EP2252648A1

EP2252648A1 - Novel macromolecular compounds having a core-shell structure for use as semiconductors

Info

Publication number: EP2252648A1
Application number: EP09721087A
Authority: EP
Inventors: Timo Meyer-Friedrichsen; Stephan Kirchmeyer; Andreas Elschner; Sergei Ponomarenko
Original assignee: HC Starck Clevios GmbH
Current assignee: Heraeus Deutschland GmbH and Co KG
Priority date: 2008-03-14
Filing date: 2009-02-10
Publication date: 2010-11-24
Also published as: US20110101318A1; WO2009112319A1; DE102008014158A1; TW201000524A; KR20100134592A; JP2011513561A; CN101970542A

Abstract

The invention relates to novel macromolecular compounds having a core-shell structure and to the use thereof in electronic components.

Description

New macromolecular compounds having a core-shell structure for use as semiconductors

The invention relates to novel macromolecular compounds having a core-shell structure and their use in electronic components.

The field of molecular electronics has developed rapidly in the last 15 years with the discovery of organic conducting and semiconducting compounds. During this time, a variety of compounds have been found, which have semiconducting or electro-optical properties. It is generally understood that molecular electronics will not displace conventional silicon-based semiconductor devices. Instead, it is expected that molecular electronic devices will open up new application areas that require the ability to cover large areas, structural flexibility, low temperature processability, and low cost. Semiconducting organic compounds are currently being developed ^"for applications such as organic field-effect transistors (OFETs), organic Luraineszenzdioden (OLEDs), sensors and photovoltaic elements. By simple structuring and integration of OFETs into integrated organic semiconductor circuits are inexpensive Solutions for smart cards or price tags, which until now could not be realized with the help of silicon technology due to the price and lack of flexibility of the silicon components, could also be used as switching elements in large-area flexible matrix displays Semiconductors, semiconductor integrated circuits and their applications are given, for example, in H. Klauk (publisher), Organic Electronics, Materials, Manufacturing and Applications, Wiley-VCH 2006.

A field effect transistor is a three-electrode element in which the conductivity of a thin conduction channel between two electrodes (called "source" and "drain") is determined by means of an electrode (called "gate") separated from the conduction channel by the third insulator layer. The most important characteristic features of a field-effect transistor are the mobility of the charge carriers, which decisively determine the switching speed of the transistor and the ratio between the currents in the switched and switched state, the so-called "on / off ratio".

Organic Feid-effect transistors have hitherto used two large classes of compounds. Compounds of both classes have continuous conjugated units and, depending on molecular weight and structure, are subdivided into conjugated polymers and conjugated oligomers. STA 457 ATD-09-01-2009.doc

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Oligomers usually have a uniform molecular structure and a molecular weight below 10,000 daltons. Polymers generally consist of chains of uniform repeating units with a molecular weight distribution. However, there is a smooth transition between oligomers and polymers.

Frequently, the distinction between oligomers and polymers indicates that there is a fundamental distinction in the processing of these compounds. Oligomers are often vaporizable and are applied to substrates by vapor deposition. As polymers are often referred to independent of their molecular structure compounds that are no longer volatile and therefore applied by other methods. In the case of polymers, as a rule compounds are sought which are soluble in a liquid medium, for example organic solvents, and which can then be applied by means of corresponding application methods. A very common application method is e.g. Spin Coating A particularly elegant method is the application of semiconducting compounds via the hikjet process, in which a solution of the semiconducting compound is applied to the substrate in the form of ultrafine droplets and dried A description of this semiconductive compound deposition method is described, for example, in Nature, Volume 401, p.

In general, the wet-chemical process has a greater potential for easily obtaining low-cost organic semiconductor integrated circuits.

An important prerequisite for the production of high-quality organic semiconductor circuits are compounds of extremely high purity. In semiconductors, order phenomena play a major role. Obstruction in uniform alignment of the bonds and grain boundary forms leads to a dramatic decrease in semiconductor properties, so that organic semiconductor circuits constructed using non-extremely high purity compounds are usually unusable. Remaining impurities can, for example, inject charges into the semiconducting compound ("doping") and thus reduce the on / off ratio or serve as charge traps, thereby drastically reducing mobility Furthermore, impurities can initiate the reaction of the semiconductive compounds with oxygen and oxidizing impurities can oxidize the semiconducting compounds and thus shorten possible storage, processing and operating times.

The usually necessary purity is so high that it is generally unachievable by the known polymer chemical processes such as washing, topping and extraction. STA 457 ATD-09-01-2009.doc

, 3.

On the other hand, oligomers, as molecularly uniform and often volatile compounds, can be purified relatively simply by sublimation or chromatography.

Some important representatives of semiconducting polymers are described below. For polyfluorenes and fluorene copolymers, for example poly (9 _s 9-dioctylfluorene-co-bithiophene) (I)

Charge mobilities, hereafter also referred to as mobilities, were up to 0.02 cmWs (Science, 2000, vol. 290, p. 2123), with regioregular poly (3-hexylthiophene-2,5-diyl) (II)

even mobilities up to 0.1 cmVVs (Science, 1998, vol. 280, p. 1741). Polyfluorene, polyfluorene copolymers and poly (3-hexylthiophene-2,5-diyl) form, like almost all long-chain polymers after application from solution, good films and are therefore easy to process. However, as high molecular weight polymers having a molecular weight distribution, they can not be purified by vacuum sublimation and are difficult to purify by chromatography.

Important representatives of oligomeric halbieitender compounds are, for example OHgothiophene, in particular those having terminal alkyl substituents according to formula (III) STA 457 ATD-09-01-2009.doc

} * ^* n = 4-6 m

R * = H, alkyl I, alkoxy

and Pentacene (IV)

Typical mobilities for, for example, α, α'-dihexylquarter, quinque and exhenophene Hegen at 0.05 - 0.1 cm ² / Vs. Oligothiophene are usually hole semiconductors, ie only positive charge carriers are transported.

The highest mobilities of a compound are obtained in single crystals, for example, a mobility of 1.1 cm water for individual crystals of α, α'-sexithiophene (Science, 2000, Volume 290, p 963) and 4.6 cm ² / Vs for rubrene single crystals (Adv. Mater., 2006, Vol. 18, p. 2320). If oil oligomers are applied from solution, the mobilities usually drop sharply. In general, the decrease in semiconducting properties when processing oligomeric compounds from solution is attributed to the moderate solubility and low tendency for film formation of the oligomeric compounds. For example, inhomogeneities are attributed to precipitation during drying from the solution (Chem. Mater., 1998, Vol. 10, p. 633).

There have therefore been attempts to combine the good processing and film-forming properties of semiconductive polymers with the properties of semiconducting oligomers. US Pat. No. 6,025,462 describes conductive star-shaped polymers which consist of a branched core and a shell of conjugated side groups. However, these have some disadvantages. If the side groups are formed from laterally unsubstituted conjugated structures, the resulting compounds are difficult or insoluble and unprocessable. Substitution of the conjugated moieties with side groups does indeed result in improved solubility, but the side groups, because of their steric needs, cause internal disorder and morphological disturbances which affect the semiconductive properties of these compounds. STA 457 ATD-09-01-2009.doc

The laid-open specification WO 02/26859 A1 describes polymers of a conjugated back wheel to which aromatic conjugated chains are attached. The polymers carry diarylamine side groups that allow electron conduction. However, these compounds are unsuitable as semiconductors due to the diarylamine side groups.

The published patent specifications EP-A 1 398 341 and EP-A 1 580 217 describe semiconducting. Connections with a core-shell structure, which are used as semiconductors in electronic components and can be processed from solution. However, these compounds tend to give poorly crystallizing films during processing, which, as crystallized films are a prerequisite for high charge carrier mobility, may be a hindrance to some applications. Although it is known that films of organic semiconductors can be subordinated by temperature treatment (deLeeuw et al., WO 2005104265), the macromolecular character of the compound can also hinder a complete subsequent order by means of temperature treatment.

In Applied Physics Letters 9O ₅ 053504 (2007), Jang et al. the production of transistors by inkjet printing process. As organic semiconductor, α, α'-

Dihexylquarterthiophen used. The mobilities of 0.043 cmVVs found in this case correspond to those of vapor-deposited layers of the material. However, they were very small

Electrode distances in the transistor of 6 μm selected. In a roil-to-roll mass printing process, such small structures can not be created. Modern printing processes currently achieve resolutions of approx. 20 - 50 μm. At these distances, homogeneity and phase boundaries in the semiconductive layer play a much greater role.

Russel et al. describe in Appl. Phys. Lett. 87, 222109 (2005) describe the use of mixtures of poly (3-hexythiophene-2,5-diyl) and α, α'-dihexyl quartet thiophene for semiconductor layers in organic field-effect transistors. Here, the α, α'-Dihexylquarterthiophen forms crystalline islands, which are connected by the polymer. However, the mobilities of the semiconductor layer found are limited by the lower mobilities of the poly (3-hexylthiophene-2, 5-diyl) s in comparison with α, α'-dihexyl quatthiophene. In Jap. J. Appl. Phys. (2005), Vol. 44, p. L1567, mixtures of poly (3-hexylthiophene-2,5-diyl) and α, α'-dihexyl exothiophene are used to make field-effect transistors. In order to achieve sufficient solubility of the compounds, however, the solutions must be heated to 190 ⁰ C, which is not suitable for industrial application. In Adv. Funct. Mater. 2007, 17, 1617 - 1622 describes a cyclohexyl-substituted quaterthiophene which crystallizes from supersaturated solution. However, this type of processing does not allow mass production. In addition, must STA 457 ATD-09-01-2009.doc

Small channel lengths in the electrode structure can be used to ensure that the crystallites have sufficient overlap over these structures. The production of such small electrode structures, in turn, requires expensive lithographic processes which can not be used in a rapid printing process for mass production.

There was thus a need for semiconductors which have improved properties after processing from solvents.

The object of the invention was to provide organic compounds which can be processed from common solvents which give semiconducting films with good properties and which remain sufficiently stable when stored in air. Such compounds would be ideal for the large-scale application of organic semiconducting layers.

It would be desirable in particular that the compounds form high quality layers of uniform thickness and morphology and are suitable for electronic applications.

Surprisingly, it has been found that organic compounds have the desired properties when they have a core-shell structure containing a core composed of multifunctional units and a shell of connecting chains and linear conjugated oligomeric chains, each at the terminal point of attachment via at least one electron-withdrawing group carrying methylene carbon atom are saturated with at least one flexible non-conjugated chains.

In particular, the film morphology and the resulting macroscopic electrical properties of the films of oligomeric organic compounds and their mixtures with macromolecular compounds having a core-shell structure and / or compounds with monomeric linear compounds over the semiconductors of pure monomeric linear compounds or pure improved macromolecular compounds with core-shell structure.

The invention relates to macromolecular compounds having a core-shell structure, the core having a macromolecular basic structure based on silicon and / or carbon and having at least 2 via a carbon-based linking chain with carbon-based linear oligomeric chains with continuously conjugated double bonds and wherein the linear conjugated chains each have at least one electron-withdrawing group-carrying methylene carbon atom STA 457 ATD-09-01-2009.doc

At least one further, in particular aliphatic, araliphatic or oxyaliphatic chain having no conjugated double bonds is saturated.

The organic macromolecular compounds having a core-shell structure may, in a preferred embodiment, be oligomers or polymers. In the context of the invention, oligomers are compounds having a molecular weight of less than 1000 daltons, and polymers are compounds having an average molecular weight of 1000 daltons or greater. Depending on the method of measurement, the average molecular weight may be the number average (M _n ) or weight average (M _w ). Here we mean the number average (M _n ).

In the context of the invention, the core-shell structure is a structure at the molecular level, i. it refers to the construction of a molecule as such.

The terminal point of attachment of the linear conjugated oligomeric chain is to be understood as meaning the point in the terminal unit of the linear oligomeric chain having conjugated double bonds via which no further linking of a further one occurs. Terminal is to be understood as furthest from the core. The linear oligomeric chain with continuously conjugated double bonds is also referred to below as shortened linear conjugated oligomeric chain.

The macromolecular compounds having a core-shell structure preferably have a core-shell structure of the general formula (Z)

wherein

K is an n-functional core,

V represents a connection chain,

L is a linear conjugated oligomeric chain, preferably one containing optionally substituted thiophene or phenylene units,

A represents an electron-withdrawing group-carrying methylene carbon atom selected from the group consisting of carbonyl, dicyanovinyl, cyanoacrylic acid ester, malonic acid ester or dihalomethylene, STA 457 ATD-09-01-2009.doc

- 8th -

R for linear or branched © C ₂ -C ₂₀ -alkyl radicals, C ₃ -C ₈ -cycloalkylene radicals, mono- or polyunsaturated C ₂ -C ₂ (r alkenyl radicals, C ₂ -C ₂ o-alkoxy radicals, C ₂ -C ₂ O-aralkyl radicals or C ₂ -C _2O -OHgO- or C ₂ -C ₂₀ -Polyetherreste,

q stands for 0 or 1, and

n is an integer greater than or equal to 2, preferably a number between 2 and 4.

When the electron-withdrawing group at A represents a cyanoacrylic acid ester or a malonic acid ester, the corresponding alkyl radical represents a linear or branched C ₁ -C ₂ -alkyl radical, preferably a linear or branched C ₁ -C 9 -alkyl radical. If the electron-withdrawing group represents a dihalogenemethylene group at A, it is understood as meaning a dibromo, dichloro, diiodo or difhormethylene group, preferably a difluoro methyl group.

The shell of the preferred compounds from the n ™ V- (A) _q ^~ LAR blocks is formed, each of which is linked to the core.

For example, for n equal to 3, 4 or 6, these are structures of formulas (Z-3), (Z-4) or (Z-6)

(Z-3) (Z-4) (Z-6)

wherein K, V, L and R have the abovementioned meaning.

Such compounds are designed so that a built-up from multi-functional units, ie branched core _"link strings bearing electron-withdrawing groups (s) methylene carbon atom (s), linear conjugated oligomeric chains and non-conjugated chains are connected to each other. STA 457 ATD-09-01-2009.doc

, 9.

The core composed of multifunctional units preferably has dendritic or hyperbranched structures.

Hyperbranched structures and their preparation are known per se to those skilled in the art. Hyperbranched polymers or oligomers have a special structure, which is predetermined by the structure of the monomers used. Monomers used are so-called ABn moieties, i. Monomers carrying two different functionalities A and B. Of these, one functionality (A) is present only once per molecule and the other functionality (B) several times (n times). The two functionalities A and B can be reacted with each other to form a chemical bond, e.g. be polymerized. Due to the monomer structure, branched polymers with a tree-like structure, so-called hyperbranched polymers, are formed during the polymerization. Hyperbranched polymers have no regular branching sites, no rings, and almost exclusively B functionalities at the chain ends. Hyperbranched polymers, their structure, the question of branching and their nomenclature are for the example of hyperbranched polymers based on silicones in LJ. Mathias, T.W. Carothers, Adv. Dendritic Macromol. (1995), 2, 101-121 and the work cited therein.

In the context of the invention, the hyperbranched structures are preferably dendritic polymers.

In the context of the invention, dendritic structures are synthetic macromolecular structures which are built up stepwise by linking in each case 2 or more monomers with each already bound monomer, so that with each step the number of monomer end groups increases exponentially and at the end a spherical tree structure is formed. In this way, three-dimensional macromolecular structures are formed with groups that have branch points and continue from one center to the periphery in a regular fashion. Such structures are usually built up layer by layer by methods known to those skilled in the art. The number of layers is usually called generation. The number of branches in each layer as well as the number of terminal groups increase with increasing generation. Due to their regular structure, dendritic structures can offer special advantages. Dendritic structures, methods of preparation and nomenclature are known in the art and described, for example, in G.R. Newkome et al., Dendrimers and Dendrons, Wiley-VCH, Weinheim, 2001.

The structures which can be used in the core made up of dendritic or hyperbranched structures, hereinafter also referred to as dendritic or hyperbranched core for short, are, for example, those described in US Pat. No. 6,025,462. These are for example STA 457 ATD-09-01-2009.doc

Hyperbranched structures such as polyphenylenes, polyetherketones, polyesters, e.g. in US-A 5,183,862, US-A 5,225,522 and US-A 5,270,402, aramids as e.g. in US-A 5,264,543, polyamides, e.g. in US-A 5,346,984, polycarbosilanes or polycarbosiloxanes, e.g. in US 6,384,172, or polyarylenes, e.g. in US-A 5,070,183 or US-A 5,145,930 or dendritic structures such as polyarylenes, polyarylene ethers or polyamidoamines, e.g. in US-A 4,435,548 and US-A 4,507,466, as well as polyethyleneimines, e.g. in US-A 4,631,337.

A dendritic core is preferably formed from siloxane and / or carbosilane units. As siloxane units it is preferred to use disiloxane and tetramethyldisiloxane units, and as carbosilane units it is preferred to use tetrapropylene-1-yl, tetraethylene-uranium,

Methyltripropylenedilane, ethyltripropylensilane, propyltripropylensilane, hexyltripropylenesilane,

Dimethyl-dipropylene-silane, diethyl-dipropylene-silane, dipropyl-dipropylene-silane,

Dihexyldipropylensilan-, hexylmethyl-dipropylensilaneinheiten used. However, other structural units can be used to construct the dendritic or hyperbranched core. The role of the dendritic or hyperbranched core is primarily to provide a variety of functionalities and thus to form a matrix to which the linking chains with the linear conjugated oligomeric chains can be attached and thus arranged in a core-shell structure. The linear conjugated oligomeric chains are preceded by attachment to the matrix, thus increasing their

Effectiveness.

The dendritic or hyperbranched core has a number of functionalities - in the sense of linking sites - which are suitable for attaching the linking chains with the linear conjugated oligomeric chains. In particular, the dendritic core, like the core composed of hyperbranched structures, has at least 2, but preferably at least 3 functionalities, more preferably at least 4 functionalities.

Preferred structures in the dendritic or hyperbranched core are 1,3,5-phenylene units (formula Va) and units of the formulas (Vb) to (Ve), where a plurality of identical or different units of the formulas (Va) to (Ve) linked together, STA 457 ATD-09-01-2009.doc

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(Va) (Vb) (VC) (Vd)

(V-e)

wherein in the units of the formulas (Vc) and (Vd) a, b, c and d are independently 0, I ₅ 2 or 3.

The positions marked with * in the formulas (V-a) to (V-e) and in other formulas used below denote the points of attachment. The units (V-a) to (V-e) are linked to the linearly conjugated oligomeric chains (L) via these or with one another via the connecting chains and via an optionally electron-withdrawing methylene carbon atom.

Examples of dendritic cores (K) composed of units of formula (V-a) are as follows:

STA 457 ATD-09-01-2009.doc

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At the positions marked with *, the linking takes place via the connecting chains (V) and optionally an electron-withdrawing group-carrying methylene carbon atom (A) with the linear conjugated oligomeric chains (L).

The shell of the macromolecular compounds having a core-shell structure is made up of linking chains (V), at least one electron-withdrawing group

Methylene carbon atom (A), linear conjugated oligomeric chains (L) and the non-conjugated chains (R) formed. Connecting chains (V) are preferably those which have a high

Flexibility, i. have a high (intra) molecular mobility and thereby cause a geometric arrangement of the segments -L-R to the core K. Flexible in the context of the invention in the sense of (intra) molecularly mobile to understand.

As connecting chains are basically linear or branched chains suitable, which have the following structural features:

Carbon atoms connected by single bonds with carbon atoms,

Carbon atoms associated with hydrogen,

Oxygen atoms associated with carbon through single bonds,

• silicon atoms bonded to carbon by single bonds and / or

Silicon atoms connected to oxygen by single bonds,

which are preferably composed of a total of 6 to 60 atoms and preferably contain no ring structures.

Suitable connecting chains are particularly preferably linear or branched C 2 -C 20 -alkylene chains, such as, for example, ethylene, n-butylene, n-hexylene, n-octylene and n-dodecylene chains, linear or branched polyoxyalkylene chains, for example -OCH-, - OCH (CH ₃ ) - or -O- (CH ₂ ) <r segments containing oligoether chains, linear or branched siloxane chains, for example those with dimethylsiloxane structural units and / or straight-chain or branched Carbosilanketten, ie chains, the silicon-carbon single bonds included, wherein the silicon and carbon atoms may be arranged in an alternating, random or block in the chains such as those having JR -S ₂ -CH ₂ -CH ₂ -CH ₂ -SiR ₂ - moieties.

As linear conjugated oligomeric chains (L) of the general formula (Z), in principle all chains are suitable which have structures which as such are electrically conductive or semiconductive STA 457 ATD-09-01-2009.doc

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Oligomers or polymers form. These are, for example, optionally substituted polyanilines, polythiophenes, polyethylenedioxythiophenes, polyphenylenes, polypyrroles, polyethylenetylenes, polyisonaphthenes, polyphenylenevinylenes, polyfluorenes, which can be used as homopolymers or oligomers or as copolymers or oligomers. Examples of such structures which can preferably be used as linear conjugated oligomeric chains are chains of 2 to 10, more preferably 2 to 8 units of the general formulas (VI-a) to (VM),

(Vl-a) <yi-t>) (VI-C)

(Vl-D

in which

R ¹ , R ² and R ^{3 may be} identical or different and are hydrogen, straight-chain or branched C ₁ -C 20 -alkyl- or C ₁ -C _{2 (r} alkoxy groups, are preferably identical and stand for hydrogen,

R ⁴ may be the same or different and represent hydrogen, straight-chain or branched CrC ₂ o-AlkyIgruppen or C ₂ o-AIkoxygruppen, preferably hydrogen or Ci-Q ₂ - alkyl groups and are STA 457 ATD-09-01-2009.doc

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R ^{s is} hydrogen or a methyl or ethyl group, preferably hydrogen, and

s, I independently represent an integer from 0 to 4 and s + 1> 3, preferably s + t = 4.

The positions of the formulas (Va) to (Vf) marked with * indicate the linking sites via which the units (Va) to (Vf) are linked to one another to form the linear conjugated oligomeric chain or the unconjugated chains (R ) wear.

Particularly preferred are linear conjugated oligomeric chains containing units of optionally substituted 2,5-thiophenes (VI-a) or (VI-b) or optionally substituted 1,4-phenylenes (VI-c). The prefixed numbers 2,5- resp. 1,4- specify the positions in the units that are linked.

Substituted is here and below, unless otherwise stated, a substitution with alkyl, in particular with Ci-Cjo-alkyl groups or with alkoxy, in particular with Ct-C ₂₀ - understood alkoxy groups.

Very particular preference is given to linear conjugated oligomeric chains with units of optionally substituted 2,5-thiophenes (VI-a) or 2,5- (3,4-ethylenedioxythiophenes) (VI-b).

The linear conjugated oligomeric chains, designated L in the general formula (Z), are each saturated at the terminal attachment sites with a nonconjugated chain (R). Non-conjugated chains are preferably those which have high flexibility, ie high (intra) molecular mobility, thereby interact well with solvent molecules and thus produce improved solubility. Flexible in the context of the invention in the sense of (intra) molecularly mobile to understand. The nonconjugated chains (R) are optionally oxygen-interrupted straight-chain or branched aliphatic, unsaturated or araliphatic chains having 2 to 20 carbon atoms, preferably having 6 to 20 carbon atoms, or C ₃ -C ₈ cycloalkylenes. Preference is given to aliphatic and oxyaliphatic groups, ie alkoxy groups or straight-chain or branched aliphatic groups interrupted by oxygen, such as oligo- or polyether groups, or C ₃ -C ₈ -cycloalkylenes. Particularly preferred are unbranched C ₂ to C _2O -AIlCyI- or C ₂ -C _2O - alkoxy groups or C ₃ -CG cycloalkylenes. Examples of suitable chains are alkyl groups such as n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl groups and also alkoxy groups such as n-hexyloxy, n-heptyloxy, n-octyloxy, n- STA 457 ATD-09-01-2009.doc

"15.

Nonyloxy, n-decyloxy and n-dodecyloxy groups or C ₃ -Q cycloalkylenes such as cyclopentyl, cyclohexyl or cycloheptyl.

As structural examples - (A) _q -LAR of the general formula (Z) consisting of linear conjugated oligomeric chains, each of which is saturated at the terminal point of attachment by a nonconjugated chain, structural elements of the general formulas (VI-aR) and (VI- bR) called:

wherein A ₅ R and q have the meaning given above for the general formula (Z) and

p is an integer from 2 to 10, preferably from 2 to 8, more preferably from 2 to 7.

Preferred embodiments of the macromolecular compounds with a core-shell structure are core-shell structures which contain siloxane and / or carbosilane units in the dendritic core, linear unbranched alkylene groups as the linking chain, or electron-withdrawing groups of the at least one electron withdrawing group, methyl carbonyl carbonyl, dicyanovinyl , Cyanoacrylsäureesler, Malonsäυreester or Dihalogenmethylen contain as linear conjugated oligomeric chains unsubstituierle oligothiophene chains and / or oligo (3,4-ethylendioxythioρhen) chains having 2 to 8, preferably 4 to 6 optionally substituted thiophene or 3,4-Ethylendioxvthiophen units and C ₆ -C) ₂ alkyl groups as flexible non-conjugated chains.

By way of example, the following compounds of the formulas (Z-2-a) to (Z-2-i) may be mentioned:

(Z-2-a) STA 457 ATD-09-01-2009.doc

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(Z-2-b)

(Z-2-c)

(Z-2-d)

(Z-2-e)

(Z-2 ~ f)

(Z-2-g) STA 457 ATD-09-01-2009.doc

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(2-2-h)

(Z-2-i)

As further examples, the following compounds (Z-4-a) to (Z-4-h) may be mentioned:

(Z-4-a)

(Z-4-b)

(Z-4-c)

(Z-4-d) STA 457 ATD-09-01-2009.doc

(Z-4-e)

(Z-4-f)

(Z-4-g)

(Z-4-h)

Layers of the macromolecular compounds of the general formula (Z) according to the invention are preferably conductive or semiconducting. Particularly preferred subject of the invention are such layers of the compounds or mixtures which are halbieitend. Particularly preferred are those layers of the compounds having a mobility of charge carriers of at least 10 ^"4 cm ² Ws are. For example, charge carriers are positive hole charges.

The compounds according to the invention are typically readily soluble in common organic solvents and thus are outstandingly suitable for processing from solution. Particularly suitable solvents are aromatics, ethers or halogenated aliphatic hydrocarbons, such as, for example, chloroform, toluene, benzene, xylenes, diethyl ether, dichloromethane, chlorobenzene, dichlorobenzene or tetrahydrofuran, or mixtures of these. STA 457 ATD-09-01-2009.doc

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The preparation of the compounds according to the invention in different ways is possible.

The preparation route is not significant for the properties of the compounds according to the invention.

The compounds of the invention are prepared in common solvents, e.g. Aromatics, ethers or halogenated aliphatic hydrocarbons, e.g. in chloroform, toluene, benzene, xylenes ,. Diethyl ether, dichloromethane, chlorobenzene, dichlorobenzene or tetrahydrofuran, at least 0.1 wt .-%, preferably at least 1 wt .-%, more preferably at least 5 wt .-% soluble.

The . Compounds of the invention form high-quality layers of uniform thickness and morphology from evaporated solutions and are therefore suitable for electronic applications.

The invention furthermore relates to the use of the compounds according to the invention as semiconductors in electronic components such as field-effect transistors, light-emitting components such as organic light-emitting diodes, or photovoltaic cells, lasers and sensors.

The compounds according to the invention are preferably used in the form of layers for these purposes.

In order to be able to ensure useful functionality as semiconductors, the compounds and mixtures according to the invention have sufficient mobility, for example at least ICT ⁴ cmWs. For example, cargo mobility can be as in M. Pope and CE. Swenberg, Electronic Processes in Organic Crystals and Polymers, 2nd ed., Pp. 709-713 (Oxford University Press, New York Oxford 1999).

For use, the compounds according to the invention are applied to suitable substrates, for example silicon wafers provided with electrical or electronic structures, polymer films or glass panes. In principle, all order procedures can be considered for the order. Preferably, the compounds of the invention and mixtures of liquid phase, that is, applied from solution, and then the solvent is evaporated. The application from solution can be carried out by the known methods, for example by spraying, dipping, printing and knife coating. Particularly preferred is the application by spin coating and by inkjet printing. STA 457 ATD-09-01-2009.doc

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The layers made from the compounds of the invention may be further modified after application, for example by a thermal treatment, e.g. while passing through a liquid crystalline phase or for structuring e.g. by laser ablation.

The invention furthermore relates to electronic components comprising the compounds according to the invention and mixtures as semiconductors.

The following examples serve to exemplify the invention and are not to be considered as limiting.

STA 457 ATD-09-01-2009.doc

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Examples

The compounds of the formula (Z) according to the invention can be prepared, for example, analogously to the synthesis listed below.

All reaction vessels were baked out prior to use in accordance with standard protective gas technology and flooded with nitrogen.

OFET preparation:

a) Substrate for OFET and purification

One-side polished p-type silicon wafers with a thermally grown oxide layer of 300 nm thickness (Sif-Chem) were cut into 25 mm x 25 mm substrates. The substrates were first carefully cleaned. The adhering silicon chips were removed by rubbing with a clean room cloth (Bemot M-3, Ashaih Kasei Corp.) under flowing distilled water and then the substrates in an aqueous 2% water / Mucasol solution at 60 ⁰ C for 15 min in an ultrasonic bath cleaned. Thereafter, the substrates were rinsed with distilled water and spun dry in a centrifuge. Immediately prior to coating, the polished surface was cleaned in a UV / ozone reactor (PR-100, UVP Inc., Cambridge, UK) for 10 minutes.

b) Dielectric layer

i. The dielectric interlayer used was octyldimethylchlorosilane (ODMC) (Aldrich,

246859). The ODMC was poured into a petri dish so that the bottom is just covered. The magazine was then placed on top of the cleaned up Si substrates. Everything was covered with an inverted Bechergfas and heated the Petri dish to 70 ⁰ C. The substrates remained in the Octyldimethylchlorsälan rich atmosphere for 15min.

above sea level. Hexamethyldisiaciazane (HMDS): The hexamethyldisiaciazane (Aldrich, 37921-2) used for the interlayer dielectric was poured into a beaker containing the magazine with the upright cleaned Si substrates. The silazane completely covered the substrates. The beaker was covered and heated to 70 ^° C. on a hot plate. The substrates remained for 24 hrs. in the silazan. Subsequently, the substrates were dried in a dry stream of nitrogen. STA 457 ATD-09-01-2009.doc

- 22 - c) Organic Semiconductor

To apply the semiconductor layer, a solution of the compounds in a suitable solvent was prepared. In order to achieve a complete solution of the components, the solution was placed for about 1 min in an ultrasonic bath at 60 ⁰ C. The concentration of the solution was 0.3% by weight.

The substrate provided with the dielectric interlayer was placed with the polished side up in the holder of a spin coater (Carl Süss, R.C8 with Gyrset®) and heated with a hair dryer to about 70 ° C. Approximately 1 ml of the still warm solution was dropped onto the surface and the solution was spun off with the organic semiconductor at 1200 rpm for 30 sec at an acceleration of 500 U / sec ² and open Gyrset® on the substrate.

d) applying the electrodes

The electrodes for source and drain were then evaporated on this layer. For this purpose, a shadow mask was used, which consisted of a galvanically produced Ni foil with 4 recesses of two intermeshing combs. The teeth of the individual combs were 100 μm wide and 4.7 mm long. The mask was placed on the surface of the coated substrate and fixed with a magnet from the back.

In a vapor deposition unit (Univex 350, Leybold), the substrates were vapor-deposited with gold.

e) capacity measurement

The electrical capacitance of the devices was determined by evaporating an identically prepared substrate, but without an organic semiconductor layer, in parallel behind the same shadow masks. The capacitance between the p-doped silicon wafer and the deposited electrode was determined with a multimeter, MetraHit 18S, Gossen Metrawatt GmbH). The measured capacitance for this arrangement was C = 0.7 nF, because of the electrode geometry the area capacity was C = 6.8 nF / cm ² .

f) electrical characterization

The characteristic curves were measured with the aid of two current voltage sources (Keithley 238). The one voltage source applies an electrical potential to the source and drain, thereby determining the flowing current, while the second sets an electrical potential at the gate and source. The source and drain were contacted with pressed-on Au pins, the highly doped Si wafer formed the gate electrode and was contacted via the oxide scratched back. The recording STA 457 ATD-09-01-2009.doc

The characteristic curves and their evaluation were carried out according to the known method, such as e.g. described in "Organic Ihin-Fum transistors: A review of recent advances", C.D. Dimitrakopoulos, D.J. Mascaro, IBM J. Res. & Dev. Vol. 45 No. 1 January 2001.

Examples The syntheses were carried out under protective gas. For this purpose, all glass apparatuses were oven-dried at 15O ⁰ C for 2 hours, assembled hot, evacuated and then subjected to inert gas. The solvents used were dried by standard methods and degassed.

example 1

l- (2,2 ^f -Bithien-5-yϊ) heptan-l-one

A solution of 5-bromo-2,2'-bithiophene (10.5 g, 42.8 mmol) in 110 mL of anhydrous THF was added dropwise to a suspension of magnesium (1.04 g, 43.7 mmol) in 10 mL of anhydrous THF. The mixture was then heated under reflux for 2 hours. The cooled solution was then added at ⁰ ° C to a solution of heptanoyl chloride (6.34 g, 34 mmol) and freshly prepared Li ₂ MgCl ₄ (1.07 mmol, 135 mg (1.07 mmol) MnCl ₂ and 95 mg (2.24 mmol) LiCl ₂ 15 ml of anhydrous THF). The mixture was then warmed to room temperature over 2 hours and stirred for 1 hour. The solution was added to 400 mL of water and 600 mL of diethyl ether. The organic phase was separated, washed with water, dried over sodium sulfate, filtered and the solvent evaporated in vacuo. There were obtained 12.1 g of crude product which was purified by chromatography on silica gel (eluent toluene-hexane 1: 1) to obtain 10.70 g (94%) of product. STA 457 ATD-09-01-2009.doc

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¹ H NMR (250 MHz, CDCl ₃ , δ, ppm): 0.88 (t, 3H, J - 6.7 Hz, -CH ₂ -CH ₅ ), 1-20 - 1.45 (overlapping signals, 6H, -CH ₂ -CH ₂ -CH ₂ -), 1.73 (m, 2H, M = 5, J = 7.3 Hz, - CH ₂ -CHrCH ₂ -CO-), 2.85 (t, 2H ₅ J = 7.3 Hz, -CH ₂ -CH ₂ -CO-), 7.15 (d, 1Η, J - 3.7 Hz), 7.30 (s, IH), 7.28-7.33 (overlapping peaks, 2H), 7.58 (d, IH, J = 4.3 Hz).

Example 2

2- (2,2 '~ Bithien-5-yl) -2-hexyl-l, 3-dioxolan

l- (2 ₎ 2'-Bithien-5-yl) heptan-1-one (10.0 g, 35.9 mmol) was dissolved in hot benzene (350 mL) and treated with p-toluenesulfonic acid (1.37 g _s 7.2 mmol) and ethylene glycol ( 80 mL, 89 g, 1.44 mol). The solution was boiled at 115 ^° C. for 18 hours on a water separator. The solution was then washed with saturated sodium bicarbonate solution, the organic phase separated, dried over sodium sulfate, filtered and the solvent evaporated in vacuo. There were obtained 11.79 g of crude product, which were purified by chromatography on silica gel (eluent toluene) and Umkπstallisation from hexane. There was obtained 8.35 g (72%) of product.

¹ H NMR (250 MHz, CDCl ₃ , δ, ppm): 0.87 (t, 3H, J - 6.7 Hz ₅ -CH ₂ -CH ₅ ), 1.20 - 1.48 (overlapping signals, 6Η, -CH ₂ -CH ₂ - CH ₂ -), 1.40 (m, 2H, M = 5, J - 7.3 Hz ₅ - CH ₂ -CH ₃ -CH ₂ -C (O-CH ₂ -CH ₂ -O) -), 1.99 (t, 2H , J - 7.3 Hz, -CH ₂ -CH ₂ -C (O-CH ₂ -CH ₂ -O) -), 4.00 (m, 4H, CH ₂ -C (O-CHrCH ₂ -O) -T), 6.88 (d, 1Η, J - 3.7 Hz), 6.99 (dd, IH, J ₁ - 4.9 Hz, J ₂ = 3.7 Hz), 7.00 (d, IH, J - 3.7 Hz) ₅ 7.12 (dd, IH ₅ Ji = 3.7 Hz, J ₂ - 1.2 Hz), 7.19 (dd, IH, Ji = 5.4 Hz, J ₂ = 1.2 Hz). STA 457 ATD-09-01 ~ 2009.doc

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Example 3

l_ [5 ^> _ (4,4,5,5-tetramethyl-l, 3,2-dioxaborolan-2-yl) -2,2'-brothien-5-yl] -2-hexyl-1,3-dioxolane

To a solution of 2- (2,2'-Bithien-5-yl) -2-hexyl-l, 3-dioxolane (8.10 g, 25.1 mmol) in 250 ml of anhydrous THF at -70 to -75 ⁰ C was a 1.6 M solution of butyllithium (15.70 ml, 25.1 mmol) in hexane was added dropwise. The reaction solution was stirred for 60 minutes at -75 ⁰ C and then 2-isopropoxy-4,4,5,54etramethyl-l, 3,2-dioxaborolane (5.124 mL, 25.1 mmol) was added in one portion. The solution was stirred for a further 1 hour at -78 ⁰ C and an additional hour at room temperature. 600 ml of freshly distilled diethyl ether and 300 ml of degassed water were added. To this was added dropwise 25 mL of 1M HCl with stirring. The organic phase was separated, washed with water, dried over sodium sulphate, filtered and the solvent evaporated in vacuo. There was obtained 11.26 g (95%) of product.

1H NMR (250 MHz, CDCl ₃ , δ, ppm): 0.84 (t, 3H, J - 6.7 Hz, -CH ₂ -CH ₅ ), 1.20 - 1.48 (overlapping peak signals at 1.33 ppm, 2OH, -CH ₂ -CHRCH ₂ - and O-C (CHV ₂ ), 1-99 (t, 2Η, J = 7.3 Hz, -CH ₂ -CH ₂ -C (O-CH ₂ -CH ₂ -O) -), 4.00 ( m, 4H, CH ₂ -C (O-CH ₂ -CH ₂ -O) -T), 6.88 (d, IH ₉ J = 3.7Hz), 7.06 (d, 3H, J = 3.7Hz), 7.18 (i.e. , IH, J - 3.7 Hz), 7.49 (d, IH, J = 3.7 Hz). STA 457 ATD-09-01-2009.doc

- 26 -

Example 4

. l- [S _'(4,4; 5,5.TetrainethyH, 3,2-dioxaborolan-2-yl) -2,2'-bithien-5-yllheptan-l-on

l- [5 '- _(? 4,4,5,5-tetramethyl-l _J 3 2-dioxaborolan-2-yl) -2 ₅ 2'-bithien-5-yl] -2-hexyl-l, 3- dioxolane (5.1 g, 11.40 mmol) was dissolved in anhydrous THF (50 mL) and treated with 1.14 mL (1 mmol) concentrated HCl. The solution was stirred for 7 hours at room temperature. Subsequently, 400 ml of freshly distilled diethyl ether and 20Θ mL degassed water were added. The organic phase was separated, washed with saturated aqueous NaHCO ₃ solution, dried over sodium sulphate, filtered and the solvent evaporated in vacuo. There was obtained 4.2 g (96%) of product.

¹ H NMR (250 MHz, CDCl ₃ , δ, ppm): 0.88 (t, 3H, J = 6.7 Hz ₅ -CH ₂ -CHj), 1.20 - 1.45 (overlapping peak signals at 1.34 ppm, 18Η, -CH ₂ -CHrCH ₂ - and 0-C (CH ₅ ^), 1.73 (m _s 2H ₅ M = 5 ₅ J - 7.3 Hz, -CH ₂ -CH ₂ -CH ₂ -CO-), 2.85 (t, 2H, J = 7.3 Hz, - CH ₂ -CH ₂ -CO-), 7.20 (d, 1Η, J - 3.7 Hz), 7.35 (d, IH ₅ J = 3.7 Hz), 7.53 (d, IH ₅ J = 3.7 Hz) ₅ 7.59 (d, IH, J = 4.3 Hz).

Example 5 1- (5'-Bromo-2,2'-bienthien-5-yl) undec-10-en-1-one

STA 457 ATD-09-01-2009.doc

- 27 -

Stufel. Synthesis of Magnesium Bromide-Diethyl Ether Complex To a solution of 1,2-dibromoethane (3.18 mL, 36.7 mmol) in 25 mL of diethyl ether was added dropwise a suspension of magnesium (969 mg, 38.6 mmol) in 15 mL anhydrous THF. The reaction was refluxed for 30 minutes, then cooled to room temperature and further used in step 2.

Step 2. Preparation of (5'-bromo-2,2'-bilhien-5-yl) magnesium bromide. A 1.6 M solution of butyllithium (19.3 mL, 30.9 mmol) in hexane became a solution of 5,5'-dibromo-2 _; 2'-Bithiophene (10.00 g, 30.9 mmol) in 450 ml of anhydrous THF at -40 ⁰ C added dropwise. The reaction was then stirred for 30 minutes at 40 ^° C. Then, the magnesium bromide-diethyl ether complex solution from Step 1 was added in one portion. The reaction solution was stirred for 30 minutes at -40 ⁰ C and then for 2 hours at room temperature.

Step 3. Order l- (5'-Bromo-2,2'-Bithien-5-yl) undec-10-en-1-one. The Grignard solution from step 2 was added to a solution of undecenoyl chloride (6.26 g, 30.9 mmol) and a freshly prepared solution of Li ₂ MgCl ₄ (1:54 mmol) was added dropwise in anhydrous THF at -5 ⁰ C. (Li ₂ MgCl ₄ was prepared from MnCl ₂ (194 mg, 15.4 mmol) and LiCl (137 mg, 32.4 mmol) by stirring in 50 mL of anhydrous THF at room temperature for 2 h.). Heated to room temperature for 2 hours and stirred for a further hour

Subsequently, the reaction solution was poured into 400 ml of water and stirred with 600 ml of diethyl ether. The organic phase was separated, washed with water, dried over sodium sulfate, filtered and the solvent removed in vacuo. There were obtained 12.06 g of crude product, which was purified by repeated recrystallization from toluene and chromatography on silica gel (eluent toluene - hexane 1: 1, 60 ⁰ C). There were obtained 8.89 g (63%) of product in the form of orange crystals.

¹ H NMR (250 MHz, CDCl _3, δ, ppm): 1:20 to 1:45 (overlapping signals, 10H, - CH ₂ -CH ₂ -CH ₂ -), 1.72 (m, _2H> M - 5, J - 7.3 Hz , -CH ₂ -CHrCH ₂ -CO-), 2.02 (dt, 2H ₅ Ji =

7.3 Hz, J ₂ = 7.1 Hz, -CH ₂ -CH ₂ -CH = CH ₂ ), 2.82 (t, 2H, J = 7.5 Hz, -CH ₂ -CHrCO-), 4.95 STA 457 ATD-09-01-2009.doc

- 28 -

(m, 2H, -CH ₂ -CH = CH ₃ ), 5.78 (m, IH, -CH ₂ -CH = CH ₂ ), 7.00 (d, IH ₅ J = 3.7 Hz), 7.05 (d, IH, J = 3.7 Hz), 7.09 (d, IH, J = 4.3 Hz), 7.30 (s, IH) ₅ 7.57 (d, IH ₅ J = 4.3 Hz).

Example 6

l- (5 ^f "~ heptanoyl-2,2 ': 5, ^t 2 ^t': 5", 2 ^"t -quaterthien-5-yl) undec" 10 ~ en-l-on

° C

A solution of 3.26 g (8:07 mmol) of l- [5 ¹ - (4,4,5,5-tetramethyl-l _J 3 ₅ 2-dioxaborolan-2-yl) - 2,2 ^l -bithien-5-yl] Heptan-1-one and 2179 g (6.78 mmol) of 1- (5'-bromo-2,2'-bithien-5-yl) undec-10-en-1-one in 120 ml of toluene was degassed and treated with 466 mg Pd (PPli3) ₄ offset. Subsequently, 24 ml of an aqueous, degassed 2M Na ₂ CO ₃ solution were added and the reaction mixture was stirred at reflux for 12 hours. 300 ml of toluene and 300 ml of water were added, and the organic phase was separated off, washed with water until neutral to pH, dried, filtered and the solvent removed in vacuo. The crude product was recrystallized from toluene. There were 4.07 g (99%) of product.

^ι n NMR (250 MHz, CDCl _3, δ, ppm): 0.90 (t, 3H, J = 6.7 Hz, -CH ₂ -CHJ), 1:22 to 1:45 (overlapping signals, 16Η, -CH ₂ -CH ₃ -CH ₂ -), 1.78 (m, 4H, M - 5, J - 7.3 Hz ₅ - CH ₂ -CH ₂ -CH ₂ -CO) ₅ 2.01 (m, 2H, M - 4, J = 6.7 Hz, -CH ₂ -C = CH ₂ ), 2.85 (t, 4H, J = 7.3 Hz, -CH ₂ -CH ₃ -CO-), 4.95 (m, 2Η, -CH ₂ -CH-CH ₂ ), 5.78 (m, 1Η , -CH ₂ -CH-CH ₂ ), 7.14 (d, 2H, J = 3.7 Hz), 7.17 (d, 2H ₅ J = 4.3), 7.22 (d, 2H, J = 3.7 Hz), 7.58 (d, 2H, J - 4.3 Hz). STA 457 ATD-09-01-2009.doc

- 29 -

Example 7

{1- [5 " ^t - (2,2-dicyano-1-hexylyvinyI) -2,2 ': 5', 2": 5 ", 2 ' ^tl- quaterthien-5-yl] undec-10-ene l-ylid en} maϊononitrü

Pyridiπ

2.5 g (4.1 mmol) 1- (5 "'- heptanoyl-2 _J 2': 5 ^r , 2": 5 ", 2"'- quaterthien-5-yl) undec-10-en-1-one ₅ 1.08 g (16.4 mmol) of malononitrile and 120 ml of anhydrous pyridine were stirred at 9O ⁰ C for 25 hours. Subsequently, the solvent was removed in vacuo and the crude product obtained was purified by chromatography (Süicagel, eluent: toluene-THF 10: 1). 1.48 g (51%) of pure product was obtained.

¹ H NMR (250 MHz, CDCl ₃ , δ, ppm): 0.89 (t, 3H, J = 6.7 Hz), 1.22 - 1.42 (overlapping signals, 12H, -CH ₂ -CTf ₂ -CH _2- ), 1.46 (m, 4H, M - 5, J = 7.3 Hz, -CHrCH ₂ -CH ₂ -C (CN) ₂ -), 1.70 (m, 4H, M = 5, J - 7.3 Hz, -CH ₂ -CH ₂ -C (CN) ₂ -), 2.02 (m, 2H, M = 4, J - 6.7 Hz, - CH ₂ -C = CH ₂ ), 2.93 (t, 4H, J - 7.3 Hz, -CH ₂ - C (CN) ₂ -), 4.95 (m, 2Η, -CH ₂ -CH-CH ₂ ), 5.78 (m, 1Η, -CH ₂ -CH = CH ₂ ), 7.20 (d, 2H, J = 4.3) , 7.28 (d, 2H ₅ J - 4.3), 7.31 (d, 2H, J - 4.3), 7.95 (d, 2H, J = 3.7). STA 457 ATD-09-01-2009.doc

- 30 -

Example 8

[l-r5 ^{> M} -f2,2-dicyclo-1-hexylvinyl] -2.2 ^t : 5 \ 2 ' ^t : 5 ^M , 2 "' - αuaterthieti-5-ylMl-fiα3,3-tetramethyldisiloxanyl) undecylidenes] malononltrile

0.24g (0:34 mmol) of {l- [5 ^m - _(2, 2-dicyano-l-hexylvinyl) -2 _J 2 ': 5', 2 ": _5") 2 ^w -quaterthäen-5-yl] undec 10- en-l-ylidene} malononitrile and 10 mL of 1,1,3,3-tetramethyldisiloxane were dissolved in 20 ml of toluene at 40 ⁰ C. Subsequently, 30 μL of a 0.1 M solution of Karstedt's catalyst in xylene was added. The reaction solution was stirred at 40 ^° C. for 2 hours. Subsequently, the excess 1,1,3,3-TetramethyldisiIoxan. withdrawn with the toluene in vacuo. The resulting crude product (0.27 g) consisting of 72% of product, 8.5% of the dimer and 19% reactant with shifted double bond was further reacted without purification.

Minutes STA 457 ATD-G9-01-2009.doc

- 31 -

GPC analysis of the crude product from Example 8.

(Dimer: peak at 7.3 min., Product: peak at 7.8 min., Educt with shifted double bond

Peak at 8.1 min.)

Example 9

l, 3-bis- {3- [5 ^{t> (-} (2,2-Bkyano-l-hexylvinyl) -2,2 ': 5 ^t, 2 ": 5 ^tl, 2 ^1" -quaterthien-5-yl ] - undecyHden] malononitrii} -14A3-tetramethyldisiloxane

[1 - [5 "'- (2,2-dicyano-1 -hexylvinyl) -2,2 ¹ : 5 ^t , 2": 5 "_> 2 ^t " -quaterthien-5-yl] - 11- (1, 1,3,3-tetramethyldisiloxanyl) indecylidene] malononitrile (0.25 g, 0.3 mmol) and {1- [5 '"- (2,2-dicyano-1-hexylvinyl) -2 ₅ 2': 5 ', 2": 5 ", 2" ^! -quaterthien-5-yl] undec-10-en-1-ylidene} malononitrile (0.27 g, 039 mmol) were dissolved in 15 mL of anhydrous toluene at 40 ⁰ C and then treated with 20 μL of a 0.1 M solution Karstedt's catalyst in xylene , The reaction was stirred at 40 ^° C. for 6 hours. The solvent was then removed in vacuo. There were obtained 0.52 g of product containing 56% of the desired product.

STA 457 ATD-09-01-2009.doc

- 32 -

Minutes

GPC analysis of the reaction product of Example 9.

(Product: peak at 7.3 min., Starting material: peak at 7.8 min., Educt with shifted double bond: peak at 8.1 min.)

Claims

STA 457 ATD-09-01-2009.doc-33 -Patent claims:

1. Macromolecular compounds having a core-shell structure wherein the core has a macromolecular basic structure based on silicon and / or carbon and having at least 2 through a carbon-based linking chain with carbon-based linear oligomeric chains with continuous conjugated

Is bonded double bonds, and wherein the linear conjugated chains are saturated in each case via at least one electron-withdrawing group-carrying methylene carbon atom with at least one further, in particular aliphatic, araliphatic or oxyaliphatic chain without conjugated double bonds.

2. Compounds according to claim 1, characterized in that the macromolecular (s) compounds having a core-shell structure are those of the general formula (Z),

κ i _v . _A i _t -AR (Z)

wherein

K is an n-functional core,

V represents a connection chain,

A represents an electron-withdrawing group-carrying methylene carbon atom selected from the group consisting of carbonyl, dicyanovinyl, cyanoacrylic acid ester, malonic acid ester or dihalomethylene,

R represents linear or branched C ₂ -C _2O -AI kylreste, C ₃ -C ₈ cycloalkylene, mono- or polyunsaturated C ₂ -C ₂₀ -A Ikenylreste, C ₂ -C ₂ O- alkoxy, C ₂ -C ₂ O- aralkyl or C ₂ -C _2O -OHgO- or C ₂ -C ₂₀ -Polyetherreste stands,

q stands for 0 or 1, and

n is an integer greater than or equal to 2, preferably a number between 2 and 4. STA 457 ATD ~ 09-01-2009.doc

- 34 -

3. Compounds according to claim 1 or 2, characterized in that the core of the macromolecular compound (s) has a dendritic or hyperbranched structure.

4. Compounds according to at least one of claims 1 to 3, characterized in that the dendritic core of the macromolecular (s) compound (s) Soxan and / or

Has carbosilane units.

5. Compounds according to at least one of claims 1 to 4, characterized in that the connecting chains V are linear or branched Cj-C _ϊ o-alkylene chains, linear or branched polyoxyalkylene, linear or branched siloxane chains and / or linear or branched Carbosüanketten

6. Compounds according to at least one of claims 1 to 5, characterized in that the shell of the macromolecular (s) compound (s) as linear conjugated oligomeric chains oligothiophene chains and / or oligo (3,4-ethylenedioxythiophene) chains having 2 to 8 optionally contains substituted thiophene or 3,4-ethylenedioxythiophene units.

7. Compounds according to at least one of claims 1 to 6, characterized in that the linear conjugated oligomeric chains of the macromolecular (s) compound (s) each at the terminal linking positions by identical or different, branched or unbranched alkyl or alkoxy groups, preferably alkyl groups are saturated.

8. Use of the compound according to at least one of claims 1 to 7 as a semiconductor in electronic components.

9. Use according to claim 8, characterized in that the components field-effect transistors, light-emitting components, in particular organic light-emitting diodes, or photovo Itaische cells, lasers and sensors.

10. Use according to claim 8 or 9, characterized in that the compound in the form of layers of solutions are applied to the device.

11. Electronic components containing compounds according to at least one of claims 1 to 7 as a semiconductor.