Materials for electronic devices

Abstract

The present application relates to fluoranthenylamine compounds of a formula (I). These compounds are suitable for use in electronic devices, The present application further relates to processes for preparing the compounds mentioned, and to electronic devices comprising the compounds mentioned.

Claims

1. A compound of formula (I) ##STR00616## wherein A is C(R.sup.1).sub.2 or is ##STR00617## where the dotted lines represent the bonds to the six-membered aromatic rings; Z is the same or different at each instance and is CR.sup.2 or N or C, where a Z group is C in the specific case when the [L.sup.1].sub.i group is bonded to it; X is the same or different at each instance and is CR.sup.3 or N or C, where an X group is C in the specific case when the [L.sup.2].sub.k group is bonded to it; L.sup.1 is the same or different at each instance and are selected from a divalent group derived from benzene, biphenyl, terphenyl, fluorene, spirobifluorene, indenofluorene, carbazole, dibenzofuran or dibenzothiophene, each optionally substituted by R.sup.4 radicals, or a combination of two or more of these groups; L.sup.2 is the same or different at each instance and selected from a divalent group derived from biphenyl, terphenyl, fluorine, spirobifluorene, indenofluorene, carbazole, dibenzofuran or dibenzothiophene, each optionally substituted by R.sup.4 radicals, or a combination of two or more of these groups; Ar.sup.1 is an aromatic ring system which has 6 to 24 aromatic ring atoms and may be substituted by one or more R.sup.5 radicals, or a heteroaromatic ring system which has 5 to 24 aromatic ring atoms and may be substituted by one or more R.sup.5 radicals, where Ar.sup.1 does not comprise any nitrogen-containing heteroaryl group bonded directly to the amine nitrogen atom of the formula (I), and where Ar.sup.1 and substituents bonded thereto do not contain any carbazole group; R.sup.1, R.sup.2, R.sup.3, R.sup.4 are the same or different at each instance and are selected from H, D, F, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.5 is the same or different at each instance and is selected from H, D, Si(R.sup.6).sub.3, OR.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, NR.sup.6, O— or —S—; R.sup.6 is the same or different at each instance and is selected from H, D, F, C(═O)R.sup.7, CN, Si(R.sup.7).sub.3, P(═O)(R.sup.7).sub.2, OR.sup.7, S(═O)R.sup.7, S(═O).sub.2R.sup.7, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.6 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.7 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.7C═CR.sup.7—, —C≡C—, Si(R.sup.7).sub.2, C═O, C═NR.sup.7, —C(═O)O—, —C(═O)NR.sup.7—, NR.sup.7, P(═O)(R.sup.7), —O—, —S—, SO or SO.sub.2; R.sup.7 is the same or different at each instance and is selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.7 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; i is 0, 1, 2 or 3; and k is 1, 2 or 3.

2. The compound according to claim 1, wherein the fluoranthene group is bonded in position 3 or 4, where the positions are numbered as follows: ##STR00618##

3. The compound according to claim 1, wherein the group of the formula ##STR00619## in formula (I) is bonded in one of positions 1, 3 and 4.

4. The compound according to claim 1, wherein Ar.sup.1 is selected from the following radicals that are optionally substituted by R.sup.5 radicals: phenyl, biphenyl, branched terphenyl, unbranched terphenyl, branched quaterphenyl, unbranched quaterphenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, fluorenylphenylene, dibenzofuranylphenylene, dibenzothiophenylphenylene, phenanthrenyl and triphenylyl.

5. The compound according to claim 1, wherein R.sup.1 is the same or different at each instance and is selected from F, Si(R.sup.6).sub.3, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 24 aromatic ring atoms, and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.6 radicals; and where two R.sup.1 groups bonded to the same carbon atom may be joined to one another to form a ring, giving rise to a spiro carbon atom.

6. The compound according to claim 1, wherein R.sup.2, R.sup.3 and R.sup.4 are the same or different at each instance and are selected from H, D, F, CN, Si(R.sup.6).sub.3, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 24 aromatic ring atoms and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl groups mentioned may be replaced by —C≡C—, —R.sup.6C═CR.sup.6—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —NR.sup.6—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.6—.

7. The compound according to claim 1, wherein R.sup.5 is the same or different at each instance and is selected from H, D, Si(R.sup.6).sub.3, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 24 aromatic ring atoms, and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.6 radicals, where R.sup.5 and substituents bonded to R.sup.5 do not contain any carbazole group.

8. The compound according to claim 1, wherein R.sup.6 is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.7).sub.3, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 24 aromatic ring atoms and heteroaromatic ring systems having 5 to 24 aromatic ring atoms; where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.7 radicals; and where one or more CH.sub.2 groups in the alkyl groups mentioned may be replaced by —C≡C—, —R.sup.7C═CR.sup.7—, Si(R.sup.7).sub.2, C═O, C═NR.sup.7, —NR.sup.7—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.7—.

9. The compound according to claim 1, wherein i is 0.

10. The compound according to claim 1, wherein k is 1.

11. The compound according to claim 1, wherein the compound corresponds to one of the formulae (I-2), (I-4), (I-6), (I-8), (I-10), or (I-12) ##STR00620## ##STR00621## where the variables that occur are as defined in claim 1.

12. A process for preparing a compound of formula (I) according to claim 1, comprising reacting a fluorenylamine with an aromatic or heteroaromatic compound in a Buchwald coupling reaction.

13. An oligomer, polymer or dendrimer containing one or more compounds of formula (I) according to claim 1, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.1, R.sup.2, R.sup.3, R.sup.4 or R.sup.5 in formula (I).

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

15. An electronic device comprising at least one compound according to claim 1.

16. The electronic device according to claim 15, wherein the electronic device is an organic electroluminescent device comprising anode, cathode and at least one emitting layer, wherein at least one organic layer of the device, which may be an emitting layer or a hole-transporting layer, comprises the at least one compound.

17. The electronic device according to claim 16, comprising at least one emitting layer comprising a red-emitting phosphorescent emitter, where the at least one compound is present in the emitting layer as matrix material.

18. A method comprising utilizing the compound according to claim 1 in an electronic device.

19. The compound according to claim 1, wherein the fluoranthene group is bonded in position 3 or 4, where the positions are numbered as follows: ##STR00622## and wherein L.sup.1, is the same or different at each instance and are selected from divalent group derived from benzene, biphenyl, terphenyl, fluorene, spirobifluorene, indenofluorene, carbazole, dibenzofuran or dibenzothiophene, each optionally substituted by R.sup.4 radicals, or a combination of two or more of these groups; and wherein L.sup.2 is the same or different at each instance and selected from a divalent group derived from biphenyl, terphenyl, fluorine, spirobifluorene, indenofluorene, carbazole, dibenzofuran or dibenzothiophene, each optionally substituted by R.sup.4 radicals, or a combination of two or more of these groups.

20. The compound according to claim 1, wherein L.sup.2 is selected from a divalent group derived from carbazole, dibenzofuran or dibenzothiophene, each optionally substituted by R.sup.4 radicals.

21. The compound according to claim 19, wherein L.sup.2 is selected from a divalent group derived from carbazole, dibenzofuran or dibenzothiophene, each optionally substituted by R.sup.4 radicals.

Description

WORKING EXAMPLES

A) Synthesis Examples

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents.

a) Biphenyl-4-yl(9,9-dimethyl-9H-fluoren-1-yl)amine (1a)

(2) ##STR00155##

(3) 36 g (212 mmol, 1.0 eq) of 4-aminobiphenyl are initially charged together with 57.8 g (177 mmol, 1.0 eq) of 1-bromodimethylfluorene and 2.4 g (212 mmol, 1.20 eq) of sodium t-pentoxide [14593-46-5] in 600 ml of absolute toluene and degassed for 30 minutes. Subsequently, 398 mg (1.77 mmol, 0.01 eq) of palladium(II) acetate [3375-31-3] and 1.46 g (3.56 mmol, 0.02 eq) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl SPHOS [657408-07-6] are added and the mixture is heated under reflux overnight. After the reaction has ended, the mixture is cooled down to room temperature and extracted with 500 ml of water. Subsequently, the aqueous phase is washed three times with toluene, the combined organic phases are dried over sodium sulfate and the solvent is removed on a rotary evaporator. The brown residue is taken up in about 200 ml of toluene and filtered through silica gel. For further purification, a recrystallization from toluene/heptane is conducted.

(4) Yield: 59 g (164 mmol), 79% of theory.

(5) The following are prepared analogously:

(6) TABLE-US-00001 Aus- beute Eintrag Edukt 1 Edukt 2 Produkt 3 [%]  2a 65  3a 0 63  4a 60  5a 62  6a 0 64  7a 68  8a 71  9a 72 10a 0 83 11a 64 12a 67 13a 0 56 14a 75 15a 85 16a 00 69 17a 01 02 03 67 18a 04 05 06 88 19a 07 08 09 81 20a 0 77 21a 70 22a 84 23a 0 91 24a 74 25a 85 26a 0 69 27a 67 28a 71 29a 70

b) Biphenyl-4-yl(4-bromophenyl)(9,9-dimethyl-9H-fluoren-4-yl)amine (1b)

(7) ##STR00240##

(8) In a 1 l four-neck flask, 51.3 g (142 mmol, 1.00 eq) of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-4-yl)amine and also 75.6 g (426 mmol, 3.00 eq) of 1-bromo-4-fluorobenzene [460-00-4] and 92.5 g (284 mmol, 2.00 eq) of caesium carbonate [534-17-8] are initially charged, and 500 ml of dimethylacetamide are added. The reaction mixture is stirred at 150° C. for three days. After the reaction has ended, the mixture is cooled down to room temperature and the solids are filtered off through Celite. The mother liquor is concentrated and the precipitated solids, after filtration, are extracted by stirring with hot methanol.

(9) Yield: 43 g (135 mmol), 95% of theory.

(10) The following were prepared analogously:

(11) TABLE-US-00002 Ausbeute Eintrag Edukt 3 Produkt 5 [%]  2b 78  3b 26  4b 84  5b 68  6b 0 67  7b 44  8d 59  9d 65 10b 67 11b 0 71 12b 70

c) Biphenyl-4-yl(9,9-dimethyl-9H-fluoren-1-yl)(4-fluoranthen-3-ylphenyl)amine (1)

(12) ##STR00263##

(13) 27 g (110.0 mmol) of fluoranthene-3-boronic acid, 56 g (110.0 mmol) of biphenyl-4-yl(4-bromophenyl)(9,9-dimethyl-9H-fluoren-1-yl)amine and 26 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. Added to this suspension are 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The product is purified via column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed under high vacuum (p=5×10.sup.−7 mbar) (99.9% purity). The yield is 56 g (88 mmol), corresponding to 80% of theory.

(14) The following compounds are prepared in an analogous manner:

(15) TABLE-US-00003 Aus- beute Edukt 1 Edukt 2 Produkt [%] 2 70 3 74 4 0 70 5 64 6 71 7 0 64 8 67 9 68 10 0 73 11 66 12 70 13 72 14 00 01 02 76 15 03 04 05 71 16 06 07 08 75 17 09 0 68 18 71 19 61 20 0 69 21 68 22 60 23 65 24 0 67 25 65

d) 3-(4-Chlorophenyl)fluoranthene (1d)

(16) ##STR00336##

(17) 30 g (156 mmol) of 1-bromo-4-chlorobenzene, 37 g (150 mmol) of fluoranthenyl-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol diamine ether and 280 ml of water. 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The yield is 30 g (97 mmol), corresponding to 65% of theory. The following compounds are prepared in an analogous manner:

(18) TABLE-US-00004 Edukt 1 Edukt 2 Produkt Ausbeutein % 2d 70 3d 0 71 4d 74 5d 77 6d 0 73 7d 61 8d 62 9d 0 72

e) 3-(4-Chlorophenyl)-7,10-diphenylfluoranthene (1e)

(19) ##STR00361##

(20) In a 500 ml four-neck flask, 25.4 g (58.7 mmol, 1.0 eq) of 3-bromo-7,10-diphenylfluoranthene, 9.17 g (58.7 mmol, 1.0 eq) of 4-chlorophenylboronic acid (CAS 1679-18-1) and 6.22 g (58.7 mmol, 1.0 eq) of sodium carbonate are dissolved in 150 ml of toluene, 36 ml of ethanol and 77 ml of water. After degassing by means of a nitrogen stream for 30 minutes, 678 mg (0.587 mmol, 0.01 eq) of tetrakis(triphenylphosphine)palladium are added and the mixture is heated at reflux overnight. After the reaction has ended, the phases are separated, the aqueous phase is extracted three times with toluene and the combined organic phases are then washed with water. The organic phases are dried over sodium sulfate and the solution is concentrated on a rotary evaporator. The residue is introduced into 250 ml of ethanol and the solids formed are filtered off with suction.

(21) The yield is 25.6 g (55 mmol), corresponding to 94% of theory.

(22) The following are prepared analogously:

(23) TABLE-US-00005 Verbin- Ausbeute dung Edukt 1 Edukt 2 Produkt [%] 1e 91 2e 32 3e 0 88 4e 91 5e 97 6e 23 7e 0 86

f) Biphenyl-4-yl(9,9-dimethyl-9H-fluoren-4-yl)(4-fluoranthen-3-ylphenyl)amine (26)

(24) ##STR00383##

(25) A mixture of 21.6 g (60 mmol) of 8-(4-chlorophenyl)fluoranthene, 18.7 g (60 mmol) of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-4-yl)amine, 7.7 g (80 mmol) of sodium tert-butoxide, 1.4 g (5 mmol) of tricyclohexylamine, 561 mg (2.5 mmol) of palladium(II) acetate and 300 ml of mesitylene is heated under reflux for 24 h. After cooling, 200 ml of water are added, the mixture is stirred for a further 30 min, the organic phase is removed and the latter is filtered through a short Celite bed and then the solvent is removed under reduced pressure. The residue is recrystallized five times from DMF and finally fractionally sublimed twice (p about 10.sup.−6 mbar, T=360-390° C.). Yield: 27 g (42 mmol), 71% of theory: 99.9% by HPLC.

(26) In an analogous manner, the following compounds are obtained:

(27) TABLE-US-00006 Ausbeute Bsp. Edukt 1 Edukt 2 Produkt [%] 27 68 28 72 29 0 70 30 69 31 74 32 00 01 75 33 02 03 04 72 34 05 06 07 70 35 08 09 0 75 36 63 37 73 38 72 39 0 77 40 72 41 63 42 0 67 43 60 44 65 45 0 73 46 70 47 69 48 77 49 0 72 50 70 51 64 52 0 71 53 60 54 64 1f 0 61 2f 65 3f 67 4f 60 5f 0 59 6f 68 7f 61 8f 0 64 55 66 56 61 57 00 70 58 01 02 03 74 59 04 05 06 77 60 07 08 09 72 61 0 71 62 78 63 74 64 0 79 65 76 66 69 67 0 73 68 75 69 78 70 77 71 0 72 72 72 73 75 74 0 76 75 78 76 79 77 0 72 78 76 79 71 80 79 81 0 74 82 77 83 72 84 0 73 85 68 86 60 87 0 71 88 65

B) Device Examples

(28) The inventive OLEDs I1 to I10 and the comparative OLEDs C1 to C3 are produced, and their properties are analysed (Tables 1 and 2).

(29) The OLEDs are produced as follows: Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plaques form the substrates to which the OLEDs are applied.

(30) 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) 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 1. The materials required for production of the OLEDs are shown in Table 3.

(31) All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by coevaporation. Details given in such a form as IC5:IC3:TEG2 (55%:35%:10%) mean here that the material IC5 is present in the layer in a proportion by volume of 55%, IC3 in a proportion of 35% and TEG2 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(32) The OLEDs are characterized in a standard manner. 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 luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined. 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 U1000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 in the course of operation with constant current. Figures given as L0;j0=a mA/cm.sup.2, L1=b % mean that the luminance in the course of operation at a mA/cm.sup.2 falls to b % of its starting value after the time LT.

(33) The data obtained for the OLEDs are collated in Table 2.

(34) TABLE-US-00007 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness thickness C1 HATCN SpMA1 SpMA3 PA1:TER5 ST2 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm 30 nm C2 HATCN SpMA1 SpMA3 PA2:TER5 ST2 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm 30 nm C3 HATCN SpMA1 SpMA3 PA3:TER5 ST2 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm 30 nm I1 HATCN SpMA1 SpMA3 EG26:TER5 ST2 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm 30 nm I2 HATCN SpMA1 SpMA3 EG87:TER5 ST2 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm 30 nm I3 HATCN SpMA1 SpMA3 EG88:TER5 ST2 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm 30 nm I4 HATCN SpMA1 SpMA3 EG23:TER5 ST2 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm 30 nm I5 HATCN SpMA1 SpMA3 EG30:TER5 ST2 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm 30 nm I6 HATCN SpMA1 SpMA3 IC5:IC3:TEG2 EG18 ST2:LiQ (50%:50%) 5 nm 230 nm 20 nm (60%:30%:10%) 30 nm 10 nm 30 nm I7 HATCN SpMA1 SpMA3 IC5:IC3:TEG2 EG71 ST2:LiQ (50%:50%) 5 nm 230 nm 20 nm (60%:30%:10%) 30 nm 10 nm 30 nm I8 HATCN SpMA1 SpMA3 IC5:IC3:TEG2 EG85 ST2:LiQ (50%:50%) 5 nm 230 nm 20 nm (60%:30%:10%) 30 nm 10 nm 30 nm I9 HATCN SpMA1 SpMA3 IC5:IC3:TEG2 ST2 EG3:LiQ (50%:50%) 5 nm 230 nm 20 nm (60%:30%:10%) 30 nm 10 nm 30 nm I10 HATCN SpMA1 SpMA3 IC5:IC3:TEG2 ST2 EG37:LiQ (50%:50%) 5 nm 230 nm 20 nm (60%:30%:10%) 30 nm 10 nm 30 nm

(35) TABLE-US-00008 TABLE 2 Performance data of the OLEDs U1000 EQE CIE x/y at LT Ex. (V) 1000 1000 cd/m.sup.2 L.sub.0; j.sub.0 L1 % (h) C1 3.4 16.8% 0.67/0.33 60 mA/cm.sup.2 95 25 C2 3.4 16.6% 0.67/0.33 60 mA/cm.sup.2 95 20 C3 3.4 16.7% 0.67/0.33 60 mA/cm.sup.2 95 15 I1 3.5 16.0% 0.67/0.33 60 mA/cm.sup.2 95 105 I2 3.4 16.4% 0.67/0.33 60 mA/cm.sup.2 95 80 I3 3.4 16.4% 0.67/0.33 60 mA/cm.sup.2 95 45 I4 3.5 16.2% 0.67/0.33 60 mA/cm.sup.2 95 115 I5 3.6 16.3% 0.67/0.33 60 mA/cm.sup.2 95 95 I6 3.3 18.1% 0.33/0.63 40 mA/cm.sup.2 80 220 I7 3.4 17.5% 0.33/0.63 40 mA/cm.sup.2 80 200 I8 3.4 17.7% 0.33/0.63 40 mA/cm.sup.2 80 210 I9 3.5 17.6% 0.33/0.63 40 mA/cm.sup.2 80 215 I10 3.6 17.3% 0.33/0.63 40 mA/cm.sup.2 80 195

(36) TABLE-US-00009 TABELLE 3 Strukturformein der verwendeten Materialien 00 01 02 03 04 05 06 07 08 09 0

(37) In experiments I1 to I5, the materials according to the present application EG26, EG87, EG88, EG23 and EG30 are used as matrix materials for red-phosphorescing emitters in the emitting layer. The OLEDs C1 to C3 differ from the OLEDs II to 15 merely by the material used as matrix in the emitting layer (PA1, PA2 and PA3). Otherwise, they are of identical construction. It is found that the inventive OLEDs I1 to I5 all have a distinctly longer lifetime than the comparative OLEDs C1 to C3.

(38) Experiments I6 to I8 show that the inventive compounds (EG18, EG71 and EG85) are of excellent suitability as hole blocker materials.

(39) Experiments I9 and I10 show that the inventive compounds (EG3, EG37) are of excellent suitability as electron transport materials.