MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

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

Claims

1.-11. (canceled)

12. A compound of formula (1) ##STR00529## where the symbols and indices used are as follows: X is the same or different at each instance and is CR or N; W is CR1 or N; Y is N or CR when p+r=0 and C when p+r0; L.sup.1, L.sup.2, L.sup.3, L.sup.4 are the same or different at each instance and are a bivalent aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4 at each instance are an aromatic or heteroaromatic ring system which has 6 to 60 aromatic ring atoms and may in each case also be substituted by one or more R.sup.2 radicals; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system, preferably an aryl or heteroaryl group, which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals; R, R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.3).sub.2, N(Ar).sub.2, C(O)Ar, P(O)Ar.sub.2, S(O)Ar, S(O).sub.2Ar, CR.sup.3CR.sup.3Ar, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.sup.3, P(O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more R.sup.2 substituents together with the atoms to which they are bonded and also with one another, or two adjacent R substituents, may form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.1 at each instance is H, D, F, Cl, Br, I, N(R.sup.5).sub.2, CN, NO.sub.2, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group which has 3 to 40 carbon atoms and may be substituted in each case by one or more R.sup.5 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CNR.sup.5, P(O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2; R3 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R4).sub.2, C(O)Ar, P(O)Ar2, S(O)Ar, S(O).sub.2Ar, CR.sup.3CR.sup.3Ar, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.sup.4, P(O)(R.sup.4), SO, SO.sub.2, NR.sup.4, O, S or CONR.sup.4 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals, or a combination of these systems; R.sup.4 is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aryl or heteroaryl group which has 5 to 40 ring atoms and may be substituted by one or more R.sup.5 radicals, or a combination of these groups; R.sup.5 is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms; q is the same or different at each instance and is 0 or 1; r is 0 or 1; p is 0 or 1, where pr; where Ar.sup.1 and Ar.sup.2 do not comprise any structure of formula (2): ##STR00530## where * indicates the bond to L.sup.1 or L.sup.2 or the base skeleton; and at least two groups selected from the (L.sup.1).sub.qAr.sup.1, (L.sup.2).sub.qAr.sup.2, and (L.sup.3).sub.r(Ar.sup.3).sub.p groups are the same.

13. The compound as claimed in claim 12, wherein the compound corresponds to the formula (3) ##STR00531## where Y is CR when p+r=0 and C when p+r0, and the further symbols and indices used have the definitions given in claim 12.

14. The compound as claimed in claim 12, wherein the compound is a compound of one of the formulae (4) to (7): ##STR00532## where the symbols and indices used have the definitions given in claim 12.

15. The compound as claimed in claim 12, wherein R.sup.1 is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms.

16. The compound as claimed in claim 12, wherein R is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms.

17. A process for preparing The compound as claimed in claim 12, wherein the compound of the formula (1) is formed by one or more coupling reactions and/or cyclizations.

18. A mixture comprising at least one compound as claimed in claim 12 and at least one fluorescent or phosphorescent dopant.

19. A formulation comprising at least one compound as claimed in claim 12 and one or more solvents.

20. A formulation comprising the mixture as claimed in claim 18 and one or more solvents.

21. A solution, a suspension or a miniemulsion comprising at least one compound as claimed in claim 12 one or more solvents.

22. A solution, a suspension or a miniemulsion comprising the mixture as claimed in claim 18 and one or more solvents.

23. An electronic device which comprises the compound as claimed in claim 12.

24. An electronic device which comprises the mixture as claimed in claim 18.

25. The electronic device as claimed in claim 23, wherein the device is selected from the group consisting of organic electroluminescent device, organic integrated circuit, organic field-effect transistor, organic thin-film transistor, organic light-emitting transistor, organic solar cell, organic dye-sensitized solar cell, organic optical detector, organic photoreceptor, organic field-quench device, light-emitting electrochemical cell, organic laser diode and organic plasmon emitting device.

26. An organic electroluminescent device comprising the compound as claimed in claim 12 is used as matrix material for a fluorescent or phosphorescent compound in an emitting layer and/or in a hole transport layer and/or in an electron blocker layer.

Description

WORKING EXAMPLES

A) Synthesis Examples

[0122] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. For the compounds known from the literature, the corresponding CAS numbers are also reported in each case.

Example 1

3,3-(5-chloro-1,3-phenylene)bis[9-phenyl-9H-carbazole]

[0123] ##STR00117##

[0124] 50 g (185 mmol) of 1,3-dibromo-5-chlorobenzene, 143 g (388 mmol) of phenylboronic acid and 78 g (369 mmol) of potassium phosphate are suspended in 250 mL of water and 500 mL of dioxane. 830 mg (3.6 mmol) of Pd(OAC).sub.2 and 3.3 g (11 mmol) of P(o-Tol).sub.3 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. The mixture is subsequently partitioned between ethyl acetate 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 recrystallized from heptane/toluene. The yield is 104 g (175 mmol, 95%).

[0125] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00001 Reactant Reactant 1 2 Product Yield 1a [00118] [00119] [00120] 89% 1b [00121] [00122] [00123] 88% 1c [00124] [00125] [00126] 75% 1e [00127] [00128] [00129] 78% 1f [00130] [00131] [00132] 69% 1g [00133] [00134] [00135] 89% 1h [00136] [00137] [00138] 87% 1i [00139] [00140] [00141] 82% 1j [00142] [00143] [00144] 87% 1k [00145] [00146] [00147] 88% 1l [00148] [00149] [00150] 85% 1i [00151] [00152] [00153] 78% 1j [00154] [00155] [00156] 77%

Example 2

3,3-[5(4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl-2yl)-1,3-phenylene]bis[9-phenyl-9H-carbazole]

[0126] ##STR00157##

[0127] 75 g (126 mmol) of 3,3-(5-chloro-1,3-phenylene)bis[9-phenyl-9H-carbazole], 41 g (163 mmol) of bis(pinacolato)diboron and 18 g (25 mmol) of tricyclohexylphosphinepalladium dichloride and 21 g (214 mmol) of potassium acetate are suspended in 1200 mL of dioxane. The reaction mixture is heated under reflux at 130 C. for 16 h. The mixture is subsequently partitioned between ethyl acetate 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 recrystallized from heptane/toluene. The yield is 76 g (110 mmol, 88%).

[0128] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00002 Reactant 1 Product Yield 2a [00158] [00159] 77% 2b [00160] [00161] 78% 2c [00162] [00163] 65% 2d [00164] [00165] 82% 2e [00166] [00167] 86% 2f [00168] [00169] 90% 2h [00170] [00171] 93% 2i [00172] [00173] 81% 2j [00174] [00175] 90% 2k [00176] [00177] 96% 2l [00178] [00179] 87% 2m [00180] [00181] 95% 2n [00182] [00183] 97% 2o [00184] [00185] 86% 2p [00186] [00187] 88% 2q [00188] [00189] 73% 2r [00190] [00191] 70% 2s [00192] [00193] 79% 2t [00194] [00195] 75% 2u [00196] [00197] 78% 2v [00198] [00199] 69% 2w [00200] [00201] 74% 2x [00202] [00203] 86% 2z [00204] [00205] 89% 2aa [00206] [00207] 76%

Example 3

Reaction with 1-bromo-2-nitrobenzene

[0129] ##STR00208##

[0130] 46 g (67 mmol) of 3,3-[5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl-2-yl)-1,3-phenylene]bis[9-phenyl-9H-carbazole], 16 g (81 mmol) of 1-bromo-2-nitrobenzene and 152 mg (0.67 mmol) of Pd(OAC).sub.2 and 178 mg (0.67 mmol) of P(o-Tol).sub.3 and 136 g (980 mmol) of potassium carbonate are suspended in 1000 mL of THF and 300 mL of water. The reaction mixture is heated under reflux at 130 C. for 16 h. The mixture is subsequently partitioned between ethyl acetate 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 recrystallized from heptane/toluene. The yield is 42 g (62 mmol, 91%).

[0131] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00003 Reactant 1 Reactant 2 3a [00209] [00210] 3b [00211] [00212] 3c [00213] [00214] 3d [00215] [00216] 3e [00217] [00218] 3f [00219] [00220] 3h [00221] [00222] 3i [00223] [00224] 3j [00225] [00226] 3k [00227] [00228] 3l [00229] [00230] 3m [00231] [00232] 3n [00233] [00234] 3o [00235] [00236] 3p [00237] [00238] 3q [00239] [00240] 3r [00241] [00242] 3s [00243] [00244] 3t [00245] [00246] 3u [00247] [00248] 3v [00249] [00250] 3w [00251] [00252] 3x [00253] [00254] 3z [00255] [00256] 3aa [00257] [00258] 3ab [00259] [00260] Product Yield 3a [00261] 90% 3b [00262] 92% 3c [00263] 97% 3d [00264] 91% 3e [00265] 93% 3f [00266] 94% 3h [00267] 91% 3i [00268] 96% 3j [00269] 95% 3k [00270] 93% 3l [00271] 92% 3m [00272] 95% 3n [00273] 98% 3o [00274] 90% 3p [00275] 93% 3q [00276] 87% 3r [00277] 86% 3s [00278] 89% 3t [00279] 78% 3u [00280] 91% 3v [00281] 76% 3w [00282] 77% 3x [00283] 89% 3z [00284] 94% 3aa [00285] 78% 3ab [00286] 87%

Example 4

9,9-Diphenyl-9H,9H,9H-[3,1; 3,3]tercarbazole

[0132] ##STR00287##

[0133] A mixture of 40 g (59 mmol) of the appropriate nitroaromatic and 239 mL (1400 mmol) of triethyl phosphite is heated under reflux to 130 C. for 12 h. Subsequently, the rest of the triethyl phosphite is distilled off (72-76 C./9 mmHg). Water/MeOH (1:1) is added to the residue, and the solids are filtered off and recrystallized. The yield is 38 g (58 mol, 99%).

[0134] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00004 Reactant 1 Product Yield 4a [00288] [00289] 89% 4b [00290] [00291] 90% 4c [00292] [00293] 91% 4d [00294] [00295] 96% 4e [00296] [00297] 94% 4f [00298] [00299] 97% 4h [00300] [00301] 93% 4i [00302] [00303] 95% 4j [00304] [00305] 99% 4k [00306] [00307] 93% 4l [00308] [00309] 92% 4m [00310] [00311] 93% 4n [00312] [00313] 97% 4o [00314] [00315] 91% 4p [00316] [00317] 87% 4q [00318] [00319] 69% 4r [00320] [00321] 86% 4s [00322] [00323] 83% 4t [00324] [00325] 80% 4u [00326] [00327] 90% 4v [00328] [00329] 77% 4w [00330] [00331] 75% 4x [00332] [00333] 83% 4z [00334] [00335] 69% 4aa [00336] [00337] 85%

Example 5

9,9,9-Triphenyl-9H,9H,9H-[3,1; 3; 3]tercarbazole

[0135] ##STR00338##

[0136] 25 g (38 mmol) of 9,9-diphenyl-9H,9H,9H-[3,1;3,3]tercarbazole and 7 g (46 mmol) of bromobenzene are dissolved in 450 mL of toluene and degassed by means of a protective gas inlet. This is followed by addition of 7 mL (7 mmol, 1 M solution in toluene) of tri-tert-butylphosphine, 633.8 mg (2.82 mmol) of Pd(OAc).sub.2 and 7 g (76 mmol) of NaOtBu. The solids are degassed beforehand, and the reaction mixture is post-degassed and then stirred under reflux for 3 h. The warm reaction solution is filtered through Alox B (activity level 1), washed with water, dried and concentrated. The yield is 27 g (37 mol, 98%).

[0137] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00005 Reactant 1 Reactant 2 Product Yield 5a [00339] [00340] [00341] 89% 5b [00342] [00343] [00344] 87% 5c [00345] [00346] [00347] 91% 5d [00348] [00349] [00350] 90% 5e [00351] [00352] [00353] 79% 5f [00354] [00355] [00356] 78% 5h [00357] [00358] [00359] 92% 5i [00360] [00361] [00362] 91% 5j [00363] [00364] [00365] 95% 5k [00366] [00367] [00368] 96% 5l [00369] [00370] [00371] 93% 5m [00372] [00373] [00374] 94% 5n [00375] [00376] [00377] 97% 5o [00378] [00379] [00380] 85% 5p [00381] [00382] [00383] 89% 5q [00384] [00385] [00386] 87% 5r [00387] [00388] [00389] 76% 5s [00390] [00391] [00392] 79% 5t [00393] [00394] [00395] 73% 5u [00396] [00397] [00398] 88% 5v [00399] [00400] [00401] 87% 5w [00402] [00403] [00404] 83% 5x [00405] [00406] [00407] 87% 5z [00408] [00409] [00410] 94% 5aa [00411] [00412] [00413] 86% 5ab [00414] [00415] [00416] 87% 5ac [00417] [00418] [00419] 95% 5ad [00420] [00421] [00422] 92% 5ae [00423] [00424] [00425] 90% 5af [00426] [00427] [00428] 86%

Example 6

6-Bromo-1,3-diphenyl-9H-carbazole

[0138] ##STR00429##

[0139] 12.7 g (40 mmol) of 1,3-diphenyl-9H-carbazole are suspended in 450 mL of acetonitrile and, at 20 C., 7.15 g (40 mmol) of N-bromosuccinimide are added in portions, in such a way that the reaction temperature does not rise above 20 C. The mixture is stirred for a further 18 h, in the course of which the reaction mixture is warmed to room temperature. The reaction mixture is then concentrated by rotary evaporation, dissolved in dichloromethane and washed with water. The mixture is dried, concentrated and then recrystallized twice from toluene. The yield is 12 g (30 mol, 76%).

[0140] In an analogous manner, it is possible to obtain the following

compounds:

TABLE-US-00006 Reactant 1 Product Yield 6a [00430] [00431] 70% 6b [00432] [00433] 86% 6c [00434] [00435] 76% 6d [00436] [00437] 78%

Example 7

1,3-Diphenyl-6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-9H-carbazole

[0141] ##STR00438##

[0142] 50 g (125 mmol) of 6-bromo-1,3-diphenyl-9H-carbazole, 40 g (161 mmol) of bis(pinacolato)diboron and 18 g (25 mmol) of tricyclohexylphosphinepalladium dichloride and 21 g (214 mmol) of potassium acetate are suspended in 1200 mL of dioxane. The reaction mixture is heated under reflux at 130 C. for 16 h. The mixture is subsequently partitioned between ethyl acetate 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 recrystallized from heptane/toluene. The yield is 48 g (108 mmol, 86%).

[0143] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00007 Reactant 1 Product Yield 7a [00439] [00440] 82%

Example 8

6-(4-Dibenzofuran-4-ylphenyl)-1,3-diphenyl-9H-carbazole

[0144] ##STR00441##

[0145] 30 g (68 mmol) of 1,3-diphenyl-6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-9H-carbazole, 26 g (81 mmol) of 4-(4-bromophenyl)dibenzofuran and 152 mg (0.67 mmol) of Pd(OAC).sub.2 and 178 mg (0.67 mmol) of P(o-Tol).sub.3 and 136 g (980 mmol) of potassium carbonate are suspended in 1000 mL of THF and 300 mL of water. The reaction mixture is heated under reflux at 130 C. for 16 h. The mixture is subsequently partitioned between ethyl acetate 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 recrystallized from heptane/toluene. The yield is 34 g (60 mmol, 90%).

[0146] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00008 Reactant 1 Reactant 1 Product Yield 8a [00442] [00443] [00444] 81% 8b [00445] [00446] [00447] 80% 8c [00448] [00449] [00450] 86% 8d [00451] [00452] [00453] 84% 8e [00454] [00455] [00456] 88% 8f [00457] [00458] [00459] 89% 8g [00460] [00461] [00462] 80% 8h [00463] [00464] [00465] 83%

Example 9

[0147] Analogously to example 5, it is possible to use the corresponding carbazole derivatives to prepare the following compounds:

TABLE-US-00009 Reactant 1 Reactant 1 Product Yield 9a [00466] [00467] [00468] 83% 9b [00469] [00470] [00471] 82% 9c [00472] [00473] [00474] 80% 9d [00475] [00476] [00477] 69% 9e [00478] [00479] [00480] 78%

[0148] Analogously to example 5, it is possible to use 0.5 eq of the corresponding carbazole derivative to prepare the following compounds:

TABLE-US-00010 Reactant 1 Reactant 1 Product Yield 9f [00481] [00482] [00483] 77% 9g [00484] [00485] [00486] 75% 9h [00487] [00488] [00489] 74% 9i [00490] [00491] [00492] 73% 9j [00493] [00494] [00495] 77%

Production of the OLEDs

[0149] In examples C1 to 120 which follow (see Tables 2 and 3), the data of various OLEDs are presented.

Pretreatment for Examples C1-I20:

[0150] Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm, for improved processing, are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS P VP Al 4083 from Heraeus Precious Metals GmbH, Germany, spun on from aqueous solution). These coated glass plaques form the substrates to which the OLEDs are applied.

[0151] The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/optional interlayer (IL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 2. The materials required for production of the OLEDs are shown in Table 1.

[0152] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer 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 co-evaporation. Details given in such a form as ST2:L1:TEG1 (55%:35%:10%) mean here that the material ST2 is present in the layer in a proportion by volume of 55%, L1 in a proportion of 35% and TEG1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0153] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. The parameter U1000 in Table 3 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L.sub.1 in the course of operation with constant current. A figure of L.sub.0; j.sub.0=4000 cd/m.sup.2 and L.sub.1=70% in Table 3 means that the lifetime reported in the LT column corresponds to the time after which the starting luminance falls from 4000 cd/m.sup.2 to 2800 cd/m.sup.2. Analogously, L.sub.0; j.sub.0=20 mA/cm.sup.2, L.sub.1=80% means that the luminance in the course of operation at 20 mA/cm.sup.2 falls to 80% of its starting value after the time LT.

[0154] The data for the various OLEDs are collated in Table 3. Examples C1 and C2 are comparative examples according to the prior art; examples 11 to 120 show data of OLEDs of the invention.

[0155] Some of the examples are elucidated in detail hereinafter, in order to illustrate the advantages of the OLEDs of the invention.

Use of Mixtures of the Invention in the Hole Transport Layer of Phosphorescent OLEDs

[0156] The materials of the invention, when used as electron blocker layer (EBL) in phosphorescent OLEDs, give significant improvements over the prior art in all parameters, particularly with regard to voltage, external quantum efficiency and power efficiency. By use of the inventive compounds e4 and f4, it is possible to observe an improvement in the voltage by about 20%-40% and an improvement in the external power efficiency by about 25% compared to the prior art PA1 and PA2. The power efficiency is improved over the prior art by about 40% (examples C1, I1 and C2, I2).

TABLE-US-00011 TABLE 1 Structural formulae of the materials for the OLEDs [00496] [00497] [00498] [00499] [00500] [00501] [00502] [00503] [00504] [00505] [00506] [00507] [00508] [00509] [00510] [00511] [00512] [00513] [00514] [00515] [00516] [00517] [00518] [00519] [00520] [00521] [00522] [00523] [00524] [00525] [00526] [00527] [00528]

TABLE-US-00012 TABLE 2 Structure of the OLEDs HIL IL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness thickness C1 SpA1 HATCN SpMA1 SdT1 IC1:TEG1 ST2:LiQ 70 nm 5 nm 70 nm 20 nm (90%:10%) (50%:50%) 30 nm 40 nm C2 SpA1 HATCN SpMA1 SdT2 IC1:TEG1 ST2:LiQ 70 nm 5 nm 70 nm 20 nm (90%:10%) (50%:50%) 30 nm 40 nm I1 SpA1 HATCN SpMA1 e4 IC1:TEG1 ST2:LiQ 70 nm 5 nm 70 nm 20 nm (90%:10%) (50%:50%) 30 nm 40 nm I2 SpA1 HATCN SpMA1 f4 IC1:TEG1 ST2:LiQ 70 nm 5 nm 70 nm 20 nm (90%:10%) (50%:50%) 30 nm 40 nm I3 SpA1 HATCN SpMA1 IC1:e:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 30 nm I4 SpA1 HATCN SpMA1 IC1:e3:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 30 nm I5 SpA1 HATCN SpMA1 IC1:TEG1 IC1 e6:LiQ 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I6 SpA1 HATCN SpMA1 IC1:TEG1 e7:ST2 LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 3 nm 30 nm 40 nm I7 SpA1 HATCN SpMA1 IC1:TEG1 e8:ST2 LiF 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 1 nm 30 nm 40 nm I8 SpA1 HATCN SpMA1 f3 IC1:TEG1 ST2:LiQ 70 nm 5 nm 70 nm 20 nm (90%:10%) (50%:50%) 30 nm 40 nm I9 SpA1 HATCN SpMA1 IC1:f7:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm I10 SpA1 HATCN SpMA1 f8:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I11 SpA1 HATCN SpMA1 IC1:f13:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm I12 SpA1 HATCN SpMA1 IC1:TEG1 f16 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I13 SpA1 HATCN SpMA1 IC1:f29:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm I14 SpA1 HATCN SpMA1 g:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I15 SpA1 HATCN SpMA1 g3:TER1 ST2:LiQ 90 nm 5 nm 130 nm (92%:8%) (50%:50%) 40 nm 40 nm I16 SpA1 HATCN SpMA1 IC1:i1:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm I17 SpA1 HATCN SpMA1 i8:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I18 SpA1 HATCN SpMA1 IC1:i11:TEG1 IC1 ST2:LiQ 70 nm 5 nm 90 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm I19 SpA1 HATCN SpMA1 IC1:k8:TEG1 IC1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm I20 SpA1 HATCN SpMA1 IC1:l7:TEG1 IC1 ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00013 TABLE 3 Data of the OLEDs CIE x/y at U1000 SE1000 LE1000 Efficiency at L1 LT Ex. (V) (cd/A) (lm/W) EQE 1000 1000 cd/m.sup.2 L.sub.0:j.sub.0 % (h) C1 4.4 52 37 14.4% 0.35/0.61 20 mA/cm.sup.2 80 100 C2 4.1 54 41 14.7% 0.34/0.63 20 mA/cm.sup.2 80 110 I1 3.3 67 64 18.0% 0.33/0.63 20 mA/cm.sup.2 80 140 I2 3.2 70 69 18.1% 0.34/0.63 20 mA/cm.sup.2 80 150 I3 3.4 59 55 16.6% 0.33/0.62 20 mA/cm.sup.2 80 140 I4 3.5 64 57 17.2% 0.32/0.64 20 mA/cm.sup.2 80 160 I5 4.2 66 49 17.6% 0.33/0.63 20 mA/cm.sup.2 80 340 I6 3.3 69 66 18.4% 0.33/0.62 20 mA/cm.sup.2 80 170 I7 3.4 66 60 17.8% 0.33/0.64 20 mA/cm.sup.2 80 140 I8 3.1 70 71 18.1% 0.34/0.63 20 mA/cm.sup.2 80 160 I9 3.2 62 61 16.9% 0.33/0.63 20 mA/cm.sup.2 80 180 I10 3.1 67 68 18.2% 0.34/0.63 20 mA/cm.sup.2 80 150 I11 3.6 63 55 17.1% 0.34/0.63 20 mA/cm.sup.2 80 160 I12 3.4 63 58 17.3% 0.32/0.63 20 mA/cm.sup.2 80 190 I13 3.3 59 56 16.4% 0.33/0.62 20 mA/cm.sup.2 80 200 I14 3.2 61 60 16.5% 0.32/0.64 20 mA/cm.sup.2 80 140 I15 4.6 11 8 11.4% 0.67/0.33 4000 cd/m.sup.2 80 310 I16 3.3 62 59 16.8% 0.34/0.62 20 mA/cm.sup.2 80 190 I17 3.2 60 59 16.2% 0.33/0.63 20 mA/cm.sup.2 80 155 I18 3.2 62 61 16.8% 0.35/0.62 20 mA/cm.sup.2 80 210 I19 3.4 59 55 15.9% 0.33/0.64 10000 cd/m.sup.2 70 220 I20 3.5 60 54 16.3% 0.32/0.63 10000 cd/m.sup.2 70 180