ORGANIC ELECTROLUMINESCENT APPARATUS

Abstract

The present invention relates to an organic electroluminescent device comprising a mixture comprising an electron-transporting host material and a hole-transporting host material, and to a formulation comprising a mixture of the host materials and to a mixture comprising the host materials. The electron-transporting host material corresponds to a compound of the formula (1) from the class of compounds containing a pyridine, pyrimidine or triazine unit substituted by a dibenzofuran or dibenzothiophene.

Claims

1.-15. (canceled)

16. An organic electroluminescent device comprising an anode, a cathode and at least one organic layer, containing at least one light-emitting layer, wherein the at least one light-emitting layer contains at least one compound of the formula (1) as host material 1 and at least one compound of the formula (2) as host material 2 ##STR01729## where the symbols and indices used are as follows: X is the same or different at each instance and is CR0 or N, where at least one symbol X is N; X.sub.1 is the same or different at each instance and is CH, CR or N, where not more than 3 symbols X.sub.1 can be N; X.sub.2 is the same or different at each instance and is CH, CR.sup.1 or N, where not more than 2 symbols X.sub.2 can be N; Y is the same or different at each instance and is selected from O or S; L and L.sub.1 are the same or different at each instance and are a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms; R.sup.0 at each instance is independently H, D or an unsubstituted or partly or fully deuterated aromatic ring system having 6 to 18 carbon atoms; R and R# are the same or different at each instance and are selected from the group consisting of D, F, Cl, Br, I, CN, NO.sub.2, C(═O)R.sup.2, P(═O)(Ar.sub.1).sub.2, P(Ar.sub.1).sub.2, B(Ar.sub.1).sub.2, Si(Ar.sub.1).sub.3, Si(R.sup.2).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, it is possible for two substituents R bonded to the same carbon atom or to adjacent carbon atoms or for one substituent R together with Ar.sub.3 to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.2 radicals; R.sup.1 is the same or different at each instance and is selected from the group consisting of CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms; at the same time, it is possible for two substituents R.sup.1 bonded to the same carbon atom or to adjacent carbon atoms to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system that may be substituted by one or more R.sup.2 radicals; R.sup.2 is the same or different at each instance and is selected from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sub.1).sub.2, NH.sub.2, N(R.sup.3).sub.2, C(═O)Ar.sub.1, C(═O)H, C(═O)R.sup.3, P(═O)(Ar.sub.1).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by HC═CH, R.sup.3C═CR.sup.3, C≡C, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═Se, C═NR.sup.3, P(═O)(R.sup.3), SO, SO.sub.2, NH, NR.sup.3, O, S, CONH or CONR.sup.3 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; where it is optionally possible for two or more adjacent substituents R.sup.2 to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.3 radicals; R.sup.3 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, it is possible for two or more adjacent R.sup.3 substituents together to form a mono- or polycyclic, aliphatic ring system; Ar.sub.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more nonaromatic R.sup.3 radicals; at the same time, two Ar.sub.1 radicals bonded to the same nitrogen atom, phosphorus atom or boron atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.3), C(R.sup.3).sub.2, O or S; Ar.sub.2 at each instance is independently an aryl or heteroaryl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; Ar.sub.3 at each instance is independently an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R.sup.2 radicals; A at each instance is independently a group of the formula (3) or (4), ##STR01730## Ar at each instance is in each case independently an aryl group which has 6 to 40 aromatic ring atoms and may be substituted by one or more R# radicals, or a heteroaryl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R# radicals; * indicates the binding site to the formula (2); a, b, c at each instance are each independently 0 or 1, where the sum total of the indices at each instance a+b+c is 1; o is 1, 2, 3 or 4; n, m and p at each instance are independently 1, 2 or 3; and q, r, s, t at each instance are each independently 0 or 1.

17. The organic electroluminescent device according to claim 16, wherein L in host material 1 is selected from a bond or the linkers from the group of L-1 to L-33 ##STR01731## ##STR01732## ##STR01733## ##STR01734## where each W is independently O or S.

18. The organic electroluminescent device according to claim 16, wherein host material 2 conforms to one of the formulae (2a), (2b) or (2c) ##STR01735## where the symbols and indices A, R.sup.1, q, r and s used are as defined in claim 16.

19. The organic electroluminescent device according to claim 16, wherein L.sub.1 in host material 1 is a single bond.

20. The organic electroluminescent device according to claim 16, wherein the device is an electroluminescent device selected from 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).

21. The organic electroluminescent device according to claim 16, wherein the device comprises, in addition to the light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), an electron injection layer (EIL) and/or a hole blocker layer (HBL).

22. The organic electroluminescent device according to claim 16, wherein the light-emitting layer, as well as the at least one host material 1 and the at least one host material 2, contains at least one phosphorescent emitter.

23. The organic electroluminescent device according to claim 22, wherein the phosphorescent emitter conforms to the formula (III) ##STR01736## where the symbols and indices for this formula (III) are defined as follows: n+m is 3, n is 1 or 2, m is 2 or 1, X is N or CR, R is H, D or a branched or linear alkyl group or a partly or fully deuterated, branched or linear alkyl group.

24. A process for producing the device according to claim 16 comprising applying the light-emitting layer by gas phase deposition or from solution.

25. The process according to claim 24, wherein the at least one compound of the formula (1) and the at least one compound of the formula (2) are deposited from the gas phase successively or simultaneously from at least two material sources, optionally with the at least one phosphorescent emitter, and form the light-emitting layer.

26. The process according to claim 24, wherein the at least one compound of the formula (1) and the at least one compound of the formula (2) are deposited from the gas phase as a mixture, successively or simultaneously with the at least one phosphorescent emitter, and form the light-emitting layer.

27. The process according to claim 24, wherein the at least one compound of the formula (1) and the at least one compound of the formula (2) are applied from a solution together with the at least one phosphorescent emitter in order to form the light-emitting layer.

28. A mixture comprising at least one compound of the formula (1) as host material 1 and at least one compound of the formula (2) as host material 2 ##STR01737## where the symbols and indices used are as follows: X is the same or different at each instance and is CR.sup.0 or N, where at least one symbol X is N; X.sub.1 is the same or different at each instance and is CH, CR or N, where not more than 3 symbols X.sub.1 can be N; X.sub.2 is the same or different at each instance and is CH, CR.sup.1 or N, where not more than 2 symbols X.sub.2 can be N; Y is the same or different at each instance and is selected from O or S; L and L.sub.1 are the same or different at each instance and are a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms; R.sup.0 at each instance is independently H, D or an unsubstituted or partly or fully deuterated aromatic ring system having 6 to 18 carbon atoms; R and R# are the same or different at each instance and are selected from the group consisting of D, F, Cl, Br, I, CN, NO.sub.2, C(═O)R.sup.2, P(═O)(Ar.sub.1).sub.2, P(Ar.sub.1).sub.2, B(Ar.sub.1).sub.2, Si(Ar.sub.1).sub.3, Si(R.sup.2).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, it is possible for two substituents R bonded to the same carbon atom or to adjacent carbon atoms or for one substituent R together with Ar.sub.3 to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.2 radicals; R.sup.1 is the same or different at each instance and is selected from the group consisting of CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms; at the same time, it is possible for two substituents R.sup.1 bonded to the same carbon atom or to adjacent carbon atoms to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system that may be substituted by one or more R.sup.2 radicals; R.sup.2 is the same or different at each instance and is selected from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sub.1).sub.2, NH.sub.2, N(R.sup.3).sub.2, C(═O)Ar.sub.1, C(═O)H, C(═O)R.sup.3, P(═O)(Ar.sub.1).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by HC═CH, R.sup.3C═CR.sup.3, C≡C, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═Se, C═NR.sup.3, P(═O)(R.sup.3), SO, SO.sub.2, NH, NR.sup.3, O, S, CONH or CONR.sup.3 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; where it is optionally possible for two or more adjacent substituents R.sup.2 to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.3 radicals; R.sup.3 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, it is possible for two or more adjacent R.sup.3 substituents together to form a mono- or polycyclic, aliphatic ring system; Ar.sub.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more nonaromatic R.sup.3 radicals; at the same time, two Ar.sub.1 radicals bonded to the same nitrogen atom, phosphorus atom or boron atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.3), C(R.sup.3).sub.2, O and S; Ar.sub.2 at each instance is independently an aryl or heteroaryl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; Ar.sub.3 at each instance is independently an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R.sup.2 radicals; A at each instance is independently a group of the formula (3) or (4), ##STR01738## Ar at each instance is in each case independently an aryl group which has 6 to 40 aromatic ring atoms and may be substituted by one or more R# radicals, or a heteroaryl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R# radicals; * indicates the binding site to the formula (2); a, b, c at each instance are each independently 0 or 1, where the sum total of the indices at each instance a+b+c is 1; o is 1, 2, 3 or 4; n, m and p at each instance are independently 1, 2 or 3; and q, r, s, t at each instance are each independently 0 or 1.

29. The mixture according to claim 28, wherein the mixture consists of at least one compound of the formula (1), at least one compound of the formula (2) and a phosphorescent emitter.

30. A formulation comprising the mixture according to claim 28 and at least one solvent.

Description

EXAMPLE 1: PRODUCTION OF THE OLEDS

[0277] The examples which follow (see tables 8 to 10) present the use of the material combinations of the invention in OLEDs by comparison with material combinations from the prior art.

[0278] Pretreatment for examples V1 to V6 and E1a to E6f: Glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating, first with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plates form the substrates to which the OLEDs are applied.

[0279] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in table 8. The materials required for production of the OLEDs, if they have not already been described before, are shown in table 10. The device data of the OLEDs are listed in table 9.

[0280] Examples V1 and V6 are comparative examples of the host materials E40 to E45 that are known from WO19007866 with a biscarbazole as hole-transporting host according to the prior art, for example WO19007866. Examples E1a to E6f show data for OLEDs of the invention.

[0281] All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least two matrix materials and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as E40:BCbz1:TE2 (32%:60%:8%) mean here that the material E40 is present in the layer in a proportion by volume of 32%, BCbz1 in a proportion of 60% and TE2 in a proportion of 8%.

[0282] Analogously, the electron transport layer may also consist of a mixture of two materials.

[0283] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) are measured. EQE and current efficiency SE (in cd/A) are calculated therefrom. SE is calculated assuming Lambertian emission characteristics.

[0284] The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U10 in table 2 refers to the voltage which is required for a current density of 10 mA/cm.sup.2. CE10 and EQE10 respectively denote the current efficiency and external quantum efficiency that are attained at 10 mA/cm.sup.2.

[0285] The lifetime LT is defined as the time after which luminance, measured in cd/m.sup.2 in forward direction, drops from the starting luminance to a certain proportion L1 in the course of operation with constant current density jo. A figure of L1=80% in table 9 means that the lifetime reported in the LT column corresponds to the time after which luminance in cd/m.sup.2 falls to 80% of its starting value.

[0286] Use of Mixtures of the Invention in OLEDs

[0287] The material combinations of the invention are used in examples E1a-i, E2a-f, E3a-f, E4a-f, E5a-g, E6a-f as matrix material in the emission layer of green-phosphorescing OLEDs. As a comparison with the prior art, materials E40 to E45 with BCbz1 to BCbz3 are used in examples V1 to V6.

[0288] On comparison of the inventive examples with the corresponding comparative examples, it is clearly apparent that the inventive examples each show a distinct advantage in device lifetime, with otherwise comparable performance data of the OLEDs.

TABLE-US-00008 TABLE 8 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness V1 SpMA1:PD1 SpMA1 SpMA2 E40:BCbz1:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1a SpMA1:PD1 SpMA1 SpMA2 E40:H3:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1b SpMA1:PD1 SpMA1 SpMA2 E40:H7:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1c SpMA1:PD1 SpMA1 SpMA2 E40:H12:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1d SpMA1:PD1 SpMA1 SpMA2 E1:H13:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1e SpMA1:PD1 SpMA1 SpMA2 E3:H18:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1f SpMA1:PD1 SpMA1 SpMA2 E10:H16:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1g SpMA1:PD1 SpMA1 SpMA2 E14:H3:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1h SpMA1:PD1 SpMA1 SpMA2 E29:H16:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E1i SpMA1:PD1 SpMA1 SpMA2 E34:H13:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm V2 SpMA1:PD1 SpMA1 SpMA2 E41:BCbz1:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E2a SpMA1:PD1 SpMA1 SpMA2 E41:H5:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E2b SpMA1:PD1 SpMA1 SpMA2 E41:H8:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E2c SpMA1:PD1 SpMA1 SpMA2 E41:H10:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E2d SpMA1:PD1 SpMA1 SpMA2 E6:H5:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E2e SpMA1:PD1 SpMA1 SpMA2 E8:H17:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E2f SpMA1:PD1 SpMA1 SpMA2 E48:H17:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm V3 SpMA1:PD1 SpMA1 SpMA2 E42:BCbz2:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E3a SpMA1:PD1 SpMA1 SpMA2 E42:H3:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E3b SpMA1:PD1 SpMA1 SpMA2 E28:H3:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E3c SpMA1:PD1 SpMA1 SpMA2 E26:H5:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E3d SpMA1:PD1 SpMA1 SpMA2 E24:H7:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E3e SpMA1:PD1 SpMA1 SpMA2 E33:H12:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E3f SpMA1:PD1 SpMA1 SpMA2 E46:H7:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm V4 SpMA1:PD1 SpMA1 SpMA2 E43:BCbz2:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E4a SpMA1:PD1 SpMA1 SpMA2 E43:H5:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E4b SpMA1:PD1 SpMA1 SpMA2 E4:H7:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E4c SpMA1:PD1 SpMA1 SpMA2 E20:H8:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E4d SpMA1:PD1 SpMA1 SpMA2 E19:H5:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E4e SpMA1:PD1 SpMA1 SpMA2 E22:H3:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E4f SpMA1:PD1 SpMA1 SpMA2 E32:H18:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm V5 SpMA1:PD1 SpMA1 SpMA2 E44:BCbz3:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (38%:50%:12%) 40 nm 5 nm (50%:50%) 30 nm E5a SpMA1:PD1 SpMA1 SpMA2 E44:H3:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (38%:50%:12%) 40 nm 5 nm (50%:50%) 30 nm E5b SpMA1:PD1 SpMA1 SpMA2 E5:H14:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (38%:50%:12%) 40 nm 5 nm (50%:50%) 30 nm E5c SpMA1:PD1 SpMA1 SpMA2 E14:H3:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (38%:50%:12%) 40 nm 5 nm (50%:50%) 30 nm E5d SpMA1:PD1 SpMA1 SpMA2 E21:H8:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (38%:50%:12%) 40 nm 5 nm (50%:50%) 30 nm E5e SpMA1:PD1 SpMA1 SpMA2 E16:H12:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (38%:50%:12%) 40 nm 5 nm (50%:50%) 30 nm E5f SpMA1:PD1 SpMA1 SpMA2 E30:H3:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (38%:50%:12%) 40 nm 5 nm (50%:50%) 30 nm E5g SpMA1:PD1 SpMA1 SpMA2 E47:H5:TE1 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (38%:50%:12%) 40 nm 5 nm (50%:50%) 30 nm V6 SpMA1:PD1 SpMA1 SpMA2 E45:BCbz3:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E6a SpMA1:PD1 SpMA1 SpMA2 E45:H3:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E6b SpMA1:PD1 SpMA1 SpMA2 E7:H3:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E6c SpMA1:PD1 SpMA1 SpMA2 E12:H7:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E6d SpMA1:PD1 SpMA1 SpMA2 E18:H13:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E6e SpMA1:PD1 SpMA1 SpMA2 E31:H5:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm E6f SpMA1:PD1 SpMA1 SpMA2 E36:H3:TE2 ST2 ST2:LiQ LiQ 1 nm (95%:5%) 20 nm 200 nm 20 nm (32%:60%:8%) 40 nm 5 nm (50%:50%) 30 nm

TABLE-US-00009 TABLE 9 Data of the OLEDs U10 EQE10 CIE x/y at j.sub.0 L1 LT Ex. (V) (%) 1000 cd/m.sup.2 (mA/cm.sup.2) (%) (h) V1 4.4 21.5 0.35/0.63 40 80 620 E1a 4.5 21.6 0.35/0.63 40 80 790 E1b 4.4 21.5 0.35/0.63 40 80 820 E1c 4.6 21.4 0.35/0.63 40 80 840 E1d 4.4 22.7 0.35/0.63 40 80 785 E1e 4.4 22.5 0.35/0.63 40 80 740 E1f 4.6 22.0 0.35/0.63 40 80 710 E1d 4.3 21.9 0.35/0.63 40 80 800 E1h 4.7 21.9 0.35/0.63 40 80 710 E1i 4.5 22.0 0.35/0.63 40 80 825 V2 4.4 23.7 0.35/0.63 40 80 510 E2a 4.5 22.2 0.35/0.63 40 80 665 E2b 4.6 22.9 0.35/0.63 40 80 740 E2c 4.4 22.6 0.35/0.63 40 80 575 E2d 4.6 21.7 0.35/0.63 40 80 800 E2e 4.6 22.1 0.35/0.63 40 80 640 E2f 4.6 21.3 0.34/0.63 40 80 665 V3 4.4 23.0 0.35/0.63 40 80 480 E3a 4.5 22.7 0.35/0.63 40 80 630 E3b 4.6 22.2 0.35/0.63 40 80 710 E3c 4.45 21.8 0.35/0.63 40 80 770 E3d 4.8 22.2 0.35/0.63 40 80 660 E3e 4.4 23.1 0.35/0.63 40 80 665 E3f 4.6 22.4 0.34/0.62 40 80 710 V4 5.0 19.2 0.34/0.62 40 80 675 E4a 5.2 19.3 0.34/0.62 40 80 1040 E4b 4.9 18.6 0.34/0.62 40 80 1160 E4c 4.9 19.5 0.34/0.62 40 80 1265 E4d 5.0 18.4 0.34/0.62 40 80 1140 E4e 4.9 19.3 0.34/0.62 40 80 830 E4f 5.1 18.2 0.34/0.62 40 80 880 V5 4.5 18.1 0.34/0.62 40 80 1070 E5a 4.6 18.4 0.34/0.62 40 80 1815 E5b 4.4 17.3 0.34/0.62 40 80 1320 E5c 4.4 18.7 0.34/0.62 40 80 1650 E5d 4.3 18.6 0.34/0.62 40 80 1295 E5e 4.7 18.4 0.34/0.62 40 80 1400 E5f 4.5 16.5 0.34/0.62 40 80 1980 E5g 4.4 18.8 0.34/0.63 40 80 1690 V6 4.5 21.9 0.35/0.63 40 80 630 E6a 4.4 22.4 0.35/0.63 40 80 765 E6b 4.4 22.9 0.35/0.63 40 80 720 E6c 4.3 23.1 0.35/0.63 40 80 990 E6d 4.5 22.1 0.35/0.63 40 80 790 E6e 4.6 22.5 0.35/0.63 40 80 835 E6f 4.3 21.5 0.35/0.63 40 80 745

TABLE-US-00010 TABLE 10 Structural formulae of the materials of the OLEDs used, if not already described before [01521] PD1 [01522] SpMA1 [01523] SpMA2 [01524] ST2 [01525] LiQ [01526] TE1 [01527] TE2 [01528] BCbz1 [01529] BCbz2 [01530] BCbz3

[0289] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

##STR01531##

[0290] To an initial charge of 1-chloro-8-bromodibenzofuran (100 g, 353.6 mmol) [CAS-2225909-61-3] and B-(9-phenyl-9H-carbazol-2-yl)boronic acid (106.6 g, 371.3 mmol) [1001911-63-2] in toluene (800 ml), 1,4-dioxane (800 ml) and water (400 ml) under inert atmosphere are added Na.sub.2CO.sub.3 (74.95 g, 0.71 mol) and tetrakis(triphenylphosphine)palladium(0) (4.09 g, 3.54 mmol), and the mixture is stirred under reflux for 16 h.

[0291] After cooling, the mixture is filtered with suction through a Celite-filled frit, and worked up by extraction with toluene and water. The aqueous phase is extracted twice with toluene (500 ml each time), and the combined organic phases are dried over Na.sub.2SO.sub.4. The solvent is removed on a rotary evaporator, and the crude product is converted to a slurry with ethanol (1200 ml) and stirred under reflux for 2 h. The solids are filtered off with suction, washed with ethanol and dried in a vacuum drying cabinet.

[0292] Yield: 138.5 g (312.2 mmol, 88%), 97% by .sup.1H NMR The following compounds can be prepared analogously: Purification can also be accomplished using column chromatography, or recrystallization or hot extraction using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00011 Reactant 1 Reactant 2 Product Yield [01532] [01533] [01534] 63% [01535] [01536] [01537] 62% [01538] [01539] [01540] 71% [01541] [01542] [01543] 77% [01544] [01545] [01546] 56% [01547] [01548] [01549] 52% [01550] [01551] [01552] 68% [01553] [01554] [01555] 69% [01556] [01557] [01558] 67% [01559] [01560] [01561] 52% [01562] [01563] [01564] 68% [01565] [01566] [01567] 72% [01568] [01569] [01570] 80% [01571] [01572] [01573] 73% [01574] [01575] [01576] 66% [01577] [01578] [01579] 60%

##STR01580##

[0293] To an initial charge of S1a (124.30 g, 280 mmol) and 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (76.20 g, 300 mmol) in 1,4-dioxane (2000 ml) under inert atmosphere are added potassium acetate (82.33 g, 1.40 mol) and trans-dichlorobis(tricyclohexylphosphine)palladium(II) (6.21 g, 83.9 mmol), and the mixture is stirred under reflux for 32 h. After cooling, the solvent is removed by rotary evaporation on a rotary evaporator, the residue is worked up by extraction with toluene/water, and the organic phase is dried over Na.sub.2SO.sub.4. The crude product is extracted by stirring under reflux with ethanol (1100 ml), and the solids are filtered off with suction after cooling and washed with ethanol.

[0294] Yield: 113.5 g (212.5 mmol, 76%), 95% by .sup.1H NMR.

[0295] The following compounds can be prepared analogously: Purification can also be accomplished using column chromatography, or recrystallization or hot extraction using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00012 Reactant 1 Product Yield [01581] [01582] 79% [01583] [01584] 70% [01585] [01586] 66% [01587] [01588] 67% [01589] [01590] 72% [01591] [01592] 64% [01593] [01594] 66% [01595] [01596] 78% [01597] [01598] 59% [01599] [01600] 71% [01601] [01602] 62% [01603] [01604] 67% [01605] [01606] 80% [01607] [01608] 82% [01609] [01610] 72% [01611] [01612] 76%

##STR01613##

[0296] To an initial charge of 9-phenyl-3-[9-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-dibenzofuran-2-yl]-9H-carbazole (22.00 g, 41.1 mmol) [2239299-50-2], 2-chloro-4-{8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(13),2(7),3,5,9,11-hexaen-5-yl}-6-phenyl-1,3,5-triazine (14.70 g, 41.1 mmol) [CAS-2142681-84-1] in THE (650 ml) and water (250 ml) under inert atmosphere are added Na.sub.2CO.sub.3 (9.58 g, 90.4 mmol) and tetrakis(triphenylphosphine)palladium(0) (710 mg, 0.62 mmol), and the mixture is stirred under reflux for 16 h. After cooling, the mixture is worked up by extraction with toluene/water, the aqueous phase is extracted 3 times with toluene (250 ml each time), and the combined organic phases are dried over Na.sub.2SO.sub.4. The crude product is subjected to extraction with hot heptane/toluene twice, recrystallized from n-butyl acetate twice and finally sublimed under high vacuum.

[0297] Yield: 15.5 g (21.2 mmol, 52%); purity: >99.9% by HPLC

[0298] The following compounds can be prepared analogously: The catalyst system used here (palladium source and ligand) may also be Pd.sub.2(dba).sub.3 with SPhos [657408-07-6] or bis(triphenylphosphine)palladium(II) chloride [13965-03-2]. Purification can also be accomplished using column chromatography, or recrystallization or hot extraction using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00013 Reactant 1 Reactant 2 Product Yield [01614] [01615] [01616] 54% [01617] [01618] [01619] 46% [01620] [01621] [01622] 51% [01623] [01624] [01625] 57% [01626] [01627] [01628] 62% [01629] [01630] [01631] 60% [01632] [01633] [01634] 54% [01635] [01636] [01637] 44% [01638] [01639] [01640] 46% [01641] [01642] [01643] 44% [01644] [01645] [01646] 49% [01647] [01648] [01649] 38% [01650] [01651] [01652] 39% [01653] [01654] [01655] 55% [01656] [01657] [01658] 41% [01659] [01660] [01661] 53% [01662] [01663] [01664] 59% [01665] [01666] [01667] 56% [01668] [01669] [01670] 54% [01671] [01672] [01673] 45% [01674] [01675] [01676] 46% [01677] [01678] [01679] 58% [01680] [01681] [01682] 32% [01683] [01684] [01685] 38% [01686] [01687] [01688] 40%

##STR01689##

[0299] To an initial charge of 9-[1,1′-biphenyl]-3-yl-3-bromo-9H-carbazole (59.88 g, 150.3 mmol) [CAS-1428551-28-3], 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indolo[3,2,1-jk]carbazole (51.1 g, 147.3 mmol) [CAS-1454807-26-1] in toluene (1200 ml), 1,4-dioxane (1200 ml) and water (600 ml) under inert atmosphere are added K.sub.3PO.sub.4 (95.7 g, 451 mmol), tri(ortho-tolyl)phosphine (2.33 g, 7.52 mmol) and Pd(OAc).sub.2 (840 mg, 3.76 mmol), and the mixture is stirred under reflux for 32 h. After cooling, the mixture is worked up by extraction with toluene/water, the aqueous phase is extracted 3 times with toluene (500 ml each time), and the combined organic phases are dried over Na.sub.2SO.sub.4. The crude product is first extracted by stirring in EtOH (1500 ml). The solids filtered off are subjected to extraction with hot heptane/toluene twice, recrystallized from DMAc twice and finally sublimed under high vacuum.

[0300] Yield: 40.5 g (72.5 mmol, 48%); purity: >99.9% by HPLC

[0301] The following compounds can be prepared analogously: The catalyst system (palladium source and ligand) used here may also be Pd.sub.2(dba).sub.3 with SPhos [657408-07-6], or tetrakis(triphenylphosphine)palladium(0) or bis(triphenylphosphine)palladium(II) chloride [13965-03-2]. Purification can also be accomplished using column chromatography, or recrystallization or hot extraction using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide N-methylpyrrolidone etc.

TABLE-US-00014 Reactant 1 Reactant 2 Product Yield [01690] [01691] [01692] 47% [01693] [01694] [01695] 59% [01696] [01697] [01698] 64% [01699] [01700] [01701] 55% [01702] [01703] [01704] 50% [01705] [01706] [01707] 45% [01708] [01709] [01710] 58% [01711] [01712] [01713] 62% [01714] [01715] [01716] 38% [01717] [01718] [01719] 46% [01720] [01721] [01722] 40% [01723] [01724] [01725] 52% [01726] [01727] [01728] 41%