84, 1 14.94, 82.74, 62.15, 32.01 , 31.74, 30.35, 29.47, 29.37, 29.31 , 29.25, 27.96, 22.81 , 14.26. Mp = 63-66¾. R,(CH₂CI₂/petroleum ether 4/6 v/v) = 0.71 . C36H50O3S4: MALDI-HRMS: (M⁺ ): calc: 658.2643; found: 658.2637.

Example 20c (R¹ = C₈H₁₇; R⁵ = (CO)-CH₃): Synthesis of (2,5-bis(5-octylthiophen- 2-yl)thieno[3,2-/3]thiophen-3-yl)methyl acetate

To a solution under argon of (2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophen-3- yl)methanol (88 mg, 0.16 mmol) in 10 mL of dry THF, was added a large excess of acetyl chloride (1 ,10 g, 14 mmol, 1 .0 mL) and the mixture was stirred for 24 hours at room temperature. 50 mL of diethyl ether was added and the mixture was washed with water. The organic phase was collected, dried over magnesium sulfate, filtered and the solvents were removed under vacuum. The residue was purified by column chromatography on silicagel using CH₂CI₂/petroleum ether 4/6 v/v as eluent. Yield=81 %.

1 H NMR (300 MHz, CDCI₃, 25 °C) 5 7.20 (s, 1 H), 7.03 (d, J = 3.5 Hz, 1 H), 7.00 (d, J = 3.6 Hz, 1 H), 6.77 (d, J = 3.5 Hz, 1 H), 6.70 (d, J = 3.6 Hz, 1 H), 5.33 (s, 2H), 2.81 (m, 4H), 2.18 (s, 3H), 1 .77 - 1 .63 (m, 4H), 1.29 (m, 20H), 0.89 (t, J = 6.0 Hz, 6H). ¹³C NMR (75 MHz, CDCI₃, 25°C) δ 170.91 , 148.08, 146.24, 139.81 , 138.67, 137.25, 136.07, 134.95, 132.48, 126.87, 125.07, 125.03, 124.43, 123.90, 1 14.98, 60.13, 32.01 , 31 .75, 30.36, 30.34, 29.47, 29.37, 29.31 , 29.25, 22.82, 20.96, 14.26. Mp = 54- 56°C. R,(CH₂CI₂/petroleum ether 4/6 v/v) = 0.54.

MALDI-HRMS: (M⁺ ): calc.: 600.2224; found: 600.2230.

Example 21 : Synthesis of compounds (7)

General procedure:

A mixture of 2,5-bis(5-octylthiophen-2-yl)thieno[3,2-0]thiophene-3-carboxaldehyde (1 eq) and 1 -alkylamine (3 eq) in dry toluene was refluxed overnight under argon, in presence of 2 g of molecular sieves (4A). After cooling to room temperature, the molecular sieves were removed by filtration and the filtrate was concentrated under vacuum. The residue was then dissolved in 15 ml_ of a 2/1 (v/v) mixture of chloroform and absolute ethanol. An excess of NaBH₃CN (30 eq) was added and the mixture was refluxed overnight under argon. After cooling to room temperature, 100 ml_ of diethyl ether was added and the mixture was washed with water. The organic layer was collected, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silicagel.

Example 21a (R¹ = C₈H₁₇; R⁶ = C₁₂H₂₅)

Synthesis of the imine

Synthesis of the amine

intermediate

R- 1- eluent used for Yield^{1 1}

NaBH₃CN Product

CHO^[a] dodecylamine chromatography (%)

[b] Yield calculated on the two steps (condensation + reduction)

¹H NMR (75 MHz, CDCI₃, 25 °C) 57.18 (s, 1H), 7.02 (d, J= 3.5 Hz, 1H), 6.96 (d, J = 3.6 Hz, 1H), 6.74 (d, J= 3.6 Hz, 1H), 6.69 (d, J= 3.6 Hz, 1H), 4.06 (s, 2H), 2.81 (m, 4H), 2.65 (t, J= 7.0 Hz, 2H), 1.69 (m, 4H), 1.59-1.19 (m, 40H), 0.94-0.83 (m, 9H). 1³C NMR (75 MHz, CDCI₃, 25 °C) δ 147.01, 145.78, 139.92, 139.13, 136.64, 135.51, 133.67, 132.64, 130.08, 126.12, 124.95, 124.70, 123.48, 114.77, 49.91, 47.50, 32.09, 32.02, 31.77, 30.37, 30.33, 30.18, 29.86, 29.82, 29.74, 29.53, 29.49, 29.38, 29.32, 29.27, 27.49, 22.85, 22.82, 14.27. Mp = 52-55°C. C₄₃H₆₇NS₄: MALDI-HRMS: (M⁺): calc: 725.4156; found: 725.4178.

Example 21b (R¹ = C₈H₁₇; R⁶ = C₆H₁₃)

Synthesis of the

Synthesis of the amine

imine intermediate

R- 1- eluent used for Yield^{l J}

NaBH₃CN Product

CHO^[a] hexylamine chromatography (%)

156

91 mg 1) CH₂CI₂ 121 mg mg 528 mg

0.90 mmol 2) CH₂CI₂/AcOEt 95/5 v/v 0.19 68

0.28 8.4 mmol

119 μΙ_ R_f=0.72 mmol mmol

[b] Yield calculated on the two steps (condensation + reduction)

1H NMR (300 MHz, CDCI₃, 25 °C) 57.18 (s, 1H), 7.02 (d, J =3.5 Hz, 1H), 6.96 (d, J = 3.5 Hz, 1H), 6.74 (d, J= 3.6 Hz, 1H), 6.69 (d, J= 3.6 Hz, 1H), 4.06 (s, 2H), 2.81 (m, 4H), 2.65 (t, J= 7.1 Hz, 2H), 1.69 (m, 4H), 1.29 (s, 28H), 0.88 (m, 9H).¹³C NMR (75 MHz, CDCI₃, 25 °C) δ 147.02, 145.80, 139.92, 139.14, 136.64, 135.51, 133.66, 132.64, 130.08, 126.13, 124.96, 124.70, 123.48, 114.79, 49.93, 47.50, 32.02, 31.94, 31.77, 30.37, 30.15, 29.49, 29.38, 29.32, 29.26, 27.17, 22.82, 14.26. Mp = 44-47°C. C₃₇H₅₅NS₄: MALDI-HRMS: (M⁺): calc: 641.3217; found: 641.3242.

Example 22: Synthesis of compound 11 : R¹⁰ is a Ci ₂o alkyl group.

The preparation of 2,7-[1 ]dialkylbenzothieno[3,2-0][1 ]benzothiophene 11 is described in Hideaki Ebata, Takafumi Izawa, Eigo Miyazaki, Kazuo Takimiya, Masaaki Ikeda, Hirokazu Kuwabara, Tatsuto Yui, J. Am. Chem. Soc, 2007, 129, 15732-15733.

Example 23: Synthesis of compound 12: Ft¹⁰ is a Ci ₂o alkyl group.

To a solution of 2,7-[1]dialkylbenzothieno[3,2-0][1 ]benzothiophene 11 (1 eq.) in dry dichloromethane is added at room temperature under argon atmosphere AICI₃ (2 eq.) and then oxalyl chloride (0.5 eq.) is added dropwise. The mixture was stirred at room temperature overnight. After cooling to 0°C, the reaction is then quenched by adding water. The mixture is extracted with an organic solvent (common example: dichloromethane) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide compound 12.

Example 24: Synthesis of compound 13: Ft¹⁰ is a Ci ₂o alkyl group.

To a solution of derivative 12 in diethylether is added AICI₃ (4 eq.) and LiAIH₄ (4 eq.). The mixture is stirred at room temperature until the total consumption of the starting material. At 0°C the reaction is poured into water, acidified with HCI solution and the mixture is extracted with an organic solvent (common example: dichloromethane) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide compound 13.

Example 25: Synthesis of ketone 14: R and R¹⁰ are selected from Ci.₂₀ alkyl groups.

To a solution of 2,7-[1]dialkylbenzothieno[3,2-0][1]benzothiophene 11 (1 eq.) in dry dichloromethane is added at room temperature under argon atmosphere AICI₃ (2 eq.) and then an acid chloride (1 eq.) is added dropwise. The mixture was stirred at room temperature overnight. After cooling to 0°C, the reaction is then quenched by adding water. The mixture is extracted with an organic solvent (common example: dichloromethane) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide ketone 14. Example 26: Synthesis of diketone 15: R and R¹⁰ are selected from Ci.₂₀ alkyl groups.

To a solution of 2,7-[1]dialkylbenzothieno[3,2-0][1 ]benzothiophene 11 (1 eq.) in dry dichloromethane is added at room temperature under argon atmosphere AICI₃ (10 eq.) and then an acid chloride (5 eq.) is added dropwise. The mixture was stirred at room temperature overnight. After cooling to 0°C, the reaction is then quenched by adding water. The mixture is extracted with an organic solvent (common example: dichloromethane) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide diketone 15.

Example 27: Synthesis of compound 16: R¹⁰ is a Ci ₂o alkyl group.

To a solution of 2,7-[1]dialkylbenzothieno[3,2-0][1 ]benzothiophene 11 (1 eq.) in dry dichloromethane is added at room temperature under argon atmosphere AICI₃ (10 eq.) and then 2-chlorobenzoyl chloride (5 eq.) is added dropwise. The mixture was stirred at room temperature overnight. After cooling to 0°C, the reaction is then quenched by adding water. The mixture is extracted with an organic solvent (common example: dichloromethane) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide diketone 16.

Example 28: Synthesis of diacid 17: Ft¹⁰ is a C1-20 alkyl group.

To a suspension of compound 16 (1 eq.) in diethyl ether is added at room temperature under argon atmosphere potassium fert-butoxide (20 eq.) and water (6 eq.). The mixture is then refluxed and vigorously stirred overnight. After cooling to room temperature, the mixture is acidified up to pH = 1 and the precipitate formed is isolated by filtration. The solid residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide diacid 17.

Example 29: Synthesis of compound 18: Ft¹⁰ is a C1 20 alkyl group.

To a solution of 2,7-[1 ]dialkylbenzothieno[3,2-0][1 ]benzothiophene 1 (1 eq.) in dry dichloromethane is added at room temperature under argon atmosphere AICI₃ (2 eq.) and then 2-chlorobenzoyl chloride (1 eq.) is added dropwise. The mixture was stirred at room temperature overnight. After cooling to 0°C, the reaction is then quenched by adding water. The mixture is extracted with an organic solvent (common example: dichloromethane) and the combined organic phases are dried over MgS0₄, filtered and the solvents are removed under vacuum. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide compound 18. Example 30: Synthesis of acid 19: Ft¹⁰ is a C1-20 alkyl group.

To a suspension of compound 18 (1 eq.) in diethyl ether is added at room temperature under argon atmosphere potassium fert-butoxide (10 eq.) and water (3 eq.). The mixture is then refluxed and vigorously stirred overnight. After cooling to room temperature, the mixture is acidified up to pH = 1 and the precipitate formed is isolated by filtration. The solid residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide acid 19.

Example 31 : Synthesis of diester 8 or ester 24 derivatives: R and R¹⁰ are selected from C1-20 alky I group.

To a solution of carboxylic diacid 17 or acid 19 derivatives (1 eq.) in a dry organic solvent (e.g. CH₂CI₂, THF,...), the desired alcohol (1 .5 to 3 eq.) and N,N- dimethylaminopyridine (0.8 to 1 .6 eq.) are added under argon. The reaction mixture is then cooled to 0°C before the addition of dicyclohexylcarbodiimide (1 .1 to 2.2 eq.). The resulting precipitate is filtered off and washed with an organic solvent (e.g. CH₂CI₂). The filtrate is washed with 0.5 M aq. HCI and saturated aqueous NaHC0₃. The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide diester 8 or ester 24.

Example 32: Synthesis of diamide 9 or amide 25 derivatives: R and R¹⁰ are selected from C1 20 alky I group.

To a solution of carboxylic diacid 17 or acid 19 derivatives (1 eq.) in a dry organic solvent (e.g. CH₂CI₂, THF,...) is added under argon the desired primary amine (1.5 to 3 eq.) and N,N-dimethylaminopyridine (0.8 to 1 .6 eq.). The reaction mixture is then cooled to 0°C before the addition of dicyclohexylcarbodiimide (1.1 to 2.2 eq.). The resulting precipitate is filtered off and washed with an organic solvent (e.g. CH₂CI₂). The filtrate is washed with 0.5 M aq. HCI and saturated aq. NaHC0₃. The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...) to provide diamide 9 or amide 25.

Example 33: Synthesis of dialdehyde 10 or aldehyde 26 derivatives: Ft¹⁰ is a C₁-₂₀ alkyl group.

To a solution of oxalyl chloride (1 .1 to 2.2 eq.) in dry CH₂CI₂ under argon at -80°C is slowly added DMSO (2.2 eq. to 4.4 eq.) Then a solution of dialcohol 21 or alcohol 28 (1 eq.) in dry CH₂CI₂ is added and the reaction is stirred for at least 30 min at -80 °C. Triethylamine (2.75 eq to 5.5 eq.) is then added dropwise and the solution is allowed to warm to room temperature. The reaction is stirred up to the total consumption of (di)alcohol derivatives. Water is then added and the mixture is extracted with an organic solvent (e.g. CH₂CI₂). The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 34: Synthesis of a primary diamine 20 and amine 27 derivatives: R, R' are H and R¹⁰ is a C1 20 alkyl group.

To a solution of dialdehyde or aldehyde derivatives 10 and 26) (1 eq.) in a saturated solution of NH₄OAc in organic solvent(s) (e.g. EtOH, CHCI₃/EtOH,...) is added a soft reductive agent (3 to 6 eq., e.g. NaCNBH₃) and an excess of aqueous NH₃ (e.g. -150 eq.). The reaction mixture is stirred under reflux until the total consumption of the starting aldehyde or dialdehyde and the subsequent reduction of the imine intermediate. The mixture is then cooled down to room temperature, poured into ice/water and extracted with an organic solvent (e.g. CH₂CI₂). The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 35: Synthesis of a secondary or a tertiary diamine 20 and amine 27 derivatives: R is either H (secondary) or is a C_{1 20} alkyl group (tertiary), R' and R¹⁰ are selected from C_{1 2}o alkyl groups.

To a solution of dialdehyde or aldehyde derivatives (10 and 26) (1 eq.) in a dry organic solvent (e.g. CH₂CI₂, THF,...) is added under argon a soft reductive agent (3 to 6 eq., e.g. NaCNBH₃) and the desired primary (if the synthesis of a secondary (di)amine derivatives are desired) or secondary amine (if the synthesis of a tertiary (di)amine derivatives are desired (1 .2 to 2.4 eq.). The reaction mixture is stirred under reflux until the total consumption of the starting aldehyde and the subsequent reduction of the imine intermediate. The mixture is then cooled down to room temperature, poured into ice/water and extracted with an organic solvent (common example: CH₂CI₂). The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 36: Synthesis of dialcohol 21 or alcohol 28 derivatives: R¹⁰ is a Ci.₂₀ alkyl group.

To a cold solution of carboxylic diacid 17 or acid 19 in dry THF under argon atmosphere is added LiAIH₄ (2 to 4 eq.). The reaction is then stirred at room temperature until the total consumption of the starting materials. The reaction is then cooled to 0°C and quenched by adding water and the mixture is extracted with an organic solvent (common example: CH₂CI₂). The combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 37: Synthesis of dihalogenated 22 or halogenated 29 derivatives: R¹⁰ is a C1-20 alkyl group

PBr₃ (4 to 8 eq) is added dropwise to a stirred solution of dialcohol 21 or alcohol 28 derivatives (1 eq) in a dry organic solvent (e.g. CH₂CI₂) at 0°C. The reaction mixture is stirred at room temperature until the complete consumption of the starting compounds 21 or 28. The reaction is then quenched by adding water. The mixture is extracted with an organic solvent (common example: CH₂CI₂) and the combined organic phases are dried over MgS0₄, filtered and concentrated under reduced pressure. The crude residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 38: Functionalization of 21 and 28 into 23 and 30 respectively,

Synthesis of an ether or a diether: R and R¹⁰ are selected from Ci.₂₀ alkyl groups.

To a solution of 21 or 28 (1 eq.) in dry THF, is added NaH (2 to 4 eq.) under argon and at 0°C. The mixture is stirred for 15 min at 0°C and an alkyl halide derivative (4 to 8 eq.) is added in one portion. The mixture is stirred up to the total consumption of starting materials and then diethyl ether is added. The mixture is washed with water and the organic phase is collected, dried over magnesium sulfate, filtered and solvents are removed under vacuum. The residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 39: Synthesis of a dicarbamate 20 or a carbamate 27: Ft¹⁰ is a C1-20 alkyl group, R is hydrogen, R' is -CO-O-R", and R" is selected from C1 20 alkyl groups and aryl groups (such as e.g. phenyl).

To a solution under argon of 20 or 27 (1 eq.) (wherein R and R' are hydrogen) in dry THF, is added NaH (1 .1 to 2.2 eq) and a large excess of an anhydride derivative of general formula R"0-CO-0-CO-OR" (2.2 to 4.4 eq) and the mixture is stirred for 24 hours at room temperature. Diethyl ether is added and the mixture is washed with water. The organic phase is collected, dried over magnesium sulfate, filtered and the solvents are removed under vacuum. The residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

Example 40: Other synthesis of a dicarbonate 23 or a carbonate 30: R¹⁰ is a C1 20 alkyl group, R is -CO-O-R", and R" is selected from C1 20 alkyl groups and aryl groups (such as e.g. phenyl).

To a solution under argon of 21 or 28 (1 eq.) in dry THF, are added DMAP (0.8 to 1 .6 eq.) and an anhydride derivative of general formula R"0-CO-0-CO-OR" (2.2 to 4.4 eq.). The mixture is then stirred overnight at room temperature. Diethyl ether is added. The mixture is washed with water and the organic phase is collected, dried over magnesium sulfate, filtered and the solvents are removed under vacuum. The residue is purified using common purification techniques (column chromatography, recrystallisation, ...).

It is to be understood that although preferred embodiments, specific constructions and configurations, as well as materials, have been discussed herein for devices according to the present invention, various changes or modifications in form and detail may be made without departing from the scope and spirit of this invention. Steps may be added or deleted to methods described within the scope of the present invention.

Claims

1.

Wherein Ar is selected from pyrenyl derivatives, pyrrolyl derivatives, carbazolyl derivatives, naphthalenyl derivatives, naphtha[1 ,8-bc:5,4- b'c']dithiophenyl derivatives, benzodithiophenyl derivatives, anthrathiophenyl derivatives, thiazolyl derivatives, thiazolothiazolyl derivatives, thiadiazolyl derivatives, thienoacenyl derivatives, tetrathiafulvalenyl derivatives, thiophenyl derivatives, thieno[3,2-b]thiophenyl derivatives, and thieno[2,3- b]thiophenyl derivatives, and

wherein Y is a substituent other than hydrogen.

2. A compound according to claim 1 , wherein Y is selected from - C(OH)RR', -COR, -X, -R, -SnR₃, -B(OR)(OR'), -BF₃ ^", -CH₂-NRR', -CH₂OR⁵, - CH₂-0-COR, -CH₂-0-CO-OR, -C(OR")RR', -C(RR')0-CO-OR", -COOR, - CONHR, -CH₂NH-CO-OR, -CH=N-Ar', and -CH₂-NH-Ar',

wherein R⁵ is selected from the group consisting of H, d-₂₀ alkyl groups, - C(0)-0-R, and C(0)R,

wherein R, R' and R" are independently selected from the list consisting of H and C1 -20 alkyl groups,

wherein X is selected from the list consisting of CI, Br, I, F and pseudohalogens

w r general formula (I)

wherein R², R³ and R⁴ are independently selected from the list consisting of - CN, -OR⁸, -SiR⁸ ₃, -halogen, -R⁸, -S-R⁸, -N0₂, wherein R⁸ is selected from the group consisting of H and d-₂o alkyl groups.

3. The compound according to claim 1 or claim 2, wherein Ar is selected from the list consisting of

Wherein R and R' are independently selected from H, d-20 alkyl groups, Wherein is 0, 1 or 2, wherein n₂ is from 1 to 3, and wherein n₃ is 0 or 1 .

The compound according to anyone of the preceding claims wherein said com ound has the general formula (I la)

5. The compound according to anyone of the preceding claims wherein Y is selected from -CH₂-NRR', -CONHR, -CH₂NH-CO-OR, -CH=N-Ar\ and -CH₂- NH-Ar".

Wherein Ar is selected from pyrenyl derivatives, pyrrolyl derivatives, carbazolyl derivatives, naphthalenyl derivatives, naphtha[1 ,8-bc:5,4- b'c']dithiophenyl derivatives, benzodithiophenyl derivatives, anthrathiophenyl derivatives, thiazolyl derivatives, thiazolothiazolyl derivatives, thiadiazolyl derivatives, thienoacenyl derivatives, tetrathiafulvalenyl derivatives, thiophenyl derivatives, thieno[3,2-b]thiophenyl derivatives, and thieno[2,3- b]thiophenyl derivatives, with the proviso that Ar is not the unsubstituted thiophenyl group.

7. A semiconducting device comprising a compound according to anyone of the preceding claims.

8. A field effect transistor (1 ) comprising an organic polycrystalline semiconducting material, said material comprising:

a. From 98.00 to 99.95 mol% of a symmetric organic semiconducting compound, and

b. From 0.05 to 2.0 mol% of an asymmetric derivative of said symmetric organic semiconducting compound, wherein the structural formula of said asymmetric derivative is the structural formula of said symmetric organic semiconducting compound wherein one or more hydrogen atoms have been replaced by a corresponding number of substituents.

9. The field effect transistor (1 ) according to claim 8, wherein at least one of said substituents is a polar substituent.

10. The field effect transistor (1 ) according to claim 8 or claim 9, wherein at least one of said substituents on said asymmetric derivative is selected from the group consisting of -C(OH)RR', -COR, -X, -R, -SnR₃, -B(OR)(OR'), -CH₂- NRR', -CH₂OR⁵, -CH₂-0-COR, -CH₂-0-CO-OR, -C(OR")RR', -C(RR')0-CO- OR", -COOR, -CONHR, -CH₂NH-CO-OR, -CH=N-Ar', and -CH₂-NH-Ar', wherein R⁵ is selected from the group consisting of H, d-20 alkyl groups, - C(0)-0-R, and C(0)R,

wherein R, R' and R" are independently selected from the list consisting of H, d-20 alkyl groups.

1 1 . The field effect transistor (1 ) according to anyone of claims 8 to 10, wherein said symmetric organic semiconducting compound is according to claim 6 and wherein said asymmetric organic semiconducting compound is according to any one of claims 1 to 5.

12. A device (2) for detecting an analyte (3) within a gaseous phase (4), said device (2) comprising:

a. One or more field effect transistors (1 ) according to anyone of claims 8 to 1 1 electrically connected to said input, and

b. Means (8) for connecting electrically said one or more field effect transistors (1 ) to a power supply (5),

c. Means for connecting said one or more field effect transistors (1 ) to signal processing means (6).

13. The device (2) according to claim 12, wherein said analyte (3) is tetrahydrothiophene.

14. The device (2) according to claim 12 or claim 13, wherein at least two of said field effect transistors (1 ) differ by the nature of the asymmetric substituted derivative of said symmetric organic semiconducting compound and/or by the amount (in weight %) of said asymmetric substituted derivative of said symmetric organic semiconducting compound.

15. Use of a compound according to anyone of claims 1 to 6 for detecting an analyte (3) within a gaseous phase (4).