EP2571886A2

EP2571886A2 - Organic compounds, process for preparing same and uses in electronics

Info

Publication number: EP2571886A2
Application number: EP11727236A
Authority: EP
Inventors: Gaëlle TRIPPE-ALLARD; Jean-Christophe Lacroix
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite Paris Diderot Paris 7
Current assignee: Centre National de la Recherche Scientifique CNRS
Priority date: 2010-05-19
Filing date: 2011-05-19
Publication date: 2013-03-27
Also published as: FR2960237A1; FR2960237B1; US9056872B2; WO2011144873A3; US20130079529A1; WO2011144873A2

Abstract

The present invention relates to novel organic compounds, to the processes for preparing same and to the uses thereof, firstly in the electronics field, in particular in the fields referred to as plastic electronics and molecular electronics, and, secondly, in the coatings field, in particular in the fields of adhesion primers and intelligent coatings. The invention also relates to a material comprising a novel compound according to the invention.

Description

ORGANIC COMPOUNDS, PROCESS FOR THE PREPARATION AND

ELECTRONIC USES

DESCRIPTION

Technical area

The present invention relates to novel organic compounds, to their methods of preparation and to their uses, firstly in the field of electronics, particularly in the fields of plastic electronics and molecular electronics and of on the other hand in the field of coatings, in particular in the fields of adhesion primers and intelligent coatings.

The invention also relates to a material comprising a novel compound according to the invention.

In the description below, references in brackets [] refer to the list of references at the end of the text.

State of the art

For several years, research aimed at developing new organic compounds, in the form of a crystal or a polymer for example, which show properties similar to inorganic compounds, continues to grow. These properties are conduction by electrons and holes, as well as the presence of a band gap. In addition, research to develop new functional coatings is also very active. Due to their elasticity, lightness, strength and plasticity, organic molecules are of great interest because of the scope of their fields of application in electronics or as functional coatings.

In contrast to materials based on inorganic compounds (inorganic materials) such as silicon for example, materials based on organic molecules (organic materials) have the advantage of being deposited and / or grafted, in the form of layers. or thin films by inexpensive techniques, on flexible substrates and light, conductive or insulating.

In addition, as inorganic materials, organic materials can be doped, that is to say the electron density (N-doping) or holes (P-doping), can be increased.

The immobilization of organic compounds, in the form of a polymer, for example, on insulating substrates, metal, semiconductor or carbon-based, makes it possible to develop new interfaces for applications that can range from the manufacture of molecular electronic devices or plastics, bio-sensor systems, anticorrosion coatings, intelligent coatings.

The formation of layers or thin films resulting from the grafting or deposition of molecules or organic polymers on the surface of the substrates, allows both to maintain the properties of the substrates and to give the surface of the material new and distinct properties. One particularly interesting property is the ability to switch between different states of electrical conduction. The nature of the organic compounds can determine the electrical potential at which the layer switches.

To date, existing organic compounds capable of forming layers deposited or grafted onto the surface of the substrates, are not entirely satisfactory for at least one of the following reasons:

they are not suitable for any type of substrate in the sense that they can not form thin layers or films by grafting or deposition on any type of substrate;

the layer (s) formed (s) are not always homogeneous (in thickness in particular), which can affect the quality and the properties of the layer and the substrate on which it is deposited or grafted, of the interface between the substrate and the layer (s) and thus the quality of the material or devices using these layers;

the number of layer (s) deposited or grafted can not be modulated, which can lead to films either too fine or too thick, and therefore affect the quality and the properties of this layer, of the substrate on which said layer is deposited or grafted, the interface and therefore the quality of the material or devices using these layers;

The nature of the interface between the substrate and the layer is not always controlled, which can lead to weakly adherent layers and / or to an interface having inadequate hole or electron injection barriers for the intended uses, and may affect the quality of devices using these layers;

the layer or layers formed often have defects of micron or subnanometric size which adversely affect the quality of the layer, the substrate on which it is deposited or grafted, the interface and consequently the quality of the material or devices using these layers ;

- Although grafted on the substrate, the layer or layers formed are not always electroactive, which can lead to properties that can not be adjusted via an electrochemical or electrical stimulus (injection of electron or holes for example) and thus affect the quality of devices using these layers;

- Although grafted on the substrate, or electroactive layers formed do not always switch between two states having different conduction properties;

the electroactive layer or layers formed do not always switch between two states having different conduction properties at the desired electrical or electrochemical potential, which can affect the quality of the devices using these layers;

the use of organic compounds and / or the formation of organic polymers can pose technical problems, particularly in terms of reproducibility and / or industrialization.

The need for new organic compounds capable of forming one or more electroactive layers that can switch between an insulating state and a conductive state on the surface of different types of substrates, overcoming the defects, disadvantages and obstacles of the state of the art, remains current. There is therefore a real need to have new organic compounds that are compatible with any type of substrate and capable of forming one or more layer (s) on their surface.

There is also a real need to propose new organic compounds whose implementation and / or polymer formation is easy and reproducible, industrially feasible and economically interesting.

Description of the invention

The present invention is specifically intended to meet these needs by providing compounds of formula (I):

in which

^■ R represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C4 alkoxy group, a -COOR ₃ group, a -COR 3 group, a group -SR 3, a -SeR3 group, - If (OR3), a group -NR ₃ R ₄ , a group -C≡N, a group -N ₃ , a group -C = CH, a heterocycle selected from the group comprising pyrrole, furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine, phenanthroline, pyrazine, pyridazine and pyrimidine, ferrocene, cobaltocene, a polyethylene group of formula - (- O-CH 2 -CH 2 -) _p -, a C 1 -C 10 alkyl group, a phenyl group, the said polyethylene, alkyl, phenyl and heterocycle groups being optionally substituted by one or more selected groups in the group comprising:

• a group -COOR 3, -COR _3, a hydroxyl group, a Ci-C ₄ alkoxy, and -CONR3R4;

^■ R 2 represents an amino group (-NH 2), a diazo group (N ⁺ _2), an aniline group, a phenyl group substituted by a diazo group (N ⁺ _2), a group - N0 _2, phenyl substituted by group -N0 ₂ ; optionally substituted with one or more groups selected from an alkyl group of C, a -COOR ₃ group, a -COR ₃ group, a hydroxyl group, a C ₁ -C ₄ alkoxy group, a -CONR ₃ R ₄ group, a -NO ₂ group, a -NR ₃ R ₄ group;

Z represents thiophene, optionally substituted with one or more groups selected from the group consisting of:

A C ₁ -C ₁₀ alkyl group, a carboxyl group, a -COOR ₃ group, a hydroxyl group or a C ₁ -C ₄ alkoxy group;

^■ R 3 and R ₄ represent, independently of one another, a hydrogen atom, an alkyl group C ₁ -C 6, phenyl group;

^■ n = 1, 2, 3, 4, 5;

- m = 0, 1, 2, 3;

^■ p = 0, 1, 2, 3, 4, 5;

it being understood that when Ri represents a hydrogen atom, m = 0, then n is different from 1.

The compounds of formula (I) have the advantage of being compatible with any type of substrate and can form one or more layer (s) on their surface. The formation of said layer (s) on the surface of the substrate may be by deposition or by grafting of the compounds of formula (I). For the purposes of the invention, deposition means the formation of one or more layers on the surface of a substrate by oxidation of the compounds of formula (I). By grafting is meant the formation of one or more layers on the surface of a substrate by reduction of said compounds of formula (I) namely: a binding of the compounds on the substrate in a substantially covalent manner.

Thus, the compounds of formula (I) may adhere to the substrates by grafting. The grafting can be done by means of any type of bonds allowing a good adhesion of said compounds on the substrate, for example by means of strong bonds.

The term "alkyl" in the sense of the present invention, a saturated carbon group, linear, branched or cyclic, optionally substituted, comprising 1 to 10 carbon atoms, for example 1 to 6 carbon atoms, for example 1 to 4 atoms of carbon. As an indication, mention may be made of methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl iso-butyl, tert-butyl, cyclobutyl, pentyl (or amyl), sec-pentyl, iso-pentyl, neopentyl, hexyl, isohexyl, tert-hexyl, neohexyl, heptyl, octyl, nonyl, decyl and their branched and / or cyclic isomers.

For the purposes of the present invention, the term "heterocycle" means a system comprising at least one aromatic ring, a saturated or unsaturated ring comprising at least one heteroatom chosen from the group comprising sulfur, oxygen, nitrogen and phosphorus. . In the context of the invention, the heterocycles may comprise from 3 to 20 carbon atoms.

The heterocycles may be substituted. By way of example of a heterocycle, mention may be made of pyrrolidine, pyrazoline, pyrazolidine, imidazole, imidazolidine, piperidine, piperazine, oxazolidine, isoxazolidine, morpholine, thiazole, thiazolidine isothiazolidine, tetrahydrofuran, pyridine, bipyridine, terpyridine, pyridazine, pyrazine, pyrimidine, pyrrole, pyrazole, triazole, imidazoline, thiazoline, oxazole, oxazoline, isooxazoline, thiadiazoline, oxadiazoline, thiophene, furan, quinoline, isoquinoline, benzopyrrole, benzofuran, benzothiophene. phosphole, tetrathiafulvalene, selenophene, phenanthroline, and the like.

For the purposes of the present invention, the term "alkoxy" means a linear, branched or cyclic, optionally substituted, saturated alkyl group bonded to an oxygen atom. For example, an alkoxy radical may be a methoxy, ethoxy, propoxy or isopropoxy radical. , n-butoxy, tert-butoxy, neopentoxy, n-hexoxy, or a similar radical.

By "aryl" group is meant an optionally substituted aromatic hydrocarbon. For example, an aryl group may be a phenyl group, a benzyl group, a tolyl group, a xylyl group, vinylbenzene.

For the purposes of the invention, the halogen atom may be chosen from the group comprising fluorine, chlorine, bromine and iodine.

The term "substituted" denotes, for example, the replacement of a hydrogen atom in a given structure with a group as defined above. When more than one position may be substituted, the substituents may be the same or different at each position. In the context of the present invention, "switching (switch in English)" means the alternation between the reduced non-conductive (or insulating) state and the conductive oxidized state of the organic compounds according to the invention.

For the purposes of the invention, the term "polymer" means a sequence of at least two compounds, identical or different, natural or synthetic. This sequence can be linear or branched. The term "polymer" includes oligomers, homopolymers, and copolymers.

For the purposes of the invention, the term "electroactive or electroactivity" refers to a state in which an exchange of electrons occurs. More particularly, an electroactive layer designates a layer capable of alternating between two different conduction states, in particular between the nonconductive (or insulating) reduced state and the conductive oxidized state.

According to a first embodiment of the invention, the compounds of the invention may be of formula (I) in which: R 1 represents a hydrogen atom or thiophene; R ₂ represents the amino group (-NH 2) or the aniline group; Z represents thiophene; n = 1, 2, 3; m = 0, 1; it being understood that when Ri represents a hydrogen atom, m = 0, then n is different from 1. The compounds according to the first embodiment are particularly advantageous since they are capable of forming layers or films on substrates by grafting. This makes it possible to obtain a layer having both the switching nature between an insulating state and a conductive state, and a very good adhesiveness to the substrate.

According to a second embodiment, the compounds of the invention may be of formula (I), in which: R ₁ represents a hydrogen atom or thiophene; R ₂ represents the aniline group, the phenyl group substituted by the diazo (N ₂ ⁺ ) group, the phenyl group substituted with the -NO ₂ group; Z represents thiophene; n = 1, 2, 3; m = 0, 1; it being understood that when R 1 represents a hydrogen atom, m = 0, then n is not equal to 1. The compounds according to the second embodiment make it possible to form thin layers or films having the switching capacity, either by grafting or by deposit, on any type of substrate.

According to the invention, it is preferable that when m = 0, n is different from 1. According to an advantageous variant of the invention, R 1 represents a hydrogen atom; R2 represents the aniline group; n = 2; and m = 0. It is therefore 2- (4-aminophenyl) -3,4,3 ', 4'-bis (ethylenedioxy) -5,2'-bithiophene (2EB).

According to another advantageous variant of the invention, Ri represents thiophene, R ₂ represents the aniline group; n = 1; and m = 0. It is therefore 2- (4-Aminophenyl) -3,4-ethylenedioxy-5,2'-bithiophene (TEB).

According to an advantageous variant of the invention, R 1 represents a hydrogen atom; R ₂ represents the aniline group; Z represents thiophene; n = 1; and m = 1. This is 2- (4-Aminophenyl) -3 ', 4'-ethylenedioxy-5,2'-bithiophene (ETB).

According to an advantageous variant of the invention, R 1 represents a hydrogen atom; R ₂ represents the aniline group; n = 3; and m = 0. It is therefore 2- (4-Aminophenyl) -3,4,3 ', 4', 3 ", 4" -ter (ethylenedioxy) -5,2 ', 5', 2 " -terthiophene (3EB).

Surprisingly, when the thin layers or films are formed from the compounds 2EB, TEB, ETB or 3EB, better adhesion to the substrate can be obtained while maintaining the switching capacity between an insulative state and a conductive state.

The compounds according to the invention offer several advantages over the organic compounds conventionally used. As already indicated, the compounds according to the invention can form one or more layers or films that can be grafted or deposited on any type of substrates, whether insulating or conductive, rigid or flexible. The thickness of these layers or films can be modulated according to the nature of the organic compounds and / or according to whether they are deposited or grafted. Thus, the thickness of these layers or films may be for example between 1 and 100 nm, for example between 1 and 20 nm, for example between 1 and 5 nm when it is a grafting by a reaction of reduction of the organic compounds of the invention (reductive route), but may also be between 10 nm and 1000 nm, for example between 1 nm and 10,000 nm, for example between 1 and 1000 nm, for example between 1 and 100 nm, when it is a deposit by an oxidation reaction of said compounds (oxidative route). These layers, advantageously having a homogeneous thickness, have the property of being electroactive and of switching between an insulating state and a conductive state. As indicated, the formation of these layers can take place reductively or oxidatively. The bond between the surface of the substrates and the compounds according to the invention may be of a strong nature (grafting by reduction) or of a less strong nature (deposition by oxidation). Whether grafted or deposited, said layers have good adhesion with the surface of the substrate. However, when the formation of the layers takes place by grafting, the adhesion of said layers to the substrates is better. The compounds according to the invention therefore allow control of the interface between the substrate and the layer or film. In the case of reduction grafting, the grafted molecules lead to films having the ability to switch between an insulating state and a conductive state comparable to that observed with conventional known organic compounds obtained by oxidative deposition. However, unlike the organic compounds of the state of the art, the compounds of the invention make it possible to significantly modulate the electric potential window allowing this switching while allowing a strong grafting on the substrate. The switching potential of these layers can be, for example, between -0.5 volts and +1 volts, for example between -0.3 volts and +1 volts, for example between 0 volts and +1 volts, and between 0 volts and +0.5 volts versus a calomel electrode.

According to a third embodiment of the invention, the compounds of the invention may be of formula (I), in which: R2 represents the group - NO2 or the phenyl group substituted by the -NO2 group. These compounds can function not only as a plastic electronic compound but also as an intermediate compound of 2EB, TEB, ETB and 3EB.

According to one characteristic of the invention, R represents a hydrogen atom; R2 is -NO2 or phenyl substituted with -NO2; n = 2; and m = 0.

According to one characteristic of the invention, Ri represents thiophene; R2 is -NO2 or phenyl substituted with -NO2; n = 1; and m = 0. According to one characteristic of the invention, R 1 represents a hydrogen atom; R2 is -NO2 or phenyl substituted with -NO2; Z represents thiophene; n = 1; and m = 1.

According to one characteristic of the invention, R 1 represents a hydrogen atom; R2 is -NO2 or phenyl substituted with -NO2; n = 3; and m = 0.

The invention also relates to the processes for preparing the compounds according to the invention.

According to a first variant, the invention relates to a process for preparing a compound of formula (I) in which a halogenated compound of formula (II) is reacted with a compound of formula (III) in the presence of at least one a palladium catalyst to obtain the compound of formula (I):

(Ml) with Z, Ri, n, m as defined above;

^■ Hal represents a halogen atom;

^■ T represents a hydrogen atom or a group -B (OR ') (OR ") wherein

^• R 'and R "represent, independently of one another, a hydrogen atom, a C1-C6 alkyl, aryl selected from the group comprising benzyl, phenyl, tolyl, xylyl , or

• R 'and R "together form a 5- or 6-membered ring optionally substituted by one or more C ₁ -C ₄ alkyl groups.

^■ X represents an -NO2 group, or a phenyl group substituted by -NO ₂ According to a second variant, the invention relates to a process in which a halogenated compound of formula (II) is reacted with a compound of formula (III) in the presence of at least one palladium catalyst to obtain the compound of formula (IV ), which compound (IV) provides the compound (I) after reduction:

(il) (III) (IV)

with Z, R _L n, m, as defined previously;

^■ Hal represents a halogen atom;

^■ T represents a hydrogen atom or a group -B (OR ') (OR ") wherein

R 'and R "represent, independently of one another, a hydrogen atom, a C ₁ -C 6 alkyl group, an aryl group selected from the group consisting of benzyl, phenyl, tolyl, xylyl, or

R 'and R "together form a 5- or 6-membered ring optionally substituted by one or more C ₁ -C ₄ alkyl groups,

^■ X represents an -N0 _{2 group,} or a phenyl group substituted by -N0 ₂ group,

with the proviso that when X is -NO _2, R ₂ is amino (-NH ₂ ), and when X is phenyl substituted with -NO _2, R ₂ is aniline. In both variants, the reaction of the halogenated compound (II) with the compound of formula (III) can be carried out in the presence of a palladium (Pd) catalyst.

The palladium catalyst may be selected from the group consisting of, for example, palladium (0) tetrakis (triphenylphosphine), palladium (0), 1,2-bis (diphenylphosphino) ethane], palladium acetate and the like. (II), palladium (II) propionate, palladium (II) chloride, palladium (II) bromide, palladium (II) acetylacetonate, palladium (0) di (benzylidene acetate), palladium on charcoal, palladium on alumina.

Said reaction can be carried out in a solvent or a mixture of polar solvents selected from the group comprising, for example, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetonitrile, acetate ethyl, triethylamine, pyridine, diethyl ether, THF, diglyme, triglyme, dichloromethane, chloroform, acetone, butanone.

In both variants, the reaction of the halogenated compound (II) with the compound of formula (III) can also be carried out in an ionic liquid chosen from ionic liquids comprising an imidazolium, for example 1-N-butyl-3-methylimidazolium. tetrafluoroborate.

Said reaction can be carried out in the presence of a base selected from the group comprising, for example, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogen carbonate, triethylamine, phosphate of potassium, silver oxide, sodium tert-butoxide, potassium t-butoxide, sodium hydroxide, potassium hydroxide, barium hydroxide, cesium fluoride, sodium ethoxide.

The compound (II) reacts with the compound (III) at a temperature of at least 20 ° C, for example between 40 and 140 ° C, for example between 60 and 120 ° C.

The duration of said reaction varies according to the compounds of formulas (II) and (III), the palladium catalyst and the solvent used. It can range from minutes to days. It can range, for example, from 30 minutes to 5 days, for example from 1 hour to 3 days. In the first variant, the compound (I) is obtained at the end of the reaction of the compound (II) with the compound (III), and can be used as it is or after purification by known methods.

In the second variant, the compound of formula (IV) is obtained at the end of the reaction between the compounds of formulas (II) and (III). Compound (I) can then be obtained after reduction of said compound of formula (IV).

The reduction of the compound of formula (IV) may be a hydrogenation reaction. The hydrogenation catalyst is advantageously chosen from palladium, rhodium and nickel catalysts, for example Lindlar's catalyst, palladium on carbon, palladium on calcium carbonate, palladium on alumina and palladium hydroxide. on charcoal, palladium (II) acetate, palladium (II) propionate, palladium (II) chloride, palladium bromide, Wilkinson catalyst and Raney nickel.

The reduction can also be done using a hydride. The hydride may be a hydride chosen from the group comprising AlH ₃ / AlCl ₃ , sodium dihydro (trithio) borate (NaBH ₂ S ₃ ), NaBH ₄ catalyzed by NiCl ₂ (PPh ₃ ) ₂ or CoCl ₂ .

The reduction can also be carried out by the action of a metal in an acid medium. The metal may be zinc, tin or iron. The acid may be for example sulfuric acid, hydrochloric acid, nitric acid.

The reduction of the compound of formula (IV) can also be carried out by the action of hydrazine in the presence of a catalyst. The catalyst may advantageously be chosen from catalysts comprising palladium, nickel, iron, zinc or carbon.

Still in the second variant, the compound (I) can be obtained after reduction of said compound of formula (IV), for example, by the action of the complex dodecacarbonyl trifer [Fe ₃ (CO) i ₂ ] in an alcoholic medium. The alcoholic medium may be one or a mixture of alcohols selected for example from methanol, ethanol or isopropanol.

The reduction of said compound of formula (IV) can also be carried out by the action of sulphides. The sulfide may be selected from sodium hydrosulfide, ammonium sulfide or polydisulfide. The reduction may, in addition, be carried out electrochemically in an acid medium or in a micellar medium, among the surfactants used may be of anionic, cationic or neutral nature.

The reduction reaction of the compound of formula (IV) to yield compound (I) may be carried out in a mixture or a suitable solvent (s) selected from the group comprising, for example, water, hydrazine, methanol, ethanol, isopropanol, methanoic acid, acetic acid, THF, dichloromethane, chloroform, carbon tetrachloride, N, N-dimethylformamide (DMF), ethyl acetate, benzene, toluene or dioxane.

The reduction reaction is advantageously carried out at the reflux temperature of the solvent or solvent mixture.

The duration of the reduction reaction is variable and can range, for example, from 30 minutes to 6 hours.

The compound of formula (I) obtained at the end of the reduction may be used as it is or may be purified by known purification methods.

The halogenated compounds of formula (II) can be prepared by any suitable halogenation process for the halogenation of a compound of formula (V)

Γ 1

X

(V)

wherein Z, m and X are as previously defined.

The halogenation reaction can be carried out by the action of a halogenating agent selected from the group comprising, for example, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, chlorine, bromine, iodine sulfuryl chloride, hypochlorous acid, hydrobromic acid, magnesium bromide, magnesium iodide.

The halogenation reaction may be carried out in the presence of a metal selected from the group consisting of, for example, zinc, mercury oxide, mercury acetate. The boronic esters of formula (VIII) correspond to the compounds of formula (III) in which T represents a group -B (OR ') (OR "). When said boronic esters of formula (VIII) are not marketed, they may be prepared, for example, by a process in which a compound of formula (VI) is reacted with a borate of formula (VII):

(VI) (VIII) wherein R 1 and n are as previously defined;

• R '"represents a hydrogen atom, a en-ι-β alkyl group, an aryl group selected from the group consisting of benzyl, phenyl, tolyl, xylyl;

R 'and R "represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group, an aryl group selected from the group comprising benzyl, phenyl, tolyl, xylyl; , or

· R 'and R "together form a 5- or 6-membered ring optionally substituted by one or more C1-C4 alkyl groups.

The reaction between the compounds of formulas (VI) and (VII) can be carried out at a temperature ranging from -85 to 25 ° C.

The duration of this reaction can be between 30 minutes and 5 hours.

The reaction between a compound of formula (VI) with a borate of formula

(VII) may be carried out in one or a mixture of polar solvents chosen from water, Ν, Ν-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-methylpyrrolidinone, ethanol propanol, isopropanol, acetonitrile, ethyl acetate, diethyl ether, THF, dioxane, anisole, ethylene glycol dimethyl ether, diglyme, triglyme, dichloromethane, chloroform, acetone, butanone.

Once prepared, the organic compounds of formula (I) are capable of forming layers deposited or grafted onto the surface of the substrates by reduction or by oxidation. The reduction or oxidation can be carried out electrochemically or by chemical reactions. In the latter case, any oxidant or reductant having a standard redox potential respectively greater than or less than the standard redox potential of the compound of formula (I) may be used.

The deposition or grafting may be carried out in a polar solvent or in a mixture of solvents chosen from the group comprising, for example, water, Ν, Ν-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N methylpyrrolidinone, ethanol, propanol, isopropanol, acetonitrile, ethyl acetate, diethyl ether, THF, dioxane, anisole, ethylene glycol, dimethyl ether, diglyme, triglyme , dichloromethane, chloroform, acetone, butanone.

The deposition or grafting of the organic compounds of formula (I) on the surface of the substrates may also be carried out in an ionic liquid chosen from ionic liquids comprising imidazolium, for example 1-N-butyl-3-methylimidazolium tetrafluoroborate.

The reduction or oxidation reactions allowing the grafting or deposition of the layers, whether chemical or electrochemical, can be carried out in a micellar medium using surfactants of anionic, cationic or neutral nature.

The deposition or grafting of the layers by oxidation or grafting reactions, whether they are carried out chemically or electrochemically, can also be carried out in aqueous medium in the presence of cyclodextrins of variable size added in order to solubilize the compounds. organic compounds of formula (I).

The processes for preparing the organic compounds of formula (I) as well as the deposition or grafting of said compounds on the surface of the substrates in the form of one or more layers have the advantage of being easy to implement, reproducible, industrially feasible and economically interesting.

The subject of the invention is the use of a compound of formula (I) as defined above, as plastic electronics, in molecular electronics. The invention particularly relates to the use of said compound of formula (I) for producing a layer on insulating, semiconductive and conductive surfaces. In this case, it is preferable that said layer is formed on a substrate by grafting.

More particularly, the compounds of the invention can be used to produce organic light-emitting diodes, transparent electrodes, organic photovoltaic cells, organic transistors, single-electron transistors, sensors and biosensors.

The invention also relates to the use of a compound the use of a compound of formula (I) as defined above, for producing anticorrosion coatings, surfaces with switchable wetting properties, self-lubricating surfaces, electrochromic coatings intelligent coatings, that is to say coatings whose properties can be switched reversibly using the external stimulus, adhesion primers that is to say, layers for snapping and the adhesion of a second layer of variable chemical nature but which would not have been adherent if this second layer had been deposited directly on the substrate.

The invention also extends to the use of a compound the use of a compound of formula (I) as defined above, in the field of energy storage as electrode materials for batteries, or supercapacitors which are electrical storage systems that can deliver large amounts of energy in a short period of time, especially as layers deposited on carbon nanotubes.

Another subject of the present invention is a material comprising a compound of formula (I) as defined above.

The materials according to the invention can be prepared by known methods.

The present invention, according to another of its aspects also relates to an article comprising a compound of formula (I), according to the invention as defined above.

EXAMPLES

Solvents and reagents Toluene is distilled under argon on sodium; tetrahydrofuran (THF) is distilled under argon on sodium and benzophenone. The other solvents used come from the VWR supplier. Nuclear Magnetic Resonance (NMR)

The ¹ H and ¹³ C spectra are made with a Bruker Avance III 300 MHz and 400 MHz device.

The chemical shifts (δ) of the ¹ H NMR and ¹³ C NMR spectra are calibrated on the reference value of the solvent as described in the article Gottlieb et al, J. Org. Chem., 1997, 62, 7512.

The measurements are carried out at 25 ° C. in tubes 5 mm in diameter. The spectra are carried out in deuterated solvents from the Eurisotop supplier. The coupling constants are given in Hertz. chromatography

Thin layer chromatography (TLC) is carried out on aluminum plates "TLC Silica gel 6OF254" from Merck. The compounds are revealed under UV lamp at 254 or 326 nm.

The chromatographic columns are made with silica gel (Silica gel 60 (40-63 μm) from Merck.

Mass spectrometry

The mass spectra were recorded on a Finigan 5890 spectrometer coupled to a DSQ1 in Electronic Impact mode, in "Analytical" quality solvents.

Synthesis of precursors

1- (Thien-2-yl) -4-nitrobenzene and 1- (3,4-ethylenedioxythien-2-yl) -4-nitrobenzene were prepared according to the protocols described in references [1] and [2] .

The biEDOT was synthesized according to the procedure described in reference [3]. Example 1: General Procedure for the Iodination of Thiophene Derivatives

To a suspension of a thiophene derivative (8 mmol) in acetic acid (150 ml), mercury oxide (1.04 equivalents, 8.32 mmol) and iodine (1.0 equivalents; 16 mmol) is added. The mixture is degassed in an ultrasonic bath for 20 minutes and then stirred overnight. The precipitate is filtered and then dissolved in dichloromethane. The organic phase is washed successively with a solution of potassium iodide, a solution of sodium bicarbonate (NaHCO ₃ ) and water. After drying over magnesium sulfate, the solvent is evaporated under vacuum. The product is used without further purification.

1- (5-iodothien-2-yl) -4-nitrobenzene

c b

The iodinated thiophene derivative was prepared according to the general procedure for iodination indicated above, with 7 mmol of thiophene derivative.

Yield: 2.10 g; 90%. A yellow powder is obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.13 (d, 1H, J = 3.6 Hz); 7.30 (d, 1H, J = 3.6 Hz);

7.66 (d, 1H, J = 8.4 Hz, CH _C ); 8.23 (d, 1H, J = 8.4 Hz, CH _b ).

¹³ C NMR (75 MHz, CDCl ₃ ) δ 76.1 (C _h ); 124.5 (C _c ); 125.9 (C _b ); 127.0 (C _f );

138.5 (C _g ); 139.4 (C _a ); 146.9 (C _d ); 147.5 (C _e ).

MS: M calc. 331; found: [M] ⁺ 331.

1- (5-Iodo-3,4-ethylenedioxythien-2-yl) -4-nitrobenzene

cb The iodinated EDOT derivative was prepared according to the general procedure for iodination indicated above, from 6.57 mmol of 3,4-ethylenedioxythiophene derivative (EDOT).

Yield: 2.52 g; 98%. A yellow powder is obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 4.37 (m, 4H); 7.78 (d, 1H, J = 9.2 Hz); 8.21 (d, 1H, J = 9.2 Hz).

¹³ C NMR (75 MHz, CDCl ₃ ) δ 52.1 (C _h ); 64.9 and 64.9 (C _f and C _g ); 120.4 (C _e ); 124.2 (C _b ); 125.7 (C _c ); 139.0 (C _a ); 139.6 (C _f or C _g ); 145.0 (C _f or C _g ); 145.7 (Cd).

MS: M calculated 389; found: [M] ⁺ 389.

Example 2: General Procedure for the Synthesis of the Boronic Ester [4]

Under an argon atmosphere, a solution of the thiophenic compound (30 mmol) in distilled THF (100 mL), with stirring, is cooled to -78 ° C. A solution of 2.5 M butyllithium (12 mL, 1 equivalent) is added dropwise and the resulting solution is stirred at -78 ° C for one hour. The triisopropylborate (21 mL, 3 equivalents) is added and the reaction mixture is allowed to come to room temperature (20 ° C.). After 2.5 h, a solution of pinacol (10.6 g) in THF (30 mL) is added. The reaction mixture is stirred for 30 minutes and the solvent is then evaporated under vacuum. The residue is dissolved in diethyl ether, washed twice with water and dried over MgSO ₄ . The solvent is evaporated under vacuum. The product is used without further purification.

4,4,5,5-Tetramethyl-2-thioDhén-2-yl-1,3,2-dioxaborolane

This compound was prepared according to the general procedure for the synthesis of the boronic ester, starting from 30 mmol of thiophene.

Yield: 5.3 g; 85%. A white powder is obtained. 1 H NMR (300 MHz, CDCl ₃ ) δ 1, 36 (s, 12H, CH ₃ ); 7.20 (dd, 1H, J = 3.6 and 4.8 Hz, H ₄ ); 7.64 (d, 1H, J = 4.8 Hz, H ₅ ); 7.66 (d, 1H, J = 3.6 Hz, H ₃ ).

¹³ C NMR (75 MHz, CDCl ₃ ) δ 24.8 (CH ₃ ); 84.1 (C-OB); 128.2 (C ₃ ); 132.4 (C ₄ ); 137.2 (C ₅ ).

MS: M calculated 210; found: [M] ⁺ 210.

2- (2,3-Dihydrothieno-3,4-diol) -4,4,5-tetramethyl-2-thio-phen-2-yl-1,3,2-dioxaborolane

This compound was prepared according to the general procedure above for the synthesis of the boronic ester, with 50 mmol of EDOT.

Yield: 11.13 g; 85%. A white powder is obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 1.34 (s, 12H, CH ₃ ); 4.17-4.20 (m, 2H, OCH ₂ ); 4.29-4.31 (m, 2H, OCH ₂ ); 6.63 (s, 1H, CH _edof ).

¹³ C NMR (75 MHz, CDCl ₃ ) δ 24.7 (CH ₃ ); 64.3 (CH ₂ -0); 65.1 (CH ₂ -0); 83.8 (C-OB); 107.5 (C _edot ); 142.3 and 149.0 (C ₃ -0 and C ₄ -0).

MS: M calculated 268; found: [M] ⁺ 268.

4,4,5,5-tetramethyl-2- (2,2 ', 3,3'-tetrahydro-5,5'-bithieno (3,4-b) Aldioxin-5-yl-1,3,2-dioxaborolane

This compound was prepared according to the general procedure above for the synthesis of the boronic ester, starting from 10 mmol of bi-EDOT.

Yield: 3.94 g; 93%. A green solid is obtained. ¹ H NMR (300 MHz, CDCl ₃ ) δ 1.28 (s, 12H, CH ₃ ); 4.23-4.25 (m, 2H, OCH ₂ ); 4.32-4.34 (m, 6H, OCH ₂ ); 6.31 (s, 1H).

¹³ C NMR (75 MHz, CDCl ₃ ) δ 24.5 (CH ₃ ); 64.6 (CH ₂ -0); 65.0 (CH ₂ -0); 83.2 (C-OB); 97.5 (CH _edoi ); 109.9 (CS); 137.0 and 141.2 (CO).

MS: M calculated 408; found: 408.

Example 3: General Procedure for the Suzuki Coupling Reaction

[4]

The boronic derivative (2 mmol), the halogenated derivative (2 mmol), sodium carbonate (3 equivalents, 6 mmol), palladium tetrakis (triphenylphosphine) (Pd °) (5%) are introduced successively into a Schlenk containing 25 mL of Ν, Ν-dimethylformamide (DMF). The reaction mixture is heated at 110 ° C for 2-3 days. After cooling to room temperature (20 ° C.), the solvent is evaporated under vacuum.

The brown residue is dissolved in dichloromethane, washed twice with water, dried over MgSO ₄ and concentrated. The crude product is purified by chromatography on silica gel.

The nitrophenyl-EDOT compound was prepared by the procedure indicated above, with 15 mmol of boronic derivative (eluent from

chromatography: petroleum ether / dichloromethane 3 / 7t).

Yield: 2.79 g; 70%. A yellow powder is obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 4.28-4.40 (m, 2H, H _g ); 4.37-4.40 (m, 2H, H _f); 6.48 (s, 1H, _hr ); 7.86 (d, J = 9.0 Hz, 2H, H _c ); 8.17 (d, J = 9.0 Hz, 2H, H _b ).

¹³ C NMR (100 MHz, CDCl ₃ ) δ 64.3 (OC _g H ₂ ); 65.1 (OC _f H ₂ ); 101.0 (C _h ); 124.1 (C _b ); 125.7 (C _c ); 139.8 (C _a ); 140.9 (C _g ); 142.9 (C _f ); 145.8 (C _d ). MS: M calculated 263; found: 263.

Elemental analysis: calculated: C 54.75, H 3.45, N 5.32, S 12.18; found: C 55.04, H 3.50, N 6.05, S 10.88. 2- (Nitrophenyl) -3,4,3 ', 4'-bis (ethylenedioxy) -5,2'-bithiophene

The nitophenyl-bi-EDOT compound was prepared by the general procedure described above, with 2 mmol of boronic derivative. The product was purified by chromatography on silica gel using a 3/7 mixture of petroleum ether / dichloromethane as eluent.

Yield: 316.3 mg; 36%. A dark powder is obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 4.23-4.27 (m, 2H, OCH ₂ ); 4.36-4.40 (m, 6H, 3x)

OCH ₂ ); 6.36 (s, 1H, H /); 7.84 (d, J = 9.2 Hz, 2H, H _c ); 8.17 (d, J = 9.2 Hz, 2H, H _b ).

¹³ C NMR (100 MHz, CDCl ₃ ) δ 63.9, 64.0, 64.4 and 64.7 (4 x OCH ₂ ); 98.6 (C /); 108.8, 1.1.5, 1.17 (C _e , C _h and C,); 123.4 (C _b ) 124.7 (C _c ); 136.7, 137.4, 139.8,

140.7 (C _f , C _g , C _j , C _k ); 139.3 (C _a ); 144.4 (C,); 145.0 (C _d ).

MS Ci ₈ H ₁₃ N0 ₆ nas2 [M + Na ^+]: Calculated: 426.0082, Found: 426.0093.

Elemental Analysis: Calculated: C 53.59, H 3.25, N 3.47, S 15.89; found: C

54.74, H 3.54, N 3.60, S 14.02.

2- (4-Nitrophenyl) -3 ', 4'-ethylenedioxy-5,2'-bithiophene

2- (4-Nitrophenyl) -3 ', 4'-ethylenedioxy-5,2'-bithiophene was prepared according to the general procedure described above, starting from 4 mmol of derivative boronic (chromatographic eluent: mixture of petroleum ether / dichloromethane 25/75).

Yield: 1.38 g; 78%. An orange powder is obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 4.28-4.31 (m, 2H, OCH ₂ ); 4.40-4.42 (m, 2H, OCH ₂ ); 6.23 (s, 1H, H,); 7.25 (d, J = 4.0 Hz, 2H, _f or _Hf ); 7.41 (d, J = 4.0 Hz,

2H, H _f or H _g); 7.73 (d, J = 8.8 Hz, 2H, H _c ); 8.24 (d, J = 8.8 Hz, 2H, H _b ).

¹³ C NMR (100 MHz, CDCl ₃ ) δ 64.6 and 65.2 (2 x OCH ₂ ); 98.1 (C,); 1 1 1.7 and

138.4 (C and C *); 123.9 and 126.0 (C _f and C _g ); 124.5 (C _b ); 125.4 (C _c ); 137.6 and 139.0 (C, and C,); 140.6 (C _a ); 142.0 (C _e ); 146.3 (C _d ).

MS C ₁₆ H N0 ₄ S 2 [M + H ⁺ ]: Calcd: 345.0130, Found: 345.0145.

Elemental analysis C ₁₆ H ₁ N0 ₄ S ₂ : calculated: C 55.64, H 3.21, N 4.06, S 18.56, found: C 55.04, H 3.13, N 4.22, S 17.97.

2- (Nitrophenyl) -3,4-ethylenedioxy-5,2'-bithiophene

2- (4-Nitrophenyl) -3,4-ethylenedioxy-5,2'-bithiophene was prepared according to the general procedure described above for the Suzuki coupling reaction, with 2 mmol of boronic derivative (chromatography eluent). : petroleum ether / dichloromethane mixture 25/75).

Yield: 690 mg; 63%. An orange powder is obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 4.43 (s, 4H, 2 x OCH ₂ ); 7.08 (dd, 1H, J = 3.2 and 5.2Hz, CH _k ); 7.30 (d, 1H, J = 5.2Hz, CH,); 7.34 (d, 1H, J = 3.2 Hz, CH _j); 7.86 (d, 1H, J = 8.8 Hz, CH _C ); 8.18 (d, 1H, J = 8.8 Hz, CH _b ).

¹³ C NMR (100 MHz, CDCl ₃ ) δ 64.7 and 65.0 (2 x OCH ₂ ); 1 12.1 (C _e ); 1 13.8 (CI); 124.0 (C); 124.1 (C); 125.0 (C _/ ); 125.6 (C _c ); 127.4 (C *); 133.9 (C); 137.9 and 140.9 (C and C _g ); 139.4 (C _a ); 145.3 (C _d ).

MS Ci ₆ H ₄ N0 ₂ S [M ^+]: calculated: 345.0130, found: 345.0139.

Elemental analysis C ₁₆ H NO ₄ S ₂ : calculated: C 55.64, H 3.21, N 4.06, S 18.56; found: C 55.27, H 3.21, N 4.09, S 17.70. 2- (4-Nitroohenyl) -3,4,3'A 3 ", 4" -ter (ethylenedioxy) -5,2 5 ', 2 "-terthiophene

The nitrophenyl-terEDOT compound was prepared according to the general procedure described above for the Suzuki coupling reaction with 2 mmol of boronic derivative. The product was purified by chromatography on alumina using dichloromethane as eluent.

Yield: 465 mg, 71%. A dark powder is obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 4.26 (m, 2H, OCH ₂ ); 4.30-4.50 (m, 10H, 5 x OCH ₂ ); 6.33 (s, 1H, CH _P ); 7.86 (d, 2H, J = 8.8 Hz, CH _C ); 8.19 (d, 2H, J = 8.8 Hz, CH _b ).

MS C ₂₄ H ₁₇ NO ₈ S ₃ [M + H ⁺ ]: calcd: 543.0116, found: 543.0126

Example 4: General procedure for the reduction of the nitro (NO ₂ ) function to amine (NH ₂ ) [5]

Palladium (10%) on charcoal (0.086 mmol, 10%) and hydrazine (1 mL) were added to a solution of the nitro derivative (0.86 mmol) in THF (20 mL). The reaction mixture is refluxed for 4 hours. After cooling to room temperature (20 ° C.), the suspension is filtered on celite and then the solvent is evaporated under vacuum. The residue dissolved in dichloromethane is washed with water and then dried over magnesium sulfate. The product is used without further purification.

2- (4-aminophenyl) -3,4,3 ', 4'-bis (ethylenedioxy) -5,2'-bithiophene

The amine derivative was prepared from 1 mmol of nitro derivative, according to the general procedure for the reduction of the nitro function to amine indicated above.

Yield: 124 mg; 76%. A red powder is obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 3.70-3.73 (broad s, 2H); 4.24-4.27 (m, 2H); 4.33-

4.37 (m, 6H); 6.27 (s, 1H); 6.69 (d, 2H, J = 8.4 Hz); 7.55 (d, 2H, J = 8.4 Hz).

³ C NMR (75 MHz, CDCl ₃ ) δ 64.6, 64.6, 64.9 and 65.0 (4 × CH ₂ O); 97.3 (C _/ H);

106.2 (C, or C _ft ); 110.2 (C, or C _h ); 1 15.2 (C _b ); 1 15.8 (C _e ); 123.7 (C _a ); 127.3 (CM); 136.3, 136.7, 137.5 and 141.3 (C _f , C _9> C _y and C *); 145.0 (C _d ).

MS C ₁₈ H ₁₅ N0 ₄ NaS ₂ [M + H ⁺ ]: Calcd .: 374.0521, Found: 374.0515.

Elemental analysis Ci ₂ H N0 ₂ S: Calculated: C 57.89, H 4.05, N 3.75, S 17.17; found: C 58.50, H 4.33, N 3.93, S 15.95. 2- (4-Amino-henyl) -3 ', 4'-ethylenedioxy-5,2'-bithiophene

The amine derivative was prepared from 0.6 mmol nitro derivative, according to the general procedure for the reduction of the nitro function to amine indicated above.

Yield: 189 mg; 83%. A yellow powder is obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 4.76 (s, 2H); 4.25-4.27 (m, 2H, H); 4.34-4.37 (m, 2H, H _k ); 6.20 (s, 1H, H,); 6.68 (d, 2H, J = 8.8 Hz, H _b ) 7.06 (d, 1H, J = 4.0 Hz, H _f ), 7.14 (d, 1H, J = 4.0 Hz, H _g ); 7.41 (d, 2H, J = 8.8 Hz, H _c ). ¹³ C NMR (75 MHz, CDCl ₃ ) δ 64.6 (OCH, H ₂ ); 65.0 (CVH ₂ ); 96.5 (C,); 12.6 (C); 1 15.3 (C _b ); 121.3 (C _f ); 123.8 (C _e ); 125.0 (C _a ); 126.8 (C _C ); 132.4 (C "); 137.2 (C _k ); 141.9 (C); 143.2 (C _e ); 145.9 (C _d ).

MS C ₁₈ H ₉ N O ₂ S ₂ [M + H ⁺ ] calcd 316.0466, found: 316.0461.

Elemental analysis C ₆ H ₉ N0 ₂ S ₂ : calculated C 60.93, H 4.15, N 4.44, S 20.33; found: C 60.82, H 4.80, N 4.01, S 17.46.

The amine derivative was prepared from 0.86 mmol of nitro derivative, according to the general procedure for the reduction of the nitro function to amine indicated above.

Yield: 270 mg; 95%. A yellow powder is obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 4.32-4.35 (m, 2H); 4.37-4.39 (m, 2H); 6.70 (d, 2H, J = 8.8 Hz, H _b ) 7.02 (dd, 1H, J = 3.6 and 5.0Hz, H _k ) 7.20 (d, 1H, J = 5.0Hz, H,); 7.22 (d , 1H, J = 3.6 Hz, H 1); 7.53 (d, 2H, J = 8.8 Hz, H _c ).

¹³ C NMR (75 MHz, CDCl ₃ ) δ 64.6 and 64.9 (2 x OCH ₂ ); 108.3 (C _e or C _h ); 115.2 (C _b ); 1 15.5 (C _a ); 122.3 (Cy); 123.3 (C /); 127.1 (C *); 127.3 (C _c ); 135.0 (C,); 136.7 (C _f or C _g ); 137.9 (C, or C _g ); 145.3 (C _d ).

MS C ₁₈ H ₉ N O ₂ S ₂ [M + H ⁺ ]: Calcd: 316.0466, Found: 316.0466.

Elemental analysis. C ₆ H ₉ N O ₂ S ₂ : calculated: C 60.93, H 4.15, N 4.44, S 20.33; found: C 61.11, H 4.61, N 4.62, S 17.95.

2- (4-Aminophenyl) -3, 4, 4, 3 ", 4" -ter (ethylenedioxy) -5.2'.5'.2 "-terthiophene

The amine derivative was prepared from 0.11 mmol of nitro derivative, according to the general procedure for the reduction of the nitro function to amine indicated above.

Yield: 56 mg; quantitative. A red powder is obtained.

¹ H NMR (300 MHz, CDCl ₃ ) δ 4.21-4.40 (m, 12H); 6.27 (s, 1H, CH _P ); 6.68 (d, 2H,

J = 7.6 Hz, CH _b ); 7.55 (d, 2H, J = 7.6 Hz, CH _C ).

MS: C ₂ 4Hi9NO ₆ S3 [M + H ^+]: Calculated: 513.0374, Found: 513.0371

Example 5: Process for the preparation of 2- (4-nitrophenyl) -3,4,3 ', 4'-bis (ethlethioxy) -5,2'-bithiophene [6]

The BiEDOT (2.2 g, 7.8 mmol, 1.3 eq.), 4-bromonitrobenzene (1.21 g, 6 mmol) and potassium acetate (1.76 g, 18 mmol, 3 eq.) Are successively introduced into a Schlenck containing 20 mL of DMF. After total dissolution of the reagents, palladium acetate (134 mg, 0.6 mmol, 0.1eq) is added, and the reaction medium is heated at 80 ° C for one hour. After returning to ambient temperature (20 ° C.), the red precipitate is filtered and washed with ethanol. The nitrated compound is subsequently used without further purification. Yield: 72%

List of references

[1] US 6130339

[2] US 6197921 B1

[3] GA Sotzing, J. R. Reynolds, P. J. Steel, Adv. Mater., 1997, 9, 10, 795-798.

[4] M. Rodrigi, C. Mostrou, A. Samat, R. Guglielmetti, Eur. J. Org. Chem., 2003,

2799-2812.

[5] L. Flamigni, B. Venture, E. Baranooff, J-P. Collin, J-P. Wild, Eur. J. of

Inorg. Chem., 2007, 33, 5189-5198.

[6] A. Borghese, G. Geldhof, L. Antoine, Tetrahedron, 2006, 47, 9249-9252.

Claims

1. Compound of formula (I):

in which

Ri represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C4 alkoxy group, a -COOR3 group, a COR3 group, a -SR3 group, a -SeR3 group or a -Si group. (OR ₃ ), a group -NR ₃ R ₄ , a group -C≡N, a group -N 3, a group -C≡CH, a heterocycle selected from the group comprising pyrrole, furan, phosphole, thiophene , tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine, phenanthroline, pyrazine, pyridazine and pyrimidine, ferrocene, cobaltocene , polyethylene group of formula - - 0-CH ₂ - CH ₂ -) p alkyl C1-C10, a phenyl group, said polyethylene, alkyl, phenyl and heterocycle being optionally substituted with one or more groups selected from the group comprising:

^• a -COOR 3 group, a -COR 3 group, a hydroxyl group, a C1-C4 alkoxy, -CONR ₃ R _4;

^■ R ₂ represents an amino group (-NH 2), a diazo group (N ⁺ _2), an aniline group, a phenyl group substituted by a diazo group (N ⁺ _2), an -N0 _{2 group,} a phenyl group substituted by a group -N0 ₂ ; optionally substituted by one or more groups selected from C1-C4 alkyl, -COOR ₃ , -COR ₃ , hydroxyl, C1-C4 alkoxy, -CONR3R4, -NO ₂ a group - NR ₃ R ₄ ;

Z represents thiophene, optionally substituted with one or more groups selected from the group consisting of: ^• a C1-C10, a carboxyl group, a group - COOR 3, a hydroxyl group, a C alkoxy group;

^■ R 3 and R ₄ represent, independently of one another, a hydrogen atom, an alkyl group Ci-C _6, a phenyl group;

■ n = 1, 2, 3, 4, 5;

^■ m = 0, 1, 2, 3;

p = 0, 1, 2, 3, 4, 5;

2. Compound of formula (I) according to claim 1, in which:

^■ R represents a hydrogen atom or thiophene;

^■ R2 is amino (-NH ₂₎ or aniline group;

^■ Z represents thiophene;

■ n = 1, 2, 3;

^■ m = 0, 1;

it being understood that when R 1 represents a hydrogen atom, m = 0, then n is not equal to 1. 3. A compound of formula (I) according to claim 1, in which:

^■ R represents a hydrogen atom or thiophene;

^■ R2 represents the aniline group, phenyl group substituted by the diazo group (N ⁺ _2), the phenyl group substituted by -N0 _2;

^■ Z represents thiophene;

■ n = 1, 2, 3;

^■ m = 0, 1;

it being understood that when R 1 represents a hydrogen atom, m = 0, then n is not 1. 4. Compound of formula (I) according to claim 2 or 3, wherein when m = 0, n is not 1 .

5. Compound of formula (I) according to any one of claims 1 to 4, wherein:

^■ R represents a hydrogen atom;

^■ R ₂ represents the aniline group;

■ n = 2; and

^■ m = 0.

6. Compound of formula (I) according to any one of claims 1 to 4, wherein:

Ri represents thiophene;

^■ R ₂ represents the aniline group;

^■ n = 1; and

^■ m = 0. 7. A compound of formula (I) according to any one of claims 1 to 4, wherein:

^■ R represents a hydrogen atom;

^■ R ₂ represents the aniline group;

^■ Z represents thiophene;

■ n = 1; and

^■ m = 1.

8. Compound of formula (I) according to any one of claims 1 to 4, wherein

Ri represents a hydrogen atom;

^■ R ₂ represents the aniline group;

^■ n = 3; and

^■ m = 0. 9. Compound of formula (I) according to claim 1 or 2 wherein R2 represents the group -NO2 or the phenyl group substituted by the group - NO2.

10. Compound of formula (I) according to claim 9, in which:

Ri represents a hydrogen atom;

^■ n = 2; and

^■ m = 0.

11. Compound of formula (I) according to claim 9, in which:

Ri represents thiophene;

^■ n = 1; and

^■ m = 0.

12. A compound of formula (I) according to claim 9, wherein:

Ri represents a hydrogen atom;

^■ Z represents thiophene;

^■ n = 1; and

^■ m = 1.

Compound of formula (I) according to claim 9, wherein

Ri represents a hydrogen atom;

^■ n = 3; and

^■ m = 0.

Process for the preparation of a compound of formula (I) according to any one of Claims 1 to 8, in which a halogenated compound of formula (II) is reacted with a compound of formula (III) in the presence of at least a palladium catalyst to obtain the compound of formula (I):

(Ml) wherein Z, n, m, are as defined in any one of claims 1 to 8;

^■ Hal represents a halogen atom;

^■ T represents a hydrogen atom or a group -B (OR ') (OR ") wherein

• R 'and R "together form a 5- or 6-membered ring optionally substituted by one or more C 1 -C ₄ alkyl groups.

^■ X represents an -N0 ₂ group, or a phenyl group substituted by -N0 ₂ group 15. A process for preparing a compound of formula (I) according to any one of claims 1 to 8, which comprises reacting a halogenated compound of formula (II) with a compound of formula (III) in the presence of at least one palladium catalyst to obtain the compound of formula (IV), which compound (IV) provides compound (I) after reduction:

(il) (III) (IV)

with Z, R 1, n, m, as previously defined;

Hal represents a halogen atom; ^■ T represents a hydrogen atom or a group -B (OR ') (OR ") wherein

^• R 'and R "represent, independently of one another, a hydrogen atom, alkyl-C CI _O, an aryl group selected from the group consisting of benzyl, phenyl, tolyl, xylyl, or

^• R 'and R "together form a 5- or 6-membered ring optionally substituted by one or more C 1 -C ₄ alkyl groups _>

^■ X represents an -N0 _{2 group,} or a phenyl group substituted by -NO _2,

it being understood that when X is the group -NO ₂ , R ₂ represents an amino group (-NH ₂ ), and when X is the phenyl group substituted with a -NO ₂ group, R ₂ represents an aniline group.

16. Use of a compound of formula (I) according to any one of claims 1 to 8, for producing a layer on insulating, semiconductive and conductive surfaces in which said layer is formed on a substrate by grafting.

17. Use of a compound of formula (I) according to any one of claims 1 to 8, for producing organic light-emitting diodes, transparent electrodes, organic photovoltaic cells, organic transistors, single electron transistors, sensors and biosensors.

18. Use of a compound of formula (I) according to any one of claims 1 to 8, for producing anticorrosive coatings, surfaces with switchable wetting properties, self-lubricating surfaces, electrochromic coatings, intelligent coatings, primary adhesion.

19. Use of a compound of formula (I) according to any one of claims 1 to 8, in the field of energy storage as electrode materials for batteries, or supercapacities in particular in the quality of layers deposited on carbon nanotubes.

20. Material comprising a compound of formula (I) as defined in any one of claims 1 to 8. 21. Article comprising a compound of formula (I) as defined in any one of claims 1 to 8.