MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

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

Claims

1.-16. (canceled)

17. A compound of the formula (1) or formula (2), ##STR00269## where the following applies to the symbols and indices used: Y is on each occurrence, identically or differently, CR or N, with the proviso that at least one group Y stands for N; X is on each occurrence, identically or differently, CR or N, where a maximum of two groups X stand for N; or two adjacent X stand for a group of the following formula (3) or (4) and the other groups X stand, identically or differently, for CR or N, ##STR00270## where ̂ indicates the corresponding adjacent groups X in formula (1) or formula (2); V is on each occurrence, identically or differently, NR, C(R).sub.2, O, S, BR, Si(R).sub.2 or C═O; Z is on each occurrence, identically or differently, CR or N, where a maximum of two groups Z stand for N; Ar.sup.1 is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R; Ar.sup.2, Ar.sup.3, Ar.sup.4 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R; Ar.sup.2 and Ar.sup.3 and/or Ar.sup.3 and Ar.sup.4 here may also be connected to one another by a single bond or by a group selected from C(R.sup.1).sub.2, C(R.sup.1).sub.2—C(R.sup.1).sub.2, NR.sup.1, O or S; R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.5).sub.2, N(R.sup.1).sub.2, C(═O)Ar.sup.5, C(═O)R.sup.1, P(═O)(Ar.sup.5).sub.2, P(Ar.sup.5).sub.2, B(Ar.sup.5).sub.2, Si(Ar.sup.5).sub.3, Si(R.sup.1).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; two adjacent substituents R here may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.sup.1; Ar.sup.5 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R.sup.1; two radicals Ar.sup.5 here which are bonded to the same N, P, B or Si atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.1), C(R.sup.1).sub.2, C(R.sup.1).sub.2—C(R.sup.1).sub.2, O or S; R.sup.1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CN or an alkyl group having 1 to 10 C atoms, where two or more adjacent substituents R.sup.1 may form a mono- or polycyclic, aliphatic ring system with one another; m is 0 or 1; n is 0 or 1; p is on each occurrence, identically or differently, 0, 1, 2, 3 or 4; q is 0, 1 or 2; r is 0, 1, 2 or 3; the following compound is excluded from the invention: ##STR00271##

18. The compound according to claim 17, wherein X stands, identically or differently on each occurrence, for CR or N, where a maximum of one group X per ring stands for N; or two adjacent groups X stand for a group of the formula (3), where Z stands, identically or differently on each occurrence, for CR and V stands for NR, C(R).sub.2, O or S and the other X stand for CR.

19. The compound according to claim 17,wherein the compound is selected from the compounds of the formulae (5) to (10), ##STR00272## ##STR00273## where the symbols and indices used have the meanings given in claim 17.

20. The compound according to claim 17, wherein p is on each occurrence, identically or differently, 0, 1 or 2 and in that q is equal to 0 or 1 and in that r is equal to 0 or 1.

21. The compound according to claim 17, wherein the compound is selected from the compounds of the formulae (5a) to (10a), ##STR00274## ##STR00275## where symbols and indices used have the meanings given in claim 17.

22. The compound according to claim 17, wherein the compounds is selected from the compounds of the formulae (5b) to (10b), ##STR00276## ##STR00277## where the symbols and indices used have the meanings given in claim 17.

23. The compound according to claim 17, wherein R is selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, N(Ar.sup.5).sub.2, C(═O)Ar.sup.3, P(═O)(Ar.sup.5).sub.2, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by 0 and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1.

24. The compound according to claim 17, wherein the group ##STR00278## in formula (1) or formula (2) is selected from the groups of the formulae (Het-Ar-1) to (Het-Ar-10), ##STR00279## where the dashed bond represents the bond to Ar.sup.1 or, for m=0, the bond to the nitrogen and R stands, identically or differently on each occurrence, for H, D or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1.

25. The compound according to claim 17, wherein n=1 and Ar.sup.2 and Ar.sup.3 are connected to one another by a single bond or in that n=0 or 1 and Ar.sup.3 and Ar.sup.4 are connected to one another by a single bond or in that n=0 or 1 and none of the groups Ar.sup.2, Ar.sup.3 and Ar.sup.4 are connected to one another.

26. The compound according to claim 17, wherein Ar.sup.2 is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R, preferably selected from the group consisting of phenylene or biphenyl, each of which may be substituted by one or more radicals R, and in that Ar.sup.3 and Ar.sup.4 represent, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R, preferably selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, naphthyl, indolyl, benzofuranyl, benzothiophenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, indenocarbazolyl, indolocarbazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, phenanthrenyl, triphenylenyl or combinations of two, three or four of these groups, each of which may be substituted by one or more radicals R.

27. The compound according to claim 17, wherein the group —[Ar.sup.2].sub.17—N(Ar.sup.3)(Ar.sup.4) in formula (1) or formula (2) is selected from the groups of the formulae (CARB-1) to (CARB-5), ##STR00280## where Ar.sup.4 has the meanings given in claim 17 and the groups may be substituted by one or more radicals R.

28. A formulation comprising at least one compound according to claim 17 and at least one further compound, in particular at least one solvent.

29. An electronic device comprising the formulation according to claim 28.

30. An electronic device comprising at least one compound according to claim 17.

31. An organic electroluminescent device which comprises the compound according to claim 17 is employed as matrix material for phosphorescent emitters in an emitting layer.

32. An organic electroluminescent device which compound according to claim 17 is employed as matrix material for a phosphorescent emitter in combination with a further matrix material.

33. An organic electroluminescent device which compound according to claim 17 is employed as matrix material for a phosphorescent emitter in combination with a further matrix material, where the further matrix material comprises pure hydrocarbon.

Description

EXAMPLES

Synthesis Examples

[0101] The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR. The numbers indicated in the case of the starting materials which are not commercially available are the corresponding CAS numbers.

Example 1a

Synthesis of N-(9,9-dimethylfluoren-2-yl)-4-amino-biphenyl

[0102] ##STR00041##

[0103] 24.0 g (142 mmol) of 4-aminobiphenyl [92-67-1] and 32.0 g (117 mmol) of 2-bromo-9,9′-dimethylfluorene [28320-31-2] are initially introduced in 950 ml of toluene. The mixture is flushed with argon for 30 minutes with vigorous stirring. 1.0 g (1.8 mmol) of 1,1′-bis(diphenylphosphino)ferrocene [12150-46-8], 355 mg (1.6 mmol) of palladium(II) acetate and 28.8 g (300 mmol) of sodium tert-butoxide are added, and the reaction mixture is heated under reflux for 15 h. After cooling to room temperature, the reaction mixture is extended with 300 ml of toluene and 1200 ml of water. The organic phase is separated off, washed three times with 250 ml of water each time and dried over sodium sulfate. The solvent is removed in a rotary evaporator. 50 ml of ethyl acetate are added to the oil which remains, and the mixture is stirred slowly into 800 ml of a heptane/ethyl acetate mixture (20:1). The solid formed is filtered off with suction, washed twice with about 50 ml of heptane and dried in vacuo, leaving 29.2 g (80 mmol, 69% of theory) of the product having a purity of 99% according to HPLC.

[0104] The following compound can be prepared analogously:

TABLE-US-00002 Ex. Starting material Product Yield 1b [00042] [00043] 74%

Example 2a

Synthesis of N-(biphenyl-2-yl)-N-(biphenyl-4-yl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylamine

[0105] ##STR00044##

[0106] 33.8 g (71 mmol) of N-(biphenyl-2-yl)-N-(biphenyl-4-yl)-N-(4-bromophenyl)-amine [1371651-92-1], 21.9 g (86 mmol) of bis(pinacolato)diborane [73183-34-3], 21.7 g (221 mmol) of potassium acetate and 1.7 g (2.1 mmol) of 1,1′-bis(diphenylphosphino)ferrocenepalladium(II) dichloride/dichloromethane adduct [95464-26-4] are heated under reflux in 1000 ml of anhydrous dioxane for 16 h. After cooling to room temperature, the organic phase is extended with 750 ml of ethyl acetate, washed three times with 300 ml of water each time and dried over sodium sulfate. The solvent is removed in a rotary evaporator, and the residue is recrystallised twice from heptane, leaving 22.6 g (43 mmol, 61% of theory) of the product as a pale-yellow solid having a purity of about 99% according to .sup.1H-NMR.

Example 3a

Synthesis of 2-(biphenyl-3-yl)-4-chloro-6-phenyl-1,3,5-triazine

[0107] ##STR00045##

[0108] 11.6 g (477 mmol) of magnesium are activated using a grain of iodine. 30 ml of a solution of 100 g (429 mmol) of 3-bromobiphenyl [2113-57-7] in 800 ml of THF are added; the reaction is initiated using a hair dryer. After commencement of the reaction, the remaining solution is added dropwise at such a rate that the reflux is maintained by the heat of reaction. When the addition is complete, the reaction mixture is heated under reflux for a further 2 h.

[0109] 79.1 g (429 mmol) of 2,4,6-trichloro-1,3,5-triazine are initially introduced in 500 ml of THF and cooled to −5° C. The above Grignard solution is added dropwise at such a rate that the internal temperature does not exceed 0° C. The cooling is removed, and the mixture is stirred for 16 h and subsequently re-cooled to −5° C., and 219 ml (438 mmol) of phenylmagnesium chloride solution (2M in THF) are added dropwise at such a rate that the internal temperature does not exceed 0° C. The cooling is removed, and the mixture is stirred for 18 h. 450 ml of 1M hydrochloric acid are slowly stirred in. After 1 h, the solid formed is filtered off with suction and dried in vacuo. Recrystallisation twice from toluene leaves 52.9 g (154 mmol, 36% of theory) of the product as a pale-brown solid having a purity of about 98% according to .sup.1H-NMR.

[0110] The following compounds can be prepared analogously:

TABLE-US-00003 Starting material Ex. Step 1 Product Yield 3b [00046] [00047] 31% 3c [00048] [00049] 37%

Example 4a

Synthesis of 10-(3-bromophenyl)-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

[0111] ##STR00050##

[0112] 150.0 g (526 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]-fluorene [1257220-47-5], 184.0 g (1.05 mol) of 1-bromo-3-fluorobenzene [1073-06-9] and 334.7 g (1.58 mol) of potassium phosphate are initially introduced in 2 l of dimethylacetamide and heated under reflux for 14 h. After cooling to room temperature, the solvent is removed as far as possible in a rotary evaporator, leaving a dark-brown oil. After vigorous rubbing of the flask wall with a glass rod, the product can be precipitated by slowly stirring in 750 ml of ethanol. The solid formed is filtered off with suction, washed four times with 250 ml of ethanol each time, dried in vacuo and finally sublimed at a pressure of about 10.sup.−5 mbar and 220° C., leaving 152.2 g (347 mmol, 66% of theory) of the product as yellow glass-like solid having a purity of about 99% according to .sup.1H-NMR.

Example 5a

Synthesis of (2-chlorophenyl)-(spiro-9,9′-bifluoren-4-yl)-amine

[0113] ##STR00051##

[0114] 54.1 g (137 mmol) of 4-bromospiro-9,9′-bifluorene [1161009-88-6], 17.9 g (140 mmol) of 2-chloroaniline [95-51-2], 68.2 g (710 mmol) of sodium tortbutoxide, 613 mg (2.7 mmol) of palladium(II) acetate and 3.03 g (5.5 mmol) of 1,1′-bis(diphenylphosphino)ferrocene are initially introduced in 1300 ml of toluene and heated under reflux for 5 h. After cooling to room temperature, the reaction mixture is extended with 700 ml of toluene and filtered through Celite. The solvent is removed in a rotary evaporator, and the residue is recrystallised from a toluene/heptane mixture (1:2). Drying in vacuo leaves 52.2 g (118 mmol, 86% of theory) of the product as pale-yellow solid.

[0115] The following compound can be prepared analogously:

TABLE-US-00004 Ex. Starting material Product Yield 5b [00052] [00053] 72%

Example 6a

1-(2-Chlorophenylamine)fluoren-9-one

[0116] ##STR00054##

[0117] 52 g (166 mmol) of 1-iodofluoren-9-one [52086-21-2], 19.0 ml (171 mmol) of 2-chloroaniline [95-51-2], 59.8 g (432 mmol) of potassium carbonate, 3.85 g (6.6 mmol) of 1,1′-(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenyl)phosphine [161265-03-8] and 746 mg (3.3 mmol) of palladium(II) acetate are initially introduced in 400 ml of toluene and heated under reflux for 15 h. After cooling to room temperature, the mixture is extended with 200 ml of toluene and 500 ml of water, and the organic phase is separated off, washed twice with 200 ml of 3M hydrochloric acid each time and twice with 200 ml of water each time and filtered through a thin layer of aluminium oxide (basic, activity grade 1). The solvent is removed in a rotary evaporator. Drying in vacuo leaves 48.0 g (157 mmol, 95% of theory) of the product as orange solid having a purity of about 97% according to .sup.1H-NMR.

Example 7a

Synthesis of spiro[9H-fluorene-9,7′(1′H)-indeno[1,2-a]-carbazole]

[0118] ##STR00055##

[0119] 45.0 g (102 mmol) of (2-chlorophenyl)-(spiro-9,9′-bifluoren-4-yl)amine (from Ex. 5a), 56.0 g (405 mmol) of potassium carbonate, 4.5 g (12 mmol) of tricyclohexylphosphonium tetrafluoroborate and 1.38 g (6 mmol) of palladium(II) acetate are suspended in 500 ml of dimethylacetamide and heated under reflux for 6 h. After cooling to room temperature, the reaction mixture is extended with 600 ml of dichloromethane and 300 ml of water and stirred for 30 minutes. The organic phase is separated off and freed from solvent in a rotary evaporator. The residue is extracted with 250 ml of hot toluene via a bed of aluminium oxide (basic, activity grade 1) and finally recrystallised once from toluene, leaving 32.5 g (80 mmol, 78% of theory) of the product as beige solid having a purity of about 98% according to .sup.1H-NMR.

[0120] The following compounds can be prepared analogously:

TABLE-US-00005 Ex. Starting material Product Yield 7b [00056] [00057] 68% 7c [00058] [00059] 87%

Example 8a

Synthesis of N-phenylspiro[9H-fluorene-9,7′(1′H)-indeno[1,2-a]carbazole]

[0121] ##STR00060##

[0122] 43.0 g (106 mmol) of spiro[9H-fluorene-9,7′(1′H)-indeno[1,2-a]carbazole] (from Ex. 7a), 17.9 g (114 mmol) of bromobenzene, 30.5 g (317 mmol) of sodium tert-butoxide, 0.5 g (2.2 mmol) of palladium(II) acetate and 4.2 ml of tri-tert-butylphosphine solution (1M in toluene) are initially introduced in 1500 ml of p-xylene and heated under reflux for 16 h. After cooling to room temperature, the organic phase is separated off from solid constituents, washed three times with 200 ml of water each time and subsequently freed from solvent in a rotary evaporator. The residue is extracted with about 300 ml of hot toluene via aluminium oxide (basic, activity grade 1) and finally recrystallised twice from toluene, leaving 37.6 g (78 mmol, 74% of theory) of the product as pale-yellow solid having a purity of about 99% according to .sup.1H-NMR.

[0123] The following compounds can be prepared analogously:

TABLE-US-00006 Starting material Starting material Ex. 1 2 8b [00061] [00062] 8c [00063] [00064] 8d [00065] [00066] 8e [00067] [00068] 8f [00069] [00070] 8g [00071] [00072] 8h [00073] [00074] 8i [00075] [00076] 8j [00077] [00078] 8k [00079] [00080] Ex. Product Yield 8b [00081] 83% 8c [00082] 77% 8d [00083] 51% 8e [00084] 54% 8f [00085] 53% 8g [00086] 61% 8h [00087] 82% 8i [00088] 58% 8j [00089] 77% 8k [00090] 67%

Example 9a

Synthesis of N-(4′-bromospiro-9,9′-bifluoren-4-yl)-N-(9,9′-dimethylfluoren-2-yl)-4-aminobiphenyl

[0124] ##STR00091##

[0125] 24.6 g (79 mmol) of 2,2′-dibromobiphenyl [13029-09-9] in 200 ml of THF are cooled to −78° C. 32 ml of n-butyllithium (2.5M in hexane) are added dropwise at such a rate that the internal temperature does not exceed −70° C. The reaction mixture is stirred for 2 h. A suspension of 26.9 g (50 mmol) of N-(9,9-dimethylfluoren-2-yl)-N-(fluorenon-4-yl)-4-aminobiphenyl (from Ex. 8j) is then added at such a rate that the internal temperature does not exceed −70° C. The cooling is removed, and the mixture is stirred for a further 14 h. After addition of 100 ml of water, the mixture is stirred for 15 minutes, and the organic phase is separated off and freed from solvent in a rotary evaporator. The residue is suspended in 500 ml of glacial acetic acid, 0.5 ml of concentrated sulfuric acid is added, and the mixture is stirred at 100° C. for 2 h. After cooling to room temperature, the solid formed is filtered off with suction, washed with 100 ml of glacial acetic acid and washed three times with 100 ml of ethanol each time and finally recrystallised from dioxane. Drying in vacuo leaves 25.5 g (34 mmol, 68% of theory) of the product as pale-red solid having a purity of about 98% according to .sup.1H-NMR.

[0126] The following compounds can be prepared analogously:

TABLE-US-00007 Ex. Starting material Product Yield 9b [00092] [00093] 69% 9c [00094] [00095] 83%

[0127] The following compounds can be prepared analogously by lithiation of 2-bromobiphenyl [2052-07-5] in the first step:

TABLE-US-00008 Ex. Starting material Product Yield 9d [00096] [00097] 74% 9e [00098] [00099] 70%

Example 10a

Synthesis of N-phenylspiro[9H-fluorene-6′-bromo-9,7′(1′H)-indeno[1,2-a]carbazole]

[0128] ##STR00100##

[0129] 85.2 g (177 mmol) of N-phenylspiro[9H-fluorene-9,7′(1′H)-indeno[1,2-a]-carbazole] (from Ex. 8a) are initially introduced in 1500 ml of THF. The reaction mixture is cooled to 0° C., and 31.5 g (177 mmol) of N-bromo-succinimide are added in portions over the course of 30 minutes. The cooling is removed, and the mixture is stirred for 14 h and subsequently concentrated to about 250 ml. 1000 ml of water are added with vigorous stirring, and the solid formed is filtered off with suction and washed by boiling twice with 800 ml of ethanol each time. Drying in vacuo leaves 87.1 g (155 mmol, 88% of theory) of the product as colourless solid having a purity of about 98% according to .sup.1H-NMR.

[0130] The following compounds can be prepared analogously:

TABLE-US-00009 Ex. Starting material Product Yield 10b [00101] [00102] 60% 10c [00103] [00104] 65% 10d [00105] [00106] 81% 10e [00107] [00108] 81% 10f [00109] [00110] 49% 10g [00111] [00112] 52% 10h [00113] [00114] 61% 10i [00115] [00116] 12% after column chroma- tography 10j [00117] [00118] 68% 10k [00119] [00120] 90% 10l [00121] [00122] 51%

Example 11a

Synthesis of N-phenylspiro[9H-fluorene-6′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,7′(1′H)-indeno[1,2-a]carbazole]

[0131] ##STR00123##

[0132] 46.0 g (82 mmol) of N-phenylspiro[9H-fluorene-6′-bromo-9,7′(1′H)-indeno-[1,2-a]carbazole] (Ex. 10a), 21.9 g (86 mmol) of bis(pinacolato)diborane, 64.4 g (656 mmol) of potassium acetate and 2.0 g (2.4 mmol) of 1,1′-bis-(diphenylphosphino)ferrocenepalladium(II) dichloride/dichloromethane adduct [95464-26-4] in 1000 ml of dioxane are heated at an internal temperature of 80° C. for 22 h. After cooling to room temperature, the solvent is removed in a rotary evaporator, 700 ml of dichloromethane and 1000 ml of water are added to the residue, and the mixture is stirred for 30 minutes. The organic phase is separated off, washed twice with 250 ml of water each time, dried over sodium sulfate and concentrated to about 100 ml. 1000 ml of heptane are stirred in, and the solid formed is filtered off with suction. Drying in vacuo leaves 43.7 g (72 mmol, 88% of theory) of the product as pale-brown solid having a purity of about 96% according to .sup.1H-NMR.

[0133] The following compounds can be prepared analogously:

TABLE-US-00010 Ex. Starting material Product Yield 11b [00124] [00125] 81% 11c [00126] [00127] 89% 11d [00128] [00129] 82% 11e [00130] [00131] 78% 11f [00132] [00133] 63% 11g [00134] [00135] 61%

Example 12a

Synthesis of spiro[9H-fluorene-6′-(N-phenylcarbazol-3-yl)-9,7′(1′H)-indeno[1,2-a]carbazole]

[0134] ##STR00136##

[0135] 31.0 g (64 mmol) of spiro[9H-fluorene-6′-bromo-9,7′(1′H)-indeno[1,2-a]carbazole] (from Ex. 10b) and 28.4 g (76 mmol) of N-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole [1126522-69-7] are initially introduced in a mixture of 250 ml of toluene, 125 ml of dioxane and 60 ml of water and flushed with argon for 30 minutes. After addition of 32.4 g (141 mmol) of tripotassium phosphate monohydrate [27176-10-9], 359 mg (1.6 mmol) of palladium(II) acetate and 974 mg (3.2 mmol) of trio-tolyl-phosphine, the reaction mixture is heated under reflux for 18 h. After cooling to room temperature, the mixture is extended with 500 ml of water. The organic phase is separated off, washed twice with 250 ml of water each time and freed from solvent in a rotary evaporator. The residue is slurried with 150 ml of heptane, and the solid formed is filtered off with suction. The latter is extracted with about 250 ml of hot cyclohexane via aluminium oxide (basic, activity grade 1); if necessary, the extraction solution is reduced by about one third. The solid formed is filtered off with suction and dried in vacuo, leaving 21.7 g (34 mmol, 53% of theory) of the product as beige solid having a purity of about 99% according to .sup.1H-NMR.

[0136] The following compounds can be prepared analogously:

TABLE-US-00011 Ex. Starting material Product Yield 12b [00137] [00138] 56% 12c [00139] [00140] 55% 12d [00141] [00142] 32% 12e [00143] [00144] 47% 12f [00145] [00146] 36% 12g [00147] [00148] 75%

[0137] The following compounds can be prepared analogously by reaction of corresponding bromides with 12,12-dimethyl-10-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10,12-dihydro-10-azaindeno[2,1-b]fluorene (Ex. 11c):

TABLE-US-00012 Ex. Starting material Product Yield 12h [00149] [00150] 50% 12i [00151] [00152] 52% 12j [00153] [00154] 28%

[0138] The following compounds can be prepared analogously by reaction of corresponding bromides with N-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole [1126522-69-7]:

TABLE-US-00013 Ex. Starting material Product Yield 12k [00155] [00156] 69% 12l [00157] [00158] 55%

[0139] The following compounds can be prepared analogously:

TABLE-US-00014 Starting Starting Ex. material 1 material 2 Product Yield 12m [00159] [00160] [00161] 36% 12n [00162] [00163] [00164] 41% 12o [00165] [00166] [00167] 44% 12p [00168] [00169] [00170] 15% after column chroma- tography

Example 13a

Synthesis of 12′-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)-phenyl]-3′-(9-phenylcarbazol-3-yl)spiro[fluorene-9,7′-indeno[1,2-a]-carbazole]

[0140] ##STR00171##

[0141] 21.7 g (34 mmol) of 3-(9-phenylcarbazol-3-yl)spiro[12H-indeno[1,2-a]-carbazole-7,9′-fluorene] (from Ex. 12a) and 13.2 g (34 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine [1233200-57-1] are initially introduced in 280 ml of toluene and flushed with argon for 30 minutes. After addition of 175 mg (0.3 mmol) of bis(dibenzylideneacetone)palladium(0), 250 mg (0.6 mmol) of dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine and 4.4 g (46 mmol) of sodium tert-butoxide, the reaction mixture is heated under reflux for 45 h. After cooling to room temperature, 350 ml of water are stirred in, and the organic phase is separated off and freed from solvent. The residue is taken up in toluene, three times the volume of heptane are then stirred in, and the solid formed is filtered off with suction and recrystallised once from toluene. The product is finally purified by column chromatography through silica gel with a toluene/heptane eluent mixture (2:1). Drying in vacuo leaves 10.8 g (12 mmol, 36% of theory) of the product as pale-yellow solid having a purity of 99.8% according to HPLC.

[0142] The following compound can also be prepared analogously:

TABLE-US-00015 Ex. Starting material Product Yield 13b [00172] [00173] 39%

Example 14a

Synthesis of 12′-(4,6-diphenyl-1,3,5-triazin-2-yl)-3′-(9-phenylcarbazol-3-yl)spiro[fluorene-9,7′-indeno[1,2-a]carbazole]

[0143] ##STR00174##

[0144] A solution of 67.9 g (105 mmol) of 3-(9-phenylcarbazol-3-yl)spiro[12H-indeno[1,2-a]carbazole-7,9′-fluorene] (Ex. 12a) in 300 ml of dimetylformamide is added dropwise with vigorous stirring to a solution of 4.2 g of sodium hydride (60% in mineral oil, 105 mmol) in 300 ml of dimethylformamide, and the mixture is stirred for 2 h. A solution of 30.0 g (112 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine [3842-55-5] in 200 ml of THF is then slowly added dropwise, and the mixture is stirred for 18 h and subsequently poured onto about 150 g of ice. The organic phase is extended with 250 ml of toluene, separated off, washed twice with 100 ml of water and freed from solvent in a rotary evaporator. The residue which remains is extracted with hot toluene via aluminium oxide (basic, activity grade 1), the suspension formed is freed from solvent in a rotary evaporator, and the residue which remains is purified by column chromatography through silica gel with a heptane/THF eluent mixture (4:1). Removal of the solvents in a rotary evaporator and heating of the residue at 180° C. and a pressure of about 10.sup.−5 mbar for 5 h leaves 31.5 g (33 mmol, 31% of theory) of the product as colourless solid having a purity of 99.9% according to HPLC.

[0145] The following compounds can be prepared analogously:

TABLE-US-00016 Starting Starting Ex. material 1 material 2 Product Yield 14b [00175] [00176] [00177] 28% 14c [00178] [00179] [00180] 37% 14d [00181] [00182] [00183] 36% 14e [00184] [00185] [00186] 40% 14f [00187] [00188] [00189] 31% 14g [00190] [00191] [00192] 35% 14h [00193] [00194] [00195] 26% 14i [00196] [00197] [00198] 30% 14j [00199] [00200] [00201] 27% 14k [00202] [00203] [00204] 41% 14l [00205] [00206] [00207] 33% 14m [00208] [00209] [00210] 36% 14n [00211] [00212] [00213] 43% 14o [00214] [00215] [00216] 45% 14p [00217] [00218] [00219] 38% 14q [00220] [00221] [00222] 39% 14r [00223] [00224] [00225] 28% 14s [00226] [00227] [00228] 17%

Examples AV2 and AV4

[0146] Comparative Examples AV2 and AV4 can be prepared by the processes described in DE 102008017591.

Example AV6

[0147] Comparative Example AV6 can be prepared by the processes described in WO 2011/132683.

DEVICE EXAMPLES

Device Example 1

Production of solution-processed OLEDs

[0148] The materials according to the invention can be processed from solution and lead, compared with vacuum-processed OLEDs, to OLEDs which can be produced significantly more simply, but nevertheless have good properties. For example, comparative materials 12m and 14o (Table 2) cannot be dissolved in toluene in a concentration of 15 mg/ml, whereas this is readily possible with materials 14a, 14g, 13b and 14e according to the invention (Table 1).

[0149] In order to check whether a solubility of 15 mg/ml or more in toluene arises for a material, the following process is followed: 30 mg of the material are initially introduced as a solid in a sample vial. 2 ml of toluene are added at room temperature. The vial is sealed, and the contents are stirred at 60° C. on a heatable magnetic stirrer for 1 h. Good thermal contact is ensured by means of an aluminium block with holes into which the vials fit accurately.

[0150] After 1 h, the vial is removed and allowed to cool to room temperature. A clear solution without relatively large particles is then present in the vial, so at least 15 mg/ml of the material are soluble in toluene.

[0151] Furthermore, the higher glass transition temperature of the matrix materials according to the invention allows drying by heating at elevated temperatures and thus offers a larger processing window than comparative materials 12m and 14o.

TABLE-US-00017 TABLE 1 Properties of selected matrix materials which are relevant for the processability from solution Solubility in toluene Compound from Ex. >15 mg/ml Tg >175° C. 12m no no 14o no no 14a yes yes 14g yes yes 13b yes yes 14e yes yes

[0152] The production of fully solution-based OLEDs has already been described many times in the literature, for example in WO 2004/037887. The production of vacuum-based OLEDs has likewise already been described many times, inter alia in WO 2004/058911. In the examples discussed below, layers applied on a solution basis and on a vacuum basis are combined within an OLED, so that the processing up to and including the emission layer was carried out from solution and the processing in the subsequent layers (hole-blocking layer and electron-transport layer) was carried out from vacuum. The general processes described above are for this purpose adapted to the circumstances described here (layer-thickness variation, materials) and combined as follows:

[0153] The structure is as follows: [0154] substrate, [0155] ITO (50 nm) [0156] PEDOT:PSS (20 or 60 nm for green or red components respectively) [0157] hole-transport layer (HTL) (20 nm) [0158] emission layer (EML) (60 nm) [0159] hole-blocking layer (HBL) (10 nm) [0160] electron-transport layer (ETL) (40 nm) [0161] cathode.

[0162] The substrate used is a glass plate coated with structured ITO (indium tin oxide) in a thickness of 50 nm. For better processing, these are coated with PEDOT:PSS (poly(3,4-ethylenedioxy-2,5-thiophene): polystyrene sulfonate, purchased from Heraeus Precious Metals GmbH & Co. KG, Germany). PEDOT:PSS is applied by spin coating from water in air and is subsequently dried by heating at 180° C. in air for 10 minutes in order to remove residual water. The interlayer and the emission layer are applied to these coated glass plates. The hole-transport layer used is crosslinkable. A polymer of the structure shown below, which can be synthesised in accordance with WO2010/097155, is used.

##STR00229##

[0163] The hole-transport polymer is dissolved in toluene. The typical solids content of such solutions is about 5 g/l if, as here, the typical layer thickness of 20 nm for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 180° C. for 60 minutes.

[0164] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). Furthermore, mixtures of a plurality of matrix materials and co-dopants may occur. An expression such as TMM-A (92%): dopant (8%) here means that material TMM-A is present in the emission layer in a proportion by weight of 92% and the dopant is present in the emission layer in a proportion by weight of 8%. The mixture for the emission layer is dissolved in toluene or optionally chlorobenzene. The typical solids content of such solutions is about 18 g/l if, as here, the typical layer thickness of 60 nm for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 160° C. for 10 minutes. Matrix materials used are shown in Table 2—these are both compounds according to the invention and also comparative examples.

TABLE-US-00018 TABLE 2 Structures of matrix materials according to the invention and comparative matrices [00230] [00231] [00232] [00233] [00234] [00235] [00236] [00237] [00238] [00239] [00240] [00241] [00242] [00243] [00244] [00245] [00246] [00247] [00248] [00249] [00250] [00251] [00252] [00253] [00254] [00255] [00256]

[0165] The dopants used in the present case are shown in Table 3.

TABLE-US-00019 TABLE 3 Dopants used [00257] [00258] [00259]

[0166] The materials for the hole-blocking layer and electron-transport layer are applied by thermal vapour deposition in a vacuum chamber. The electron-transport layer here may consist, for example, of more than one material which are admixed with one another in a certain proportion by volume by co-evaporation. An expression such as ETM1:ETM2 (50%:50%) here means that materials ETM1 and ETM2 are present in the layer in a proportion by volume of 50% each. The materials used in the present case are shown in Table 4.

TABLE-US-00020 TABLE 4 HBL and ETL materials used [00260] [00261]

[0167] The cathode is formed by the thermal vapour deposition of an aluminium layer with a thickness of 100 nm. The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, current/voltage/luminous density characteristic lines (IUL characteristic lines), assuming Lambert emission characteristics, and the (operating) lifetime are determined. The IUL characteristic lines are used to determine characteristic numbers, such as the operating voltage U (in V) and the external quantum efficiency (in %) at a certain luminance. LT80 @ 8000 cd/m.sup.2 is the lifetime by which the OLED has dropped to 80% of the initial intensity from an initial luminance of 8000 cd/m.sup.2, i.e. to 6400 cd/m.sup.2. Correspondingly, LT80 @ 10000 cd/m.sup.2 is the lifetime by which the OLED has dropped to 80% of the initial intensity from an initial luminance of 10000 cd/m.sup.2, i.e. to 8000 cd/m.sup.2.

[0168] The data of OLEDs whose EMLs consist of TMM-A, TMM-B and dopant D (in accordance with Table 2 and Table 3) are shown in Table 5. ETM-1 is used as HBL and ETM1:ETM2 (50%:50%) as ETL.

TABLE-US-00021 TABLE 5 Results of solution-processed OLEDs comprising EML mixtures of the type x % of TMM-A, (100-x-y) % of TMM-B, y % of dopant D Effi- ciency Voltage LT80 at at at 1000 1000 8000 TMM-A TMM-B Dopant D cd/m.sup.2 cd/m.sup.2 cd/m.sup.2 Ex. Material % Material % Material % % EQE [V] [h] V1 12m 40 AV2 30 D2 30 19.0 5.5 236 1 14b 40 AV2 30 D2 30 19.8 5.2 289 V2 12m 40 AV2 40 D2 20 16.0 5.2 166 V6 AV6 40 AV2 40 D2 20 18.4 5.1 267 2 14b 40 AV2 40 D2 20 19.4 5.1 417 3 14c 40 AV2 40 D2 20 19.5 4.9 410 4 14a 40 AV2 40 D2 20 18.9 5.1 380 5 14f 40 AV2 40 D2 20 19.5 5.0 337 6 14h 40 AV2 40 D2 20 17.2 5.5 293 7 14g 40 AV2 40 D2 20 19.7 5.3 406 8 14i 40 AV2 40 D2 20 19.5 5.0 392 9 14d 40 AV2 40 D2 20 19.4 5.1 364 10 13b 40 AV2 40 D2 20 19.3 5.1 374 11 14k 40 AV2 40 D2 20 18.4 5.4 359 12 14j 40 AV2 40 D2 20 18.6 5.5 344 13 14e 40 AV2 40 D2 20 19.0 5.3 317 14 8d 40 AV2 40 D2 20 18.8 5.1 331 15 8e 40 AV2 40 D2 20 18.5 5.0 332 16 14n 40 AV2 40 D2 20 19.5 5.1 367 17 14l 40 AV2 40 D2 20 19.4 5.2 350 18 14m 40 AV2 40 D2 20 19.4 5.1 364 19 14p 40 AV2 40 D2 20 18.8 5.2 308 20 14q 40 AV2 40 D2 20 19.2 5.2 324 21 14r 40 AV2 40 D2 20 19.0 5.1 341 22 14s 40 AV2 40 D2 20 19.4 5.0 288 V3 12m 20 AV2 60 D2 20 18.6 5.3 240 23 14c 20 AV2 60 D2 20 20.1 5.2 551

[0169] The data of OLEDs whose EMLs consist of TMM-A, TMM-B, co-dopant D1 and dopant D (in accordance with Table 2 and Table 3) are shown in Table 6. ETM-1 is used as HBL and ETM1:ETM2 (50%:50%) as ETL here.

TABLE-US-00022 TABLE 6 Results of solution-processed OLEDs comprising EML mixtures of the type x % of TMM-A, (100-x-y-z) % of TMM-B, z % of co-dopant C, y % of dopant D Eff. Co- at U at LT80 TMM- TMM- dopant Dopant 1000 1000 at A B C D cd/m.sup.2 cd/ 8000 Ma- Ma- Ma- Ma- % m.sup.2 cd/m.sup.2 Ex. terial % terial % terial % terial % EQE [V] [h] V4 12m 39 AV2 45 D1 10 D3 6 14.1 7.3 75 24 14f 39 AV2 45 D1 10 D3 6 14.2 6.9 178 V5 12m 40 AV2 24 D1 30 D3 6 13.2 6.7 162 25 14f 40 AV2 24 D1 30 D3 6 13.4 6.6 244

Device Example 2

Production of Vacuum-Processed OLEDs

[0170] Many of the materials according to the invention can also be applied by vacuum vapour deposition. In the examples discussed below, exclusively layers applied on a vacuum basis are used. The general processes described above are for this purpose adapted to the circumstances described here (layer-thickness variation, materials). The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs and the results obtained are shown in Table 8. The auxiliary materials required for the production of the OLEDs are shown in Table 7; materials according to the invention and comparative materials are shown in Table 2.

TABLE-US-00023 TABLE 7 Structures of the auxiliary materials used [00262] [00263] [00264] [00265] [00266] [00267] [00268]

TABLE-US-00024 TABLE 8 Structure of vacuum-processed OLEDs HTL IL EBL EML HBL ETL Thick- Thick- Thick- Thick Thick- Thick Ex. ness ness ness ness ness ness V6 SpA1 HATCN SpMA1 12k:TEG1 SDT1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 10 nm 50%:50%) 30 nm 30 nm 26 SpA1 HATCN SpMA1 14b:TEG1 SDT1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm 27 SpA1 HATCN SpMA1 12m:14e:TEG1 SDT1 ST2:LiQ 70 nm 5 nm 90 nm (58%:30%:12%) 10 nm (50%:50%) 30 nm 30 nm 28 SpA1 HATCN SpMA1 14b:AV4:TEG1 SDT1 ST2:LiQ 70 nm 5 nm 90 nm (58%:30%:12%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00025 TABLE 9 Results of vacuum-processed OLEDs Efficiency at Voltage at LT80 at Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 20 mA/cm.sup.2 V6 3.3 15.60% 110 26 3.3 15.80% 145 27 3.0 17.90% 72 28 3.4 19.10% 205