WO2016046077A1

WO2016046077A1 - Crosslinkable host materials

Info

Publication number: WO2016046077A1
Application number: PCT/EP2015/071415
Authority: WO
Inventors: Daniel Volz
Original assignee: Cynora Gmbh
Priority date: 2014-09-25
Filing date: 2015-09-18
Publication date: 2016-03-31
Also published as: CN106715420A; JP6826031B2; JP2017532323A; CN115572284A

Abstract

The invention relates to a crosslinkable organic molecule having a structure of the formula (1) and to the use thereof, wherein Ar = independently of one another, an unsaturated or aromatic carbo- or heterocyclic unit with 5 to 30 ring atoms, selected from the group consisting of naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, tetracene, pentacene, benzpyrene, furan, benzofuran, isobenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazol, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine-imidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, isothiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,3,4- oxatriazole, 1,2,3,4-oxatriazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazin, purine, pteridine, indolizine, benzothiadiazole, indenocarbazole, indenofluorene, spirobifluorene, and indolocarbazole; D1 = a donor group having a structure of the formula (1a); and D2 = a donor group having a structure of the formula (1b).

Description

Crosslinkable host materials

The invention relates to organic molecules of general formula 1 and their use as crosslinkable, liquid processable host materials in OLEDs (organic light-emitting diodes) and other opto-electronic components.

introduction

Organic electronic devices are increasingly being used in commercial products or are about to be launched on the market. Examples of already commercial products include organic or polymeric light-emitting diodes (OLEDs, PLEDs) in display and display devices. Organic solar cells (O-SCs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic switching elements (O-ICs), organic optical amplifiers or organic laser diodes (O-lasers) are all in one Research stage and could be very important in the future. The general structure of organic electroluminescent devices is described, for example, in US Pat. No. 4,539,507 A, US Pat. No. 5,151,629 A, EP 0676461 A and WO 98/27136 A. However, there is room for improvement with these devices:

1 . The operational lifetime is still low, especially with blue or green emission, so that only simple applications could be realized commercially until now.

2. The compounds used are sometimes difficult to dissolve in common organic solvents, which makes their purification in the synthesis, but also the processing of the materials from solution and the cleaning of equipment in the manufacture of electronic devices difficult.

3. The materials used in the prior art, often have a low triplet energy. This results in quenching (quenching) of the emission, and thus in a reduction in efficiency, when combined with materials that emit from the triplet state.

Many of these electronic or opto-electronic devices, regardless of their intended use, have the following general layer structure, which can be adapted to the respective application:

(1) substrate,

(2) Electrode, which can often be metallic or inorganic, but also composed of organic or polymeric conductive materials, (3) optionally one or more charge injection layer (s) to compensate for unevenness of the electrode, often from a or a plurality of conductive, doped polymer (s) is / are (4) at least one layer of an organic semiconductor, (5) optionally one or more further charge-transport or charge-blocking layer (s),

(6) counter electrode using the materials mentioned under (2), (7) encapsulation.

The present invention is particularly, but not exclusively, directed to organic light-emitting diodes (OLEDs), which are often referred to as polymeric light emitting diodes (PLED = Polymer Light Emitting Diode) when using polymeric materials. The above arrangement represents the general structure of an optoelectronic device, wherein different layers can be combined, so that in the simplest case there is an arrangement of two electrodes, between which an organic layer is located. The organic semiconductor layer in this case fulfills all functions, including the emission of light. Such a system is described, for example, in WO 9013148 A1 on the basis of poly (p-phenylenes).

The properties of OLEDs are not only determined by the emitters used. Here are in particular the other materials used, such as matrix materials, hole blocking materials, electron transport materials, hole transport materials and Elektronenbzw. Exciton blocking materials of particular importance. Improvements to these materials can thus also lead to significant improvements in the OLED properties. Even for fluorescent OLEDs there is still room for improvement with these materials. Ketones (or phosphine oxides are used as matrix materials for phosphorescent emitters, inter alia, in the prior art.) However, with the use of these matrix materials, as with other matrix materials, there is still room for improvement, in particular with regard to the efficiency and the lifetime of the device.

The present invention relates to the provision of compounds which are suitable for use in a fluorescent or phosphorescent or temperature-activated delayed-fluorescence OLED (TADF-OLED), in particular a phosphorescent or TADF-OLED For example, as a matrix material or as a hole transport EIektronenblockiermaterial or Exzononenblockiermaterial or as an electron transport or Lochblockiermaterial.

description

The invention is based on a development of a new crosslinking unit PG as a basic structure in crosslinkable organic semiconductors (Formula 1 a). Such crosslinking units can be used in organic semiconductors, which thereby obtain crosslinking capabilities themselves. This results in numerous new organic semiconductors, which are summarized in Formula 1. In this respect, in a first aspect, the invention relates to a crosslinking unit PG and its use in the crosslinking of organic semiconductors.

The invention provides organic molecules of general formula 1,

Formula 1 with

Ar = independently of one another an unsaturated or aromatic carbo- or heterocyclic unit having 5 to 30 ring atoms, selected from the group consisting of naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, tetracene, pentacene, benzpyrene , Furan, benzofuran, isobenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo -7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine-imidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, isothiazole, 1,3-thiazole , Benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1, 2,3-triazole, 1, 2,4-triazole, benzotria zol, 1, 2,3-oxadiazole, 1, 2,4-oxadiazole, 1, 2,5-oxadiazole, 1, 3,4-oxadiazole, 1, 2,3-thiadiazole, 1, 2,4-thiadiazole, 1, 2,5-thiadiazole, 1, 3,4-thiadiazole, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,3-triazine, tetrazole, 1, 2,3,4- Oxatriazole, 1, 2,3,4-oxatriazole, 1, 2,4,5-tetrazine, 1, 2,3,4-tetrazine, 1, 2,3,5-tetrazine, purine, pteridine, indolizine, benzothiadiazole, Indenocarbazole, indenofluorene, spirobifluorene and indolocarbazole, each of which may be substituted with one or more R ¹ radicals, where two or more R ^{1 's may} be linked together and form one or more rings;

D1 = a donor group with electron-donating properties, having a structure of formula 1 a;

#

Formula 1a and

D2 = a donor group with electron-donating properties, having a structure of formula 1 b;

Formula 1 b where the symbols and indices used are:

n is an integer between 1 and 5;

o is an integer between 1 and 5;

peine integer between 0 and 5;

PG are two identical or different polymerizable units that can be polymerized by thermal and / or acid or base catalyzed processes, UV irradiation in the presence or absence of a photoinitiator or by microwave radiation. In a preferred embodiment, a functionalization takes place at the 3 and the 6-position of the structure.

X, Y independently of each occurrence are identically or differently a covalent single bond or a divalent organic bridge selected from the group consisting of substituted and unsubstituted alkylene (unbranched, branched or cyclic), alkenylene, alkynylene, arylene and heteroarylene Groups, O, NR ³ , C =CR ³ ₂ , C =NR ³ , SiR ³ ₂ S, S (O), S (O) ₂ , Se, Se (O), Se (O) ₂ , BR ³ , PR ³ , P (O) R ³ , as well as combinations of these units (eg, alkylene (unbranched, branched or cyclic), alkenylene, alkynylene, arylene and heteroarylene groups interrupted by O);

Z is the same or different CR ² or N at each occurrence;

R and R ¹ are the same or different at each occurrence, H, D, F, Cl, Br, I, B (OR ³ ) ₂ , CHO,

C (= O) R ³ , CR ³ = C (R ³ ) ₂ , CN, C (= O) OR ³ , C (= O) N (R ³ ) ₂ , Si (R ³ ) ₃ , NO ₂ , P (= O) (R ³ ) ₂ , OSO ₂ R ³ , OR ³ , S (= O) R ³ , S (= O) ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C Atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups each may be substituted with one or more radicals R ³ and wherein one or more CH ₂ - groups in the abovementioned groups by -R ³ C = CR ³ -, -C C-, Si (R ³ ) ₂ , C = 0 , C = S, C = NR ³ , -C (= O) O-, -C (= O) NR ³ -, NR ³ , P (= O) (R ³ ), -O-, -S-, SO or S0 ₂ may be replaced and wherein one or more H atoms in the abovementioned groups may be replaced by D, F, Cl, Br, I, CN or N0 ₂ , or an aromatic ring system having 6 to 30 aromatic

Ring atoms, which may be substituted by one or more radicals R ³ , or an aryloxy group having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R ³ , wherein two or more radicals R and R ^{1 may} be linked together and can form a ring;

R ² is identical or different on each occurrence H, D, F, Cl, Br, I, B (OR ³ ) ₂ , CHO, C (= O) R ³ , CR ³ = C (R ³ ) ₂ , CN, C (= O) OR ³ , C (= O) N (R ³ ) ₂₎ Si (R ³ ) ₃ , N (R ³ ) ₂ , NO ₂ , P (= O) (R ³ ) ₂ , OSO ₂ R ³ , OR ³ , S (= O) R ³ , S (= O) ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups can each be substituted by one or more radicals R ³ and where one or more CH ₂ groups in the above groups by -R ³ C = CR ³ -, -C C-, Si (R ³ ) ₂ , C = 0, C = S, C = NR ³ , -C (= 0) 0-, -C (= 0) NR ³ -, NR ³ , P (= 0) (R ³ ), -O-, -S-, SO or S0 ₂ may be replaced and wherein one or more H atoms in the above groups by D, F, Cl, Br, I, CN or N0 ₂ may be replaced, or an aromatic or heteroaromatic ring system having 5 to 30 aroma table ring atoms, each of which may be substituted by one or more radicals R ³ , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ³ , wherein two or more radicals R ² linked together can be and form a ring;

R ³ is the same or different at each occurrence H, D, F, Cl, Br, I, B (OR ⁴ ) ₂ , CHO, C (= O) R ⁴ , CR ⁴ = C (R ⁴ ) ₂ , CN, C (= O) OR ⁴ , C (= O) N (R ⁴ ) ₂ , Si (R ⁴ ) ₃ , N (R ⁴ ) ₂ , NO ₂ , P (= O) (R ⁴ ) ₂ , OSO ₂ R ⁴ , OR ⁴ , S (= O) R ⁴ , S (= O) ₂ R ⁴ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or Thioalkyl group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein the above-mentioned groups may each be substituted by one or more radicals R ⁴ and wherein one or more CH ₂ groups in the above groups represented by -R ⁴ C =CR ⁴ -, -C =C-, Si (R ⁴ ) ₂ , C =O, C =S, C =Se, C =NR ⁴ , -C (= O) O- , -C (= O) NR ⁴ -, NR ⁴ , P (= O) (R ⁴ ), -O-, -S-, SO or S0 ₂ may be replaced and wherein one or more H atoms in the above be replaced by D, F, Cl, Br, I, CN or N0 ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁴ , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ⁴ , wherein two or more radicals R ³ linked together can be and form a ring; is identical or different at each occurrence H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which also one or more H atoms may be replaced by D or F; It can have two or more

Substituents R ⁴ be linked together and form a ring;

and wherein the linkage with Ar takes place in each case at the point marked # in the form of a single bond.

The polymerizable group PG in one embodiment is a compound independently selected from the group consisting of

wherein the wavy line indicates the attachment position to the body of D1.

The group Ar of the organic molecule has, in one embodiment, the following structure

Formula 2 wherein W is the same or different CR ¹ or N at each occurrence (as defined above) and in particular at least one W is not equal to CR ¹ .

In a further embodiment, the compounds according to the invention are PYD2-type compounds such as, for example

In a further preferred embodiment, the compounds according to the invention are mCPy-type compounds, for example

mCPy-like

In a further preferred embodiment, the compounds according to the invention are DIHAPY-type compounds, for example

In addition, the compounds shown below are also preferred embodiments of compounds of formula 1

Surprisingly, significant advantages over the prior art were found. Known crosslinking concepts using oxetanes require additional reagents and are unfavorable for the component life. In the crosslinking of di (4-vinylaryl) amines with UV radiation, the high temperatures and long reaction times required by such approaches are unfavorable. The crosslinking of divinyl-substituted compounds in which the vinyl radicals are attached to different carbazole radicals is also known. In this case, however, no positive interaction was found between the polymerizable groups.

Surprisingly, it has now been found that by introducing the crosslinkable groups on a conjugated spacer (basic body of formula 1 a) unexpected advantages occur: By the introduction of two polymerizable groups which are on bridges such as carbazole, phenoxazine, phenothiazine and comparable fused heterocycles in conjugation , two possible growth positions for polymer chains are available. The radical is delocalized over the entire spacer, d. H. Chain growth can occur at both molecular positions. A possible synthesis of N-aryl-divinylcarbazoles can be carried out by the vinyl radicals are built by Kumadareaktion from the corresponding dibromide (Tetrahedron, 54 (1998), 12707-12714). The combination of cross-linkable moiety and functional molecule in a single functional moiety minimizes the synthetic effort required to produce the materials since only one dibromocarbazole moiety must be introduced into the functional material rather than multiple moieties (see Example 3). This dibromocarbazole residue can be easily and selectively converted by palladium-catalyzed cross-coupling reaction into the desired divinylcarbazole radical. The further synthetic adaptation to z. For example, to set the electronic properties and / or solubility can be carried out so much easier. The electronic coupling between the two vinyl groups makes it easy to activate the material, allowing it to be crosslinked at lower temperatures or less UV dose compared to electronically decoupled divinyl-substituted systems, which is significantly gentler on the functional materials.

This has advantages: The cross-linking of organic, amorphous thin films is often inhibited. Such a process is diffusion-controlled, since the rate depends primarily on how fast an activated radical can encounter an attackable monomer upon diffusion through the solid. The creation of a radical that can be attacked by two spatially separated sides doubles the likelihood that another elementary step of networking will occur in one time unit. As a result, higher reaction conversions and shorter crosslinking times can be realized.

Furthermore, the increased delocalization decreases the activation barrier of the addition, so that it runs faster in the time average.

A third optional advantage is achieved in the optional use of carbazole (Y = single bond): a known degradation mechanism of this structural unit an oligomerization / formation of new bonds when using carbazole groups based (Figure 2). The properties of the components are changed by these processes in such a way that their energy levels shift and in the medium term a destruction of the component occurs. By saturating the reactive positions of the hole transporting units, e.g. For example, by tert-butyl groups this problem could be avoided. However, this results in the disadvantage that, on the one hand, parameters such as charge carrier mobility change negatively, resulting in problems with morphology, in particular phase separation, for example. B. can lead to the crystallization of the host materials and / or the emitter molecules contained therein. On the other hand, these protective groups can be split off in the long-term operation of the components, which leads to the problems just described. In one embodiment of the invention, unstable tertiary alkyl groups are replaced by more stable secondary alkyl groups.

The molecules according to the invention have donor groups D2 of the formula 1b, which have a planar structure, as a result of which the charge carrier mobility is markedly increased in comparison to molecules with unbridged arylamines. Unbridged arylamines are significantly more unstable in comparison to the donor units according to the invention in OLEDs, since the unlinked aryl radicals can be split off relatively easily. In addition, triplet energy is significantly higher for unbridged arylamines. With inappropriate triplet energy, the compounds are not suitable as host materials for thermally activated delayed fluorescence (TADF) emitters and phosphorescence emitters, especially not blue for the industrially significant color.

Furthermore, the polymerizable groups PG are optionally used in mirror-symmetric compounds. By introducing two crosslinkable units PG in each case only one carbazole unit, the symmetry of these molecules is lowered (Figure 3), whereby the solubility increases and the suitability for printing and coating processes is increased. By suppressing the crystallization, the film-forming properties are also improved.

In one embodiment, in the compounds of the invention, two polymerizable groups PG are in conjugation and close proximity to each other. For crosslinking at least two PG are necessary in the molecule. The presence of exactly two polymerizable groups is preferred since, statistically, the likelihood of non-crosslinked units remaining as radicals after polymerization in the polymer film increases with the number of polymerizable groups PG in the molecule. These radicals would act as so-called charge carrier traps in an optoelectronic device and would degrade its efficiency.

In a preferred embodiment of the invention, carbazole is used as the donor residue. A disadvantage of the known, unsubstituted carbazole units is the low HOMO energy. Depending on the substitution, this is -6.0 to -5.6 eV. This will adapt to commonly used Hole injection layers such as PEDOT: PSS, which often show a HOMO energy around -5.1 eV, make this difficult. In order to achieve a low turn-on voltage in OLED components, it is favorable if the energy difference between the HOMO of the carbazole derivative and the hole injection layer is as small as possible. The substituents increase the HOMO energy by 50 to 200 meV, which reduces this energy difference compared to unsubstituted carbazole derivatives.

One aspect of the invention is based on using the crosslinking unit in known organic semiconductors in order to vary the optoelectronic properties to the extent that the requirements for this material are optimally achieved in a component, depending on the intended use (HOMO and LUMO, T1, S1, hole transport , Electron transport, hole blocker, electron blocker, solubility, orthogonal solubility and crosslinkability to allow for a multilayer component of solution). In order to further establish these components in terms of luminous efficacy and lifetime, several high-purity organic layers are used in the component itself, each individual layer having a separate function (charge injection, charge transport, charge blocking layer, emission layer, electrode, etc.). These layers generally become one after the other applied in a high vacuum by sublimation on a corresponding substrate. As the number of mass-market-ready products in the field of organic electronics, especially organic light-emitting diodes (OLEDs) for the display and lighting market, there is a potential compulsion to realize alternative and less expensive manufacturing paths than the established vacuum-based production techniques.

The use of polymerizable groups causes the film previously made from solution to transform into an insoluble network. In this way, a further layer of solution can be applied to the already coated substrate without causing mixing at the interface and without dissolving the previously deposited layer.

These innovations realize the purity of small molecules according to the invention with the cost-effective, solvent-based manufacturing processes. This allows the production of state-of-the-art multilayer components with less material loss in comparison to the deposition from and optionally the reduction of the number of functional layers in an OLED component.

Surprisingly, it has been found that the compounds determined by formula 1 lead to significant improvements of the organic electroluminescent device, in particular with regard to the lifetime, the efficiency and the operating voltage. This is especially true for green and blue phosphorescent electroluminescent devices, especially when using the compounds of the invention as a matrix material. These materials as well as organic Electroluminescent devices containing such compounds are therefore the subject of the present invention.

In addition, the compounds of the invention allow the use of crosslinking processes by photochemical or thermal crosslinking, without which the production of efficient, durable liquid-processed OLEDs will not be possible.

One aspect of the invention is thus to provide novel ambipolar host materials which have improved performance, lifetime, and operating potential when used in an opto-electronic device by introducing two conjugated crosslinkable groups PG onto a functional donor moiety such as carbazole, phenoxazine, or phenothiazine.

In a further aspect, the invention relates to the use of an organic molecule of the type described herein in an emitting layer as matrix material (host material) for luminescent emitters and / or as electron transport material and / or as hole injection material and / or as hole blocking material in an optoelectronic component.

In one embodiment of the invention, the organic molecule of the type described herein is used in an emitting layer of an optoelectronic component, preferably in admixture with at least one further compound. It is preferred here that the organic molecule in the mixture represents the matrix material.

In a preferred embodiment of the invention, an organic molecule of the type described herein is used accordingly as a matrix material for luminescent emitters in an optoelectronic component.

An optoelectronic component according to the present invention is preferably selected from the group consisting of:

- organic light-emitting devices (OLEDs),

- light-emitting electrochemical cells,

- OLED sensors, in particular in non-hermetically shielded gas and vapor sensors,

- organic solar cells,

Organic field effect transistors,

- Organic lasers and

- Down conversion elements. Another aspect of the invention relates to mixtures containing at least one organic molecule of the type described herein and at least one luminescent emitter.

In a further aspect, the invention relates to formulations comprising at least one organic molecule of the type described herein or a mixture described herein and at least one solvent.

In one embodiment, the proportion of organic material as matrix material in optical light-emitting components, in particular in OLEDs, is between 50% and 99%.

In a further aspect, the invention relates to an optoelectronic device comprising an organic molecule of the type described herein. Here, an optoelectronic device according to the invention contains at least one anode to cathode layer comprising an organic molecule of the type described herein, for example as a luminescent emitter host material and / or as an electron transport material and / or as a hole injection material and / or as a hole blocking material. Here, the optoelectronic component may be selected from the group consisting of organic light-emitting component, organic diode, organic solar cell, organic transistor, organic light-emitting diode, light-emitting electrochemical cell, organic field effect transistor and organic laser.

In another aspect, the invention relates to a method of making an optoelectronic device using an organic molecule of the type described herein.

Part of such a process may be the application of an organic molecule of the invention to a carrier. The application can optionally be carried out by evaporation in vacuo or wet-chemical.

The methods customary for this purpose are known to the person skilled in the art and can readily be applied by him to optoelectronic components containing an organic molecule of the type described herein.

When used in optoelectronic components, the organic molecules according to the invention have in particular the following advantages over the prior art:

a. The charge carrier mobility in the component is improved in comparison to systems according to the prior art.

b. The efficiency of the components is higher compared to prior art systems.

c. The stability of the components is higher compared to systems according to the prior art. d. The life of the components is higher compared to systems according to the prior art.

The following examples illustrate the invention without restricting it.

Examples

Example 1: Inventive molecules

The following list shows all molecules with the crosslinkable group ethylene. It is known to the person skilled in the art how alternative crosslinkable groups PG can be introduced into a molecule, so that further molecules according to the invention result.

15







20

21



Example 2 Synthesis Sequence for the Synthesis of Molecules According to the Invention Using the Example of 2-N- (carbazolyl) 6-N- (3,6-divinylcarbazolyl) -pyridine (Molecule 1)

First substitution step:

Carbazole (10 mmol, 1, 00 equiv.) Is treated with sodium hydride (60% with paraffin, 500 mg, 13 mmol, 1.3 equiv.) And dissolved under nitrogen in portions with a total of 1 10 ml of dioxane. The rate of addition is adapted to the formation of hydrogen to avoid foaming. After complete addition, the reaction was held at r.t. for 15 min. stirred and then heated at reflux for 15 min. This formed a clear, yellow solution that fluoresces strongly under UV light (366 nm excitation). 2,6-Difluoropyridine (1.15 g, 10 mmol, 1.00 equiv.) Is added dropwise to the reaction mixture. The fluorescence attenuates considerably under UV light. The reaction mixture is heated to complete conversion of the starting materials (reaction control by HPLC, GC-MS or TLC, typically 4 h) at reflux. After cooling to room temperature, excess base is quenched by dropwise addition of 10 mL of water under nitrogen. The reaction mixture was added to 200 ml of saturated sodium chloride solution and the crude product was separated by suction and washed with water (300 ml) and methanol (60 ml). The resulting solid was digested with 200 mL of hot toluene and the insoluble residue discarded. The solvent was removed under reduced pressure and the product was washed with pentane (300 mL) and diethyl ether (200 mL) and dried in vacuo. The product was isolated as a beige solid and usually reacted further without further purification. Analytically pure product could be obtained by vacuum sublimation at 250 ° C., 0.002 mbar or by MPLC purification (mobile phase gradient cyclohexane-dichloromethane).

Second substitution step:

The synthesis was carried out analogously to the first step, but using instead of carbazole dibromocarbazole and instead of 2,6-difluoropyridine, the reaction product of the first substitution step and instead of a clear yellow solution prior to addition of the 2,6-difluoropyridine, a suspension was present.

2-N- (carbazoyl) -6-N- (3, 6-di-bromocarbazole) -pyridine (h6-2).

White powder (95%) - Due to insolubility in conventional NMR solvents, no evaluable NMR spectra could be recorded.- IR (ATR) 1650 (vw), 1571 (m), 1466 (vs), 1447 (vs), 1429 (m), 1375 (m), 1331 m, 1308 m, 1277 m, 1222 m, 1 183 w, 1 159 w, 1058 w, 1020 w , 867 (w), 825 (w), 809 (m), 794 (m), 741 (s), 720 (s), 660 (w), 634 (vw), 616 (vw), 563 (w) , 526 (w), 491 (w), 436 (w), 418 (m) cm ^-1 . - HRMS (FAB-MS, 3-NBA): C2 ₉ Hi ₇ N3 ⁷⁹ Br ₂ calc. 564.9784, et. 564.9733.

Coupling reaction for introducing the polymerizable units PG:

2-N-carbazolyl) -6-N- (3,6-dibromocaebazole) -pyridine (h6-2) (10 mmol, 1 equiv) was treated with Pd (PPh ₃ ) ₄ (5 mol% per Br) and Boron derivative KF ₃ BCH = CH ₂ (2 equiv per Br) was dissolved under argon (50 mL toluene / ethanol / KOH _aq = 3/3/1) and heated at reflux for 24 h. The reaction mixture was filtered through alumina (Brockman 1) and purified by MPLC (mobile phase gradient cyclohexane-dichloromethane).

2-N-carbazoyl) -6-N- (3,6-divinylcarbazoyl) -pyridine (molecule 1).

Beige solid (36%). ¹ H NMR (500 MHz, chloroform-c /) δ = 8.20-7.98 (m, 7H), 7.72-7.61 (m, 2H), 7.61-7.50 (m, 2H), 7.50-7.31 (m, 4H) , 6.94 (dd, J = 17.5, 10.9 Hz, 2H), 5.91 - 5.79 (m, 2H), 5.39 - 5.25 (m, 2H). ¹³ C NMR (126 MHz, chloroform-d) δ = 151.5, 140.7, 140.4, 139.6, 139.5, 137.0, 131.3, 126.4, 124.9, 124.6, 121.3, 120.2, 1 18.0, 1 14.9, 1 14.6 , 1 12.3, 1 12.2, 1 12.0, 100.0.

Example 3: Molecule 2

2-N- (carbazoyl) -6-N- (3, 6-di- (4-vinylphenyl) -carbazoyl) -pyridine (molecule 2)

The synthesis was carried out analogously to the synthesis of the molecule 1, except that (HO) 2BPhCH = CH _{2 was used} as the boron derivative. Beige solid (50%). ¹ H NMR (500 MHz, chloroform-c /) δ = 8.47-8.41 (m, 2H), 8.25-8.04 (m, 7H), 7.80-7.62 (m, 8H), 7.61-7.52 (m, 4H) , 7.47 (ddd, J = 8.5, 7.2, 1.3 Hz, 2H), 7.38 (td, J = 7.5, 1 .0 Hz, 2H), 6.82 (dd, J = 17.6, 10.9 Hz, 2H), 5.84 (dd , J = 17.5, 0.9 Hz, 2H), 5.31 (dd, J = 10.9, 0.9 Hz, 2H) ppm. ¹³ C NMR (126 MHz, chloroform-d) δ = 151.6, 151.41, 140.96, 139.49, 139.37, 136.51, 136.17, 134.37, 127.33, 127.0, 126.7, 126.7, 126.4, 125.8, 125.3, 124.6, 121.4, 120.2, 1 18.4, 1 14.6, 1 13.7, 1 12.5, 1 1 1.9 ppm. IR (ATR) 2922 (vw), 1730 (vw), 1625 (vw), 1570 (m), 1477 (m), 1439 (vs), 1375 (m), 1324 (m), 1220 (m), 1 186 (m), 1029 (w), 987 (vw), 902 (w), 841 (w), 794 (m), 747 (s), 721 (s), 668 (vw), 640 (vw) , 597 (vw), 560 (vw), 499 (vw), 420 (w) cm ^-1 . -HRMS (FAB-MS, 3-NBA, C4 ₅ H ₃ 2N ₃ ), 614.2591, 614.2593 ,

characters

Show it:

FIG. 1: By introducing two polymerizable groups which are conjugated via bridges such as carbazole, phenoxazine, phenothiazine and comparable annealed heterocycles, two possible growth positions for polymer chains are available in principle.

FIG. 2: Unsubstituted carbazoles are prone to a degradation path leading to the formation of 3,6-linked polymers. This is prevented by the introduction of substituents according to the invention.

FIG. 3: The introduction of the polymerizable units PG on one side of mirror-symmetrical compounds reduces the symmetry of these molecules, which increases the solubility and increases the suitability for printing and coating processes. By suppressing the crystallization, the film-forming properties are also improved.

Claims

claims

1 . An organic molecule comprising a structure of formula 1

Formula 1 with

Ar = independently of one another an unsaturated or aromatic carbo- or heterocyclic unit having 5 to 30 ring atoms, selected from the group consisting of naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, tetracene, pentacene, benzpyrene , Furan, benzofuran, isobenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo -7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine-imidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, isothiazole, 1,3-thiazole , Benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1, 2,3-triazole, 1, 2,4-triazole, benzotria zol, 1, 2,3-oxadiazole, 1, 2,4-oxadiazole, 1, 2,5-oxadiazole, 1, 3,4-oxadiazole, 1, 2,3-thiadiazole, 1, 2,4-thiadiazole, 1, 2,5-thiadiazole, 1, 3,4-thiadiazole, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,3-triazine, tetrazole, 1, 2,3,4- Oxatriazole, 1, 2,3,4-oxatriazole, 1, 2,4,5-tetrazine, 1, 2,3,4-tetrazine, 1, 2,3,5-tetrazine, purine, pteridine, indolizine, benzothiadiazole, Indenocarbazole, indenofluorene, spirobifluorene and indolocarbazole, which are each optionally substituted with one or more R1 groups, optionally two or more R1 groups being linked together and forming one or more rings;

D1 = a donor group having a structure of formula 1 a;

#

Formula 1a and

D2 = a donor group, having a structure of formula 1 b;

Formula 1 b wherein the linkage with Ar takes place in each case at the point marked # in the form of a single bond;

and where the symbols and indices used are:

n is an integer between 1 and 5;

o is an integer between 1 and 5;

peine integer between 0 and 5;

PG: one or more of the same or different polymerisable units which can be polymerized by thermal and / or acid or base catalyzed processes, UV irradiation in the presence or absence of a photoinitiator or by microwave radiation;

X, Y is the same or different on each occurrence, a covalent single bond or a bivalent organic bridge selected from the group consisting of substituted and unsubstituted alkylene (unbranched, branched or cyclic), alkenylene, alkynylene, arylene and heteroarylene groups, O, NR ³ , C = CR ³ ₂ , C = NR ³ , SiR ³ ₂ S, S (O), S (O) ₂ , Se, Se (O), Se (O) ₂ , BR ³ , PR ³ , P (0) R ³ , whereby combinations of these units are also possible;

Z is the same or different CR ² or N at each occurrence;

C (= O) R ³ , CR ³ = C (R ³ ) ₂ , CN, C (= O) OR ³ , C (= O) N (R ³ ) ₂ , Si (R ³ ) ₃ , NO ₂ , P (= O) (R ³ ) ₂ , OSO ₂ R ³ , OR ³ , S (= O) R ³ , S (= O) ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C Atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups are each substituted by one or more radicals R ³ and where one or more CH ₂ groups in the abovementioned groups are represented by -R ³ C =CR ³ -, -C CC-, Si (R ³ ) ₂ , C =O, C =S, C =NR ³ , -C (= O) O-, -C (= O) NR ³ -, NR ³ , P (= O) (R ³ ), -O-, -S-, SO or S0 ₂ may be replaced and wherein a or more H atoms in the abovementioned groups may be replaced by D, F, Cl, Br, I, CN or N0 ₂ , or an aromatic ring system having from 6 to 30 aromatic

Ring atoms which may each be substituted by one or more radicals R ³ , or an aryloxy group having 6 to 30 aromatic ring atoms which are replaced by one or more radicals R ³ may be substituted, wherein two or more radicals R and R ^{1 may} be linked together and form a ring;

R ² is identical or different on each occurrence H, D, F, Cl, Br, I, B (OR ³ ) ₂ > CHO, C (= O) R ³ , CR ³ = C (R ³ ) ₂ , CN, C (= O) OR ³ , C (= O) N (R ³ ) ₂₎ Si (R ³ ) ₃ , N (R ³ ) ₂ , NO ₂ , P (= O) (R ³ ) ₂ , OSO ₂ R ³ , OR ³ , S (= O) R ³ , S (= O) ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the abovementioned groups can each be substituted by one or more radicals R ³ and where one or more CH ₂ groups in the above groups by -R ³ C = CR ³ -, -C C-, Si (R ³ ) ₂ , C = 0, C = S, C = NR ³ , -C (= 0) 0-, -C (= 0) NR ³ -, NR ³ , P (= 0) (R ³ ), -O-, -S-, SO or S0 ₂ may be replaced and wherein one or more H atoms in the above groups by D, F, Cl, Br, I, CN or N0 ₂ may be replaced, or an aromatic or heteroaromatic ring system having 5 to 30 aroma table ring atoms, each of which may be substituted by one or more radicals R ³ , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ³ , wherein two or more radicals R ² linked together can be and form a ring;

R ³ is the same or different at each occurrence H, D, F, Cl, Br, I, B (OR ⁴ ) ₂ , CHO, C (= O) R ⁴ , CR ⁴ = C (R ⁴ ) ₂ , CN, C (= O) OR ⁴ , C (= O) N (R ⁴ ) ₂ , Si (R ⁴ ) ₃ , N (R ⁴ ) ₂ , NO ₂ , P (= O) (R ⁴ ) ₂ , OSO ₂ R ⁴ , OR ⁴ , S (= O) R ⁴ , S (= O) ₂ R ⁴ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or Thioalkyl group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein the above-mentioned groups may each be substituted by one or more radicals R ⁴ and wherein one or more CH ₂ groups in the above groups represented by -R ⁴ C =CR ⁴ -, -C =C-, Si (R ⁴ ) ₂ , C =O, C =S, C =Se, C =NR ⁴ , -C (= O) O- , -C (= O) NR ⁴ -, NR ⁴ , P (= O) (R ⁴ ), -O-, -S-, SO or S0 ₂ may be replaced and wherein one or more H atoms in the above be replaced by D, F, Cl, Br, I, CN or N0 ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁴ , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ⁴ , wherein two or more radicals R ³ linked together can be and form a ring;

R ⁴ is the same or different H, D, F or an aliphatic at each occurrence,

aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which also one or more H atoms may be replaced by D or F; It can have two or more

Substituents R ⁴ be linked together and form a ring;

2. Organic molecule according to claim 1, wherein Ar has the following structure

W

W'W

I II

w. _w , w

Formula 2 wherein W is the same or different CR ¹ or N at each occurrence, and at least one W is other than CR ¹

With

R ¹ is the same or different at each occurrence H, D, F, Cl, Br, I, B (OR ³ ) ₂ , CHO, C (= O) R ³ , CR ³ = C (R ³ ) ₂ , CN, C (= O) OR ³ , C (= O) N (R ³ ) ₂ , Si (R ³ ) ₃ , NO ₂ , P (= O) (R ³ ) ₂ , OSO ₂ R ³ , OR ³ , S (= 0) R ³ , S (= O) ₂ R ³ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C Atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, where the abovementioned groups may each be substituted by one or more radicals R ³ and wherein one or more CH ₂ - groups in the abovementioned groups by -R ³ C = CR ³ -, -C = C-, Si (R ³ ) ₂ , C = O, C = S, C = NR ³ , - C (= O) O-, -C (= O) NR ³ -, NR ³ , P (= O) (R ³ ), -O-, -S-, SO or S0 ₂ may be replaced and where one or more H atoms in the abovementioned groups by D, F, Cl, Br, I, CN or N0 ₂ may be replaced, or an aromatic ring system having 6 to 30 aromatic ring atoms, each by one or more radicals R ³ may be substituted, or an aryloxy group having 6 to 30 aromatic ring atoms which may be substituted by one or more radicals R ³ , wherein two or more radicals R and R ^{1 may} be linked together and form a ring ;

R ³ is the same or different at each occurrence H, D, F, Cl, Br, I, B (OR ⁴ ) ₂ , CHO, C (= O) R ⁴ , CR ⁴ = C (R ⁴ ) ₂ , CN, C (= O) OR ⁴ , C (= O) N (R ⁴ ) ₂ , Si (R ⁴ ) ₃ , N (R ⁴ ) ₂ , NO ₂ , P (= O) (R ⁴ ) ₂ , OSO ₂ R ⁴ , OR ⁴ , S (= O) R ⁴ , S (= O) ₂ R ⁴ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or Thioalkyl group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein the above-mentioned groups may each be substituted by one or more radicals R ⁴ and wherein one or more CH ₂ groups in the above groups represented by -R ⁴ C =CR ⁴ -, -C =C-, Si (R ⁴ ) ₂ , C =O, C =S, C =Se, C =NR ⁴ , -C (= O) O- , -C (= O) NR ⁴ -, NR ⁴ , P (= O) (R ⁴ ), -O-, -S-, SO or S0 ₂ may be replaced and wherein one or more H atoms in the above be replaced by D, F, Cl, Br, I, CN or N0 ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁴ , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, the may be substituted by one or more radicals R ⁴ , where two or more radicals R ^{3 may} be linked together and form a ring;

R ⁴ is identical or different at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which also one or more H atoms may be replaced by D or F; In this case, two or more substituents R ^{4 may} be linked together and form a ring.

3. An organic molecule according to claim 1 or 2, wherein (Ar) _{n is} selected from the group consisting of:

where * represents the attachment positions to D1 and D2, respectively, and the indicated moieties and moieties are as defined in claim 1 or 2.

4. Organic molecule according to claim 1 to 3, wherein the crosslinkable group PG

is selected from the group consisting of:

5. A process for preparing an organic molecule according to claim 1 to 4, comprising the following step:

Carrying out a reaction of a donor group D2 with a bis-fluorinated Ar and subsequent reaction with a bis-brominated donor group D1 and subsequent introduction of a PG unit,

in which

Ar = an aromatic or heteroaromatic ring system having 5 to 30 ring atoms selected from the group consisting of naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, thiophene, Benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, Phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine imidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, isothiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, Benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1, 2,3-triazole, 1, 2,4-triazole, benzotriazole, 1, 2,3-oxadiazole, 1, 2,4-oxadiazole, 1 , 2,5-oxadiazole, 1, 3,4-oxadiazole, 1, 2,3-thiadiazole, 1, 2,4-thiadiazole, 1, 2,5-thiadiazole, 1, 3,4-thiadiazole, 1, 3, 5-triazine, 1, 2,4-triazine, 1, 2,3-triazine, tetrazole, 1, 2,3,4-oxatriazole, 1, 2,3,4-oxatriazole, 1, 2,4,5- Tetrazine, 1, 2,3,4-tetrazine, 1, 2,3,5-tetrazine, purine, pteridine, indolizine, benzothiadiazole, indenocarbazole, indenofluorene, spirobifluorene and indolocarbazole, which are each optionally substituted by one or more R1 radicals, optionally two or more radicals R1 are linked together and form one or more rings;

D1 = a donor group having a structure of formula 1 a;

#

Formula 1a

D2 = a donor group, having a structure of formula 1 b; ^:; Formula 1 b

wherein the linkage with Ar takes place in each case at the point marked # in the form of a single bond;

and wherein the other symbols have the meanings given in claims 1 to 3.

6. The method of claim 5, wherein the reaction is carried out with the addition of a strong base.

7. The method of claim 5 or 6, further comprising the step of adding an oxidizing agent independently selected from the group consisting of hydrogen peroxide, hydrogen peroxide-urea adduct, oxygen or ozone and optionally further comprising the further step of adding selenium or sulfur or Lawesson's reagent.

8. Use of an organic molecule according to claim 1 to 4 in an optoelectronic component.

9. Use according to claim 8, wherein the organic molecule in an emitting layer, preferably as matrix material, in particular for luminescent emitters and / or as electron transport material and / or as hole injection material and / or as hole blocking material in an optoelectronic component.

10. Use according to claim 8 or 9, wherein the optoelectronic component is selected from the group consisting of:

- organic light-emitting devices (OLEDs),

- light-emitting electrochemical cells,

- organic solar cells,

Organic field effect transistors,

- Organic lasers and

- Down conversion elements.

1 1. An optoelectronic component, comprising an organic molecule according to claim 1 to 4.

12. The optoelectronic component according to claim 11, characterized in that the organic molecule is used in an emitting layer, preferably as matrix material, in particular for luminescent emitters and / or electron transport material and / or as hole injection material and / or as hole blocking material.

13. Mixture containing at least one organic molecule according to claim 1 to 4 and at least one luminescent emitter.

14. A formulation comprising at least one organic molecule according to claim 1 to 4 or a mixture according to claim 13 and at least one solvent.

15. A method for producing an optoelectronic component, wherein an organic molecule according to claim 1 to 4 is used.

16. The method according to claim 15, characterized by the application of an organic molecule according to claim 1 to 4 on a support.

17. The method according to claim 16, characterized in that the application takes place wet-chemically.

18. The method according to claim 16, characterized in that the application takes place by evaporation in a vacuum.