Compounds for electronic devices

Abstract

The present invention relates to compounds for use in electronic devices, preferably organic electroluminescent devices. The invention furthermore relates to processes for the preparation of these compounds and to electronic devices comprising these compounds, preferably in a function as matrix materials and/or as electron-transport materials.

Claims

1. A compound of formula (or formula (II) ##STR00318## wherein R* is, identically or differently on each occurrence, —CN, or a group selected from a keto group the formula (K) ##STR00319## a Phosphorus oxide group of the formula (P) ##STR00320## a sulfur oxide group of the formula (S) ##STR00321##  wherein a is 1 or 2, or a group of the formulae (H-1) to (H-10) ##STR00322## wherein the dashed bond marks the bonding, position, and W is, identically or differently on each occurrence, CR.sup.2 or N, with the proviso that at least one group W per formula is N, and U is NR.sup.2, O, or S; X, Y are, identically or differently on each occurrence, a single bond, C(R.sup.1).sub.2, NR.sup.1, O, or S, wherein at least one of the two groups X and Y of a ring is NR.sup.1, O, or S; V is a single bond, CO, CS, P(O)R.sup.1, SO, or SO.sub.2, with the proviso that V may only be a single bond if at least one of the groups Z in the rings bonded to V is N; T is, identically or differently on each occurrence, a single bond, C(R.sup.1).sub.2, CO, CS, Si(R.sup.1).sub.2, NR.sup.1, P(O)R.sup.1, O, S, SO, or SO.sub.2; Z is, identically or differently on each occurrence, CR.sup.1 or N if no group is bonded to Z, and C if a group is bonded to Z; R.sup.1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O)OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, or an alkenyl or alkynyl group having 2 to 20 C atoms, wherein each is optionally substituted by one or more radicals R.sup.2, and wherein one or more CH.sub.2 groups are optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), O—, —S—, SO, or SO.sub.2, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, optionally substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, optionally substituted by one or more radicals R.sup.2, wherein two or more radicals R.sup.1 optionally define a ring system; R.sup.2 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, or an alkenyl or alkynyl group having 2 to 20 C atoms, wherein each is optionally substituted by one or more radicals R.sup.3, and wherein one or more CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═S, C═NR.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, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, optionally substituted by one or more radicals R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, optionally substituted by one or more radicals R.sup.3, wherein two or more radicals R.sup.2 optionally define a ring system; R.sup.3 is, identically or differently on each occurrence, H, D, F, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by D car F, and wherein two or more substituents R.sup.3 optionally define a ring system; m is, identically or differently on each occurrence, 0 or 1, where at least one m in formula (I) or formula (II) is 1; n is, identically or differently on each occurrence, 0 or 1, where at least one n in formula (I) is 1, and wherein the groups X and Y are each bonded in adjacent positions to the six-membered ring of the spirobifluorene derivative.

2. The compound of claim 1, wherein said compound contains no condensed aryl groups having more than 16 aromatic ring atoms.

3. The compound of claim 1, wherein X or Y is independently, C(R.sup.1).sub.2 or NR.sup.1, and R.sup.1 is on each occurrence, identical or different, selected from H, D, F, CN, Si(R.sup.2).sub.3, or a straight-chain alkyl or alkoxyl group having 1 to 20 C or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms.

4. The compound of claim 1, wherein the group R* is bonded to the modified spirobifluorene skeleton in position 2′ or in position 7′.

5. The compound of claim 1, wherein one of the two groups X and Y is a single bond and the other of the two groups X and Y is a group NR.sup.1.

6. The compound of claim 1, wherein the group T is, identically or differently on each occurrence, a single bond, C(R.sup.1).sub.2, O, or S.

7. The compound of claim 1, wherein one of the two indices m in formula (I) or formula (II) is 1 and the other is zero.

8. The compound of claim 1, wherein one of the two indices n in formula (I) is 1 and the other is zero.

9. An oligomer, polymer, or dendrimer, comprising one or more compounds of claim 1, wherein the bond(s) to the polymer, oligomer, or dendrimer, may be localised at any desired positions in formula (I) or (II) that are substituted by R.sup.1, or R.sup.2.

10. A formulation comprising at least one compound of claim 1 and at least one solvent.

11. A formulation comprising at least one oligomer, polymer, or dendrimer of claim 9 and at least one solvent.

12. A process for the preparation of the compound of claim 1, wherein a heteroaryl group is condensed onto a spirobifluorene group which is substituted by an electron-deficient group, or wherein a cyclisation reaction is carried out via which a modified spirobifluorene group is obtained.

13. An electronic device comprising at least one compound of claim 1.

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

15. The electronic device of claim 13, wherein the electronic device is an organic electroluminescent device, and wherein the compound is matrix material in an emitting layer, electron-transport material in an electron-transport or electron-injection layer, or hole-blocking material in a hole-blocking layer.

16. An electronic device comprising at least one oligomer, polymer, or dendrimer, of claim 9.

17. The electronic device of claim 16, wherein the electronic device is selected from the group consisting of organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes, and organic electroluminescent devices.

18. The electronic device of claim 16, wherein the electronic device is an organic electroluminescent device, and wherein the oligomer, polymer, or dendrimer, is matrix material in an emitting layer, electron-transport material in an electron-transport or electron-injection layer, or hole-blocking material in a hole-blocking layer.

19. The compound of claim 1, wherein R.sup.2 in the formulae (K), (P), and (S), and formulae (H-1) to (H-10) is selected from an aryl or heteroaryl group having 5 to 10 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3.

20. The compound of claim 1, wherein a compound of formula (I) is selected from the group consisting of ##STR00323## ##STR00324## ##STR00325## and for each of the formulae (I-1) to (I-12) not more than one group Z per aromatic ring is N and the other groups Z are CR.sup.1.

Description

WORKING EXAMPLES

1. Synthesis of Intermediates A to D

(1) Synthesis of Intermediate A:

(2) ##STR00239##

(3) 10.3 mmol of 9,9′-spirobifluorene are dissolved in 30 ml of CH.sub.2Cl.sub.2 and protected against the incidence of light. 10.3 mmol of NBS are added in portions over the course of 30 min with stirring. After 24 h, water is added to the mixture. The organic phase is dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue is recrystallised with MeOH.

(4) The following compounds are obtained analogously:

(5) TABLE-US-00006 Ex. Starting material 1 Product Yield B 0   1125547-88-7 44% C   1174660-93-5 38% D   1092539-80-4 42%

2. Synthesis of Compounds 1 to 8 According to the Invention

(6) ##STR00246##

2′-Bromo-9H,9′H-[9,9′]bifluorenyl-2-carbonyl chloride

(7) 20 ml (274 mmol) of thionyl chloride is initially introduced with 0.16 ml of DMF at room temperature. 9 g (20 mmol) of 2′-bromo-9H,9′H-[9,9′]bifluorenyl-2-carboxylic acid are then added. The reaction mixture is stirred at 60° C. for 1 h. The remaining thionyl chloride is then distilled off and recrystallised from toluene.

(8) Yield: 9.1 g (19 mmol), 98% of theory, purity according to .sup.1H-NMR about 97%.

2-(2′-Bromo-9H,9′H-[9,9′]bifluorenyl-2-yl)-4,6-diphenyl-1,3,5-triazine

(9) 42 g (89 mmol) of 2′-bromo-9H,9′H-[9,9′]bifluorenylcarbonyl chloride, 11.90 g (89 mmol) of aluminium trichloride and 1.9 ml (27 mmol) of thionyl chloride are suspended in 260 ml of dichlorobenzene. 19.3 ml (187 mmol) of benzonitrile are then added slowly. The reaction mixture is stirred at 100° C. for 1 h. 9.55 g (179 mmol) of ammonium chloride are added, and the batch is stirred at 100° C. for 16 h. After cooling to room temperature, the reaction solution is added to 3.5 I of methanol and stirred for 45 min. The precipitated solid is filtered off and recrystallised from toluene.

(10) Yield: 51 g (80 mmol), 90% of theory, purity according to .sup.1H-NMR about 97%.

[2′-(4,6-Diphenyl-1,3,5-triazin-2-yl)-9H,9′H-[9,9′]bifluorenyl-2-yl]phenylamine

(11) 117 g (183 mmol) of 2-(2′-bromo-9H,9′H-[9,9′]bifluorenyl-2-yl)-4,6-diphenyl-1,3,5-triazine, 20 ml of aniline (220 mmol), 1.5 g of DPPF (2.7 mmol), 0.5 g of palladium(II) acetate and 45 g of sodium tert-butoxide (486 mmol) are heated at the boil in 1.5 I of toluene for 18 h under protective atmosphere. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue remaining is recrystallised from heptane/ethyl acetate.

(12) Yield: 106 g (162 mmol), 89% of theory, purity according to .sup.1H-NMR about 97%.

12-[2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-9H-fluoren-9-yl]-10,12-dihydro-10-azaindeno[2,1-b]fluorene

(13) 35 ml of pivalic acid are added to 22.8 g (35 mmol) of [2′-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H,9′H-[9,9′]bifluorenyl-2-yl]phenylamine, 0.4 g of palladium(II) acetate (1.78 mmol) and 0.5 g of potassium carbonate (3.62 mmol), and the mixture is stirred at 120° C. for 9 h. After this time, 0.4 g of palladium(II) acetate (1.78 mmol) is added, and the mixture is stirred at 120° C. for a further 9 h. 200 ml of dichloromethane and 0. μM Na.sub.2CO.sub.3 solution are then added. The mixture is partitioned between water and dichloromethane, the aqueous phase is extracted three times with dichloromethane, the combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue is recrystallised from toluene/heptane.

(14) Yield: 18.2 g (28 mmol), 80% of theory, purity according to .sup.1H-NMR about 97%.

12-[2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-9H-fluoren-9-yl]-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene (Example 1)

(15) ##STR00247##

(16) 69 g (106 mmol) of 12-[2-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-fluoren-9-yl]-10,12-dihydro-10-azaindeno[2,1-b]fluorene, 17.8 g (114 mmol) of bromobenzene and 30.5 g of NaOtBu are suspended in 1.5 I of p-xylene. 0.5 g (2.11 mmol) of Pd(OAc).sub.2 and 1.6 ml of a 1M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene and finally sublimed in a high vacuum, purity is 99.9%.

(17) Yield: 74 g (102 mmol), 97% of theory

(18) The following compounds are obtained analogously:

(19) TABLE-US-00007 Starting Starting Ex. material 1 material 2 Product Yield 2   1233200-68-4 0 59% 3   905853-26-1   103068-20-8 Only the last three steps in the scheme are carried out 66% 4   1262330-86-8   Only the last three steps in the scheme are carried out 69% 5   876173-84-1   Only the last three steps in the scheme are carried out 54% 6 0   B   Only the last three steps in the scheme are carried out 45% 7   C   Only the last three steps in the scheme are carried out 56% 8   D   Only the last three steps in the scheme are carried out 49%

3. Synthesis of Compounds 9-13 According to the Invention

(20) ##STR00269##

2-Phenylaminofluoren-9-one

(21) 47 g (183 mmol) of 2-bromofluorenone, 20 ml of aniline (220 mmol), 1.5 g of DPPF (2.7 mmol), 0.5 g of palladium(II) acetate and 45 g of sodium tert-butoxide (486 mmol) are heated at the boil in 1.5 I of toluene for 18 h under protective atmosphere. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue remaining is recrystallised from heptane/ethyl acetate.

(22) Yield: 43 g (159 mmol), 87% of theory, purity according to .sup.1H-NMR about 97%.

10H-10-Azaindeno[2,1-b]fluoren-12-one

(23) 35 ml of pivalic acid are added to 9.5 g (35 mmol) of 2-phenylaminofluoren-9-one, 0.4 g of palladium(II) acetate (1.78 mmol) and 0.5 g of potassium carbonate (3.62 mmol), and the mixture is stirred at 120° C. for 9 h. After this time, 0.4 g of palladium(II) acetate (1.78 mmol) is added, and the mixture is stirred at 120° C. for a further 9 h. 200 ml of dichloromethane and 0.1 M Na.sub.2CO.sub.3 solution are then added. The mixture is partitioned between water and dichloromethane, the aqueous phase is extracted three times with dichloromethane, the combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue is recrystallised from toluene/heptane.

(24) Yield: 7.4 g (27 mmol), 79% of theory, purity according to .sup.1H-NMR about 97%.

10-Phenyl-10H-10-azaindeno[2,1-b]fluoren-12-one

(25) 28.5 g (106 mmol) of 10H-10-azaindeno[2,1-b]fluoren-12-one, 17.8 g (114 mmol) of bromobenzene and 30.5 g of NaOtBu are suspended in 1.5 I of p-xylene. 0.5 g (2.11 mmol) of Pd(OAc).sub.2 and 1.6 ml of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene and finally sublimed in a high vacuum, purity is 99.9%.

(26) Yield: 32 g (95 mmol), 90% of theory, purity according to .sup.1H-NMR about 97%.

(27) Synthesis of the Spiro Compound (Example 9)

(28) ##STR00270##

(29) 65 ml (160 mmol) of n-butyllithium (2.5 M in hexane) are added over the course of 30 minutes at −78° C. to a solution of 43.6 g (143 mmol) of 2-(−2-bromophenyl)-2-phenyl-1,3-dioxolane, dissolved in 200 ml of anhydrous THF, and the mixture is then brought to 0° C. The lithiated compound is transferred into a dropping funnel using a syringe and slowly added dropwise at 0° C. to a suspension of 48 g (140 mmol) of 10-phenyl-10H-10-azaindeno[2,1-b]fluoren-12-one in 30 ml of anhydrous THF. The solution is brought to room temperature and kept at this temperature for 4 h, then saturated ammonium chloride solution is added. The aqueous phase is extracted with CH.sub.2Cl.sub.2 (3×15 ml), and the organic phases are dried over anhydrous sodium sulfate. After removal of the solvent, a reddish liquid is obtained which is a mixture of several isomers. The liquid is dissolved in 100 ml of glacial acetic acid and heated under reflux, a few drops of concentrated HCl are then added, and the mixture is heated under reflux for a further minute. Water is added until cloudiness forms, the mixture is then cooled to room temperature and filtered. The acidic aqueous phase is extracted with CH.sub.2Cl.sub.2 and dried over anhydrous sodium sulfate. The solvent is subsequently removed in a rotary evaporator.

(30) Yield: 34 g (68 mmol), 50% of theory, purity according to .sup.1H-NMR about 93%.

(31) The following compounds are obtained analogously:

(32) TABLE-US-00008 Starting Starting Ex. material 1 material 2 Product Yield 10   3096-56-8 72% 11   354816-92-5 Only the final reaction step in the scheme is carried out 68% 12   354816-91-4 Only the final reaction step in the scheme is carried out 72% 13   121073-95-8 Only the final reaction step in the scheme is carried out 70%

4. Synthesis of Compounds 14-17 According to the Invention

(33) ##STR00280##
NBS Bromination:

(34) 20.4 g (40.18 mmol) of the indenocarbazole derivative (Example 9) are suspended in 450 ml of acetonitrile, and 7.15 g (40.18 mmol) of N-bromosuccinimide are added in portions at −20° C. at such a rate that the reaction temperature does not rise above −20° C. The mixture is stirred for a further 18 h. During this time, the temperature is allowed to come to RT. The reaction mixture is subsequently evaporated in a rotary evaporator, dissolved with dichloromethane and washed with water. The mixture is dried, evaporated and subsequently recrystallised from toluene to a purity of 99.0%, giving 19 g (81%) of the product as white solid.

(35) Suzuki Reaction (Synthesis of Compound 14):

(36) 12 g (42 mmol) of (9-phenylcarbazol-3yl)boronic acid and 30 g (52.4 mmol) of the indenocarbazole derivative which is brominated in the 2-position (CAS 854952-58-2) are dissolved in a degassed mixture of 135 ml of water, 315 ml of dioxane and 315 ml of toluene, and 5.33 g (50.31 mmol) of Na.sub.2CO.sub.3 are added. The reaction mixture is degassed, and 0.96 g (0.84 mmol) of Pd tetrakistriphenylphosphine catalyst is added. The mixture is heated under reflux for 18 h. After cooling, dichloromethane is added (heterogeneous mixture), the water phase is separated off, and the organic phase is evaporated azeotropically with toluene. The reaction product is crystallised from DMSO, giving 29 g (67%) of the product having a purity of 99.98% as white solid.

(37) The following compounds are obtained analogously:

(38) TABLE-US-00009 Starting Starting Ex. material 1 material 2 Product Yield 15   128388-54-5 79% 16 81% 17   100124-06-9 77%

5. Device Examples: Production of OLEDs

(39) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 04/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

(40) The data for various OLEDs are presented in Examples V1-E19 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 Clevios Deutschland, applied by spin coating from aqueous solution, dried at 180° in air for 10 min after the spin coating) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate/optional hole-injection layer (HIL)/holetransport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer 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.

(41) 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 coevaporation. An expression such as ST1:2:TEG1 (65%:25%:10%) here means that material ST1 is present in the layer in a proportion by volume of 65%, material 2 is present in the layer in a proportion of 25% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(42) 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× 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. The lifetime LT is defined as the time after which the luminous density has dropped to a certain proportion L1 from the initial luminous density LO on operation at constant current. An expression of L0=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 has dropped from 4000 cd/m.sup.2 to 3200 cd/m.sup.2.

(43) The data for the various OLEDs are summarised in Table 2. Examples V1-V5 are comparative examples in accordance with the prior art, Examples E1-E19 show data of OLEDs comprising materials according to the invention.

(44) 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.

(45) Use of Compounds According to the Invention as Matrix Materials for Phosphorescent Dopants

(46) On use of materials in accordance with the prior art which contain an anthracene between the spiro unit and the electron-withdrawing unit, an external quantum efficiency of 8.1% is achieved in the case of green emission and an external quantum efficiency of 6.7% is achieved in the case of red emission. The lifetime at an initial luminous density of 10000 cd/m.sup.2 (green, drop to 70%) or 4000 cd/m.sup.2 (red, drop to 80%) is significantly less than 100 h (Examples V1, V2). These values are very low for phosphorescent dopants, which is shown, for example, by Example E2 comprising materials according to the invention: external quantum efficiencies of greater than 17% and lifetimes of greater than 250 h can be achieved with the compounds according to the invention.

(47) Similar situations arise if material S1 is used in combination with a second material in a mixed-matrix system (cf. Examples V3, V4, E3, E5, E13, E14, E19).

(48) Good performance data are already obtained with materials in accordance with the prior art in which the electron-deficient group (for example a triazine) is bonded to the carbazole unit of the compound. An external quantum efficiency of almost 15%, a power efficiency of 44 lm/W and a lifetime of 220 h are achieved with a compound IC.sub.4 of this type, for example. However, if the electron-deficient group is, as in the case of the materials according to the invention, bonded to the spirobifluorene unit, a significant improvement in the power efficiency by 25% is obtained, the external quantum efficiency increases by about 10%, the lifetime by about 30% and the operating voltage improves by 0.4 V (Examples V5, E1).

(49) TABLE-US-00010 TABLE 1 Structure of the OLEDs HIL HTL IL EBL HBL EIL Thick- Thick- Thick- Thick- EML Thick- ETL Thick- Ex. ness ness ness ness Thickness ness Thickness ness V1 — SpA1 HATCN SpMA1 S1:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm V2 — SpA1 HATCN SpMA1 S1:TER1 IC1 ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (92%:8%) 40 nm 10 nm 30 nm V3 — SpA1 HATCN SpMA1 ST1:S1:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (60%:30%:10%) 30 nm 10 nm 30 nm V4 — SpA1 HATCN SpMA1 S1:IC3:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60:%10%) 30 nm 10 nm 30 nm V5 — SpA1 HATCN SpMA1 IC4:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E1 — SpA1 HATCN SpMA1 1:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E2 — SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — 1 LiQ 70 nm 5 nm 90 nm 30 nm 40 nm 3 nm E3 HATCN SpA1 HATCN SpMA1 ST1:2:TEG1 ST1 ST2:LiQ (50%:50%) — 5 nm 140 nm  5 nm 20 nm (65%:25%:10%) 40 nm  5 nm 25 nm E4 — SpA1 HATCN SpMA1 3:TEG1 (90%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 10 nm 30 nm E5 — SpA1 HATCN SpMA1 IC1:3:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (25%:65%:10%) 30 nm 10 nm 30 nm E6 — SpA1 HATCN SpMA1 4:TER1 IC1 ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (92%:8%) 40 nm 10 nm 30 nm E7 — SpA1 HATCN SpMA1 6:TER1 IC1 ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (92%:8%) 40 nm 10 nm 30 nm E8 — SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — 7 LiF 70 nm 5 nm 90 nm 30 nm 40 nm 1 nm E9 — SpA1 HATCN SpMA1 7:TER1 IC1 ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (92%:8%) 40 nm 10 nm 30 nm E10 — SpA1 HATCN SpMA1 9:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E11 — SpA1 HATCN SpMA1 9:TEG1 (90%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 10 nm 30 nm E12 — SpA1 HATCN SpMA1 10:TEG1 (90%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 10 nm 30 nm E13 — SpA1 HATCN SpMA1 11:IC3:TEG1 IC1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (65%:25%:10%) 30 nm 10 nm 30 nm E14 — SpA1 HATCN SpMA1 12:IC3:TEG1 IC1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (60%:30%:10%) 30 nm 10 nm 30 nm E15 — SpA1 HATCN SpMA1 13:TER1 IC1 ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (90%:10%) 40 nm 10 nm 30 nm E16 — SpA1 HATCN SpMA1 16:TEG1 (90%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 10 nm 30 nm E17 — SpA1 HATCN SpMA1 17:TEG1 (90%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 10 nm 30 nm E18 — SpA1 HATCN SpMA1 14:TEG1 (90%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 10 nm 30 nm E19 — SpA1 HATCN SpMA1 IC2:14:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (40%:50%:10%) 30 nm 10 nm 30 nm

(50) TABLE-US-00011 TABLE 2 Data for the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at L1 LT Ex. (V) (cd/A) (Im/W) 1000 1000 cd/m.sup.2 L0 % (h) V1 3.8 29 24  8.1% 0.32/0.61 10000 70 70 V2 4.8 6.2 4.1  6.7% 0.66/0.33 4000 80 75 V3 3.6 30 26  8.3% 0.32/0.62 10000 70 95 V4 3.7 27 23  7.4% 0.32/0.61 10000 80 80 V5 3.8 53 44 14.8% 0.33/0.62 10000 70 220 E1 3.4 59 55 16.5% 0.33/0.62 10000 70 285 E2 3.3 63 59 17.4% 0.33/0.62 10000 70 255 E3 3.1 64 65 17.7% 0.33/0.63 8000 80 430 E4 3.7 55 47 15.2% 0.33/0.62 10000 80 210 E5 3.6 56 49 15.5% 0.33/0.63 10000 70 300 E6 4.6 9.6 6.6 10.4% 0.67/0.33 4000 80 330 E7 4.8 12.1 8.0 13.1% 0.67/0.33 4000 80 345 E8 3.6 57 49 15.9% 0.33/0.62 10000 70 230 E9 4.7 11.0 7.4 11.9% 0.67/0.33 4000 80 360 E10 3.5 51 46 14.3% 0.33/0.62 10000 80 195 E11 3.5 58 51 16.0% 0.33/0.62 10000 80 220 E12 3.7 56 48 15.7% 0.33/0.62 10000 80 235 E13 3.6 55 48 15.3% 0.34/0.62 10000 70 310 E14 3.6 58 51 16.1% 0.33/0.62 10000 70 335 E15 4.6 11.1 7.6 12.1% 0.67/0.33 4000 80 360 E16 3.6 52 46 14.5% 0.33/0.62 10000 70 230 E17 3.8 55 45 15.2% 0.33/0.62 10000 70 205 E18 3.4 49 46 13.8% 0.32/0.62 10000 70 240 E19 3.3 59 55 16.2% 0.33/0.62 10000 70 340

(51) TABLE-US-00012 TABLE 3 Structural formulae of the materials for the OLEDs 0   HATCN   ST1   LiQ   IC1   SpA1 (prior art)   ST2   TEG1   IC2   IC3   SpMA1 00   IC4 (prior art) 01   2 02   4 03   6 04   TER1 05   S1 (prior art) 06   1 07   3 08   5 09   7 0   9   11   13   16   10   12   14   17