Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds according to formula (1), a method for producing these compounds and electronic devices, in particular organic electroluminescent devices containing said compounds.

Claims

1. A compound of formula (1), ##STR00456## wherein: X is on each occurrence, identically or differently, CR or N; or two adjacent groups X together stand for a group selected from NR, O or S, resulting in the formation of a five-membered ring; Y is on each occurrence, identically or differently, Z═Z, O, S or NR, where R is not H; Z is on each occurrence, identically or differently, CR or N or the adjacent groups Z═Z together stand for a group of formula (2), ##STR00457## where X has the meanings given above and the dashed bonds indicate the linking of this group; L is not present for n=1 and is a single bond or a divalent group for n=2 and a trivalent group for n=3 and a tetravalent group for n=4 and a pentavalent group for n=5 and a hexavalent group for n=6; L here is bonded at any desired point of the basic structure instead of a group R; R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.1).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.1, P(═O)(Ar.sup.1).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms optionally is replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally in each case substituted by one or more radicals R.sup.1, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1, an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1, or a combination of these systems, where two or more adjacent substituents R may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which is optionally substituted by one or more radicals R.sup.1; Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R.sup.1; two radicals Ar.sup.1 here which are bonded to the same N atom or P atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.1), C(R.sup.1).sub.2 or O; R.sup.1 is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or an alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms, where two or more adjacent substituents R.sup.1 may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; n is 1, 2, 3, 4, 5 or 6; where the following compound is excluded from the invention: ##STR00458##

2. The compound according to claim 1, selected from the compounds of formula (5) and formula (9), ##STR00459## where the radical R on the nitrogen in formula (9) is not equal to H.

3. The compound according to claim 1, selected from compounds of formula (6), ##STR00460## where n=2 or 3.

4. The compound according to claim 1, selected from compounds of formulae (7), (8), (10) and (11), ##STR00461## where n stands for 2 or 3, a maximum of one group X per ring stands for N and the other groups X stand for CR and the radical R on the nitrogen in formula (10) and (11) is not equal to H.

5. The compound according to claim 1, selected from compounds of formulae (7a), (8a), (10a) and (11a), ##STR00462## where n stands for 2 or 3, and the radical Ron the nitrogen in formula (10a) and (11a) is not equal to H.

6. The compound according to claim 1, selected from compounds of formulae (7c), (8c), (10c) and (11c), ##STR00463## where n stands for 2 or 3, and the radical R on the nitrogen in formula (10c) and (11c) is not equal to H.

7. The compound according to claim 1, selected from compounds of formula (12), ##STR00464##

8. The compound according to claim 1, characterised in that L, for n=2, is selected from a single bond, CR.sub.2, O, NR or C(═O) or, for n=3, stands for N or, for n>2, is selected from an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which is optionally substituted by one or more radicals R.

9. The compound according to claim 1, characterised in that at least one radical R is selected from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1, and/or in that at least one radical R is selected from —C(═O)Ar.sup.1 or —P(═O)(Ar.sup.1).sub.2 and/or in that at least one radical R is selected from triaryl- or heteroarylamine derivatives and/or at least one substituent R stands for —N(Ar.sup.1).sub.2.

10. The compound according to claim 1, characterised in that at least one group R is selected from the group consisting of benzene, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzothiophene, dibenzofuran, 1,3,5-triazine, pyridine, pyrimidine, pyrazine, pyridazine, indenocarbazole, bridged carbazole, indolocarbazole, anthracene, phenanthrene, pyrene, triphenylene, benzanthracene, quinoline, isoquinoline, phenanthridine, phenanthroline, azacarbazole, imidazole, pyrazole, thiazole, oxazole, oxadiazole, triazole, benzimidazole and combinations of two, three or four of these groups, where the groups are each optionally substituted by one or more radicals R.sup.1.

11. A formulation comprising at least one compound according to claim 1 and at least one further compound.

12. The formulation according to claim 11, wherein the at least one further compound is an organic solvent.

13. A method comprising incorporating the compound according to claim 1 in an electronic device.

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

15. The electronic device according to claim 14, wherein the electronic device is an organic electroluminescent device, characterised in that the at least one compound is employed as matrix material for a fluorescent or phosphorescent emitter and/or in a hole-blocking layer and/or in an electron-transport layer.

16. The electronic device according to claim 14, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light-emitting transistors, organic solar cells, organic dye sensitised solar cells, organic optical detectors, organic photo receptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

Description

EXAMPLES

(1) The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere. The starting materials can be purchased from ALDRICH or ABCR (palladium(II) acetate, tri-o-tolylphosphine, inorganics, solvents). The numbers in the case of the literature-known starting materials are the CAS numbers.

Example 1: 5,6-Dihydrophenanthridine

(2) ##STR00169##

(3) 8.78 g (153 mmol) of LiAlH.sub.4 are initially introduced in 1000 ml of THF under protective-gas atmosphere. 30 g (153 mmol) of 5H-phenanthridin-6-one are added in portions and subsequently heated under reflux for 8 h. The solvent is removed in vacuo and employed further without further application. The yield is 27 g (97%).

(4) The following compounds are obtained analogously:

(5) TABLE-US-00002 Ex. Starting material 1 Product Yield 1a 0 73% 1b 70% 1c 75%

Example 2: 15-(2-Iodobenzoyl)-5H-phenanthridin-6-one

(6) ##STR00176##

(7) 20 g (113 mmol) of 5,6-dihydrophenanthridine are dissolved in 500 ml of THE under protective-gas atmosphere and cooled to −25° C. 49.9 g (113 mmol) of 2-iodobenzoyl chloride are dissolved in 300 ml of THE and added dropwise to the reaction mixture at such a rate that the temperature does not exceed −25° C. After 1 h at −25° C., the mixture is allowed to come slowly to room temperature and is then stirred at room temperature for 1 h. After this time, the reaction mixture is poured onto ice and extracted three times with ethyl acetate. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from n-heptane. The yield is 40 g (90%).

(8) The following compounds are obtained analogously:

(9) TABLE-US-00003 Ex. Starting material 1 Starting material 2 Product Yield 2a 76% 2b 0 87% 2c 91% 2d 90% 2e 0 87% 2f 78% 2g 76% 2h 00 77% 2j 01 02 03 73%

Example 3: 5-(2-Bromobenzyl)-5,6-dihydrophenanthridine

(10) ##STR00204##

(11) 9.7 g (243 mmol) of 60% NaH in mineral oil are dissolved in 500 ml of dimethylformamide under protective-gas atmosphere. 43.9 g (243 mmol) of 5,6-dihydrophenanthridine are dissolved in 500 ml of DMF and added dropwise to the reaction mixture. After 1 h at room temperature, a solution of 60.6 g (242 mmol) of 2-bromobenzyl bromide in 500 ml of DMF is added dropwise. The reaction mixture is then stirred at room temperature for 1 h. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is extracted with hot toluene and recrystallised from toluene/n-heptane. The yield is 62 g (75%).

(12) The following compounds are obtained analogously:

(13) TABLE-US-00004 Ex. Starting material 1 Starting material 2 Product Yield 3a 05 06 07 83% 3b 08 09 0 90% 3c 95%

Example 4: 8a-Azabenzo[fg]naphthacene-8,9-dione

(14) ##STR00214##

(15) 35 g (158 mmol) of 5-(2-bromobenzyl)-5H-phenanthridin-6-one are dissolved in 1000 ml of dimethylformamide under protective-gas atmosphere. 75.7 g (234 mmol) of tetrabutylammonium bromide, 2.15 g (9.5 mmol) of palladium acetate and 10 g (102 mmol) of potassium acetate are added to this solution. The mixture is subsequently stirred at 130° C. for 2 h. After this time, the reaction mixture is cooled to room temperature. The residue is filtered off with suction and washed with EtOH. The residue is recrystallised from n-heptane/toluene. The yield is 17.7 g (74%).

(16) The following compounds are obtained analogously:

(17) TABLE-US-00005 Ex. Starting material 1 Product Yield 4a 80% 4b 83% 4c 0 67% 4d 73% 4e 79% 4f 82% 4g 77% 4h 0 78% 4j 73%

Example 5: 8H,9H-8a-Azabenzo[fg]naphthacene

(18) ##STR00233##

(19) 55.3 g (158 mmol) of 5-(2-bromobenzyl)-5,6-dihydrophenanthridine are dissolved in 500 ml of dimethylformamide under protective-gas atmosphere. 17.3 g (75 mmol) of benzyltrimethylammonium bromide and 31.28 g (226 mmol) of potassium carbonate are added to this solution. 5.08 g (22 mmol) of Pd(OAC).sub.2 is subsequently added under protective gas, and the mixture is stirred at 120° C. for 9 h. After this time, the reaction mixture is cooled to room temperature and extracted with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from n-heptane. The yield is 34 g (81%).

(20) TABLE-US-00006 Ex. Starting material 1 Product Yield 5a 82% 5b 80% 5c 74%

Example 6: 8a-Azabenzo[fg]naphthacene-8,9-dione

(21) ##STR00240##

(22) 32 g (115 mmol) of 9H-8a-azabenzo[fg]naphthacen-8-one are dissolved in 1500 ml of acetone. 54.7 g (346 mmol) of potassium permanganate are added to this solution in portions and stirred at room temperature for two days. After this time, the remaining potassium permanganate is filtered off, the solution is evaporated and purified by chromatography (eluent:heptane/dichloromethane, 5:1). The residue is recrystallised from n-heptane. The yield is 24 g (73%).

(23) The following compounds are obtained analogously:

(24) TABLE-US-00007 Ex. Starting material 1 Product Yield 6a 60% 6b 69% 6c 71% 6d 65% 6e 0 72% 6f 77% 6g 62% 6h 65% 6j 64%

(25) The following compounds are obtained analogously using 6 eq. of KMnO.sub.4:

(26) TABLE-US-00008 Ex. Starting material 1 Product Yield 6i 0 83% 6k 86% 6l 79% 6m 70%

Example 7: 2-Bromo-8a-azabenzo[fg]naphthacene-8,9-dione

(27) ##STR00267##

(28) 18.6 g (62.5 mmol) of 8a-azabenzo[fg]naphthacene-8,9-dione are initially introduced in 1800 ml of CH.sub.2Cl.sub.2. 25.6 (312 mmol) of sodium acetate and 24.9 g (156 mmol) of bromine are subsequently added to the reaction mixture, and the mixture is stirred at 80° C. for 30 h. 150 ml of water and 60 g of NaOH pellets are subsequently added to the mixture, and the solid which precipitates out is filtered off with suction. The product is washed with EtOH and dried. Yield: 19 g (51 mmol), 81% of theory, purity according to .sup.1H-NMR about 96%.

(29) The following compounds are obtained analogously:

(30) TABLE-US-00009 Ex. Starting material 1 Product Yield 7a 83% 7b 0 82% 7c 80% 7d 78% 7e 34% 7f 50% 7h 0 70% 7j 30% 7i 42% 7k 82% 7l 85% 7m 0 86% 7n 67% 7o 65%

Example 8: 2-Dibenzofuran-4-yl-8a-azabenzo[fg]naphthacene-8,9-dione

(31) ##STR00296##

(32) 41.3 g (110.0 mmol) of 4-dibenzofuranboronic acid, 38 g (110.0 mmol) of 2-bromo-8a-azabenzo[fg]naphthacene-8,9-dione and 44.6 g (210.0 mmol) of tripotassium phosphate are suspended in 500 ml of toulene, 500 ml of dioxane and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene and from dichloromethane/isopropanol and finally sublimed in a high vacuum, purity is 99.9%. The yield is 40 g (88 mmol), corresponding to 80% of theory.

(33) The following compounds are obtained analogously:

(34) TABLE-US-00010 Ex. Starting material 1 Starting material 2 Product Yield. 8a 82% 8b 00 01 02 81% 8c 03 04 05 84% 8e 06 07 08 88% 8f 09 0 67% 8g 75% 8h 76% 8j 0 83% 8i 85% 8k 80% 8l 89% 8m 0 88% 8n 86% 8o 82% 8p 0 86% 8q 87% 8r 81% 8s 0 79% 8t 86% 8u 87% 8v 80% 8w 0 81% 8y 83% 8z 84%

(35) The following compounds are obtained analogously using 0.5 eq. of bromine:

(36) TABLE-US-00011 Ex. Starting material 1 Starting material 2 Product Yield 8w 0 86% 8y 81%

Example 9: 2-{3-Phenyl-6-[(E)-((Z)-1-propenyl)buta-1,3-dienyl]carbazol-9-yl}-8a-azabenzo[fg]naphthacene-8,9-dione

(37) ##STR00375##

(38) 32 g (102-4 mmol) of 3,6-diphenyl-9H-carbazole, 42 g (112 mmol) of 2-bromo-8a-azabenzo[fg]naphthacene-8,9-dione and 2.3 (10-2 mmol) of 1,3-di[2-pyridyl]-1,3-propanedione, 28.3 g (204 mmol) of potassium carbonate and 1.9 g (10.2 mmol) of copper iodide are stirred under reflux in 1000 ml of DMF for 90 h. The solution is diluted with water and extracted twice with ethyl acetate, the combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator and purified by chromatography (EtOAc/hexane:2/3). The residue is recrystallised from toluene and from dichloromethane and finally sublimed in a high vacuum, purity is 99.9%. The yield is 46 g (75 mmol), corresponding to 68% of theory.

(39) The following compounds are obtained analogously:

(40) TABLE-US-00012 Starting Starting Ex. material 1 material 2 Product Yield 9a 65%

Example 10: 2-(Bisbiphenyl-4-ylamino)-8a-azabenzo[fg]naphthacene-8,9-dione

(41) ##STR00379##

(42) Under protective gas, 24.5 g (79.8 mmol) of bisbiphenyl-4-ylamine, 32.7 g (87 mmol) of 2-bromo-8a-azabenzo[fg]naphthacene-8,9-dione, 15.9 ml (15.9 mmol) of 1 mol/l tri-tert-butylphosphine and 1.79 g (7.9 mmol) of palladium acetate are suspended in 120 ml of p-xylene. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene and finally sublimed in a high vacuum. The purity is 99.9%, yield 44 g (72 mmol), 83% of theory.

(43) The following compounds are obtained analogously:

(44) TABLE-US-00013 Starting Starting Ex. material 1 material 2 Product Yield 10a 0 85% 10b 76%

Example 11: 1-(2-Bromobenzyl)-3-phenyl-1,3-dihydrobenzoimidazol-2-one

(45) ##STR00386##

(46) 1-Phenyl-1,3-dihydrobenzoimidazol-2-one 52 g (250 mmol) and 38 g (275 mmol) of K.sub.2CO.sub.3 are initially introduced in 100 ml of DMF. After 1 h at room temperature, a solution of 62 g (250 mmol) of 2-bromobenzyl bromide in 500 ml of DMF is added dropwise. The reaction mixture is then stirred at room temperature for 25 h. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is extracted with hot toluene and recrystallised from toluene/n-heptane. The yield is 65 g (70%).

(47) The following compounds are obtained analogously:

(48) TABLE-US-00014 Starting Starting Ex. material 1 material 2 Product Yield 11a 76% 11b 0 71%

(49) The following compounds are obtained analogously using 125 mmol of 1,3-dihydro-2H-benzimidazol-2-one [615-16-7]:

(50) TABLE-US-00015 Ex. Starting material 1 Starting material 2 Product Yield. 11c 86% 11d 82%

(51) The cyclisation is carried out analogously to Example 5:

(52) TABLE-US-00016 Ex. Starting material 1 Product Yield 5d 00 62% 5e 01 02 63% 5f 03 04 74% 5h 05 06 66% 5j 07 08 64%

(53) The further oxidation is carried out analogously to Example 6:

(54) TABLE-US-00017 Ex. Starting material 1 Product Yield 6n 09 0 60% 6o 69% 6p 71% 6q 70% 6r 67%

(55) The bromination is carried out analogously to Example 7:

(56) TABLE-US-00018 Ex. Starting material 1 Product Yield 7n 0 60% 7o 69% 7p 71% 7q 70% 7r 67%

(57) The following compounds are prepared analogously to Example 9 via Ullmann reaction:

(58) TABLE-US-00019 Starting Starting Ex. material 1 material 2 Product Yield 9b 0 64% 9c 63% 9d 65% 9e 0 66% 9f 71%

Example 12: Production of OLEDs

(59) The data of various OLEDs are presented in the following Examples E1 to 7 (see Tables 1 and 2). Glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Germany, applied by spin coating from aqueous solution) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs is shown in Table 1. The materials required for the production of the OLEDs are shown in Table 3. A designation such as “8a” here refers to the corresponding compound from the above-mentioned Example 8a. This applies analogously to all materials according to the invention that are used.

(60) 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 co-evaporation. An expression such as IC1:8c:TER1 (55%:35%:10%) here means that material IC1 is present in the layer in a proportion by volume of 55%, 8c is present in the layer in a proportion of 35% and TER1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(61) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics, and the lifetime are determined. The electroluminescence spectra are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The term U1000 in Table 2 denotes the voltage required for a luminous density of 1000 cd/m.sup.2. CE1000 and PE1000 denote the current and power efficiency respectively which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminous density drops from the initial luminous density to a certain proportion L1 on operation at constant current. An expression of L0;j0=4000 cd/m.sup.2 and L1=80% in Table 2 means that the lifetime indicated in column LT corresponds to the time after which the initial luminous density drops from 4000 cd/m.sup.2 to 3200 cd/m.sup.2. Analogously, L0;j0=20 mA/cm.sup.2, L1=70%, means that the luminous density drops to 70% of its initial value after time LT on operation at 20 mA/cm.sup.2.

(62) The data of the various OLEDs are summarised in Table 2. On use of the compounds according to the invention both on use as electron-transport material (Examples E1, E2, E13, E17, E18) and also as matrix material for phosphorescent emitters (remaining examples), very good values for efficiency, voltage and lifetime are obtained. This applies on use as single matrix and also in mixed-matrix systems in combination with various materials, such as IC1, IC2, Cbz1. In particular, the excellent voltages and thus power efficiencies at the same time as a very good lifetime should be emphasised (see, for example, E10).

(63) TABLE-US-00020 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. Thickness Thickness Thickness Thickness Thickness Thickness Thickness E1 SpA1 HATCN SpMA1 M1:D1 (95%:5%) — 8k LiQ 140 nm 5 nm 20 nm 20 nm 30 nm 3 nm E2 SpA1 HATCN SpMA1 M1:D1 (95%:5%) — 8s:LiQ (50%:50%) — 140 nm 5 nm 20 nm 20 nm 30 nm E3 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — 8s:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E4 SpA1 HATCN SpMA1 8:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E5 SpA1 HATCN SpMA1 8a:TER1 (92%:8%) — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm 40 nm 40 nm E6 SpA1 HATCN SpMA1 8b:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E7 SpA1 HATCN SpMA1 8b:TER1 (92%:8%) — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm 40 nm 40 nm E8 SpA1 HATCN SpMA1 IC1:8c:TER1 IC1 ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm (55%:35%:10%) 5 nm 35 nm 40 nm E9 SpA1 HATCN SpMA1 8e:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E10 SpA1 HATCN SpMA1 8e:IC2:TEG1 — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 40 nm E11 SpA1 HATCN SpMA1 8e:Cbz1:TEG1 IC1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (60%:35%:5%) 10 nm 30 nm 30 nm E12 SpA1 HATCN SpMA1 8k:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E13 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — 8o LiQ 70 nm 5 nm 90 nm 30 nm 40 nm 3 nm E14 SpA1 HATCN SpMA1 8r:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E15 SpA1 HATCN SpMA1 8s:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E16 SpA1 HATCN SpMA1 8s:TER1 (92%:8%) — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm 40 nm 40 nm E17 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — 8s LiF 70 nm 5 nm 90 nm 30 nm 40 nm 1 nm E18 SpA1 HATCN SpMA1 M1:D1 (95%:5%) — 8v LiQ 140 nm 5 nm 20 nm 20 nm 30 nm 3 nm E19 SpA1 HATCN SpMA1 8w:TER1 (92%:8%) — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm 40 nm 40 nm E20 SpA1 HATCN SpMA1 8w:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E21 SpA1 HATCN SpMA1 8y:TER1 (92%:8%) — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm 40 nm 40 nm E22 SpA1 HATCN SpMA1 9:TER1 (92%:8%) — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm 40 nm 40 nm E23 SpA1 HATCN SpMA1 9a:TER1 (92%:8%) — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm 40 nm 40 nm E24 SpA1 HATCN SpMA1 9b:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E25 SpA1 HATCN SpMA1 9c:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E26 SpA1 HATCN SpMA1 9f:TER1 (92%:8%) — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm 40 nm 40 nm E27 SpA1 HATCN SpMA1 IC2:10:TER1 IC1 ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm (70%:20%:10%) 5 nm 35 nm 40 nm

(64) TABLE-US-00021 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at L1 LT Ex. (V) (cd/A) (lm/W) 1000 1000 cd/M1 L0; j0 % (h) E1 4.7 8.1 5.4 7.2% 0.13/0.14 60 mA/cm.sup.2 70 200 E2 4.5 8.5 5.9 7.3% 0.13/0.14 60 mA/cm.sup.2 70 225 E3 3.4 61 57 16.7% 0.33/0.62 20 mA/cm.sup.2 70 220 E4 3.3 56 53 15.3% 0.32/0.62 20 mA/cm.sup.2 70 240 E5 4.4 12.2 8.6 13.2% 0.67/0.33 4000 cd/m.sup.2 80 360 E6 3.5 54 48 14.7% 0.33/0.63 20 mA/cm.sup.2 70 195 E7 4.6 11.0 7.5 11.9% 0.67/0.33 4000 cd/m.sup.2 80 345 E8 4.1 12.6 9.6 13.6% 0.67/0.33 4000 cd/m.sup.2 80 490 E9 3.0 54 57 14.8% 0.32/0.62 20 mA/cm.sup.2 70 260 E10 3.0 61 65 16.7% 0.34/0.63 20 mA/cm.sup.2 80 310 E11 3.3 63 61 17.4% 0.32/0.62 20 mA/cm.sup.2 80 265 E12 3.4 52 48 14.4% 0.33/0.61 20 mA/cm.sup.2 80 180 E13 3.6 57 50 15.6% 0.32/0.62 10000 cd/m.sup.2 70 220 E14 3.2 55 54 15.0% 0.32/0.62 20 mA/cm.sup.2 70 230 E15 3.3 54 51 14.7% 0.33/0.61 20 mA/cm.sup.2 80 145 E16 4.6 10.6 7.3 11.4% 0.67/0.33 4000 cd/m.sup.2 80 310 E17 3.4 59 55 16.1% 0.33/0.62 20 mA/cm.sup.2 70 245 E18 4.9 7.0 4.9 6.7% 0.13/0.14 60 mA/cm.sup.2 70 230 E19 3.1 56 56 15.5% 0.34/0.61 20 mA/cm.sup.2 80 160 E20 3.8 10.1 8.4 10.9% 0.67/0.33 4000 cd/m.sup.2 80 385 E21 4.5 12 8.4 13.0% 0.67/0.33 4000 cd/m.sup.2 80 405 E22 4.8 11 7.2 11.9% 0.67/0.33 4000 cd/m.sup.2 80 370 E23 4.3 12.8 9.3 13.8% 0.67/0.33 4000 cd/m.sup.2 80 420 E24 3.0 61 63 17.0% 0.33/0.62 20 mA/cm.sup.2 80 165 E25 3.2 59 58 16.4% 0.32/0.62 20 mA/cm.sup.2 80 150 E26 4.6 11.1 7.6 12.0% 0.67/0.33 4000 cd/m.sup.2 80 405 E27 4.3 12.2 8.9 13.2% 0.67/0.33 4000 cd/m.sup.2 80 520

(65) TABLE-US-00022 TABLE 3 Structural formulae of the materials for the OLEDs HATCN SpA1 M1 D1 ST1 LiQ 0 TER1 TEG1 IC1 IC2 SpMA1 Cbz1