MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to compounds suitable for use in electronic devices, and to electronic devices, especially organic electroluminescent devices, comprising these compounds.

Claims

1.-14. (canceled)

15. A compound of formula (1) ##STR01052## where the R radicals may also occur more than once and the symbols used are: Z is O or S; R* is a group of the formula (2) or (3), where the dotted bond represents the bond to the base skeleton in formula (1), ##STR01053## X is the same or different at each instance and is CR or N, where not more than two X groups are N, or two adjacent X groups are a group of the following formula (4) or (5): ##STR01054## where the dotted bonds indicate the linkage of this group in formula (2); Y is the same or different at each instance and is CR or N; W is the same or different at each instance and is NAr.sup.2, O, S or C(R).sub.2; L is a single bond or an aromatic or heteroaromatic ring system which has 5 to 24 aromatic ring atoms and may be substituted by one or more R radicals; Ar.sup.1, Ar.sup.2 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R radicals; R is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, OR.sup.1, SR.sup.1, COOR.sup.1, 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 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 group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and may be substituted in each case by one or more R.sup.1 radicals; at the same time, two R radicals together may also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, OR.sup.2, SR.sup.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 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 group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S or CONR.sup.2 and where one or more hydrogen atoms in the alkyl, alkenyl or alkynyl group may be replaced by D, F, Cl, Br, I or CN, 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; at the same time, two or more R.sup.1 radicals together may form an aliphatic ring system; R.sup.2 is the same or different at each instance and is H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

16. The compound according to claim 15, selected from the compounds of the formulae (6) and (7) ##STR01055## where the R radicals may also occur more than once, and the symbols have the definitions given in claim 15.

17. The compound according to claim 15, selected from the compounds of the formulae (6a), (6b), (7a) and (7b) ##STR01056## where the R radicals may also occur more than once, and the symbols have the definitions given in claim 15.

18. The compound according to claim 15, wherein the compound contains not more than two substituents R that are a group other than H or D.

19. The compound according to claim 15, selected from the compounds of the formulae (6a-1) to (7b-4) ##STR01057## ##STR01058## ##STR01059## ##STR01060## where the symbols have the definitions given in claim 15.

20. The compound according to claim 15, wherein L is selected from a single bond and an ortho-, meta- or para-bonded phenylene group.

21. The compound according to claim 15, wherein, in formula (2), all X are the same or different at each instance and are CR, or in that two adjacent X are a group of the formula (4), where the Y in formula (4) are the same or different at each instance and are CR, and the other two X are the same or different at each instance and are CR.

22. The compound according to claim 15, wherein the group of the formula (2) is selected from the formulae (2a) to (2g) ##STR01061## ##STR01062## where the symbols have the definitions given in claim 15.

23. A process for preparing the compound according to claim 15, comprising the following steps: (1) synthesizing the base skeleton of the compound of the formula (1) containing a reactive leaving group in place of the R* group; (2) introducing the R* group by a coupling reaction.

24. A formulation comprising at least one compound according to claim 15 and at least one solvent.

25. A method comprising providing the compound according to claim 15 and including the compound in an electronic device.

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

27. The electronic device according to claim 26 which is an organic electroluminescent device, wherein the compound is used in an emitting layer in combination with at least one phosphorescent emitter.

28. The electronic device according to claim 27, wherein the emitting layer contains at least one further material selected from the compounds of the formulae (7), (8), (9) and (10) ##STR01063## where R is the same or different at each instance and is H or an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and which may be substituted by one or more R.sup.1 radicals.

Description

EXAMPLES

[0119] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. For the compounds known from the literature, the corresponding CAS numbers are also reported in each case.

##STR00849##

[0120] A vessel is initially charged under an inert atmosphere with DMSO (50 ml), K.sub.3PO.sub.4 (53.08 g, 250 mmol), pyridine-2-carboxylic acid (1.53 g, 12.44 mmol) and Cul (1.19 g, 6.22 mmol). Subsequently, 3-chlorophenol (19.20 g, 150 mmol) [108-43-0] and 3-bromo-1-chlorobenzene (23.93 g, 125 mmol) [108-37-2] are gradually added successively, and the reaction mixture is stirred at 85° C. for 16 h. After cooling, the reaction mixture is worked up by extraction with aqueous ammonia solution and methyl tert-butyl ether. The organic phase is washed five times with water and twice with saturated NaCl solution, the combined phases are dried over Na.sub.2SO.sub.4, and the solvent is drawn off on a rotary evaporator. The crude product is purified further via fractional distillation. Yield: 26.88 g (106 mmol), 85%; purity; 96% by .sup.1H NMR

[0121] The following compounds can be prepared analogously. Purification can be effected not only by distillation but also using column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00005 Reactant 1 Reactant 2 Product Yield [00850] [00851] [00852] 80% [00853] [00854] [00855] 86%% [00856] [00857] [00858] 74% [00859] [00860] [00861] 75% [00862] [00863] [00864] 68%

##STR00865##

[0122] An initial charge of S1a (23.90 g, 100 mmol) in THE (150 ml) under an inert atmosphere is cooled down to −75° C. Subsequently, n-butyllithium (2.5 mol/I in hexane, 80 ml, 200 mmol) is gradually added dropwise in such a way that the internal temperature does not exceed −65° C. The mixture is left to stir at −75° C. for a further 4 h, and then bromine (5.6 ml, 109.3 mmol) is added dropwise in such a way that the internal temperature does not exceed −65° C. After the addition has ended, the mixture is stirred at −75° C. for 1 h, then allowed to warm up gradually to 10° C. within 1 h and stirred at 10° C. for 1 h. This is followed by cooling to 0° C. and cautious quenching of the mixture with saturated Na.sub.2SO.sub.3 solution (50 ml). The mixture is worked up by extraction with toluene and water, the combined organic phases are washed three times with water and once with saturated NaCl solution and dried over Na.sub.2SO.sub.4, and the solvent is removed on a rotary evaporator. The crude product is twice extracted by stirring with 2-propanol under reflux. Yield: 24.21 g (86 mmol, 86%), purity: 97% by .sup.1H NMR.

[0123] The following compounds can be prepared analogously. Purification can be effected not only by extractive stirring but also by distillation or column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00006 Reactant 1 Product Yield [00866] [00867] 70% [00868] [00869] 79% [00870] [00871] 79% [00872] [00873] 74% [00874] [00875] 53%

##STR00876##

[0124] An initial charge of S1b (39.19 g, 140.0 mmol), 4-methoxyphenylboronic acid (22.79 g, 150.0 mmol) [5720-07-0] and K.sub.2CO.sub.3 (38.70 g, 280.0 mmol) in THE (70 ml) and water (170 ml) is inertized for 30 min. Subsequently, tetrakis(triphenylphosphine)palladium [14221-01-3] (1.78 g, 1.54 mmol) is added and the reaction mixture is stirred under reflux for 20 h. The mixture is worked up by extraction with toluene and water, the combined organic phases are washed with water and saturated NaCl solution and dried over Na.sub.2SO.sub.4, and the solvent is drawn off on a rotary evaporator. The crude product is recrystallized from ethanol. Yield: 33.7 g (109 mmol, 78%), 96% by .sup.1H NMR.

[0125] The following compounds can be prepared analogously. Purification can be effected by column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield [00877] [00878] [00879] 64% S2b 98-80-6 S2c [00880] [00881] [00882] 69% S3b 98-80-6 S3c [00883] [00884] [00885] 62% S4b S4c [00886] [00887] [00888] 59% S5b 98-80-6 S5c [00889] [00890] [00891] 51% S6b 98-80-6 S6c [00892] [00893] [00894] 56% S1b 5720-06-9 S7c [00895] [00896] [00897] 36% S1b 144647-45-0 S8c [00898] [00899] [00900] 75% S1b 98-80-6 S9c [00901] [00902] [00903] 70% 450412-29-0 133730-34-4 S10c [00904] [00905] [00906] 64% S10c 3900-89-8 S11c

##STR00907##

[0126] To an initial charge of S1c (30.88 g, 100 mmol) and K.sub.2CO.sub.3 (41.46 g, 300 mmol) under an inert atmosphere is added DMAc (450 ml), and the mixture is inertized for 30 min. Subsequently, Pd(OAc).sub.2 (447 mg, 1.99 mmol) and 1,3-bis(2,6-diisopropylphenyl)-3H-imidazol-1-ium chloride (1.69 g, 3.98 mmol) are added, and the reaction mixture is stirred at 150° C. for 16 h. After cooling, the mixture is poured into ethanol/water (1:1, 600 ml) and stirred for a further 30 min. The precipitated solids are filtered off with suction and washed five times with water and 3 times with ethanol. The crude product is extracted by stirring under reflux with 2-propanol, and the solids are filtered off with suction after cooling. Yield: 22.9 g (84 mmol, 84%), 98% by .sup.1H NMR.

[0127] The following compounds can be prepared analogously. It is possible here to use not only 1,3-bis(2,6-diisopropylphenyl)-3H-imidazol-1-ium chloride but also tri-tert-butylphosphine or tricyclohexylphosphine, or as Pd source to use not only Pd(OAc).sub.2 but also Pd.sub.2(dba).sub.3. Purification can be effected by column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00008 Reactant 1 Product Yield [00908] [00909] 75% S2c S2d [00910] [00911] 73% S3c S3d [00912] [00913] 78% S4c 4d [00914] [00915] 80% S5c S5d [00916] [00917] 63% S6c S6d [00918] [00919] 46% S7c S7d [00920] [00921] 25% S8c S8d [00922] [00923] 81% S9c S9d [00924] [00925] 75% S11c S10d

##STR00926##

[0128] An initial charge of S1d (27.23 g, 100 mmol) in dichloromethane (620 ml) is cooled in an ice bath to 0° C. Subsequently, BBr.sub.3 (6.0 ml, 63.2 mmol) is cautiously added dropwise. After the addition has ended, the mixture is allowed to warm up to room temperature. On completion of conversion, the mixture is cooled again to 0° C. and quenched cautiously with MeOH (150 ml). The solvent is drawn off on a rotary evaporator. Subsequently, each of three additions of 300 ml of MeOH to the mixture is followed by removal thereof on a rotary evaporator. Another 200 ml of MeOH is added, and the solids are filtered off with suction. The crude product is dried and used in the next stage without further purification.

[0129] Yield: 17.05 g (66 mmol, 66%).

[0130] The following compounds can be prepared analogously. Purification can be effected by column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00009 Reactant 1 Product Yield [00927] [00928] 64% S2d S2e [00929] [00930] 71% S3d S3e [00931] [00932] 72% 4d 4e [00933] [00934] 63% S5d S5e [00935] [00936] 49% S6d S6e [00937] [00938] 57% S7d S7e [00939] [00940] 55% S8d S8e [00941] [00942] 61% S10d S9e

##STR00943##

[0131] An initial charge of S1e (12.91 g, 50.0 mmol) and triethylamine (20.8 ml, 150 mmol) in dichloromethane (700 ml) is cooled to 0° C. in an ice bath. Subsequently, trifluoromethanesulfonic anhydride (10.9 ml, 65.0 mmol) is slowly added dropwise. After the addition has ended, the mixture is allowed to warm up to room temperature. On completion of conversion, the mixture is subjected to extractive workup with dichloromethane and water, the combined organic phases are dried over Na.sub.2SO.sub.4, and the solvent is removed on a rotary evaporator. The residue is taken up in 300 ml of cyclohexane, and the mixture is stirred at room temperature for 30 min. The solids are filtered off with suction and dried in a vacuum drying cabinet. Yield 13.74 g (35.2 mmol, 70%).

[0132] The following compounds can be prepared analogously. Purification can be effected by column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00010 Reactant 1 Product Yield [00944] [00945] 76% S2e S2f [00946] [00947] 79% S3e S3f [00948] [00949] 67% 4e S4f [00950] [00951] 64% S5e S5f [00952] [00953] 50% S6e S6f [00954] [00955] 56% S7e S7f [00956] [00957] 47% S8e S8f

##STR00958##

[0133] An initial charge of S9c (24.23 g, 100 mmol) in 300 ml of THE is cooled to −75° C. Subsequently, hexyllithium (44.0 ml, c=2.5 mol/1, 110 mmol) is added dropwise in such a way that the temperature does not rise above −65° C. After the addition has ended, the mixture is stirred at −75° C. for 1 h. Subsequently, the reaction mixture is allowed to warm up gradually to room temperature and stirred at room temperature for 1 h. Subsequently, the reaction mixture is cooled back down to −75° C., and trimethyl borate (15.59 g, 150.0 mmol) is added dropwise in such a way that the temperature does not rise above −65° C. The mixture is allowed to come to room temperature overnight and quenched cautiously the next day with HCl (c=5 mol/1, 50 ml). The mixture is worked up by extraction with water, and the organic phase is washed three times with water. The THF is removed by rotary evaporation down to 50 ml, then 150 ml of n-heptane is added, and the precipitated solids are filtered off with suction and washed with n-heptane. Yield: 24.03 g (84.2 mmol, 84%), 96% by .sup.1H NMR.

##STR00959##

[0134] An initial charge of S1f (11.71 g, 30.0 mmol), bis(pinacolato)diboron (9.40 g, 36.3 mmol) and KOAc (8.90 g, 90.68 mmol) in 1,4-dioxane (200 ml) is inertized with argon for 30 min. Subsequently, Pd(dppf)Cl.sub.2 (740 mg, 0.91 mmol) is added, and the mixture is stirred under reflux for 20 h. After cooling, the solvent is removed on a rotary evaporator, and the residue is worked up by extraction with dichloromethane and water. The combined organic phases are dried over Na.sub.2SO.sub.4, ethanol (150 ml) is added, and the dichloromethane is drawn off on a rotary evaporator. The precipitated solids are filtered off with suction and dried in a vacuum drying cabinet. The crude product is used in the next stage without further purification. Yield: 9.06 g (24.6 mmol, 82%), purity 95% by .sup.1H NMR.

[0135] The following compounds can be prepared analogously. As an alternative, the catalyst system used may also be Pd(PCy.sub.3).sub.2Cl.sub.2 or Pd.sub.2(dba).sub.3 with S-Phos (1:3). Purification can be effected not only by column chromatography but also by hot extraction, or recrystallization or hot extraction can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization can be effected using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00011 Reactant 1 Product Yield [00960] [00961] 80% S2f S2h [00962] [00963] 85% S3f S3h [00964] [00965] 74% S4f S4h [00966] [00967] 70% S5f S5h [00968] [00969] 37% S6f S6h

##STR00970##

[0136] An initial charge of S9e (27.28 g, 100 mmol) and K.sub.3PO.sub.4 (42.7 g, 200 mmol) in DMAc (1000 ml) under inert atmosphere is stirred at 140° C. for 16 h. After cooling, the DMAc is largely drawn off on a rotary evaporator, and the residue is worked up by extraction with dichloromethane and water. The crude product is purified via column chromatography. Yield: 18.33 g (71.1 mmol; 71%).

[0137] Preparation of the Compounds of the Invention

##STR00971##

[0138] An initial charge of S1f (19.13 g, 49.0 mmol), 9-phenyl-9H,9′H-[3,3′]biscarbazole (22.04 g, 53.9 mmol) [1060735-14-9] and LiOtBu (8.76 g, 108.3 mmol) in o-xylene (1000 ml) is inertized with argon for 30 min. Subsequently, Pd(OAc).sub.2 (221 mg, 1.0 mmol) and S-Phos (815 mg, 2.0 mmol) are added successively, and the reaction mixture is heated to reflux for 18 h. The mixture is worked up by extraction with toluene/water. The combined organic phases are dried over Na.sub.2SO.sub.4, and the solvent is drawn off on a rotary evaporator. The crude product is subjected to basic hot extraction four times with toluene over aluminium oxide, then recrystallized twice from DMAc and finally sublimed under high vacuum.

[0139] Yield: 13.63 g (21.0 mmol; 43%).

[0140] The following compounds can be prepared analogously. The catalyst system used may not only be S-Phos with Pd(OAc).sub.2 or Pd.sub.2(dba).sub.3 but also X-Phos with Pd(OAc).sub.2 or Pd.sub.2(dba).sub.3 as palladium source. The solvent used may not only be o-xylene but also toluene inter alia. Purification can be effected using column chromatography, hot extraction or recrystallization. Recrystallization or hot extraction can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization can be effected using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00012 Reactant 1 Reactant 2 Product Yield [00972] [00973] [00974] 24% S7f CAS-1644054-07-8 P2a [00975] [00976] [00977] 28% S3f CAS-1615703-28-0 P3a [00978] [00979] [00980] 48% S1f CAS-2073065-40-2 P4a [00981] [00982] [00983] 52% S2f CAS-1826013-08-4 P5a [00984] [00985] [00986] 49% S8f CAS-1643526-99-1 P6a [00987] [00988] [00989] 33% S5f P7a 2 equiv. [00990] [00991] [00992] 40% S7f CAS-1456606-60-2 P8a [00993] [00994] [00995] 46% S3f CAS-1800580-10- P9a [00996] [00997] [00998] 39% S5f CAS-1345202-03-0 P10a [00999] [01000] [01001] 34% S1f P11a

##STR01002##

[0141] An initial charge of S3f (15.61 g, 40.0 mmol), (B-[3-(9′-phenyl[3,3′-bi-9H-carbazole]-9-yl)phenyl]boronic acid (22.72 g, 43.0 mmol) [CAS-1398394-64-3] and K.sub.3PO.sub.4 (15.54 g, 73.2 mmol) in THE (400 ml) and water (100 ml) is degassed with argon for 30 min. Subsequently, Pd(OAc).sub.2 (204 mg, 0.91 mmol) and X-Phos (905 mg, 1.82 mmol) are added successively, and the mixture is stirred under reflux for 30 h. The precipitated solids are filtered off with suction, washed twice with water and THF, and then washed with ethanol. The crude product is subjected to basic hot extraction five times with toluene over aluminium oxide, and finally sublimed under high vacuum. Yield: 15.95 g (22.0 mmol, 55%); purity: >99.9% by HPLC.

[0142] The following compounds can be prepared analogously. The catalyst system used may also be S-Phos or P(o-tol).sub.3 with Pd.sub.2(dba).sub.3 or Pd(OAc).sub.2. Purification can be effected using column chromatography, hot extraction or recrystallization. Recrystallization or hot extraction can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization can be effected using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00013 Reactant 1 Reactant 2 Product Yield [01003] [01004] [01005] 21% S7f CAS-2079874-18-1 P2b [01006] [01007] [01008] 51% S2f CAS-1438536-76-5 P3b

##STR01009##

[0143] An initial charge of S1g (28.61 g, 100 mmol), bis(biphenyl-4-yl)(4-bromophenyl)amine (47.64 g, 100 mmol) and K.sub.3PO.sub.4 (63.79 g, 300 mmol) in THE (1200 ml) and water (300 ml) is inertized with argon for 30 min. Subsequently, Pd(OAc).sub.2 (448 mg, 2.00 mmol) and X-Phos (1.99 g, 4.00 mmol) are added successively, and the mixture is stirred under reflux for 16 h. After cooling, the precipitated solids are filtered off with suction and washed with water and ethanol. The crude product is subjected to basic hot extraction four times with o-xylene over aluminium oxide, and finally sublimed under high vacuum.

[0144] Yield: 54.58 g (62.3 mmol, 62%), purity: >99.9% by HPLC.

[0145] The following compounds can be prepared analogously. The catalyst system used may not only be X-Phos but also S-Phos with not only Pd(OAc).sub.2 but also Pd.sub.2(dba).sub.3, or Pd(PPh.sub.3).sub.2Cl.sub.2 or Pd(PPh.sub.3).sub.4. The solvent used may not only be o-xylene but also toluene inter alia. Purification can be effected using column chromatography, hot extraction or recrystallization. Recrystallization or hot extraction can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization can be effected using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00014 Reactant 1 Reactant 2 Product Yield [01010] [01011] [01012] 34% CAS-1260032-02-7 S1h P2c [01013] [01014] [01015] 45% CAS-2134579-41-0 S2h P3c [01016] [01017] [01018] 50% CAS-1609381-11-4 S5h P4c [01019] [01020] [01021] 18% CAS-2226483-41-4 S6h P5c [01022] [01023] [01024] 37% CAS-2108078-04-0 S5h P6c [01025] [01026] [01027] 46% CAS-2108078-04-0 S4h P7c [01028] [01029] [01030] 58% CAS-854952-47-9 S3h P8c [01031] [01032] [01033] 44% CAS-1240963-69-2 S5h P9c [01034] [01035] [01036] 38% CAS-2413560-27-5 S1h P10c

[0146] Production of the OLEDs

[0147] The examples which follow (see tables 1 to 3) present the use of the compounds of the invention in OLEDs by comparison with materials from the prior art.

Pretreatment for Examples V1 to V8 and E1a to E8c

[0148] Glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating, first with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plates form the substrates to which the OLEDs are applied.

[0149] 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)/optional electron injection layer (EIL) 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, if they have not already been described before, are shown in table 3. The device data of the OLEDs are listed in table 2. Examples V1 to V8 are comparative examples. Examples E1a-f, E2a-e, E3a, E3b, E4a-c, E5a-e, E6a, E7a, E7b and E8a-c show data for OLEDs of the invention.

[0150] All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least two matrix materials and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation.

[0151] Details given in such a form as E1:P1a:TE2 (32%:60%:8%) mean here that the material E1 is present in the layer in a proportion by volume of 32%, P1a in a proportion by volume of 60% and TE2 in a proportion by volume of 8%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0152] 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 U10 in table 9 refers to the voltage which is required for a current density of 10 mA/cm.sup.2. EQE10 denotes the external quantum efficiency which is attained at 10 mA/cm.sup.2. The lifetime LT is defined as the time after which luminance, measured in cd/m.sup.2 in forward direction, drops from the starting luminance to a certain proportion L1 in the course of operation with constant current density j.sub.0. A figure of L1=80% in table 9 means that the lifetime reported in the LT column corresponds to the time after which luminance in cd/m.sup.2 falls to 80% of its starting value.

[0153] Use of Compounds of the Invention in OLEDs

[0154] The materials of the invention are used in examples E1a-f, E2a-d, E3a, E3b, E4a-c, E5a-e, E6a, E7a, E7b and E8a-c as matrix materials, electron blockers or hole transport materials in the emission, electron blocker or hole transport layer of green-phosphorescing OLEDs. As a comparison from the prior art, materials SdT1, SdT2, SdT3 and SdT4 are used in combination with the host materials E1, E2 and E3 in comparative examples V1 to V8. On comparison of the inventive examples with the corresponding comparative examples, it is clearly apparent that the inventive examples each show a distinct advantage in the lifetime of the OLEDs, with otherwise comparable performance data of the OLEDs.

TABLE-US-00015 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness V1 SpMA1:PD1 SpMA1 SpMA2 E1:SdT2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1a SpMA1:PD1 SpMA1 SpMA2 E1:P1a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1b SpMA1:PD1 SpMA1 SpMA2 E1:P4a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1c SpMA1:PD1 SpMA1 SpMA2 E1:P5a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1d SpMA1:PD1 SpMA1 SpMA2 E1:P10a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1e SpMA1:PD1 SpMA1 SpMA2 E1:P1b:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1f SpMA1:PD1 SpMA1 SpMA2 E3:P1a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V2 SpMA1:PD1 SpMA1 SpMA2 E2:SdT2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (22%:70%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2a SpMA1:PD1 SpMA1 SpMA2 E2:P1a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (22%:70%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2b SpMA1:PD1 SpMA1 SpMA2 E2:P4a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (22%:70%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2c SpMA1:PD1 SpMA1 SpMA2 E2:P9a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (22%:70%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2d SpMA1:PD1 SpMA1 SpMA2 E2:P2b:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (22%:70%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2e SpMA1:PD1 SpMA1 SpMA2 E2:P11a:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (22%:70%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V3 SpMA1:PD1 SpMA1 SpMA2 E2:SdT1:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (46%:46%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E3a SpMA1:PD1 SpMA1 SpMA2 E2:P2a:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (46%:46%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E3b SpMA1:PD1 SpMA1 SpMA2 E2:P7a:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (46%:46%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V4 SpMA1:PD1 SpMA1 SpMA2 E1:SdT2:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4a SpMA1:PD1 SpMA1 SpMA2 E1:P2a:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4b SpMA1:PD1 SpMA1 SpMA2 E1:P6a:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4c SpMA1:PD1 SpMA1 SpMA2 E1:P2c:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V5 SpMA1:PD1 SpMA1 SpMA2 E2:SdT2:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (28%:60%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E5a SpMA1:PD1 SpMA1 SpMA2 E2:P3a:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (28%:60%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E5b SpMA1:PD1 SpMA1 SpMA2 E2:P5c:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (28%:60%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E5c SpMA1:PD1 SpMA1 SpMA2 E2:P6c:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (28%:60%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E5d SpMA1:PD1 SpMA1 SpMA2 E2:P7c:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (28%:60%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E5e SpMA1:PD1 SpMA1 SpMA2 E2:P9c:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (28%:60%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V6 SpMA1:PD1 SpMA1 SpMA2 E2:SdT3:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (46%:46%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E6a SpMA1:PD1 SpMA1 SpMA2 E2:P8a:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (46%:46%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V7 SpMA1:PD1 SpMA1 SdT4 E1:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E7a SpMA1:PD1 SpMA1 P2a E1:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E7b SpMA1:PD1 SpMA1 P8a E1:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V8 SpMA1:PD1 SdT1 SpMA2 E1:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E8a SpMA1:PD1 P3b SpMA2 E1:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E8b SpMA1:PD1 P10c SpMA2 E1:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E8c SpMA1:PD1 P1c SpMA2 E1:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm

TABLE-US-00016 TABLE 2 Data of the OLEDs CIE x/y at U10 EQE10 1000 j.sub.0 L1 LT Ex. (V) (%) cd/m.sup.2 (mA/cm.sup.2) (%) (h) V1 4.4 19.6 0.34/0.63 40 80 330 E1a 4.2 22.8 0.34/0.63 40 80 1070 E1b 4.4 22.5 0.34/0.63 40 80 1240 E1c 4.3 22.9 0.34/0.63 40 80 790 E1d 4.3 23.0 0.35/0.63 40 80 755 E1e 4.1 22.2 0.34/0.63 40 80 945 E1f 4.2 23.0 0.33/0.63 40 80 1490 V2 4.3 20.0 0.34/0.62 40 80 275 E2a 4.0 23.3 0.34/0.63 40 80 820 E2b 4.3 23.0 0.34/0.63 40 80 990 E2c 4.1 23.5 0.33/0.63 40 80 835 E2d 4.2 23.2 0.33/0.63 40 80 625 E2e 4.1 23.2 0.33/0.63 40 80 560 V3 5.2 14.5 0.34/0.62 40 80 225 E3a 4.8 19.1 0.33/0.62 40 80 490 E3b 4.9 17.3 0.33/0.62 40 80 380 V4 5.0 15.1 0.34/0.62 40 80 540 E4a 5.2 16.8 0.33/0.63 40 80 670 E4b 5.3 16.0 0.33/0.63 40 80 705 E4c 5.2 17.0 0.34/0.62 40 80 880 V5 5.0 15.4 0.34/0.62 40 80 490 E5a 5.2 16.8 0.33/0.63 40 80 565 E5b 5.3 16.4 0.34/0.63 40 80 570 E5c 5.2 15.2 0.34/0.63 40 80 995 E5d 5.3 16.0 0.34/0.63 40 80 820 E5e 5.e 15.7 0.34/0.63 40 80 610 V6 5.2 17.8 0.34/0.62 40 80 190 E6a 5.4 18.2 0.33/0.62 40 80 275 V7 4.2 22.5 0.34/0.63 40 80 560 E7a 4.1 23.0 0.34/0.63 40 80 730 E7b 4.2 22.6 0.33/0.63 40 80 800 V8 4.8 22.4 0.34/0.63 40 80 285 E8a 4.5 22.4 0.34/0.63 40 80 550 E8b 4.6 22.0 0.34/0.63 40 80 430 E8c 4.6 22.8 0.34/0.63 40 80 675

TABLE-US-00017 TABLE 3 Structural formulae of the materials of the OLEDs used, if not already described before: [01037] [01038] PD1 (CAS Reg. No. 1224447-88-4) SpMA1 [01039] [01040] SpMA2 ST2 [01041] [01042] LiQ TE1 [01043] [01044] TE2 H2 [01045] [01046] SdT1 SdT2 [01047] [01048] SdT3 SdT4 [01049] [01050] E1 E2 [01051] E3