EP3928360A1

EP3928360A1 - Composition for organic electronic devices

Info

Publication number: EP3928360A1
Application number: EP19827743.6A
Authority: EP
Inventors: Amir Parham; Jonas Kroeber; Jens ENGELHART; Christian Ehrenreich; Christian EICKHOFF
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2019-02-18
Filing date: 2019-12-20
Publication date: 2021-12-29
Also published as: WO2020169241A1; JP2022520284A; CN113424332A; US20230080974A1; TW202043218A; KR20210132673A

Abstract

The invention relates to a composition comprising an electron-transporting host and a hole-transporting host, to the use thereof in electronic devices and electronic devices containing said composition. The electron-transporting host is most preferably selected from the class of triazine dibenzofuran carbazole systems or the class of triazine dibenzothiophene carbazol systems. The hole-transporting host is preferably selected from the class of biscarbazoles.

Description

Composition for organic electronic devices

The present invention relates to a composition which comprises an electron-transporting host and a hole-transporting host, their use in electronic devices and electronic devices containing this composition. The electron-transporting host is particularly preferably selected from the class of the triazine-dibenzofuran-carbazole systems or the class of the triazine-dibenzothiophene-carbazole systems. The hole-transporting host is preferably selected from the class of the biscarbazoles.

The structure of organic electroluminescent devices (e.g. OLEDs - organic light emitting diodes or OLECs - organic light emitting electro-chemical cells), in which organic semiconductors are used as functional materials, has been known for a long time. In addition to fluorescent emitters, more and more emitting materials are used

organometallic complexes used, the phosphorescence instead

Show fluorescence. For quantum mechanical reasons is under

Using organometallic compounds as phosphorescence emitters, an up to fourfold increase in energy and power efficiency is possible. In general, with OLEDs, in particular also with OLEDs, the

Show triplet emission (phosphorescence), however, still

Need for improvement, for example with regard to efficiency,

Operating voltage and service life.

The properties of organic electroluminescent devices are not only determined by the emitters used. In particular, the other materials used, such as host and matrix materials, hole blocking materials, electron transport materials, hole transport materials and electron or exciton blocking materials are of particular importance here, and of these in particular the host or matrix materials. Improvements in these materials can lead to significant improvements in electroluminescent devices.

Host materials for use in organic electronic

Devices are well known to those skilled in the art. In the prior art, the term matrix material is also often used when a host material for phosphorescent emitters is meant. This use of the term also applies to the present invention. Meanwhile, a variety of host materials have been used for both fluorescent and

phosphorescent electronic devices developed.

Another possibility of improving the performance data of electronic devices, in particular of organic electroluminescent devices, consists in using combinations of two or more materials, in particular host materials or matrix materials.

No. 6,392,250 B1 discloses the use of a mixture consisting of an electron transport material, a hole transport material and a fluorescent emitter in the emission layer of an OLED. With the help of this mixture, the service life of the OLED could be improved compared to the prior art.

No. 6,803,720 B1 discloses the use of a mixture containing a phosphorescent emitter and also a hole and an electron transport material in the emission layer of an OLED. Both the hole and electron transport materials are small organic molecules.

According to WO 2015/169412, for example, triazine-dibenzofuran-carbazole derivatives and triazine-dibenzothiophene-carbazole derivatives can also be used in a mixture. According to the description, the carbazole derivative is not bound to the dibenzofuran or dibenzothiophene base via the N atom of the carbazole. So will For example, the production of the OLED with identification E34 is described, which contains the host materials EG1, IC6 and the phosphorescent emitter TEG1 in the light-emitting layer. The structures of the compounds used are listed below:

According to WO 2015/165563, for example, triazine-dibenzofuran-carbazole derivatives and triazine-dibenzothiophene-carbazole derivatives can also be used in a mixture. Carbazole derivatives also include compounds such as indenocarbazole and indolocarbazole. The connection of the carbazole derivative to the dibenzofuran or

Dibenzothiophene basic body takes place according to the description via the N atom of the carbazole at position 8 of the dibenzofuran / dibenzothiophene. The triazine substituent is in the 4-position of the directly or via a linker

Dibenzofuran / dibenzothiophene bound. For example, the production of the OLED with the E9 label is described, the host materials EG9, IC3 and the host materials in the light-emitting layer

Contains phosphorescent emitter TEG1. The structures of the

The compounds EG9 and IC3 used are listed below:

According to WO 2015/014435, triazine-dibenzofuran-carbazole derivatives, for example, triazine-dibenzothiophene-carbazole derivatives can be used as host material in a light-emitting layer.

In CN 107973786, triazine-dibenzofuran-carbazole and triazine-dibenzothiophene-carbazole compounds are also described. Of the

Triazine substituent is directly or via a linker in the 1 position

Dibenzofurans / Dibenzothiophens bound. The carbazole derivative is bound directly or via a linker in the 6-position of the dibenzofuran / dibenzothiophene. It is further reported that these materials can be mixed with a biscarbazole H2 in a ratio of 10:90 to 90:10. KR20160046077 describes special triazine-dibenzofuran-carbazole and triazine-dibenzothiophene-carbazole derivatives in a light-emitting layer together with a further host material.

US20160293853 describes special dibenzofuran derivatives that can be used in combination with other host materials.

US9771373 describes an organic light-emitting device with a light-emitting layer containing two host materials, the host materials each being made up of special groups of

Connections are selected.

In WO 2016/015810 triazine-dibenzofuran-carbazole and triazine-dibenzothiophene-carbazole compounds are described, the

Triazine substituent directly or via a linker in the 1 position

Dibenzofurans / Dibenzothiophens is bound, and where the

Carbazole substituent via its N atom in the 8-position of the

Dibenzofurans / Dibenzothiophens is bound. The mentioned According to the description, compounds can be used in a mixture with another matrix material.

KR2018010149 describes similar compounds as in WO

2016/015810.

The disclosures WO 2018/174678 and WO 2018/174679 disclose devices containing a mixture of carbazole-dibenzofuran derivatives with biscarbazoles in an organic layer, the

Linking of the carbazole unit to the dibenzofuran structure is possible at any position of the dibenzofuran, but is preferably in the 6- or 7-position.

The disclosure EP3415512 describes, among other things

Dibenzofuran derivatives of the formula 1 -1, where a phenyl, pyridine,

Pyrimidine or triazine substituent can be attached directly or via a linker in position 1 of the dibenzofuran and at least two identical substituents L2-Ar3 must be attached in the 6- and 8-position of the dibenzofuran. Ar3 can be a carbazole bonded via N. In the examples, such compounds are used in combination with a specific biscarbazole.

However, when using these materials or when

Use of mixtures of materials still needs improvement, especially with regard to efficiency, operating voltage and / or

Life span of the organic electronic device.

The object of the present invention is therefore to provide materials which are suitable for use in an organic

electronic devices, especially in an organic

Electroluminescent devices, and in particular in one

Phosphorescent OLED are suitable and have good device properties, in particular with regard to improved current efficiency, improved Operating voltage and / or improved service life, lead, as well as the provision of the corresponding electronic device.

It has now been found that compositions containing compounds of the formula (1) and a hole-transporting host of the formula (2), or organic electronic devices that contain the

Contain composition, solve this problem and eliminate the disadvantages of the prior art. Such compositions lead to very good properties of organic electronic devices, in particular organic electroluminescent devices, in particular with regard to current efficiency, operating voltage and / or service life and in particular also in the presence of a light-emitting device

Component in the emission layer, in particular in combination with emitters of the formula (3), at concentrations between 2 and 25% by weight. The devices according to the invention show, in particular, very good current efficiency.

A first aspect of the present invention is therefore one

Composition comprising at least one compound of the formula (1) and at least one compound of the formula (2),

The following applies to the symbols and indices used:

Xi is on each occurrence, identically or differently, CR ° or N, with the proviso that at least one group Xi stands for N;

X is on each occurrence, identically or differently, C or N, where two adjacent X can be bonded to a ring system of the formula A,

, where * means the binding point to an X at each occurrence,

Y ¹ is selected from NAr-i, C (R ^* ) 2, 0 or S;

Y is selected from 0 or S;

L is, identically or differently, a simple at each occurrence

bond or an aromatic ring system with 6 to 30

aromatic ring atoms which can be substituted by one or more radicals R ⁵ ;

n and m are independently 0, 1, 2 or 3 on each occurrence,

o, p and q are independently 0, 1, 2, 3 or 4 on each occurrence;

An is on each occurrence, independently of one another, an aryl or heteroaryl group with 5 to 40 aromatic ring atoms which can be substituted by one or more radicals R ³ ;

RA is H, -I_3-Ar4, or -Li-N (Ar) 2;

RB is Ar3 or -l_2-N (Ar) 2; Li _, l_ _2, are identical or different on each occurrence

Single bond or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which can be substituted by one or more radicals R ³ ;

| _3 is a single bond or an aromatic or

heteroaromatic ring system with 5 to 30 aromatic

Ring atoms which can be substituted by one or more radicals R ³ , where a substituent R ³ can form a ring with a substituent R ² on the carbazole;

Ar3 is an aromatic ring system with 6 to 40 aromatic rings

Ring atoms or a heteroaromatic ring system with 10 to 40 aromatic ring atoms which can be substituted with one or more radicals R ³ ;

Ar4 is on each occurrence, identically or differently, an unsubstituted or substituted 9-aryl-carbazolyl or unsubstituted or substituted carbazol-9-yl, which can be substituted by one or more radicals R ⁴ and where, independently of one another, one or more radicals in each case ⁴ or a radical R ⁴ together with a radical R ^{2 can form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring, where aryl denotes an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms which can be substituted by R ³ ;

R * is on each occurrence, identically or differently, a straight-chain alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to

12 carbon atoms, where two substituents R * can together form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more substituents R ⁵ ;

R °, R, R ¹ 'R ² are identical or different on each occurrence

selected from the group consisting of H, D, F, CI, Br, I, CN, N0 ₂ , N (Ar) ₂ , N (R ³ ) ₂ , C (= 0) Ar, C (= 0) R ³ , P (= 0) (Ar) ₂ , P (Ar) ₂ , B (Ar) ₂ , Si (Ar) 3, Si (R ³ ) 3, a straight chain alkyl, alkoxy or

Thioalkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 carbon atoms or an alkenyl group with 2 to 20 carbon atoms, each of which can be substituted by one or more radicals R ³ , where one or more non-adjacent CF groups are represented by R ³ C = CR ³ , Si (R ³ ) ₂ , C = 0, C = S, C = NR ³ , P (= 0) (R ³ ), SO , S0 ₂ , NR ³ , O, S or CONR ³ can be replaced and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or N0 ₂ , an aromatic or heteroaromatic ring system with 5 to

40 aromatic ring atoms, each of which can be substituted with one or more radicals R ³ , an aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms which can be substituted with one or more radicals R ³ , or an aralkyl or heteroaralkyl group with 5 to 40 aromatic ring atoms which can be substituted by one or more radicals R ³ ; optionally two substituents R ° and / or R and / or R ¹ and / or R ² which are bonded to the same carbon atom or to adjacent carbon atoms can be monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic

Form ring system which can be substituted with one or more radicals R ³ ;

R ³ is selected identically or differently on each occurrence from the group consisting of H, D, F, CN, N (Ar) ₂ , an aliphatic hydrocarbon radical with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms in which one or more Fl atoms can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; this can be two or more adjacent

R ³ substituents form a mono- or polycyclic, aliphatic ring system with one another; R ⁴ is selected identically or differently on each occurrence from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, in which a or several Fl atoms through D, F, CI, Br,

I, a straight or branched alkyl group with 1 to 4

Carbon atoms or CN can be replaced; two or more adjacent substituents R ^{4 here} can form a mono- or polycyclic ring system with one another;

R ⁵ is selected identically or differently on each occurrence from the group consisting of D, F, CN and an aryl group with 6 to 18 carbon atoms, two or more adjacent substituents R ⁵ can be a mono- or polycyclic, aliphatic Form ring system;

Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which can be substituted by one or more non-aromatic radicals R ³ ; two radicals Ar, which bond to the same N atom, P atom or B atom, can also be formed by a single bond or a bridge selected from N (R ³ ), C (R ³ ) ₂ , O or S, with one another be bridged and

r is independently 0, 1, 2 or 3 on each occurrence;

s means 0, 1, 2, 3 or 4 independently of one another on each occurrence.

Other objects of the invention include specific ones

Material combinations, formulations, such

Compositions contain that use this

Compositions in an organic electronic device, organic electronic devices preferred

Electroluminescent devices incorporating such compositions contain, and thereby preferably contain the composition in one layer, as well as methods for producing such devices. The corresponding preferred embodiments, as described below, are also the subject of the present invention. The surprising and beneficial effects are due to specific

Selection of known materials achieved, in particular as regards the selection of the compounds of formula (1).

The layer comprising the composition comprising at least one

Compound of the formula (1) and at least one compound of the formula (2), as described above or preferably described below, is in particular a light-emitting layer (EML), an electron transport layer (ETL), an electron injection layer (EIL) and / or a hole blocking layer (HBL).

If it is a light-emitting layer, then it is preferably a phosphorescent layer, which is characterized in that, in addition to the composition, it comprises the

Matrix materials of formula (1) and formula (2), as described above, contains a phosphorescent emitter.

Adjacent carbon atoms in the context of the present invention are carbon atoms that are directly linked to one another. Under the wording that two or more radicals unite with one another

Can form ring, is to be understood in the context of the present description, inter alia, that the two radicals are linked to one another by a chemical bond with formal elimination of two hydrogen atoms. This is illustrated by the following scheme. However, the above formulation should also include

be understood that in the event that one of the two residues

Represents hydrogen, the second radical bonds to the position to which the hydrogen atom was attached to form a ring. This should be made clear by the following scheme:

For the purposes of this invention, an aryl group contains 6 to 40 aromatic ring atoms, preferably carbon atoms. For the purposes of this invention, a fleteroaryl group contains 5 to 40 aromatic ring atoms, the ring atoms comprising C atoms and at least one fletero atom, with the proviso that the sum of C atoms and fletero atoms is at least 5. The fleteroatoms are preferably selected from N, O and / or S. An aryl group or fleteroaryl group is either a simple aromatic cycle, that is phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene , or a condensed aryl or fleteroaryl group, for example derived from naphthalene, anthracene, phenanthrene,

Quinoline or isoquinoline, understood. An aryl group with 6 to 18 carbon atoms is therefore preferably phenyl, naphthyl, phenanthryl or

Triphenylenyl, whereby the attachment of the aryl group as a substituent is not restricted. An arylene group with 6 to 18 carbon atoms is therefore preferably phenylene, naphthylene, phenanthrylene or triphenylenylene, the arylene group not being linked as a linker

is restricted. An aromatic ring system for the purposes of this invention contains 6 to 40 carbon atoms in the ring system and can be substituted by one or more radicals R ³ , where R ^{3 has} a meaning described below. An aromatic ring system also contains aryl groups as previously described.

An aromatic ring system with 6 to 18 carbon atoms is preferably composed of phenylene, biphenylene, naphthylene, phenanthrenylene and

Triphenylenylene selected, it being possible for the particular aromatic ring system to be substituted by one or more radicals R ⁵ .

A heteroaromatic ring system for the purposes of this invention contains 5 to 40 ring atoms and at least one heteroatom and can be substituted by one or more radicals R ³ , R ^{3 being} one below

has the meaning described. A preferred heteroaromatic

Ring system has 10 to 40 ring atoms and at least one heteroatom and can be substituted by one or more radicals R ³ , where R ^{3 has} a meaning described below. A heteroaromatic one

Ring system also contains heteroaryl groups as previously described. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O and / or S.

An aromatic or heteroaromatic ring system in the context of this invention is understood to mean a system which does not necessarily contain only aryl or heteroaryl groups, but also in which several aryl or heteroaryl groups are formed by a non-aromatic unit

(preferably less than 10% of the atoms other than H), e.g. B. a C, N or O atom or a carbonyl group, can be interrupted. For example, systems such as 9,9‘-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. should also be used as aromatic or

heteroaromatic ring systems are understood in the context of this invention, and also systems in which two or more aryl groups, for example by a linear or cyclic alkyl group or by a silyl group are interrupted. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as. B. biphenyl, terphenyl, quaterphenyl or bipyridine, also included in the definition of the aromatic or heteroaromatic ring system.

Under an aromatic or heteroaromatic ring system with 5 - 40 aromatic ring atoms, which each with the mentioned

R ³ can be substituted and which can be linked via any positions on the aromatic or heteroaromatic, examples are understood as groups that are derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, Benzfluoranthene, naphthacene, pentacene, benzpyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cisenzoindenofluorene, truenzoindenofluorene, or trans-dibenzoindenofluorene , Isotruxes, spirotruxes, spiroisotruxes, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, benzo-5-cridine, isoquinidine, quinanthridine, benzo-5-cridine, isoquinidine, quinonehridine , 6-quinoline, benzo-6,7-quinoline, benzo-

7.8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole,

Benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole,

Anthroxazole, phenanthroxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline,

1,5-diazaanthracene, 2,7-diazapyren, 2,3-diazapyren, 1,6-diazapyren,

1.8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, 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, 2,4,5-tetrazine, 1, 2, 3, 4- tetrazine, 1, 2,3,5- Tetrazine, purine, pteridine, indolizine and benzothiadiazole.

The abbreviation Ar is, identically or differently, an aromatic or heteroaromatic ring system with 5 to 30 on each occurrence

aromatic ring atoms that do not have one or more

aromatic radicals R ³ can be substituted; two radicals Ar, which bond to the same N atom, P atom or B atom, can also be formed by a single bond or a bridge selected from N (R ³ ), C (R ³ ) 2, O or S, with one another be bridged. The substituent R ³ has been described above or is preferably described below.

Under a cyclic alkyl, alkoxy or thioalkyl group in the context of this invention is a monocyclic, a bicyclic or a

polycyclic group understood.

In the context of the present invention, a C1 to C20 alkyl group in which individual H atoms or Chh groups can also be substituted by the groups mentioned above, for example the radicals methyl, ethyl, n-propyl, i-propyl, Cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1 -methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1 - Methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo [2.2.2] octyl, 2-bicyclo [2.2.2] octyl, 2- (2,6-dimethyl) octyl, 3- ( 3,7-dimethyl) octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1 -yl-, 1,1-dimethyl-n-hept-1 -yl-, 1,1-dimethyl-n-oct-1 -yl-, 1,1-dimethyl-n-dec-1 -yl-, 1,1-dimethyl-n-dodec-1 -yl-, 1 , 1 - dimethyl-n-tetradec-1 -yl-, 1, 1-dimethyl-n-hexadec-1 -yl-, 1, 1 -dimet hyl-n-octadec-1 -yl-, 1,1-diethyl-n-hex-1 -yl-, 1,1-diethyl-n-hept-1 -yl-, 1,1-diethyl-n-oct -1 -yl-, 1, 1 -Diethyl-n-dec-1 -yl-, 1, 1 -Diethyl-n-dodec-1 -yl-, 1, 1 -Diethyl-n-tetradec-1 -yl- , 1, 1-diethyln-n-hexadec-1 -yl-, 1, 1-diethyl-n-octadec-1 -yl-, 1 - (n-propyl) -cyclohex-l -yl-, 1 - (n-butyl) -cyclohex-l -yl-, 1 - (n-hexyl) -cyclohex- 1 -yl-, 1- (n-octyl) -cyclohex-1 -yl- and 1 - (n-decyl) -cyclohex-1 -yl- understood.

An alkenyl group includes, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl,

Cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl understood.

An alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

A C1 to C2o alkoxy group is understood as meaning, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy. A Ci- to C20-thioalkyl group includes, for example, S-

Understood alkyl groups, for example thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propoyl, 1-thio-i-butyl, 1-thio-n-butyl or 1-thio-t-butyl.

An aryloxy or heteroaryloxy group with 5 to 40 aromatic

Ring atoms means O-aryl or O-heteroaryl and means that the aryl or heteroaryl group is bonded via an oxygen atom.

An aralkyl or heteroaralkyl group having 5 to 40 aromatic

Ring atoms means that an alkyl group, as described above, is substituted with an aryl group or heteroaryl group.

A phosphorescent emitter within the meaning of the present invention is a compound which shows luminescence from an excited state with a higher spin multiplicity, that is to say a spin state> 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides are intended be regarded as phosphorescent emitters. A more precise definition is given below.

If the composition comprises at least one compound of the formula (1), as described above or as preferred below

described, and at least one compound of the formula (2), as described above or described below, is used as matrix material for a phosphorescent emitter, it is preferred if its triplet energy is not significantly smaller than the triplet energy of the phosphorescent emitter. For the triplet level Ti (emitter) - Ti (matrix) <0.2 eV, particularly preferably <0.15 eV, very particularly preferably <0.1 eV applies. Ti (matrix) is the triplet level of the matrix material in the emission layer, this condition applying to each of the two matrix materials, and T-i (emitter) is the triplet level of the phosphorescent emitter. If the emission layer contains more than two matrix materials, the above-mentioned relationship preferably also applies to any further matrix material.

Compounds of the formula (1) and their preferred embodiments are described below, which are used in the invention

Composition and / or device are contained, for example as electron-transporting floes.

The composition of the invention contains at least one

Compound of formula (1) as previously described.

In compounds of formula (1), Y is selected from O or S.

In a preferred embodiment of the invention, compounds of the formula (1) in which Y is O are selected.

In a preferred embodiment of the invention, compounds of the formula (1) in which Y is S are selected. In compounds of the formula (1) the symbol Xi stands at least once for N, preferably twice for N and once for CR ° or three times for N. The substituent

therefore has the following meanings, where * denotes the point of attachment with the dibenzofuran or dibenzothiophene and R ° and Ar ^{1 have} one of the meaning given above or a preferred meaning given:

R ° is on each occurrence, identically or differently, preferably selected from the group consisting of H, D, F or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms. R ° is particularly preferably H.

Compounds of the formula (1) in which Xi denotes N on each occurrence are represented by the formula (1 a),

where Y, X, L, An, R, R ¹ , n, m, o and p have a meaning given above or have a meaning given below.

At least one compound of the formula (1 a) is particularly preferably selected for the composition, with substituents which are described above, preferably described or preferably described below.

Another object of the invention is accordingly a

Composition as described above, where the compound of the formula (1) corresponds to the compound of the formula (1 a), preferably when the symbol Y corresponds to 0.

Another object of the invention is accordingly a

Composition as described above, wherein the compound of formula (1) corresponds to the compound of formula (1 a), preferably when the symbol Y corresponds to S.

If in compounds of the formulas (1) or (1 a) or in compounds of the formulas (1) or (1 a) described with preference n or m is greater than 0, the substituent R is preferably selected identically or differently on each occurrence from the Group consisting of D, F, one

An alkyl group with 1 to 40 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms. The heteroaromatic ring system with 5 to 40 aromatic ring atoms is in this case preferably derived from dibenzofuran or for R

Dibenzothiophene. The aromatic ring system with 6 to 40 aromatic ring atoms is in this case for R preferably phenyl, biphenyl or terphenyl, particularly preferably phenyl or [1, 1 ', 2', 1 "] -terphenyl-5'-yl.

In this case, the alkyl group with 1 to 40 carbon atoms for R is preferably a linear or branched alkyl group with 1 to 4 carbon atoms, particularly preferably methyl, ethyl, n-propyl or n-butyl, very particularly preferably methyl.

In compounds of the formulas (1) or (1 a), n and m are preferably 0.

In compounds of the formulas (1) or (1 a) or preferred compounds of the formulas (1) or (1 a), the symbol X preferably stands eight times for C and is correspondingly substituted by R ¹ or the symbol X preferably stands six times for C and is correspondingly substituted by R ¹ and the

remaining two symbols X correspond to formula A.

Preferred compounds of the formulas (1) or (1 a) in which n and m denote 0 and the symbols X have a meaning, as preferably described above, are accordingly compounds of the formulas (1 b), (1 c), (1 d),

(1 e), (1 f), (1 g) and (1 h),

Formula (1 b) Formula (1 c) where Y, Y ¹ , L, An and R ^{1 have} a meaning given above or have a meaning given below.

In compounds of the formulas (1), (1 a) to (1 h) or preferably

The compounds of the formulas (1), (1 a) to (1 h) described, the substituents R ¹ are preferably selected independently of one another from group H, D or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which can in each case be substituted by one or more radicals R ³ , where R ^{3 has} a meaning given above or below and where two substituents R ^{1 are} adjacent carbon atoms form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R ³ . In one embodiment of the invention, the substituents R ^{1 are} in

Compounds of the formulas (1), (1a) and (1b) or preferably described compounds of the formulas (1), (1 a) and (1 b), each independently

preferably selected from one another from the group H, D or an aromatic ring system with 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ , where R ^{3 has} a meaning given above or below. In this embodiment, there are preferably six or seven substituents R ¹ Fl and the remaining substituents have a meaning as indicated above and are not equal to Fl. In this embodiment, the carbazole in the compounds of the formulas (1), (1a) and (1b) preferably bears a substituent R ¹ that is different from Fl and one

aromatic ring system with 5 to 40 aromatic ring atoms

corresponds. In one embodiment of the invention, the substituents R ^{1 are} in

Compounds of the formulas (1), (1a) and (1b) or preferably described compounds of the formulas (1), (1a) and (1b) each independently

preferably selected from one another from the group F1, D or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which can be substituted by one or more radicals R ³ , where R ^{3 is} one given above or given below

Has meaning. In this embodiment, seven are preferred Substituents R ¹ H and the remaining substituent has a meaning as stated above and is not equal to H. In this embodiment, the carbazole in the compounds of the formulas (1), (1 a) and (1 b) preferably bears a substituent R ¹ , which is different from H and corresponds to a heteroaromatic ring system with 5 to 40 aromatic ring atoms.

In compounds of the formulas (1), (1 a) to (1 h) or preferably

compounds described by formulas (1), (1 a) (h 1) to the substituents R ¹ are each independently preferably selected from the group Fl or unsubstituted or mono- or polysubstituted by R ³ substituted phenyl, 1, 2-biphenyl , 1,3-biphenyl, 1,4-biphenyl, triphenylenyl, 1-naphthyl, 2-naphthyl, carbazol-9-yl or 9-aryl-carbazolyl, where aryl is an aromatic or heteroaromatic

Ring system with 5 to 30 aromatic ring atoms means which can be substituted in each case by one or more radicals R ³ .

In compounds of the formula (1b), six or seven substituents R ¹ preferably have the meaning Fl and two or one substituent R ¹ have / has another meaning, as described above or described as preferred.

In compounds of the formulas (1 c) to (1 h), preference is given to all

Substituents R ¹ Fl.

In compounds of the formulas (1), (1a) to (1h) or preferred

described compounds of the formulas (1), (1 a), (1 b), (1 c), (1 d), (1 e),

(1 f), (1 g) or (1 h), An on each occurrence, independently of one another, preferably represents an aryl group having 6 to 40 carbon atoms, as before

described or preferably described, which can be substituted with one or more radicals R ³ or for a dibenzofuranyl or dibenzothiophenyl group which can be substituted with one or more radicals R ³ or a carbazolyl group which is bonded both via C and via N. can be and those with one or more radicals R ³ can be substituted. The linkage of the carbazolyl group via a carbon atom is not restricted. The carbazolyl group is preferably bonded via N and is substituted by an R ³ radical. In compounds of the formulas (1), (1 a) to (1 h) or preferably

described compounds of the formulas (1), (1a), (1 b), (1 c), (1 d), (1 e),

(1 f), (1 g) or (1 h), An each occurrence, independently of one another, preferably represents an aryl group with 6 to 40 carbon atoms, as described above or preferably described, which is substituted by one or more radicals R ³ can be or for a dibenzofuranyl or dibenzothiophenyl group which can be substituted by one or more radicals R ³ .

The linkage of the aryl group or the dibenzofuranyl or

Dibenzothiophenyl group is not restricted here.

An can therefore preferably be selected from the following groups Ar-i-1 to Ar-i-12, where R ^{3 has} a meaning given above or preferably given:

Particularly preferably, at least one An stands for An-1 and the other aromatic substituent An stands for an aryl group with 6 to 40 C-

Atoms which can be substituted by one or more radicals R ³ or for a dibenzofuranyl or a dibenzothiophenyl group, preferably selected from An-1 to An-12. Particularly preferably at least one An stands for phenyl and the other aromatic substituent stands for a phenyl group which can be substituted by one or more radicals R ³ or for dibenzofuranyl or dibenzothiophenyl.

Both groups An are very particularly preferably the same. Both groups An are very particularly preferably phenyl. Both groups An are preferably each, independently of one another, An-5, An-6, An-7 or An-11, particularly preferably both groups An are An-6.

When in compounds of formulas (1) or (1a) to (1 h) or preferably described compounds of formulas (1) or (1 a) to (1 h) An in each case independently of one another, as described above or preferred

described, means an aryl or fleteroaryl group which are substituted by one or more radicals R ³ , the substituent R ³ in each

Occurring identically or differently, preferably selected from the group consisting of D, F or an aromatic or heteroaromatic Ring system with 5 to 40 aromatic ring atoms. The heteroaromatic ring system with 5 to 40 aromatic ring atoms is in this case for R ³ preferably derived from dibenzofuran or dibenzothiophene. The aromatic ring system with 6 to 40 aromatic ring atoms is in this case for R ³ preferably phenyl, biphenyl or terphenyl, particularly preferably phenyl. The aryl group or fleteroaryl group in An is preferably each independently substituted once with R ³ . The aryl group or fleteroaryl group in An is particularly preferably substituted once by R ³ .

The substituent R ³ on dibenzofuranyl or dibenzothiophenyl is preferably Fl. The substituent R ³ on the aryl group with 6 to 40 carbon atoms is preferably phenyl or F1 when it occurs. The aryl group or fleteroaryl group are very particularly preferably unsubstituted in An.

In compounds of the formulas (1), (1 a), (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h) or preferably described compounds of the formulas (1 ), (1a), (1 c),

(1 d), (1 e), (1 f), (1 g) and (1 h), Y ^{1 means} NAn, C (R *) 2, O or S, where An is given a meaning given above or is preferred has given meaning.

NAn preferably has the meaning N-phenyl. Y ¹ preferably denotes NAn or C (R ^* ) _2.

In one embodiment of the invention, compounds of the formulas (1), (1a) and (1c) or preferably described compounds of the formulas (1), (1a) and (1c) in which Y ^{1 has} a meaning given above or are preferred in which Y ^{1 is} NAn and C (R *) ₂ , particularly preferably C (R *) ₂ .

In one embodiment of the invention, compounds of the formulas (1), (1 a), (1 d) and (1 e) or preferably described compounds are

Formulas (1), (1 a), (1 d) and (1 e) are preferred in which Y ^{1 has} a previously or in which Y ¹ denotes NAn and 0, particularly preferably NAn denotes.

(1 d), (1 e), (1 f), (1 g) and (1 h), the substituent R * is on each occurrence, identically or differently, a straight-chain alkyl group with 1 to 10 carbon atoms or an aryl group with 6 up to 12 carbon atoms, where the two substituents R * can together form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more substituents R ⁵ . R * is preferably the same on each occurrence or two substituents R * together form a monocyclic or polycyclic,

aliphatic, aromatic or heteroaromatic ring system.

R * is particularly preferably selected from methyl, ethyl or phenyl. Particularly preferably, two substituents R * together with the carbon atom to which they are attached form a ring system selected from

Cyclopentyl or dibenzocyclopentyl, which with one or more

Substituents R ⁵ can be substituted. The ring system formed by two substituents R * particularly preferably corresponds to a spirobifluorene.

Y ¹ is particularly preferably selected from N-phenyl, C (methyl) 2, O or S. Y ^{1 is} very particularly preferably C (methyl) 2. In compounds of the formulas (1), (1a), (1 b), (1 c), (1 d), (1 e), (1 f), (1g) or (1 h) or in preferred compounds of the formulas (1), (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g) or (1 h) is L at each occurrence identically or differently a single bond or an aromatic ring system with 6 to 30 aromatic ring atoms which can be substituted by one or more radicals R ⁵ , where R ^{5 has} a meaning as described above. R ⁵ is preferably selected from the group consisting of D or phenyl. L is preferably a single bond or aromatic ring system with 6 to 18 carbon atoms, preferably for phenylene, biphenylene, naphthylene, phenanthrenylene or triphenylenylene, the attachment to the other substituents not being restricted. Phenylene can be linked to the dibenzofuran / dibenzothiophene unit in the ortho, meta or para position, for example.

L can therefore preferably be selected from the following linkers L-1 to L-20, which are unsubstituted or can be substituted by R ⁵ , as described above:

The linkers L-1 to L-20 are preferably unsubstituted.

The linkers L-1 to L-7 are particularly preferably used. L is preferably a single bond or a linker selected from the group L-1 to L7 or L-2 and L-3. L is particularly preferably a

Single bond. Particularly preferred compounds of the formula (1) correspond to the formulas (1 b) and (1 c), as described above.

In compounds of the formulas (1), (1 b) and (1 c), Y is preferably 0, Y ¹ is preferably C (R *) 2, An is independently preferably phenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl-N- for each occurrence. phenylenyl,

Dibenzofuranyl-phenylenyl, phenyl-carbazol-N-yl, 1,3-and 1,4-biphenyl, as previously described, and L is a single bond.

In compounds of the formulas (1), (1 b) and (1 c), Y is preferably 0, Y ¹ is preferably C (R *) 2, An is independently preferably phenyl, dibenzofuranyl, dibenzothiophenyl and biphenyl on each occurrence, as before and L is a single bond.

In compounds of the formulas (1), (1 b) and (1 c), Y is preferably S, Y ¹ is preferably C (R *) 2, An is independently preferably phenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl-N- for each occurrence phenylenyl,

In compounds of the formulas (1), (1 b) and (1 c), Y is preferably S, Y ¹ is preferably C (R *) 2, An is independently preferably phenyl, dibenzofuranyl, carbazolyl-N-phenylenyl and each occurrence 1,3-biphenyl as previously described and L is a single bond.

Compounds of the formulas (1 b) and (1 c) with substituents Y, Y ¹ , An, L and R ¹ , as described above or preferably described, are preferably selected for the composition according to the invention. Examples of suitable compounds of the formulas (1), (1a), (1b), (1c), (1 d), (1 e), (1 f), (1g) or (1h), which are selected according to the invention, are the structures of Table 1 given below or compounds 1 to 36 and 67 to 81.

Table 1:

30th

Particularly suitable compounds of the formulas (1), (1a), (1 b), (1 c), (1 d),

(1 e), (1 f), (1g) or (1 h), which are selected according to the invention, are the compounds 1 to 36 and 67 to 81:

30th

The preparation of the compounds of the formula (1) or the preferred compounds of the formulas (1a) to (1h) and of the compounds 1 to 36 and 67 to 81 is known to the person skilled in the art. The compounds can be prepared by synthesis steps known to the person skilled in the art, such as halogenation, preferably bromination, and a subsequent organometallic coupling reaction, eg Suzuki coupling, Heck coupling or Hartwig-Buchwald coupling. The preparation of the compounds of the formula (1) or the preferred compounds of the formulas (1 a) to (1 h) and the compounds 1 to 36 and 67 to 81 can be derived in particular from WO 2016/015810, in particular page 35 and the

Synthesis examples on pages 44 to 64.

The compounds of the formulas (1) to (1h) can be prepared according to the following scheme 1, where L, Xi, Y, R, R ¹ , An, n, m, o, p has one of the meanings given above.

Scheme 1:

In the following, compounds of the formula (2) and their preferred embodiments are described which are contained in the composition and / or device according to the invention, for example as hole-transporting flosts.

The composition according to the invention contains at least one compound of the formula (2),

The following applies to the symbols and indices used:

RA is H, -L3-Ar4, or -Li-N (Ar) 2;

RB is Ar3 or -l_2-N (Ar) 2; Li _, \ -2, are on each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which can be substituted by one or more radicals R ³ ;

l_3 is a single bond or an aromatic or

heteroaromatic ring system with 5 to 30 aromatic

Ar3 is an aromatic ring system with 6 to 40 aromatic rings

R ² is selected identically or differently on each occurrence from the group consisting of H, D, F, CI, Br, I, CN, NO2, N (Ar) 2, N (R ³ ) 2, C (= 0) Ar , C (= 0) R ³ , P (= 0) (Ar) ₂ , P (Ar) ₂ , B (Ar) ₂ , Si (Ar) ₃ , Si (R ³ ) ₃ , a straight chain alkyl, alkoxy - Or thioalkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 carbon atoms or an alkenyl group with 2 to 20 carbon atoms, each of which is substituted by one or more radicals R ³ can be, where one or more non-adjacent CH ₂ groups are replaced by R ³ C = CR ³ , Si (R ³ ) ₂ , C = 0, C = S, C = NR ³ , P (= 0) (R ³ ), SO, SO2, NR ³ , 0, S or CONR ³ can be replaced and one or more H atoms being replaced by D, F, CI, Br, I, CN or NO2 can, an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which can each be substituted with one or more radicals R ³ , an aryl oxy or heteroaryloxy group with 5 to 40 aromatic ring atoms, which can be substituted with one or more radicals R ³ may be substituted, or an aralkyl or heteroaralkyl group with 5 to 40 aromatic ring atoms, which can be substituted with one or more radicals R ³ ; optionally two substituents R ² attached to the same carbon atom or to adjacent ones

Carbon atoms are bonded to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more radicals R ³ ;

R ³ is selected identically or differently on each occurrence from the group consisting of H, D, F, CN, N (Ar) 2, an aliphatic hydrocarbon radical with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms in which one or more Fl atoms can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; two or more adjacent substituents R ^{3 here} can form a mono- or polycyclic, aliphatic ring system with one another;

R ⁴ is on each occurrence, identically or differently, selected from the group consisting of Fl, D, F, CN, an aliphatic hydrocarbon radical with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, in which a or several Fl atoms through D, F, CI, Br, I, a straight-chain or branched alkyl group with 1 to 4

Carbon atoms or CN can be replaced; two can or more adjacent substituents R ⁴ with one another form a mono- or polycyclic ring system;

r is independently 0, 1, 2 or 3 on each occurrence; s means, independently of one another, on each occurrence 0, 1, 2, 3 or

4th

In one embodiment of the invention, compounds of the formula (2) are selected as described above, those with compounds of the formulas

(1), (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g) and (1 h), as previously described or preferably described , or with the compounds of Table 1 or compounds 1 to 36 and 67 to 81, can be used in the composition.

Compounds of the formula (2) can be represented by the following formulas (2a), (2b), (2c) and (2d),

Formula (2c) Formula (2d)

where Li, l_2, L3, Ar, Ar3, Ar4, R ² , r and s have a meaning mentioned above or below.

Preferred compounds of the formula (2) or (2a) are compounds of the formulas (2e), (2f), (2g), (2h) and (2i),

where R _B , Ar3, aryl, R ² , R ⁴ , r and s have a meaning given above or below, l_3 in formulas (2h) and (2i)

aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms means that with one or more radicals R ³ can be substituted, where a substituent R ² on the carbazole can form a ring with a substituent R ³ , Z is C (R ³ ) 2, N-Ar, 0 or S and t is 0 or 1.

Preferred compounds of the formula (2) or (2c) in which at least r is 1 are compounds of the formulas (2j), (2k), (2I),

Formula (21)

where Ar3, R ² , R ³ and s have a previously mentioned meaning or preferred meaning and u, v and w each independently

denote 0 or 1 from one another at each occurrence.

R ³ in the compounds of the formulas (2j), (2k) and (2I) is preferably Fl or an aromatic or heteroaromatic ring system with 5 to 40

Ring atoms which can be substituted by R ⁵ . In the event that u, v and / or w are 1, R ³ in the compounds of the formulas (2j), (2k) and (2I) is preferably phenyl. In preferred compounds of the formulas (2j), (2k) and (2I) an index u, v or w stands for 1. U, v and w 0 are particularly preferred.

In compounds of the formulas (2a) to (2I), H is excluded from the definition of the substituents R ² if r and / or s is / are greater than 1.

Another object of the invention is accordingly a

Composition as described above, wherein the compound of formula (2) is one of the compounds of formulas (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) , (2i), (2j), (2k) or (2I). In the compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), a substituent R ² and a substituent R ^{4 form} a ring, for example also defined in formula (2f) by [Z] _t , the following rings Z-1 to Z-7 preferably being formed and the dashed lines each representing the bond to the carbazoles:

In the compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j) and ( 2I) two substituents R ² can form a ring together one or more times or two substituents R ⁴ , if present, can form a ring together once or more times, this ring being independently of one another preferably composed of the following structures (S1) to ( S9) is selected, where # and # represent the respective point of attachment with the carbon atoms and the structures can each be substituted with one or more substituents R ³ :

R ³ in the substructures (S1) to (S9) is preferably H or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which can be substituted by R ⁵ , preferably H or phenyl.

In the compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i) the linkers Li, L2 and L3 if they are not

Single bonds are each independently selected from the linkers L-2.1 to L-2.33,

where W is N-Ar, 0, S or C (CH3) 2, Ar has the meaning given above, the linkers L-2.1 to L-2.33 can be substituted by one or more radicals R ³ and the dashed lines indicate the connection to which mean carbazoles. For the linker L3, a radical R ³ on one of the linkers L-2.1 to L-2.33 can form a ring with a radical R ^{2 of} the carbazole. The linkers L-2.1 to L-2.33 are preferably unsubstituted or substituted by a phenyl.

Preferred linkers for Li are selected from the structures L-2.1 to L-2.33, in which W has the meaning S or 0, particularly preferably the meaning 0. Preferred linkers for L3 are selected from the structures L-2.1 to L-2.33, in which W has the meaning 0, S or N-Ar, particularly preferably 0 or N-Ar. In a preferred embodiment of the compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i) are the two Carbazoles linked to one another in the 3-position.

In compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), r is preferably 0, 1 or 2, where R ^{2 is} a previously given

Has meaning or a meaning given below. Particularly preferred is r 0 or 1. Very particular preferred is r 0.

If in compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i) r is greater than 0, then becomes the substituent R ² on each

Occurrence identically or differently preferably selected from the group consisting of D, F, an alkyl group with 1 to 40 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 40

aromatic ring atoms which can be substituted by one or more radicals R ³ . The aromatic or heteroaromatic

Ring system with 5 to 40 aromatic ring atoms in this R ² is preferably derived from benzene, dibenzofuran, dibenzothiophene, 9-phenyl-carbazole, indolo [3,2,1-y / c] carbazole, biphenyl and terphenyl, which with one or more R ³ radicals can be substituted. The preferred position of the substituent (s) [R ² ] _r is position 1, 2, 3 or 4 or the

Combinations of positions 1 and 4 and 1 and 3, particularly preferably 1 and 3, 2 or 3, very particularly preferably 3, where R ^{2 has} one of the preferred meanings given above and r is greater than 0. Particularly preferred substituents R ² in [R ² ] _r are carbazol-9-yl, biphenyl,

Terphenyl and dibenzofuranyl. In compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2k) and (21 ) s is in each case, independently of one another, on each occurrence, preferably 0, 1 or 2, where R ² and R ^{4 have} a meaning given above or a meaning given below. Particularly preferably s is 0 or 1 independently of one another in each occurrence, and s is very particularly preferably 0 in each occurrence.

If in compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f),

(2g), (2h) and (2i) s is greater than 0, the substituent R ^{4 is} preferably selected on each occurrence, identically or differently, from the group consisting of D, F, an alkyl group with 1 to 20 carbon atoms or one aromatic or heteroaromatic ring system with 5 to 30

aromatic ring atoms in which one or more Fl atoms are replaced by D, F, CI, Br, I, a straight-chain or branched alkyl group with 1 to 4

Carbon atoms or CN can be replaced. Two or more adjacent substituents R ⁴ can form a monocyclic or polycyclic ring system with one another. The aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms in this R ⁴ is preferably derived from benzene, dibenzofuran, dibenzothiophene, 9-phenyl-carbazole, biphenyl, terphenyl and triphenylene.

The preferred position of the substituent ( _s ) [R ⁴ ] _s is position 1, 2 or 3, particularly preferably 3, where R ^{4 has} one of the preferred meanings given above and s is greater than 0. Ar in N (Ar) 2 is preferably derived from benzene, dibenzofuran, fluorene, spirobiflurene, dibenzothiophene, 9-phenyl-carbazole, biphenyl and

Terphenyl, which can be substituted with one or more substituents R ³ . Ar is preferably unsubstituted here. The substituent R ² is on each occurrence, identically or differently, preferably selected from the group consisting of D, F, CI, Br, I, CN, N0 ₂ , N (Ar) ₂ , NH ₂ , N (R ³ ) _2I C ( = 0) Ar, C (= 0) H, C (= 0) R ³ , P (= 0) (Ar) ₂ , one straight-chain alkyl, alkoxy or thioalkyl group with 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 40 carbon atoms or an alkenyl or alkynyl group with 2 to 40 carbon atoms, each can be substituted with one or more radicals R ³ , an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can each be substituted with one or more radicals R ³ , an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which with one or more radicals R ³ can be substituted. The substituent R ² is particularly preferably aromatic or heteroaromatic when it occurs

Ring system, as described above, preferably selected and derived from the group benzene, carbazole, 9-phenyl-carbazole, dibenzofuran, dibenzothiophene, fluorene, terphenyl or spirobifluorene, very particularly preferably derived from a dibenzofuran.

If in compounds of the formulas (2j), (2k) and (2I) s is greater than 0, the substituent R ^{2 is,} on each occurrence, identically or differently preferably selected from the group consisting of D, F, an alkyl group with 1 to 40 C atoms or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R ³ . The preferred position of the substituent ( _s ) [R ² ] _s is position 1, 3 and 4, particularly preferably 3, where R ^{2 has} one of the meanings given above. Preferably s is 0 or 1. If in compounds of the formulas (2j), (2k) and (2I) s is 1, R ² in [R ² ] _{s is} preferably phenyl.

In the case of the substitution of one of the substituents R ² , as described above, with a substituent R ³ , the meanings of R ³ apply as described above or preferably described.

In compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2k) and (2i ), as previously described, Ar3 is each independent from each other an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 10 to 40 aromatic ring atoms, which can be substituted by one or more radicals R ³ .

In compounds of formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i), as described above, is aryl an aromatic or

heteroaromatic ring system with 5 to 30 aromatic ring atoms, which can be substituted by R ³ . Ar3 and aryl are preferably derived from benzene, dibenzofuran, fluorene, spirobiflurene, dibenzothiophene, 9-phenyl-carbazole, naphthalene,

Phenanthrene, triphenyl, biphenyl and terphenyl, which can be substituted by one or more substituents R ³ , where R ³ has the meaning given above.

In the case of the heteroaromatic ring systems with 10 to 40 carbon atoms, which can be substituted with one or more of the substituents R ³ , electron-rich ring systems are particularly preferred

Ring system optionally substituted by R ³ preferably contains only one N atom in its entirety or the ring system optionally substituted by R ³ contains one or more O and / or S atoms in its entirety.

In compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k ) and (2I) or preferably described compounds of

Formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and ( 2I), aryl and Ar3 are preferably selected independently of one another on each occurrence from the aromatic or heteroaromatic ring systems Ar-1 to Ar-24,

Ar-14

where Y ³ denotes, identically or differently, 0, NR ^# , S or C (R ^# ) ₂ on each occurrence, where the radical R ^# which is bonded to N is not equal to H. and R ^{3 has} the meaning mentioned above or a preferred meaning below and the dashed bond represents the bond to the N atom.

The radical R ^# is on each occurrence, identically or differently, H, D, F, CI, Br, I, CN, N0 ₂ , N (Ar) ₂ , N (R ³ ) ₂ , C (= 0) Ar, C ( = 0) R ³ , P (= 0) (Ar) ₂ , P (Ar) ₂ , B (Ar) ₂ , Si (Ar) 3, Si (R ³ ) 3, a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 carbon atoms or an alkenyl group with 2 to 20 carbon atoms, each of which can be substituted by one or more radicals R ³ , where one or more non-adjacent CH ₂ groups are represented by R ³ C = CR ³ , Si (R ³ ) ₂ , C = 0, C = S, C = NR ³ , P (= 0) (R ³ ), SO , S0 ₂ , NR ³ , O, S or CONR ³ can be replaced and one or more H atoms can be replaced by D, F, CI, Br, I, CN or N0 ₂ , an aromatic or heteroaromatic ring system with 5 up to 40 aromatic ring atoms, each of which can be substituted by one or more radicals R ³ , an aryloxy or fleteroaryloxy group with 5 to 40 aromatic ring atoms, which are linked with one or more radicals R ³ it can be substituted by several R ³ radicals, or an aralkyl or fleteroaralkyl group with 5 to 40 aromatic ring atoms which can be substituted by one or more R ³ radicals; optionally two substituents R ^# bonded to the same carbon atom or to adjacent carbon atoms can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R ³ .

Y ³ is preferably O, S or C (CH3) _2. Y ³ is very particularly preferably O.

In the structures Ar-1 to Ar-24, the substituent R ^{3 is} selected identically or differently on each occurrence from the group consisting of Fl, D,

F, CN, an aliphatic hydrocarbon radical with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, in which one or more F1 atoms are replaced by D, F, CI, Br, I or CN can be replaced and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; two or more adjacent substituents R ^{3 here} can form a mono- or polycyclic, aliphatic ring system with one another. In structures Ar-1 through Ar-22, the substituent R ^{3 is} preferred for each

Occur identically or differently selected from the group consisting of H, F, CN, an aliphatic hydrocarbon radical with 1 to 10 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms. In the structures Ar-1 to Ar-24, the substituent R ^{3 is} preferably selected identically or differently on each occurrence from the group consisting of Fl or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, as described above, but preferably dibenzofuran ,

Dibenzothiophene, 9-phenyl-carbazole or spirobifluorene.

In the structures Ar-1 to Ar-24, the substituent R ^{3 is} particularly preferably Fl on each occurrence.

Examples of suitable compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h), (2i), (2j), (2k) and (2I), according to the invention

are selected are the structures of Table 2 below or the preferred compounds 37 to 66a.

Table 2:

30th

Particularly suitable examples of compounds of the formula (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) and (2i) selected according to the invention connections 37 to 66a are:

The preparation of the compounds of the formula (2) or the preferred compounds of the formulas (2), (2a), (2b), (2c), (2d), (2e), (2f), (2g), (2h) , (2i), (2j), (2k) and (21), and the compounds of Table 2 and 37 to 66a are known to the person skilled in the art. The compounds can be prepared by synthesis steps known to the person skilled in the art, such as halogenation, preferably bromination, and a subsequent organometallic coupling reaction, eg Suzuki coupling, Heck coupling or Hartwig-Buchwald coupling. Some of the compounds of the formula (2) are commercially available.

The aforementioned host materials of the formulas (1), (1 a), (1 b), (1 c),

(1 d), (1 e), (1 f), (1 g) or (1 h), as well as their preferred described

Embodiments or the compounds of Table 1 and

Compounds 1 to 36 and 67 to 81 can according to the invention arbitrarily with the host materials mentioned of the formulas (2), (2a), (2b), (2c), (2d), (2e),

(2f), (2g), (2h), (2i), (2j), (2k) and (2I) and their preferred embodiments or the compounds of Table 2 or the

Connections 37 to 66a are combined.

Particularly preferred mixtures of the host materials of the formula (1) with the host materials of the formula (2) for the inventive

Composition or organic electronic according to the invention Apparatus is obtained by combining compounds 1 to 36 and 67 to 81 with the compounds in Table 2.

Very particularly preferred mixtures of the host materials of the formula (1) with the host materials of the formula (2) for the inventive

Composition or for the organic according to the invention

electronic device is obtained by combining compounds 1 to 36 and 67 to 81 with compounds 37 to 66a as shown in Table 3 below.

Table 3:

The concentration of the electron-transporting host material of the formula (1), as described above or preferably described, in the composition or mixture according to the invention or in the light-emitting layer of the device according to the invention is in

Range from 5% by weight to 90% by weight, preferably in the range from 10% by weight

% to 85% by weight, more preferably in the range of 20% by weight to 85% by weight

%, even more preferably in the range from 30% by weight to 80% by weight, very particularly preferably in the range from 20% by weight to 60% by weight and most preferably in the range from 30% by weight to 50% by weight, based on the total composition / mixture or based on the total composition of the light-emitting layer.

The concentration of the hole-transporting host material of the formula (2), as previously described or described as preferred, in the The composition or mixture or the light-emitting layer of the device according to the invention is in the range from 10% by weight to 95% by weight, preferably in the range from 15% by weight to 90% by weight, more preferably in the range from 15% by weight. -% to 80% by weight, even more preferably in the range from 20% by weight to 70% by weight, very particularly preferably in the range from 40% by weight to 80% by weight and most preferably in the range from 50% by weight to 70% by weight based on the total

Composition / mixture or based on the whole

Composition of the light-emitting layer.

In a further preferred embodiment, the composition according to the invention can contain at least one compound of the formula (1), as described above or as described as preferred, and at least one compound of the formula (2), as described above or as described as preferred, also further compounds, in particular organic functional materials. The composition according to the invention is a physical mixture of the at least one compound of the formula (1), the at least one compound of the formula (2) and optionally further organic functional materials as

Part of an organic layer in an electronic device, as described below.

The present invention therefore also relates to a composition which, in addition to the materials mentioned above, contains at least one further compound selected from the group consisting of hole injection materials, hole transport materials, hole blocking materials, wide band gap materials, fluorescent emitters, phosphorescent emitters , Host materials,

Electron blocking materials, electron transport materials, and

Electron injection materials, n-dopants and p-dopants. The person skilled in the art has no difficulty in selecting these from a large number of materials known to him. In this context, n-dopants are understood to mean reducing agents, ie electron donors. In this context, p-dopants are understood to mean oxidizing agents, ie electron acceptors.

Wide-band-gap-material is understood here to mean a material within the meaning of the disclosure of US Pat. No. 7,294,849, which is characterized by a band gap of at least 3.5 eV, the band gap being understood to mean the distance between the HOMO and LUMO energy of a material .

It is preferred if the composition according to the invention comprising at least one hole-transporting host of the formula (2) and at least one electron-transporting host of the formula (1), as described above or preferably described, additionally contains at least one light-emitting compound or an emitter, with phosphorescent emitters are particularly preferred. The present invention also relates to a composition / mixture which, in addition to the aforementioned host materials 1 and 2, as previously described or preferably described, in particular mixtures M1 to M1597, also contains at least one phosphorescent emitter. The present invention also relates to an organic one

electroluminescent device, as described above or below or preferably described, wherein the light-emitting layer in addition to the host materials 1 and 2 mentioned above, as described above or preferably described, in particular the

Material combinations M1 to M1597, at least one more

Contains phosphorescent emitter. The term phosphorescent emitter typically encompasses compounds in which the light emission is prohibited by a spin

Transition from an excited state with higher spin multiplicity, that is to say a spin state> 1, takes place, for example, through a transition from a triplet state or a state with an even higher one

Spin quantum number, for example a quintet state. A transition from a triplet state is preferably understood here.

Phosphorescent emitters (= triplet emitters) are suitable

in particular compounds which, when appropriately stimulated, emit light, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferred phosphorescence emitters are compounds that contain copper, molybdenum, tungsten, rhenium,

Ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are used, especially compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds which contain the metals mentioned above are regarded as phosphorescent emitters.

In general, all phosphorescent complexes such as are used according to the prior art for phosphorescent OLEDs and as are known to the person skilled in the art in the field of organic electroluminescent devices are suitable.

Examples of the emitters described above can be found in the applications WO 2016/015815, WO 00/70655, WO 2001/41512, WO 2002/02714,

WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/102709, WO 2011/032626, WO 2011/066898, WO 2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO 2014/094961, WO 2014/094960, WO 2015/036074, WO 2015/104045, WO 2015/117718, WO 2016/015815, WO 2016/124304, WO 2017/032439, WO 2015/036074, WO 2015/117718 and WO 2016/015815.

Preferred phosphorescent emitters contain a dibenzofuran or an azadibenzofuran structure in at least one ligand.

Preferred phosphorescent emitters correspond to the formula (3),

Formula (3)

where the symbols and indices for this formula (3) have the meanings: n + m is 3, n is 1 or 2, m is 2 or 1,

X is N or CR,

R is H, D, a branched or linear alkyl group with 1 to 10 carbon atoms or a partially or fully deuterated branched or linear alkyl group with 1 to 10 carbon atoms or a cycloalkyl group with 4 to 7 carbon atoms, partially or completely can be substituted with deuterium.

In emitters of the formula (3), n is preferably 1 and m is preferably 2.

In emitters of the formula (3), one X is preferably selected from N and the other X are CR.

In emitters of the formula (3), at least one R is preferably different from H. In emitters of the formula (3), two, three or four R are preferably different from H and have one of the meanings otherwise given above for the emitters of the formula (3).

Preferred examples of phosphorescent emitters are listed in Table 4 below.

Table 4:

30th

Preferred examples of phosphorescent polypodal emitters are listed in Table 5 below. Table 5:

In the composition / mixture according to the invention, each mixture M1 to M1597, as described above, is preferably combined with a compound of the formula (3) or a compound from Table 4 or 5. The composition according to the invention preferably consists of at least one compound of the formula (1), at least one compound of the formula (2) and one or two emitters selected from

Compounds of the formula (3), Table 4 or Table 5.

The light-emitting layer in the organic electroluminescent device containing a composition as previously described or preferably described and at least one phosphorescent emitter is preferably an infra-red emitting, yellow, orange, red, green, blue or ultra-violet emitting layer, particularly preferably a yellow or green emitting layer and very particularly preferably a green emitting layer containing at least one phosphorescent emitter preferably forms an infra-red emitting, yellow, orange, red, green, blue or ultra-violet emitting layer, particularly preferably a yellow or green emitting layer and very particularly preferably a green-emitting layer.

A yellow-emitting layer is understood to mean a layer whose photoluminescence maximum is in the range from 540 to 570 nm. An orange-emitting layer is understood to mean a layer whose photoluminescence maximum is in the range from 570 to 600 nm. A red-emitting layer is understood to mean a layer whose photoluminescence maximum is in the range from 600 to 750 nm. A green-emitting layer is understood to mean a layer whose

Photoluminescence maximum is in the range from 490 to 540 nm. A blue-emitting layer is understood to mean a layer whose photoluminescence maximum is in the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, the layer having the composition according to the invention, ie containing emitter and matrix. The photoluminescence spectrum of the layer is recorded, for example, with a commercially available photoluminescence spectrometer.

The photoluminescence spectrum of the selected emitter is usually measured in an oxygen-free solution, 10-5 molar, the measurement being made at room temperature and any solvent in which the selected emitter dissolves in the stated concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also

Dichloromethane. It is measured with a commercially available

Photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First the peak maximum Plmax. (in nm) of the photoluminescence spectrum determined. The peak maximum Plmax. (in nm) is then converted into eV according to: E (T1 in eV) = 1240 / E (T1 in nm) = 1240 / Plmax. (in nm).

Preferred phosphorescent emitters are therefore infra-red emitters, preferably of the formula (3) or from Table 4 or 5, their

Triplet energy Ti is preferably from ~ 1.9 eV to ~ 1.0 eV. Preferred phosphorescent emitters are therefore red emitters, preferably of the formula (3) or from Table 4 or 5, their

Triplet energy Ti is preferably ~ 2.1 eV to ~ 1.9 eV.

Preferred phosphorescent emitters are therefore yellow emitters, preferably of the formula (3) or from Table 4 or 5, their

Triplet energy Ti is preferably ~ 2.3 eV to ~ 2.1 eV.

Preferred phosphorescent emitters are accordingly green emitters, preferably of the formula (3) or from Table 4 or 5, their

Triplet energy Ti is preferably from ~ 2.5 eV to ~ 2.3 eV. Preferred phosphorescent emitters are therefore blue emitters, preferably of the formula (3) or from Table 4 or 5, their

Triplet energy Ti is preferably ~ 3.1 eV to ~ 2.5 eV. Preferred phosphorescent emitters are therefore ultra-violet emitters, of the formula (3) or from Table 4 or 5, whose triplet energy Ti is preferably from ~ 4.0 eV to ~ 3.1 eV.

Accordingly, particularly preferred phosphorescent emitters are green or yellow emitters, preferably of the formula (3) or from Table 4 or 5, as described above.

Accordingly, very particularly preferred phosphorescent emitters are green emitters, preferably of the formula (3) or from Table 4 or 5, whose triplet energy Ti is preferably from ~ 2.5 eV to ~ 2.3 eV.

Green emitters are very particularly preferred, preferably the

Formula (3) or from Table 4 or 5, as described above, for the composition according to the invention or according to the invention

emitting layer selected.

Preferred fluorescent emitters are selected from the class of the arylamines. For the purposes of this invention, an arylamine or an aromatic amine is understood to mean a compound which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a condensed ring system, particularly preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic

Chrysendiamines. An aromatic anthracenamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to one anthracene group, preferably in the 9,10 position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysendiamines are defined analogously thereto, the diarylamino groups on the pyrene preferably being bonded in the 1-position or in the 1,6-position. Further preferred fluorescent emitters are indenofluorenamines or diamines, for example according to WO 2006/108497 or WO 2006/122630, benzoindenofluorenamines or diamines, for example according to WO 2008/006449, and dibenzoindenofluorenamines or diamines, for example according to WO 2007 / 140847, as well as the indenofluorene derivatives with condensed aryl groups disclosed in WO 2010/012328.

In a further preferred embodiment of the invention, the composition according to the invention is used as a component of mixed matrix systems. The mixed matrix systems preferably comprise three or four different matrix materials, particularly preferably three different matrix materials (that is, a further matrix component in addition to the one according to the invention

Composition). Particularly suitable matrix materials, which in combination with the composition according to the invention as

Matrix components of a mixed matrix system that can be used are selected from wide-band-gap materials,

Electron Transport Materials (ETM) and Hole Transport Materials (HTM).

Mixed matrix systems are preferably used in phosphorescent organic electroluminescent devices. More detailed information on mixed matrix systems is contained, inter alia, in the application WO 2010/108579. Particularly suitable matrix materials which can be used in combination with the composition according to the invention as matrix components of a mixed matrix system in phosphorescent or fluorescent organic electroluminescent devices are selected from the preferred matrix materials for phosphorescent emitters given below or the preferred matrix materials for fluorescent emitters, as the case may be what type of emitter is used. The mixed matrix system is preferably optimized for an emitter of the formula (3) or from table 4 or 5. As further host materials, preferably for fluorescent emitters, in addition to the composition according to the invention, as described above, including particularly preferably a mixture of materials selected from M1 to M1597, various classes of substances come into consideration. Preferred further fluff materials are selected from the classes of oligoarylenes (e.g. 2,2 ', 7,7'-tetraphenylspirobifluorene according to EP 676461 or

Dinaphthylanthracene), in particular containing oligoarylene

condensed aromatic groups, the oligoarylenvinylenes (e.g. DPVBi or Spiro-DPVBi according to EP 676461), the polypodal metal complexes (e.g. according to WO 2004/081017), the hole-conducting compounds (e.g. according to WO 2004/058911) , the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (e.g. according to

WO 2005/084081 and WO 2005/084082), the atropisomers (e.g. according to WO 2006/048268), the boronic acid derivatives (e.g. according to

WO 2006/117052) or the benzanthracene (e.g. according to

WO 2008/145239). Particularly preferred floss materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes, containing anthracene, benzanthracene,

Benzphenanthrene and / or pyrene or atropisomers of these compounds. For the purposes of this invention, an oligoarylene is to be understood as a compound in which at least three aryl or arylene groups are bonded to one another.

Other matrix materials, preferably for phosphorescent emitters, in addition to the composition according to the invention, come as before described, particularly preferably comprising a mixture

Materials selected from M1 to M1597, different substance classes in question. Preferred further matrix materials are selected from the classes of aromatic amines, especially triarylamines, e.g. B. according to US 2005/0069729, carbazole derivatives (e.g. CBP, N, N-

Biscarbazolylbiphenyl) or compounds according to WO 2005/039246,

US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851, bridged carbazole derivatives, e.g. B. according to WO 2011/088877 and

WO 2011/128017, indenocarbazole derivatives, e.g. B. according to WO 2010/136109 and WO 2011/000455, azacarbazole derivatives, e.g. B. according to EP 1617710,

EP 1617711, EP 1731584, JP 2005/347160, indolocarbazole derivatives, e.g. B. according to WO 2007/063754 or WO 2008/056746, ketones, e.g. B. according to WO 2004/093207 or WO 2010/006680, phosphine oxides, sulfoxides and sulfones, e.g. B. according to WO 2005/003253, Oligophenylenes, bipolar

Matrix materials, e.g. B. according to WO 2007/137725, silanes, e.g. B. according to WO 2005/111172, azaboroles or boronic esters, e.g. B. according to WO 2006/117052, triazine derivatives, e.g. B. according to WO 2010/015306, WO 2007/063754 or WO 2008/056746, zinc complexes, e.g. B. according to EP 652273 or

WO 2009/062578, aluminum complexes, e.g. B. BAIq, Diazasilol and

Tetraazasilol derivatives, e.g. B. according to WO 2010/054729, diazaphosphole derivatives, e.g. B. according to WO 2010/054730 and aluminum complexes, e.g. B. BAIQ.

According to an alternative embodiment of the present invention, the composition contains in addition to the ingredients

electron-transporting host and hole-transporting host do not have any further components, i.e. functional materials. In this embodiment, it is a question of material mixtures which are used as such for producing the organic layer, preferably the emitting layer. These systems are also known as premix systems, which are used as the only material source for vapor deposition and which have a constant mixing ratio for the Have vapor deposition. This enables the vapor deposition of a layer with a uniform distribution of the components to be achieved in a simple and fast manner, without the need for precise control of a large number of material sources.

Another object of the invention is accordingly a

Composition consisting of a compound of the formula (1), (1a) to (1h) or a compound selected from 1 to 36 and 67 to 81 and a compound of the formula (2), (2a) to (2I) or a compound selected from 37 to 66a.

The composition according to the invention, as described above or preferably described, is suitable for use in a

organic electronic device. It is under a

Organic electronic device understood a device which contains at least one layer that contains at least one organic compound. The device can also be inorganic

Contain materials or layers that are made entirely of inorganic materials.

The invention accordingly also relates to the use of a composition as described above or preferably described, in particular a mixture selected from M1 to M1597, in an organic electronic device.

The components or constituents of the compositions can be processed by vapor deposition or from solution. If the compositions are applied from solution, are

Formulations of the composition according to the invention containing at least one further solvent are required. These formulations can be, for example, solutions, dispersions or emulsions. It It may be preferred to use mixtures of two or more solvents for this purpose.

The present invention therefore also provides a formulation comprising a composition according to the invention and at least one solvent.

Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-) -Fenchone, 1, 2,3,5-tetramethylbenzene, 1, 2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4 - dimethyl anisole, 3,5-dimethyl anisole, acetophenone, a-terpineol,

Benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone,

Cyclohexylbenzene, decalin, dodecylbenzene, ethylbenzoate, indane,

Methyl benzoate, NMP, p-cymene, phenetol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol, triethylene glycol, dimethyl ether, diethylene glycol, methyl propylene glycol, tetra propylene glycol, methyl propylene glycol, triphyleneglycol, 2-propylene glycol, triphyleneglycol, 2-propylene glycol, triphylene glycol, hexropylene glycol, triphyleneglycol. Octylbenzene, 1,1-bis (3,4-dimethylphenyl) ethane, hexamethylindane or mixtures of these solvents. The formulation can also contain at least one further organic or inorganic compound which is also in the

Electronic device is used, in particular an emitting compound, in particular a phosphorescent emitter and / or a further matrix material. Suitable emitting compounds and further matrix materials have already been listed above. The present invention also relates to the use of the composition according to the invention in an organic

electronic device, preferably in an electron-transporting and / or in an emitting layer.

The organic electronic device is preferably selected from the organic integrated circuits (OlCs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors and organic photo receptors, wherein the organic electroluminescent devices are particularly preferred.

Very particularly preferred organic electroluminescent devices containing at least one compound of the formula (1) and at least one compound of the formula (2), as previously described or described as preferred, are organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O lasers) and organic light-emitting diodes (OLEDs), OLECs and OLEDs are particularly preferred and OLEDs are most preferred.

The composition according to the invention is preferably used, as described above or described as preferred, in an electronic device in a layer with an electron-transporting function. The layer is preferably an electron injection layer (EIL), an electron transport layer (ETL), a hole blocking layer (HBL) and / or an emission layer (EML), particularly preferably an ETL, EIL and / or an EML. The composition according to the invention is very particularly preferably used in an EML,

especially as a matrix material or as a premix system. Another object of the present invention is therefore an organic electronic device which is selected in particular from one of the electronic devices mentioned above and which contains the summary according to the invention, as previously described or preferably described, preferably in an emission layer (EML), in an electron transport layer (ETL), in one

Electron injection layer (EIL) and / or in a hole blocking layer (HBL), very preferably in an EML, EIL and / or ETL and entirely

especially preferred in an EML.

If it is an emissive layer, then it is

particularly preferably a phosphorescent layer, which is characterized in that, in addition to the composition, as previously described or preferably described, a

Contains phosphorescent emitter, in particular together with an emitter of the formula (3) or from Table 4 or 5 or a preferred emitter, as described above.

In a particularly preferred embodiment of the present

In accordance with the invention, the electronic device is therefore an organic electroluminescent device, very particularly preferably an organic light-emitting diode (OLED), which contains the composition according to the invention, as described above or preferably described, together with a phosphorescent emitter

Contains emission layer (EML).

In a particularly preferred embodiment of the present

Invention is therefore an organic one

Electroluminescent device comprising an anode, a cathode and at least one organic layer containing at least one light-emitting layer, the at least one light-emitting layer at least one compound of formula (1) as host material 1 and contains at least one compound of the formula (2) as host material 2, the compounds of the formulas (1) and (2) having structures as described above or preferably described or described in combination as a special composition or mixture.

In a particularly preferred embodiment of the present

Invention is therefore an organic one

electroluminescent device comprising an anode, a cathode and at least one organic layer containing at least one light-emitting layer, the at least one light-emitting layer

Layer contains at least one compound of formula (1) as floss material 1 and at least one compound of formula (2) as host material 2, the compounds of formulas (1) and (2) having structures as described above or preferably described or in combination described as a special composition or mixture, and wherein the at least one emission layer contains a phosphorescent emitter.

The light-emitting layer in the device according to the invention, as described above, preferably contains between 99.9 and 1% by volume, more preferably between 99 and 10% by volume, particularly preferably between 98 and 60% by volume, very particularly preferably between 97 and 80% by volume of matrix material composed of at least one compound of the formula (1) and at least one compound of the formula (2), as above

described, based on the entire composition of emitter and matrix material. Accordingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99% by volume, more preferably between 1 and 90% by volume, particularly preferably between 2 and 40% by volume, very particularly preferably between 3 and 20 Vol .-% of the emitter based on the total composition of the light-emitting layer consisting of emitter and matrix material. If the compounds are processed from solution, instead of the above specified amounts in% by volume, preferably the corresponding amounts in% by weight are used.

The light-emitting layer in the device according to the invention, as described above, preferably contains the matrix material of the formula (1) and the matrix material of the formula (2) in a volume percentage ratio between 3: 1 and 1: 3, preferably between 1: 2.5 and 1: 1 , particularly preferably between 1: 2 and 1: 1. If the compounds are processed from solution, the corresponding ratio in% by weight is preferably used instead of the ratio in% by volume given above.

In addition to the cathode, anode and the layer containing the composition according to the invention, an electronic device can also contain further layers. These are selected, for example, from one or more hole injection layers, hole transport layers,

Hole blocking layers, light emitting layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers (interlayers),

Charge-Generation Layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and / or organic or inorganic p / n transitions. It should be noted, however, that it is not necessary for each of these layers to be present.

The sequence of the layers in an organic electroluminescent device is preferably the following:

Anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer /

Cathode.

This sequence of layers is a preferred sequence. It should be pointed out again that not all of the

The layers mentioned must be present and / or that additional layers can also be present. An organic electroluminescent device according to the invention can contain a plurality of light-emitting layers. According to the invention, at least one of the light-emitting layers contains the combination of compounds of the formula (1) and compounds of the formula (2), as previously described. In this case, these emission layers particularly preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, i.e. H. in the light-emitting layers are different emitting

Compounds used that can fluoresce or phosphoresce and that emit blue or yellow or orange or red light. Three-layer systems are particularly preferred, that is to say systems with three light-emitting layers, the three layers showing blue, green and orange or red emission (for the basic structure, see, for example, WO 2005/011013). It should be noted that for the

For the generation of white light, instead of a plurality of color emitting emitter connections, a single emitter connection which is used and which emits in a broad wavelength range can also be suitable.

Suitable charge transport materials, such as those in the hole injection or hole transport layer or electron blocking layer or in the electron transport layer of the organic electro according to the invention

Luminescent devices can be used, for example, those disclosed in Y. Shirota et al., Chem. Rev. 2007, 107 (4), 953-1010

Compounds or other materials as used in these layers according to the prior art. All materials can be used as materials for the electron transport layer, as are used according to the prior art as electron transport materials in the electron transport layer. Aluminum complexes, for example Alq3, zirconium complexes, for example Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, are particularly suitable,

Lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives.

Further suitable materials are derivatives of the abovementioned

Compounds as described in JP 2000/053957, WO 2003/060956,

WO 2004/028217, WO 2004/080975 and WO 2010/072300 are disclosed.

Particularly preferred hole transport materials are materials which can be used in a hole transport, hole injection or electron blocking layer, such as indenofluorenamine derivatives (e.g. according to WO 06/122630 or WO 06/100896), the amine derivatives disclosed in EP 1661888, Hexaazatriphenylene derivatives (e.g. according to WO 01/049806), amine derivatives with condensed aromatics (e.g. according to US Pat. No. 5,061,569), the amine derivatives disclosed in WO 95/09147, monobenzoindenofluorenamines (e.g. according to WO 08/006449) , Dibenzoindenofluorenamines (e.g. according to WO 07/140847), spirobifluorenamines (e.g. according to WO 2012/034627 or the as yet unpublished EP 12000929.5), fluorene amines (e.g. according to WO 2014/015937, WO 2014/015938 and WO 2014/015935), spiro-dibenzopyran amines (e.g. according to WO 2013/083216) and dihydroacridine derivatives (e.g. WO 2012/150001).

As the cathode of electronic devices, metals are less

Work function, metal alloys or multilayer structures

various metals preferred, such as alkaline earth metals,

Alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Furthermore, alloys made of an alkali or alkaline earth metal and silver such as an alloy of

Magnesium and silver. In the case of multi-layer structures, in addition to the metals mentioned, other metals can be used that have a relatively high work function, such as. B. Ag or Al, in which case combinations of metals such as Ca / Ag, Mg / Ag or Ba / Ag are then usually used. It can also be preferred to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor. For example, alkali metal or

Alkaline earth metal fluorides, but also the corresponding oxides or

Carbonates in question (e.g. LiF, L12O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used for this. The

The layer thickness of this layer is preferably between 0.5 and 5 nm. Materials with a high work function are preferred as the anode. The anode preferably has a work function greater than 4.5 eV vs. Vacuum on. On the one hand, metals with a high redox potential are suitable for this, such as Ag, Pt or Au. On the other hand, metal / metal oxide electrodes (for example Al / Ni / NiO _x , Al / PtO _x ) can also be preferred. For some applications, at least one of the electrodes must be transparent or

be partially transparent to either the irradiation of the organic

Materials (organic solar cell) or the extraction of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide. The organic electronic device is appropriately structured, contacted and finally sealed during manufacture (depending on the application), since the service life of the devices according to the invention is shortened in the presence of water and / or air.

In a further preferred embodiment, the organic electronic device containing the composition according to the invention is characterized in that one or more organic layers containing the composition according to the invention are coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10 ⁷ mbar. An organic electroluminescent device is also preferred, characterized in that one or more layers are coated with the OVPD (Organic Vapor Phase Deposition) process or with the aid of a carrier gas sublimation. The materials are applied at a pressure between 10 ^-5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and structured in this way (e.g. BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301). Also preferred is an organic electroluminescent device, characterized in that one or more organic layers containing the composition according to the invention from solution, such as. B. by spin coating, or with any printing process, such as. B. screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing (inkjet printing) can be produced. For this purpose, soluble compounds of the components are of the invention Composition necessary. High solubility can be achieved by suitable substitution of the corresponding compounds. Processing from solution has the advantage that the layer containing the

composition according to the invention can be applied very easily and inexpensively. This technique is particularly suitable for mass production of organic electronic devices.

Hybrid processes are also possible in which, for example, one or more layers are applied from solution and one or more additional layers are vapor-deposited.

These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices. Another object of the invention is therefore a method for

Production of an organic electronic device containing a composition according to the invention, as described above or preferably described, characterized in that at least one organic layer containing a composition according to the invention by gas phase deposition, in particular with a

Sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the help of a carrier gas sublimation, or from solution, in particular by spin coating or with a

Printing process, is applied.

In the production of an organic electronic device by means of gas phase deposition, there are basically two ways in which an organic layer which is intended to contain the composition according to the invention and which can comprise several different constituents can be applied or vapor-deposited on any substrate. On the one hand, the materials used can each be in a

Material source submitted and finally from the various Material sources are evaporated ("co-evaporation"). On the other hand, the different materials can be premixed (“premixed”, premix systems) and the mixture can be presented in a single material source from which it is finally evaporated (“premix evaporation”). This enables the vapor deposition of a layer with a uniform distribution of the components to be achieved in a simple and fast manner, without the need for precise control of a large number of material sources.

The invention accordingly further provides a method, characterized in that the at least one compound of the formula (1), as described above or described as preferred, and the at least one compound of the formula (2), as described above or described as preferred , successively or simultaneously from at least two material sources, optionally with further materials, as described above or preferably described, are deposited from the gas phase and form the organic layer.

In a preferred embodiment of the present invention, the at least one organic layer is applied by means of gas phase deposition, the constituents of the composition being premixed and evaporated from a single material source. For this

Embodiments are in particular the mixtures M4 (1 +40), M5 (1 +41), M24 (2 + 37), M26 (2 + 39), M33 (2 + 46), M44 (2 + 57), M48 (3 +38), M50 (3 + 40), M70 (4 + 37), M72 (4 + 39), M81 (4 + 48), M100 (5 + 44), M101 (5 + 45), M117 (6+ 38), M130 (6 + 51), M146 (7 + 44), M165 (8 + 40), M166

(8 + 41), M238 (11 +44), M285 (13 + 42), M301 (13 + 58), M330 (15 + 38), M332 (15 + 40), M333 (15 + 41), M358 ( 16 + 43), M359 (16 + 44), M379 (17 + 41),

M380 (17 + 42), M543 (24 + 44), M562 (25 + 40), M592 (26 + 44), M655

(29 + 38), M657 (29 + 40), M726 (32 + 40), M727 (32 + 41), M772 (34 + 40) and M773 (34 + 41) are suitable. The invention accordingly also relates to a method, characterized in that the composition according to the invention, as described above or preferably described, is used as a material source for the gas phase deposition of the host system, and

optionally with other materials that form the organic layer.

Another object of the invention is a method for producing an organic electronic device containing a

Composition according to the invention, as described above or preferably described, characterized in that the

formulation according to the invention, as described above, is used to apply the organic layer.

The compositions according to the invention or the

Devices according to the invention are characterized by the following

surprising advantages compared to the state of the art:

The use of the compositions according to the invention in organic electronic devices, in particular in an organic electroluminescent device, and in particular in an OLED or OLEC, leads to significant increases in current efficiency with a comparable or improved service life of the devices.

As can be seen in Example 1 given below, by using compounds according to the prior art, for example the compound SoA1, at low emitter concentrations in the EML of 8% in Example V1, a good voltage, but a relatively low one

Achieve electricity efficiency. An improvement in the current efficiency and / or service life at a comparable operating voltage can be achieved by the inventive Combination of the compounds of the formula (1), as described above, with compounds of the formula (2), as described above, can be achieved.

This improvement in power efficiency at comparable

Operating voltage can be preferred by the invention

Combination of the compounds of the formula (1), as described above, with compounds of the formula (2), as described above

Emitter concentrations of 2 to 25 percent by volume, preferably at emitter concentrations of 5 to 15 percent by volume, particularly preferably at emitter concentrations of 7, 8 and 12 percent by volume, in the

Emission layer can be achieved.

This improves electricity efficiency and lifespan

comparable operating voltage for special combinations can preferably be achieved by the inventive combination of the compounds of the formula (1), as described above, with compounds of the formula (2), as described above, at emitter concentrations of 2 to 25

Volume percent, preferably at emitter concentrations of 5 to 15 volume percent, particularly preferably at emitter concentrations of 7, 8 and 12 volume percent, can be achieved in the emission layer.

The difference of the compound of the formula (1) represented by

Compound 4 to compounds of the prior art, such as SoA1, is in the 8-position in the connection to the dibenzofuran.

Unforeseeable for the person skilled in the art, this change in position of the substituent causes an improvement in the current efficiency of

electronic devices, in particular OLEDs, from approx. 10 to 30%, with a comparable or improved service life. The compositions according to the invention are very suitable for use in an emission layer and show improved performance data, in particular for service life, operating voltage and / or Current efficiency versus prior art compounds as previously described.

The compositions according to the invention can easily be processed and are therefore very suitable for mass production in commercial use.

The compositions according to the invention can be premixed and vapor-deposited from a single material source, so that an organic layer with an even distribution of the components used can be produced in a simple and rapid manner.

These advantages mentioned above are not accompanied by a deterioration in the other electronic properties of an electronic device.

It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Each feature disclosed in the present invention can, unless this is explicitly excluded, be replaced by alternative features that serve the same, an equivalent or a similar purpose. Thus, unless otherwise stated, each feature disclosed in the present invention is to be regarded as an example of a generic series, or as an equivalent or similar feature.

All the features of the present invention can be combined with one another in any way, unless certain features and / or steps are mutually exclusive. This is particularly true of preferred features of the present invention. Likewise can Features of non-essential combinations are used separately (and not in combination).

The teaching on technical action disclosed with the present invention can be abstracted and combined with other examples.

The invention is explained in more detail by the following examples, without wishing to restrict it thereby.

General methods:

Determination of orbital energies and electronic states

The HOMO and LUMO energies as well as the triplet level and the

Singlet levels of the materials are quantum chemical

Bills determined. The program package “Gaussian09, Revision D.01” (Gaussian Inc.) is used for this purpose. To calculate organic substances without metals (designated with the "org." Method), a geometry optimization with the semi-empirical method AM1 (Gaussian input line "# AM1 opt") with the charge (charge) 0 and the multiplicity (multiplicity) 1 carried out. This is followed by an energy calculation (single point) for the electronic ground state and the triplet level based on the optimized geometry. The TDDFT method (time dependent density functional theory) B3PW91 with the basic set 6-31 G (d) (Gaussian input line "# B3PW91 / 6-31 G (d) td = (50-50, nstates = 4) “) Is used (charge 0, multiplicity 1). For

organometallic compounds (designated with the "M-org." method), the geometry is optimized using the Hartree-Fock method and the LanL2MB basic set (Gaussian input line "# HF / LanL2MB opt") (charge 0,

Multiplicity 1). The energy calculation is carried out, as described above, in the same way as for organic substances, with the difference that the basic set "LanL2DZ" is used for the metal atom and the basic set "6- 31 G (d)" is used for the ligands (Gaussian input line " # B3PW91 / gen

pseudo = lanl2 td = (50-50, nstates = 4) "). From the energy bill you get the HOMO as the last orbital occupied by two electrons (Alpha occ. eigenvalues) and LUMO as the first unoccupied orbital (Alpha virt.

eigenvalues) in Hartree units, where HEh and LEh stand for the HOMO energy in Hartree units and for the LUMO energy in Hartree units. This becomes the based on

Cyclic voltammetry measurements calibrated HOMO and LUMO values in electron volts are determined as follows:

HOMO (eV) = (HEh * 27.212) * 0.8308-1.118;

LUMO (eV) = (LEh * 27.212) * 1.0658-0.5049.

The triplet level T1 of a material is defined as its relative

Excitation energy (in eV) of the triplet state with the lowest energy, which results from the quantum chemical energy calculation.

The singlet level S1 of a material is defined as its relative

Excitation energy (in eV) of the singlet state with the second lowest energy, which results from the quantum chemical energy calculation.

The energetically lowest singlet state is called SO.

The method described here is independent of the software package used and always delivers the same results. Examples of programs often used for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). The program package "Gaussian09, Revision D.01" is used to calculate the energies. Example 1: Production of the OLEDs

In the following examples E1 to E55 (see Table 6) the use of the material combinations according to the invention in OLEDs is presented in comparison to examples V1 to V11.

Pretreatment for examples V1 to E55: glass flakes coated with structured ITO (indium tin oxide) with a thickness of 50 nm, are first treated with an oxygen plasma, followed by an argon plasma, before coating. These plasma-treated glass plates form the substrates on which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electrons

blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs is shown in Table 6. The materials required to produce the OLEDs are shown in Table 8. The device data of the OLEDs are listed in Table 7. Examples V1, V2, V3, V10 and V11 are comparative examples with an electron-transporting host according to the prior art CN107973786. Examples C4, C5, C6 and C7 are comparative examples with the host according to the prior art WO 2015/014435. The examples V8 and V9 are

Comparative examples with the host according to the prior art

KR20160046077. Examples E1 to E55 show data from

OLEDs according to the invention.

All materials are thermally vapor deposited in a vacuum chamber. The emission layer always consists of at least two

Matrix materials and an emitting dopant (dopant, emitter), which is added to the matrix material or the matrix materials by co-vaporization in a certain volume proportion. A specification such as SoA1: 40: TEG3 (32%: 60%: 8%) means that the material SoA1 in a volume proportion of 32%, the connection 40 as co-host in a proportion of 60% and TEG3 in a proportion of 8% is present in the layer. Similarly, the electron transport layer can also consist of a mixture of two materials. The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra and the current efficiency (SE, measured in cd / A) as a function of the luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a

Lambertian radiation characteristics and the service life are determined. The electroluminescence spectra are determined at a luminance of 1000 cd / m ² and the CIE 1931 x and y color coordinates are calculated therefrom. The specification U 10 in Table 7 denotes the voltage that is required for a current density of 10 mA / cm ² . SE10 denotes the current efficiency which is achieved at 10mA / cm ² .

The service life LT is defined as the time after which the luminance drops to a certain proportion L1 during operation with the same starting brightness L0. An indication of L1 = 80% in Table 7 means that the service life specified in column LT in hours (h) corresponds to the time after which the luminance drops to 80% of its initial value.

That means, for example, with an L0 of 20,000 cd / m ² , that would be the time that is required so that the sample only has a luminance of

L1 = 0.8xL0 = 16000 cd / m ² . Use of mixtures according to the invention in OLEDs

The material combinations according to the invention can be used in the

Emission layer can be used in phosphorescent green OLEDs. The combinations according to the invention of compounds 2, 3, 4, 5, 6, 9, 11, 13, 14, 17, 18, 22, 28, 30, 31, 32, 33, 34, 67, 69, 70, 72, 75 , 76, 77 and 79 with connection 37, 38, 40, 41, 42, 43, 44, 47, 48, 49, 52, 56, 58,

60, 61, 62, 63, 64, 65, 66 or 66a are used as matrix material in the emission layer in Examples E1 to E55, as described in Table 6. The results of Table 7 are directly comparable if the same emitter was used, for example V1 with E1 or E1 with E4 and V2 with E2.

So when comparing the examples according to the invention with the

corresponding comparative examples, such as E1 in conjunction with V1, E2 in conjunction with V2, E3 iV for V3, E27 iV for V4, E28, iV for V5, E29 iV for V6, E30 iV for V7, E31 iV for V8, E32 iV for V9, E33 iV for E10 and E34 iV for V11, clearly recognizable that the Examples according to the invention each show a clear advantage in service life.

Table 6: Structure of the OLEDs

Table 7: Data of the OLEDs

Table 8: Structural formulas of the materials in the OLEDs

Example 2: Synthesis of Compounds

a) 2- {12-chloro-8-oxatricyclo [7.4.0.0 ² ' ⁷ ] trideca-1 (13), 2 (7), 3, 5, 9,11 - hexaen-3-yl} -4- { 8-oxatricyclo [7.4.0.0 ² ' ⁷ ] trideca-1 (9), 2,4,6,10,12-hexaen-3-yl} -6-phenyl-1,3,5-triazine

58 g (210 mmol; 1.00 eq.) 1-boronyl-8-chloro-dibenzofuran [CAS 162667-19-4], 90.2 g (252 mmol; 1.20 eq.) 2-chloro-4- {8-oxatricyclo [7.4.0.0 ^2J ] trideca- 1 (9), 2 (7), 3, 5, 10, 12-hexaen-3-yl} -6-phenyl-1, 3,5-triazine [CAS 1883265-32-4] and 44.5 g (420 mmol, 2.00 eq.) Sodium carbonate [CAS 497-19-8] are in a mixture of 1000 ml_ dioxane [CAS 123-91-1], 1000 ml_ toluene [CAS 108-88-3] and 400 ml_ water suspended. To this

4.85 g (4.20 mmol; 0.02 eq.) Of tetrakis (triphenylphosphine) palladium (O) [CAS 14221-01-3] are added to the suspension, and the

The reaction mixture is refluxed for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The yield is 79.1 g (151 mmol; 72% of theory).

Instead of 1-boronyl-8-chloro-dibenzofuran [CAS 162667-19-4], 8-chloro-1- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) - dibenzothiophene

[CAS-2140848-96-8] can be used.

The following compounds can be obtained analogously:

1 (9), 2 (7), 3,5,12-hexaen-3-yl} -4,6-diphenyl-1,3,5-triazine [CAS 1822310-63-3], 13.0 g ( 40.7 mmol; 1.10 eq.) 3-Biphenyl-3-yl-9H-carbazole [CAS 1643526-99-1] and 7.82 g (81.4 mmol; 2.00 eq.) sodium te / f-butylate [CAS 865-47-4] are dissolved in 500 ml_ o / f / 70-xylene [CAS 95-47-6 ] suspended. 1.50 g (3.66 mmol; 9 mol%) of dicyclohexyl- (2 ', 6'-dimethoxy-biphenyl-2-yl) - phosphane (SPhos) [CAS 657408-07-6] and 1 , 12 g (1, 22 mmol, 3 mol%)

Tris (dibenzylideneacetone) dipalladium [CAS 51364-51-3] was added and the reaction mixture was refluxed for 16 h. The reaction mixture is cooled to room temperature and the solvent is removed under reduced pressure. The solid obtained is washed with 300 ml of ethanol and recrystallized several times from a mixture of heptane and xylene. After hot filtration through Alox and subsequent sublimation in a high vacuum, the purified product is obtained as a colorless solid 21.1 g (29.5 mmol; 69%).

The following compounds can be obtained analogously:

30th

Claims

The following applies to the symbols and indices used:

, where ^* means the binding point to an X at each occurrence,

Y ¹ is selected from NAr-i, C (R ^* ) 2, 0 or S; Y is selected from 0 or S;

L is, identically or differently, a simple at each occurrence

bond or an aromatic ring system with 6 to 30

aromatic ring atoms which can be substituted by one or more radicals R ⁵ ;

n and m are independently 0, 1, 2 or 3 on each occurrence,

o, p and q are independently 0, 1, 2, 3 or 4 on each occurrence;

RA is H, -I_3-Ar4, or -Li-N (Ar) 2;

RB is Ar3 or -l_2-N (Ar) 2;

Li _, l_2 _, are identical or different on each occurrence

l_3 is a single bond or an aromatic or

heteroaromatic ring system with 5 to 30 aromatic

Ar3 is an aromatic ring system with 6 to 40 aromatic rings

Ar4 is on each occurrence, identically or differently, an unsubstituted or substituted 9-aryl-carbazolyl or unsubstituted or substituted carbazol-9-yl which has one or more radicals

R ⁴ can be substituted and where, independently of one another, two radicals R ⁴ or one radical R ⁴ together one or more times with a radical R ^{2 can form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring, where aryl means an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms which can be substituted by R ³ ;

R * is on each occurrence, identically or differently, a straight-chain alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 12 carbon atoms, where two substituents R * can together form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more substituents R ⁵ ;

R °, R, R ¹ 'R ² are identical or different on each occurrence

Thioalkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 carbon atoms or an alkenyl group with 2 to 20 carbon atoms, each of which can be substituted by one or more radicals R ³ , with one or more non-adjacent CH ₂ groups through

R ³ C = CR ³ , Si (R ³ ) ₂ , C = 0, C = S, C = NR ³ , P (= 0) (R ³ ), SO, S0 ₂ , NR ³ , O, S or CONR ³ can be replaced and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or N0 ₂ , an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each with one or more

R ³ can be substituted, an aryloxy or fleteroaryloxy group with 5 to 40 aromatic ring atoms, which can be substituted with one or more R ³ , or an aralkyl or fleteroaralkyl group with 5 to 40 aromatic ring atoms, which with one or several radicals R ³ can be substituted; optionally two substituents R ° and / or R and / or R ¹ and / or R ² can be attached to the same carbon atom or to adjacent ones Carbon atoms are bonded to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more radicals R ³ ;

R ³ is selected identically or differently on each occurrence from

Group consisting of H, D, F, CN, N (Ar) 2, an aliphatic hydrocarbon radical with 1 to 20 C atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms in which one or more H atoms can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; two or more adjacent substituents R ^{3 here} can form a mono- or polycyclic, aliphatic ring system with one another;

R ⁴ is selected identically or differently on each occurrence from

Group consisting of H, D, F, CN, an aliphatic hydrocarbon radical with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms in which one or more Fl atoms are replaced by D, F, CI, Br, I, a straight-chain or branched alkyl group with 1 to 4

R ⁵ is on each occurrence, identically or differently, selected from the group consisting of D, F, CN and an aryl group with 6 to 18

C atoms, two or more adjacent R ⁵ substituents can form a mono- or polycyclic, aliphatic ring system with one another;

Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 30 aromatic rings

Ring atoms which can be substituted by one or more non-aromatic radicals R ³ ; two residues Ar, which bond to the same N atom, P atom or B atom, also by a single bond or a bridge selected from N (R ³ ), C (R ³ ) ₂ , O or S, be bridged to one another and

r is independently 0, 1, 2 or 3 on each occurrence;

s means 0, 1, 2, 3 or 4 independently of one another on each occurrence.

2. Composition according to claim 1, characterized in that Y in formula (1) is 0.

3. Composition according to claim 1 or 2, characterized in that the compound of formula (2) corresponds to one of formulas (2a) to (2d),

Formula (2c) Formula (2d)

where the symbols and indices Li, L ₂ , L3, Ar, Ar3, Ar4, R ² , r and s used have a meaning as in claim 1.

4. Composition according to one or more of claims 1 to 3, characterized in that the composition contains at least one further compound which is selected from the group consisting of hole injection materials, hole transport materials, Hole blocking materials, wide band gap materials, fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron blocking materials, electron transport materials and electron injection materials, n-dopants and p-dopants.

5. Composition according to one or more of claims 1 to 4, characterized in that the composition consists of a compound of the formula (1) and a compound of the formula (2).

6. Formulation containing a composition according to one or more of claims 1 to 5 and at least one solvent.

7. Use of a composition according to one or more of claims 1 to 5 in an organic electronic device.

8. Use according to claim 7, characterized in that the

organic electronic device is selected from the group of organic integrated circuits (OlCs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors and organic photoreceptors.

9. Organic electronic device containing at least one

Composition according to one or more of Claims 1 to 5 in at least one organic layer.

10. The device according to claim 9, characterized in that it is selected from the group of organic integrated circuits (OlCs), organic field-effect transistors (OFETs), organic

Thin Film Transistors (OTFTs), organic Electroluminescent devices, organic solar cells (OSCs), organic optical detectors, and organic photoreceptors.

11.Vorrichtung according to claim 9 or 10, characterized in that it is an electroluminescent device which is selected from the organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic

light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O lasers) and the organic

light emitting diodes (OLEDs).

12. Device according to one or more of claims 9 to 11,

characterized in that this the composition according to one or more of claims 1 to 6 in an emission layer

(EML), in an electron transport layer (ETL), in a

Electron injection layer (EIL) and / or in a hole blocking layer (HBL).

13. Device according to claim 11 or 12 comprising an anode, a cathode and at least one organic layer

at least one light-emitting layer, characterized in that it contains the composition according to one or more of Claims 1 to 5 in the at least one emission layer together with a phosphorescent emitter.

14. The method for producing a device according to one or more of claims 9 to 13, characterized in that at least one organic layer containing a composition according to one or more of claims 1 to 5 is applied by gas phase deposition or from solution.

15. The method according to claim 14, characterized in that the at least one compound of the formula (1) and the at least one compound of the formula (2), as described in one of claims 1 to 4, sequentially or simultaneously from at least two material sources, optionally with other materials from which

Gas phase are deposited and form the organic layer.

16. The method according to claim 14, characterized in that the

The composition of claim 5 as a source of material for

Gas phase deposition of the floss system is used and

optionally forms the organic layer with other materials.

17. The method according to claim 14, characterized in that the

Formulation according to claim 6 is used to apply the organic layer.