Carbazole derivatives for organic electroluminescence devices

Abstract

The present invention describes carbazole derivatives formula (1), where the following applies to the symbols used: Y is on each occurrence, identically or differently, CR or N; X is selected from C(R1)2, O, S, PR1, P(═O)R1 or BR1; characterized in that at least one group R is present which stands, identically or differently on each occurrence, for a group of the following formula (2), and/or in that at least one group R1 is present which stands for a group of the following formula (3) or (4), in particular for use as triplet matrix materials in organic electroluminescent devices. The invention furthermore relates to a process for the preparation of the compounds according to the invention and to electronic devices comprising same.

Claims

1. A compound of the formulae (6b), (7b) and (8b), ##STR00165## where the following applies to the symbols used: R and R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.2).sub.2, N(Ar).sub.2, C(═O)Ar, P(═O)Ar.sub.2, S(═O)Ar, S(═O).sub.2Ar, CR.sup.2═CR.sup.2Ar, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.2C═CR.sup.2, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sub.2 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; two or more substituents R here, together with the atoms to which they are bonded, or two substituents R.sup.1, together with the atom to which they are bonded, may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.3).sub.2, N(Ar).sub.2, C(═O)Ar, P(═O)Ar.sub.2, S(═O)Ar, S(═O).sub.2Ar, CR.sup.3═CR.sup.3Ar, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.3, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.3C═CR.sup.3, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, P(═O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or a combination of these systems; R.sup.3 is on each occurrence, identically or differently, H, D or an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aryl or heteroaryl group having 5 to 40 ring atoms or a combination of these groups; with the proviso that, if one or more of the groups R, R.sup.1, R.sup.2, R.sup.3, Ar or Ar.sup.1 contain heteroaryl groups which do not conform to the formulae (2), (3) these are not electron-deficient heteroaryl groups; wherein at least one group R is present which stands, identically or differently on each occurrence, for a group of the following formula (2), ##STR00166## where the dashed bond indicates the linking of the group of the formula (2), R.sup.2 has the above-mentioned meanings, and furthermore: Q is C if the group of the formula (2) is linked to Ar.sup.1 or to the remainder of the molecule via this group; or is, identically or differently on each occurrence, CR.sup.2 or N in the other cases; Z is NR.sup.2 or S; Ar.sup.1 is a divalent aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; p is 0 or 1; and/or in that at least one group R.sup.1 is present which stands for a group of the following formula (3) ##STR00167## where the dashed bond indicates the linking of the group of the formula (3), R.sup.2, Ar.sup.1, Q and p have the above-mentioned meanings, and furthermore: W is NR.sup.2, O or S, and wherein in the compound of formula (6b) at least one group R is present which stands for a group of the formula (2) or at least one group R.sup.1 is present which stands for a group of the formula (3); and wherein in the compounds of formula (7b) or (8b) at least one group R is present which stands for a group of the formula (2).

2. The compound according to claim 1, wherein the radical R.sup.1 which is bonded to the nitrogen atom stands for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may also be substituted by one or more radicals R.sup.2, or for a group of the formula (3).

3. The compound according to claim 1 where R.sup.1 stands, identically or differently on each occurrence, for a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, O, S or CONR.sup.2 and where one or more H atoms is optionally replaced by D, F or CN, or for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may also be substituted by one or more radicals R.sup.2; the radicals R.sup.1 here may also form an aromatic or aliphatic ring system with one another.

4. The compound according to claim 1, wherein the groups of the formulae (2) to (3) are selected from the groups of the formulae (2a) to (3a), ##STR00168## where the symbols and indices used have the meanings given in claim 1, and, in formula (2a) and (3a), no group R.sup.2 is bonded at the position at which the group is linked to Ar.sup.1 or the remainder of the molecule.

5. The compound according to claim 1, wherein the groups of the formulae (2) to (3) are selected from the structures of the formulae (2b), (2c), (2d), (3b), (3c), and (3d), ##STR00169## where the dashed bond indicates the linking of the group to the remainder of the molecule, and the other symbols and indices used have the meanings given in claim 1.

6. Compound according to claim 4, wherein the radicals R.sup.2 which are bonded to a carbon atom in formula (2a) to (3a) stand for H.

7. Compound according to claim 5, wherein the radicals R.sup.2 which are bonded to a carbon atom in formula (2b), (2c), (2d), (3b), (3c), and (3d), stand for H.

8. The compound according to claim 1, wherein Z or W stands for NR.sup.2, where R.sup.2 stands for an aromatic or heteroaromatic ring system.

9. A process for the preparation of a the compound according to claim 1, which comprises introducing the group of the formula (2) or (3) by a Suzuki coupling, an Ullmann coupling or by a Hartwig-Buchwald coupling.

10. A mixture comprising at least one compound according to claim 1 and at least one fluorescent or phosphorescent dopant.

11. A formulation comprising at least one compound according to claim 1 and one or more solvents.

12. The formulation according to claim 11, wherein the formulation is a solution, a suspension or a miniemulsion.

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

14. The electronic device according to claim 13, wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic dye-sensitised solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

15. An organic electroluminescent device which comprises the compound according to claim 1 is employed as matrix material for a phosphorescent compound in an emitting layer.

Description

EXAMPLES

(1) The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. In each case, the corresponding CAS numbers are also indicated for the compounds known from the literature.

(2) Part A: Synthesis of the Precursors

(3) ##STR00035##

S1: 3-Bromo-9-[1,1′;3′,1″]terphenyl-5′-yl-9H-carbazole

(4) 10 g (41 mmol) of 3-bromo-9H-carbazole (CAS 86-74-8) and 16 g (45 mmol, 1.1 eq) of 5′-iodo-[1,1′;3′,1″]terphenyl are dissolved in 500 ml of p-xylene together with 51 g (270 mmol, 6.6 eq) of elemental copper, 115 g (540 mmol, 13 eq) of potassium carbonate and 0.52 g (4.5 mmol, 0.11 eq) of 18-crown-6 and heated under reflux. When the reaction is complete, the mixture is extracted three times with water, the organic phase is dried over sodium sulfate, the solvent is removed in vacuo, and the solid obtained is purified by means of column chromatography (ethyl acetate/heptane), giving 17 g (36 mmol, 53%) of the product.

(5) The following synthones are prepared analogously:

(6) TABLE-US-00001 Yield Ex. E1 E2 Product [%] S2   CAS 86-74-8   CAS 20442-79-9 48 S3   CAS 86-74-8 0   CAS 28320-31-2 63 S4   CAS 16807-11-7   CAS 591-50-4 54

(7) ##STR00045##

S5: 9-[1,1′;3′,1″]-Terphenyl-5′-yl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

(8) 20 g (42 mmol) of 3-bromo-9-[1,1′;3′,1″]terphenyl-5′-yl-9H-carbazole S1, 13 g (50 mmol, 1.2 eq.) of bis(pinacolato)diborane (CAS 73183-34-4) and 12 g (130 mmol, 3 eq.) of potassium acetate are initially introduced in 300 ml of 1,4-dioxane and degassed with nitrogen for 30 minutes. 470 mg (0.84 mmol, 0.02 eq) of 1,1′-bis(diphenylphosphino)ferrocene and 190 mg (0.84 mmol, 0.02 eq) of palladium(II) acetate are subsequently added and heated to an internal temperature of 100° C. When the reaction is complete, ethyl acetate is added to the batch, and the mixture is extracted three times with water. The organic phase is evaporated, and the boronic ester is precipitated from heptane. Recrystallisation from acetonitrile gives 20 g (38 mmol, 91%) of the product.

(9) The following synthones are prepared analogously:

(10) TABLE-US-00002 Ex. Starting material E3 Product Yield [%] S6   CAS 1153-85-1 97 S7   CAS 57103-20-5   2.4 equivalents of the diborane 89
Part B: Synthesis of the Compounds According to the Invention

(11) ##STR00050##

B1: 12,12-Dimethyl-10-(9-[1,1′;3′,1″]terphenyl-5′-yl-9H-carbazol-3-yl)-10,12-dihydro-10-azaindeno[2,1-b]fluorene

(12) 7.6 g (33 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene (WO 2010/136109), 17 g (36 mmol, 1.1 eq) of 3-bromo-9-[1,1′;3′,1″]-terphenyl-5′-yl-9H-carbazole S1 and 12.1 g (12 mmol, 0.36 eq) of copper(I) iodide are suspended in 1 l of 1,4-dioxane with 150 g (706 mmol, 4 eq) of potassium phosphate. The reaction mixture is subsequently degassed for 30 minutes, and 17.6 ml (147 mmol, 0.83 eq) of trans-cyclohexylamine are added under a protective gas. The batch is heated under reflux for 12 h, and, when the reaction is complete, dichloromethane is added. The precipitated solid is filtered off with suction, dissolved in toluene and filtered through silica gel. After removal of the solvent in vacuo, the residue is recrystallised a number of times from toluene/heptane and finally sublimed, giving 17.6 g (33.5 mmol, 57%) of a colourless solid having an HPLC purity >99.9%.

(13) The following compounds are prepared analogously to B1:

(14) TABLE-US-00003 Ex. E5 E4 B2   WO 2010/136109   CAS 1153-85-1 B3   WO 2010/136109   S2 B4   WO 2010/136109   S3 B5   WO 2010/136109   S4 B6   WO 2010/136109 0   CAS 1153-85-1 B7   WO 2010/136109   CAS 1141017-78-8 B8   WO 2010/136109   CAS 94994-62-4 B9   WO 2010/136109   CAS 1160294-85-8 B10   WO 2010/136109 2.2 equivalents     CAS 1153-85-1 B11   WO 2010/136109 0   CAS 57102-42-8 B12   CAS 1246308-83-7   CAS 1153-85-1 B13   CAS 1255309-04-6   CAS 1153-85-1 B14   WO 2010/136109   CAS 1153-85-1 B15   WO 2010/136109   CAS 1186644-47-2 B16   WO 2010/136109 0   CAS 86-76-0 B17   WO 2010/136109   CAS 22439-61-8 B18   WO 2010/136109   CAS 89827-45-2 B19   WO 2010/136109   CAS 26608-06-0 B20   WO 2010/136109   CAS 955959-86-1 B21   WO 2010/136109 0   CAS 1153-85-1 B22   WO 2010/136109   CAS 1153-85-1 B23   WO 2010/136109   CAS 1153-85-1 B24   WO 2010/136109   CAS 1153-85-1 B25   WO 2010/136109   CAS 607739-92-4 B26   WO 2010/136109 00   CAS 212385-73-4 B27 01   WO 2010/136109 2.2 equivalents   02   CAS 1153-85-1 Yield Ex. Product [%] B2 03 54 B3 04 74 B4 05 65 B5 06 53 B6 07 59 B7 08 49 B8 09 53 B9 0 45 B10 64 B11 61 B12 57 B13 48 B14 78 B15 58 B16 54 B17 45 B18 57 B19 0 51 B20 54 B21 62 B22 43 B23 54 B24 56 B25 54 B26 53 B27 45

(15) ##STR00129##

B28: 12,12-Dimethyl-10-phenyl-7-(9-[1,1′;3′,1″]terphenyl-5′-yl-9H-carbazol-3-yl)-10,12-dihydro-10-azaindeno[2,1-b]fluorene

(16) 20 g (38 mmol) of 9-[1,1′;3′,1″]-terphenyl-5′-yl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole S5 and 17 g (38 mmol, 1 eq) of 7-bromo-12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene (WO 2010/136109) are initially introduced in 250 ml of acetone, and 62 ml (84 mmol, 2.2 eq) of tetraethylammonium hydroxide (20% solution in water) are added. The reaction mixture is degassed with nitrogen for 30 minutes, and 0.88 g (0.76 mmol, 0.02 eq) of tetrakis(triphenylphosphine)palladium(0) are subsequently added, and the mixture is stirred overnight at 50° C. The precipitated solid is filtered off with suction and purified by means of hot extraction, repeated recrystallisation from heptane/toluene and final sublimation, giving 14 g (19 mmol, 51%) of the product having an HPLC purity >99.9%.

(17) The following compounds are prepared analogously:

(18) TABLE-US-00004 Ex. E6 E7 B29 0   S6   WO 2010/136109 B30   S7 2 equivalents     WO 2010/136109 Yield Ex. Product [%] B29 63 B30 53

(19) ##STR00136##

3,7-Dibromo-5-phenyldibenzophosphole 5-oxide

(20) 66 ml (106 mmol, 2.0 eq) of n-butyllithium (1.6 M in hexane) are added to a solution of 30 g (53 mmol) of 4,4′-dibromo-2,2′-diiodobiphenyl in 500 ml of dry THF at −78° C., and the mixture is stirred at this temperature for 30 minutes. 11 g (56 mmol, 1.06 eq) of dichlorophenylphosphine oxide are subsequently added dropwise, and, when the reaction is complete, the reaction mixture is warmed to room temperature. After hydrolysis using water, the organic phase is extracted with ether, and the combined organic phases are dried over sodium sulfate. The solvent is removed in a rotary evaporator, and the crude product obtained is purified by column chromatography (heptane/ethyl acetate 6:1), giving 20 g (45 mmol, 85%) of the product.

3-Bromo-5-phenyldibenzophosphole 5-oxide

(21) 20 g (45 mmol) of 3,7-dibromo-5-phenyldibenzophosphole 5-oxide in 400 ml of dry THF are cooled to −78° C., and 28 ml (45 mmol, 1.0 eq) of n-butyllithium (1.6 M in hexane) are slowly added at this temperature. After 1 h, the mixture is slowly warmed to room temperature, 50 ml of 1M HCl are added, and the mixture is stirred for a further 2 h. The mixture is subsequently extracted with ethyl acetate, washed with water, and the combined organic phases are dried over sodium sulfate. The solvents are removed in a rotary evaporator, and the product obtained is used without further purification steps, giving 16 g (43 mmol, 96%) of the monobromide.

(2-Chlorophenyl)-(5-oxo-5-phenyl-5H-5lambda*5*-dibenzophosphol-3-yl)amine

(22) 16 g (43 mmol) of 3-bromo-5-phenyldibenzophosphole 5-oxide are initially introduced in 400 ml of toluene together with 6.6 ml (52 mmol, 1.2 eq) of 2-chloroaniline and 11 g (112 mmol, 2.6 eq) of sodium tert-butoxide, and 480 mg (0.86 mmol, 0.2 eq) of DPPF and 97 mg (0.43 mmol, 0.01 eq) of palladium acetate are added. The reaction mixture is heated under reflux overnight, and, when the reaction is complete, 200 ml of water are added. The phases are separated, and the aqueous phase is extracted with toluene. The combined organic phases are dried over sodium sulfate and filtered through aluminum oxide. The solvent is removed in vacuo, and the residue obtained is purified by column chromatography (heptane/ethyl acetate 5:1), giving 16 g (39 mmol, 91%) of the product.

12-Phenyl-10H-10-aza-12-phosphaindeno[2,1-b]fluorene 12-oxide

(23) 16 g (39 mmol) of (2-chlorophenyl)-(5-oxo-5-phenyl-5H-5lambda*5*-dibenzophosphol-3-yl)amine and 14 g (100 mmol, 2.6 eq) of potassium carbonate are initially introduced in 250 ml of NMP, and 1.4 g (13 mmol, 0.34 eq) of pivalic acid are added. 3.1 ml of a 1M tri-tert-butylphosphine solution in toluene (3.1 mmol, 0.08 eq) and 440 mg (2.0 mmol, 0.05 eq) of palladium acetate are subsequently added, and the reaction mixture is heated overnight at an internal temperature of 130° C. The batch is cooled to room temperature, and 300 ml of toluene and 100 ml of water are added. The aqueous phase is extracted three times with toluene, and the combined organic phases are likewise washed three times with water and finally dried over sodium sulfate. After removal of the solvent, the crude product obtained is purified by column chromatography, giving 13 g (35 mmol, 89%) of the product.

B31: 12-Phenyl-10-(9-phenyl-9H-carbazol-3-yl)-10H-10-aza-12-phosphaindeno[2,1-b]fluorene 12-oxide

(24) The experiment is carried out analogously to B1, giving 14 g (23 mmol, 67%) of the target product B31.

(25) Part C: Comparison of the Thermal Stability

(26) If 100 mg of the compound ICvCbz1 are melted in a glass ampoule in vacuo (pressure about 10.sup.−2 mbar) and this is stored at 310° C. for 14 days in an oven, the purity according to HPLC changes from 99.7% to 89.2%. With compound B29, the purity according to HPLC in the same procedure changes from 99.8% to 99.6%, i.e. far fewer decomposition products form under the same thermal load. This is a significant industrial advantage, since the materials in the industrial production of organic electroluminescent devices are subjected to high temperatures for a long time.

(27) Part D: Organic Electroluminescent Devices

(28) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

(29) The data of various OLEDs are presented in Examples V1 to E17 below (see Tables 1 and 2). Glass plates 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 A14083 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. The OLEDs have 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 an aluminium cathode with a thickness of 100 nm. The precise structure of the OLEDs is shown in Table 1. The materials required 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 materials in a certain proportion by volume by coevaporation. An expression such as IC1:IC2:TEG1 (30%:60%:10%) here means that material IC1 is present in the layer in a proportion by volume of 30%, IC2 is present in the layer in a proportion by volume of 60% and TEG1 is present in the layer in a proportion by volume of 10%. An analogous situation applies to the electron-transport layer.

(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 expression 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 efficiencies 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. The lifetime LT defines the time after which the luminous density on operation at constant current drops from the initial luminous density L0 to a certain proportion L1. A specification of L0=10000 cd/m.sup.2 and L1=70% in Table 2 means that the lifetime indicated in column LT corresponds to the time after which the initial luminous density drops from 10000 cd/m.sup.2 to 7000 cd/m.sup.2.

(32) The data of the various OLEDs are summarised in Table 2. Example V1-V8 are comparative examples in accordance with the prior art, Examples E1-E17 show data of OLEDs comprising materials according to the invention.

(33) 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. As can be seen from the table, significant improvements compared with the prior art are also achieved on use of the compounds according to the invention that are not described in greater detail.

(34) Use of Compounds According to the Invention as Component of a Mixed-Matrix System

(35) In the following examples, data of OLEDs in which the mixing ratio is selected in such a way that a maximum lifetime is obtained are shown.

(36) If Examples V2 and E1 are compared, it can be seen that compound B2 according to the invention, which carries a carbazole substituent on the nitrogen, gives significantly better values than compound IC2 in accordance with the prior art having a terphenyl substituent. With B2, the power efficiency is improved by almost 15%, the lifetime by about 20%.

(37) A significant improvement is also obtained on replacement of an indenocarbazole by a carbazole substituent (Examples V1 and E2). In this case, the lifetime increases to virtually double, and the improvement in the power efficiency of 20% is likewise very high. A significantly improved lifetime and power efficiency are also obtained with B29 compared with the biscarbazole BCbz1 (Examples V3 and E2).

(38) On replacement of a bridged carbazole by an unbridged carbazole (Examples V5 and E2), the lifetime increases by 60%. Although a somewhat better quantum efficiency is obtained with compound ICvCbz1 in accordance with the prior art than with compound B29 according to the invention, the same power efficiency arises, however, owing to the better voltage.

(39) If the emitter concentration in OLEDs comprising materials in accordance with the prior art is reduced to significantly below 10%, the efficiency and lifetime are reduced significantly. On use of compound IC2, for example, the external quantum efficiency is reduced by almost 10% when the emitter concentration is reduced from 10% to 4%. Much more significant is the impairment in the lifetime by a factor of more than 1.5 (Examples V7 and V8). With materials according to the invention, by contrast, no reduction in performance (Example E1 compared with E12) or even a slight improvement (Example E2 compared with E13-E15) can be observed.

(40) On use as matrix materials in phosphorescent OLEDs, the materials according to the invention thus give rise to significant improvements compared with the prior art in some or all parameters. Furthermore, OLEDs having low emitter concentrations can be achieved with materials according to the invention without reductions in performance.

(41) TABLE-US-00005 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness thickness V1 SpA1 HATCN SpMA1 IC1:BIC1:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (60%:30%:10%) 30 nm 10 nm 30 nm V2 SpA1 HATCN SpMA1 IC1:IC2:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm V3 SpA1 HATCN SpMA1 IC1:BCbz1:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm V4 SpA1 HATCN SpMA1 IC1:IC3:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (70%:20%:10%) 30 nm 10 nm 30 nm V5 SpA1 HATCN SpMA1 IC1:ICvCbz1:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (60%:30%:10%) 30 nm 10 nm 30 nm V6 SpA1 HATCN BPA1 ST1:BIC2:TEG1 ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm V7 SpA1 HATCN PA1 IC1:IC2:TEG1 ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm V8 SpA1 HATCN PA1 IC1:IC2:TEG1 ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (32%:64%:4%) 30 nm 10 nm 30 nm E1 SpA1 HATCN SpMA1 IC1:B2:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm E2 SpA1 HATCN SpMA1 IC1:B29:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (55%:35%:10%) 30 nm 10 nm 30 nm E3 SpA1 HATCN SpMA1 IC1:B30:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (65%:25%:10%) 30 nm 10 nm 30 nm E4 SpA1 HATCN BPA1 ST1:B26:TEG1 ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm E5 SpA1 HATCN SpMA1 IC1:B27:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (65%:25%:10%) 30 nm 10 nm 30 nm E6 SpA1 HATCN SpMA1 IC1:B5:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm E7 SpA1 HATCN SpMA1 IC1:B8:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm E8 SpA1 HATCN SpMA1 IC1:B14:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm E9 SpA1 HATCN SpMA1 ST1:B12:TEG1 ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (25%:65%:10%) 30 nm 10 nm 30 nm E10 SpA1 HATCN SpMA1 IC1:B24:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (50%:50%:10%) 30 nm 10 nm 30 nm E11 SpA1 HATCN SpMA1 ST1:B18:TEG1 ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm E12 SpA1 HATCN SpMA1 IC1:B2:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (32%:64%:4%) 30 nm 10 nm 30 nm E13 SpA1 HATCN SpMA1 IC1:B29:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (60%:39%:1%) 30 nm 10 nm 30 nm E14 SpA1 HATCN SpMA1 IC1:B29:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (59%:37%:4%) 30 nm 10 nm 30 nm E15 SpA1 HATCN SpMA1 IC1:B29:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (57%:36%:7%) 30 nm 10 nm 30 nm E16 SpA1 HATCN SpMA1 IC1:B10:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm E17 SpA1 HATCN SpMA1 IC1:B23:TEG1 IC1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm

(42) TABLE-US-00006 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at LT Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 L0 L1 % (h) V1 3.6 51 44 14.1% 0.34/0.62 10000 cd/m.sup.2 70 240 V2 3.6 52 46 14.5% 0.33/0.62 10000 cd/m.sup.2 70 270 V3 3.6 56 49 15.6% 0.34/0.62 10000 cd/m.sup.2 70 220 V4 3.2 54 54 15.1% 0.33/0.62 10000 cd/m.sup.2 80 190 V5 3.5 58 52 16.1% 0.32/0.63 10000 cd/m.sup.2 70 280 V6 3.8 51 43 14.3% 0.33/0.63 10000 cd/m.sup.2 70 210 V7 3.5 53 48 14.7% 0.33/0.62 10000 cd/m.sup.2 70 240 V8 3.5 49 44 13.6% 0.33/0.63 10000 cd/m.sup.2 70 140 E1 3.4 56 52 15.6% 0.33/0.63 10000 cd/m.sup.2 70 320 E2 3.3 55 52 15.5% 0.34/0.62 10000 cd/m.sup.2 70 450 E3 3.4 57 54 16.0% 0.33/0.62 10000 cd/m.sup.2 70 410 E4 3.4 55 51 15.2% 0.33/0.63 10000 cd/m.sup.2 70 270 E5 3.2 57 56 15.9% 0.33/0.63 10000 cd/m.sup.2 80 250 E6 3.5 53 48 14.8% 0.33/0.63 10000 cd/m.sup.2 70 290 E7 3.5 55 49 15.2% 0.33/0.62 10000 cd/m.sup.2 70 300 E8 3.6 55 49 15.4% 0.33/0.62 10000 cd/m.sup.2 70 330 E9 3.6 53 46 14.6% 0.33/0.63 10000 cd/m.sup.2 70 250 E10 3.4 58 54 16.2% 0.33/0.63 10000 cd/m.sup.2 70 330 E11 3.5 55 49 15.3% 0.32/0.62 10000 cd/m.sup.2 70 270 E12 3.3 55 52 15.3% 0.33/0.63 10000 cd/m.sup.2 70 310 E13 3.3 61 58 16.9% 0.33/0.62 10000 cd/m.sup.2 70 510 E14 3.2 63 62 17.7% 0.33/0.63 10000 cd/m.sup.2 70 460 E15 3.3 59 57 16.6% 0.33/0.62 10000 cd/m.sup.2 70 480 E16 3.5 54 49 15.1% 0.33/0.63 10000 cd/m.sup.2 70 290 E17 3.4 57 52 15.8% 0.33/0.62 10000 cd/m.sup.2 70 310

(43) TABLE-US-00007 TABLE 3 Structural formulae of the materials for the OLEDs HATCN SpA1 ST1 0 BPA1 PA1 LiQ TEG1 BCbz1 IC1 IC2 SpMA1 BIC1 IC3 0 BIC2 ICvCbz1 B30 B27 B26 B2 B5 B8 B14 B12 0 B18 B24 B10 B23 B29