HK1063053B - Organic compounds having a core-shell structure - Google Patents

Description

Organic compounds having a core-shell structure

The invention relates to an organic substance containing a core-shell structure, to a process for its preparation and to its use as a semiconductor electronic component.

The field of molecular electronics has developed rapidly over the last 15 years with the discovery of organic conducting and semiconducting organic compounds. During this time, many compounds with semiconducting and electrooptical properties were discovered. It is widely believed that molecular electronics will not replace the traditional silicon semiconductor field. In contrast, molecular electronic components are believed to open up new application areas in large area coatings, structural flexibility, low temperature, low cost processing. Semiconducting organic compounds are currently used in Organic Field Effect Transistors (OFETs), Organic Light Emitting Diodes (OLEDs), sensors and photovoltaic elements. The mere incorporation of OFETs into organic semiconductor circuit structures makes it possible to find a low-cost solution to the hitherto unsolved problem of smart cards or price signs due to the price and lack of flexibility of silicon chips. Meanwhile, OFETs can be used as circuit elements for large-area flexible matrix displays. Organic semiconductors, semiconductor integrated circuits and their use are reviewed in electronics 2002, 15, 38.

A field effect transistor is a three-electrode device in which the conductivity of a thin conductive channel between two electrodes (known as the "source" and the "source") is controlled by a third electrode (known as the "gate") separated by a thin insulating layer. The most important characteristic of a field effect transistor is the carrier mobility, which has a significant effect on the switching speed of the transistor, the ratio of the currents in the on and off states, i.e., the "on/off ratio".

There are two main classes of organic substances that have been used in organic field effect transistors to date. These organic substances all contain long conjugated units, which are classified into conjugated polymers and conjugated oligomers according to molecular weight and structure.

Oligomers generally have a uniform molecular structure and a molecular weight of less than 10,000 daltons. Polymers generally contain chains of uniform repeat units and molecular weight distribution. However, there is a continuous transition between the oligomer and the polymer.

The distinction between oligomers and polymers is generally reflected in the fundamental difference in the processing of these compounds. The oligomers are typically vaporized and applied to a substrate by a vapor deposition process. The term polymer generally refers to compounds that are no longer evaporative and therefore are applied by other means regardless of their molecular structure. It is generally necessary for the polymers to be soluble in liquid media, such as organic solvents, and then to be applied by corresponding methods. A commonly used application method is for example spin coating. A particularly good method of applying the semiconductive compound is by the inkjet process. In this process, the semiconductive solution is dropped onto the substrate in the form of very fine droplets, which are then dried. This method allows the formation of structures during application. Such a method of applying semiconductive compounds is already described, for example, in Nature 401, page 685.

In general, the wet chemical process is considered to have a greater potential in obtaining inexpensive organic semiconductor integrated circuits by a simple method.

An important prerequisite for the production of high-quality organic semiconductor circuits is compounds of particularly high purity. Ordering phenomena play an important role in semiconductors. The lack of uniform alignment of the compounds and the sharp grain boundaries can lead to a significant reduction in semiconductor properties. Therefore, organic semiconductor circuits produced without particularly high purity compounds are generally unusable. For example, residual impurities can inject charge into the semiconductive compound ("doping"), thereby reducing the on/off ratio, or act as a charge scavenger significantly reducing its conductive properties. Furthermore, impurities can cause reactions between the semiconductive compounds and oxygen, and impurities which undergo oxidation can oxidize the semiconductive compounds, thereby shortening the possible storage, processing and working life.

The generally required purity is generally not achievable by known polymer chemistry methods such as washing, reprecipitation and extraction. On the other hand, oligomers which are molecularly uniform and generally volatile can be purified relatively simply by sublimation and chromatography.

Important representatives of some semiconductive polymers are described below. Copolymers of polyfluorenes and fluorenes, e.g. poly (9, 9-dioctylfluorene-co-bithiophene) (I)

Can reach 0.02cm²Charge mobility of/Vs (science, 2000, volume 290, p. 2123), hereinafter referred to as mobility for short, and partially regular poly (3-hexyl-2, 5-thiophene) (II)

Can reach 0.1cm²(ii) mobility of Vs (science 1998, volume 280, page 1741). Polyfluorenes, copolymers of fluorene and poly (3-hexyl-2, 5-thiophene), like virtually all long-chain polymers, form good films after application from solution and are therefore easy to process. However, high molecular weight polymers with molecular weight distributions cannot be sublimed in vacuo, can only be purified by chromatography, and have certain difficulties.

Important representatives of oligomeric semiconducting compounds, for example oligothiophenes, in particular those whose radicals are alkyl substituents, are represented by the formula (III),

R^xh, alkyl, alkoxy

And pentacene (IV)

Typical mobilities of alpha, alpha' -diethyltetrathiophene, -pentathiophene and-hexathiophene are from 0.05 to 0.1cm²/Vs。

Mesophases, in particular liquid-crystalline phases, play an important role in semiconductive organic compounds, but scientists have not yet fully understood this field. For example, the mobility of α, α' -diethyltetrathiophene crystals is the highest reported to date (chem. mater., 1998, volume 10, page 457), and these crystals are crystallized from a doubly denatured liquid crystal phase at a temperature of 80 ℃ (synth. met., 1999, volume 101, page 544). Particularly high mobilities can be achieved using single crystals, e.g., single crystals of α, α' -hexathiophene have been reported to be 1.1cm²(ii) mobility of/Vs (science, 2000, volume 290, page 963). If the oligomer is applied in solution, the mobility is usually significantly reduced.

Overall, the weakening of the semiconducting properties of the oligomeric compounds processed from solution is due to the moderate solubility and the poor tendency to form films of the oligomeric compounds. Thus, for example, the heterogeneity is due to precipitates formed during the drying of the solution (chem. mater., 1998, volume 10, page 633).

Therefore, attempts have been made to combine the excellent processability and film-forming properties of semiconductive polymers with the properties of semiconductive oligomers. US-a6025462 describes conductive polymers with a star-like structure consisting of a dendritic core and a conjugated pendant base shell. However, these compounds have a number of disadvantages. If these side groups consist of conjugated structures which are not laterally substituted, the resulting compounds are sparingly soluble or insoluble and cannot be processed. If the conjugated units are substituted with side groups, the solubility must be increased, but the side groups cause internal disorder and morphological disruption due to the space they occupy, leading to a weakening of the semiconducting properties of these compounds.

WO02-26859 describes polymers having aromatic conjugated chains attached to conjugated backbones. These polymers have diarylamine side groups that enable electron conduction. However, these diarylamine side groups are not suitable as semiconductors.

Thus, there is a continuing need for compounds that combine the properties of organic semiconductive oligomers and polymers.

It is therefore an object of the present invention to provide organic compounds which are processed from common solvents and have good semiconducting properties. These organic semiconductive compounds are particularly suitable for large area coating.

The compounds are necessary to form high quality coatings of uniform thickness and morphology to be suitable for electronic applications.

It has now surprisingly been found that organic compounds having the desired properties have a core-shell structure with a core consisting of multifunctional units and a shell consisting of linear conjugated oligomeric chains linked at the ends by flexible nonconjugated chains.

According to the invention, compounds of core-shell structure are prepared which are characterized by a core consisting of multifunctional units and a shell consisting of linear conjugated oligomeric chains linked at the ends by flexible nonconjugated chains.

In a preferred embodiment, the compounds of the present invention are oligomers or polymers.

According to the invention, this core-shell structure is at the molecular level, i.e. it relates to the structure of one molecule.

For the purposes of the present invention, the terminal linkage point of a linear conjugated oligomeric chain is the point in the terminal unit of the linear conjugated oligomeric chain at which no further such linkage is present.

The compound of the present invention preferably has a core-shell structure represented by the formula (Z)

Wherein the content of the first and second substances,

k is an n-functional core

L is a linear conjugated oligomeric chain

R is a straight or branched chain C₂-C₂₀Alkyl, mono-or polyunsaturated C₂-C₂₀-alkenyl radical, C₂-C₂₀-alkoxy radical, C₂-C₂₀-aralkyl radical, C₂-C₂₀Oligo-ether groups, or C₂-C₂₀Polyether radical

n is an integer of 3 or more, preferably 6 or more.

The shell is formed by n linear conjugated chains L supported by R.

For example, if n is 3 or 6, this is the structure represented by the formula (Z-3) or (Z-6)

Wherein K, L and R are as defined above.

Such compounds have a structure in which a core composed of multifunctional units, for example, a branched core, linear conjugated oligomeric chains and tough nonconjugated chains are linked together.

The core composed of multifunctional units has a dendritic structure or hyperbranched structure.

Hyperbranched structures and their preparation are well known to those skilled in the art. Hyperbranched polymers or oligomers have a unique structure determined by the structure of the monomers used. Monomer used is AB_nMonomers, i.e. monomers, have two different functional groups a and B. Wherein the functional group A is present only one in one molecule, and the other functional group B appears plural times (n times). The two functional groups A and B are capable of reacting with each other to form a chemical bond, that is to say, being polymerized.

Due to the structure of the monomers, a branched polymer with a dendritic structure, i.e. a hyperbranched polymer, is formed by polymerization. Hyperbranched polymers have no regular branching points, no rings and no B functions at the chain ends. Hyperbranched polymers, their structure, branching problems and nomenclature have been described in the examples of silicone based hyperbranched polymers in L.J.Mathias, T.W.Carothers, adv.Dendritic Macromol (1995), 2, 101-121, which are incorporated herein by reference.

Preferred hyperbranched structures for the purposes of the present invention are hyperbranched polymers.

However, cores composed of polyfunctional units are particularly preferably dendritic structures, which are particularly suitable owing to their regular composition.

For the purposes of the present invention, dendritic structures are synthetic macromolecular structures formed step by connecting two or more monomers to previously connected monomers, so that the number of monomers in a group increases exponentially per step, resulting in a globular dendritic structure. This results in a three-dimensional macromolecule comprising branch points and regularly extending structures from the center to the periphery. Such structures are typically formed layer by methods well known to those skilled in the art. The number of layers is often referred to as generations. The number of branches per layer and the number of end groups increases as generations increase. Dendritic structure preparation and nomenclature is well known to those skilled in the art and is described, for example, in Dendrimers and Dendrons, Wiley-VCH, Weiheim, 2001, G.R. Newkome et al.

Structures useful in the core consist of dendritic structures, also referred to below simply as dendritic cores, in principle those described in USA6,025,462. For example, these are hyperbranched structures, such as polyphenylenes, polyetherketones, polyesters, aramids which have been described, for example, in USA5,183,862, USA5,225,522 and USA5,270,402, in USA5,264,543, aramids which have been described, for example, in USA5,346,984, polycarbosilanes or polycarbosiloxanes which have been described, for example, in US6,384,172, polyarylenes which have been described, for example, in USA5,070,183 or USA5,145,930, or dendritic structures such as the polyarylenes, polyarylenes esters, or polyamidoamines which have been described, for example, in USA4,435,548 and USA4,507,466, and polyaziridines which have been described, for example, in USA4,631,337.

However, other structural units may also be used to form the dendritic core. The dendritic core functions primarily to form a number of different functional groups and thus a matrix to which the linear conjugated oligomeric chains are attached to create a core-shell structure. The linear conjugated oligomeric chains are predetermined by the attachment to the matrix, and their action is therefore increased.

The dendritic core has a series of functionalities-i.e., attachment points-suitable for attaching linear conjugated oligomeric chains. According to the invention, the dendritic core and the core consisting of hyperbranched structures have at least three, preferably at least six, different functionalities.

The preferred structure of the dendritic core is 1,3, 5-phenylene units (formula V-a) and units of formulae (V-b) to (V-e) in which a large number of identical or different units are linked to one another.

The positions marked by the numbers in the chemical formulae (V-a) to (V-e) and the chemical formulae used below are the points of attachment. The units in (V-a) to (V-e) are linked to each other or to the linear conjugated oligomeric chain by their linkage.

Examples of dendritic cores composed of units of the formula (V-a) are the following:

the point of attachment to the linear conjugated oligomeric chain occurs at the marked position.

The shell of the compounds of the present invention is formed by linear conjugated oligomeric chains attached to a core. Suitable linear conjugated oligomeric chains have in principle all chain structures of oligomers or polymers which are known as conductive or semiconductive. They are, for example, substituted or unsubstituted polyanilines, polythiophenes, polyethylenedioxythiophenes, polyphenylenes, polypyrroles, polyacetylenes, polyisonaphthenes, polyphenylenevinylenes, polyfluorenes, which can be used as homopolymers or homooligomers or as copolymers or cooligomers. Examples of these preferred structures as linear conjugated oligomeric chains are chains of from 2 to 10, in particular from 2 to 7, units of the formulae (VI-a) to (VI-e),

wherein

R¹，R²And R³May be the same or different and are each a hydrogen atom or a straight or branched C₁-C₂₀Alkyl or branched C₁-C₂₀Alkoxy radicals, which are preferably identical and are all hydrogen atoms,

R⁴may be the same or different and are each a hydrogen atom or a straight or branched C₁-C₂₀Alkyl or branched C₁-C₂₀An alkoxy radical, preferably a hydrogen atom or C₆-C₁₂-an alkyl group,

R⁵is a hydrogen atom or a methyl or ethyl group, preferably a hydrogen atom.

The positions marked by the symbol in the formulae (VI-a) to (VI-e) are the attachment points. The units in (V-a) to (V-e) are linked to each other by means of them to form linear conjugated oligomeric chains, or to the core at the ends of the chains by means of linking points, forming flexible non-conjugated chains.

It is particularly preferred that linear conjugated oligomeric chains are present comprising substituted or unsubstituted 2, 5-thiophene (VI-a) or (VI-b) units, or substituted or unsubstituted 1, 4-phenylene (VI-c) units. The above numbers 2, 5-or 1, 4-indicate the location of the cell attachment point.

It is particularly preferred that the polymer comprises substituted or unsubstituted 2, 5-thiophene (VI-a) or 2, 5- (3, 4-ethylenedioxythiophene) (VI-b).

Examples which may be mentioned are compounds of the formula (Z-6-1).

Wherein R is as defined for formula (Z).

p is an integer from 2 to 10, preferably from 2 to 7.

The linear conjugated oligomeric chains represented by R in the formula (Z) are held at the terminal linkage points by flexible, nonconjugated chains. Flexible chains are understood to mean those havingHigh (internal) molecular mobility and consequent reaction with solvent molecules increases solubility. For the purposes of the present invention, flexibility refers to (internal) molecular mobility. The flexible nonconjugated chains formed by the linear conjugated oligomeric chains at the terminal linkage points are straight or branched aliphatic saturated or unsaturated chains containing from 2 to 20 carbon atoms, preferably from 6 to 20 carbon atoms, possibly interrupted by oxygen atoms. Preferably aliphatic or oxyaliphatic groups, i.e.alkoxy groups or straight-chain or branched, for example oligoether or polyether groups, interrupted by oxygen atoms. It is particularly preferred that C is present without branching₂-C₂₀-alkyl or C₂-C₂₀-alkoxy groups. Examples of suitable chains are alkyl groups, such as n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl, or alkoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy and n-dodecyloxy.

Preferred embodiments of the invention are preferably oligothiophene or oligo (3, 4-ethylenedioxythiophene) unsaturated chains having 1,3, 5-phenylene units, 2 to 4 thiophene or 3, 4-ethylenedioxythiophene units as linear conjugated oligomeric chains in the dendritic core, C₆-C₁₂-compounds with alkyl groups as flexible nonconjugated chain.

Two compounds represented by the formulae (XII) and (XIII) are illustrated below:

the compounds of the invention are conductive or semiconductive. According to the invention, the semiconductive compounds are preferably at least 10^-4cm²Migration of/VsThe compound of the ratio is optimum.

The organic compounds of the present invention can be easily dissolved in common solvents such as chloroform, toluene, diethyl ether, dichloromethane, tetrahydrofuran, and thus are very suitable for processing in solution. It is particularly surprising that the linear conjugated oligomeric chains of the compounds according to the invention which have units of unsaturated thiophene or 3, 4-ethylenedioxythiophene are very soluble and the internal order and morphology is not broken by large side chains. Thus, the organic compounds of the present invention have good semiconducting properties and very good film-forming properties. They are therefore very suitable for large-area coating. Furthermore, the organic compounds according to the invention have very good thermal stability and good ageing resistance.

The compounds of the invention can in principle be prepared by two different routes, namely convergent and divergent preparation processes.

In the convergent preparation method, the linear conjugated oligomeric chains are held by the non-conjugated flexible chains prepared in the first step. In the case of a dendritic core, it is linked to a structural element called a monodendron, that is to say a structural element which comprises part of the dendritic structure and can be linked to form a dendritic structure. In the last step of the preparation a number of single branches are connected to form the final structure.

In the divergent preparation method, dendritic cores or cores comprising hyperbranched structures are prepared in a first step. The linear conjugated oligomeric chains held by the non-conjugated flexible chains can be attached to the core in a next step.

As regards the properties of the compounds according to the invention, the preparation process is in principle unproductive. Many variations in the preparation process already described are possible. Thus, for example, it is possible to modify the order of the individual preparation steps and, for example, to link the nonconjugated flexible chains and the linear conjugated oligomeric chains as a final step in the preparation.

However, depending on the structure to be produced, it may be useful, for example, to link nonconjugated flexible chains to linear conjugated oligomeric chains in the preparation, since the flexible chains increase the solubility of the structural units and thus facilitate the preparation of the compounds of the invention.

In principle, those skilled in the art are familiar with a series of chemical reactions for forming a core composed of multifunctional units, for linking it to linear conjugated oligomeric chains, and for linking nonconjugated flexible chains to these.

The invention therefore also provides a process for the preparation of the compounds of the invention, which is characterized in that they are prepared by organometallic reactions.

For organometallic reactions it is necessary to introduce suitable functional groups to the dendritic or hyperbranched core to which the linear conjugated oligomeric chains and the flexible nonconjugated chains are attached in turn.

For example, these functional groups are halogens such as chlorine, bromine, iodine, preferably bromine, organotin groups such as trimethyltin or triethyltin groups, organosilicon groups such as trimethylsilyl or tetramethylsilane groups, or organoboron groups such as boric acid.

Particularly preferred organometallic reactions for coupling the individual components of the compounds of the invention are Kumada coupling of two bromine groups by means of Grignard reagents using palladium catalysts, for example 1, 1-bis (diphenylphosphino) ferrocene dichloropalladium (II), and Suzuki coupling of boron-containing groups under basic conditions with bromine groups using palladium catalysts. The steps for performing these ligation reactions are well known to those skilled in the art.

The intermediates between the two separate preparation steps and the final compound are preferably purified. This can be done by known methods: distillation, sublimation, recrystallization, extraction, reprecipitation, washing or chromatography. The intermediates and the final compounds are preferably purified by distillation, sublimation and chromatography, since these ensure the highest purity.

This has the advantage over known semiconductive polymers that the present invention enables the preparation of high purity compounds by simple conventional purification methods, thus making them suitable for use in semiconductor technology.

The compounds of the invention are capable of forming mesophases (mesomorphic states), that is, physical states between solid and liquid states. This also relates to liquid crystalline phases and helps to predetermine the compounds of the invention. The compounds of the invention preferably form liquid-crystalline phases at from 50 ℃ to 300 ℃, particularly preferably from 80 ℃ to 180 ℃.

The compounds of the invention are soluble in at least 0.1%, preferably at least 1%, particularly preferably at least 5%, of the customary solvents, for example chloroform, toluene, benzene, diethyl ether, dichloromethane or tetrahydrofuran.

The compounds of the present invention form high quality thin film layers of uniform thickness and morphology and are therefore suitable for electronic applications.

Finally, the invention also provides compounds of the invention as semiconductors in electronic components such as field effect transistors, light-emitting components such as organic light-emitting diodes or photocells, lasers and sensors.

For these purposes, the compounds of the invention are preferably used in the form of films.

In order for them to function effectively as semiconductors, the compounds of the invention have sufficient mobility, for example at least 10^-4cm²Vs. For applications, the compounds of the invention are applied on suitable substrates, for example silicon wafers, polymer films, glass sheets provided in electricity or electronics. Application can in principle be carried out by all application methods. The compounds of the invention are preferably applied in the liquid phase, i.e. in solution, after which the solvent is evaporated. Application in solution is carried out by known methods, for example spraying, dipping, printing and knife coating. Application by spin coating and ink-jet method is preferable.

The layer of the compounds of the invention can be further processed after application, for example by thermal treatment, for example by transformation by liquid-crystalline phases, or else structured, for example by laser ablation.

Further, the present invention provides an electronic component comprising the compound of the present invention as a semiconductor.

Examples

5-decyl-2, 2': 5', 2 "Trithiophene (Synthesis, 1993, page 1099; chem. Mater., 1993, volume 5, 430) (3, 5-dibromophenyl) trimethylsilane (J. organometamet. chem., 1983, volume 215, page 149) has been prepared by known procedures cited herein.

Example 1: (intermediate comprising linear conjugated oligomeric chains and terminal chains).

Preparation of (5 "-decyl-2, 2 ': 5', 2" terthienyl-5-yl) magnesium bromide (VII): butyllithium (1.6M n-BuLi in 8.8ml, 14.0mmol hexanes) was added drop-by-drop by syringe to 5-decyl-2, 2': 5', 2 "Trithiophene (6.60g, 14.4mmol) in anhydrous THF (100mL) in N₂Stirring was carried out at 2 ℃. After completion of the dropwise addition, the solution was warmed to room temperature (23 ℃ C.) and stirred for one more hour. Then cooled to 2 ℃ and MgBr was added immediately₂-Et₂O (3.67, 14.2 mmol). The reaction mixture was again warmed to room temperature and stirred for an additional hour. (5 "-decyl-2, 2 ': 5', 2" trithiophen-5-yl) magnesium bromide was not isolated, but the solution obtained was used directly for further reactions.

Example 2: (preparation of a Monodendron intermediate containing silane functional groups)

[3, 5-bis 5 "-decyl-2, 2': 5 ', 2' Trithien-5-yl) phenyl]Preparation of (trimethyl) silane (VIII): freshly prepared 5-decyl-2, 2': a solution of 5 ', 2' trithiophene (14.0mmol) in anhydrous THF (example 1) was added drop-by-drop at room temperature to (3, 5-dibromobenzene) trimethylsilane (1.54g, 5mmol) and Pd (dppf) Cl₂(70mg, 0.1mmol) (dppf ═ diphenylphosphine) was dissolved in a solution of 50ml anhydrous THF. After the addition was complete the solution was stirred for an additional two hours. Completion of the reaction was monitored by TLC. The reaction mixture was then poured into 300ml of cold anhydrous ether and then 200ml of ice water containing 20ml of 1M (1 mole) HCl was added. The ether phase containing the yellow precipitate (desired product) was separated and washed three times with 100ml of ice-water each. The ether phase is filtered through a G3 glass filter and the isolated products are washed 3 times with in each case 50ml of cold, anhydrous ether and dried under reduced pressure. This gave 3.36g of a dark yellow crystalline crude product. After purification by column chromatography (eluent: n-hexane/chloroform 4: 1) at 40 ℃ and recrystallization in n-hexane, 2.64g of pale yellow crystals were finally obtained. Yield: 57 percent. Melting point: 120 ℃ is adopted.¹HNMR(400MHz，CDCl₃TMS/ppm): 0.353(s, 9H), 0.884(t, 6H, J ═ 6.9), 1.20-1.45 (overlapping peak, 28H), 1.688(M, 4H, J ═ 7.3, M ═ 5), 2.798(t, 4H, J ═ 7.6), 6.692(d, 2H, J ═ 3.9), 6.696(d, 2H, J ═ 3.9), 7.021(d, 2H, J ═ 3.9), 7.109(d, 2H, 3.9), 7.156(d, 2H, 3.4), 7.287(d, 2H, 3.9), 7.623(d, 2H, J ═ 2.0), 7.763(t, 1H, J ═ 1.7).

Example 3: (preparation of boron-functional Monodendron intermediate)

2- [3, 5-bis (5 '-decyl-2, 2': 5 ', 2' trithiophen-5-yl) phenyl]Preparation of 4,4, 5, 5-tetramethyl-1, 3, 2-dioxaborane (IX): a100 ml three-neck round-bottom flask was connected to a reflux condenser, a septum and a shielding gas inlet, and the flask was filled with a gasFull N₂. Compound (VIII) (2.31g, 2.5mmol) and 40ml of anhydrous tetrachloromethane were added. Then 5ml of 1MBBr was added via septum with a disposable polypropylene syringe₃The reaction mixture was refluxed for 40 hours. The reaction mixture was then cooled to room temperature and transferred by syringe into a 500ml Erlenmeyer flask containing 250ml of 1M NaOH solution. 200ml of water were added and the mixture was stirred vigorously, the aqueous phase was decanted off and the remaining wet salt was suspended in a mixture of diethyl ether (200ml), THF (100ml) and 2M HCl (300 ml). The mixture was stirred vigorously for 3 hours until two phases were formed. The ether phase is separated off, the aqueous phase is washed with diethyl ether, the mixed ether phases are washed 3 times with 100ml of water each and with Na₂SO₄Dried and the solvent removed on a rotary evaporator. This gave 4g of the boronic acid derivative as a wet brown solid, to which were added pinacol (330mg, 2.75mmol) and 100ml of anhydrous toluene. The mixture was refluxed overnight using a dean-Stark apparatus (water separator). After cooling and removal of the toluene on a rotary evaporator, 3g of crude product are obtained as a brown solid. After purification by column chromatography (eluent: toluene), 2.64g of dark yellow crystals were obtained. Yield: 61 percent.¹H NMR(400MHz，CDCl₃TMS/ppm): 0.884(t, 6H, J ═ 6.9), 1.20-1.45 (overlapping peak, 28H), 1.388(s, 12H), 1.688(M, 4H, M ═ 5, J ═ 7.5), 2.798(t, 4H, J ═ 7.6), 6.692(d, 2H, J ═ 3.4), 6.995(d, 2H, J ═ 3.4), 7.071(d, 2H, J ═ 3.9), 7.104(d, 2H, 3.9), 7.148(d, 2H, 3.9)7.334(d, 2H, 3.4), 7.868(t, 1H, J ═ 1.7), 7.935(d, 2H, J ═ 2.0)

Example 4: (preparation of silane-functional Monodendron intermediate)

Trimethyl [3, 3 ", 5, 5" -tetrakis (5 "-decyl-2, 2 ': 5 ', 2" trithiophen-5-yl) 1, 1 ': 3, 1 '-terphenyl-5' -yl]Preparation of silane (X): 100ml of magnetic stirrer, reflux condenser, protective gas inlet and partitionThree-necked flask for tablets in N₂(3, 5-dibromophenyl) trimethylsilane (215g, 0.7mmol) was added next. Pd (PPh) was then added to the glove box₃)₄(170mg，1.5×10^-4mol). The glass unit is mounted and removed from the glove box. Then, the preparation compound (IX) (1.47g, 1.5mmol) was dissolved in 30ml of toluene and Na₂CO₃(2Maq. (aqueous phase), 10ml) and then purified by passing N through₂The method of (3) is deoxygenated. Adding the solution to a reaction vessel and reacting the mixture in N₂Reflux for 36 hours. The reaction mixture is then cooled to room temperature and poured into a container containing 100ml of water and 300ml of CH₂Cl₂In a flask, the organic phase was separated and the aqueous phase was purified using 100ml of CH₂Cl₂And (6) washing. Hybrid CH₂Cl₂The phases are washed with water over MgSO₄Dried and evaporated. The product was purified by recrystallization from a 4: 1 mixture of n-hexane/chloroform to give 763mg of pure product as a brown solid. Yield: 59 percent. Melting point: 158 ℃. GPC (polystyrene standard): MP 1540.¹H NMR(400MHz，CDCl₃TMS/ppm): 0.421(s, 9H), 0.882(t, 12H, J ═ 7.1), 1.20-1.45 (overlapping peak, 56H), 1.684(M, 8H, M ═ 5J ═ 7.6), 2.792(t, 8H, J ═ 7.6), 6.684(d, 4H, J ═ 3.9), 6.992(d, 4H, J ═ 3.4), 7.012(d, 4H, 3.9), 7.117(d, 4H, 3.9), 7.179(d, 4H, 3.4)7.369(d, 4H, 3.4), 7.753(d, 4H, J ═ 1.5), 7.802(d, 2H, J ═ 1.5), 7.816(t, 2H, J ═ 1.5), 7.865(t, 1H, J ═ 7.7).

Example 5 (preparation of boron-functional Monodendron intermediate)

4,4, 5, 5-tetramethyl-2- [3, 3 ", 5, 5" -tetrakis (5 "-decyl-2, 2 ': 5 ', 2" trithiophen-5-yl) -1, 1 ': 3 ', 1 ' -terphenyl-5 ' -yl]Preparation of 1,3, 2-dioxaborane (XI): using compound (X) (610mg, 0.33mmol), 2ml of 1M BBr₃Dissolved in tetrachloromethaneAnd pinacol (44mg, 0.37mmol) were prepared by the procedure described in example 3. The washing procedure described in example 3 and drying under reduced pressure gave 650mg of crude product as a brown solid. After purification by column chromatography (eluent: toluene), 310mg of yellowish brown crystals were obtained. Yield: 49 percent.¹H NMR(400MHz，CDCl₃TMS/ppm): 0.882(t, 12H, J ═ 7.1), 1.20 to 1.45 (overlapping peak, 56H), 1.683(M, 8H, M ═ 5, J ═ 7.6), 2.790(t, 8H, J ═ 7.6), 6.682(d, 4H, J ═ 3.4), 6.987(d, 4H, J ═ 3.4), 7.001(d, 4H, 3.9), 7.112(d, 4H, 3.9), 7.175(d, 4H, 3.9), 7.374(d, 4H, 3.9), 7.785(d, 4H, J ═ 2.0), 7.799(t, 2H, J ═ 1.7), 7.988(t, 1H, J ═ 1.7), 8.123(d, 2H, J ═ 1.5).

Example 6 (example of preparation of Compounds according to the invention)

1,3, 5-tris [3, 5-bis (5 '-decyl-2, 2': 5 ', 2' trithiophen-5-yl) phenyl]Production of benzene (XII): with Compound (IX) (450mg, 4.6X 10)^-4mol), 1,3, 5-tribromobenzene (40mg, 1.27X 10)^-4mol) and Pd (PPh)₃)₄(17mg，1.5×10^-5mol) was prepared by the procedure described in example 4. After 16 hours of reflux under nitrogen, a yellow solid precipitate was the predominant product. The reaction mixture was cooled to room temperature and poured into 100ml of water and 400ml of CH₂Cl₂In (1). The organic phase containing the yellow precipitate is washed 3 times with 100ml of water and filtered through a G3 glass filter, the residue (product) on the filter being in each case 20ml of CH₂Cl₂Washed three times. Drying under high vacuum overnight gave 330mg of pure product. Yield: 99 percent. Melting point: 202 ℃.

Example 7: (preparation of the Compound according to the invention)

1,3, 5-tris [3, 3 ", 5, 5" -tetrakis (5 "-decyl-2, 2 ': 5 ', 2" trithiophen-5-yl) -1, 1 ': 3 ', 1 ' -terphenyl-5 ' -yl]Preparation of benzene (XIII): with Compound (XI) (250mg, 1.3X 10)^-4mol), 1,3, 5-tribromobenzene (12mg, 3.8X 10)^-5mol) and Pd (PPh)₃)₄(10mg，8.7×10^-6mol) was prepared by the procedure described in example 4. After 24 hours of reflux under nitrogen, the compound was isolated using the procedure described in example 4. 275mg of the crude product in the form of a brown solid are purified by column chromatography (eluent: toluene) to give 210mg of a glassy brown solid. Yield: 76 percent. GPC (polystyrene standard): MP is 6900 and DPI is 1.02.

Claims (18)

1. A compound having a core-shell structure comprising a core composed of polyfunctional units and a shell composed of linear conjugated oligomeric chains linked at the ends with flexible nonconjugated chains, said compound having a core-shell structure represented by the formula (Z)

Wherein the content of the first and second substances,

k is an n-functional core composed of units selected from the formulae (V-a) to (V-b);

r is a straight or branched chain C₂-C₂₀Alkyl, mono-or polyunsaturated C₂-C₂₀-alkenyl radical, C₂-C₂₀-alkoxy radical, C₂-C₂₀-aralkyl radical, C₂-C₂₀Oligo-ether groups, or C₂-C₂₀-a polyether group,

the positions marked by the symbol in the formulae (V-a) and (V-b) are the points of attachment by which the units in (V-a) and (V-b) are linked to each other or to the linear conjugated oligomeric chain L,

l is a linear conjugated oligomeric chain consisting of units selected from the formulae (VI-a) to (VI-b):

wherein:

R¹are identical or different and are each a hydrogen atom or a straight-chain or branched C₁-C₂₀Alkyl or branched C₁-C₂₀-an alkoxy group,

the positions marked by the symbol in the formulae (VI-a) to (VI-b) are the points of attachment,

n is an integer greater than or equal to 3,

wherein the linear conjugated oligomeric chain is a chain composed of from 2 to 10 units represented by the formula (VI-a) or (VI-b).

2. The compound of claim 1, wherein R is¹Are identical and are all hydrogen atoms.

3. A compound according to any one of claims 1 to 2 wherein the core is a dendritic structure.

4. A compound as claimed in claim 3 wherein the dendritic core has the structure of a 1,3, 5-phenylene unit.

5. A compound according to any one of claims 1 to 2 wherein the core is a hyperbranched structure.

6. A compound according to claim 5, wherein the hyperbranched core is a hyperbranched polymer.

7. A compound according to any of claims 1-2, wherein the linear conjugated oligomeric chain is a chain having a chain length of 2 to 7 units.

8. A compound according to any one of claims 1 to 2, wherein the linear conjugated oligomeric chains are linked at the end-point linkages to identical or different, straight or branched C chains₂-C₂₀-alkyl or C₂-C₂₀-alkoxy groups.

9. The compound of claim 8, wherein the alkyl or alkoxy group is unbranched C₂-C₂₀-alkyl or C₂-C₂₀-alkoxy groups.

10. A compound as claimed in claim 8 wherein the alkyl or alkoxy groups are n-hexyl, n-decyl and n-dodecyl.

11. A process for the preparation of a compound according to any one of claims 1 to 10, wherein the compound is prepared by an organometallic reaction comprising: introducing a suitable functional group selected from halogen, organotin group, organosilicon group or organoboron to the core and introducing the linear conjugated oligomeric chain and the flexible nonconjugated chain and connecting them in sequence.

12. A process for the preparation of a compound as claimed in claim 11, characterized in that the compound is prepared by a Kumada coupling reaction comprising coupling of two bromo groups with a palladium catalyst via a grignard reagent.

13. A process for the preparation of a compound as claimed in claim 11, characterized in that the compound is prepared by a Suzuki coupling reaction which comprises coupling a boron-containing group under basic conditions with a bromine group using a palladium catalyst.

14. Use of a compound according to any of claims 1 to 10 as a semiconductor in an electronic component.

15. Use of a compound as claimed in claim 14 as a semiconductor in field effect tubes, light emitting elements, lasers and sensors.

16. Use of a compound according to claim 14 or 15 in the form of a film applied in solution.

17. Use of a compound as claimed in claim 15 wherein the light emitting element is a light emitting diode or a photovoltaic cell.

18. An electronic component comprising the compound as a semiconductor according to any one of claims 1 to 10.