WO2009156623A1

WO2009156623A1 - Novel mesomorphic macromolecular organic semiconductor materials

Info

Publication number: WO2009156623A1
Application number: PCT/FR2009/000787
Authority: WO
Inventors: Fabien Nekelson; Frédéric OSWALD; Fabrice Mathevet; Patrice Rannou; André-Jean Attias
Original assignee: Commissariat A L´Energie Atomique; Universite Pierre Et Marie Curie (Paris 6 ); Centre National De La Recherche Scientifique
Priority date: 2008-06-27
Filing date: 2009-06-25
Publication date: 2009-12-30
Also published as: FR2933238A1; FR2933238B1

Abstract

The invention relates to ambipolar, macromolecular, organic, semiconductor thermotropic liquid-crystal materials and the use thereof in organic electronics. These materials have a D- or A-type macromolecular semiconductor architecture, onto which are grafted D- or A-type semiconductor mesogenic functional groups, said type being different from that chosen for the macromolecular architecture.

Description

NEW SEMI-CONDUCTIVE MACROMOLECULAR MATERIALS

MESOMORPHIC ORGANICS

The invention relates to novel mesomorphic ambipolar organic semiconducting macromolecular materials, as well as their applications in organic electronics for the production of organic field effect transistors. OFETs: Organic Field-Effect Transistors), organic light-emitting diodes. OLEDs: Organic Light-Emitting Diodes), organic solar photovoltaic cells. OSCs: Organic Solar Cells), electroluminescent organic field effect transistors. OLETs: Organic Light-Emitting Transistors) and organic lasers.

In particular, it relates to macromolecular materials; organic, crystal-liquid type, semiconductor, injection and ambipolar transport, and more particularly π-conjugated macromolecules (polymers and dendrimers) thermotropic liquid crystal. In recent years, the microelectronics industry has developed another class of materials that conventional semiconductors: organic semiconductors. These are so-called "π-conjugated" materials, divided into two classes: small molecules and polymers. The 2000 Nobel Prize in Chemistry was awarded to AJ. Heeger, A. G. MacDiarmid, H. Shirakawa for "The Discovery and Development of Conductive Polymers". These materials are the basis of organic electronics, also called "plastic" electronics, which uses them as semiconductor active layers of components such as OLEDs, OFETs, OLETs, OSCs and Organic Lasers.

The most recent developments concerning this type of material and their application in OFETs configuration for example can be found in: T. Mori, J. Phys: Condens. Matter 2008, 20, 184010; M. Mas-Torrent & C. Rovira, Chem. Soc. Rev. 2008, 37, 827; S. Allard et al., Angew. Chem. Int. Ed. 2008, 47, 4070; A.R. Murphy & J.M.J. Frechet, Chem. Rev. 2007, 107, 1066.

A key point for improving the performance of these components lies in the understanding of the relationship "morphology of the films / transport properties of the charge carriers" and in its control. At present, relatively high load carrier mobilities (0.1-10 cm / Vs for electrons / holes) are reached in well-ordered materials such as molecular crystals, self-organized polymers in lamellar structure or mesomorphic compounds ( liquid crystals). H. Iino & J. Hanna, Opto-Electron. Rev. 2005, 13, 295 and J. Hanna, Opto-

Electron. Rev. 2005, 13, 259 studied ambipolar semiconducting organic materials (mobility in holes and electrons observed in devices having as active layers mesomorphic organic semiconductors) and more general electronic transport properties of organic semiconductor liquid crystals.

With the exception of very few cases of crystalline polymers such as polyacetylene, semiconductor polymers remain disordered materials and are generally characterized by an amorphous state or consist of amorphous and crystalline zones (semi-crystalline polymers).

This disorder has important consequences on the electronic properties of these materials. Indeed, the conduction process, described by the jump of the charge carriers between polymer chains (hopping), is here limited by the zones

-5 2 amorphous, which induces a low mobility (<10 cm / V s).

This is why many studies have aimed at controlling the crystallinity of π-conjugated polymers, the orientation of nanocrystallites and their morphology, which are important points for obtaining a high mobility of charge carriers. An important advance was obtained by H. Sirringhaus et al, Nature

1999, 401, 685 and WO99 / 54936 (and also RJ Kline et al., NaL Mater., 2006, 5, 222 and RJ Kline et al., Appl Phys L Lett 2007, 90, 0621 17), which were successful to organize a regioregular poly (3-alkylthiophene) into a lamellar structure consisting of self-organized sheets by inter-chain stacking within microcrystalline domains. Depending on the conditions of use, the lamellar structure can adopt two different orientations (parallel or normal to the substrate), affecting mobility by a factor of 100. Thus high values of mobility (0.1 cm / Vs) could be measured in transistor configuration (OFET), in the case of an orientation of the lamellae parallel to the substrate.

Another approach for the nano-structuring of high mobility conjugated polymer films has been developed more recently, from the crystalline liquid state of mesomorphic polymers derived from thieno [3,2-ό] thiophene (I. McCulloch et al. Nat Mater 2006, 5, 328, T. Umeda et al., J. Appl Phys 2007, 101, 054517). The major results in OFET configuration are:

obtaining broad crystalline domains of dimensions greater than that of the channel (width of the channel: 200 nm), by cooling and orientation from the mesophase present at high temperature,

the measurement of load carrier mobilities of the order of 0.2-0.6 cm / Vs.

In all cases, the aforementioned polymers are used as active layers for p-channel OFETs.

Π-conjugated liquid crystals, and more particularly columnar compounds, constitute another class of organized organic semiconductors having high charge carrier mobilities (M. Funahashi et al., Struct Bond. 2008, 128, 151). The molecules generally used for these assemblies are discotic molecules, consisting of a rigid aromatic core and flexible aliphatic flexible chains of variable length and number, such as, for example, hexabenzocoronene (Mϋllen, K. et al., Chem. 15, 124). Because of their incompatibility (aromatic heart / aliphatic chains), these elements induce a phase separation at the molecular level and lead to an organization of the aromatic parts in the form of columns, this quasi-one-dimensional organization being at the origin of the increase in transport properties (S. Sergeyev et al, Chem Soc Rev. 2007, 36, 1902). Thus mobilities of the order of 0.1-1 cm / Vs could be measured (D. Adam et al., Nature 1994, 371, 141, AM van de Craats et al, Adv.Mat., 1999, 11, 1469; Iino et al., Appl Phys Lett, 2005, 87, 132102).

In parallel with the self-organization generated by the crystalline liquid state, the other advantage of this class of materials is the access to a wide range of compounds facilitating the injection of holes (triphenylene, hexabenzocoronene, phthalocyanine) and electrons (Perylenediimide, hexaazatrinaphthylene) (H. Bock et al, Eur J Or g Chem 2006, 13, 2889, S. Alibert-Fouet et al, Chem Eur J 2007, 13, 1746, AJ Attias et al. Al, Chem Mater 2002, 14, 375).

Liquid crystal polymers, and especially columnar polymers, have been widely studied over the last 20 years. The vast majority of these materials are polymers with mesogenic pendant groups π-conjugated discotic type. However, the main chain is still unconjugated (of the polyacrylate, polystyrene or polysiloxane type) (Kumar, S., Cryst, L., 2005, 32, 1089, RJ Bushby et al., Liq.Cryst.Revised, 1, 47; H. Grubbs, Macromolecules, 1997, 30, 6430, M. Werth et al, Makromol Chem, Rapid Commun 1993, 14, 329, JH Wendorff et al., Liq Cryst 1996, 20, 459 CD Favre Nucolin et al., Macromolecules 1996, 29, 6143, CT Imrie et al., J. Mater Chem 1998, 8, 47, SJ Picken et al., Macromolecules 2000, 33, 4336, SJ Picken et al, J. Am. Soc., 2001, 123, 4645) and none of these materials is characterized from the point of view of its electronic transport properties vis-à-vis applications in organic electronics. More recently, there have been reported some examples of liquid crystal polymers with π-conjugated main chain and mesogenic pendant groups. But these are only calamitic type electron donors (p) and therefore are not suitable for electron injection (n). In addition, only syntheses and characterizations of the polymers are described (Akagi, Bull, Chem Soc, 2007, 80, 649, H. Goto et al, J. Polym, ScI, Part A. Polym, Chem. 2005, 43, 616, H Goto et al, Macromolecules 2004, 37, 2353, H. Goto et al, Macromolecules 2002, 35, 2545). Their electronic transport properties for application in organic electronics are not evaluated. SJ. Rowan & PT Mather, Struct. Jump. 2008, 128, 119 characterizes recent developments in the field of mesomorphic polymers.

Dendritic architectures (dendrimers and dendrons) mesomorphic and some of their applications in organic electronics, have been the subject of several studies: R. Deschenaux et al, New. J. Chem. 2007, 31, 1064; B. Donnio et al., Chem. Soc.

Rev. 2007, 36, 1495; LM. Saez & J.W. Goodby, Struct. Jump. 2008, 128, 1; Lo & P.L.

Burn, Chem. Rev. 2007, 107, 1097.

Ambipolar transport in organic semiconductors in device configurations has been the subject of several studies: J. Cornil et al, Adv. Mater. 2007, 19, 1791; J. Zaumseil & H. Sirringhaus, Chem. Rev. 2007, 707, 1296; V. Coropceanu et al, Chem. Rev. 2007, 107, 926.

The electron transport properties (charge carrier mobility in the field-effect transistor configuration and TOF cell) of mesomorphic organic semiconductors (molecular and polymer) have been described by Y. Shimidzu et al., J. Mater. Chem. 2007, 17, 4223; M. Funahashi et al, Struct. Jump. 2008, 128, 151. However none of these documents describes compounds with ambipolar transport and injection.

There remained the need for a macromolecular material composed of two entities, one electron donor (D) and the other electron acceptor (A), covalently bonded, these entities being suitable for the self -organization and being individually suitable for injection and transport, for the entity D holes (p) and for the entity A electrons (n), so as to have within the same material of the self- organization and injection of the two types of carriers.

For this purpose, new materials have been developed comprising a macromolecular architecture on which functional groups are grafted, the macromolecular architecture and the functional groups being chosen so that the assembly is semiconductor, transportable and ambipolar injection, and self-organized through a crystalline liquid phase

More precisely, these are thermotropic organic semiconductor semiconducting materials comprising a semiconducting macromolecular architecture of electron donor (D) or electron acceptor (A) type, on which mesogenic functional groups are grafted. semi-conductors of type A or D, distinct from that chosen for macromolecular architecture

This set of characteristics can be obtained by means of two large families of macromolecular materials whose characteristics will be detailed below. And surprisingly, it has been discovered that these materials are of the liquid crystal type.

By macromolecular architecture is meant a macromolecule resulting from the formation of covalent bonds, or between monomers linearly or branched, to lead to linear or branched polymers, or between dendrons according to a controlled tree process around a multifunctional central core to lead to dendrimers.

The material is generally in three different states: the solid state, the liquid state and the gaseous state. However, there is another state, intermediate, and thermodynamically stable, called liquid-crystalline (or mesomorphic) state. Liquid crystals are partially ordered anisotropic fluids which lie between the crystalline solid state and the isotropic liquid state.

Liquid-crystalline materials are divided into two categories, thermotropic liquid crystals and lyotropic liquid crystals. In the case of the materials of the invention which are thermotropic liquid crystals, the appearance of a mesophase is related to a change in temperature.

Self-organized molecules are molecules capable of organizing themselves into a higher-order supramolecular structure by so-called "weak" interactions, such as hydrogen bonds, Van der Waals, dipolar interactions, in response to a stimulus such as a change in solvency. Regioregular poly (3-alkyl) thiophenes, for example, constitute a known family of self-organized polymers.

More specifically, the materials of the invention are macromolecular materials: this encompasses polymeric and dendritic architectures such as dendrimers and dendrons. And these macromolecular materials have the following three characteristics:

-These are Organic Semi Conductors (SCO),

these are mesomorphic and nanostructured materials, these materials comprise SCO blocks / units of type A and of type D connected / connected by covalent bonds within macromolecular architectures (polymer, dendrons and dendrimers).

V. Percéé et al, Nature 2002, 419, 384 describes macromolecular materials (polymers and dendrons) Organic, mesomorphic and nanostructured semi-conductors but the molecules described are not ambipolar and to obtain an ambipolar electronic transport, it is necessary to mix type D and type A semiconductors.

Y. Kunugi et al., J Mater. Chem. 2004, 14, 2840 and N. Negishi et al., Chem. Lett. 2007, 36, 544 discloses macromolecular materials (dendrons) of the SCO type having ambipolar transport. However, these materials are neither mesomorphic nor self-organized and therefore have low mobility.

N. Negishi et al., Chem. Lett. 2007, 36, 544 (2007) describes macromolecular materials (dendrons) which are of the ambipolar SCO type but the active layer of the OFET is not based on a liquid crystal and the DA dyade used as a sensitive layer is not a mesomorphic material.

N. Kawasaki et al., Appl. Phys. Lett. 2007, 91, 243515 discloses a macromolecular material (dendron) of the unipolar nanostructured SCO type of type n which is not mesomorphous.

According to a first variant, self-organized macromolecules consisting of a D-type semi-conductive main polymer chain, suitable for the injection and transport of holes (p) or of type A, suitable for injection and injection are selected. transport of electrons (n) and mesogenic semiconductor side groups of type D or A distinct from that chosen for the main polymer chain.

According to a first embodiment of this variant, a macromolecular architecture based on entities D which are suitable for the injection and transport of the holes (p), and a grafting by functional groups (entities A) capable of injection and transport of electrons (n). According to this embodiment, the subject of the invention is macromolecules consisting of a D-type semiconductive π-conjugated main polymer chain and organic semiconductor type A mesogenic discogenic side groups. These macromolecules are of the crystal type. -liquid, they are self-organized, ambipolar, spontaneous nano-structuring. By mesogenic group is meant in the sense of the present invention a molecular group with sufficient anisotropy to contribute to the formation of a mesophase of the macromolecule, and in particular of a liquid crystal type mesophase.

The skilled person can refer to the document Handbook of liquid crystals ISBN 3-527-29502-X. Wiley-VCH, June 1998. The main π-conjugated D-type polymer chain can in particular be chosen from: a polythiophene (PT) chain, polyparaphenylenevinylene (PPV), polyparaphenylene (PPP), polythieno [2,3-b] thiophene such as illustrated below or a block copolymer of at least two of these polymers.

v_ / \

\ // AT //

The type A discogenic mesogenic side groups may be chosen from derivatives: perylene-3,4,9,10-tetracarboxylic acid tetraester, perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTDA), perylene-3,4,9,10-tetracarboxylic acid diimide (PTCDI), 1,4,5,8-naphthalene tetracarboxylic acid dianhydride (NTDA), 1,4-naphthalene acid diimide, 8-tetracarboxylic acid (NTCDI), anthracene-1,2,6,7-tetracarboxylic acid diimides, anthracene-1, 2,6,7-tetracarboxylic acid anhydrides, perfluoropentacene, tetracyanoquinodimethane, tetracyanophenylenedimethane, perfluoroalkyl grafted oligothiophene , 1,2,3,4,8,9,10,11,15, 16, 17,18,22,23, 24,25-hexadécafluoro-29H, 31H-phthalocyanine copper (II) (FI _O CUPC) , 4,5,7-Trinitro-9-oxo-PH-fluorene-2-carboxylic acid monoesters (4,5,7, TNF-2-COOR), such as those illustrated below as example:

perylene tetracarboxylic dianhydride

perylene tetraester perylene tetracarboxylic diimide

naphthalene tetracarboxylic dianhydride naphthalene tetracarboxylic diimide

anthracene tetracarboxylic anhydride

anthracene tetracarboxylic diimide

4,5,7-TNT-2-COOR: 4,5,7-Trinitro-9-oxo-9H-fluorene-2-carboxylic acid monoester

and R represents a group selected from H, a C ₁ -C ₂ alkyl

perfluoropentacene

tetracyano phenylenedimethane tetracyaπo quinodimethane

perfluoroalkylated oligothiophenes

These examples are given by way of illustration, but all the known type A mesogenic discotic groups, especially those described in T. Mori, J. Phys .: Condens, can be used in the present invention. Matter 2008, 20, 184010; C.R.

Newman et al., Chem. Mater. 2004, 46, 4436; J. Zaumseil & H. Sirringhaus H., Chem.

Rev. 2007, 707, 1296.

Preferably, a spacer group connects the side groups to the main chain. These spacers may be selected ^'from: a polyalkylene glycol group, an alkanediyl group Ci-C ₂ O alkoxy, C ₁ -C 20, alkane di-oxy C ₁ -C _{20 alkyl,} optionally interrupted by one or more functions selected from: a phenyl ring (C ₀ H ₀ ), an ether bridge (-O-), an amine bridge (-NH-), a carbonyl group (-CO-), carboxyl (-COO-), amide ( -CONH-).

The structural and electronic properties of these macromolecules can be modulated by changing the length of the spacer chain and / or the degree of polymerization of the polymer (length of the polymer chains). These characteristics of the polymer can in particular change the clarification temperature

(or "isotropisation") of the material of the invention.

The length of the spacer is chosen according to the nature of the discotic mesogenic group, its bulk, and expected electronic properties. In fact, depending on whether it is desired to avoid or favor the interactions between the π-conjugated main chain and the mesogenic lateral groups, a spacer of greater or lesser length is chosen.

The construction of the polymer from a π-conjugated D-type main chain and mesogenic side groups of type A leads to a self-organized and nanostructured structure of these two entities (lamellae and columns respectively-see FIG. 1) and favors the injection and transport of both types of charge carriers (n and p). In addition, a liquid crystal polymer is obtained. Preferably, the main polymer chain is a polythiophene chain. And each thiophene unit is carrier, in position 3, of a side chain composed of a mesogenic mesogenic group of type A and advantageously a spacer. The preparation of a polythiophene is well known to those skilled in the art. For example, reference can be made to EP-1028136, which describes a method of polymerization by the GRIM_ method (GRIgnard Metathesis). The GRIM method has several advantages for the preparation of the polymers of the invention: it makes it possible to control both the size of the polymer and its regioregularity, that is to say the fact that the side chain is always carried by the same carbon of thiophene. And for the implementation of the invention, polymers having a substantially homogeneous (low polymolecularity) and regioregular chain length are preferred. Preferably, the polymer comprises between 6 and 100 thiophene units, and advantageously between 6 and 50 thiophene units. Indeed, a minimum of 6 units is necessary to have the properties of a π-conjugated polymer and the GRIM method does not make it possible to obtain very high molecular weights.

Two ways of synthesis are possible:

• The post-functionalization of a poly (3-alkylthiophene) regioregular low polymolecularity and known degree of polymerization (number of units) previously synthesized. • The polymerization by GRIM (GRIgnard Metathesis) of a thiophene monomer previously substituted in position 3 by a mesogenic group of type A.

These two variants are illustrated in the diagram below in which the spacer is an alkyl chain (CH ₂ ) _X , the degree of polymerization is y and the meso functional group

And it can also be expected that the main polymer chain is grafted by several distinct discotic side groups. This variant is feasible in particular by assembling between them different blocks of oligomers bearing different discotic side groups.

According to a second embodiment of this variant, a macromolecular architecture of type A, suitable for the injection and transport of electrons (n), and a grafting by functional groups of type D, suitable for injection, are chosen. holes (p). According to this embodiment, the subject of the invention is macromolecules consisting of a main π-conjugated semiconducting polymer chain of type A and of mesogenic semiconductive discogenic side groups of type D. These macromolecules are of liquid crystal type. (self-organized and nanostructured), and ambipolar ,.

The π-conjugated main polymer chain of type A may be chosen from: a cyano-polyphenylenevinylene (CN-PPV), polyfluorenone chain, as illustrated below, or a copolymer consisting of blocks of at least two of these polymers .

The mesogenic side groups of type D can be chosen from: a triphenylene, a copper phthalocyanine, a hexabenzocoronene, some of which are illustrated below, without this list being limiting.

and R represents a group selected from H, a C ₁ -C ₂₀ alkyl. Preferably, a spacer group connects the side groups to the main chain. These spacers may be chosen from: a polyalkylene glycol group, a C ₁ -C ₂₀ _{alkanediyl group} , C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkane di-oxy groups _, optionally interrupted by one or more selected functions. among: a phenyl ring (CeH ₆ ), an ether bridge (-O-), an amino bridge (-NH-), a carbonyl (-CO-), carboxyl (-COO-), amide (-CONH-) .

According to the second variant, the subject of the invention is macromolecules consisting of dendrimers: based on a dendritic architecture, this system consists of a type D or type A core, branches, and mesogenic surface functions. semiconductors of type A or type D distinct from that chosen for the core.

Dendrimers are well-defined, nano-sized tree structures characterized by a branched structure extending from the core to the periphery. They thus have a large number of identical terminal groups and since the growth of the dendrimer is carried out in the three directions of space, these macromolecules gradually take on a globular form.

According to a first embodiment of this variant, a macromolecular architecture of type A, suitable for the injection and transport of electrons (n), and a grafting by mesogenic functional groups of D type suitable for injection are chosen. and transporting the holes (p). According to this embodiment, the subject of the invention is macromolecules consisting of a semiconductor core of type A and semiconducting mesomeric branches and surface functions of type D. These macromolecules are of the liquid crystal type, they are self-organized, ambipolar, spontaneous nano-structuring. The core (type A) may be selected from: fullerenes include fullerenes C _6O, C ₇ o discotic mesogenic molecules, and in particular: tetraester of perylene-3,4,9,10-tetracarboxylic acid dianhydride perylene-3,4,9,10-tetracarboxylic acid (PTDA), perylene-3,4,9,10-tetracarboxylic acid diimide (PTCDI), 1,4,5,8-naphthalene acid dianhydride tetracarboxylic acid (NTDA), naphthalene-1,4,5,8-tetracarboxylic acid diimide (NTCDI), anthracene-1, 2,6,7-tetracarboxylic acid diimides, anthracene-1,2-acid anhydrides, 6,7-tetracarboxylic, perfluoropentacene, tetracyanoquinodimethane, tetracyanophenylenedimethane, perfluoroalkyl-grafted oligothiophene, 1,2,3,4,8,9,10,1 1,15,16,17,18,22,23,24,25 - Copper (II) hexadecafluoro-29H, 31H-phthalocyanine (Fi ₆ CuPc), 4,5,7-tri-nitro-9-oxo-9H-fluorene-2-carboxylic acid monoester (4,5,7- TNF-2-COOR), which have already been illustrated above.

The branches may be constructed from groups chosen from: benzylethers, a polyalkylene glycol group, an alkane di-yl group C ₁ -C ₂₀ -alkoxy-C ₂₀ alkanediyl-oxy Ci-C _2O optionally interrupted by one or more functions chosen from: a phenyl ring (CeH _6), an ether linkage (-O-) , an amino bridge (-NH-), a carbonyl (-CO-), carboxyl (-COO-), amide (-CONH-) group.

The mesogenic surface functions of type D can be chosen from: an oligothiophene, an oligophenylenevinylene, a tetracene, a pentacene, a phthalocyanine of copper (II) (CuPc), some of which are illustrated below, without this list being limiting .

CuPc

And it is also possible to use as a surface function in the present invention all known type D groups, especially those described in T. Mori, J. Phys .: Condens. Matter 2008, 20, 184010.

The type A core dendri- tic architecture, in particular fullerene core, and mesogenic D-type dendrons, leads to a self-organized nanostructure of these two entities (lamellar or columnar -Figure 2) which favors injection and transport. both types (holes and electrons) of charge carriers. Several modes of synthesis are usable. They are based on the classical methods of synthesis of dendrimers.

In particular, it is possible to use a divergent synthesis. This method of synthesis consists of growing the dendrimer step by step starting from the heart to the periphery. However, it involves the realization of an increasing number of reactions on the surface of the dendrimer, which can cause statistical defects in the branches.

Another method of synthesis of dendrimers was developed in 1990 by Fréchet et al. on polyether dendrimers, this is the convergent method. The convergent method progresses from the periphery to the heart. It limits the amount of defects in the structure by a smaller number of reaction sites at each step. On the other hand, it is sometimes limited by steric hindrance and difficult access to the heart.

And we can also combine these two methods. Examples of dendrimer structures and synthesis strategies are given in LM. Saez & J.W. Goodby, Struct. Jump. 2008, 128, 1; S.-C. Lo & P.L. Burn, Chem. Rev. 2007, 107, 1097.

According to a second embodiment of this variant, a macromolecular architecture of type D, suitable for the injection of holes (p), and a grafting by functional groups of type A, suitable for the injection of electrons, are chosen ( not).

According to this embodiment, the subject of the invention is macromolecules consisting of a semiconductor core of type D and semiconducting branches and surface functions of type A semiconductors. These macromolecules are of the liquid crystal type (self organized and nano structured), and ambipolar. The type D semiconductor core may be chosen from: triphenylene, copper phthalocyanine, hexabenzocoronene such as those already described above.

A type of the mesogenic side groups can be chosen from derivatives of: fullerenes include fullerenes C _6O, C ₇ o; discotic molecules, and in particular: perylene-3,4,9,10-tetracarboxylic acid tetraester, perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTDA), perylene-3 acid diimide, 4,9,10-tetracarboxylic acid (PTCDI), 1,4,5,8-naphthalene tetracarboxylic acid dianhydride (NTDA), naphthalene-1,5,5,8-tetracarboxylic acid diimide

(NTCDI), anthracene-1,2,6,7-tetracarboxylic acid diimides, anthracene-1,2,6,7-tetracarboxylic acid anhydrides, perfluoropentacene, tetracyanoquinodimethane, tetracyanophenylenedimethane, perfluoroalkyl grafted oligothiophene,

1, 2,3,4,8,9, 10, 11, 15, 16, 17, 18,22,23, 24,25-hexadecafluoro-29H, 31H-phthalocyanine Copper (II) (F _{I Ô} CUPC), 4,5,7-Trinitro-9-oxo-PH-fluorene-2-carboxylic acid monoesters (4,5,7-TNF-2-COOR), which have already been illustrated above

The invention further relates to an electronic component comprising at least one layer of a material of the invention. Advantageously, the electronic component comprises at least one substrate on which at least one layer of a material of the invention is deposited.

When it is desired to fabricate a transistor, the substrate is preferably selected from conventional substrates of microelectronics and nanoelectronics, such as SiO ₂ silicon wafers. Advantageously, the substrate is subjected to a preparation step before the deposition of the material of the invention. This preparation aims to modify the nature of the surfaces and in particular the anchoring properties (hydrophilic / hydrophobic character). This preparation step may consist of a treatment with a silanizing agent (deposit of a SAM: Self-Assembled Monolayer or self-assembled monolayer), a chemical cleaning, a plasma treatment. Among the silanization agents, there may be mentioned hexamethyldisalazane (ΗMDS), or an alkyltrichlorosilane (OTS for example), which has the effect of replacing the surface hydroxyl groups with alkyl groups.

And if one wishes to manufacture an OSC or an OLED, one preferentially uses as substrate an ITO glass plate (Indium Tin Oxide: Glass coated with a transparent electrode of Indium Etain Oxide).

But it can also provide a fully organic substrate such as a substrate of PMMA (polymethyleneméthacrylate) or polyaniline.

The subject of the invention is also a method for manufacturing an electronic component, this method comprising at least one step of depositing a material as described above on a substrate under conditions favoring the self-organization of the material. .

The deposition of the macromolecular material of the invention can be done in several ways:

- From a solution in a suitable solvent (organic solvents such as chloroform, dichloromethane, ethanol, acetone, pentane ethyl ether, hexane), advantageously by the method of Spin-coating or by the ink-jet or dip-printing method or by the so-called "zone melting" techniques (or casting zone, it is a technique comprising a solution deposit, followed by a controlled and localized evaporation of the solvent) as described in Η. N. Tsao et al. , Phys. SIAT. Ground. (a) 2008, 205, 421.

- Without solvent, directly on the device with a shaping via a fluid phase (isotropic liquid phase for example) as described in JC Maunoury et al., Adv. Mater. 2007, 19, 805 (2007). Whatever the deposition method chosen, annealing of the films obtained can advantageously make it possible to take optimal advantage of the prior preparation of the substrates and of the self-organization and orientation properties of the liquid crystal materials. The deposition of the material is preferably carried out under an inert atmosphere, for example under nitrogen or under argon.

The macromolecular material of the invention is advantageously deposited in layers with a thickness ranging from 100 Å to 1 μm.

The deposition of the macromolecular material of the invention on the substrate using the techniques described above leads to the formation of a nanostructured structure that can be of the lamellar, columnar or lamellar-columnar type, thus creating for the charge carriers channels whose orientation can be controlled on the substrates depending on the deposition conditions and the surface treatment.

The materials of the invention, compared to the materials of the prior art, make it possible to have an electron injection and a hole injection, within the same material, and with a high mobility, both for the electrons. only for the holes.

The electronic device may be an organic field effect transistor (OFETs: Organic Field-Effect Transistors), an organic light-emitting diode (OLEDs: Organic Light-Emitting Diodes), an organic photovoltaic solar cell (OSCs: Organic Solar Cells), an organic electroluminescent field effect transistor (OLETs: Organic Light-Emitting Transistors) or an organic laser. This electronic device is advantageously an OFET or an OLET, and a schematic example of a transistor is illustrated in FIG. 3. A transistor is composed of a doped silicon substrate (1) serving as a gate, on which a layer of silicon has been deposited. SiO ₂ silicon-based insulator (2) and a layer of the material (3) described in Example 1 below. Two electrodes, the source (4) and the drain (5) are placed on the set.

EXPERIMENTAL PART Abbreviations:

CC: column chromatography

DCC: N, N'-dicyclohexylcarbodiimide

DPTS: 4- (dimethylamino) pyridinium toluene-p-sulfonate

4-PPy: 4-pyrrolidinopyridine Example 1 (Scheme 1)

HT-2,5-poly (3-decylthiophene) substituted with perylene-3,4,9,10-tetracarboxylate group-type discs (5) was prepared as shown in Scheme 1 below. The first step is the preparation of the perylene triester (1) which was carried out according to the slightly modified protocols described by H. -Z. Chen et al., Chem. Phys. Lett. 2006, 417, 457. and H. Bock et al, Angew. Chem. Int. Ed. 2001, 40, 2060 for the synthesis of 3,4,9,10-tetra- ("-alkoxycarbonyl) -perylene. The discotic compound (1) obtained was then grafted onto the functional poly (3-alkylthiophene) (4) which was prepared according to the method of McCullough (RD McCullough et al, Macromolecules 2003, 36, 61). This grafting step being adapted from the method of functionalization of poly (bromoalkyl) thiophene already described by A. Iraqi et al., J. Mater. Chem., 1998, 8, 31 and A. Iraqi et al., Polym. Int., 2006, 55, 780.

i) KOH, Br (CH ₂ ) ₅ CH ₃ , Water, TBAB, reflux; ii) BuLi, THF, Br (CH ₂₎ ₁₀ Br, - 40 ⁰ C; iii) NBS, DMF, rt; iv) ¹ PrMgCl, THF, Ni (dppp) Cl ₂ , where ⁰ C; iv) 1, DBU, DMF, 140 ° C, 24h. Diagram 1

Preparation of 4,9,10-tri ((hexyloxy) carbonyl) perylene-3-carboxylic acid (1) (Scheme 1):

The perylene-3,4,9,10-tetracarboxylic acid dianhydride (5.0 g, 13 mmol) was converted to potassium tetracarboxylate with stirring in 1 M aqueous KOH (100 mL) at 100 ⁰ C. When the whole perylene dissolved in solution, the brown mixture was adjusted to pH 8-9 with aqueous 6M hydrochloric acid. Tetrabutylammonium bromide (0.7 g, 10 mol%) and 1-bromohexane (125 mL, 900 mmol) were added to the solution. The mixture was refluxed with vigorous stirring for one day. The brown solution was cooled to room temperature and extracted with dichloromethane (100 mL). The organic phase was washed several times with a saturated aqueous solution of NaCl (50 mL), dried over MgSO ₄ and concentrated under reduced pressure. The crude product was chromatographed on silica gel using a 3: 1 mixture of dichloromethane / ethyl acetate as eluent. The final product was obtained in the form of red crystals (65 mg, 0.4%) after evaporation of the solvent and drying under vacuum at 70 ^° C. Mp 192-193 ^° C, v _max (KBr) / cm ^' ' 3416 (COO-H), 2956, 2927, 2857 (alkyl), 1716, 1696 (C = O ester), 1655 (C = O acid), 1594 (Ar C = C), 1384 (OC = O), 1264 (CO), 747 (Ar-H); MS: m / z (%): 662.37 (100) [MH ₂ O] ⁺ ; δ _H (200 MHz, CDCl ₃₎ 8.43 (2H, d, J 8, 2H _arom), 8.21 (4H, dd, J 5 & 8 7 & 8 _310n-H,), 8 , 00 (2H, d, J 8, 1-H _arom ), 4.35 (4H, t, J 7.0, OCH ₂ ), 4.18 (2H, t, J 7.6, OCH ₂ ), 1.81 ( 6H, m, H _a , i _ph ), 1.52-1.32 (18H, m, H _aliph ), 0.93 (9H, m, -CH ₃ ).

Preparation of 3- (10-bromodecyl) thiophene (2) (Scheme 1): 3-Bromothiophene (3 mL, 31 mmol) was dissolved in 50 mL of freshly distilled hexane, all under an argon atmosphere. The resulting solution was cooled to -40 ° C. and stirred for 10 minutes. "-Buli (19.4 mL, 31 mmol, 1.6 M in hexanes) was added dropwise through syringe while keeping the temperature of the solution at -40 ° C. 10 mL of THF was added to the resulting pale yellow solution which was kept for 1 h. The resulting white suspension was gradually warmed to -10 ^° C. 1.10-Dibromodecane (28.7 mL, 120 mmol) was added all at once and the mixture was warmed to room temperature and then left stirring. for 2 hours. The reaction was stopped by pouring 15 mL of distilled water into the flask and the solution extracted with diethyl ether (2 x 30 mL). The organic phase was washed with water (3 x 30 mL) and dried over MgSO ₄ . The crude product consisted of a yellowish oil which was purified by fractional distillation under reduced pressure. Excess dibromodecane was isolated first (Bp 105 ⁰ C @ 0.08 mm Hg) followed by the final product (Bp 135 ⁰ C @ 0.08 mm Hg) which was obtained in the form of a transparent oil ( 3.52 g, 37%) after filtration over silica gel gel using petroleum ether as eluent; R _f 0.40 (hexane); v _max (pure ^? cm ^? 13104 (Ar-H), 3003, 2926, 2853 (alkyl), 1536 (Ar C = C), 1463 (C = S), 772 (Ar- H), 635 (Ar-H); δ _H (250 MHz, CD ₂ Cl ₂ ) 7.24 (1H, dd, J 3 & 4.9, 5-Haro _m ), 6.94 (1H, dd, J 1.2 & 4.6, 4-Ha _r _m ) , 6.92 (1H, d, J 1.2, 2-H _arom ), 3.42 (2H, t, J 6.9, CH ₂ -Br), 2.62 (2H, t, J 7.4, CH ₂ -Ar). 1.84 (2H, m, H _aliph ), 1.60 (2H, m, H), 1.40-1.26 (12H, m, H _aliph ); δ _c (250 MHz, CDCl ₃ ) 143.20, 128.25, 125.00, 119.74, 33.96, 32.81, 31.81, 30.52, 30.26, 29.42, 29.38, 29.27, 28.73, 28.16.

Preparation of 3- (10-bromodecyl) -2,5-dibromothiophene (3) (Scheme 1):

3- (10-Bromodecyl) thiophene (1.61 g, 5 mmol) was dissolved in 5 mL of dimethylformamide under a nitrogen atmosphere. N-Bromosuccinimide (2.3 g, 13 mmol) in 10 mL of DMF was added dropwise into the solution at room temperature. After stirring overnight, the reaction mixture was poured into water (50 mL) and extracted with 3 x 30 mL of diethyl ether. The organic phase was washed with water (3 x 30 mL), dried over MgSO ₄ and concentrated under reduced pressure. The crude product was passed over silica gel using hexane as eluent to give the final product (1.98 g, 81%) as a colorless oil; R _f 0.63 (hexane); v _max (neat) / cm ^~ 3090 (Ar-H), 2925, 2853 (alkyl), 1541 (Ar C = C), 1463 (C = S), 722 (Ar-H), 647 (Ar-H); ); δ _H (250 MHz, CDCl ₃ ) 6.78 (1H, s, 4-H ₃ T _0n ), 3.42 (2H, t, J 6.6, -CH ₂ Br), 2.51 (2H, t , J 7.9, -CH ₂ Ar), 1.87 (2H, m, H _a , _iph ), 1.56 (2H, m, H _aliph ), 1.51-1.29 (12H, m, H _aliph ) _; δ _c (250 MHz, CDCl ₃ ) 143.20, 128.25, 125.00, 119.74, 33.96, 32.81, 31.81, 30.52, 30.26, 29.42, 29.38, 29.27, 28.73, 28.16.

Preparation of HT 2,5-poly [3- (10-bromodecyl) thiophene] (4) (Scheme 1):

All glassware and solvents were carefully dried before use. 2,5-Dibromo-3- (10-bromodecyl) thiophene (0.4 g, 0.9 mmol) was poured into 5 mL of dry THF at 0 ^° C. under an argon atmosphere. A solution of isopropyl magnesium chloride (0.4 mL, 0.9 mmol, 2.0 M in THF) was added via syringe and the resulting yellow solution stirred for 1 h. A suspension of Ni (dppp) Cl ₂ (7 mg, 0.014 mmol, 1.6 mol%) in THF (5 mL) was rapidly injected into the flask. The resulting red solution was gently warmed to room temperature and left stirring overnight. Polymerization was terminated by addition of 6 M HCl solution (10 mL) followed by extraction with chloroform (20 mL). The organic phase was successively washed with water (3 x 30 mL), dried over MgSO ₄ and concentrated under reduced pressure. The crude polymer was precipitated in methanol and the resulting violet solid filtered through a Soxhlet cartridge. The final product was obtained (0.129 g, 50%) after successive extractions with methanol and hexane; M _n = 10560; M _w / M _n = 1.2 (GPC); Mp 95 ⁰ C; v _max (KBr) / cm ^"3059 (Ar-H), 2820, 2851 (alkyl), 1561, 1512 (Ar C = C), 1464 (C = S), 720 (Ar-H); δ _H ( 250 MHz, CDCl ₃ ) 6.99 (1H, s, H _arom ), 3.39 (2H, t, J 6.8, CH ₂ Br), 2.79 (2H, m, Ar-CH ₂ -), 1.85 (2H, m, -Haiip _h), OU (2H, m, H _alipll), from 1.38 to 1 , 32 (12H, m, H _a , _ip h).

Preparation of the HT (5) polymer (Scheme 1):

To a solution of perylene triester 1 (50 mg, 0.07 mmol) in DMF (10 ml) under argon was added 1,8-diazabicyclo [5.4.0] undec-7-ene (0). 1 mL, 0.7 mmol). The mixture was heated at 80 ^° C. for 30 minutes. Polythiophene 4 (11 mg, 0.04 mmol) was then added to the solution under an inert atmosphere and heated at 140 ° C with stirring for 24 h. The reaction was cooled to ambient temperature and then extracted with 2 x 30 mL of dichloromethane. The organic phase was washed with distilled water (3 x 30 mL), dried over MgSO ₄ anhydride and concentrated under reduced pressure. The crude product was precipitated in methanol and the red solid filtered through a Soxhlet cartridge. Compound 5 was obtained after successive extractions with methanol and ethanol.

EXAMPLE 2 (Schemes 2, 3, 4) Intermediates 2 (Lacoudre et al., Mol., Cryst., Liq., Cryst.

155, 13), 3 (TM Miller et al, Macromolecules 1992, 25, 3143) and 4 (J. Leroy et al., J. Org Chem 2007, 1256) (Scheme 2) were prepared according to procedures described in the literature. Compound 4 is converted to the corresponding carboxylic acid by treatment with nBuLi followed by the addition of CO ₂ . Esterification of 5 with a large excess of 1,4 butanediol in the presence of DCC, DPTS and 4-PPy provides the corresponding monoester 6 in good yield. The first-generation protected dendron 7 is obtained by esterification of the acidic core 3 with the alcohol 6. The hydrolysis under mild conditions of the TBDMS protective group gives rise to the first-generation phenol 8. The esterification of the acidic core 3 with the phenol 8 leads to the formation of the second generation protected dendron 9. The hydrolysis under mild conditions of the protective group TBDMS gives rise to the second generation phenol 10. The esterification of 10 with the spacer 2 provides the compound 11. Finally the precursor aldehyde 12 is obtained by esterification of 11 with 4-carboxybenzoaldehyde. Fullerene is then introduced according to the procedure described by M. Maggini et al., J. Am. Chem. Soc., 1993, 115, 9798, to lead to the formation of target compound 1 as illustrated in Schemes 3 and 4 below.

Scheme 2: Chemical Structure of Intermediates 2, 3 and 4. Compound 5 (Scheme 3):

A solution of 4 (1.0 g, 2.77 mmol) in anhydrous THF (100 ml) is cooled to -78 ° C. and then a solution of nBuLi (ca. 1.6 M in hexane; mmol) is added. The reaction mixture is stirred for 10 min at -78 ° C and then CO ₂ gas is bubbled in this solution. The reaction mixture is then stirred at room temperature overnight before slowly adding water. After evaporation of the THF, the yellow precipitate is filtered and then dried under vacuum to give 5 (673 mg, 60%).

¹ H NMR (200 MHz, CDCl ₃ ): δ 7.44 (d, 1H, J = 3.6Hz), 6.95 (d, 1H, 3.8Hz), 6.91 (d, 1H, J = 3.8Hz), 6.81 (d. , IH, J = 3.8Hz), 6.80 (d, 1H, J = 3.6Hz), 6.49 (d, 1H, J = 3.6Hz), 2.58 (t, 2H, J = 7.6Hz), 1.47 (q, 2H) ), 1.21-0.98 (m, 10H), 0.67 (t, 3H, J = 6.0Hz).

FT-IR (cm ^-1 ): 3092, 2955, 2921, 2884, 2872, 2849, 1687, 1681.

Compound 6 (Scheme 3):

To a solution of 5 (200 mg, 0.49 mmol) and 1,4 butanediol (40 ml) in anhydrous CH ₂ Cl ₂ (50 ml) cooled to 0 ^° C. are added DCC (300 mg; 48 mmol), DPTS (142 mg, 0.99 mmol) and 4-PPy (a spatula tip). The mixture is stirred under argon at 0 ° C for 30 min and then 16h at room temperature before being evaporated to dryness. The solid residue is purified by CC (silica gel, eluent: CH ₂ Cl ₂ / Et ₂ O, 200: 10) to give 6 as a yellow solid (156 mg, 69%).

¹ H-NMR (200 MHz, CDCl ₃ ): δ 7.69 (d, 1H, J = 4.0Hz), 7.15 (d, 1H, J = 1.2Hz), 7.13 (d, 1H, J = 1.6Hz) , 7.01 (d, 1H, J = 3.8Hz), 7.00 (d, 1H, J = 3.6Hz), 6.69 (dt, 1H, J = 3.4Hz), 4.34 (t, 2H _: J = 6.0Hz), 3.73 (qua, 2H ₅ J = 5.6Hz), 2.79 (t, 2H, J = 7.4Hz), 2.00-1.60 (m, 4H), 1.50-1.10 (m, 10H), 0.88 (t, 3H, J = 5.4 Hz).

¹³ C NMR (50 MHz, CDCl ₃ ): 5162.1, 146.3, 144.0, 138.7, 134.2, 134.1, 133.9, 131.1, 125.8, 124.9, 123.9, 123.6, 123.5, 64.9, 62.3, 31.8, 31.5, 30.2, 29.3, 29.2, 29.1, 29.0, 25.2, 22.6, 14.1.

HRMS-ESI: [M + N f C ₂₅ H ₃₂ O ₃ NaS ₃ , m / z calc. 499.141 1, m / z found: 499.1417.

FT-IR (cm ^-1 ): 3315, 3092, 2955, 2918, 2872, 2850, 1704.

Compound 7 (Scheme 3): To a solution of 6 (592 mg, 1.24 mmol) and 3 (183 mg, 0.62 mmol) in anhydrous CH ₂ Cl ₂ (100 ml) cooled to 0 ^° C. are added DCC (385 mg). 1.86 mmol), DPTS (365 mg, 1.24 mmol) and 4-PPy (a spatula tip). The mixture is stirred under argon at 0 ⁰ C for 30 min and then 16h at room temperature before being evaporated to dryness. The solid residue is purified by CC (silica gel, eluent: CH ₂ Cl ₂ / Et ₂ O, 200: 1) to give 7 as a yellow solid (685 mg, 90%).

¹ H NMR (200 MHz, CDCl ₃ ): δ 8.17 (t, 1H, J = 1.6Hz), 7.58 (d, 2H,

J = 4.0Hz), 7.57 (d, 2H, J = 1.2Hz), 7.03 (d, 2H, J = 3.8Hz), 6.98 (d, 2H, J = 4.0Hz), 6.89 (d,

4H, J = 3.8Hz), 6.56 (dt, 2H, J = 3.6Hz), 4.50-4.20 (m, 8H), 2.68 (t, 4H, J = 7.4Hz), 2.00-1.70 (m, 8H), 1.56 (q, 4H), 1.40-1.00 (m, 20H), 0.88 (s, 9H), 0.77 (t, 6H, J = 6.8Hz), 0.12 (s,

6H).

¹³ C NMR (50 MHz, CDCl ₃ ): δ 165.5, 161.9, 155.9, 146.3, 144.1, 138.7, 134.3, 134.1, 133.9, 131.9, 131.0, 125.8, 125.3, 124.9, 123.9, 123.6, 123.5, 64.8, 64.6 , 31.8, 31.5, 30.2, 29.3, 29.2, 29.1, 25.6, 25.4, 22.6, 18.2, 14.1. HRMS-ESI: [M + Na] ⁺ C ₆₄ H ₈₀ O ₉ NaSiS ₆ , m / z calc. 1235.3793, m / z found: 1235.3802.

FT-IR (cm- ¹ ): 3094, 2956, 2924, 2873, 2851, 1704, 1697. Compound 8 (Scheme 3):

To a solution of 7 (620 mg, 0.51 mmol) in 70:20 THF / H ₂ O (90 ml) was added Zn (BF ₄ ) ₂ (234 mg, 1.02 mmol). The solution is stirred at ambient temperature for 12 hours. The aqueous phase is extracted with CH ₂ Cl ₂ which is then evaporated to dryness. The solid residue is purified by CC (silica gel, eluent: CH ₂ Cl ₂ / Et ₂ O, 200:20) to afford 8 as a yellow solid (535 mg, 95%).

¹ H-NMR (200 MHz, CDCl ₃ ): δ 8.29 (t, 1H, J = 1.2 Hz), 7.79 (d, 2H, J = I.4Hz), 7.72 (d, 2H, J = 3.8Hz) , 7.18 (d, 2H, J = 3.8Hz), 7.13 (d, 2H, J = 4.4Hz), 6.73 (d, 4H, J = 4.0Hz), 6.73 (dt, 2H, J = 4.0Hz), 6.17 (s, 1H), 4.60-4.30 (m, 8H), 2.83 (t, 4H, J = 7.2Hz), 2.20-1.70 (m, 8H), 1.72 (q, 4H), 1.60-1.20 (m, 20H). ), 0.92 (t, 6H, J = 6.2Hz).

¹³ C NMR (50 MHz, CDCl ₃ ): δ 165.5, 162.2, 156.1, 146.3, 144.3, 134.4, 134.0, 133.9, 132.0, 130.9, 125.9, 124.9, 123.9, 123.7, 123.6, 122.8, 120.8, 65.0, 64.8 , 31.8, 31.6, 30.2, 29.3, 29.2, 29.1, 25.6, 25.3, 22.6, 14.1.

HRMS-ESI: [M + Na] ⁺ C ₅₈ H ₆₆ O ₉ NaS ₆ , m / z calc. 121.2929, m / z found: 1121.2928.

FT-IR (cm- ¹ ): 3364, 3094, 2956, 2921, 2873, 2850, 1703, 1698. Compound 9 (Scheme 3): To a solution of 8 (235 mg, 0.21 mmol) and 3 ( 31 mg, 0.1 mmol) in anhydrous CH ₂ Cl ₂ (50 ml) cooled to 0 ° C. are added DCC (64 mg, 0.32 mmol), DPTS (62 mg, 0.21 mmol). ) and 4-PPy (a spatula tip) The mixture is stirred under argon at 0 ⁰ C for 30 min and then 16h at room temperature before being evaporated to dryness. The solid residue is purified by CC (silica gel, eluent: CH ₂ Cl ₂ / Et ₂ O, 200: 5) to afford 9 as a yellow solid (270 mg, 80%).

¹ H NMR (200 MHz, CDCl ₃ ): δ 8.64 (t, 1H, J = I.4Hz), 8.62 (t, 2H,

J = I.4Hz), 8.11 (d, 4H, J = 1.6Hz), 7.90 (d, 2H, J = 1.6Hz), 7.66 (d, 4H, J = 3.8Hz), 7.13 (d, 4H, J); = 3.8Hz), 7.07 (d, 4H, J = 4.2Hz), 6.98 (d, 8H, J = 3.8Hz), 6.67 (dt, 4H, J = 3.8Hz), 4.60-

4.30 (m, 16H), 2.78 (t, 8H, J = 7.4Hz), 1.93 (m, 16H), 1.67 (q, 8H), 1.27 (m, 4OH), 1.01 (s,

9H), 0.88 (t, 12H, J = 6.4Hz), 0.28 (s, 6H).

¹³ C NMR (50 MHz, CDCl ₃ ): δ 164.8, 163.6, 161.9, 156.5, 150.7, 146.3,

144.1, 138.7, 134.3, 134.0, 133.9, 132.2, 131.0, 130.8, 128.3, 127.2, 126.8, 125.9, 124.9, 123.9, 123.6, 123.5, 65.2, 64.5, 31.8, 31.6, 30.2, 29.3, 29.2, 29.1, 25.6, 25.4, 22.6, 14.1.

HRMS-ESI: [M + Na] ⁺ Cl ₃ OHi ₄₈ O ₂ INaSiSi ₂ , m / z calc. 2479.6828, m / z found: 2479.6828.

FT-IR (cm- ¹ ): 3092, 2954, 2925, 2870, 2852, 1705, 1698. Compound 10 (Scheme 3): To a solution of 9 (410 mg, 0.17 mmol) in THF / H ₂ O

100: 20 (120 ml) is added Zn (BF ₄ ) ₂ (80 mg, 0.33 mmol). The solution is stirred at ambient temperature for 24 hours. The aqueous phase is extracted with CH ₂ Cl ₂ which is then evaporated to dryness. The solid residue is purified by CC (silica gel, eluent: CH ₂ Cl ₂ / Et ₂ O, 200:20) to afford 10 as a yellow solid (405 mg, 100%). ¹ H-NMR (200 MHz, CDCl ₃ ): δ 8.65 (t, 2H, J = 1.6Hz), 8.60 (t, 1H,

J = 1.6Hz), 8.15 (d, 4H, J = 1.6Hz), 7.98 (d, 2H, J = 1.2Hz), 7.70 (d, 4H, J = 4.2Hz), 7.16 (d, 4H, J = 3.8Hz), 7.10 (d, 4H, J = 4.0Hz), 7.02 (d, 8H, J = 4.0Hz), 6.71 (dt, 4H, J = 3.6Hz), 6.63 (s, 1H), 4.60; -4.30 (m, 16H), 2.81 (t, 8H, J = 7.6Hz), 2.10-1.90 (m, 16H), 1.70 (q, 8H), 1.50-1.20 (m, 4OH), 0.92 (t, 12H). , J = 5.2 Hz). ¹³ C NMR (50 MHz, CDCl ₃ ): δ 164.7, 163.5, 162.1, 157.0, 150.7, 146.3,

144.2, 38.7, 134.4, 134.0, 133.9, 132.2, 130.8, 128.2, 127.1, 125.9, 125.5, 124.9, 123.9, 123.6, 123.5, 122.3, 65.2, 64.7, 34.2, 31.8, 31.5, 30.3, 30.2, 29.7, 29.3, 29.1, 25.5, 25.3, 22.6, 21.1, 14.1.

HRMS-ESI: [M + Na] ⁺ C ₁₂₄ H ₃₄ O _2I NaSi ₂ , m / z calc. 2365.5964, m / z found: 2365.601 1.

FT-IR (cm ^-1 ): 3400, 3090, 2956, 2923, 2870, 2853, 1720, 1697.

Compound 11 (Scheme 4):

To a solution of 10 (100 mg, 0.04 mmol) and 2 (12 mg, 0.04 mmol) in anhydrous CH ₂ Cl ₂ (50 ml) cooled to 0 ^° C. are added DCC (17 mg 0.08 mmol), DPTS (25 mg, 0.08 mmol) and 4-PPy (a spatula tip). The mixture is stirred under argon at 0 ⁰ C for 30 min and then 16h at room temperature before being evaporated to dryness. The solid residue is purified by CC (silica gel, eluent: CH ₂ Cl ₂ / Et ₂ O, 200: 6) to give 11 as a yellow solid (90 mg, 81%). ¹ H NMR (200 MHz, CDCl ₃ ): δ 8.91 (t, 1H, J = 1.2 Hz), 8.63 (t, 2H,

J = 1.2 Hz), 8.33 (d, 2H, J = 1.6Hz), 8.15 (d, 2H, J = 9.0Hz), 8.12 (d, 4H, J = 1.8Hz), 7.65 (d,

4H, J = 3.8Hz), 7.12 (d, 4H, J = 3.8Hz), 7.07 (d, 4H, J = 4.0Hz), 6.98 (d, 8H, J = 9.2Hz), 6.97;

(d, 8H, J = 3.8Hz), 6.67 (d, 4H, J = 4.0Hz), 4.40 (dt, 16H), 4.04 (t, 2H, J = 6.4Hz), 3.64 (t, 2H, J = 6.4Hz), 2.77 (t, 8H, J = 7.6Hz), 2.05-1.50 (m, 16H), 1.40-1.00 (m, 40H), 0.88 (t, 16H).

¹³ C NMR (50 MHz, CDCl ₃ ): δ 165.2, 164.8, 164.4, 163.4, 162.4, 152.0, 151.0, 146.7, 144.5, 139.1, 134.7, 134.5, 134.4, 132.9, 132.8, 131.4, 129.5, 128.9, 127.6 , 126.3, 125.4, 124.3, 124.1, 123.9, 120.7, 1 14.9, 65.7, 65.0, 63.5, 33.2, 32.3, 32.0, 30.6, 30.1, 29.9, 29.8, 29.7, 29.6, 29.5, 26.4, 26.2, 25.9, 25.8, 23.1, 14.1. HRMS-ESI: [M + Na] ⁺ C ₁₄ O ₂₄ NaS IHI _58] _2, m / z calc. 2641.7689, m / z found: 2641.7716.

FT-IR (cm- ¹ ): 3325, 3092, 2956, 2922, 2870, 2852, 1720, 1698. Compound 12 (Scheme 4):

To a solution of 11 (150 mg, 0.06 mmol) and 4-carboxybenzaldehyde (26 mg, 0.17 mmol) in anhydrous CH ₂ Cl ₂ (50 ml) cooled to 0 ^° C. are added DCC ( 54 mg, 0.26 mmol), DPTS (51 mg, 0.17 mmol) and 4-PPy (a spatula tip). The mixture is stirred under argon at 0 ⁰ C for 30 min and then 16h at room temperature before being evaporated to dryness. The solid residue is purified by CC (silica gel, eluent: CH ₂ Cl ₂ / Et ₂ O, 200: 10) to give 12 as a yellow solid (154 mg, 98%).

¹ H-NMR (200 MHz, CDCl ₃ ): δ 10.09 (s, 1H), 8.91 (t, 1H, J = 1.6Hz), 8.64 (t, 2H, J = 1.2Hz), 8.33 (d, 2H); , J = 1.2 Hz), 8.19 (d, 4H, J = 8.4Hz), 8.13 (d, 4H, J = 1.6Hz), 7.94 (d, 2H, J = 8.6Hz), 7.65 (d, 4H). , J = 3.8Hz), 7.12 (d, 4H, J = 3.8Hz), 7.06 (d, 4H, J = 3.8Hz), 6.97 (d, 4H, J = 9.0Hz), 6.98 (d, 4H, J); = 3.8Hz), 6.66 (d, 4H, J = 4.0Hz), 4.50-4.20 (m, 16H), 4.03 (t, 2H, J = 6.4Hz), 2.77 (t, 8H, J = 7.2Hz), 2.05-1.10 (m, 56H), 0.88 (t, 12H). ¹³ C NMR (50 MHz, CDCl ₃ ): δ 191.6, 165.6, 164.7, 164.3, 163.9, 163.0, 161.9, 151.6, 146.2, 144.1, 139.0, 138.6, 134.3, 134.0, 133.9, 132.5, 132.3, 130.9, 130.0 , 129.5, 129.0, 127.1, 125.8, 124.9, 123.9, 123.6, 123.5, 120.3, 14.4, 68.3, 62.7, 65.2, 64.5, 31.8, 31.5, 30.1, 29.4, 29.3, 29.2, 29.0, 28.6, 25.9, 25.4, 25.4, 22.6, 14.1. HRMS-ESI: [M + Na] ⁺ C ₄₉ H ₆₂ O ₂₆ NaSi ₂ , m / z calc. 2773.7900, m / z found: 2773.7939.

FT-IR (cm- ¹ ): 3091, 2955, 2924, 2871, 2852, 1719, 1698. Compound 1 (Scheme 4):

To a solution of C ₆ o (100 mg; 0.14 mmol) in chlorobenzene (100 ml) was added 12 (75 mg, 0.03 mmol) and N-methylglycine (25 mg; 0.28 mmol) . The mixture is stirred at reflux for 20 h and then evaporated to dryness. The solid residue is purified by

CC (silica gel, eluent: toluene / Et ₂ O, 200:20) and then precipitated in acetone to provide

1 as a brown solid (70 mg, 73%). ¹ H NMR (200 MHz, CDCl ₃ ): δ 8.95 (t, 1H, J = 1 · 4Hz), 8.68 (t, 2H, J = 1.2 Hz), 8.37 (d, 2H, J = 1.2 Hz). ), 8.16 (d, 4H, J = 1.8Hz), 8.16 (d, 4H, J = 1.4Hz), 7.95-7.85 (m, 2H), 7.70 (d, 4H, J = 3.8Hz), 7.17. (d, 4H, J = 3.8Hz), 7.1 1 (d, 4H, J = 3.8Hz), 7.02 (d, 4H, J = 4.0Hz), 6.98 (d, 4H, J = 3.8Hz), 6.71 ( d, 4H, J = 3.6Hz), 5.01 (t, 2H, J = 4.8Hz), 4.60-4.20 (m, 20H), 4.07 (t, 2H, J = 6.4Hz), 2.80-2.70 (m, 12H). 2.10-1.60 (m, 16H), 1.60-1.20 (m, 74H), 0.91 (t, 12H).

¹³ C NMR (50 MHz, CDCl ₃ ): δ 166.9, 165.2, 164.8, 164.4, 163.4, 162.4, 154.2, 153.1, 152.0, 151.0, 146.7, 146.6, 146.5, 146.3, 146.2, 145.9, 145.7, 145.6, 145.5 , 144.9, 144.8, 144.5, 143.5, 143.4, 143.0, 142.9, 142.6, 142.4, 142.3, 142.2, 142.1, 141.9, 140.6, 140.3, 139.9, 139.1, 134.7, 134.5, 134.4, 133.0, 131.5, 131.0, 130.3, 129.7 , 129.7, 129.5, 128.9, 127.6, 126.3, 125.4, 124.3, 124.1, 124.0, 14.9, 83.5, 70.4, 65.7, 65.0, 40.4, 32.3, 32.0, 30.6, 30.1, 29.8, 29.7, 29.6, 29.5, 29.1, 26.4, 26.3, 25.9, 25.8, 23.1, 14.1.

HRMS-ESI: [M + H] ⁺ C _{21 I} H ⁺ ₆₈ NO ₂₅ S ₁₂ , m / z hold. 3498.85541, m / z found: 3498.8524. FT-IR (cm- ¹ ): 3081, 2955, 2922, 2886, 2867, 2852, 1718, 1698.

diagram 3

diagram 4

Claims

1. Organic semiconducting thermotropic mesomorphic material comprising a semiconductor macromolecular architecture of the electron donor (D) or electron acceptor (A) type, on which are grafted semiconductor functional groups of type A or D , distinct from that chosen for the macromolecular architecture

2. The material according to claim 1, which is chosen from self-organized macromolecules consisting of a D-type or A-type semiconducting main polymer chain and of D or A type mesogenic semiconductor side groups, distinct from that chosen for the main polymer chain.

3. Material according to claim 2, selected from macromolecules consisting of a main polymer chain π-conjugated semi-conductor type D and discogenic lateral groups mesogens organic semi-conductors type A.

4. The material according to claim 3, in which the main π-conjugated D-type polymer chain is chosen from: a polythiophene (PT), polyparaphenylenevinylene (PPV), polyparaphenylene (PPP) and polythieno [2,3-b] thiophene chain. a copolymer consisting of blocks of at least two of these polymers.

5. The material according to claim 3 or claim 4, wherein the type A discogenic mesogenic side groups are chosen from derivatives: perylene-3,4,9,10-tetracarboxylic acid tetraester, perylene acid dianhydride. 3,4,9,10-tetracarboxylic acid (PTDA), perylene-3,4,9,10-tetracarboxylic acid diimide (PTCDI), 1,4,5,8-naphthalene tetracarboxylic acid dianhydride (NTDA) 1,4-naphthalene-4,5,8-tetracarboxylic acid diimide (NTCDI), anthracene-1, 2,6,7-tetracarboxylic acid diimides, anthracene-1, 2,6,7- tetracarboxylic, perfluoropentacene, tetracyanoquinodimethane, tetracyanophenylenedimethane, perfluoroalkyl-grafted oligothiophene, 1,2,3,4,8,9,10,1 1,15,16,17,18,22,23,24,25-hexadecafluoro-29H , 31H-phthalocyanine of copper (II) (Fi ₆ CuPc) and monoesters of 4,5,7-trinitro-9-oxo-9H-fluorene-2-carboxylic acid (4,5,7-TNF-2- COOR).

6. Material according to one of claims 3 to 5, wherein one or more spacer groups connect the side groups to the main chain, these spacers being chosen from: a polyalkylene glycol group, a C1-C6 alkanediyl group; _2O alkoxy, C) -C _2O, alkanediyl-oxy-Ci -C _20, optionally interrupted by one or more functions chosen from: phenyl, an ether bridge, an amino bridge, carbonyl, carboxyl, amide.

7. Material according to one of claims 3 to 6, wherein the main polymer chain is a regioregular polythiophene having a substantially homogeneous chain length, comprising between 6 and 100 thiophene units.

8. The material according to claim 1, which is selected from dendrimer-type macromolecules comprising a D-type or A-type core, D or A type semiconducting mesomeric branches and surface functions distinct from that chosen for the D-type or A-type core. heart.

9. The material according to claim 8, wherein the semiconductor core is of type A and the branches and the semiconducting mesogenic surface functions are of type D.

10. The material as claimed in claim 9, in which the core is chosen from: fullerenes and in particular fullerenes Cβo, C ₇₀ ; discotic mesogenic molecules, and in particular: perylene-3,4,9,10-tetracarboxylic acid tetraester, perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTDA), perylene-3-acid diimide , 4,9,10-tetracarboxylic acid (PTCDI), 1,4,5,8-naphthalene tetracarboxylic acid dianhydride (NTDA), naphthalene-1,4,5,8-tetracarboxylic acid diimide (NTCDI), anthracene-1,2,6,7-tetracarboxylic acid diimides, anthracene-1,2,6,7-tetracarboxylic acid anhydrides, perfluoropentacene, tetracyanoquinodimethane, tetracyanophenylenedimethane, perfluoroalkyl-grafted oligothiophene, 1,2,3, 4,8,9,10,1 l, 15,16,17,18,22,23,24,25-hexadécafluoro-29H, 31H-phthalocyanine copper (II) (Fi _é CuPc) and acid monoesters 4,5,7-Trinitro-9-oxo-PH-fluorene-2-carboxylic acid (4,5,7-TNF-2-COOR).

11. Material according to any one of claims 9 and 10, wherein the legs are constructed from groups selected from: benzyl ethers, polyalkylene glycol group, an alkanediyl group Ci-C _2O, alkoxy -C ₂₀ alkanediyl-oxy-C -C _2o1 optionally interrupted by one or more functions chosen from: phenyl, an ether bridge, an amino bridge, carbonyl, carboxyl, amide.

The material according to any of claims 9 and 10, wherein the mesogenic surface functions are selected from: oligothiophene, oligophenylenevinylene, tetracene, pentacene, CuPc.

13. Electronic component comprising at least one layer of a material according to any one of claims 1 to 12.

14. Component according to claim 13, which is chosen from: an OFET, an OLET, an OSC, an OLED, an Organic Laser.

The component of claim 13 or claim 14, which comprises a layer of material according to any one of claims 1 to 12 having a thickness of 100 to 1 μm.

16. A method of manufacturing an electronic component according to one of claims 13 to 15, this method comprising at least a step of depositing a material according to any one of claims 1 to 12 on a substrate under conditions favoring self-organization of the material.

17. The method of claim 16, wherein the deposition of the material is from a solution in a suitable solvent by a method selected from: the method of spin coating, the method of printing by ink jet , by dipping, by zone melting.

18. The method of claim 16, wherein the deposition of the material is without solvent, directly on the device with shaping through a fluid phase.