Materials for electronic devices

Abstract

The present invention relates to a compound of a formula (I), in which an electron-deficient group and an arylamino group are connected to one another via an intermediate group. The compound of the formula (I) is suitable as functional material in electronic devices.

Claims

1. A compound of the formula (I) ##STR00470## where: Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system selected from the groups of the formula (Ar.sup.1-1) to (Ar.sup.1 10) and (Ar.sup.1-14) to (Ar.sup.1-17),which may be substituted by one or more radicals R.sup.2 ##STR00471## ##STR00472## Ar.sup.2 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 12 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, where the aromatic ring system contains no condensed aryl or heteroaryl group having more than 10 aromatic ring atoms; R.sup.1, R.sup.2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(O)(R.sup.3).sub.2, OR.sup.3, S(O)R.sup.3, S(O).sub.2R.sup.3, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3 and where one or more CH.sub.2 groups in the above-mentioned groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, where two or more radicals R.sup.2 may be linked to one another and may form a ring; R.sup.3 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.3).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.4 and where one or more CH.sub.2 groups in the above-mentioned groups may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)OR), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.4, where two or more radicals R.sup.3 may be linked to one another and may form a ring; R.sup.4 is on each occurrence, identically or differently, H, D, F or an aliphatic, heteroaliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by D or F; two or more substituents R.sup.4 here may be linked to one another and may form a ring; n is equal to 1, 2, 3 or 4; with the proviso that the following is excluded: when n=1, the group Ar.sup.1 is a group of the formula (Ar.sup.1-1) or (Ar.sup.1-14), and when n=2, both groups Ar.sup.1 correspond to a group of the formula (Ar.sup.1-1).

2. The compound according to claim 1, wherein the compound contains precisely one amino group.

3. The compound according to claim 1, wherein the compound contains precisely one triazine group.

4. The compound according to claim 1, wherein the compound contains no condensed aryl group having more than 14 aromatic ring atoms.

5. The compound according to claim 1, wherein R.sup.1 is selected on each occurrence, identically or differently, from CN, an alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms, where the above-mentioned groups may be substituted by one or more radicals R.sup.3, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3.

6. An oligomer, polymer or dendrimer containing one or more compounds according to claim 1, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any positions in formula (I) which are substituted by R.sup.1 or R.sup.2.

7. A formulation comprising at least one compound according to claim 1 and at least one solvent.

8. A formulation comprising at least one polymer, oligomer or dendrimer according to claim 6 and at least one solvent.

9. An electronic device comprising the compound according to claim 1.

10. An electronic device comprising anode, cathode and at least one organic layer, where the organic layer comprises at least one compound according to claim 1.

11. The electronic device according to claim 9, wherein the device is selected from the group consisting of organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

12. An organic electroluminescent device comprising the compound according to claim 1 is employed as matrix material in an emitting layer in combination with one or more emitter compounds.

13. A compound of the formula (I) ##STR00473## where: Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system selected from the groups of the formula (Ar.sup.1-1) to (Ar.sup.1 10) and (Ar.sup.1-14) to (Ar.sup.1-17), which may be substituted by one or more radicals R.sup.2 ##STR00474## ##STR00475## Ar.sup.2 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, where at least one group Ar.sup.2 in the compound of the formula (I) represents a group Ar.sup.2*; Ar.sup.2* is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 12 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, where the aromatic ring system contains no condensed aryl or heteroaryl group having more than 10 aromatic ring atoms; R.sup.1, R.sup.2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(O)(R.sup.3).sub.2, OR.sup.3, S(O)R.sup.3, S(O).sub.2R.sup.3, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3 and where one or more CH.sub.2 groups in the above-mentioned groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R).sub.2, CO, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, where two or more radicals R.sup.2 may be linked to one another and may form a ring; R.sup.3 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.3).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.4 and where one or more CH.sub.2 groups in the above-mentioned groups may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.4, where two or more radicals R.sup.3 may be linked to one another and may form a ring; R.sup.4 is on each occurrence, identically or differently, H, D, F or an aliphatic, heteroaliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by D or F; two or more substituents R.sup.4 here may be linked to one another and may form a ring; n is equal to 1, 2, 3 or 4; with the proviso that the following is excluded: when n=1 or 2, the group Ar.sup.1 is a group of the formula (Ar.sup.1-1) or (Ar.sup.1-14).

14. The compound according to claim 13, wherein the compound contains precisely one amino group.

15. The compound according to claim 13, wherein the compound contains precisely one triazine group.

16. The compound according to claim 13, wherein the compound contains no condensed aryl group having more than 14 aromatic ring atoms.

17. The compound according to claim 13, wherein both groups Ar.sup.2 are selected from identical or different groups Ar.sup.2*.

18. The compound according to claim 13, wherein Ar.sup.2 is selected on each occurrence, identically or differently, from an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2.

19. The compound according to claim 13, wherein Ar.sup.2 is selected on each occurrence, identically or differently, from phenyl, biphenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, indenofluorenyl, naphthyl, anthracenyl, phenanthrenyl, chrysenyl, benzanthracenyl, pyrenyl, triphenylenyl, fluoranthenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, indolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolinyl, acridyl, dihydroacridyl, pyrazolyl, imidazolyl, benzimidazolyl, pyridazyl, pyrimidyl, pyrazinyl and phenanthrolyl, each of which is optionally substituted by one or more radicals R.sup.2.

20. The compound according to claim 13, wherein R.sup.1 is selected on each occurrence, identically or differently, from CN, an alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms, where the above-mentioned groups may be substituted by one or more radicals R.sup.3, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3.

21. An oligomer, polymer or dendrimer containing one or more compounds according to claim 13, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any positions in formula (I) which are substituted by R.sup.1 or R.sup.2.

22. A formulation comprising at least one compound according to claim 13 and at least one solvent.

23. A formulation comprising at least one polymer, oligomer or dendrimer according to claim 21 and at least one solvent.

24. An electronic device comprising the compound according to claim 13.

25. An electronic device comprising anode, cathode and at least one organic layer, where the organic layer comprises at least one compound according to claim 13.

26. The electronic device according to claim 24, wherein the device is selected from the group consisting of organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

27. An organic electroluminescent device comprising the compound according to claim 13 is employed as matrix material in an emitting layer in combination with one or more emitter compounds.

Description

WORKING EXAMPLES

A) Synthesis Examples

Step 1: Synthesis of the Amine Building Block

(1) ##STR00192##

(2) 24.0 g (142 mmol, 1.2 eq.) of 4-aminobiphenyl 1a (CAS 92-67-1) are initially introduced in 950 ml of toluene together with 32.0 g (117 mmol, 1.0 eq.) of 2-bromo-9,9-dimethylfluorene 2a (CAS 28320-31-2) and saturated with argon for 30 minutes. 1.0 g (1.8 mmol, 0.02 eq.) of 1,1*bis(diphenylphosphino)ferrocene (CAS 12150-46-8), 350 mg (1.6 mmol, 0.01 eq.) of palladium(II) acetate (CAS 3375-31-3) and 29 g (300 mmol, 2.6 eq.) of sodium tert-butoxide (CAS 865-48-5) are subsequently added, and the mixture is heated under reflux overnight. When the reaction is complete, the batch is diluted with 300 ml of toluene and extracted with water. The organic phase is dried over sodium sulfate, and the solvent is removed in a rotary evaporator. 50 ml of ethyl acetate are added to the brown oil, and the mixture is added to a mixture of heptane/ethyl acetate 20:1. The solid formed is filtered off with suction and washed with heptane. Drying gives 29 g (80 mmol, 69%) of the desired product 3a having an HPLC purity of 99.1%.

(3) The following compounds can be obtained analogously:

(4) TABLE-US-00003 Starting Starting No. material 1 material 2 Product Yield 3b 71% 3c 61% 3d 00 01 78% 3e 02 03 04 82% 3f 05 06 07 62% 3g 08 09 0 47% 3h 92% 3i 75% 3j 84% 3k 0 62% 3l 78% 3m 74% 3n 0 62% 3o 67% 3p 93% 3q 0 88% 3r 74%

Step 2: Introduction of the Bridge

(5) ##STR00244##

(6) 29 g (80 mmol, 1.0 eq.) of the intermediate 3a are dissolved in 600 ml of toluene together with 25 g (80 mmol, 1.0 eq.) of 3,3-dibromo-1,1-biphenyl 4a (CAS 16400-51-4) and degassed for 30 minutes. 45 g (240 mmol, 3.0 eq.) of sodium tert-butoxide, 890 mg (0.40 mmol, 0.050 eq.) of palladium(II) acetate and 8 ml (8.0 mmol, 0.10 eq.) of a 1M tri-tert-butylphosphine solution are subsequently added. The batch is heated under reflux overnight and, when the reaction is complete, filtered twice through aluminium oxide with toluene. After removal of the solvent in a rotary evaporator, the oil is dissolved in a little THF and introduced into heptane. The solid formed is filtered off with suction and purified by means of hot extraction in heptane/toluene 1:1, giving 16.6 g (28 mmol, 35%) of the desired product 5a.

(7) The following compounds can be obtained analogously:

(8) TABLE-US-00004 No. Starting material 3 Starting material 4 5b 5c 5d 0 5e 5f 5g 5h 5i 0 5j 5k 5l 5m 5n 0 5o 5p 5q 5r 5s 0 5t 5u 5v No. Product Yield 5b 49% 5c 37% 5d 72% 5e 0 28% 5f 82% 5g 32% 5h 46% 5i 41% 5j 31% 5k 27% 5l 38% 5m 56% 5n 33% 5o 00 47% 5p 01 24% 5q 02 81% 5r 03 57% 5s 04 29% 5t 05 36% 5u 06 44% 5v 07 89%

Regarding Example 5v

(9) ##STR00308##

(10) 50.0 g (125 mmol, 1.0 eq.) of 3,6-dibromo-9-phenylcarbazole (CAS 57103-20-5) are initially introduced in a mixture of 400 ml of water, 400 ml of dioxane and 400 ml of toluene together with 19.5 g (125 mmol, 1.0 eq.) of 3-chlorobenzeneboronic acid (CAS 6350-60-6) and degassed for 30 minutes. After addition of 280 mg (1.25 mmol, 1 mol-%) of palladium(II) acetate and 1.14 g (3.75 mmol, 3 mol-%) of tri-o-tolylphosphine, the batch is heated under reflux overnight, and, when the reaction is complete, a little water is added. The organic phase is separated off and extracted twice with water, After the organic phase has been dried over sodium sulfate, the residue is recrystallised from heptane/toluene, giving 44.8 g (103 mmol, 83%) of a beige solid.

Step 3: Boronation

(11) ##STR00309##

(12) 16.6 g (28 mmol, 35%) of the bromide 5a are dissolved in 120 ml of dry DMF together with 8.5 g (34 mmol, 1.2 eq.) of bis(pinacolato)diborane (CAS 73183-34-3) under protective gas in a 500 ml flask and degassed for 30 minutes. 8.2 g (84 mmol, 3.0 eq.) of potassium acetate and 690 mg (0.84 mmol, 3 mol-%) of [1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloride complex with dichloromethane (CAS 95464-05-4) are subsequently added, and the batch is heated at 90 C. overnight. When the reaction is complete, the mixture is diluted with 300 ml of toluene and extracted with water. The solvent is removed in a rotary evaporator, and the solid obtained, 14.7 g (23 mmol, 82%), is dried. The boronic ester 6a is reacted without further purification.

(13) The following compounds can be obtained analogously:

(14) TABLE-US-00005 No. Starting material 5 Product 6 Yield 6b 0 88% 6c 81% 6d 75% 6e 67% 6f 79% 6g 0 93% 6h 44% 6i 87% 6j 28% 6k 35% 6l 0 77% 6m 38% 6n 55% 6o 41% 6p 67% 6q 0 82% 6r 91% 6s 87% 6t 96% 6u 58% 6v 0 94%

Step 4

Synthesis of the Triazine Building Block Step 1

(15) ##STR00352##

(16) 7.9 g (330 mmol, 1.2 eq.) of magnesium turnings are initially introduced in a 1 l four-necked flask, and a THF solution of 63 g (270 mmol, 1.0 eq.) of 3-bromobiphenyl 8a (CAS 2113-57-7) is added sufficiently slowly to maintain the reflux of the reaction mixture. When the addition is complete, the batch is heated under reflux for a further two hours. 50 g (270 mmol, 1 eq.) of 2,4,6-trichloro-1,3,5-triazine 7a (CAS 108-77-0) in 500 ml of THF in a 2 l four-necked flask are cooled to 10 C. The Grignard solution is added dropwise at this temperature sufficiently slowly that the temperature does not exceed 0 C., and finally the batch is stirred at room temperature overnight. For work-up, 270 ml of 1N hydrochloric acid are added dropwise, and the mixture is stirred for one hour. The aqueous phase is subsequently separated off and extracted with diethyl ether. The combined organic phases are dried over sodium sulfate, and the solvent is removed in a rotary evaporator, giving 56 g (69%) of a colourless oil 9a.

(17) The following compounds can be obtained analogously:

(18) TABLE-US-00006 No. Starting material 7 Starting material 8 Product 9 Yield 9b 56% 9c 27% 9d 0 48% 9e 71%

Synthesis of the Triazine Building Block Step 2

(19) ##STR00365##
Variant A:

(20) 18 g (50 mmol, 1 eq.) of 9,9-spirobifluoren-2-ylboronic acid 10a (CAS 1207595-22-9) are dissolved in a mixture of 200 ml of dioxane, 200 ml of toluene and 70 ml of water together with 15 g (50 mmol, 1 eq.) of 2-biphenyl-3-yl-4,6-dichloro-1,3,5-triazine 9a and 5.8 g (55 mmol, 1.1 eq.) of sodium carbonate and degassed for 30 minutes. 580 mg (0.50 mmol, 1 mol-%) of tetrakis(triphenylphosphine) (CAS 14221-01-3) are subsequently added, and the batch is heated under reflux overnight. The reaction mixture is cooled, and 300 ml of water are added. The aqueous phase is extracted three times with ethyl acetate, the organic phases are combined, and the solvent is removed in a rotary evaporator. Hot extraction in heptane/toluene 4:1 gives 15 g (26 mmol, 51%) of a colourless solid.

(21) Variant B: Analogous to Step 1

(22) The following compounds can be prepared analogously:

(23) TABLE-US-00007 Variant Starting material 9 Starting material 10 9b B 9c A 9d A 0 9e A 9f A 9g A 9h B Product 11 Yield 9b 0 68% 9c 81% 9d 63% 9e 71% 9f 53% 9g 68% 9h 67%

Step 5: Preparation of the End Product by Means of Suzuki Coupling

(24) ##STR00387##

(25) 14.7 g (23 mmol, 1.0 eq.) of the boronic ester 6a and 14.7 g (25 mmol, 1.1 eq.) of the triazine building block 11a are suspended in 190 ml of toluene and 190 ml of water and degassed for 30 minutes. 7.0 g (51 mmol, 2.2 eq.) of potassium carbonate, 150 mg (6.9 mmol, 3 mol-%) of palladium(II) acetate and 300 mg (1.2 mmol, 5 mol-%) of triphenylphosphine are subsequently added, and the mixture is heated under reflux overnight. The precipitated solid is filtered off with suction and purified by means of hot extraction with heptane/toluene 1:1 and recrystallisation three times from a heptane/toluene mixture. Sublimation gives 11.2 g (11 mmol, 46%) of the desired product 12a having an HPLC purity of >99.9%.

(26) The following compounds can be obtained analogously:

(27) TABLE-US-00008 No. Starting material 6 Starting material 11 12b 12c 0 12d 12e 12f 12g 12h 00 01 12i 02 03 12j 04 05 12k 06 07 12l 08 09 12m 0 12n 12o 12p 12q 12r 0 12s 12t 12u 12v No. Product 12 Yield 12b 0 54% 12c 31% 12d 49% 12e 68% 12f 52% 12g 71% 12h 41% 12i 44% 12j 37% 12k 21% 12l 0 51% 12m 17% 12n 58% 12o 74% 12p 29% 12q 14% 12r 36% 12s 82% 12t 75% 12u 66% 12v 0 73%

B) Device Examples

B-1) Production of the OLEDs

(28) Cleaned glass plates (cleaning in laboratory dishwasher, detergent Merck Extran) which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS P VP Al 4083 from Heraeus Precious Metals GmbH, Germany, applied by spin coating from aqueous solution) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied.

(29) The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML) hole-blocking layer (HBL)/electron-transport layer (ETL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs is shown in Table 1. The materials used for the production of the OLEDs are shown in Table 3.

(30) All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as 12r:IC1:TEG1 (60%:30%:10%) here means that material 12r is present in the layer in a proportion by volume of 60%, IC1 is present in the layer in a proportion of 30% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer consists of a mixture of two materials.

(31) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics, and the lifetime are determined. The electroluminescence spectra are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The term U1000 in Table 2 denotes the voltage required for a luminous density of 1000 cd/m.sup.2. CE1000 and PE1000 denote the current and power efficiency respectively which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2.

(32) The lifetime LT is defined as the time after which the luminous density drops from the initial luminous density to a certain proportion L1 on operation at constant current. An expression of L0; j0=4000 cd/m.sup.2 and L1=80% in Table 2 means that the lifetime indicated in column LT corresponds to the time after which the initial luminous density drops from 4000 cd/m.sup.2 to 3200 cd/m.sup.2. Analogously, L0; j0=20 mA/cm.sup.2, L1=80%, means that the initial luminous density drops to 80% of its initial value after time LT on operation at 20 mA/cm.sup.2.

(33) The data of the various OLEDs are summarised in Table 2. Examples V1-V3 are comparative examples in accordance with the prior art, examples E1-E8 show data of OLEDs comprising materials according to the invention.

(34) Some of the examples are explained in greater detail below in order to illustrate the advantages of the compounds according to the invention. However, it should be pointed out that this only represents a selection of the data shown in Table 2.

(35) In general, very good performance data of the OLEDs, in particular a very good lifetime, power efficiency and operating voltage, are achieved with the compounds according to the invention (see Examples E1 to E8).

(36) Compared with compound C1, compounds 12r and 12i, which are substituted by relatively large aromatic systems on the amino group, exhibit improvements with respect to efficiency and voltage, but in particular with respect to lifetime, on use as matrix material (Examples V1, E1 and E6).

(37) An improvement also arises compared with compound C2, which likewise contains only small aromatic systems on the amino group (Examples V2, E1 and E6).

(38) Compared with compound C3, in which amine and triazine are linked via a phenyl group, significantly better efficiency and a comparable lifetime are achieved with, for example, the similar compound 12t according to the invention (Examples V3, E2).

(39) TABLE-US-00009 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness Thickness V1 SpA1 HATCN SpMA1 C1:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm V2 SpA1 HATCN SpMA1 C2:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm V3 SpA1 HATCN SpMA1 C3:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E1 SpA1 HATCN SpMA1 12r:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E2 SpA1 HATCN SpMA1 12t:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E3 SpA1 HATCN SpMA1 12b:TER3 IC1 ST2:LiQ 90 nm 5 nm 130 nm (92%:8%) 40 nm 10 nm (50%:50%) 30 nm E4 SpA1 HATCN SpMA1 12c:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E5 SpA1 HATCN SpMA1 12d:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E6 SpA1 HATCN SpMA1 12i:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E7 SpA1 HATCN SpMA1 12p:TER3 IC1 ST2:LiQ 90 nm 5 nm 130 nm (92%:8%) 40 nm 10 nm (50%:50%) 30 nm E8 SpA1 HATCN SpMA1 12v:TER3 IC1 ST2:LiQ 90 nm 5 nm 130 nm (92%:8%) 40 nm 10 nm (50%:50%) 30 nm

(40) TABLE-US-00010 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at L1 LT Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 L0; j0 % (h) V1 3.3 60 57 16.9% 0.34/0.62 20 mA/cm.sup.2 80 70 V2 3.6 50 44 14.3% 0.36/0.61 20 mA/cm.sup.2 80 95 V3 3.4 55 50 15.4% 0.34/0.62 20 mA/cm.sup.2 80 125 E1 3.2 63 62 17.8% 0.34/0.62 20 mA/cm.sup.2 80 110 E2 3.3 61 58 17.1% 0.34/0.62 20 mA/cm.sup.2 80 135 E3 4.3 11.0 8.0 11.9% 0.67/0.33 4000 cd/m.sup.2 80 330 E4 3.4 58 53 16.3% 0.34/0.62 20 mA/cm.sup.2 80 90 E5 3.3 64 61 18.1% 0.34/0.62 20 mA/cm.sup.2 80 120 E6 3.2 60 59 17.0% 0.35/0.62 20 mA/cm.sup.2 80 115 E7 4.8 10.4 6.8 11.3% 0.67/0.33 4000 cd/m.sup.2 80 270 E8 4.4 12.4 8.8 12.8% 0.66/0.34 4000 cd/m.sup.2 80 305

(41) TABLE-US-00011 TABLE 3 Structural formulae of the materials for the OLEDs HATCN SpA1 LiQ TEG1 ST2 IC1 SpMA1 TER3 C1 0 C2 C3 12b 12c 12r 12t 12i 12d 12p 12v