MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present application relates to compounds of formula (I), to processes for preparation thereof, and to the use thereof in electronic devices.

Claims

1.-18. (canceled)

19. A compound of the formula (I) ##STR00827## where the variables that occur are as follows: Z.sup.1 is the same or different at each instance and is selected from CR.sup.1 and CR.sup.3; Ar.sup.1 is an aryl group which has 6 to 20 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a heteroaryl group which has 5 to 20 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals; X.sup.1 is the same or different at each instance and is a divalent group selected from C(R.sup.4).sub.2, C(R.sup.4).sub.2C(R.sup.4).sub.2, CR.sup.4CR.sup.4 and Si(R.sup.4).sub.2; R.sup.1 is the same or different at each instance and is a group of the formula (N) ##STR00828## Ar.sup.L is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.5 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.5 radicals; Ar.sup.2 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.5 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.5 radicals; E is a single bond or a divalent group selected from the group consisting of C(R.sup.5).sub.2, Si(R.sup.5).sub.2, N(R.sup.5), O, and S; R.sup.2 is selected from H, D, F, C(O)R.sup.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, P(O)(R.sup.7).sub.2, OR.sup.7, S(O)R.sup.7, S(O).sub.2R.sup.7, 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 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.7 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.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sup.7, C(O)O, C(O)NR.sup.7, P(O)(R.sup.7), O, S, SO or SO.sub.2; R.sup.3, R.sup.4, R.sup.5 are the same or different at each instance and are selected from H, D, F, C(O)R.sup.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, P(O)(R.sup.7).sub.2, OR.sup.7, S(O)R.sup.7, S(O).sub.2R.sup.7, 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 or R.sup.4 or R.sup.5 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.7 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.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sup.7, C(O)O, C(O)NR.sup.7, NR.sup.7, P(O)(R.sup.7), O, S, SO or SO.sub.2; R.sup.6 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.7, CN, Si(R.sup.7).sub.3, P(O)(R.sup.7).sub.2, OR.sup.7, S(O)R.sup.7, S(O).sub.2R.sup.7, 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.6 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.7 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.7CCR.sup.7, CC, Si(R.sup.7).sub.2, CO, CNR.sup.7, C(O)O, C(O)NR.sup.7, NR.sup.7, P(O)(R.sup.7), O, S, SO or SO.sub.2; R.sup.7 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.8, CN, Si(R.sup.7).sub.3, N(R.sup.8).sub.2, P(O)(R.sup.8).sub.2, OR.sup.8, S(O)R.sup.8, S(O).sub.2R.sup.8, 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.7 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.8 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.8CCR.sup.8, CC, Si(R.sup.8).sub.2, CO, CNR.sup.8, C(O)O, C(O)NR.sup.8, NR.sup.8, P(O)(R.sup.8), O, S, SO or SO.sub.2; R.sup.8 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.8 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; k is 0 or 1, where, in the case that k=0, the Ar.sup.L group is absent and the nitrogen atom of the group of the formula (N) constitutes the attachment position; m is 0 or 1, where, in the case that m=0, the E group is absent and the Ar.sup.2 groups are not bonded to one another; i is 0 or 1, where, in the case that i=0, the R.sup.1 group is absent; and where there is at least one Z.sup.1 group that is CR.sup.1.

20. The compound according to claim 19, wherein either i) one Z.sup.1 group is CR.sup.1, and the two other Z.sup.1 groups are CR.sup.3, or ii) two Z.sup.1 groups are CR.sup.1, and the other Z.sup.1 group is CR.sup.3.

21. The compound according to claim 19, wherein the Z.sup.1 group in the meta position to the bond to X.sup.1 is CR.sup.1.

22. The compound according to claim 19, wherein Ar.sup.1 is selected from phenyl and naphthyl groups that may each be substituted by one or more R.sup.3 radicals.

23. The compound according to claim 19, wherein the X.sup.1 is C(R.sup.4).sub.2.

24. The compound according to claim 19, wherein the group of Ar.sup.2 that binds directly to the nitrogen atom is an aromatic ring system.

25. The compound according to claim 19, wherein m=0.

26. The compound according to claim 19, wherein m=1, and the unit ##STR00829## from the group of the formula (N) is selected from the following groups: ##STR00830## ##STR00831## ##STR00832## ##STR00833## ##STR00834## ##STR00835## where the groups may each be substituted by an R.sup.5 radical at their unoccupied positions and where the dashed bonds represent the bonds to the rest of the formula.

27. The compound according to claim 19, wherein R.sup.2 is H.

28. The compound according to claim 19, wherein R.sup.6 is H.

29. The compound according to claim 19, wherein the compounds corresponds to one of the following formulae (I-1) to (I-9): ##STR00836## ##STR00837## where the variables that occur are as defined in claim 19, and where the compounds may each be substituted by an R.sup.3 or R.sup.6 radical at the unoccupied positions on the aromatic rings.

30. A process for preparing the compound of formula (I) according to claim 19, which comprises reacting a benzene compound that bears two carboxylic ester groups, an aromatic or heteroaromatic ring system and a reactive group in a Suzuki reaction with a benzene compound that contains a boronic acid group and a group selected from reactive groups, diarylamino groups, diarylaminoaryl groups and diarylaminoheteroaryl groups.

31. An oligomer, polymer or dendrimer containing one or more compounds of formula (I) according to claim 19, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any position substituted by R.sup.1, R.sup.2, R.sup.3, R.sup.4 or R.sup.5 in formula (I).

32. A formulation comprising at least one compound according to claim 19 and at least one solvent.

33. A formulation comprising at the polymer, oligomer or dendrimer according to claim 31 and at least one solvent.

34. An electronic device comprising at least one compound according to claim 19.

35. An electronic device comprising the polymer, oligomer or dendrimer according to claim 31.

36. The electronic device according to claim 34, wherein the electronic device is an organic electroluminescent device comprising anode, cathode and at least one emitting layer, where it is at least one organic layer of the device selected from emitting layers and hole-transporting layers that comprises the at least one compound.

37. The organic electroluminescent device according to claim 36, comprising anode, cathode and at least one emitting layer, characterized in that the at least one compound is present in an electron blocker layer.

Description

EXAMPLES

A) Synthesis Examples

Example 1-1: Synthesis of the Inventive Compound 1-1 and Variants

[0149] ##STR00464##

[0150] Intermediate 1-1

[0151] 10 g of phenylboronic acid (81 mmol) and 30 g of dibromodicarboxylic ester (CAS No. 18013-97-3) (77 mmol) are suspended in 750 ml of THF. 160 ml of 2 M potassium carbonate solution are slowly added dropwise. The solution is degassed and saturated with N.sub.2. Thereafter, 0.89 g (0.8 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. The remaining residue is purified by means of column chromatography. The yield is 15.3 g (52% of theory).

[0152] Intermediate 11-1

[0153] 7 g of 4-chlorophenylboronic acid (44.6 mmol) and 15.3 g of the bromo derivative I-1 (40.56 mmol) are suspended in 300 ml of THF. 81 ml of 1 M potassium carbonate solution are slowly added dropwise. The solution is degassed and saturated with N.sub.2. Thereafter, 0.45 g (0.4 mmol) of Pd(Ph.sub.3P).sub.4 are added. The reaction mixture is heated to boiling under a protective atmosphere for 12 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 14.5 g (80% of theory).

[0154] Analogously, the following compounds are prepared (yield 30-90% of theory):

TABLE-US-00006 Boronic acid Boronic acid Reactant 1 derivative 1 derivative 2 Product II-2 [00465] [00466] [00467] [00468] II-3 [00469] [00470] [00471] II-4 [00472] [00473] [00474] [00475] II-5 [00476] [00477] [00478] [00479] II-6 [00480] [00481] [00482] [00483] II-7 [00484] [00485] [00486] [00487] II-8 [00488] [00489] [00490] [00491] II-9 [00492] [00493] [00494] [00495] II-10 [00496] [00497] [00498] [00499] II-11 [00500] [00501] [00502] [00503] II-12 [00504] [00505] [00506] [00507] II-13 [00508] [00509] [00510] [00511] II-14 [00512] [00513] [00514] [00515] II-15 [00516] [00517] [00518] [00519] II-16 [00520] [00521] [00522] [00523] II-17 [00524] [00525] [00526] [00527] II-18 [00528] [00529] [00530] [00531] II-19 [00532] [00533] [00534] [00535] II-20 [00536] [00537] [00538] [00539] II-21 [00540] [00541] [00542] [00543] II-22 [00544] [00545] [00546] [00547] II-23 [00548] [00549] [00550] [00551] II-24 [00552] [00553] [00554] [00555] II-25 [00556] [00557] [00558] [00559] II-26 [00560] [00561] [00562] [00563]

[0155] Intermediate III-1

[0156] 14.0 g (34.2 mmol) of intermediate II-1 are dissolved in a baked-out flask in 250 ml of dried THF. The solution is saturated with N.sub.2. The clear solution is cooled down to 5 C. and then 68.5 ml (205 mmol) of a 3M methylmagnesium chloride solution are added. The reaction mixture is gradually warmed to room temperature and then quenched with ammonium chloride. The mixture is subsequently partitioned between ethyl acetate and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation.

[0157] The solution that has been concentrated by rotary evaporation is dissolved in toluene, and 6.6 g of Amberlyst 15 are added. The mixture is heated to 110 C. and kept at this temperature for 8 h. During this time, a white solid precipitates out. The mixture is then cooled to room temperature, and the precipitated solid is filtered off with suction and washed with heptane. The residue is dried at 40 C. under reduced pressure. After the crude product has been filtered through silica gel with heptane:ethyl acetate (1:1), 10.2 g (86% of theory) of the product III-1 are obtained.

[0158] Analogously, the following compounds are prepared (yields 50-95% of theory):

TABLE-US-00007 Reactant 1 Reactant2 Product III-2 [00564] MeMgBr [00565] III-3 [00566] MeMgBr [00567] III-4 [00568] MeMgCl [00569] III-5 [00570] MeMgCl [00571] III-6 [00572] MeMgCl [00573] III-7 [00574] MeMgBr [00575] III-8 [00576] MeMgCl [00577] III-9 [00578] MeMgCl [00579] III-10 [00580] MeLi [00581] III-11 [00582] MeMgBr [00583] III-12 [00584] MeMgCl [00585] III-13 [00586] MeMgCl [00587] III-14 [00588] MeMgCl [00589] III-15 [00590] MeMgCl [00591] III-16 [00592] MeMgBr [00593] III-17 [00594] MeLi [00595] III-18 [00596] MeMgCl [00597] III-19 [00598] EtMgBr [00599] III-20 [00600] i-PrMgBr [00601] III-21 [00602] i-OctMgBr [00603] III-22 [00604] PhLi [00605] III-23 [00606] MeMgBr [00607] III-24 [00608] MeMgBr [00609] III-25 [00610] MeMgCl [00611] 1-33 [00612] MeMgBr [00613] 1-34 [00614] MeMgBr [00615] 2-18 [00616] MeMgCl [00617] 2-19 [00618] MeMgBr [00619] #: Compounds can be separated by chromatography or by means of recrystallization.

[0159] Compound 1-1

[0160] 14.6 g of 4-biphenyl(9,9-dimethyl-9H-fluoren-2-yl)amine (40.6 mmol) and 14 g of the intermediate III-1 (40.6 mmol) are dissolved in 400 ml of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 0.33 g (0.81 mmol) of S-Phos and 0.46 g (1.75 mmol) of Pd.sub.2(dba).sub.3 are added thereto, and then 5.85 g of sodium tert-butoxide (80.9 mol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 6 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 20 g (75% of theory). Finally, the material is sublimed under high vacuum. The purity is 99.9%.

[0161] Analogously, the following compounds are prepared (yields 20-80% of theory):

TABLE-US-00008 Reactant 1 Reactant 2 Product 1-2 [00620] [00621] [00622] 1-3 [00623] [00624] [00625] 1-4 [00626] [00627] [00628] 1-5 [00629] [00630] [00631] 1-6 [00632] [00633] [00634] 1-7 [00635] [00636] [00637] 1-8 [00638] [00639] [00640] 1-9 [00641] [00642] [00643] 1-10 [00644] [00645] [00646] 1-11 [00647] [00648] [00649] 1-12 [00650] [00651] [00652] 1-13 [00653] [00654] [00655] 1-14 [00656] [00657] [00658] 1-15 [00659] [00660] [00661] 1-16 [00662] [00663] [00664] 1-17 [00665] [00666] [00667] 1-18 [00668] [00669] [00670] 1-19 [00671] [00672] [00673] [00674] 1-20 [00675] [00676] [00677] 1-21 [00678] [00679] [00680] 1-22 [00681] [00682] [00683] 1-23 [00684] [00685] [00686] [00687] 1-24 [00688] [00689] [00690] 1-25 [00691] [00692] [00693] 1-26 [00694] [00695] [00696] 1-27 [00697] [00698] [00699] 1-28 [00700] [00701] [00702] 1-29 [00703] [00704] [00705] 1-30 [00706] [00707] [00708] 1-31 [00709] [00710] [00711] 1-32 [00712] [00713] [00714] 1-35 [00715] [00716] [00717] 1-36 [00718] [00719] [00720] 1-37 [00721] [00722] [00723] 1-38 [00724] [00725] [00726] 1-39 [00727] [00728] [00729] 1-40 [00730] [00731] [00732] 1-41 [00733] [00734] [00735] 1-42 [00736] [00737] [00738] #: Compounds can be separated by chromatography or by means of recrystallization. [00739]

Example 2-1

[0162] Synthesis of the Inventive Compound 2-1 and Variants

##STR00740##

[0163] 19.6 g (34.8 mmol) of the pinacolboronic ester derivative (CAS No.: 1616632-73-5) and 12.05 g (45 mmol) of intermediate III-1 are suspended in 350 ml of dioxane and 10.6 g of caesium fluoride (69.9 mmol). 1.02 g (1.39 mmol) of bis(tricyclohexylphosphine)palladium dichloride are added to this suspension, and the reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 80 ml of water and then concentrated to dryness. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The yield is 20 g (78% of theory). Finally, the material is sublimed under high vacuum. The purity is 99.9%.

[0164] Analogously, the following compounds are prepared (yields 60-85% of theory):

TABLE-US-00009 Reactant 2 Reactant 2 Product 2-2 [00741] [00742] [00743] 2-3 [00744] [00745] [00746] 2-4 [00747] [00748] [00749] 2-5 [00750] [00751] [00752] 2-6 [00753] [00754] [00755] 2-7 [00756] [00757] [00758] 2-8 [00759] [00760] [00761] 2-9 [00762] [00763] [00764] 2-10 [00765] [00766] [00767] 2-11 [00768] [00769] [00770] 2-12 [00771] [00772] [00773] 2-13 [00774] [00775] [00776] 2-14 [00777] [00778] [00779] 2-15 [00780] [00781] [00782] 2-16 [00783] [00784] [00785] 2-17 [00786] [00787] [00788] 2-19 [00789] [00790] [00791]

B) Device Examples

[0165] Example OLEDs are produced according to the following general method:

[0166] The substrates used are glass plaques coated with a 50 nm-thick layer of structured ITO (indium tin oxide). The following layer structure is applied thereto: hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/electron transport layer (ETL) electron injection layer (EIL)/cathode. The cathode consists of an aluminium layer of thickness 100 nm. The materials that are used in the corresponding layers of the example OLEDs are specified in Table 1, and the chemical structures of these materials are listed in Table 3.

[0167] The materials are applied by means of thermal gas phase 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 added to the matrix material(s) in a particular proportion by volume by coevaporation. The expression TMM:TEG (12%) means here that the TMM material is present in the layer in a proportion by volume of 88%, and that the TEG material is present in a proportion by volume of 12%. The same applies to layers other than the emitting layer. These may likewise correspondingly contain two or more materials.

[0168] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra and the external quantum efficiency (EQE, measured in %), as a function of luminance, calculated from current flow-voltage-luminance characteristics (IUL characteristics), are determined. This is done assuming Lambertian emission characteristics. In addition, the operating voltage is determined (U, in V).

[0169] EQE @ 10 mA/cm.sup.2 is the external quantum efficiency at an operating current density of 10 mA/cm.sup.2. LT80 @ 40 mA/cm.sup.2 is the time until the initial luminance of 5000 cd/m.sup.2 of an OLED has dropped to 80% of this luminance, i.e. to 4000 cd/m.sup.2, without taking account of any acceleration factor.

[0170] B-1) Use of the Compounds of the Invention in Green-Fluorescing OLEDs

[0171] OLED examples E-0 to E-17 have the layer structure shown in Table 1, with one of the inventive compounds EBL-0 to EBL-17 (Table 3) present in the EBL in each case.

[0172] In all cases, the OLEDs of the invention achieve good results with regard to operating voltage, lifetime and EQE (Table 2).

TABLE-US-00010 TABLE 1 Device construction HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm E-0 HTM:p-dopant HTM EBL-0 TMM-1:TMM-2 ETM:LiQ (50%) LiQ (5%) 220 nm 10 nm (28%):TEG (12%) 30 nm 1 nm 20 nm 30 nm E-1 * * EBL-1 * * * 10 nm E-2 * * EBL-2 * * * 10 nm E 3 * * EBL-3 * * * 10 nm E-4 * * EBL-4 * * * 10 nm E-5 * * EBL-5 * * * 10 nm E-6 * * EBL-6 * * * 10 nm E-7 * * EBL-7 * * * 10 nm E-8 * * EBL-8 * * * 10 mil E-9 * * EBL-9 * * * 10 nm E-10 * * EBL-10 * * * 10 nm E-15 * * EBL-15 * * * 10 nm E-16 * * EBL-16 * * * 10 nm E-17 * * EBL-17 * * * 10 nm

TABLE-US-00011 TABLE 2 Data of the OLEDs U EQE @ 10 mA/cm.sup.2 LT80 @ 40 mA/cm.sup.2 Example [V] [%] [h] E-0 3.9 >16.5 >250 E-1 3.7 >16.0 >300 E-2 4.1 >17.0 >300 E-3 4.1 >18.0 >200 E-4 4.1 >16.0 >250 E-5 4.0 >16.5 >200 E-6 4.0 >17.0 >250 E-7 3.9 >15.5 >250 E-8 3.8 >15.0 >250 E-9 4.1 >15.5 >300 E-10 4.0 >17.0 >250 E-15 4.2 >16.0 >350 E-16 4.1 >16.0 >250 E-17 4.1 >14.0 >300

TABLE-US-00012 TABLE 3 Materials used [00792] [00793] [00794] [00795] [00796] [00797] [00798] [00799] [00800] [00801] [00802] [00803] [00804] [00805] [00806] [00807] [00808] [00809] [00810] [00811] [00812] [00813]

[0173] B-2) Comparison of the Inventive Compounds EBL-12, EBL-13 and EBL-14 with Compound EBL-11 According to the Prior Art

[0174] OLED examples E-12, E-13 and E-14 each contain one of the inventive compounds EBL-12, EBL-13 and EBL-14 in the electron blocker layer. Comparative example OLED E-11 contains the compound EBL-11 in the electron blocker layer. Higher values for EQE are found for the OLEDs E-12, E-13 and E-14 than in the case of the comparative OLED Ell. More particularly, in the case of the inventive OLED E-14, an EQE@ 10 mA/cm.sup.2 of more than 16% is obtained, whereas, in the case of comparative example E-11, an EQE@ 10 mA/cm.sup.2 of less than 15% is obtained, at a voltage in both cases of 4.1 V.

TABLE-US-00013 TABLE 1b Device construction HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm E-11 HTM:p-dopant (5%) HTM EBL-11 TMM-1:TMM-2 ETM:LiQ (50%) LiQ 20 nm 220 nm 10 nm (28%):TEG (12%) 30 nm 1 nm 30 nm E-12 * * EBL-12 * * * 10 nm E-13 * * EBL-13 * * * 10 nm E-14 * * EBL-14 * * * 10 nm

TABLE-US-00014 TABLE 3b Materials used [00814] [00815] [00816] [00817]

[0175] B-3) Use of the Compounds of the Invention in Blue-Fluorescing OLEDs

[0176] OLED examples E-19 and E-20 have the layer structure shown in Table 1c, with one of the inventive compounds EBL-15 or EBL-16 (see Table 3c) present in the EBL in each case.

[0177] In all cases; the OLEDs of the invention achieve good results with regard to operating voltage, lifetime and EQE (Table 2c).

TABLE-US-00015 TABLE 1c Device construction HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm E-19 HTM:p-dopant HTM EBL-15 SMB-1:SEB-1 ETM:LiQ (50%) LiQ (5%) 180 nm 10 nm (5%) 30 nm 1 nm 20 nm 20 nm E-20 * * EBL-16 * * * 10 nm

TABLE-US-00016 TABLE 2c Data of the OLEDs U EQE @ 10 mA/cm.sup.2 LT80 @ 60 mA/cm.sup.2 Example [V] [%] [h] E-19 4.0 about 8.5 about 350 E-20 4.0 about 8.5 about 350

TABLE-US-00017 TABLE 3c Materials used [00818] [00819] [00820] [00821] [00822] [00823] [00824] [00825] [00826]