SPIROBIFLUORENE DERIVATIVES FOR USE IN ELECTRONIC DEVICES

Abstract

The present application relates to a spirobifluorene derivative of a specific formula (I) which is suitable for use in electronic devices.

##STR00001##

Claims

1. A compound of formula (I) ##STR00574## where the variables are defined as follows: A is C or Si; Z.sup.1 is, identically or differently on each occurrence, selected from CR.sup.1, CR.sup.2 and N; Z.sup.2 is, identically or differently on each occurrence, selected from CR.sup.2 and N; Z.sup.3 is, identically or differently on each occurrence, selected from CR.sup.3 and N; Ar.sup.L is, identically or differently on each occurrence, selected from aromatic ring systems having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4; Ar.sup.1 is, identically or differently, selected from aromatic ring systems having 6 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.4; E is a single bond or is a divalent group selected from C(R.sup.4).sub.2, N(R.sup.4), O, and S; R.sup.1 is selected, identically or differently on each occurrence, from ##STR00575## Si(R.sup.5).sub.3, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms, branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the said alkyl, alkoxy and thioalkyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5; R.sup.2, R.sup.3 are selected, identically or differently on each occurrence, from H, D, F, Cl, Br, I, C(O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(O)(R.sup.5).sub.2, OR.sup.5, S(O)R.sup.5, S(O).sub.2R.sup.5, SCN, SF.sub.5, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals selected from radicals R.sup.2 and R.sup.3 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CNR.sup.5, C(O)O, C(O)NR.sup.5, NR.sup.5, P(O)(R.sup.5), O, S, SO or SO.sub.2; R.sup.4 is, identically or differently at each occurrence, selected from H, D, F, C(O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(O)(R.sup.5).sub.2, OR.sup.5, S(O)R.sup.5, S(O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.4 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CNR.sup.5, C(O)O, C(O)NR.sup.5, NR.sup.5, P(O)(R.sup.5), O, S, SO or SO.sub.2; R.sup.5 is, identically or differently at each occurrence, selected from H, D, F, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(O)(R.sup.6).sub.2, OR.sup.6, S(O)R.sup.6, S(O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.5 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CNR.sup.6, C(O)O, C(O)NR.sup.6, NR.sup.6, P(O)(R.sup.6), O, S, SO or SO.sub.2; R.sup.6 is selected, identically or differently at each occurrence, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.6 may be connected to each other to form a ring; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by F and CN; k is on each occurrence, identically or differently, 0 or 1; where in the case of k=0, the group Ar.sup.L is not present and the nitrogen atom and the spirobifluorene group are directly connected; m is on each occurrence, identically or differently, 0 or 1, where in the case of m=0, the group E is not present and the groups Ar.sup.1 are not connected; characterized in that at least one of groups Z.sup.1 is CR.sup.1.

2. The compound according to claim 1, characterized in that Ar.sup.L is selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthyl, fluorenyl, indenofluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl, which may each be substituted by one or more radicals R.sup.4.

3. The compound according to claim 1, characterized in that groups Ar.sup.1 are, identically or differently, selected from radicals derived from the groups phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl and triazinyl, which are each optionally substituted by one or more radicals R.sup.4, or from combinations of 2 or 3 radicals derived from these groups, which are each optionally substituted by one or more radicals R.sup.4.

4. The compound according to claim 1, characterized in that index m is 0.

5. The compound according to claim 1, characterized in that groups R.sup.1 are selected, identically or differently, from ##STR00576## phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzofused dibenzofuranyl, benzofused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, each of which may optionally be substituted by one or more radicals R.sup.5.

6. The compound according to claim 1, characterized in that groups R.sup.1 are groups which conform to the following groups ##STR00577## ##STR00578## ##STR00579## ##STR00580## ##STR00581## ##STR00582## ##STR00583## ##STR00584## ##STR00585## ##STR00586## ##STR00587## ##STR00588## ##STR00589## ##STR00590## ##STR00591## ##STR00592## ##STR00593## ##STR00594## ##STR00595## ##STR00596## ##STR00597## ##STR00598## ##STR00599## ##STR00600## ##STR00601## ##STR00602## ##STR00603## ##STR00604## ##STR00605## ##STR00606## ##STR00607## ##STR00608## ##STR00609## ##STR00610## where the groups may be substituted at the free positions with groups R.sup.5, and where the dotted line symbolizes the bonding position to the spirobifluorene moiety of formula (I).

7. The compound according to claim 1, characterized in that R.sup.2 is H.

8. The compound according to claim 1, characterized in that R.sup.3 is selected, identically or differently, from H, F, methyl, tert-butyl, and phenyl.

9. The compound according to claim 1, characterized in that the group Z.sup.1 which is located in the ortho-position to the bond between the two six-rings is CR.sup.1, and the other groups Z.sup.1 are CR.sup.2.

10. The compound according to claim 1, characterized in that the compound conforms to one of formulae (I-A-1-1) to (I-C-2-2) ##STR00611## ##STR00612## ##STR00613## where the variables occurring are defined in one or more of claims 1 to 9, and where R.sup.31 is selected, identically or differently, from H, D, F, C(O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(O)(R.sup.5).sub.2, OR.sup.5, S(O)R.sup.5, S(O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.31 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.5, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.5CCR.sup.5, CC, Si(R.sup.5).sub.2, CO, CNR.sup.5, C(O)O, C(O)NR.sup.5, NR.sup.5, P(O)(R.sup.5), O, S, SO or SO.sub.2, where at least one group R.sup.31 is different from H and D.

11. A process for preparation of the compound according to claim 1, characterized in that it comprises the reactions steps 1) metallation of a biphenyl derivative which has one reactive group in a position which is ortho to the phenyl-phenyl bond, and which bears two additional reactive groups in other positions, where the metallation takes place in the position which is ortho to the phenyl-phenyl bond; 2) addition of the metallated biphenyl derivative to a fluorenone derivative; 3) cyclisation of the resulting addition product to a spirobifluorene derivative, where the cyclisation takes place under acidic conditions or with a Lewis acid, and where the spirobifluorene derivative bears two reactive groups; and 4) coupling of the spirobifluorene derivative with groups selected from aromatic ring systems, heteroaromatic ring systems and amine groups, in the positions of the two reactive groups.

12. An oligomer, polymer or dendrimer, comprising one or more compounds of formula (I) according to claim 1, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any desired positions in formula (I) substituted by R.sup.1, R.sup.2, R.sup.3 or R.sup.4.

13. A formulation comprising at least one compound of formula (I) according to claim 1 and at least one solvent.

14. An electronic device comprising at least one compound according to claim 1.

15. The electronic device according to claim 14, characterized in that it is an organic electroluminescent device, comprising anode, cathode and at least one emitting layer, where at least one organic layer of the device, which is an emitting layer, a hole transport layer, an electron blocking layer or a hole injection layer, comprises the at least one compound.

16. (canceled)

17. A formulation comprising at least one polymer, oligomer or dendrimer according to claim 12, and at least one solvent.

18. An electronic device comprising at least one polymer, oligomer or dendrimer according to claim 12.

19. The compound according to claim 1, characterized in that groups R.sup.1 are selected, identically or differently, from ##STR00614## phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzofused dibenzofuranyl, benzofused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, each of which may optionally be substituted by one or more radicals R.sup.5.

Description

EXAMPLES

A) Synthesis Examples

[0153] 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 5-bromo-2-chloro-9,9-spirobifluorene 1a

[0154] ##STR00270##

[0155] A solution of 2, 2-dibromo-4-chloro-biphenyl (84 g, 239 mmol) in THF (200 ml) is treated with 109 mL of n-BuLi (2.2 M in hexane, 239 mmol) under argon at 78 C. The mixture is stirred for 30 minutes. A solution of fluoren-9-one (44 g, 239 mmol) in 150 mL THF 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 solution of the alcohol in 966 mL toluene and 2.9 g p-toluenesulfonic acid is refluxed overnight. After cooling, the organic phase is washed with water and the solvent is removed under vacuum. The product is isolated in the form of a white solid (60 g, 91% of theory).

[0156] The synthesis of further halogenated spirobifluorene derivatives is carried out analogously:

TABLE-US-00004 Bromo-biphenyl Aryl-fluorenone Product Yield 1b [00271] [00272] [00273] 86% 1c [00274] [00275] [00276] 84% 1d [00277] [00278] [00279] 90% 1f [00280] [00281] [00282] 90% 1g [00283] [00284] [00285] 66% 1h [00286] [00287] [00288] 81% 1i [00289] [00290] [00291] 77% 1j [00292] [00293] [00294] 85% 1k [00295] [00296] [00297] 81% [00298] 1l [00299] [00300] [00301] 80% [00302]

Synthesis of 2-chloro-5-phenyl-9,9-spirobifluorene 2a

[0157] ##STR00303##

[0158] 31.5 g (251 mmol) of of phenyl-boronic acid, 110 g (251 mmol) of 5-bromo-2-chloro-9,9-spirobifluorene, 9.9 g (8.5 mmol) of Pd(P(Ph.sub.3)).sub.4, and 66.8 g (627 mmol) of Na.sub.2CO.sub.3 are dissolved in 903 mL of water, 278 mL of ethanol and 1.9 L 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 product is isolated in the form of an off-white solid (100 g 94% of theory).

[0159] The following compounds are synthesized analogously:

TABLE-US-00005 Ex. Halogenated spiro Boronic acid Product Yield 2b [00304] [00305] [00306] 86% 2c [00307] [00308] [00309] 82% 2d [00310] [00311] [00312] 43% 2e [00313] [00314] [00315] 92% 2f [00316] [00317] [00318] 90% 2g [00319] [00320] [00321] 85% 2h [00322] [00323] [00324] 55% 2i [00325] [00326] [00327] 54% 2j [00328] [00329] [00330] 40% 2k [00331] [00332] [00333] 50% 2l [00334] [00335] [00336] 80% 2m [00337] [00338] [00339] 85% 2n [00340] [00341] [00342] 60%

Synthesis of N-{[1,1-biphenyl]-4-yl}-N-(9,9-dimethyl-9H-fluoren-2-yl)-5-phenyl-9,9-spirobi[fluorene]-2-amine 3a

[0160] ##STR00343##

[0161] Tri-tert-butylphosphine (1.32 mL of a 1.0 M solution in toluene, 1.32 mmol), Pd.sub.2(dba).sub.3 (607 mg, 0.66 mmol) and sodium tert-butoxide (4.8 g, 49.7 mmol) are added to a solution of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine (11.9 g, 33.1 mmol) and 2-chloro-5-phenyl-9,9-spirobifluorene (14.7 g, 33.1 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 6 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 toluene/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 an off-white solid (9.5 g, 38% of theory).

[0162] The following compounds are obtained analogously:

TABLE-US-00006 Halogenated Ex. spiro Amine Product Yield 3b [00344] [00345] [00346] 43% 3c [00347] [00348] [00349] 85% 3d [00350] [00351] [00352] 55% 3e [00353] [00354] [00355] 64% 3f [00356] [00357] [00358] 56% 3g [00359] [00360] [00361] 73% 3h [00362] [00363] [00364] 65% 3i [00365] [00366] [00367] 67% 3j [00368] [00369] [00370] 66% 3k [00371] [00372] [00373] 50% 3l [00374] [00375] [00376] 62% 3m [00377] [00378] [00379] 73% 3n [00380] [00381] [00382] 69% 3o [00383] [00384] [00385] 57% 3p [00386] [00387] [00388] 65% 3q [00389] [00390] [00391] 71% 3r [00392] [00393] [00394] 71% 3s [00395] [00396] [00397] 72% 3t [00398] [00399] [00400] 62% 3u [00401] [00402] [00403] 45% 3v [00404] [00405] [00406] 66% 3w [00407] [00408] [00409] 66% 3x [00410] [00411] [00412] 71% 3y [00413] [00414] [00415] 49% 3z [00416] [00417] [00418] 65% 3aa [00419] [00420] [00421] 73% 3ab [00422] [00423] [00424] 70% 3ac [00425] [00426] [00427] 80% 3ad [00428] [00429] [00430] 75% 3ae [00431] [00432] [00433] 60% 3af [00434] [00435] [00436] 85% 3ag [00437] [00438] [00439] 80% 3ah [00440] [00441] [00442] 76% 3ai [00443] [00444] [00445] 67% 3aj [00446] [00447] [00448] 50% 3ak [00449] [00450] [00451] 40% 3al [00452] [00453] [00454] 50% 3am [00455] [00456] [00457] 38% 3an [00458] [00459] [00460] 35% 3ao [00461] [00462] [00463] 45% 3ap [00464] [00465] [00466] 50% 3aq [00467] [00468] [00469] 55% 3ar [00470] [00471] [00472] 60% 3as [00473] [00474] [00475] 55% 3at [00476] [00477] [00478] 45% 3au [00479] [00480] [00481] 52% 3av [00482] [00483] [00484] 47% 3aw [00485] [00486] [00487] 51% 3ax [00488] [00489] [00490] 48% 3ay [00491] [00492] [00493] 46% 3az [00494] [00495] [00496] 38% 3ba [00497] [00498] [00499] 55%

Synthesis of N-{[1,1-biphenyl]-4-yl}-9,9-dimethyl-N-(4-{4-phenyl-9,9-spirobi[fluorene]-7-yl}phenyl)-9H-fluoren-2-amine 4a

[0163] ##STR00500##

[0164] 59.1 g (101.8 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, 43.5 g (101.8 mmol) of 2-chloro-5-phenyl-9,9-spirobifluorene, 3.88 g (5.14 mmol) of PdCl.sub.2(Cy).sub.3, 31.2 g (205.6 mmol) of cesium fluoride are dissolved in 800 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 white solid (42 g, 51% of theory).

[0165] The following compounds are synthesized analogously:

TABLE-US-00007 Halogenated Ex. Spiro Amine Product Yield 4b [00501] [00502] [00503] 50% 4c [00504] [00505] [00506] 55% 4d [00507] [00508] [00509] 60% 4e [00510] [00511] [00512] 63% 4f [00513] [00514] [00515] 70% 4g [00516] [00517] [00518] 75% 4h [00519] [00520] [00521] 55% 4i [00522] [00523] [00524] 64% 4j [00525] [00526] [00527] 60% 4k [00528] [00529] [00530] 59% 4l [00531] [00532] [00533] 75% 4m [00534] [00535] [00536] 81% 4n [00537] [00538] [00539] 85% 4o [00540] [00541] [00542] 77% 4p [00543] [00544] [00545] 62% 4q [00546] [00547] [00548] 60% 4r [00549] [00550] [00551] 72% 4s [00552] [00553] [00554] 45%

B) Device Examples

[0166] 1) General Procedure

[0167] OLEDs comprising compounds according to the present application, and OLEDs comprising reference compounds are prepared by the following general process: 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 (HIL)/hole-transport layer (HTL)/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. The specific device setup of the OLEDs is shown in Table 1, and the materials required for the production of the OLEDs are shown in Table 3.

[0168] 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:SEB (5%) here means that material H1 is present in the layer in a proportion by volume of 95% and SEB is present in the layer in a proportion by volume of 5%. Analogously, other layers may also consist of a mixture of two or more materials.

[0169] The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra 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 expression EQE @ 10 mA/cm.sup.2 denotes the external quantum efficiency at an operating current density of 10 mA/cm.sup.2. LT80 @60 mA/cm2 is the lifetime until the OLED has dropped from its initial luminance of i.e. 5000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4000 cd/m.sup.2 without using any acceleration factor. The data for the various OLEDs containing inventive and comparative materials are summarised in Table 2.

[0170] In particular, compounds according to the invention are suitable as HIL, HTL, or EBL materials, or as matrix materials in the EML in OLEDs. They are suitable for use as a single material in a layer, but also for use as a mixed component in HIL, HTL, EBL or within the EML.

[0171] 2) Examples for Use of Compounds According to the Application in HIL, HTL and EBL of OLEDs

[0172] Table 2 shows the performance data which is obtained with the specific OLED examples shown in Table 1. OLEDs C1 and C2 are reference examples, which comprise the prior art compounds HTM-b and EBM. OLEDs E1, E2 and E3 are OLEDs according to the present application, which comprise the inventive compounds HTM-1, HTM-2 and HTM-3. Compared with the OLEDs according to the prior art (C1 to C2), the samples comprising the compounds according to the invention (E1 to E3) exhibit better performance both in singlet blue devices (C1 compared to E1 and E3) and also in triplet green devices (C2 compared to E2).

[0173] It can be shown, that lifetime of device E1 is better than the reference example C1. This shows the improved performance of the compound HTM-1, compared to the reference material HTM-b. Similarly, lifetime of device E3 is better than the one of the device C1. This shows the improved performance of the compound HTM-3, compared to the reference material HTM-b.

[0174] Finally, device E2 shows better lifetime than the reference example C2. This shows the improved performance of the compound HTM-2, compared to the reference compound EBM.

TABLE-US-00008 TABLE 1 Device Setup HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm C1 HTM-b: HTM-b EBM H:SEB (5%) ETM:LiQ (50%) LiQ p-doped (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm C2 HTM-a: HTM-a EBM TMM-1: TMM-2 p-doped (5%) 220 nm 10 nm (28%): TEG (12%) ETM:LiQ (50%) LiQ 20 nm 30 nm 30 nm 1 nm E1 HTM-1: HTM-1 EBM H:SEB (5%) ETM:LiQ (50%) LiQ p-doped (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E2 HTM-a: HTM-a HTM-2 TMM-1: TMM-2 ETM:LiQ (50%) LiQ p-doped (5%) 220 nm 10 nm (28%): TEG (12%) 30 nm 1 nm 20 nm 30 nm E3 HTM-3: HTM-3 EBM H:SEB (5%) ETM:LiQ (50%) LiQ p-doped (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm

TABLE-US-00009 TABLE 2 Data for the OLEDs LT80 @ 60/40* U EQE mA/cm.sup.2 [V] [%] [h] C1 4.3 8.5 130 C2 3.8 17.7 270* E1 3.9 8.6 180 E2 3.8 16.0 320* E3 4.1 9.0 170

[0175] 3) Comparison Between an OLED Comprising the Compound HTM-1 According to the Invention, and an OLED Comprising the Compound HTM-c, in the HIL and HTL of a Singlet Blue Device

[0176] The two OLEDs are prepared according to the general process described above under 1).

[0177] The stack structures are shown in Table 1b below:

TABLE-US-00010 TABLE 1b Device Setup HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm C3 HTM-c: HTM-c EBM H:SEB ETM:LiQ LiQ p-doped (5%) 180 nm 10 nm (5%) 20 nm (50%) 30 nm 1 nm 20 nm E4 HTM-1: HTM-1 EBM H:SEB (5%) ETM:LiQ (50%) LiQ p-doped (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm

[0178] While the operating voltage and the lifetime remain similar, a strong increase in EQE is found for the OLED E4 comprising the compound according to the invention HTM-1, compared to the OLED C3 comprising the comparative compound HTM-c. OLED E4 has an EQE of 9.1%, whereas OLED C3 has an EQE of 7.9%.

[0179] 4) Comparison Between an OLED Comprising the Compound HTM-1 According to the Invention, and an OLED Comprising the Compound HTM-c, in the EBL of a Triplet Green Device

[0180] The two OLEDs are prepared according to the general process described above under 1).

[0181] The stack structures are shown in Table 1c below:

TABLE-US-00011 TABLE 1 Device Setup Ex. HIL HTL EBL EML ETL1 ETL2 EIL Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm C4 HTM-a: HTM-a HTM-c TMM-1: TMM-2 ETM ETM: LiQ p-doped (5%) 220 nm 10 nm (29%):TEG (12%) 10 nm LiQ (50%) 1 nm 20 nm 30 nm 30 nm E5 HTM-a: HTM-a HTM-1 TMM-1: TMM-2 ETM ETM:LiQ (50%) LiQ p-doped (5%) 220 nm 10 nm (29%):TEG (12%) 10 nm 30 nm 1 nm 20 nm 30 nm

[0182] While the operating voltage and the lifetime remain similar, a strong increase in EQE is found for the OLED E5 comprising the compound according to the invention HTM-1, compared to the OLED C4 comprising the comparative compound HTM-c. OLED E5 shows an EQE of 15.9%, whereas OLED C4 shows an EQE of 14.9%.

[0183] 5) Further Device Examples with Compounds HTM-4 to HTM-7

[0184] OLEDs E6, E7, E8 and E9 are OLEDs according to the present application, which comprise the inventive compounds HTM-4, HTM-5, HTM-6 and HTM-7.

[0185] E6 shows the performance of the inventive compound HTM-4 as a HIL and HTL material in a singlet blue device (for detailed stack see below). Here, a lifetime LT80@60 mA/cm.sup.2 of 290 h is found, along with good efficiency and voltage.

[0186] E7, E8 and E9 show the performance of the inventive compounds HTM-5, HTM-6 and HTM-7 as EBL materials in a triplet green device (for detailed stack see below). Here, lifetimes LT80@40 mA/cm.sup.2 of 390 h (E7), 280 h (E8), and 310 h (E9) are found, along with good efficiency and voltage.

TABLE-US-00012 TABLE 1d Device Setup HIL HTL EBL EML ETL EIL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm E6 HTM-4: HTM-4 EBM H:SEB (5%) ETM:LiQ (50%) LiQ p-doped (5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E7 HTM-a: HTM-a HTM-5 TMM-1: TMM-2 ETM:LiQ (50%) LiQ p-doped (5%) 220 nm 10 nm (28%):TEG (12%) 30 nm 1 nm 20 nm 30 nm E8 HTM-a: HTM-a HTM-6 TMM-1: TMM-2 ETM:LiQ (50%) LiQ p-doped (5%) 220 nm 10 nm (28%):TEG (12%) 30 nm 1 nm 20 nm 30 nm E9 HTM-a: HTM-a HTM-7 TMM-1: TMM-2 ETM:LiQ (50%) LiQ p-doped (5%) 220 nm 10 nm (28%):TEG (12%) 30 nm 1 nm 20 nm 30 nm

TABLE-US-00013 TABLE 3 Materials used [00555] [00556] [00557] [00558] [00559] [00560] [00561] [00562] [00563] [00564] [00565] [00566] [00567] [00568] [00569] [00570] [00571] [00572] [00573]