ELECTRONIC DEVICE

Abstract

The present application relates to an electronic device comprising a xanthene or thioxanthene compound of a particular formula. The electronic device is preferably an organic electroluminescent device (OLED). The application further relates to particular xanthene or thioxanthene compounds as such, and to the use thereof in the abovementioned devices, and to processes for preparation thereof.

Claims

1.-19. (canceled)

20. An electronic device comprising, in this sequence, an anode, a hole-transporting layer, an emitting layer and a cathode, wherein said hole-transporting layer comprises a compound of a formula (I) ##STR00535## where: A is an arylamino group optionally substituted by one or more R.sup.1 radicals, or a carbazole-containing group optionally substituted by one or more R.sup.1 radicals; E is a single bond; X is O or S; Z is the same or different at each instance and is CR.sup.2 or N or C, where a Z group is C in the specific case when an A or E group is bonded to the Z group in question; R.sup.1 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(O)(R.sup.3).sub.2, OR.sup.3, S(O)R.sup.3, S(O).sub.2R.sup.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.3 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), O, S, SO or SO.sub.2; R.sup.2 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(O)(R.sup.3).sub.2, OR.sup.3, S(O)R.sup.3, S(O).sub.2R.sup.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.3 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), O, S, SO or SO.sub.2; R.sup.3 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2; R.sup.4 is the same or different at each instance and is selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.4 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; i is 0 or 1; n is the same or different at each instance and is 0 or 1, where the sum total of all the indices n is 1, 2, 3 or 4; where at least one condition selected from conditions a) and b) is met: a) the hole-transporting layer directly adjoins the anode; b) there are at least two further layers arranged between the hole-transporting layer and the emitting layer, and there are no further emitting layers arranged between the emitting layer and the anode.

21. The electronic device according to claim 20, wherein X is O.

22. The electronic device according to claim 20, wherein i is 1.

23. The electronic device according to claim 20, wherein the sum total of the indices n is 1 or 2.

24. The electronic device according to claim 20, wherein R.sup.1 is the same or different at each instance and is selected from H, F, CN, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.3 radicals.

25. The electronic device according to claim 20, wherein R.sup.2 is the same or different at each instance and is selected from H, F, CN, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.3 radicals.

26. The electronic device according to claim 20, wherein R.sup.3 is the same or different at each instance and is selected from H, F, CN, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.4 radicals.

27. The electronic device according to claim 20, wherein the A group is an arylamino group which may be substituted by one or more R.sup.1 radicals.

28. The electronic device according to claim 20, wherein the arylamino group as A group corresponds to a formula (A) ##STR00536## where: L.sup.1 is the same or different at each instance and is CO, Si(R.sup.1).sub.2, PR.sup.1, P(O)(R.sup.1), O, S, SO, SO.sub.2, an alkylene group having 1 to 20 carbon atoms or an alkenylene or alkynylene group having 2 to 20 carbon atoms, where one or more CH.sub.2 groups in the groups mentioned may be replaced by CO, CNR.sup.1, COO, CONR.sup.1, Si(R.sup.1).sub.2, NR.sup.1, P(O)(R.sup.1), O, S, SO or SO.sub.2 and where one or more hydrogen atoms in the abovementioned groups may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; Y is selected from a single bond, BR.sup.1, C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, Si(R.sup.1).sub.2, Si(R.sup.1).sub.2Si(R.sup.1).sub.2, CO, CNR.sup.1, CC(R.sup.1).sub.2, C(O)N(R.sup.1), O, S, SO, SO.sub.2 and NR.sup.1; k is 0, 1, 2 or 3; m is 0 or 1; where the A group is bonded to the rest of the compound of the formula (I) via the bond marked with *.

29. The electronic device according to claim 20, wherein the compound of the formula (I) corresponds to one of the following formulae: ##STR00537## ##STR00538## ##STR00539## ##STR00540## ##STR00541## ##STR00542## where X, L.sup.1, Ar.sup.1 and k are as defined in claim 20, and where the compounds may each be substituted on the benzene rings at the positions shown as unsubstituted by R.sup.2 radicals as defined in claim 20.

30. The electronic device according to claim 20, wherein there is at least one further layer that does not include any compound of the formula (I) between the layer comprising the compound of the formula (I) and the emitting layer closest to the anode.

31. The electronic device according to claim 30, wherein the at least one further layer is a hole-transporting layer comprising a monoamine compound containing at least one group selected from spirobifluorenyl groups, phenanthrenyl groups, fluorenyl groups, carbazolyl groups, dibenzofuranyl groups and dibenzothiophenyl groups.

32. The electronic device according to claim 20, wherein the hole-transporting layer directly adjoins the anode, in that there are at least two further layers arranged between the hole-transporting layer and the emitting layer, and in that there are no further emitting layers arranged between the emitting layer and the anode.

33. A compound of a formula (S) ##STR00543## where an A group has to be bonded to at least one group selected from the B.sub.1 and B.sub.2 groups, and where the variables that occur are as follows: B.sub.1, B.sub.2 are the same or different at each instance and are N or CR.sup.2 or C, where a B.sub.1 or B.sub.2 group is C in the specific case when an A group is bonded to it; Z is the same or different at each instance and is CR.sup.2 or N or C, where a Z group is C in the specific case when an E group is bonded to the Z group in question; A is an arylamino group optionally substituted by one or more R.sup.1 radicals, or a carbazole-containing group optionally substituted by one or more R.sup.1 radicals; E is a single bond; X is O or S; R.sup.1 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(O)(R.sup.3).sub.2, OR.sup.3, S(O)R.sup.3, S(O).sub.2R.sup.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.3 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), O, S, SO or SO.sub.2; R.sup.2 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(O)(R.sup.3).sub.2, OR.sup.3, S(O)R.sup.3, S(O).sub.2R.sup.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.3 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), O, S, SO or SO.sub.2; R.sup.3 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(O)(R.sup.4).sub.2, OR.sup.4, S(O)R.sup.4, S(O).sub.2R.sup.4, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.4 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or SO.sub.2; R.sup.4 is the same or different at each instance and is selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; i is 0 or 1.

34. The compound according to claim 33, wherein X is O.

35. The compound according to claim 33, wherein i is 1.

36. The compound according to claim 33, wherein an A group is bonded to exactly one of the two B.sub.1 and B.sub.2 groups, and in that no A group is bonded to the other of the two B.sub.1 and B.sub.2 groups.

37. The compound according to claim 33, wherein the compound corresponds to a formula (S-1-1) ##STR00544## where the compounds may each be substituted on the benzene rings at the positions shown as unsubstituted by R.sup.2 radicals, and where the variables that occur as follows: L.sup.1 is the same or different at each instance and is CO, Si(R.sup.1).sub.2, PR.sup.1, P(O)(R.sup.1), O, S, SO, SO.sub.2, an alkylene group having 1 to 20 carbon atoms or an alkenylene or alkynylene group having 2 to 20 carbon atoms, where one or more CH.sub.2 groups in the groups mentioned may be replaced by CO, CNR.sup.1, COO, CONR.sup.1, Si(R.sup.1).sub.2, NR.sup.1, P(O)(R.sup.1), O, S, SO or SO.sub.2 and where one or more hydrogen atoms in the abovementioned groups may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; k is 0, 1, 2 or 3; R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are as defined in claim 33.

38. A process for preparing the compound according to claim 33, wherein it comprises an addition of a metallated ether or thioether compound onto a diaryl ketone and a subsequent ring-closure reaction.

Description

WORKING EXAMPLES

A) Synthesis Examples

Example 1-1

[0183] Synthesis of the Inventive Compound 1-1 and Variants

##STR00383##

[0184] Intermediate I-1

[0185] 26.8 g of phenyl(9,9-dimethyl-9H-fluoren-2-yl)amine (87.6 mmol) and 25 g of iodobenzofluorenone (87.6 mmol) are dissolved in 700 ml of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 3.5 ml (3.5 mmol) of a 1 M tri-tert-butylphosphine solution and 0.46 g (1.75 mmol) of palladium(II) acetate are added thereto, and then 16.8 g of sodium tert-butoxide (175 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 5 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The yield is 33 g (81% of theory).

[0186] The following compounds are prepared in an analogous manner:

TABLE-US-00004 Reactant 1 Reactant 2 Product Yield I-2 [00384] [00385] [00386] 85% I-3 [00387] [00388] [00389] 71% I-4 [00390] [00391] [00392] 82% I-5 [00393] [00394] [00395] 72% I-6 [00396] [00397] [00398] 74% I-7 [00399] [00400] [00401] 74% I-8 [00402] [00403] [00404] 62% I-9 [00405] [00406] [00407] 35% I-10 [00408] [00409] [00410] 70% I-11 [00411] [00412] [00413] 67%

[0187] Compound 1-1

[0188] 17.37 g (69.6 mmol) of 1-bromo-2-diphenyl ether are dissolved in a baked-out flask in 300 ml of dried THF. The reaction mixture is cooled to 78 C. At this temperature, 30 ml of a 2.5 M solution of n-BuLi in hexane (69.7 mmol) are slowly added dropwise. The mixture is stirred at 70 C. for a further 1 hour. Subsequently, 30 g of the bromofluorenone derivative (63 mmol) are dissolved in 200 ml of THF and added dropwise at 70 C. After the addition has ended, the reaction mixture is warmed gradually to room temperature, quenched with NH.sub.4Cl and then concentrated on a rotary evaporator.

[0189] 300 ml of acetic acid are added cautiously to the concentrated solution and then 20 ml of fuming HCl are added. The mixture is heated to 75 C. and kept there for 6 hours. During this time, a white solid precipitates out. The mixture is then cooled to room temperature, and the precipitated solids are filtered off with suction and washed with water and methanol. Yield: 35 g (88%)

[0190] The solids are recrystallized from heptane/toluene and finally sublimed under high vacuum.

[0191] The following compounds are prepared in an analogous manner:

TABLE-US-00005 Reactant 1 Reactant 2 Product Yield 1-2 [00414] [00415] [00416] 70% 1-3 [00417] [00418] [00419] 77% 1-5 [00420] [00421] [00422] 65% 1-6 [00423] [00424] [00425] 69% 1-7 [00426] [00427] [00428] 79% 1-8 [00429] [00430] [00431] 81% 1-9 [00432] [00433] [00434] 80% 1-10 [00435] [00436] [00437] 40% 1-11 [00438] [00439] [00440] 79%

Example 2-1

[0192] Synthesis of the Inventive Compound 2-1 and Variants

##STR00441##

[0193] Intermediate II-1

[0194] 38 g of 4-chlorophenylboronic acid (243 mmol) and 60 g of 1-bromofluoren-9-one (232 mmol) are suspended in 800 ml of THF. 230 ml of 2 M potassium carbonate solution are slowly added dropwise. The solution is degassed and saturated with N.sub.2. Thereafter, 8 g (7 mmol) of Pd(Ph.sub.3P).sub.4 are added. The reaction mixture is heated to boiling under a protective atmosphere for 16 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from MeOH. The yield is 63 g (90% of theory).

[0195] The following compounds are prepared in an analogous manner:

TABLE-US-00006 Reactant 1 Reactant 2 Product Yield II-2 [00442] [00443] [00444] 80% II-3 [00445] [00446] [00447] 88% II-4 [00448] [00449] [00450] 82% II-5 [00451] [00452] [00453] 89% II-6 [00454] [00455] [00456] 64% II-7 [00457] [00458] [00459] 80% II-8 [00460] [00461] [00462] 83%

[0196] Intermediate III-1

[0197] 30 g (120 mmol) of 1-bromo-2-diphenyl ether are dissolved in a baked-out flask in 500 ml of dried THF. The reaction mixture is cooled to 78 C. At this temperature, 480 ml of a 2.5 M solution of n-BuLi in hexane (120 mmol) are slowly added dropwise. The mixture is stirred at 70 C. for a further 1 hour. Subsequently, 33 g of 1-(4-chlorophenyl)fluorenone (114 mmol) are dissolved in 100 ml of THF and added dropwise at 70 C. After the addition has ended, the reaction mixture is warmed gradually to room temperature, quenched with NH.sub.4Cl and then concentrated on a rotary evaporator.

[0198] 300 ml of acetic acid are added cautiously to the concentrated solution and then 20 ml of fuming HCl are added. The mixture is heated to 75 C. and kept there for 6 hours. During this time, a white solid precipitates out. The mixture is then cooled to room temperature, and the precipitated solids are filtered off with suction and washed with water and methanol. Yield: 38 g (70%).

[0199] Finally, the residue is recrystallized.

[0200] The following compounds are prepared in an analogous manner:

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield III-2 [00463] [00464] [00465] 70% III-3 [00466] [00467] [00468] 77% III-4 [00469] [00470] [00471] 67% III-5 [00472] [00473] [00474] 65% III-6 [00475] [00476] [00477] 73% III-7 [00478] [00479] [00480] 69% III-8 [00481] [00482] [00483] 83% III-9 [00484] [00485] [00486] 71%

[0201] Compound 2-1

[0202] 16.3 g of biphenyl-3-yl(9,9-dimethyl-9H-fluoren-2-yl)amine (45.26 mmol) and 29 g of the chloro derivative III-1 (45.2 mmol) are dissolved in 400 ml of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 740 mg (1.81 mmol) of S-Phos and 830 mg (0.9 mmol) of Pd.sub.2(dba).sub.3 are added thereto, and then 6.5 g of sodium tert-butoxide (67.7 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 5 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The yield is 27 g (78% of theory). The solids are recrystallized from heptane/toluene and finally sublimed under high vacuum.

[0203] The following compounds are prepared in an analogous manner:

TABLE-US-00008 Reactant 1 Reactant 2 Product Yield 2-2 [00487] [00488] [00489] 78% 2-3 [00490] [00491] [00492] 71% 2-4 [00493] [00494] [00495] 82% 2-5 [00496] [00497] [00498] 89% 2-6 [00499] [00500] [00501] 69% 2-7 [00502] [00503] [00504] 88% 2-8 [00505] [00506] [00507] 85% 2-9 [00508] [00509] [00510] 75% 2-10 [00511] [00512] [00513] 75%

B) Use Examples

[0204] OLED devices according to the present application and comparative devices are produced in order to show the technical effects of the OLED devices of the invention. The OLEDs are produced according to the general method described in the working examples of published specification WO 2004/058911, unless stated otherwise below.

[0205] The OLEDs produced have glass plaques coated with structured ITO (indium tin oxide) in a thickness of 50 nm as substrates. The layers that follow the substrate, the thickness thereof and the substances of which they consist are listed separately for each example device in one of the tables which follow. The counterelectrode applied as the last layer is an aluminium layer in a thickness of 100 nm.

[0206] All materials are applied by thermal gas phase deposition in a vacuum chamber. In the examples, the emission layer always consists of at least one matrix material and an emitting compound as dopant. The latter is added to the matrix material(s) by coevaporation. An expression SMB:SEB (5%) means here that the material SMB is present in the layer in a proportion of 95% by volume, and the material SEB is present in the layer in a proportion of 5% by volume. Not just the emission layer but also other layers may analogously consist of a mixture of two or more materials.

[0207] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in %) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and the lifetime are determined. In that case, the expression EQE @ 40 mA/cm.sup.2 means, for example, the external quantum efficiency at an operating luminance of 40 mA/cm.sup.2. The lifetime is measured at 20 mA/cm.sup.2 for green-emitting devices, and at 60 mA/cm.sup.2 for blue-emitting devices. Assuming an exponential drop in the OLEDs, the LT80 values for the lifetime are then approximated with an acceleration factor of 1.8 to the lifetime at 1000 cd/m.sup.2. LT80 @ 1000 cd/m.sup.2 is then the approximated lifetime by which the OLED has dropped from a starting luminance of 1000 cd/m.sup.2 to a luminance of 800 cd/m.sup.2.

[0208] The chemical structures of the materials that are used in the examples are given in Table A. The synthesis of the spiroxantheneamines is effected as in the preceding Synthesis Examples section, or it can be effected as in the prior art, for example as disclosed in WO 2014/072017.

TABLE-US-00009 TABLE A [00514] [00515] [00516] [00517] [00518] [00519] [00520] [00521] [00522] [00523] [00524] [00525] [00526] [00527] [00528] [00529] [00530] [00531] [00532] [00533] [00534]

[0209] 1) Use of Spiroxantheneamines as HTL and HIL Materials

[0210] The following OLEDs C3 (comparative example) and I3, I5, I7, I9, I10, I14, I15 and I16 (inventive examples) are produced.

[0211] C3 as a comparative example comprises the compound HIM (a spirobifluorene derivative) as HTL and HIL material. The abovementioned use examples I3, I5, I7, I9, I10, I14, I15 and I16 comprise the materials HTM2, HTM4, HTM5, HTM6, HTM7, HTM8, HTM9, HTM13, HTM14 and HTM15 as HTL and HIL materials. Otherwise, the construction thereof is identical to that of C3 (Table 1).

[0212] For all the devices of the invention, a significant rise in lifetime is observed compared to example C3 (Table 2).

[0213] This shows the excellent suitability of the spiroxantheneamines as HIL and HTL materials, compared to the HTL/HIL material HIM according to the prior art.

TABLE-US-00010 TABLE 1 Structure of the OLEDs HIL HTL EBL EML ETL EIL Thick- Thick- Thick- Thick- Thick- Thick- ness/ ness/ ness/ ness/ ness/ ness/ Ex. nm nm nm nm nm nm C3 HIM: HIM HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I3 HTM2: HTM2 HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I5 HTM4: HTM4 HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I7 HTM6: HTM6 HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I9 HTM8: HTM8 HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I10 HTM9: HTM9 HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I14 HTM5: HTM13 HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I15 HTM6: HTM14 HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I16 HTM7: HTM15 HTMC2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm

TABLE-US-00011 TABLE 2 Data of the OLEDs U LT80 @ 10 mA/cm.sup.2 @ 1000 cd/m.sup.2 Ex. [V] [h] C3 3.8 4790 I3 4.4 6800 I5 4.3 4960 I7 3.8 5610 I9 4.3 5180 I10 4.2 7390 I14 3.9 5500 I15 3.8 6600 I16 4.0 7400

[0214] A comparison between OLEDs that differ merely by the fact that the spiroxantheneamines are present in the EBL rather than in the HTL/HIL is shown in Tables 3 and 4 below.

[0215] Table 3 shows the construction of the comparative OLEDs.

[0216] Table 4 shows the results of the direct comparisons with respect to one another. One line lists the data to be compared with one another in each case. In all cases, if the spiroxanthenes are present in the HIL/HTL, significantly higher lifetimes are obtained (examples on the right-hand side of Table 4).

[0217] This shows the advantages that are obtained through the use of the spiroxantheneamine compounds in the HIL and the HTL of OLEDs.

TABLE-US-00012 TABLE 3 Structure of the OLEDs HIL HTL EBL EML ETL EIL Thick- Thick- Thick- Thick- Thick- Thick- ness/ ness/ ness/ ness/ ness/ ness/ Ex. nm nm nm nm nm nm I17 HIM: HIM HTM2 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I19 HIM: HIM HTM4 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I21 HIM: HIM HTM6 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I23 HIM: HIM HTM8 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm I24 HIM: HIM HTM9 SMB: ETM: LiQ F4TCNQ(5%) 180 nm 10 nm SEB(5%) LiQ(50%) 1 nm 20 nm 20 nm 30 nm

TABLE-US-00013 TABLE 4 Data of the OLEDs U @ 10 mA/ LT80 LT80 U cm.sup.2 @ 1000 cd/m.sup.2 @ 1000 cd/m.sup.2 @ 10 mA/cm.sup.2 Ex. [V] [h] [h] [V] Ex. I17 3.9 3082 6800 4.4 E3 I19 3.8 2278 4960 4.3 E5 I21 3.9 2464 5610 3.8 E7 I23 3.7 3881 5180 4.3 E9 I24 3.7 4126 7390 4.2 E10

[0218] 2) Use of Spiroxanthenes Substituted by an Amino Group in the 1 Position as EBL Materials

[0219] The following OLEDs C1, C2, I1 and I2 are produced (for construction see Table 5).

[0220] C1 and C2 are comparative examples that use a 4-spirobifluoreneamine (HTMC2) as EBL material. C1 differs from C2 in that a different spirobifluoreneamine is used as HIL and HTL material (HTMC1 in C1, and HTMC2 in C2).

[0221] I1 is a direct comparison with C1. In I1, the spiroxantheneamine HTM1 is used as EBL material in place of the spirobifluoreneamine HTMC2. I2 is a direct comparison with C2. In I2, the spiroxantheneamine HTM1 is used as EBL material in place of the spirobifluoreneamine HTMC2.

[0222] Both for I1 and for I2, a significant relative rise in lifetime (LT80) is observed compared to examples C1 and C2. In parallel, there is an improvement in the efficiency of the OLEDs (Table 6).

[0223] This shows the technical effect which is achieved with 1-spiroxantheneamines, especially when used as EBL materials.

TABLE-US-00014 TABLE 5 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Thick- Thick- Thick- Thick- Thick- Thick- Thick- ness/ ness/ ness/ ness/ ness/ ness/ ness/ Ex. nm nm nm nm nm nm nm C1 HTMC1: HTMC1 HTMC2 H1:H2(29%): ETM ETM: LiQ F4TCNQ(5%) 220 nm 10 nm TEG(12%) 10 nm LiQ(50%) 1 nm 20 nm 30 nm 30 nm I1 HTMC1: HTMC1 HTM1 H1:H2(29%): ETM ETM: LiQ F4TCNQ(5%) 220 nm 10 nm TEG(12%) 10 nm LiQ(50%) 1 nm 20 nm 30 nm 30 nm C2 HTMC2: HTMC2 HTMC2 H1:H2(29%): ETM ETM: LiQ F4TCNQ(5%) 220 nm 10 nm TEG(12%) 10 nm LiQ(50%) 1 nm 20 nm 30 nm 30 nm I2 HTMC2: HTMC2 HTM1 H1:H2(29%): ETM ETM: LiQ F4TCNQ(5%) 220 nm 10 nm TEG(12%) 10 nm LiQ(50%) 1 nm 20 nm 30 nm 30 nm

TABLE-US-00015 TABLE 6 Data of the OLEDs U EQE LT80 @ 2 mA/cm.sup.2 @ 2 mA/cm.sup.2 @ 1000 cd/m.sup.2 Ex. [V] % [h] C1 3.1 17.4 53400 I1 3.3 18.0 69900 C2 3.2 17.7 69000 I2 3.5 17.9 76400