Heterocyclic compounds

Abstract

The invention concerns heterocyclic compounds and electronic devices, in particular organic electroluminescent devices, containing these compounds.

Claims

1. A compound of the general formula (1) ##STR00335## where the symbols used are as follows: Q is the same or different at each instance and is XX, O, NR, S, SO, SO.sub.2, PR, POR or BR, where at least one Q is XX; X.sup.1 is CR or N; X is the same or different at each instance and is N or CR; Y is the same or different at each instance and is CR; R is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, NR.sup.1, O, S or CONR.sup.1 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, or 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.1 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.1 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two adjacent R radicals together may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 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, CO, NR.sup.2, O, S or CONR.sup.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 60 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 an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, two or more adjacent R.sup.1 radicals together, or R.sup.1 together with R, may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; R.sup.2 is the same or different at each instance and is H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; at the same time, two or more R.sup.2 substituents together may also form a mono- or polycyclic aliphatic ring system; which is characterized in that the respective R radicals of the two Y groups together with the carbon atoms of the heteroaromatic ring form a ring of the following formulae: ##STR00336## where A.sup.1, A.sup.3 is the same or different at each instance and is C(R.sup.3).sub.2, O, S, NR.sup.3 or C(O); A.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.3 or C(O); G is a bivalent group selected from O, S, N(R.sup.2), B(R.sup.2), Si(R.sup.2).sub.2, CO, CNR.sup.2, CC(R.sup.2).sub.2, SO, SO.sub.2, P(R.sup.2) and P(O)R.sup.2, an alkylene group which has 1, 2 or 3 carbon atoms and may be substituted by one or more R.sup.2 radicals, CR.sup.2CR.sup.2- or an ortho-bonded arylene or heteroarylene group which has 5 to 14 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; and where the carbon-carbon double bond shown in the formulae (5) to (11) corresponds to an aromatic double bond from the heteroaromatic ring to which the groups of the formulae (5) to (11) bind; R.sup.3 is the same or different at each instance and is F, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 10 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, CO, NR.sup.2, O, S or CONR.sup.2, and where one or more hydrogen atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system which has 5 to 24 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 24 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 24 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, two R.sup.3 radicals bonded to the same carbon atom together may form an aliphatic or aromatic ring system and thus form a Spiro system; in addition, R.sup.3 with an adjacent R or R.sup.1 radical may form an aliphatic ring system; with the proviso that no two identical heteroatoms in the aforementioned groups are bonded directly to one another and no two CO groups are bonded directly to one another, and, in addition, if the two Y groups together are a ring structure of the formulae (12) or (13) ##STR00337## the X.sup.1 radical is not a group of the formula (14) ##STR00338## in which X is as defined above and the dotted lines represent the bonds of the carbon atom of the X.sup.1 radical to two further carbon atoms of the ring including the X.sup.1 radical of formula (1); wherein, in the ring structures of one of the formulae (5), (6), (7), (8), (9), (10), and/or (11), not more than one of the A.sup.1, A.sup.2, and A.sup.3 groups is O, S or NR.sup.3.

2. The compound of claim 1, wherein the heteroaromatic ring system having the X.sup.1 radical is a system having 10 to 30 aromatic ring atoms.

3. The compound of claim 1, wherein the compound has a general structure having the formula (15): ##STR00339## where X is the same or different at each instance and is CR.sup.1 or N, where the symbols used are each as defined above.

4. The compound of claim 1, wherein Q is the same or different at each instance and is XX.

5. The compound of claim 1, wherein, in the ring structures of one of the formulae (5), (6), (7), (8), (9), (10) and/or (11), the A.sup.1 and A.sup.3 groups are the same or different at each instance and are C(R.sup.3).sub.2 and A.sub.2 is C(R.sup.1).sub.2.

6. The compound of claim 1, wherein, in the ring structures of formulae (8), (9), (10) and/or (11), the R.sup.1 radicals bonded to the bridgehead are H, D, F or CH.sub.3.

7. The compound of claim 1, wherein, in the structure of formula (1), the two Y groups form a ring structure of one of the following formulae (5-A), (5-B), (5-C), (5-D), (5-E) or (5-F): ##STR00340## where A.sup.1, A.sup.2 and A.sup.3 are the same or different at each instance and are 0 or NR.sup.3, the dotted lines represent the bonds of the two Y radicals to the ring comprising the X.sup.1 radical of formula (1) and R.sup.1 and R.sup.3 are each as defined above.

8. The compound of claim 1, wherein, in the structure of formula (1), the two Y groups form a ring structure of one of the following formulae (6-A) to (6-F): ##STR00341## where A.sup.1, A.sup.2 and A.sup.3 are the same or different at each instance and are 0 or NR.sup.3, the dotted lines the bonds of the two Y radicals to the ring comprising the X.sup.1 radical of formula (1), R.sup.1 and R.sup.3 are each as defined above.

9. The compound of claim 1, wherein, in the structure of formula (1), the two Y groups form a ring structure of one of the following formulae (8-A) to (8-C): ##STR00342## where the symbols used are each as defined above and the dotted lines represent the bonds of the two Y radicals to the ring comprising the X.sup.1 radical of formula (1).

10. The compound of claim 1, wherein, in the structure of formula (1), the two Y radicals together with the groups present for formation of the A ring form a ring structure of one of the following formulae (9-A), (10-A) and (11-A): ##STR00343## where the symbols used are each as defined above and the dotted lines represent the bonds of the two Y radicals to the ring comprising the X.sup.1 radical of formula (1).

11. The compound of claim 1, wherein the compound has at least two ring structures of the formulae (5) to (11).

12. The compound of claim 1, wherein the compound has a structure of the formula CyG(CyH).sub.n where CyG and CyH together in each case form a ring and the symbols and indices are as follows: n is 2 or 3; CyG is a structural element selected from the formulae ##STR00344## ##STR00345## ##STR00346## ##STR00347## and CyH is at least one structural element of the following formula: ##STR00348## where the symbols used are as defined above, U is selected from the group consisting of O, S, C(R).sub.2, N(R), B(R), Si(R).sub.2, CO, SO, SO.sub.2, P(R) and P(O)R, the dotted lines in formulae CyH indicate the bonds to CyG, and CyH binds to CyG in each case at the positions indicated by o to form a ring.

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 additional organic functional material.

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

16. A process for preparing a compound as claimed in claim 1, the process comprising reacting at least one primary arylamine with at least one -keto vinyl alcohol to give a -keto enamine compound which is subsequently cyclized.

17. An electronic device comprising a hole blocker material, electron injection material or electron transport material comprising the compound as claimed in claim 1.

18. The electronic device according to claim 17, wherein the electronic device is selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, and organic photoreceptors.

19. The electronic device as claimed in claim 18, wherein the electronic device is an organic electroluminescent device selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs).

20. The compound of claim 1, wherein, in the ring structures of one of the formulae (5), (6), (7), (8), (9), (10), and/or (11), none of the A.sup.1, A.sup.2, and A.sup.3 groups is O, S or NR.sup.3.

21. The compound of claim 1, wherein the compound is selected from the group consisting of: ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355##

Description

EXAMPLES

(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.

A: Synthesis of the Synthons

Example S1

5-[1-Hydroxymeth-(E)-ylidene]-2,2-4,4-tetramethylcyclopentanone [81887-98-1]

(2) ##STR00200##

(3) To a well-stirred suspension of 9.6 g (100 mmol) of sodium tert-butoxide in 300 mL of methyl tert-butyl ether is added dropwise a mixture of 14.0 g (100 mmol) of 2,2,4,4-tetramethylcyclopentanone [4694-11-5], 9.6 g (130 mmol) of ethyl formate [109-94-4] and 250 mL of methyl tert-butyl ether (caution: exothermic). After the addition has ended, the mixture is heated to 60 C. for 16 h. After cooling, the precipitated beige-red solid is filtered off with suction, washed once with a little methyl tert-butyl ether, resuspended in 300 mL of methyl tert-butyl ether and hydrolyzed by addition of 200 mL of saturated ammonium chloride solution. The clear organic phase is removed, washed three times with 100 mL each time of water and once with 100 mL of saturated sodium chloride solution and dried over magnesium sulfate, and then the solvent is removed under reduced pressure, leaving a yellow oil which crystallizes over time and which can be used in the next step without further purification. Yield: 14.5 g (86 mmol), 86%; purity: about 95% by .sup.1H NMR.

(4) In an analogous manner, it is possible to prepare the following compounds:

(5) TABLE-US-00002 Ex. Ketone Product Yield S2 01 5455-94-7 02 7441-66-9 78% S3 03 497/-38 04 122901-79-5 82% S4 05 464-49-3 06 14681-31-3 77% S5 07 2716-23-6 08 935-82-0 80% S6 09 24669-56-5 0 81%

(6) It is well-known to those skilled in the art that the products S1 to S6 may be present not just in the Z form but also in the E form. In addition, it is well-known to those skilled in the art that the enol form of the products S1 to S6 shown is not the only form in which the products may be present. In fact, keto-enol tautomerism is present, and so the products S1 to S6 may also be present in the keto form.

B: Synthesis of the Inventive Heterocycles H

Example H1

7,7,9,9-Tetramethyl-8,9-dihydro-7H-benzo[h]cyclo-penta[c]quinoline

(7) ##STR00211##

(8) A mixture of 16.8 g (100 mmol) of 5-[1-hydroxymeth-(E)-ylidene]-2,2-4,4-tetramethylcyclopentanone, S1, and 14.3 g (100 mmol) of 1-amino-naphthalene, [134-32-7], is heated gradually to 160 C. on a water separator, in the course of which the water formed in the reaction is distilled gradually out of the melt. After 10 h at 160 C., 100 mL of toluene are slowly added dropwise and the latter is distilled off by means of the water separator, in order to remove the rest of the water from the melt and the apparatus. To the deep brown melt thus obtained are added, in an argon countercurrent, about 300 g of polyphosphoric acid (Merck KGaA) and then the mixture is stirred at 160 C. for a further 16 h. After cooling to 120 C., 400 mL of water are added dropwise to the black viscous melt (caution: exothermic!) and the mixture is stirred further until the melt has fully homogenized, with precipitation of a brown solid. The suspension is transferred to a beaker containing 2 L of water and stirred for a further 1 h, and the solids are filtered off with suction and washed once with 300 mL of water. After sucking the solids dry, they are resuspended in 1 L of 15% by weight ammonia solution and the mixture is stirred for a further hour, and the solids are filtered off with suction again, washed to neutrality with water and then sucked dry. The solids are dissolved in 500 mL of dichloromethane, the solution is washed with saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate. After the desiccant has been removed, the solution is concentrated and the glassy residue is columned once on Alox, basic, activity level 1, and once on silica gel with dichloromethane. The viscous oil thus obtained is freed of low boilers and nonvolatile secondary components by fractional Kugelrohr distillation twice. Yield: 15.2 g (55 mmol), 55%; purity: about 99.5% by .sup.1H NMR.

Example H2

(9) ##STR00212##

(10) A mixture of 19.2 g (100 mmol) of 5-[1-hydroxymeth-[E]-ylidene-9-tricyclo[4.3.1.1*3,8*]undecan-4-one, S6, and 21.7 g (100 mmol) of 1-amino-pyrene, [1606-67-3], is heated gradually to 160 C. on a water separator, in the course of which the water formed in the reaction is distilled gradually out of the melt. After 10 h at 160 C., 100 mL of toluene are slowly added dropwise and the latter is distilled off by means of the water separator, in order to remove the rest of the water from the melt and the apparatus. To the deep brown melt thus obtained are added, in an argon countercurrent, about 300 g of polyphosphoric acid (Merck KGaA) and then the mixture is stirred at 160 C. for a further 16 h. After cooling to 120 C., 400 mL of water are added dropwise to the black viscous melt (caution: exothermic!) and the mixture is stirred further until the melt has fully homogenized, with precipitation of a brown solid. The suspension is transferred to a beaker containing 2 L of water and stirred for a further 1 h, and the solids are filtered off with suction and washed once with 300 mL of water. After sucking the solids dry, they are resuspended in 1 L of 15% by weight ammonia solution and the mixture is stirred for a further hour, and the solids are filtered off with suction again, washed to neutrality with water and then sucked dry. The solids are dissolved in 500 mL of dichloromethane, the solution is washed with saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate. After the desiccant has been removed, the solution is concentrated and the glassy residue is columned once on Alox, basic, activity level 1, and twice on silica gel with dichloromethane. The solids thus obtained are recrystallized three times from DMF/EtOH and then fractionally sublimed twice (p about 10.sup.5 mbar, T 290 C.). Yield: 13.5 g (36 mmol), 36%; purity: about 99.9% by .sup.1H NMR.

(11) In an analogous manner, it is possible to prepare the following compounds, where the ratio of amine to -hydroxymethylene ketone in the case of the di-, tri- and tetraamines is correspondingly adjusted stoichiometrically:

(12) TABLE-US-00003 -Hydroxymethylene Ex. ketone Product Yield Monoamine H3 S1 78832-53-8 46% H4 S1 4523-45-9 51% H5 S1 0 87833-80-5 53% H6 S1 216059-99-3 46% H7 S1 50358-40-2 42% H8 S1 64485-52-5 0 44% H9 S1 610-49-1 36% H10 S1 36946-70-0 32% H11 S2 20335-61-9 24% H12 0 S3 13456-80-9 38% H13 S4 4176-50-5 49% H14 S5 613-13-8 44% H15 S6 0 4176-50-5 50% H16 S6 50358-40-2 43% H17 S6 161431-57-8 28% H18 S6 175229-87-5 0 29% H19 S6 175229-87-5 44% H20 S6 139266-08-3 30% H21 S6 36946-70-0 26% H22 0 S6 1318253-36-9 27% H23 S6 2693-46-1 46% H24 S6 17169-81-2 42% H25 S5 0 1606-67-3 31% Diamine H26 S1 95-94-5 28% H27 S1 481-91-4 26% H28 S1 2243-62-1 0 30% H29 S1 79014-49-9 23% H30 S1 139312-39-3 28% H31 S5 2243-62-1 18% H32 00 S5 01 14923-84-3 02 34% H33 03 S6 04 30269-04-6 05 30% H34 06 S1 07 67665-45-6 08 29% H35 09 S6 0 117110-85-7 27% Triamines H36 S6 108-72-5 11% Tetraamines H37 S1 376356-61-5 17%

Example H38

6-Phenyl-1,1,3,3-tetramethyl-2,3-dihydro-1H-12-azaindeno[5,4-a]anthracene, H37

(13) ##STR00318##

a) 6-Bromo-1,1,3,3-tetramethyl-2,3-dihydro-1H-12-azaindeno[5,4-a]anthracene, H38a

(14) ##STR00319##

(15) A mixture of 3.3 g (10 mmol) of 1,1,3,3-tetramethyl-2,3-dihydro-1H-12-azaindeno[5,4-a]anthracene, H9, 2.0 g (11 mmol) of N-bromosuccinimide and 50 mL of DMF is stirred at 90 C. for 12 h. After cooling, the DMF is removed under reduced pressure, and the residue is subjected to hot extraction from 50 mL of ethanol and then recrystallized from dioxane/EtOH. Yield: 2.8 g (7 mmol) 70%. Purity: about 98% by .sup.1H NMR.

b) 6-Phenyl-1,1,3,3-tetramethyl-2,3-dihydro-1H-12-azaindeno[5,4-a]anthracene, H38

(16) A mixture of 2.8 g (7 mmol) of 6-bromo-1,1,3,3-tetramethyl-2,3-dihydro-1H-12-azaindeno[5,4-a]anthracene, H38a, 1.2 g (10 mmol) of phenylboronic acid [98-80-6], 5.8 g (30 mmol) of tripotassium phosphate, 123 mg (0.5 mmol) of palladium(II)acetate, 913 mg (3 mmol) of tri-o-tolylphosphine, 20 mL of toluene, 10 mL of dioxane and 30 mL of water is heated under reflux for 16 h. After cooling, the precipitated solids are filtered off with suction and dissolved in 200 mL of dichloromethane, the solution is filtered through a Celite bed, the filtrate is concentrated, and the solids thus obtained are crystallized three times from DMF/EtOH and fractionally sublimed (p about 10.sup.5 mbar, T 310 C.). Yield: 1.4 g (3.5 mmol), 50%; purity: about 99.9% by .sup.1H NMR.

Example H39

(17) ##STR00320##

(18) To a suspension of 264 mg (11 mmol) of sodium hydride in 50 mL of DMF are added 2.9 g (10 mmol) of H21 in portions, and the mixture is stirred at 50 C. for 30 min. Then 3.2 g (12 mmol) of 1-chloro-3,5-diphenyltriazine are added in portions and the mixture is stirred at 50 C. for a further 16 h. After adding 5 mL of methanol, the solvent is removed under reduced pressure, and the residue is taken up in 100 mL of dichloromethane, washed twice with 50 mL of water and dried over magnesium sulfate. After the solvent has been removed, the residue is recrystallized five times from DMF/EtOH and fractionally sublimed twice (p ca. 10.sup.5 mbar, T 320 C.). Yield: 3.4 g (6.6 mmol), 66%; purity: about 99.9% by .sup.1H NMR.

Example H40

(19) ##STR00321##

(20) A mixture of 21.6 g (100 mmol) of 3-hydroxy-3-phenylbicyclo[2.2.2]octan-2-one [95800-12-7], 5.1 mL (100 mmol) of hydrazine hydrate and 200 mL of o-dichlorobenzene is heated stepwise on a water separator until the separation of water has ended. Then 1.0 g (5 mmol) of p-toluenesulfonic acid monohydrate [6192-52-4] is added and the mixture is heated again on the water separator until the separation of water has ended. Subsequently, 21.7 g (250 mmol) of activated manganese dioxide are added and the mixture is heated again until the separation of water has ended. After cooling to 70 C., the manganese salts are filtered off using a Celite bed (3 cm) and washed with a little o-dichlorobenzene, and then the o-dichlorobenzene is removed under reduced pressure. The residue is chromatographed on silica gel with n-heptane/ethyl acetate/methanol (5:1:0.1). Yield: 5.5 g (26 mmol), 26%; purity: about 99.8% by .sup.1H NMR.

(21) It is possible to prepare the following analogously:

(22) ##STR00322##

(23) Production of the OLEDs

(24) 1) Vacuum-Processed Devices:

(25) 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 used).

(26) In the examples which follow, the results for various OLEDs are presented. Glass plaques with structured ITO (indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate/hole transport layer 1 (HTL1) consisting of HTM doped with 3% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 2 (HTL2)/optional hole transport layer 3 (HTL3)/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.

(27) First of all, vacuum-processed OLEDs are described. For this purpose, all the 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 M3:M2:Ir dopant (55%:35%:10%) mean here that the material M3 is present in the layer in a proportion by volume of 55%, M2 in a proportion of 35% and Ir dopant in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 1. The materials used for production of the OLEDs are shown in Table 4.

(28) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the power efficiency (measured in cd/A) and the voltage (measured at 1000 cd/m.sup.2 in V) are determined from current-voltage-brightness characteristics (IUL characteristics). For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminance has fallen from a particular starting luminance to a certain proportion. The figure LD50 means that the lifetime specified is the time at which the luminance has dropped to 50% of the starting luminance, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.2. According to the emission color, different starting brightnesses are selected. 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.

(29) Use of Compounds of the Invention as Emitter Materials in Phosphorescent OLEDs

(30) The uses of the compounds of the invention include uses as triplet matrix material (TMM), electron transport material (ETM), hole blocker material (HBM), blue singlet matrix material (SMB) and blue singlet emitter (SEB) in OLEDs.

(31) TABLE-US-00004 TABLE 1 Structure of the OLED HTL2 HBL thick- HTL-003 EML thick- ETL Ex. ness thickness thickness ness thickness Use as TMM green D1 HTM H6:M2:Ir-G M1 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D2 HTM H20:M2:Ir-G M1 ETM1:ETM2 220 nm (45%:50%:5%) 10 nm (50%:50%) 25 nm 20 nm D3 HTM H39:M2:Ir-G M1 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm red D4 HTM H12:M2:Ir-R M1 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 20 nm D5 HTM H19:M2:Ir-R M1 ETM1:ETM2 220 nm (70%:20%:10%) 10 nm (50%:50%) 30 nm 20 nm D6 HTM H22:M2:Ir-R M1 ETM1:ETM2 220 nm (60%:35%:5%) 10 nm (50%:50%) 30 nm 20 nm D7 HTM H23:M2:Ir-R M1 ETM1:ETM2 220 nm (60%:35%:5%) 10 nm (50%:50%) 30 nm 20 nm D8 HTM H27:M2:Ir-R M1 ETM1:ETM2 220 nm (50%:45%:5%) 10 nm (50%:50%) 30 nm 20 nm D9 HTM H28:M2:Ir-R M1 H32:ETM2 220 nm (50%:45%:5%) 10 nm (50%:50%) 30 nm 20 nm D10 HTM H37:M2:Ir-R M1 H37:ETM2 220 nm (45%:50%:5%) 10 nm (50%:50%) 30 nm 20 nm Use as ETM D11 HTM M1:M2:Ir-G M1 H32:ETM2 220 nm (65%:30%:5%) 10 nm (70%:30%) 25 nm 30 nm D12 HTM M1:M2:Ir-G M1 H34:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 30 nm Use as SEB/SMB D13 HTM H25:SEB ETM1:ETM2 190 nm (95%:5%) (50%:50%) 20 nm 30 nm D14 HTM H37:SEB ETM1:ETM2 190 nm (95%:5%) (50%:50%) 20 nm 30 nm

(32) TABLE-US-00005 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y LD50 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Use as TMM green D1 18.8 4.2 0.35/0.64 D2 17.5 4.0 0.35/0.64 D3 19.1 4.1 0.35/0.64 80000 red D4 8.9 3.7 0.67/0.33 75000 D5 15.0 3.6 0.67/0.33 D6 16.6 3.6 0.66/0.34 D7 10.0 3.8 0.66/0.34 D8 15.8 3.6 0.67/0.33 90000 D9 15.7 3.6 0.66/0.34 100000 D10 10.1 3.5 0.68/0.31 Use as ETM D11 17.6 3.8 0.35/0.64 80000 D12 18.4 4.0 0.34/0.63 Use as SEB/SMB D12 6.0 4.6 0.15/0.18 5000 D13 6.3 4.5 0.15/0.17

(33) 2) Solution-Processed Devices:

(34) A: From Soluble Functional Materials

(35) The compounds of the invention may also be processed from solution and lead therein to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887).

(36) The structure is composed of substrate/ITO/PEDOT (80 nm)/interlayer (80 nm)/emission layer (80 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with Dl water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in the cleanroom, as a buffer layer, an 80 nm layer of PEDOT (PEDOT is a polythiophene derivative (Baytron P VAI 4083sp.) from H. C. Starck, Goslar, which is supplied as an aqueous dispersion) is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry (typical value for 80 nm: 4500 rpm). In order to remove residual water from the layer, the substrates are baked on a hotplate at 180 C. for 10 minutes. The interlayer used serves for hole injection; in this case, HIL-012 from Merck is used. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfill the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the emitters of the invention are dissolved together with the matrix materials in toluene. The typical solids content of such solutions is between 16 and 25 g/l when, as here, the layer thickness of 80 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed devices contain an emission layer composed of (polystyrene):matrix1:matrix2:Ir-G-Sol (25%:25%:30%:20%). The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 130 C. for 30 min. Lastly, a cathode composed of barium (5 nm) and then aluminum (100 nm) (high-purity metals from Aldrich, particularly barium 99.99% (cat. no. 474711); vapor deposition systems from Lesker or the like, typical vapor deposition pressure 510.sup.6 mbar) is applied by vapor deposition. It is optionally possible first to apply a hole blocker layer and then an electron transport layer and only then the cathode (e.g. Al or LiF/Al) by vapor deposition under reduced pressure. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; Table 3 summarizes the data obtained.

(37) TABLE-US-00006 TABLE 3 Results with materials processed from solution Matrix1 EQE (%) Voltage (V) CIE x/y Ex. Matrix2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Green OLEDs D-Sol1 H27 16.0 5.6 0.35/0.62 M2 D-Sol1 H37 15.9 5.8 0.34/0.63 M3

(38) TABLE-US-00007 TABLE 4 Structural formulae of the materials used HTM EBM M1 = HBM M2 M3 M4 Ir-R 0 Ir-G Ir-G-Sol SEB ETM1 ETM2