SPIROBIFLUORENE COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.

Claims

1.-15. (canceled)

16. A compound of formula (1): ##STR00798## wherein Ar.sup.1 and Ar.sup.2 are, identically or differently on each occurrence, selected from formulae (11) to (66) ##STR00799## ##STR00800## ##STR00801## ##STR00802## ##STR00803## ##STR00804## ##STR00805## ##STR00806## ##STR00807##  where the dashed bond indicates the bond to the nitrogen, and the groups may be substituted by one or more radicals R.sup.5; Ar.sup.S is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 6 to 60 C atoms, which may in each case also be substituted by one or more radicals R.sup.5; R.sup.1, R.sup.2, R.sup.3, R.sup.4 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, Si(R.sup.6).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, each of which may be substituted by one or more radicals R.sup.6, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by Si(R.sup.6).sub.2, C═NR.sup.6, P(═O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6 and where one or more H atoms may be replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms, which may in each case be substituted by one or more radicals R.sup.6, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.6, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.6, where two or more adjacent substituents R.sup.1 or R.sup.2 or R.sup.3 or R.sup.4 may optionally form a mono- or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R.sup.6; R.sup.5 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, Si(R.sup.6).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, each of which may be substituted by one or more radicals R.sup.6, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by Si(R.sup.6).sub.2, C═NR.sup.6, P(═O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or CONR.sup.6 and where one or more H atoms may be replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms, which may in each case be substituted by one or more radicals R.sup.6, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.6, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.6, where two or more adjacent substituents R.sup.5 may optionally form a mono- or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R.sup.6; R.sup.6 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, in which one or more H atoms may be replaced by D or F, where two or more adjacent substituents R.sup.6 may form a mono- or polycyclic, aliphatic ring system with one another; i is on each occurrence, identically or differently, 0 or 1; m is 0, 1 or 2; n is on each occurrence, identically or differently, 0, 1, 2, 3 or 4; p, q are 0; and r, s are on each occurrence, identically or differently, 0, 1, 2, 3 or 4, where p+r≤4 and q+s≤4.

17. The compound according to claim 16, wherein the index i is 0.

18. The compound according to claim 16, wherein the compound is a compound of formulae (2, (5) or (8), ##STR00808## where the symbols and indices used are defined as in claim 16.

19. The compound according to claim 16, wherein the compound is a compound of formulae (2a), (5a) or (8a), ##STR00809## where the symbols and indices used are defined as in claim 16.

20. The compound according to claim 16, wherein the compound is a compound of formulae (2b, (5b) or (8b), ##STR00810## where the symbols used are defined as in claim 16.

21. The compound according to claim 16, wherein groups Ar.sup.1 and Ar.sup.2 are, identically or differently on each occurrence, selected from the group consisting of the formulae (11), (13), (16), (20), (28), (29), (33), (34), (35), (37), (38), (39), (40), (44), (48), (49), (51), and (59).

22. The compound according to claim 16, wherein groups Ar.sup.1 and Ar.sup.2 are, identically or differently on each occurrence, selected from the group consisting of the formulae (11), (13), (20), (29), (35), (38), (39), (49), (51), and (59).

23. The compound according to claim 16, wherein the groups Ar.sup.1 and Ar.sup.2 are selected identically.

24. The compound according to claim 16, wherein R.sup.1 to R.sup.4 are selected, identically or differently on each occurrence, from the group consisting of H, F, CN, 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, each of which may be substituted by one or more radicals R.sup.6, where one or more non-adjacent CH.sub.2 groups may be replaced by O and where one or more H atoms may be replaced by F, 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.sup.6.

25. The compound according to claim 16, wherein the radical R.sup.5 which is bonded to Ar.sup.1 or Ar.sup.2 or Ar.sup.S is selected, identically or differently on each occurrence, from the group consisting of H, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R.sup.6.

26. The compound according to claim 16, wherein R.sup.1 to R.sup.4 are selected, identically or differently on each occurrence, from the group consisting of H, F, CN, 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, each of which may be substituted by one or more radicals R.sup.6, where one or more non-adjacent CH.sub.2 groups may be replaced by O and where one or more H atoms may be replaced by F, 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.sup.6; R.sup.5 is, if the radical R.sup.5 is bonded to Ar.sup.1 or Ar.sup.2 or Ar.sup.S, selected, identically or differently on each occurrence, from the group consisting of H, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R.sup.6; or R.sup.5 which is bonded to the carbon bridge in the formulae (20) to (23), (53), (54), (68) and (72) is, identically or differently, an alkyl group having 1 to 10 C atoms, in particular methyl, or a phenyl group, which may be substituted by one or more radicals R.sup.6; or R.sup.5 which is bonded to the nitrogen bridge in the formulae (28) to (31), (40) to (43) or (55) to (58), (63) to (66), (71) and (73) is a phenyl group, which may be substituted by one or more radicals R.sup.6; R.sup.6 is selected on each occurrence, identically or differently, from the group consisting of H, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic ring system having 6 to 24 C atoms; i is 0; m is 0 or 1; n is 0 or 1; r is 0 or 1; and s is 0 or 1.

27. A process for the preparation of the compound according to claim 16, wherein the diarylamino group is introduced by a C—N coupling reaction between a 1- or 3- or 4-halogenated spirobifluorene and a diarylamine.

28. A method comprising including the compound according to claim 16 in an electronic device.

29. An electronic device comprising at least one compound according to claim 16, selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic dye-sensitised solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

30. The electronic device according to claim 29, wherein the devise is an organic electroluminescent devices, and wherein the compound is comprised as hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer, or is comprised as matrix material for fluorescent or phosphorescent emitters in an emitting layer.

Description

EXAMPLES

A) Synthesis Examples

[0162] The following syntheses are carried out under a protective-gas atmosphere, unless indicated otherwise. The starting materials can be purchased from ALDRICH or ABCR. The numbers in square brackets in the case of the starting materials known from the literature are the corresponding CAS numbers.

Example 1: Synthesis of the Brominated Spirobifluorene Derivatives (Starting Materials)

1a) Synthesis of 1-bromospiro-9,9′-bifluorene

[0163] ##STR00536##

[0164] The corresponding Grignard reagent is prepared from 2.7 g (110 mmol) of iodine-activated magnesium turnings and a mixture of 25.6 g (110 mmol) of 2-bromobiphenyl, 0.8 ml of 1,2-dichloroethane, 50 ml of 1,2-dimethoxyethane, 400 ml of THE and 200 ml of toluene with secondary heating using an oil bath at 70° C. When the magnesium has reacted completely, the mixture is allowed to cool to room temperature, and a solution of 25.9 g (100 mmol) of 1-bromofluorenone [36804-63-4] in 500 ml of THE is then added dropwise, the reaction mixture is warmed at 50° C. for 4 h and then stirred at room temperature for a further 12 h. 100 ml of water are added, the mixture is stirred briefly, the organic phase is separated off, and the solvent is removed in vacuo. The residue is suspended in 500 ml of glacial acetic acid at 40° C., 0.5 ml of conc. sulfuric acid is added to the suspension, and the mixture is subsequently stirred at 100° C. for a further 2 h. After cooling, the precipitated solid is filtered off with suction, washed once with 100 ml of glacial acetic acid, three times with 100 ml of ethanol each time and finally recrystallised from dioxane. Yield: 26.9 g (68 mmol), 68%; purity about 98% according to .sup.1H-NMR.

1b) Synthesis of 4-bromospiro-9,9′-bifluorene

[0165] ##STR00537##

[0166] A solution of 2, 2′-dibromo-biphenyl (250 g, 785 mmol) in THE (1900 ml) is treated with 318 mL of n-BuLi (2.5 M in hexane, 785 mmol) under argon at −78° C. The mixture is stirred for 30 minutes. A solution of Fluoren-9-one (144 g, 785 mmol) in 1000 mL THE is added dropwise. The reaction proceeds at −78° C. for 30 minutes and then is stirred at room temperature overnight. The reaction is quenched with water and the solid is filtered. Without further purification, a mixture of the alcohol (299 g, 92%), acetic acid (2200 mL) and concentrated HCl (100 mL) is refluxed for 2 hours. After cooling, the mixture is filtered and washed with water and dried under vacuum. The product is isolated in the form of a white solid (280 g, 98% of theory).

[0167] The synthesis of further brominated spirobifluorene derivatives is carried out analogously:

TABLE-US-00007 Product: Ex. Bromo-biphenyl Bromo-fluorenone Bromo-Spirobifluorene Yield 1c [00538] [00539] [00540] 85% 1d [00541] [00542] [00543] 90% 1e [00544] [00545] [00546] 85% 1f [00547] [00548] [00549] 90% 1g [00550] [00551] [00552] 85% 1h [00553] [00554] [00555] 90% 1i [00556] [00557] [00558] 87% 1j [00559] [00560] [00561] 85% 1k [00562] [00563] [00564] 80% 1l [00565] [00566] [00567] 80% 1m [00568] [00569] [00570] 90% 1n [00571] [00572] [00573] 80%

Example 2: Synthesis of 4-biphenyl-2-(9,9′-dimethylfluorenyl)-1-spiro-9,9′-bifluorenylamine

Synthesis of 1-(1-biphen-4-yl)-(9,9′-dimethylfluoren-2-yl)amine-9H-Fluoren-9-one

[0168] ##STR00574##

[0169] Tri-tert-butylphosphine (4.5 ml of a 1.0 M solution in toluene, 1.9 mmol), palladium acetate (217 mg, 0.97 mmol) and sodium tert-butoxide (13.9 g, 145 mmol) are added to a solution of 1-biphenyl-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (40.0 g, 111 mmol), 1-Bromo-Fluoren-9-one, (25 g, 96 mmol) in degassed toluene (200 ml), and the mixture is heated under reflux overnight. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from toluene/heptane The product is isolated in the form of a pale-yellow solid (43 g, 82% of theory).

Synthesis of 4-biphenyl-2-(9,9′-dimethylfluorenyl)-1-spiro-9,9′-bifluorenylamine

[0170] ##STR00575##

[0171] A solution of 2-Bromo-biphenyl (17 g, 70 mmol) in THE (90 ml) is treated with 35 mL of n-BuLi (2.1 M in hexane, 70 mmol) under argon at −78° C. The mixture is stirred for 30 minutes. A solution of 1-(1-biphen-4-yl)(9,9′-dimethylfluoren-2-yl)amine-9H-Fluoren-9-one (38 g, 70 mmol) in 90 mL THE is added dropwise. The reaction proceeds at −78° C. for 30 minutes and then is stirred at room temperature overnight. The reaction is quenched with water and extracted with ethyl acetate. The intermediate alcohol is obtained after the solvent is removed (31 g, 64%). Without further purification, a mixture of the alcohol, acetic acid (700 mL) and concentrated HCl (62 mL) is refluxed for 2 hours. After cooling, the mixture is filtered and washed with water. The residue is crystallised from toluene. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo. The product is isolated in the form of a pale-yellow solid (13 g, 43% of theory, purity >99.99% according to HPLC).

Example 3a: Synthesis of 4-biphenyl-2-(9,9′-dimethylfluorenyl)-1-spiro-9,9′-bifluorenylamine

[0172] ##STR00576##

[0173] Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide (16.0 g, 166 mmol) are added to a solution of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (40.0 g, 111 mmol) and 4-bromo-9,9′-spirobifluorene (56.9 g, 144 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from ethyl acetate/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice (p=3×10.sup.−4 mbar, T=29800). The product is isolated in the form of a pale-yellow solid (20.4 g, 27% of theory, purity >99.99% according to HPLC).

[0174] The following compounds are obtained analogously

TABLE-US-00008 Ex. Br-spiro Amine 3b [00577] [00578] 3c [00579] [00580] 3d [00581] [00582] 3e [00583] [00584] 3f [00585] [00586] 3g [00587] [00588] 3h [00589] [00590] 3i [00591] [00592] 3j [00593] [00594] 3k [00595] [00596] 3l [00597] [00598] 3m [00599] [00600] 3n [00601] [00602] 3o [00603] [00604] 3p [00605] [00606] 3q [00607] [00608] 3r [00609] [00610] 3s [00611] [00612] 3t [00613] [00614] 3u [00615] [00616] 3v [00617] [00618] 3w [00619] [00620] 3x [00621] [00622] 3y [00623] [00624] 3z [00625] [00626] 3aa [00627] [00628] 3ab [00629] [00630] 3ac [00631] [00632] 3ad [00633] [00634] 3ae [00635] [00636] 3af [00637] [00638] 3ag [00639] [00640] 3ah [00641] [00642] 3ai [00643] [00644] 3aj [00645] [00646] 3ak [00647] [00648] 3al [00649] [00650] 3am [00651] [00652] 3an [00653] [00654] 3ao [00655] [00656] 3ap [00657] [00658] 3aq [00659] [00660] Ex. Product Yield 3b [00661] 43% 3c [00662] 56% 3d [00663] 61% 3e [00664] 72% 3f [00665] 65% 3g [00666] 75% 3h [00667] 80% 3i [00668] 85% 3j [00669] 55% 3k [00670] 64% 3l [00671] 56% 3m [00672] 66% 3n [00673] 46% 3o [00674] 60% 3p [00675] 72% 3q [00676] 85% 3r [00677] 50% 3s [00678] 70% 3t [00679] 67% 3u [00680] 85% 3v [00681] 43% 3w [00682] 76% 3x [00683] 41% 3y [00684] 50% 3z [00685] 59% 3aa [00686] 71% 3ab [00687] 70% 3ac [00688] 75% 3ad [00689] 80% 3ae [00690] 85% 3af [00691] 48% 3ag [00692] 46% 3ah [00693] 41% 3ai [00694] 50% 3aj [00695] 43% 3ak [00696] 53% 3al [00697] 33% 3am [00698] 46% 3an [00699] 41% 3ao [00700] 40% 3ap [00701] 51% 3aq [00702] 47%

Example 4a: Synthesis of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9′-spirobifluoren-4-yl)amine

[0175] ##STR00703##

a) Synthesis of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine

[0176] 1,1′-Bis(diphenylphosphino)ferrocene (1.5 g, 2.7 mmol), palladium acetate (616 mg, 2.7 mmol) and sodium tert-butoxide (22.9 g, 238 mmol) are added to a solution of biphenyl-2-ylamine (31.0 g, 183 mmol) and 2-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) in degassed toluene (400 ml), and the mixture is heated under reflux for 20 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is extended with water, re-extracted with toluene, and the combined organic phases are dried and evaporated in vacuo. The residue is filtered through silica gel (heptane/dichloromethane) and crystallised from isopropanol. Biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine is obtained in the form of a pale-yellow solid (63.0 g, 95% of theory).

b) Synthesis of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9′-spirobifluoren-4-yl)amine

[0177] Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide (16.0 g, 166 mmol) are added to a solution of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (40.0 g, 111 mmol) and 4-bromo-9,9′-spirobifluorene (56.9 g, 144 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from ethyl acetate/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice (p=3×10.sup.−4 mbar, T=29800). The product is isolated in the form of a pale-yellow solid (20.4 g, 27% of theory, purity >99.99% according to HPLC).

[0178] The following compounds are obtained analogously

TABLE-US-00009 Ex. Starting material 1 Starting material 2 Starting material 3 Product Yield 4b [00704] [00705] [00706] [00707] 78% 4c [00708] [00709] [00710] [00711] 73% 4d [00712] [00713] [00714] [00715] 75% 4e [00716] [00717] [00718] [00719] 79% 4f [00720] [00721] [00722] [00723] 78%

Example 5a: Synthesis of Synthesis of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(9,9′-spiro-bifluoren-4-yl)-phenyl]-amine

Synthesis of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine

[0179] ##STR00724##

[0180] 102 g (198 mmol) of Biphenyl-4-yl-(4-bromo-phenyl)-(9,9-dimethyl-9H-fluoren-2-yl)-amine, 4.8 g (5.9 mmol) of Pd(dppf)Cl.sub.2, 61.6 g (238 mmol) of bis(pinacolato)diboron and 58.3 g (594 mmol) of potassium acetate are dissolved in 1300 mL of 1,4-dioxane. The reaction mixture is refluxed and agitated under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from heptane. The product is isolated in the form of a pale-yellow solid (87 g, 78% of theory).

Synthesis of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(9,9′-spiro-bifluoren-4-yl)-phenyl]-amine

[0181] ##STR00725##

[0182] 28 g (49.4 mmol) of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine, 20 g (49.4 mmol) of 4-bromspirobifluorene, 1.8 g (2.5 mmol) of PdCl.sub.2(Cy).sub.3, 15 g (99 mmol) of cesium fluoride are dissolved in 500 mL of toluene. The reaction mixture is refluxed and agitated under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice. The product is isolated in the form of a pale-yellow solid (9 g, 24% of theory, purity >99.99% according to HPLC).

[0183] The following compounds are synthesized analogously:

TABLE-US-00010 Ex. Br-Spiro Amine Product Yield 5b [00726] [00727] [00728] 43% 5c [00729] [00730] [00731] 55% 5d [00732] [00733] [00734] 60% 5e [00735] [00736] [00737] 63% 5f [00738] [00739] [00740] 70% 5g [00741] [00742] [00743] 75% 5h [00744] [00745] [00746] 55% 5i [00747] [00748] [00749] 64% 5j [00750] [00751] [00752] 60% 5k [00753] [00754] [00755] 67% 5l [00756] [00757] [00758] 58%

Example 6a: 9-Spiro-4-yl-3,6-diphenyl-9H-carbazol

[0184] ##STR00759##

[0185] 19.2 g (47 mmol) 4-Brom-9-spirobifluorene, 15 g (47 mmol) 3,6-Diphenyl-9-H-carbazole and 29.2 g Rb.sub.2CO.sub.3 are suspended in 250 mL p-Xylol. To the suspension are given 0.95 g (4.2 mmol) Pd(OAc).sub.2 and 12.6 ml of a 1M solution of Tri-tert-butylphosphine. The mixture is stirred 24 h under reflux. After cooling the organic phase is separated, washed three times with 150 mL water and is subsequently concentrated to dryness in vacuo. The residue is hot extracted with toluene, recrystallized three times from toluene and subsequently sublimated at high vacuum. Yield is 19.6 g (30.9 mmol) corresponding to 66% of theory. Purity is according to HPLC 99.9%.

[0186] The following compounds are obtained analogously:

TABLE-US-00011 starting material 1 starting material 2 product yield 6b [00760] [00761] [00762] 76% 6c [00763] [00764] [00765] 65% 6d [00766] [00767] [00768] 77% 6e [00769] [00770] [00771] 69%

B) Device Examples

[0187] OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

[0188] The data for various OLEDs are presented in the following Examples 1 to 5 below (see Tables 1 to 7).

[0189] The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs basically have the following layer structure: substrate/hole-injection layer (IL)/hole-transport layer (HTL)/hole-injection layer (IL)/electron-blocking layer (EBL)/emission layer (EML)/electron-transport layer (ETL) and finally a cathode. In the device structure according to Table 3, the analogous structure is used, only that the first hole injection layer is omitted.

[0190] Other examples are presented with the following general device structure shown in Table 6: substrate/p-doped hole transport layer (HIL1)/hole-transport layer (HTL)/p-doped electron blocking layer (HIL2)/electron-blocking layer (EBL)/emission layer (EML)/electron-transport layer (ETL)/electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm.

[0191] Other examples are presented with the following general device structure shown in Table 7. This structure differs from the structure of Examples of Table 6 in that the second p-doped electron blocking layer is omitted, and in that a hole blocking layer (HBL) is present between emitting layer and electron transport layer.

[0192] The precise structures of all the OLEDs prepared in the present examples are shown in Tables 1, 3, 6 and 7. The materials required for the production of the OLEDs are shown in Table 5. Data obtained are either in the text and/or shown in Tables 2 and 4.

[0193] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by coevaporation. An expression such as H1:SEB1 (95%:5%) here means that material H1 is present in the layer in a proportion by volume of 95% and SEB1 is present in the layer in a proportion of 5%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

[0194] The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics, and the lifetime are determined. The electroluminescence spectra are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The expression EQE @ 1000 cd/m.sup.2 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. LT80 @ 6000 cd/m.sup.2 is the lifetime until the OLED has dropped from a luminance of 6000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4800 cd/m.sup.2. LT80 @ 60 mA/cm.sup.2 is the lifetime until the OLED has dropped from its initial luminance at a constant current of 60 mA to 80% of the initial luminance. The data obtained for the various OLEDs are summarised either in the text and/or shown in Tables 2 and 4.

Use of Compounds According to the Invention as Hole-Transport Materials in Fluorescent and Phosphorescent OLEDs

[0195] In particular, compounds according to the invention are suitable as HIL, HTL or EBL in OLEDs. They are suitable as a single layer, but also as mixed component as HIL, HTL, EBL or within the EML.

Example 1

[0196] Singlet blue devices are shown in Tables 1 and 2, and triplet green devices are shown in Tables 3 and 4.

[0197] Compared with devices which comprise NPB as reference (V1, V3), the samples comprising the compounds according to the invention exhibit both higher efficiencies and also significantly improved lifetimes both in singlet blue and also in triplet green devices. Compared with the reference material HTMV1 (V2, V4), the compound according to the invention HTM1 has significantly improved efficiencies and significantly better lifetimes.

TABLE-US-00012 TABLE 1 Structure of the OLEDs IL HTL IL EBL EML ETL Thick- Thick- Thick- Thick- Thick- Thick- ness/ ness/ ness/ ness/ ness/ ness/ Ex. nm nm nm nm nm nm V1 HIL1 HIL2 HIL1 NPB H1(95%): ETM1(50%): 5 nm 140 nm 5 nm 20 nm SEB1(5%) LiQ(50%) 20 nm 30 nm V2 HIL1 HIL2 HIL1 HTMV1 H1(95%): ETM1(50%): 5 nm 140 nm 5 nm 20 nm SEB1(5%) LiQ(50%) 20 nm 30 nm E1 HIL1 HIL2 HIL1 HTM1 H1(95%): ETM1(50%): 5 nm 140 nm 5 nm 20 nm SEB1(5%) LiQ(50%) 20 nm 30 nm

TABLE-US-00013 TABLE 2 Data for the OLEDs EQE LT80 @ 1000 @ 6000 cd/m2 cd/m.sup.2 CIE Ex. % [h] x y V1 4.8  70 0.14 0.17 V2 4.3  45 0.13 0.15 E1 6.8 130 0.13 0.16

TABLE-US-00014 TABLE 3 Structure of the OLEDs HTL IL EBL EML ETL Thick- Thick- Thick- Thick- Thick- ness/ ness/ ness/ ness/ ness/ Ex. nm nm nm nm nm V3 HIL2 HIL1 NPB H2(88%): ETM1(50%): 70 nm 5 nm 90 nm TEG(12%) LiQ(50%) 30 nm 40 nm V4 HIL2 HIL1 HTMV1 H2(88%): ETM1(50%): 70 nm 5 nm 90 nm TEG(12%) LiQ(50%) 30 nm 40 nm E2 HIL2 HIL1 HTM1 H2(88%): ETM1(50%): 70 nm 5 nm 90 nm TEG(12%) LiQ(50%) 30 nm 40 nm

TABLE-US-00015 TABLE 4 Data for the OLEDs Efficiency LT80 @ 1000 @ 8000 CIE Ex. cd/m2 cd/m.sup.2 x y V3 14.4%  85 h 0.32 0.63 V4 16.6%  60 h 0.37 0.6  E2 17.3% 195 h 0.37 0.61

TABLE-US-00016 TABLE 5 Structures of the materials used [00772] [00773] [00774] [00775] [00776] [00777] [00778] [00779] [00780] [00781] [00782] [00783] [00784] [00785] [00786] [00787] [00788] [00789] [00790] [00791] [00792] [00793] [00794] [00795] [00796] [00797]

Example 2

[0198] In a different blue fluorescent device structure (Table 6) the reference devices V5 and V6, using materials according to the state of the art (NPB and HTMV1), have lower efficiencies (EQE @ 10 mA/cm.sup.2 of 6.2% for V5 and 5.8% for V6) compared to the devices comprising the compounds according to the invention E3 (8.5%), E4 (8.3%), E5 (7.9%), E6 (7.6%), E7 (7.8%), E8 (8.9%), E9 (8.4%), E10 (8.1%) and E11 (8.2%).

[0199] The reference samples V5 and V6 have also lower lifetimes (V5 of 120 h (LT80 @ 60 mA) and V6 of 105 h) compared to the samples E3 (305 h), E4 (290 h), E5 (320 h), E6 (390 h), E7 (365 h), E8 (165 h), E9 (280 h), E10 (285 h) and E11 (340 h).

Example 3

[0200] In a different green phosphorescent device structure (Table 6), the reference device V7 has lower efficiency (EQE @ 2 mA/cm.sup.2) of 11.7% compared to the samples comprising the compounds according to the invention E12 (20.0%), E13 (19.6%), E14 (18.9%), E15 (19.2%) and E16 (20.2%). The reference sample V6 has also lower lifetime of 80 h (LT80 @20 mA) compared to the samples E12 (90 h), E13 (185 h), E14 (105 h), E15 (205 h) and E16 (185 h).

TABLE-US-00017 TABLE 6 Structure of the OLEDs HIL1 HTL HIL2 EBL EML ETL EIL Dicke/ Dicke/ Dicke/ Dicke/ Dicke/ Dicke/ Dicke/ Bsp. nm nm nm nm nm nm nm V5 HIL3: HIL3 NPB: NPB H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm V6 HIL3: HIL3 HTMV1: HTMV1 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E3 HIL3: HIL3 HTM2: HTM2 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E4 HIL3: HIL3 HTM3: HTM3 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E5 HIL3: HIL3 HTM4: HTM4 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E6 HIL3: HIL3 HTM5: HTM5 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E7 HIL3: HIL3 HTM6: HTM6 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E8 HIL3: HIL3 HTM7: HTM7 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E9 HIL3: HIL3 HTM8: HTM8 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E10 HIL3: HIL3 HTM9: HTM9 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm E11 HIL3: HIL3 HTM10: HTM10 H1: ETM2(50%): LiQ F4TCNQ(3%) 155 nm F4TCNQ(3%) 20 nm SEB1(5%) LiQ(50%) 1 nm 20 nm 20 nm 20 nm 30 nm V7 HIL3: HIL3 NPB: NPB H2: ETM2(50%): LiQ F4TCNQ(3%) 210 nm F4TCNQ(3%) 20 nm TEG(10%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm 40 nm E12 HIL3: HIL3 HTM2: HTM2 H2: ETM2(50%): LiQ F4TCNQ(3%) 210 nm F4TCNQ(3%) 20 nm TEG(10%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm 40 nm E13 HIL3: HIL3 HTM3: HTM3 H2: ETM2(50%): LiQ F4TCNQ(3%) 210 nm F4TCNQ(3%) 20 nm TEG(10%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm 40 nm E14 HIL3: HIL3 HTM4: HTM4 H2: ETM2(50%): LiQ F4TCNQ(3%) 210 nm F4TCNQ(3%) 20 nm TEG(10%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm 40 nm E15 HIL3: HIL3 HTM5: HTM5 H2: ETM2(50%): LiQ F4TCNQ(3%) 210 nm F4TCNQ(3%) 20 nm TEG(10%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm 40 nm E16 HIL3: HIL3 HTM6: HTM6 H2: ETM2(50%): LiQ F4TCNQ(3%) 210 nm F4TCNQ(3%) 20 nm TEG(10%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm 40 nm

TABLE-US-00018 TABLE 7 Structure of the OLEDs HIL1 HTL EBL EML HBL ETL EIL Dicke/ Dicke/ Dicke/ Dicke/ Dicke/ Dicke/ Dicke/ Bsp. nm nm nm nm nm nm nm V8 HIL3: HIL3 H3:TEG(10%) H2 ETM2(50%): F4TCNQ(3%) 230 nm 40 nm 5 nm LiQ(50%) 20 nm 25 nm E17 HIL3: HIL3 H3:HTM3(60%): H2 ETM2(50%): F4TCNQ(3%) 230 nm TEG(10%) 5 nm LiQ(50%) 20 nm 40 nm 25 nm V9 HIL3: HIL3 HTM3 H4:TEG(10%) ETM2(50%): LiQ F4TCNQ(3%) 220 nm 10 nm 40 nm LiQ(50%) 1 nm 20 nm 30 nm E18 HIL3: HIL3 HTM3 H4:HTM4(10%): ETM2(50%): LiQ F4TCNQ(3%) 220 nm 10 nm TEG(10%) LiQ(50%) 1 nm 20 nm 40 nm 30 nm E19 HIL3: HIL3 HTM3 H4:HTM11(45%): ETM2(50%): LiQ F4TCNQ(3%) 220 nm 10 nm TEG(10%) LiQ(50%) 1 nm 20 nm 40 nm 30 nm

Use of Compounds According to the Invention as Matrix Materials in Phosphorescent OLEDs

Example 4

[0201] In a different green phosphorescent device structure (Table 7), the reference device V8, which does not have the compound according to the invention as a matrix material of the emitting layer, has lower efficiency (EQE @ 2 mA/cm.sup.2 of 14.4%) compared to the sample E17 comprising the compound according to the invention HTM3 (EQE @ 2 mA/cm.sup.2 of 16.1%), used as a mixed matrix component in the EML. The reference sample V8 has also lower lifetime of 305 h (LT80 @ 20 mA) compared to sample E17 of 330 h.

Example 5

[0202] In a different green phosphorescent device structure (Table 7) it is shown that the compounds according to the invention show favorable effects as a mixed matrix component in the emitting layer, in combination with a lactam compound H4. The reference device V9 has an efficiency (EQE @ 2 mA/cm.sup.2) of 17.6% and a lifetime of 255 h. Lifetime can be improved by adding a compound according to the invention to the emitting layer as a co-matrix material, as shown by examples E18 and E19 compared to V9.

[0203] Device E18 shows an efficiency of 13.4% and a lifetime of 400 h, and device E19 shows an efficiency of 17.9% and a lifetime of 270 h, which are both improvements compared to reference device V9.