Heterocyclic compounds with dibenzazapine structures

Abstract

The present invention relates to heterocyclic compounds and electronic devices, in particular organic electroluminescent devices, containing these compounds.

Claims

1. A compound of the formula (II) ##STR00498## where the symbols used are as follows: X is CR.sup.1; W is a bond; R.sup.1 is H; R.sup.2 is the same or different at each instance and is H, D F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(O)R.sup.3, CR.sup.3C(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 thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.3CCR.sup.3, Si(R.sup.3).sub.2, Si(R.sup.2).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, CO, CS, CSe, 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 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.2 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.3 is the same or different at each instance and is H, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, in which hydrogen atoms may also be replaced by F; at the same time, two or more adjacent R.sup.3 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.a and R.sup.b are independently an aromatic group having 10 to 40 carbon atoms or a heteroaromatic group having 6 to 40 carbon atoms, where the aromatic and/or heteroaromatic group comprises at least two adjacent aromatic and/or heteroaromatic rings, each of which may be fused or unfused and/or may be substituted by one or more R.sup.1 radicals, wherein R.sup.1 is the same or different at each instance and is H, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(O)R.sup.2, CR.sup.2C(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 thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, CNR.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 where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.1 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system.

2. A compound as claimed in claim 1, wherein the compound is a compound of formula (IV) ##STR00499## where for the symbols used have the definition given in claim 1, and R.sup.a and R.sup.b are selected independently of each other.

3. A compound as claimed in claim 1, wherein at least one of the R.sup.a and/or R.sup.b radicals is a hole transport group or an electron transport group.

4. A compound as claimed in claim 1, wherein the R.sup.b radical in one of the formulae (II), and/or (IV) is a hole transport group and the R.sup.a radical in one of the formulae (II), and/or (IV) is a hole transport group.

5. A compound as claimed in claim 1, wherein the R.sup.b radical in one of the formulae (II), and/or (IV) is an electron transport group and the R.sup.a radical in one of the formulae (II), and/or (IV) is a hole transport group.

6. A compound as claimed in claim 1, wherein the R.sup.b radical in one of the formulae (II), and/or (IV) is a hole transport group and the R.sup.a radical in one of the formulae (II), and/or (IV) is an electron transport group.

7. A compound as claimed in claim 1, wherein the R.sup.b radical in one of the formulae (II), and/or (IV) is an electron transport group and the R.sup.a radical in one of the formulae (II), and/or (IV) is an electron transport group.

8. A compound as claimed in claim 1, wherein, in the structure of formula (I), (II), and/or (IV), at least one R.sup.a, and/or R.sup.b radical is a group independently selected from the formulae (R.sup.1-2) to (R.sup.1-72) ##STR00500## ##STR00501## ##STR00502## ##STR00503## ##STR00504## ##STR00505## ##STR00506## ##STR00507## ##STR00508## ##STR00509## ##STR00510## ##STR00511## ##STR00512## has, where the symbols used are as follows: Y is O, S or NR.sup.2; j independently at each instance is 0, 1, 2 or 3; h independently at each instance is 0, 1, 2, 3 or 4; g independently at each instance is 0, 1, 2, 3, 4 or 5; the dotted bond marks the attachment position; and R.sup.2 is as defined in claim 1.

9. A compound as claimed in claim 8, wherein the sum total of the indices g, h and j in the structures of the formula (R.sup.1-2) to (R.sup.1-72) is at most 3 in each case.

10. A compound as claimed in claim 3, wherein the electron transport group of R.sup.a and/or R.sup.b has independently of each other at least one structure of the formula (E-24) to (E-38) ##STR00513## ##STR00514## ##STR00515## where the dotted bond marks the attachment position.

11. A compound as claimed in claim 3, wherein the electron transport group of R.sup.a and/or R.sup.b has at least one structure of the formula (E-17) to (E-23) ##STR00516## where the dotted bond marks the attachment position and R.sup.1# in the electron-transporting group E are independently of each other selected from the group consisting of H and an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals.

12. A compound as claimed in claim 3, wherein the hole transport group of R.sup.a and/or R.sup.b has at least one structure of the formula (L-1) to (L-9) ##STR00517## ##STR00518## where the dotted bond marks the attachment position, e is 0, 1 or 2, j is 0, 1, 2 or 3, h is 0, 1, 2, 3 or 4, n is 0 or 1, Ar is an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms which may be substituted by one or more R.sup.1 radicals, and R.sup.1+ is the same or different at each instance and is H, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(O)R.sup.2, CR.sup.2C(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 thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, CNR.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 where one or more hydrogen atoms may be replaced by F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.1 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system.

13. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1, wherein one or more bonds of the compound to the polymer, oligomer or dendrimer are present.

14. A composition comprising at least one compound as claimed in claim 1 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

15. A formulation comprising at least one compound as claimed in claim 1, and at least one solvent.

16. A method comprising providing the compound as claimed in claim 1, and including the compound in an electronic device as electron blocker material, hole injection material and/or hole transport material.

17. An electronic device comprising at least one compound as claimed in claim 1.

18. The electronic device as claimed in claim 17, wherein the electronic device is preferably 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 optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells and organic laser diodes.

19. A compound according to claim 1, selected from the group consisting of ##STR00519## ##STR00520## ##STR00521## ##STR00522## ##STR00523## ##STR00524## ##STR00525## ##STR00526##

Description

EXAMPLE

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

Preparation Examples

a) 6,12-Dibromo-9H-9-azatribenz[b,d,f]azapine

(2) ##STR00203##

(3) 100 g (373.2 mmol) of 9H-tribenz[b,d,f]azapine are initially charged in 800 mL of DMF. Subsequently, 132.8 g (746.4 mmol) of NBS are added in portions and stirring is continued at this temperature for 4 h. Subsequently, 150 mL of water are added to the mixture and extraction is effected with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4 and the solvents are removed under reduced pressure. The product is subjected to extractive stirring with hot hexane and filtered off with suction. Yield: 122 g (295 mmol), 79% of theory, purity by .sup.1H NMR about 97%.

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

(5) TABLE-US-00002 Reactant 1 Product Yield a1 04 05 78% a2 06 07 77% a3 08 09 84% a4 0 83% a5 80%

b) 6,12-Bis-(9,9-dimethyl-9H-fluoren-4-yl)-9H-9-azatribenzo[a,c,e]cycloheptene

(6) ##STR00214##

(7) 70.0 g (168 mmol) of 6,12-dibromo-9H-9-azatribenz[b,d,f]azapine, 71 g (343 mmol) of 9,9-dimethylfluorene-4-boronic acid and 6.8 g (71 mmol) of K.sub.2CO.sub.3 are suspended in 200 mL of toluene, 250 mL of 1,4-dioxane and 150 mL of water. To this suspension are added 9.6 g (8.3 mmol) of tetrakis(triphenylphosphine)palladium(0). The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, washed three times with 100 mL of water and then concentrated to dryness. The residue is subjected to hot extraction with toluene, recrystallized from toluene and finally sublimed under high vacuum. The yield is 61 g (98 mmol), 57% of theory, purity by .sup.1H NMR about 98%.

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

(9) TABLE-US-00003 Reactant 1 Reactant 2 b1 b2 b3 0 b4 b5 b6 b7 b8 0 b9 b10 b11 b12 b13 0 b14 b15 b16 b18 b19 0 b20 b21 b22 b23 b24 0 b25 b26 b27 b28 Product Yield b1 64% b2 0 78% b3 63% b4 78% b5 69% b6 61% b7 62% b8 58% b9 54% b10 59% b11 62% b12 0 60% b13 81% b14 89% b15 87% b16 88% b18 86% b19 78% b20 89% b21 78% b22 74% b23 0 73% b24 78% b25 67% b26 60% b27 58% b28 69%

Synthesis of 6-carbazol-9-yl-12-(4,6-diphenyl[1,3,5]triazin-2-yl)-9H-9-azatribenzo[a,c,e]cycloheptene

(10) ##STR00296##

(11) To 80 g (159.5 mmol) of 6-chloro-12-(4,6-diphenyl-[1,3,5]triazin-2-yl)-9H-9-azatribenzo[a,c,e]cycloheptene in 150 mL of di-n-butyl ether are added 67.7 g (145 mmol) of carbazole, and the solution is degassed. Subsequently added to the mixture are 10 g (0.158 mmol) of copper powder, 1.38 g (0.007 mmol) of copper iodide and 22 g (159.6 mmol) of K.sub.2CO.sub.3, and the mixture is stirred under protective gas at 144 C. for 4 days. The organic phase is dried over MgSO.sub.4 and the solvent is removed under reduced pressure.

(12) Yield: 32 g (50 mmol), 40% of theory.

c) 9-(2-Chlorophenyl)-6,12-bis-(9,9-dimethyl-9H-fluoren-4-yl)-9H-9-azatribenzo[a,c,e]cycloheptene

(13) ##STR00297##

(14) Under protective gas, 43.9 g (70 mmol) of 6,12-bis-(9,9-dimethyl-9H-fluoren-4-yl)-9H-9-azatribenzo[a,c,e]cycloheptene and 14 g (73 mmol) of 1-bromo-2-chlorobenzene, 8 g (84 mmol) of sodium tert-butoxide, 3.5 mL of tris-tert-butylphosphine (1 M in toluene) and 0.393 mg (1.7 mmol) palladium acetate are suspended in 300 mL of p-xylene. The reaction mixture is heated under reflux at 110 C. for 12 h. After cooling, the organic phase is removed, 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). The yield is 45 g (61.6 mmol), 88% of theory, purity by .sup.1H NMR about 94%.

(15) In an analogous manner, it is possible to obtain the following compounds

(16) TABLE-US-00004 Ex- am- ple Reactant 1 Reactant 2 c1 c2 00 01 c3 02 03 c4 04 05 c5 06 07 c6 08 09 c7 0 c8 c9 c10 c11 c12 0 c13 c14 c15 c16 C17 0 c18 c19 c20 c21 c22 0 c23 Ex- am- ple Product Yield c1 64% c2 78% c3 63% c4 78% c5 69% c6 61% c7 0 62% c8 58% c9 54% c10 59% c11 62% c12 60% c13 81% c14 89% c15 87% c16 88% C17 0 86% c18 76% c19 74% c20 72% c21 73% c22 74% c23 73%

d) Cyclization

(17) ##STR00367##

(18) Under protective gas, 45 g (61 mmol) of 9-(2-chlorophenyl)-6,12-bis-(9,9-dimethyl-9H-fluoren-4-yl)-9H-9-azatribenzo[a,c,e]cycloheptene are dissolved in 250 mL of dimethylacetamide. Added to this solution are 21 g (154 mmol) of K.sub.2CO.sub.3, 10 ml of tri-tert-butylphosphine (1 mol/L) and 2.7 g (12.5 mmol) of Pd(OAc).sub.2 and 1.8 g (18.5 mmol) of pivalic acid. Then the mixture is stirred at 130 C. for 80 h. After this time, the reaction mixture is cooled to room temperature extracted with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated. The residue is subjected to hot extraction with toluene, recrystallized from toluene and finally sublimed under high vacuum. The yield is 37 g (52 mmol), 87% of theory, purity by HPLC about 99.9%.

(19) In an analogous manner, it is possible to obtain the following compounds:

(20) TABLE-US-00005 Reactant 1 d1 d2 d3 0 d4 d5 d6 d7 d8 d9 c10 d11 d12 d13 0 d14 d15 d16 d17 d18 d19-a d19-b d-20a d20-b Product Yield d1 0 68% d2 78% d3 65% d4 69% d5 65% d6 61% d7 60% d8 58% d9 63% c10 60% d11 00 62% d12 01 64% d13 02 61% d14 03 69% d15 04 66% d16 05 68% d17 06 72% d18 07 83% d19-a 08 35% d19-b 09 23% d20-a 0 37% d20-b 29%

e) 2-[2-(6,12-Bis-[1,1;3,1]terphenyl-5-yl-9-aza-tribenzo[a,c,e]cyclohepten-9-yl)phenyl]propan-2-ol

(21) ##STR00412##

(22) 177 g (213 mmol) of methyl 2-(6,12-bis-[1,1;3,1]terphenyl-5-yl-9-azatribenzo[a,c,e]-cyclohepten-9-yl)benzoate are dissolved in 1500 mL of dried THF and degassed. The mixture is cooled to 78 C., and 569 mL (854 mmol) of methyllithium are added within 40 minutes. The mixture is allowed to warm up to 40 C. within 1 h, and the conversion is monitored via TLC. On completion of conversion, the mixture is quenched cautiously with MeOH at 30 C. The reaction solution is concentrated to 1/3 and 1 L of CH.sub.2Cl.sub.2 is added, the mixture is washed and the organic phase is dried over MgSO.sub.4 and concentrated. The yield is 158 g (189 mmol), 89% of theory.

(23) In an analogous manner, it is possible to prepare the following compound:

(24) TABLE-US-00006 Example Reactant 1 e1 e2 Example Product Yield e1 72% e2 74%

f) Cyclization

(25) ##STR00417##

(26) 36 g (43.6 mmol) of 2-[2-(6,12-bis-[1,1;3,1]terphenyl-5-yl-9-azatribenzo[a,c,e]cyclohepten-9-yl)phenyl]propan-2-ol are dissolved in 1200 mL of degassed toluene, a suspension of 40 g of polyphosphoric acid and 28 mL of methanesulfonic acid is added and the mixture is heated to 60 C. for 1 h. The mixture is cooled down and admixed with water. A solid precipitates out and is dissolved in CH.sub.2Cl.sub.2/THF (1:1). The solution is cautiously alkalized with 20% NaOH, and the phases are separated and dried over MgSO.sub.4. The residue is subjected to hot extraction with toluene, recrystallized from toluene/heptane (1:2) and finally sublimed under high vacuum. The yield is 28 g (35 mmol), 81% of theory.

(27) In an analogous manner, it is possible to obtain the following compounds:

(28) TABLE-US-00007 Example Reactant 1 f1 f2 Example Product Yield f1 0 73% f2 72%

g) 8-Chloro-9-(2-nitrophenyl)-9H-9-azatribenz[b,d,f]azapine

(29) ##STR00422##

(30) Under protective gas, 24.6 g (89 mmol) of 8-chloro-9H-9-azatribenz[b,d,f]azapine, 17.9 g (89 mmol) of 1,2-bromonitrobenzene and 0.8 g (0.88 mmol) of tris(dibenzylideneacetone)dipalladium, 1.79 g (7.9 mmol) of palladium acetate are suspended in 500 mL of toluene. The reaction mixture is heated under reflux for 8 h. After cooling, the organic phase is removed, washed three times with 200 mL of water and then concentrated to dryness. The purity is 87%. Yield: 25.5 g (63 mmol), 72% of theory.

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

(32) TABLE-US-00008 Reactant 1 Reactant 2 g1 g2 g3 g4 0 g5 g6 Product Yield g1 64% g2 78% g3 g4 g5 g6 0

h) 2-(8-Chloro-9H-9-azatribenz[b,d,f]azapinyl)phenylamine

(33) ##STR00441##

(34) 16.7 g (42 mmol) of 8-chloro-9-(2-nitrophenyl)-9H-9-azatribenz[b,d,f]azapine are suspended in 200 mL of ethanol. While stirring at 60 C., 26 g (140 mmol) of SnCl.sub.2 dissolved in 25 mL of concentrated HCl are added in portions and the mixture is boiled under reflux for 8 h. Thereafter, the precipitate is filtered off and dried under reduced pressure. The purity is 90%. Yield: 14.2 g (38 mmol), 92% of theory.

(35) In an analogous manner, it is possible to obtain the following compounds:

(36) TABLE-US-00009 Reactant 1 Product Yield h1 71% h2 73% h3 70% h4 74% h5 0 78% h6 72%

i) Cyclization

(37) ##STR00454##

(38) Under protective gas, 9.9 g (27 mmol) of 2-(8-chloro-9H-9-azatribenz[b,d,f]azapinyl)phenylamine, 0.24 g (0.26 mmol) of tris(dibenzylideneacetone)dipalladium, 0.53 g (2.37 mmol) of palladium acetate are suspended in 150 mL of toluene. The reaction mixture is heated under reflux for 8 h. Subsequently, 4 g (26 mmol) of 4-bromobenzene and are added and the mixture is boiled under reflux for a further 8 h. After cooling, the organic phase is removed, washed three times with 80 mL of water and then concentrated to dryness. The residue is subjected to hot extraction with toluene, recrystallized from toluene/heptane (1:2) and finally sublimed under high vacuum. The purity is 99.9% by HPLC. Yield: 7.9 g (19.4 mmol), 72% of theory.

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

(40) TABLE-US-00010 Reactant 1 Reactant 2 i1 i2 i3 0 i4 i5 i6 Product Yield i1 60% i2 67% i3 69% i4 0 68% i5 65% i6 73%

Device Examples

(41) Production of the OLEDs

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

(43) In examples C1-I6-4 which follow (see tables 1 and 2), the data of various OLEDs are presented. Cleaned glass plaques (cleaning in laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm, for improved processing, are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution). These coated glass plaques form the substrates to which the OLEDs are applied.

(44) The OLEDs basically have the following layer structure: substrate/optional hole injection layer (HIL)/hole transport layer (HTL)/optional interlayer (IL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum 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.

(45) All materials are applied by thermal vapor 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 co-evaporation. Details given in such a form as ST1:CBP:TER1 (55%:35%:10%) mean here that the material ST1 is present in the layer in a proportion by volume of 55%, CBP in a proportion of 35% and TER1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(46) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, and the lifetime are measured. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color 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. CE1000 denotes the current efficiency which is achieved at 1000 cd/m.sup.2.

(47) 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. A figure of L0;j0=4000 cd/m.sup.2 and L1=80% in Table X2 means that the lifetime reported in the LT column corresponds to the time after which the starting luminance falls 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 starting luminance in the course of operation at 20 mA/cm.sup.2 falls to 80% of its starting value after the time LT.

(48) The values for the lifetime can be converted to a figure for other starting luminances with the aid of conversion formulae known to those skilled in the art. In this context, the lifetime for a starting luminance of 1000 cd/m.sup.2 is a standard figure.

(49) The data for the various OLEDs are collated in Table 2. Examples C1-C5 are comparative examples according to the prior art; examples I1-I6-4 show data of OLEDs comprising inventive materials.

(50) Some of the examples are elucidated in detail hereinafter, in order to illustrate the advantages of the compounds of the invention. However, it should be pointed out that this is merely a selection of the data shown in Table 2. As can be inferred from the table, even when the compounds of the invention that have not been specifically detailed are used, distinct improvements over the prior art are achieved, in some cases in all parameters, but in some cases only an improvements in efficiency or voltage or lifetime is observed. However, improvement in one of the parameters mentioned is already a significant advance because various applications require optimization with regard to different parameters.

(51) The OLEDs C1-C5 are comparative examples according to the prior art.

(52) Use of Compounds of the Invention as Electron Transport Materials

(53) Through the use of compounds of the invention in the electron transport layer of OLEDs, it is possible to achieve distinct increases in terms of operating voltage, external quantum efficiency and hence in particular power efficiency as well. In addition, improved lifetimes are obtained in the case of phosphorescent dopants.

(54) Use of Compounds of the Invention as Hole Blocker Materials

(55) The use of compounds of the invention on the hole blocker side of OLEDs thus gives significant improvements with regard to operating voltage, power efficiency, lifetime and processing complexity.

(56) Use of Compounds of the Invention as Matrix Materials in Phosphorescent OLEDs

(57) The materials of the invention, when used as matrix materials in phosphorescent OLEDs, thus give significant improvements over the prior art in all parameters, particularly with regard to lifetime and in some cases also in power efficiency.

(58) TABLE-US-00011 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness C1 SpA1 HATCN SpMA1 PA4:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm C2 SpA1 HATCN SpMA1 PA2:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm C3 SpA1 HATCN SpMA1 PA3:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm C4 SpA1 HATCN SpMA1 PA4:IC1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm C5 SpA1 HATCN SpMA1 PA5:IC1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm I1 SpA1 HATCN SpMA1 IV1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm I2 SpA1 HATCN SpMA1 IV2:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm I3 SpA1 HATCN SpMA1 IV3:IC1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm I4 SpA1 HATCN SpMA1 IV4:IC1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm I1-1 SpA1 HATCN SpMA1 IV1:TER1 ST2:LiQ (50%:50%) 90 nm 5 nm 130 nm (92%:8%) 30 nm 40 nm I2-1 SpA1 HATCN SpMA1 IV2:TER1 ST2:LiQ (50%:50%) 90 nm 5 nm 130 nm (92%:8%) 30 nm 40 nm I5 SpA1 HATCN SpMA1 IV5:IC1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm I6 SpA1 HATCN SpMA1 IV6:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm I7 SpA1 HATCN SpMA1 IV7:IC1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 92 nm (45%:45%:10%) 30 nm 10 nm 30 nm I8 SpA1 HATCN SpMA1 IV8:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm I6-1 SpA1 HATCN SpMA1 IC1:TEG1 IV6 LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm I6-2 SpA1 HATCN SpMA1 IC1:TEG1 IC1 IV6:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm I6-3 SpA1 HATCN SpMA1 IC1:TEG1 IV6 ST2:LiQ (50%:50%) 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm I6-4 HATCN SpMA1 SpMA2 IV6:L1:TEY1 ST1 LiQ 5 nm 70 nm 15 nm (45%:45%:10%) 25 nm 45 nm 3 nm

(59) TABLE-US-00012 TABLE 2 Data of the OLEDs U1000 CE1000 CIE x/y at L1 LT Ex. (V) (cd/A) 1000 cd/m.sup.2 L.sub.0; j.sub.0 % (h) C1 3.9 51 0.33/0.63 20 mA/cm.sup.2 80 90 C2 4.3 53 0.33/0.62 20 mA/cm.sup.2 80 105 C3 4.4 54 0.33/0.64 20 mA/cm.sup.2 80 110 C4 3.8 58 0.32/0.64 20 mA/cm.sup.2 80 190 C5 4.0 56 0.33 0.64 20 mA/cm.sup.2 80 170 I1 3.8 52 0.33/0.62 20 mA/cm.sup.2 80 110 I2 4.2 53 0.33/0.62 20 mA/cm.sup.2 80 130 I3 3.7 59 0.33/0.63 20 mA/cm.sup.2 80 250 I4 3.6 58 0.32/0.63 20 mA/cm.sup.2 80 210 I1-1 4.3 12 0.66/0.34 4000 cd/m.sup.2 80 310 I2-1 4.5 11 0.67/0.34 4000 cd/m.sup.2 80 320 I5 4.1 48 0.33/0.63 20 mA/cm.sup.2 80 170 I6 3.9 50 0.33/0.62 20 mA/cm.sup.2 80 80 I7 3.4 62 0.34/0.63 20 mA/cm.sup.2 80 190 I8 3.8 49 0.33/0.62 20 mA/cm.sup.2 80 70 I6-1 3.9 63 0.33/0.63 20 mA/cm.sup.2 80 125 I6-2 4.2 60 0.34/0.63 20 mA/cm.sup.2 80 165 I6-3 3.6 59 0.34/0.63 20 mA/cm.sup.2 80 140 I6-4 3.0 75 0.44/0.55 50 mA/cm.sup.2 90 80

(60) TABLE-US-00013 TABLE 3 Structural formulae of the materials for the OLEDs HATCN SpA1 SpMA1 LiQ SpMA2 TER1 L1 0 TEY1 ST2 IC3 TEG1 ST1 PA1 PA2 PA3 PA4 PA5 0 IV1 IV2 IV3 IV4 IV5 IV6 IV7 IV8