Compounds for electronic devices

Abstract

The present invention relates to compounds of the formula (I) and to the use thereof in organic electronic devices, and to organic electronic devices which comprise compounds of the formula (I), preferably as hole-transport materials and/or as matrix materials, in particular in combination with a further matrix material.

Claims

1. A compound of the formula (I) ##STR00412## where the following applies to the symbols and indices occurring: Y is on each occurrence, identically or differently, a single bond or C(R.sup.2).sub.2, where at least one group Y which represents a single bond is present; Ph is a phenyl group, which may be substituted by one or more radicals R.sup.1; Ar.sup.1 is an aromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; R.sup.1, R.sup.2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(R.sup.3).sub.2, C(O)R.sup.3, P(O)(R.sup.3).sub.2, S(O)R.sup.3, S(O).sub.2R.sup.3, CR.sup.3C(R.sup.3).sub.2, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, OSO.sub.2R.sup.3, OH, 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.sub.3, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, CO, CS, CSe, 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 H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more non-aromatic radicals R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R.sup.3, or a combination of these systems, where two or more radicals R.sup.1 and/or R.sup.2 may be linked to one another and may form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.3 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(R.sup.4).sub.2, C(O)R.sup.4, P(O)(R.sup.4).sub.2, S(O)R.sup.4, S(O).sub.2R.sup.4, CR.sup.4C(R.sup.4).sub.2, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, OH, 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.4, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.4CCR.sup.4, CC, Si(R.sup.4).sub.2, Ge(R.sup.4).sub.2, Sn(R.sup.4).sub.2, CO, CS, CSe, 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 H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or a mono- or polycyclic aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more non-aromatic radicals R.sup.4, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R.sup.4, or a combination of these systems, where two or more radicals R.sup.3 may be linked to one another and may form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.4 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by D or F; two or more identical or different substituents R.sup.4 here may also be linked to one another and may form a mono- or polycyclic, aliphatic or aromatic ring system; n is on each occurrence, identically or differently, 0 or 1, where the sum of the values of n is equal to 1 or 2 and where, for n=0, a group R.sup.1 is bonded instead of a group Y; and where not more than one group R.sup.1 which represents a group of the formula N(R.sup.3).sub.2, where R.sup.3 is an aryl group, may be bonded to a single triarylamine group in formula (I).

2. The compound according to claim 1, wherein the sum of the values of n is equal to 1.

3. The compound according to claim 1, wherein precisely one group Y is a single bond and precisely one further group Y is C(R.sup.2).sub.2.

4. The compound according to claim 1, wherein R.sup.1 is selected on each occurrence, identically or differently, from H, D, F, CN, Si(R.sup.3).sub.3 or a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which may be substituted by one or more radicals R.sup.3, where one or more adjacent or non-adjacent CH.sub.2 groups may be replaced by CC, R.sup.3CCR.sup.3, Si(R.sup.3).sub.2, CO, CNR.sup.3, NR.sup.3, O, S, COO or CONR.sup.3, or an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3.

5. The compound according to claim 1, wherein R.sup.2 is selected on each occurrence, identically or differently, from H, D, a straight-chain alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, where the said groups may each be substituted by one or more groups R.sup.3.

6. The compound according to claim 1, wherein at least one group R.sup.2 which represents an aryl group having 6 to 10 carbon atoms which is substituted by one or more radicals R.sup.3 must be present.

7. The compound according to claim 1, wherein R.sup.3 is selected on each occurrence, identically or differently, from H, D, F, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2 or a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which may be substituted by one or more radicals R.sup.4, where one or more adjacent or non-adjacent CH.sub.2 groups may be replaced by CC, R.sup.4CCR.sup.4, Si(R.sup.4).sub.2, CO, CNR.sup.4, NR.sup.4, O, S, COO or CONR.sup.4, or an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.4.

8. The compound according to claim 1, wherein R.sup.4 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by D or F.

9. The compound according to claim 1, wherein Ar.sup.1 conforms to a formula (Ar.sup.1-1) ##STR00413## where the bonds to the group Ph and to the nitrogen atom are represented by the dashed lines, and where the group may be substituted in all free positions by radicals R.sup.1 as defined in claim 1.

10. The compound according to claim 1, wherein the group Ph conforms to one of the formulae (Ph-1) and (Ph-2): ##STR00414## where the bonds to the nitrogen atom and to the group Ar.sup.1 are represented by the dashed lines, and the symbols # mark the position of the bond to a group Y, if present, and where the structures may be substituted in all free positions by radicals R.sup.1 as defined in claim 1.

11. The compound according to claim 1, wherein the compound conforms to one of the following formulae (I-16) to (I-20): ##STR00415## where L is C(R.sup.2).sub.2; and R.sup.1 is as defined in claim 1.

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

13. A formulation comprising at least one compound according to claim 1 and at least one solvent.

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

15. A Process for the preparation of the compound according to claim 1, which comprises at least one ring-closure reaction is carried out for the introduction of a bridging group Y or L.

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

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

18. The electronic device according to claim 16 wherein the device is selected from the group consisting of organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

19. An organic electroluminescent device comprising the compound according to claim 1 is employed as hole-transport material in a hole-transport layer or hole-injection layer and/or as matrix material.

20. An organic electroluminescent device comprising the compound according to claim 1 is employed as hole-transport material in a hole-transport layer or hole-injection layer and/or as matrix material, in combination with one or more further matrix materials, in an emitting layer.

Description

WORKING EXAMPLES

A) Syntheses of Compounds According to the Invention in Accordance with Examples 1 to 30

(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 synthesis of 8,8-dimethylindolo[3,2,1-de]acridine and 7,7,11,11-tetramethyl-7H,11H-benz[1,8]indolo[2,3,4,5,6-de]acridine can be carried out in accordance with the literature (Chemische Berichte 1980, 113 (1), 358-84). The syntheses of 8H-indolo[3,2,1-de]phenazine (Journal of the Chemical Society 1958, 4492-4) and B-[4-(1-phenyl-1H-benzimidazol-2-yl)phenyl]boronic acid (Advanced Functional Materials 2008, 18 (4), 584-590), 2-bromoindolo[3,2,1-jk]carbazole and indolo[3,2,1-jk]carbazoleboronic acid (Chemistry A European Journal, 2009, 15 (22), 5482-5490), N-[1,1-biphenyl]-4-yl-9,9-dimethyl-9H-fluoren-2-amine (WO 2006073054) and 7-bromo-2,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene (see as yet unpublished application DE 102009023155.2) are likewise known from the literature.

Example 1: 3-Bromo-8,8-dimethyl-8H-Indolo[3,2,1-de]acridine

(2) ##STR00253##

Methyl 2-(3-bromo-9H-carbazole)benzoate

(3) 62 g (207 mmol) of methyl 2-(9H-carbazole)benzoate are cooled to 10 C. in 2000 ml of DMF, 37.3 g (207 mmol) of NBS are added in portions, and the mixture is stirred at room temperature for 6 h. 500 ml of water are subsequently added to the mixture, which Is then extracted with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4, and the solvent is removed in vacuo.

(4) The product is washed by stirring with hot toluene and filtered off with suction.

(5) Yield: 72 g (190 mmol), 92% of theory, purity according to .sup.1H-NMR about 98%.

2-[2-(3-Bromocarbazol-9-yl)phenyl]propan-2-ol

(6) 81 g (213 mmol) of methyl 2-(3-bromo-9H-carbazole)benzoate are dissolved in 1500 ml of dried THF and degassed. The mixture is cooled to 78 C., and 569 ml (854 mmol) of methyllithium are added over the course of 40 min. The mixture is allowed to warm to 40 C. over the course of 1 h, and the reaction is monitored by TLC. When the reaction is complete, it is carefully quenched at 30 C. using MeOH. The reaction solution is evaporated to , and 1 l of CH.sub.2Cl.sub.2 is added, the mixture is washed, and the organic phase is dried over MgSO.sub.4 and evaporated.

(7) Yield: 73 g (193 mmol), 91% of theory, purity according to .sup.1H-NMR about 94%.

6-Bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

(8) 16.3 g (44 mmol) of 2-[2-(3-bromocarbazol-9-yl)phenyl]propan-2-ol are dissolved in 1200 ml of degassed toluene, a suspension of 40 g of polyphosphoric acid and 28 ml of methanesulfonic acid is added, and the mixture is heated at 60 C. for 1 h. The batch is cooled, and water is added. A solid precipitates out and is dissolved in CH.sub.2Cl.sub.2/THF (1:1). The solution is carefully rendered alkaline using 20% NaOH, and the phases are separated and dried over MgSO.sub.4. The solid obtained is washed by stirring with heptane. Yield: 13.5 g (37 mmol), 87% of theory, purity according to .sup.1H-NMR about 95%.

Example 2: 6-Bromo-8,8-dimethyl-3-phenyl-8H-lndolo[3,2,1-de]-acridine

(9) ##STR00254##

Methyl 2-(3-phenyl-9H-carbazole)benzoate

(10) 85 g (350 mmol) of 3-phenyl-9H-carbazole, 63 ml (262 mmol) of methyl 2-iodobenzoate, 87 g (631 mmol) of potassium carbonate and 9.3 g (35 mmol) of 18-crown-6 are initially introduced in 1200 ml of DMF under a protective gas and heated at 130 C. for 86 h. The mixture is subsequently evaporated, washed by stirring with hot heptane and purified by chromatography (heptane/CH.sub.2Cl.sub.2 1:1). The product is washed by stirring with hot hexane and filtered off with suction.

(11) Yield: 82 g (219 mmol), 62% of theory, purity according to .sup.1H-NMR about 97%.

Methyl 2-(3-bromo-6-phenyl-9H-carbazole)benzoate

(12) 78.4 g (207 mmol) of methyl 2-(3-phenyl-9H-carbazole)benzoate are cooled to 10 C. in 2000 ml of DMF, 37.3 g (207 mmol) of NBS are added in portions, and the mixture is stirred at room temperature for 6 h. 500 ml of water are subsequently added to the mixture, which is then extracted with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4, and the solvent is removed in vacuo. The product is washed by stirring with hot toluene and filtered off with suction.

(13) Yield: 91.4 g (200 mmol), 95% of theory, purity according to .sup.1H-NMR about 98%.

2-[2-(3-Bromo-6-phenylcarbazol-9-yl)phenyl]propan-2-ol

(14) 97 g (213 mmol) of methyl 2-(3-bromo-6-phenyl-9H-carbazole)benzoate are dissolved in 1500 ml of dried THF and degassed. The mixture is cooled to 78 C., and 569 ml (854 mmol) of methyllithium are added over the course of 40 min. The mixture is allowed to warm to 40 C. over the course of 1 h, and the reaction is monitored by TLC. When the reaction is complete, it is carefully quenched at 30 C. using MeOH. The reaction solution is evaporated to , and 1 l of CH.sub.2Cl.sub.2 is added, the mixture is washed, and the organic phase is dried over MgSO.sub.4 and evaporated.

(15) Yield: 93.4 g (204 mmol), 96% of theory, purity according to .sup.1H-NMR about 96%.

6-Bromo-8,8-dimethyl-3-phenyl-8H-indolo[3,2,1-de]acridine

(16) 20 g (43.6 mmol) of 2-[2-(3-bromo-6-phenylcarbazol-9-yl)phenyl]propan-2-ol are dissolved in 1200 ml of degassed toluene, a suspension of 40 g of polyphosphoric acid and 28 ml of methanesuffonic acid is added, and the mixture is heated at 60 C. for 1 h. The batch is cooled, and water is added. A solid precipitates out and is dissolved in CH.sub.2Cl.sub.2/THF (1:1). The solution is carefully rendered alkaline using 20% NaOH, and the phases are separated and dried over MgSO.sub.4. The solid obtained is washed by stirring with heptane. Yield: 16.3 g (37 mmol), 84% of theory, purity according to .sup.1H-NMR about 95%.

Example 3: 3-Bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

(17) ##STR00255##

(18) 6.3 g (22.2 mmol) of 8,8-dimethylindolo[3,2,1-de]acridine are initially introduced in 150 ml of CH.sub.2Cl.sub.2. A solution of 3.9 g (22.3 mmol) of NBS in 100 ml of acetonitrile is subsequently added dropwise at 15 C. with exclusion of light, and the mixture is stirred at room temperature for a further 4 h. For work-up, 150 ml of water are added to the mixture, which is then extracted with CH.sub.2C.sub.2. The organic phase is dried over MgSO.sub.4, and the solvent is removed in vacuo. The product is washed by stirring with hot hexane and filtered off with suction.

(19) Yield: 4.5 g (12 mmol), 57% of theory, purity according to .sup.1H-NMR about 97%.

Example 4: 3,6-Dibromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

(20) ##STR00256##

(21) 6.3 g (22.2 mmol) of 8,8-dimethylindolo[3,2,1-de]acridine are initially introduced in 150 ml of CH.sub.2Cl.sub.2. A solution of 8 g (45.1 mmol) of NBS in 100 ml of acetonitrile is subsequently added dropwise at 15 C. with exclusion of light, and the mixture is stirred at room temperature for a further 4 h. For work-up, 150 ml of water are added to the mixture, which is then extracted with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4, and the solvents are removed in vacuo. The product is washed by stirring with hot hexane and filtered off with suction.

(22) Yield: 7.3 g (16 mmol), 75% of theory, purity according to .sup.1H-NMR about 97%.

Example 5: 10-Bromo-8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]-acridine

(23) ##STR00257##

8,8-Dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine

(24) 19.8 g (45 mmol) of 3,6-dibromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine, 11.4 g (94 mmol) of phenylboronic acid and 164 ml of saturated NaHCO.sub.3 solution are suspended in 1500 ml of toluene and 150 ml of ethanol. 1.9 g (1.6 mmol) of Pd(PPh.sub.3).sub.4 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.

(25) Yield: 18.5 g (42 mmol), 95% of theory, purity according to .sup.1H-NMR about 98%.

10-Bromo-8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine

(26) 9.6 g (22.2 mmol) of 8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine are initially Introduced in 150 ml of CH.sub.2Cl.sub.2. A solution of 3.9 g (22.3 mmol) of NBS in 100 ml of acetonitrile is subsequently added dropwise at 15 C. with exclusion of light, and the mixture is stirred at room temperature for a further 4 h. For work-up, 150 ml of water are added to the mixture, which is then extracted with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4, and the solvent is removed in vacuo. The product is washed by stirring with hot hexane and filtered off with suction.

(27) Yield: 10.7 g (20.8 mmol), 94% of theory, purity according to .sup.1H-NMR about 97%.

Example 6: 3-Bromo-8H-8,12b-diazabenzo[a]aceanthrylene

(28) ##STR00258##

Fluoro-9-(2-nitrophenyl)-9H-carbazole

(29) A degassed solution of 97 ml (990 mmol) of 2-fluoroaniline and 165 g (862 mmol) of 2-bromochlorobenzene in 1000 ml of NMP is saturated with N.sub.2 for 1 h. Then firstly 28.9 g (100 mmol) of trichlorohexylphosphine, then 11.2 g (50 mmol) of palladium(II) acetate are added to the solution, and 549 g (2.5 mol) of potassium carbonate in the solid state are subsequently added. The reaction mixture is heated under reflux for 18 h. After cooling to room temperature, 1000 ml of water are carefully added. The organic phase is washed with 450 ml of water and dried over MgSO.sub.4, and the solvent is removed in vacuo. The pure product is obtained by recrystallisation.

(30) Yield: 111 g (760 mmol), 70% of theory, purity according to .sup.1H-NMR about 98%.

6-Bromo-1-fluoro-9-(2-nitrophenyl)-9H-carbazole

(31) 6.7 g (22.2 mmol) of fluoro-9-(2-nitrophenyl)-9H-carbazole are initially duced in 150 ml of CH.sub.2Cl.sub.2. A solution of 3.9 g (22.3 mmol) of NBS in 100 ml of acetonitrile is subsequently added dropwise at 15 C. with exclusion of light, and the mixture is stirred at room temperature for a further 4 h. For work-up, 150 ml of water are added to the mixture, which is then extracted with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4, and the solvent is removed in vacuo. The product is washed by stirring with hot hexane and filtered off with suction.

(32) Yield: 8 g (20 mmol), 97% of theory, purity according to .sup.1H-NMR about 97%.

2-(6-Bromo-1-fluorocarbazol-9-yl)phenylamine

(33) 67 g (219 mmol) of 6-bromo-1-fluoro-9-(2-nitrophenyl)-9H-carbazole are dissolved in 820 ml of EtOH, 143 g (755 mmol) of ZnCl.sub.2 are added at room temperature, and the mixture is heated under reflux for 6 h. The mixture is subsequently warmed to room temperature over the course of 1 h, 20% NaOH is added, and, after phase separation, the solvent is removed, and the residue is purified by chromatography.

(34) Yield: 44 g (125 mmol), 72% of theory, purity according to .sup.1H-NMR about 97%.

3-Bromo-8H-8,12b-diazabenzo[a]aceanthrylene

(35) 25 g (72 mmol) of 2-(6-bromo-1-fluorocarbazol-9-yl)phenylamine are dissolved in 200 ml of DMF under a protective gas, 2.8 g (72 mmol) of NaH (60% in oil) are added at room temperature, and the mixture is boiled under reflux for 6 h. The mixture is subsequently warmed to room temperature over the course of 1 h, the solvent is removed, and the residue is purified by chromatography.

(36) Yield: 19 g (54 mmol), 78% of theory, purity according to .sup.1H-NMR about 98%.

Bromo-8-phenyl-8H-8,12b-diazabenzo[a]aceanthrylene

(37) A degassed solution of 30 g (86.6 mmol) of 3-bromo-8H-8,12b-diazabenzo[a]aceanthrylene and 8.8 g (95.9 mmol) of phenylamine in 1000 ml dioxane is saturated with N.sub.2 for 1 h. Then firstly 0.9 ml (4.3 mmol) of P(tBu).sub.3, then 0.48 g (2.1 mmol) of palladium(II) acetate are added to the solution, and 12.6 g (131 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 18 h. After cooling to room temperature, 1000 ml of water are carefully added. The organic phase is washed with 450 ml of water and dried over MgSO.sub.4, and the solvent is removed in vacuo. The pure product is obtained by recrystallisation.

(38) Yield: 27 g (64 mmol), 76% of theory, purity according to .sup.1H-NMR about 98%.

Example 7: 8,8-Dimethyl-8H-indolo[3,2,1-de]acridine-3-boronic acid

(39) ##STR00259##

(40) 93.9 g (259 mmol) of 3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine are dissolved in 1500 ml of dry THF, 135 ml (337 mmol) of a 2.5 M solution of n-butyllithium in cyclohexane are added dropwise at 70 C., after 1 h 37 ml of trimethyl borate (336 mmol) are added dropwise, the mixture is warmed to room temperature over the course of 1 h, the solvent is removed, and the residue, which is uniform according to .sup.1H-NMR, is employed in the subsequent reaction without further purification.

(41) Yield: 77 g (235 mmol), 91% of theory, purity according to .sup.1H-NMR about 98%.

Example 8: 8,8-Dimethyl-8H-indolo[3,2,1-de]acridine-6-boronic acid

(42) ##STR00260##

(43) 93.7 g (259 mmol) of 6-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine are dissolved in 1500 ml of dry THF, 135 ml (337 mmol) of a 2.5 M solution of n-butyllithium in cyclohexane are added dropwise at 70 C., after 1 h 37 ml of trimethyl borate (336 mmol) are added dropwise, the mixture is warmed to room temperature over the course of 1 h, the solvent is removed, and the residue, which is uniform according to .sup.1H-NMR, is employed in the subsequent reaction without further purification.

(44) Yield: 67 g (204 mmol), 80% of theory, purity according to .sup.1H-NMR about 96%.

Example 9: 8,8-Dimethyl-6-phenyl-8H-indolo[3,2,1-de]acridine-3-boronic acid

(45) ##STR00261##

(46) 113.4 g (259 mmol) of 6-bromo-8,8-dimethyl-3-phenyl-8H-indolo[3,2,1-de]-acridine are dissolved in 1500 ml of dry THF, 135 ml (337 mmol) of a 2.5 M solution of n-butyllithium in cyclohexane are added dropwise at 70 C., after 1 h 37 ml of trimethyl borate (336 mmol) are added dropwise, the mixture is warmed to room temperature over the course of 1 h, the solvent is removed, and the residue, which is uniform according to .sup.1H-NMR, is employed in the subsequent reaction without further purification.

(47) Yield: 92 g (229 mmol), 89% of theory, purity according to .sup.1H-NMR about 98%.

Example 10: 8,8-Dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine-10-boronic

(48) ##STR00262##

(49) 133 g (259 mmol) of 10-bromo-8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine are dissolved in 1500 ml of dry THF, 135 ml (337 mmol) of a 2.5 M solution of n-butyllithium in cyclohexane are added dropwise at 70 C., after 1 h 37 ml of trimethyl borate (336 mmol) are added dropwise, the mixture is warmed to room temperature over the course of 1 h, the solvent is removed, and the residue, which is uniform according to .sup.1H-NMR, is employed in the subsequent reaction without further purification.

(50) Yield: 111 g (233 mmol), 90% of theory, purity according to .sup.1H-NMR about 98%.

Example 11: 8,8-Dimethyl-3-(9-phenyl-9H-carbazol-3-yl)-8H-indolo-[3,2,1-de]acridine (compound H5)

(51) ##STR00263##

(52) 36 g (110 mmol) of 8,8-dimethyl-8H-indolo[3,2,1-de]acridine-3-boronic acid, 35 g (110 mmol) of 3-bromo-9-phenyl-9H-carbazole and 9.7 g (92 mmol) of sodium carbonate are suspended in 350 ml of toluene, of dioxane and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and 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 CH.sub.2Cl.sub.2/isopanol and finally sublimed in a high vacuum.

(53) Yield: 52 g (100 mmol), 91% of theory, purity according to HPLC 99.9%.

Example 12: 4-(8,8-Dimethyl-8H-indolo[3,2,1-de]acridin-3-yl)phenyl]-diphenylamine (compound HTM2)

(54) ##STR00264##

(55) The compound is synthesised by the same procedure as Example 13 by reaction of the corresponding indolo[3,2,1-de]acridineboronic acid with 35.6 g (110 mmol) of 4-bromophenyldiphenylamine.

(56) The residue is recrystallised from toluene and from CH.sub.2Cl.sub.2/isopropanol and finally sublimed in a high vacuum.

(57) Yield: 51 g (97 mmol), 89% of theory, purity according to HPLC 99.9%.

Example 13: 8,8,8,8-Tetramethyl-8H,8H-[3,3]bi(indolo[3,2,1-de]-acridinyl) (compound H7)

(58) ##STR00265##

(59) The compound is synthesised by the same procedure as Example 13 by reaction of the corresponding indolo[3,2,1-de]acridineboronic acid with 39 g (110 mmol) of 3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine. The residue is recrystallised from toluene and from CH.sub.2Cl.sub.2/isopropanol and finally sublimed in a high vacuum.

(60) Yield: 55 g (100 mmol), 92% of theory, purity according to HPLC 99.9%.

Example 14: 8,8,8,8-Tetramethyl-8H,8H-[3,6]bi(indolo[3,2,1-de]-acridinyl) (compound H8)

(61) ##STR00266##

(62) The compound is synthesised by the same procedure as Example 13 by reaction of the corresponding indolo[3,2,1-de]acridineboronic acid with 39 g (110 mmol) of 6-bromo-8,8-dimethyl-8H-lndolo[3,2,1-de]acridine.

(63) The residue is recrystallised from toluene and from CH.sub.2Cl.sub.2/isopropanol and finally sublimed in a high vacuum.

(64) Yield: 49.5 g (90 mmol), 82% of theory, purity according to HPLC 99.9%.

Example 15: (8,8-Dimethyl-8H-indolo[3,2,1-de]acridin-3-yl)diphenylamine (compound HTM4)

(65) ##STR00267##

(66) A degassed solution of 31 g (86.6 mmol) of 3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine and 16 g (95.9 mmol) of diphenylamine in 1000 ml of dioxane is saturated with N.sub.2 for 1 h. Then firstly 0.9 ml (4.3 mmol) of P(tBu).sub.3, then 0.48 g (2.1 mmol) of palladium(II) acetate are added to the solution, and 12.6 g (131 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 18 h. After cooling to room temperature, 1000 ml of water are carefully added. The organic phase is washed with 450 ml of water and dried over MgSO.sub.4, and the solvent is removed in vacuo. The pure product is obtained by recrystallisation and final sublimation.

(67) Yield: 34 g (76 mmol), 89% of theory, purity according to HPLC 99.9%.

Example 16: 3-(9,9-Dimethyl-9H-acridin-10-yl)-8,8-dimethyl-8H-lndolo[3,2,1-de]acridine (compound HTM5)

(68) ##STR00268##

(69) The compound is synthesised by the same procedure as Example 18 by reaction of 31 g (86.6 mmol) of 3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]-acridine and 20 g (95.9 mmol) of 9,9-dimethyl-9,10-dihydroacridine.

(70) The residue is recrystallised from toluene and finally sublimed in a high vacuum.

(71) Yield: 37 g (76 mmol), 80% of theory, purity according to HPLC 99.9%.

Example 17: (8,8-Dimethyl-6-phenyl-8H-indolo[3,2,1-de]acridin-3-yl)diphenylamine (compound HTM6)

(72) ##STR00269##

(73) The compound is synthesised by the same procedure as Example 18 by reaction of 37.6 g (86.6 mmol) of 6-bromo-8,8-dimethyl-3-phenyl-8H-indolo[3,2,1-de]acridine with the corresponding amine.

(74) The residue is recrystallised from toluene and finally sublimed in a high vacuum.

(75) Yield: 39 g (79 mmol), 87% of theory, purity according to HPLC 99.9%.

Example 18: (8,8-Dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridin-10-yl)diphenylamine (compound HTM7)

(76) ##STR00270##

(77) The compound is synthesised by the same procedure as Example 18 by reaction of 44 g (86.6 mmol) of 10-bromo-8,8-dimethyl-3,6-diphenyl-8H-indolo[3,2,1-de]acridine with the corresponding amine.

(78) The residue is recrystallised from toluene and finally sublimed in a high vacuum.

(79) Yield: 39 g (64 mmol), 75% of theory, purity according to HPLC 99.9%.

Example 19: 3-Carbazol-9-yl-8,8-dimethyl-8H-indolo[3,2,1-de]acridine compound H9)

(80) ##STR00271##

(81) The compound is synthesised by the same procedure as Example 18 by reaction of 31 g (86.0 mmol) of 3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]-acridine with 16 g (95.9 mmol) of carbazole.

(82) The residue is recrystallised from toluene and finally sublimed in a high vacuum.

(83) Yield: 38 g (64 mmol), 85% of theory, purity according to HPLC 99.9%.

Example 20: 8-Carbazol-9-yl-2-eth-(E)-ylidene-3-phenyl-1-prop-2-en-(E)-ylidene-2,3-dihydro-1H-pyrazino[3,2,1-jk]carbazole (compound HTM9)

(84) ##STR00272##

(85) The compound is synthesised by the same procedure as Example 18 by reaction of 37 g (86.6 mmol) of 3-bromo-8H-8,12b-diazabenzo[a]aceanthrylene with 16 g (95.9 mmol) of carbazole.

(86) The residue is recrystallised from toluene and finally sublimed in a high vacuum.

(87) Yield: 31 g (60 mmol), 70% of theory, purity according to HPLC 99.9%.

Example 21: N4,N4-Bis-(8,8-dimethyl-8H-Indolo[3,2,1-de]acridin-3-yl)-N4,N4-diphenylbiphenyl-4,4-diamine (compound HTM8)

(88) ##STR00273##

(89) A degassed solution of 31 g (86.6 mmol) of 3-bromo-8,8-dimethyl-8H-indolo[3,2,1-de]acridine and 13.4 g (40 mmol) of N,N-diphenylbenzidine in 1000 ml of dioxane is saturated with N.sub.2 for 1 h. Then firstly 0.9 ml (4.3 mmol) of P(tBu).sub.3, then 0.48 g (2.1 mmol) of palladium(II) acetate are added to the solution, and 12.6 g (131 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 18 h. After cooling to room temperature, 1000 ml of water are carefully added. The organic phase is washed with 450 ml of H.sub.2O and dried over MgSO.sub.4, and the solvent is removed in vacuo. The pure product is obtained by recrystallisation.

(90) Yield: 29 g (32 mmol), 81% of theory, purity according to HPLC 99.9%.

Example 22: Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(8,8-dimethyl-8H-indolo[3,2,1-de]acridin-3-yl)phenyl]amine (compound HTM3)

(91) ##STR00274##

Biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine

(92) A degassed solution of 490 mg (0.16 mmol) of copper(I) chloride and 906 mg (5 mmol) of 1,10-phenanthroline in 100 ml of toluene is saturated with N.sub.2 for 1 h and heated to 130 C. 18 g (50 mmol) of N-[1,1-biphenyl]-4-yl-9,9-dimethyl-9H-fluoren-2-amine and 14 g (50 mmol) of 1-bromo-4-iodobenzene are subsequently added to the solution, which is then heated at 180 C. for 2 h. After cooling, 180 ml of water are added to the mixture, the organic phase is separated off, and the solvent is removed in vacuo. The product is recrystallised from n-hexane.

(93) Yield: 15 g (29 mmol), 58% of theory, purity according to .sup.1H-NMR about 98%.

Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(8,8-dimethyl-8H-indolo[3,2,1-de]acridin-3-yl)phenyl]amine

(94) The compound is synthesised by the same procedure as Example 13 by reaction of the corresponding indolo[3,2,1-de]acridineboronic acid with 15 g (29 mmol) of biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine.

(95) The residue is recrystallised from ethyl acetate/heptane and finally sublimed in a high vacuum.

(96) Yield: 14.4 g (20 mmol), 69% of theory, purity according to HPLC 99.9%.

Example 23: 3-(12,12-Dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)-8,8-dimethyl-8H-indolo[3,2,1-de]acridine (compound H10)

(97) ##STR00275##

(98) The compound is synthesised by the same procedure as Example 13 by reaction of the corresponding indolo[3,2,1-de]acridineboronic acid with 48 g (110 mmol) of 7-bromo-2,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene.

(99) The residue is recrystallised from toluene and from CH.sub.2Cl.sub.2/isopropanol and finally sublimed in a high vacuum.

(100) Yield: 54.5 g (85 mmol), 78% of theory, purity according to HPLC 99.9%.

Example 24: [4-(8,12b-Diazabenzo[a]aceanthrylen-8-yl)biphenyl-4-yl]-diphenylamine (compound HTM10)

(101) ##STR00276##

1-Fluoro-9-(2-aminophenyl)-9H-carbazole

(102) 50 g (163 mmol) of 1-fluoro-9-(2-nitrophenyl)-9H-carbazole are dissolved in 600 ml of EtOH, 67 g (489 mmol) of ZnCl.sub.2 are added at room temperature, and the mixture is heated under reflux for 6 h. The mixture is subsequently warmed to room temperature over the course of 1 h, 20% NaOH is added, and, after phase separation, the solvent is removed, and the residue is purified by chromatography.

(103) Yield: 33 g (119 mmol), 73% of theory, purity according to .sup.1H-NMR about 98%.

8H-8,12b-Diazabenzo[a]aceanthrylene

(104) 30 g (109 mmol) of 1-fluoro-9-(2-aminophenyl)-9H-carbazole are dissolved in 200 ml of DMF under a protective gas, 4.4 g (109 mmol) of NaH (60% in oil) are added at room temperature, and the mixture is boiled under reflux for 6 h. The mixture is subsequently warmed to room temperature over the course of 1 h, the solvent is removed, and the residue is purified by chromatography.

(105) Yield: 23.4 g (86 mmol), 79% of theory, purity according to .sup.1H-NMR about 98%.

[4-(8,12b-Diazabenzo[a]aceanthrylen-8-yl)biphenyl-4-yl]diphenylamine

(106) A degassed solution of 35.6 g (89 mmol) of (4-bromobiphenyl-4-yl)diphenylamine and 22.0 g (81 mmol) of 8H-8,12b-diazabenzo[a]aceanthrylene in 1000 ml of dioxane is saturated with N.sub.2 for 1 h. Then firstly 1.0 ml (4 mmol) of P(tBu).sub.3, then 0.4 g (2 mmol) of palladium(II) acetate are added to the solution, and 11.7 g (122 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 18 h. After cooling to room temperature, 1000 ml of water are carefully added. The organic phase is separated off, washed with 450 ml of water and dried over MgSO.sub.4, and the solvent is removed in vacuo. The pure product is obtained by recrystallisation and final sublimation in a high vacuum.

(107) Yield: 33.4 g (58 mmol), 72% of theory, purity according to HPLC 99.9%.

Example 25: 3-Bromo-8,8-diphenyl-8H-indolo[3,2,1-de]acridine

(108) ##STR00277##

Methyl 2-(3-bromo-9H-carbazole)benzoate

(109) 62 g (207 mmol) of methyl 2-(9H-carbazole)benzoate are cooled to 10 C. in 2000 ml of DMF, 37.3 g (207 mmol) of NBS are added in portions, and the mixture is stirred at room temperature for 6 h. 500 ml of water are subsequently added to the mixture, which is then extracted with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4, and the solvent is removed in vacuo.

(110) The product is washed by stirring with hot toluene and filtered off with suction.

(111) Yield: 72 g (190 mmol), 92% of theory, purity according to .sup.1H-NMR about 98%.

[2-(3-Bromocarbazol-9-yl)phenyl]diphenylmethanol

(112) 21.3 g (86.7 mmol) of Ce(III) chloride are initially introduced in 250 ml of THF. 30 g (78.9 mmol) of methyl 2-(3-bromo-9H-carbazole)benzoate (dissolved in 600 ml of dried THF) are added dropwise to this solution at room temperature, and the mixture is stirred for 2.5 hours. The mixture is cooled to 0 C., and 118.3 ml (236 mmol) of 2 M phenylmagnesium bromide in THF are added, and the mixture is stirred overnight. When the reaction is complete, it is carefully quenched at 30 C. using MeOH. The reaction solution is evaporated to , 1 l of CH.sub.2Cl.sub.2 is added, and the mixture is washed. The organic phase is subsequently dried over MgSO.sub.4 and evaporated.

(113) Yield: 38.7 g (76.7 mmol), 97% of theory, purity according to .sup.1H-NMR about 94%.

Bromo-8,8-diphenyl-8H-indolo[3,2,1-de]acridine

(114) 38.7 g (76.7 mmol) of 2-[2-(3-bromocarbazol-9-yl)phenyl]propan-2-ol are dissolved in 750 ml of degassed dichloromethane, a suspension of 49.6 g of polyphosphoric acid and 33 ml of methanesulfonic acid is added, and the mixture is heated at 60 C. for 1 h. The batch is cooled, and water is added. A solid precipitates out and is dissolved in CH.sub.2Cl.sub.2/THF (1:1). The solution is carefully rendered alkaline using 20% NaOH, and the phases are separated and dried over MgSO.sub.4. The solid obtained is washed by stirring with heptane. Yield: 22 g (45 mmol), 59% of theory, purity according to .sup.1H-NMR about 95%.

(115) The following compounds are obtained analogously:

(116) TABLE-US-00002 Starting Starting Ex. material 1 material 2 Product Yield 25a 0 63% 25b 74% 25c 59%

Example 26: 8,8-Diphenyl-8H-Indolo[3,2,1-de]acridine-6-boronic acid

(117) ##STR00287##

(118) 125.9 g (259 mmol) of bromo-8,8-diphenyl-8H-indolo[3,2,1-de]acridine are dissolved in 1500 ml of dry THF. 135 ml (337 mmol) of a 2.5 M solution of n-butyllithium in cyclohexane are added dropwise at 70 C., and, after 1 h, 37 ml of trimethyl borate (336 mmol) are added dropwise. The mixture is warmed to room temperature over the course of 1 h, the solvent is removed, and the residue, which is uniform according to .sup.1H-NMR, is employed in the subsequent reaction without further purification.

(119) Yield: 87.6 g (194 mmol), 75% of theory, purity according to .sup.1H-NMR about 96%.

(120) The following compounds are obtained analogously:

(121) TABLE-US-00003 Ex. Starting material Product Yield 26a 61% 26b 0 55% 26c 56% 26d 51%

Example 27: Biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine

(122) ##STR00296##

(123) A degassed solution of 24.6 g (87 mmol) of 1-bromo-4-iodobenzene and 28.8 g (80 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine in 1000 ml of dioxane is saturated with N.sub.2 for 1 h. Then firstly 0.9 ml (4.3 mmol) of P(tBu).sub.3, then 0.48 g (2.1 mmol) of palladium(II) acetate are added to the solution. 12.6 g (131 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 18 h. After cooling to room temperature, 1000 ml of water are carefully added. The organic phase is washed with 450 ml of water and dried over MgSO.sub.4, and the solvent is removed in vacuo. The pure product is obtained by recrystallisation and final sublimation.

(124) Yield: 31.5 g (61 mmol), 70% of theory, purity according to HPLC 98%.

Example 28: Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[4-(8,8-diphenyl-8H-Indolo[3,2,1-de]acridin-3-yl)phenyl]amine (HTM14)

(125) ##STR00297##

(126) 85 g (190 mmol) of 8,8-diphenyl-8H-indolo[3,2,1-de]acridine-3-boronic acid, 98 g (190 mmol) of biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)amine and 13 g (123 mmol) of sodium carbonate are suspended in 180 ml of toluene, 180 ml of dioxane and 60 ml of water. 3.0 mg mmol) of Pd(PPh.sub.3).sub.4 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. The purity is 99.9%. The yield is 124 g (147 mmol), corresponding to 78% of theory.

(127) The following compounds are obtained analogously:

(128) TABLE-US-00004 Ex. Starting material Product Yield 28a 00 64% 28b 01 02 03 62% 28c 04 05 06 63% 28d 07 08 09 68% 28e 0 59% 28f 57% 28g 52% 28h 0 55% 28i 75% 28j 66% 28k 0 64%

Example 29: (8,8-Diphenyl-8H-indolo[3,2,1-de]acridin-3-yl)diphenylamine (HTM21)

(129) ##STR00331##

(130) A degassed solution of 42 g (86.6 mmol) of 3-bromo-8,8-diphenyl-8H-indolo[3,2,1-de]acridine and 16 g (95.9 mmol) of diphenylamine in 1000 ml of dioxane is saturated with N.sub.2 for 1 h. Then firstly 0.9 ml (4.3 mmol) of P(tBu).sub.3, then 0.48 g (2.1 mmol) of palladium(II) acetate are added, and 12.6 g (131 mmol) of NaOtBu in the solid state are subsequently added to the solution. The reaction mixture is heated under reflux for 18 h. After cooling to room temperature, 1000 ml of water are carefully added. The organic phase is washed with 450 ml of water and dried over MgSO.sub.4, and the solvent is removed in vacuo. The pure product is obtained by recrystallisation and final sublimation.

(131) Yield: 39 g (69 mmol), 80% of theory, purity according to HPLC 99.9%.

(132) The following compounds are obtained analogously:

(133) TABLE-US-00005 Starting Ex. material Product Yield 29a 64% 29b 72% 29c 0 61% 29d 66% 29e 72% 29f 67% 29g 0 58%

Example 30: 3-(9,9-Dimethyl-10-phenyl-9,10-dihydroacridin-2-yl)-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

2-Chloro-9,9-dimethyl-9,10-dihydroacridine

(134) ##STR00353##

(135) 30.3 g (116 mmol) of 2-[2-(4-chlorophenylamino)phenyl]propan-2-ol are dissolved in 700 ml of degassed toluene, a suspension of 93 g of polyphosphoric acid and 61.7 g of methanesulfonic acid is added, and the mixture is stirred at room temperature for 1 h and heated at 50 C. for 1 h. The batch is cooled and poured onto ice and extracted three times with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over magnesium sulfate and evaporated. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gives 25.1 g (89%) of 2-chloro-9,9-dimethyl-9,10-dihydroacridine as pale-yellow crystals.

2-Chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine

(136) ##STR00354##

(137) A degassed solution of 16.6 ml (147 mmol) of 4-iodobenzene and 30 g (123 mmol) of 2-chloro-9,9-dimethyl-9,10-dihydroacridine in 600 ml of toluene is saturated with N.sub.2 for 1 h. Then firstly 2.09 ml (8.6 mmol) of P(tBu).sub.3 and then 1.38 g (6.1 mmol) of palladium(II) acetate are added to the solution. 17.7 g (185 mmol) of NaOtBu as solid are subsequently added. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 ml of water are carefully added. The aqueous phase is washed with 350 ml of toluene and dried over MgSO.sub.4, and the solvent is removed in vacuo. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gives 32.2 g (81%) of 2-chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine as pale-yellow crystals.

3-(9,9-Dimethyl-10-phenyl-9,10-dihydroacridin-2-yl)-8,8-dimethyl-8H-indolo[3,2,1-de]acridine

(138) ##STR00355##

(139) 36 g (110 mmol) of 8,8-dimethyl-8H-indolo[3,2,1-de]acridine-3-boronic acid, 35.2 g (110 mmol) of 2-chloro-9,9-dimethyl-10-phenyl-9,10-dihydroacridine and 9.7 g (92 mmol) of sodium carbonate are suspended in 350 ml of toluene, 350 ml of dioxane and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and 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 CH.sub.2Cl.sub.2/isopropanol and finally sublimed in a high vacuum.

(140) Yield: 52 g (100 mmol), 91% of theory, purity according to HPLC 99.9%.

B) Device Examples C1-I63: Production of OLEDs

(141) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 04/058911, which is adapted to the circumstances described here (layer-thickness variation, materials used).

(142) Data for various OLEDs are presented in the examples C1 to 163 below (see Tables 1-3). Glass plates coated with structured ITO (indium tin oxide) in a thickness of 150 nm are coated with 20 nm of PEDOT (poly(3,4-ethylenedioxy-2,5-thiophene, applied by spin coating from water; purchased from H. C. Starck, Goslar, Germany) 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/optional hole-injection layer (HIL)/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL) I/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 4.

(143) 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 materials in a certain proportion by volume by coevaporation. An expression such as H3:CBP:TER1 (55%:35%:10%) here means that material H3 is present in the layer in a proportion by volume of 55%, CBP 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.

(144) 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-luminance characteristic lines (IUL characteristic lines), and the lifetime are determined. The lifetime is defined as the time after which the luminous density has dropped to a certain proportion from a particular initial luminous density. The designation LD80 means that the said lifetime is the time at which the luminous density has dropped to 80% of the initial luminous density, i.e. from, for example, 4000 cd/m.sup.2 to 3200 cd/m.sup.2. Analogously, LD50 denotes the time after which the initial luminance has dropped to half. The values for the lifetime can be converted to a figure for other initial luminous densities with the aid of conversion formulae known to the person skilled in the art. The lifetime for an initial luminous density of 1000 cd/m.sup.2 is a usual expression here.

(145) OLEDs which comprise the blue-fluorescent emitter D1 are started at an initial luminous density of 6000 cd/m.sup.2 for determination of the lifetime. OLEDs which comprise the green-fluorescent emitter D2 are started at a luminous density of 25,000 cd/m.sup.2. OLEDs comprising the phosphorescent emitters TER1 and TEG1 are started at 4000 cd/m.sup.2.

(146) The data for the various OLEDs are summarised in Tables 2 and 3. Examples C1-C22 are comparative examples in accordance with the prior art, Examples I1-I63 show data for OLEDs in which materials according to the invention are employed.

(147) Some of the examples are explained in greater detail below in order to illustrate the advantages of the compounds according to the invention. However, it should be pointed out that this only represents a selection of the data shown in Tables 2 and 3. As can be seen from the table, significant improvements over the prior art are also achieved on use of the compounds according to the invention that are not described in greater detail, in some cases in all parameters, but in some cases only an improvement in the efficiency or voltage or lifetime is observed. However, even the improvement in one of the said parameters represents a significant advance.

(148) Use of Compounds According to the Invention as Hole-Transport or Electron-Blocking Materials

(149) The materials according to the invention can be employed in accordance with the invention, inter alia, on the hole-transport side of OLEDs, more precisely as hole-transport or electron-blocking materials. This is shown with reference to Examples I1-I26, I40-I55, I57. Comparative Examples C1-C9, C11, C12 and C19-C22 in accordance with the prior art comprise materials HTM1 and HTM12 as hole-transport materials and NPB, EBM1, HTM11 and HTM12 as electron-blocking materials.

(150) If Example I1 is compared with Example C3, it can be seen that the operating voltage can be reduced by 0.2 V through the use of material HTM8 according to the invention in the hole-transport layer, which, in combination with slightly improved quantum efficiency, results in an improvement in the power efficiency from 10.7 lm/W to 12.1 lm/W, i.e. by about 15%. A similar improvement is also observed in the case of a hole-transport layer with a thickness of 200 nm (Examples C5 and I2). Furthermore, it is evident that the difference between the voltage for a thick HTL (200 nm) and a thinner HTL (110 nm) reduces from 0.5 V (Examples C3 and C5) to 0.3 V (Examples I1 and I2). This is an important aspect, since thicker hole-transport layers are often desirable for optimisation of the optical coupling-out. It is desirable here for the operating voltage to remain as low as possible. A further advantage of material HTM8 is the increase in the lifetime. In the case of a layer with a thickness of 110 nm, although the improvement is 10%, material HTM1 in accordance with the prior art exhibits a significant drop in the lifetime to 250,000 h in an OLED having an HTL with a thickness of 200 nm compared with an OLED having an HTL with a thickness of 110 nm, while an OLED comprising 200 nm of the material according to the invention even exhibits a slight improvement in the lifetime to 340,000 h (Examples C3, C5, I1 and I2). Compared with the triarylamine-substituted compound HTM12 in accordance with the prior art, material HTM8 exhibits an even more significant improvement in the performance data (Examples C19, C20, I1 and I2).

(151) If HTM3 is used as electron-blocking material together with fluorescent dopants D1 and D2, a significant improvement in the operating voltage and efficiency is obtained compared with NPB (Examples C1-3, C5, I3-I6). However, it is much more important that the lifetime can be increased through the use of HTM3 in the case of blue emission (Examples Cl, C2, I3 and I4) to about 7700 h compared with 5200 h with NPB (with ETM1 as electron-transport material). This corresponds to a significant increase of 50%. In the case of green emission, the improvement in the lifetime is somewhat less, with an increase of about 25% being obtained (Examples C3, C5, I5 and I6). Similar improvements can be achieved through the use of compound HTM2 according to the invention (Examples I7-I9). In particular, a combination of the novel materials HTM8 as hole-transport material and HTM3 as electron-blocking material gives very good performance data: compared with the prior art, the lifetime is improved by about 50% and the power efficiency by about 25% (Examples C2 and I12).

(152) Furthermore, the compounds according to the invention can also be employed as single layers, which represents a significant advantage over the combination of HTM1 and NPB with respect to the processing complexity. This is demonstrated with reference to materials HTM2 and HTM3 in combination with the blue-fluorescent dopant D1. Although the two-layer structure HTM1/HTM2 (Ex. 18) or HTM1/HTM3 (Ex. 14) exhibits a better voltage and efficiency than the single layer (Examples I10 and I11), the single layer is, however, still significantly superior to the prior art (Ex. C2) with respect to the lifetime. The voltage and efficiency are approximately the same.

(153) In phosphorescent OLEDs, the compounds according to the invention exhibit, in particular, a significant improvement in the lifetime and an improvement in the quantum or current efficiency on use as electron-blocking layer (Examples C4, C6-C9, C1, C12 and I13-I26, I41, I43, I44, I46, I50-I53, I57). For example, if compound HTM3 according to the invention is used in an OLED comprising the green-phosphorescent emitter TEG1, the lifetime is increased by up to more than 60% compared with material EBM1 in accordance with the prior art (Examples C12 and I17). The quantum efficiency is increased by about 10%, which, owing to the virtually unchanged operating voltage, has the consequence that the power efficiency is also increased by about 10%. The increase in efficiency can be explained by the greater triplet gap of the compounds according to the invention. Compared with materials HTM11 and HTM12 in accordance with the prior art, significant improvements likewise arise on use of HTM3 as electron-blocking material (Examples C21, C22 and I15). The other materials according to the invention exhibit similar improvements compared with the prior art. In the case of red emission, the compounds according to the invention exhibit, in particular, a significant improvement in the lifetime compared with NPB in accordance with the prior art (Examples C4, C6, 125 and I26).

(154) Thus, the use of compounds according to the invention on the hole-transport side of OLEDs produces significant improvements, in particular with respect to the lifetime and the operating voltage, power efficiency, lifetime and processing complexity.

(155) Use of Compounds According to the Invention as Component in Mixed-Matrix Systems

(156) Mixed-matrix systems, i.e. OLEDs having an emission layer consisting of three or more components, in some cases exhibit significant advantages over systems comprising single-matrix materials. The said systems are described in detail, inter alia, in the application WO 10/108579. The compounds can also be employed in such systems in accordance with the present invention. Compared with mixed-matrix components in accordance with the prior art, significant improvements arise with respect to the efficiency, voltage and lifetime. The compounds in accordance with the prior art used are the materials CBP, TCTA and FTPh (see Table 4). The corresponding OLEDs are denoted by C6, C10 and C14-C18. The materials according to the invention employed are compounds H5-H17 in combination with matrix materials H3, Ket1 and DAP1. The corresponding OLEDs are denoted by I27-I39, I56, I58-I63.

(157) Firstly, mixed-matrix systems comprising the green-emitting dopant TEG1 are compared. On replacement of CBP or TCTA with the compounds according to the invention, a significant improvement is observed in the operating voltage, power efficiency and especially also the lifetime. On use of compound H10 according to the invention in combination with H3, for example, the power efficiency is increased by 60% compared with the use of CBP and by about 70% compared with TCTA (Examples C10, C18 and 127). The lifetime is increased by almost 60% compared with CBP, and virtually a quadrupling of the lifetime is observed compared with TCTA. Similar improvements are also obtained on combination of H10 with the ketone matrix Ket1 and diazaphosphole matrix DAP1 (Examples C14-C17, I28 and I29). Very good lifetimes can also be achieved with compounds H12 and H14, in which the bridge atoms are substituted by phenyl rings (Examples I58, I60). Other compounds according to the invention also exhibit significant improvements with respect to the voltage, power efficiency and lifetime.

(158) In red-emitting mixed-matrix systems, significant improvements are likewise obtained on use of the compounds according to the invention (cf. Example C6 with I37-I39, I62, I63). On replacement of CBP with H10, for example, an improvement in the voltage of 1.1 V, an increase in the power efficiency by about 50% and a virtually doubled lifetime are obtained (Examples C6 and I37). Similarly good performance data can be achieved with compounds H7 and H9 according to the invention. Furthermore, significant improvements compared with the prior art are also obtained with compounds H16 and H17, which are substituted by phenyl rings on the bridge atoms (I62, I63).

(159) The use of materials according to the invention in mixed-matrix systems thus produces significant improvements with respect to the voltage, efficiency and especially also the lifetime of the OLEDs. These improvements can be achieved in combination with very different classes of matrix materials (ketones: Ket1, spirotriazines: H3, diazaphospholes: DAP1). It can thus be assumed that similar improvements are also achievable through combination of the compounds according to the invention with other classes of material.

(160) TABLE-US-00006 TABLE 1 Structure of the OLEDs HIL HTL EML EIL Ex. Thickness Thickness IL Thickness EBL Thickness Thickness HBL Thickness ETL Thickness Thickness C1 HIL1 5 nm HTM1 NPB H1:D1 (95%:5%) Alq.sub.3 LiF 1 nm 140 nm 20 nm 30 nm 20 nm C2 HIL1 5 nm HTM1 NPB H1:D1 (95%:5%) ETM1:LiQ 140 nm 20 nm 30 nm (50%:50%) 20 nm C3 HIL1 5 nm HTM1 NPB H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm C4 HTM1 NPB H3:TER1 (85%:15%) Alq.sub.3 LiF 1 nm 20 nm 20 nm 30 nm 20 nm C5 HIL1 5 nm HTM1 NPB H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 200 nm 20 nm 30 nm 20 nm C6 HTM1 NPB H3:CBP:TER1 H3 Alq.sub.3 LiF 1 nm 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm C7 HTM1 EBM1 H3:TEG1 (90%:10%) H3 ETM1:LiQ 160 nm 20 nm 30 nm 10 nm (50%:50%) 30 nm C8 HTM1 EBM1 H3:TEG1 (90%:10%) ETM1:LiQ 160 nm 20 nm 30 nm (50%:50%) 40 nm C9 HTM1 HIL1 5 nm EBM1 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm C10 HTM1 HIL1 5 nm EBM1 H3:CBP:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm C11 HTM1 HIL1 5 nm EBM1 H3:TEG1 (90%:10%) H3 H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 10 nm 30 nm C12 HTM1 HIL1 5 nm EBM1 H3:TEG1 (90%:10%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm C14 HIL1 EBM1 Ket1:FTPh:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C15 HIL1 EBM1 Ket1:TCTA:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C16 HIL1 EBM1 Ket1:CBP:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C17 HTM1 HIL1 5 nm EBM1 DAP1:CBP:TEG1 H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm C18 HTM1 HIL1 5 nm EBM1 H3:TCTA:TEG1 H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm C19 HIL1 5 nm HTM12 NPB H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm C20 HIL1 5 nm HTM12 NBP H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 200 nm 20 nm 30 nm 20 nm C21 HTM1 HIL1 5 nm HTM11 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm C22 HTM1 HIL1 5 nm HTM12 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I1 HIL1 5 nm HTM8 NPB H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm I2 HIL1 5 nm HTM8 NPB H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 200 nm 20 nm 30 nm 20 nm I3 HIL1 5 nm HTM1 HTM3 H1:D1 (95%:5%) Alq.sub.3 LiF 1 nm 140 nm 20 nm 30 nm 20 nm I4 HIL1 5 nm HTM1 HTM3 H1:D1 (95%:5%) ETM1:LiQ 140 nm 20 nm 30 nm (50%:50%) 20 nm I5 HIL1 5 nm HTM1 HTM3 H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm I6 HIL1 5 nm HTM1 HTM3 H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 200 nm 20 nm 30 nm 20 nm I7 HIL1 5 nm HTM1 HTM2 H1:D1 (95%:5%) Alq.sub.3 LiF 1 nm 140 nm 20 nm 30 nm 20 nm I8 HIL1 5 nm HTM1 HTM2 H1:D1 (95%:5%) ETM1:LiQ 140 nm 20 nm 30 nm (50%:50%) 20 nm I9 HIL1 5 nm HTM1 HTM2 H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm I10 HIL1 5 nm HTM2 H1:D1 (95%:5%) ETM1:LiQ 160 nm 30 nm (50%:50%) 20 nm I11 HIL1 5 nm HTM3 H1:D1 (95%:5%) ETM1:LiQ 160 nm 30 nm (50%:50%) 20 nm I12 HIL1 5 nm HTM8 HTM3 H1:D1 (95%:5%) ETM1:LiQ 140 nm 20 nm 30 nm (50%:50%) 20 nm I13 HTM1 HTM3 H3:TEG1 (90%:10%) H3 ETM1:LiQ 160 nm 20 nm 30 nm 10 nm (50%:50%) 30 nm I14 HTM1 HTM3 H3:TEG1 (90%:10%) ETM1:LiQ 160 nm 20 nm 30 nm (50%:50%) 40 nm I15 HTM1 HIL1 5 nm HTM3 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I16 HTM1 HIL1 5 nm HTM3 H3:TEG1 (90%:10%) H3 H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 10 nm 30 nm I17 HTM1 HIL1 5 nm HTM3 H3:TEG1 (90%:10%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I18 HTM1 HIL1 5 nm HTM2 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I19 HTM1 HIL1 5 nm HTM4 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I20 HTM1 HIL1 5 nm HTM5 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I21 HTM1 HIL1 5 nm HTM6 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I22 HTM1 HIL1 5 nm HTM7 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I23 HTM1 HIL1 5 nm HTM9 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I24 HTM1 HIL1 5 nm HTM10 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I25 HTM1 HTM3 H3:TER1 (85%:15%) Alq.sub.3 LiF 1 nm 20 nm 20 nm 30 nm 20 nm I26 HTM1 HTM3 H3:CBP:TER1 H3 Alq.sub.3 LiF 1 nm 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm I27 HTM1 HIL1 5 nm EBM1 H3:H10:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I28 HIL1 EBM1 Ket1:H10:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm I29 HTM1 HIL1 5 nm EBM1 DAP1:H10:TEG1 H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I30 HTM1 HIL1 5 nm EBM1 H3:H7:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I31 HIL1 EBM1 Ket1:H7:TEG1 Ket1 ETM2 LiF 20 nm 20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm I32 HTM1 HIL1 5 nm EBM1 DAP1:H7:TEG1 H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I33 HTM1 HIL1 5 nm EBM1 H3:H5:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I35 HTM1 HIL1 5 nm EBM1 H3:H8:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I36 HTM1 HIL1 6 nm EBM1 H3:H9:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I37 HTM1 NPB H3:H10:TER1 H3 Alq.sub.3 LiF 1 nm 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm I38 HTM1 NPB H3:H7:TER1 H3 Alq.sub.3 LiF 1 nm 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm I39 HTM1 NPB H3:H9:TER1 H3 Alq.sub.3 LiF 1 nm 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm I40 HIL1 5 nm HTM1 HTM13 H1:D1 (95%:5%) ETM1:LiQ 140 nm 20 nm 30 nm (50%:50%) 20 nm I41 HTM1 HIL1 5 nm HTM13 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I42 HIL1 5 nm HTM1 HTM14 H1:D1 (95%:5%) ETM1:LiQ 140 nm 20 nm 30 nm (50%:50%) 20 nm I43 HTM1 HIL1 5 nm HTM14 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I44 HTM1 HIL1 5 nm HTM15 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I45 HIL1 5 nm HTM17 NPB H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm I46 HTM1 HIL1 5 nm HTM18 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I47 HIL1 5 nm HTM19 NPB H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm I48 HIL1 5 nm HTM1 HTM20 H1:D1 (95%:5%) ETM1:LiQ 140 nm 20 nm 30 nm (50%:50%) 20 nm I49 HIL1 5 nm HTM1 HTM20 H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm I50 HTM1 HIL1 6 nm HTM21 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I51 HTM1 HIL1 5 nm HTM22 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I52 HTM1 HIL1 5 nm HTM23 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I53 HTM1 HIL1 5 nm HTM24 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I54 HIL1 5 nm HTM25 NPB H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm I55 HIL1 5 nm HTM1 HTM26 H2:D2 (90%:10%) Alq.sub.3 LiF 1 nm 110 nm 20 nm 30 nm 20 nm I56 HTM1 HIL1 5 nm EBM1 H3:H11:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I57 HTM1 HIL1 5 nm HTM16 H4:TEG1 (85%:15%) H3:LiQ (50%:50%) 70 nm 90 nm 30 nm 40 nm I58 HTM1 HIL1 5 nm EBM1 H3:H12:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I60 HTM1 HIL1 5 nm EBM1 H3:H14:TEG1 H3 10 nm H3:LiQ (50%:50%) 70 nm 90 nm (30%:60%:10%) 30 nm 30 nm I62 HTM1 NPB H3:H16:TER1 H3 Alq.sub.3 LiF 1 nm 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm I63 HTM1 NPB H3:H17:TER1 H3 Alq.sub.3 LiF 1 nm 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm

(161) TABLE-US-00007 TABLE 2 Data of the OLEDs Voltage for Efficiency at Efficiency at EQE at CIE x/y at LD80 from Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 4000 cd/m.sup.2 C1 6.4 V 5.1 cd/A 2.5 lm/W 4.2% 0.14/0.15 5500 h C2 4.7 V 8.1 cd/A 5.4 lm/W 6.3% 0.14/0.16 5200 h C3 5.0 V 17.1 cd/A 10.7 lm/W 5.0% 0.28/0.61 300000 h C4 5.0 V 7.2 cd/A 4.5 lm/W 12.0% 0.69/0.31 14000 h C5 5.5 V 15.9 cd/A 9.1 lm/W 4.8% 0.31/0.58 250000 h C6 5.2 V 8.1 cd/A 4.9 lm/W 11.4% 0.68/0.32 15000 h C19 5.2 V 16.8 cd/A 10.1 lm/W 4.9% 0.28/0.61 280000 h C20 5.7 V 15.5 cd/A 8.6 lm/W 4.7% 0.31/0.58 220000 h I1 4.8 V 18.6 cd/A 12.1 lm/W 5.4% 0.28/0.61 330000 h I2 5.1 V 17.2 cd/A 10.6 lm/W 5.2% 0.30/0.59 340000 h I3 5.8 V 5.8 cd/A 3.2 lm/W 4.8% 0.14/0.15 7800 h I4 4.4 V 8.8 cd/A 6.3 lm/W 6.8% 0.14/0.15 7700 h I5 4.7 V 19.5 cd/A 13.0 lm/W 5.7% 0.28/0.61 380000 h I6 5.2 V 18.2 cd/A 11.0 lm/W 5.5% 0.31/0.58 350000 h I7 6.0 V 5.7 cd/A 3.0 lm/W 4.7% 0.14/0.15 7100 h I8 4.7 V 8.5 cd/A 5.7 lm/W 6.6% 0.14/0.15 6700 h I9 4.8 V 19.1 cd/A 12.5 lm/W 5.6% 0.28/0.61 340000 h I10 4.7 V 8.0 cd/A 5.3 lm/W 6.2% 0.14/0.16 6700 h I11 4.6 V 8.3 cd/A 5.7 lm/W 6.5% 0.14/0.16 6300 h I12 4.2 V 9.1 cd/A 6.8 lm/W 7.0% 0.14/0.15 7900 h I25 4.9 V 7.5 cd/A 4.8 lm/W 12.5% 0.69/0.31 21000 h I26 5.1 V 8.3 cd/A 5.1 lm/W 11.6% 0.68/0.32 21000 h I37 4.1 V 9.6 cd/A 7.4 lm/W 13.3% 0.68/0.32 29000 h I38 4.0 V 9.2 cd/A 7.2 lm/W 12.8% 0.68/0.32 27000 h I39 4.0 V 9.3 cd/A 7.3 lm/W 13.0% 0.68/0.32 24000 h I40 4.6 V 9.0 cd/A 6.1 lm/W 7.0% 0.14/0.15 6500 h I42 4.6 V 8.7 cd/A 6.0 lm/W 6.7% 0.14/0.16 7200 h I45 5.1 V 18.5 cd/A 11.3 lm/W 5.4% 0.28/0.61 280000 h I47 4.9 V 17.5 cd/A 11.1 lm/W 5.1% 0.28/0.61 310000 h I48 4.8 V 8.5 cd/A 5.6 lm/W 6.6% 0.14/0.16 6700 h I49 5.0 V 17.8 cd/A 11.2 lm/W 5.2% 0.28/0.61 340000 h I54 5.0 V 18.0 cd/A 11.3 lm/W 5.3% 0.28/0.61 320000 h I55 4.9 V 18.8 cd/A 11.9 lm/W 5.5% 0.28/0.81 340000 h I62 4.2 V 8.7 cd/A 6.5 lm/W 12.2% 0.68/0.32 19000 h I63 4.4 V 77.7 cd/A 5.5 lm/W 10.8% 0.68/0.32 16000 h

(162) TABLE-US-00008 TABLE 3 Data of the OLEDs Voltage for Efficiency at Efficiency at EQE at CIE x/y at LD50 from Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 C7 4.7 V 55 cd/A 37 lm/W 16.4% 0.36/0.61 350 h C8 4.6 V 54 cd/A 37 lm/W 15.0% 0.37/0.60 320 h C9 3.6 V 52 cd/A 45 lm/W 14.6% 0.37/0.60 430 h C10 4.4 V 48 cd/A 34 lm/W 13.3% 0.37/0.60 450 h C11 4.4 V 54 cd/A 39 lm/W 15.0% 0.36/0.60 320 h C12 4.3 V 55 cd/A 40 m/W 15.3% 0.37/0.61 300 h C14 4.0 V 46 cd/A 36 lm/W 12.8% 0.36/0.61 430 h C15 3.9 V 42 cd/A 34 lm/W 11.6% 0.35/0.60 160 h C16 4.1 V 44 cd/A 34 lm/W 12.3% 0.36/0.61 320 h C17 4.6 V 47 cd/A 32 lm/W 13.2% 0.36/0.60 480 h C18 4.2 V 43 cd/A 32 lm/W 12.0% 0.35/0.60 190 h C21 3.6 V 55 cd/A 48 lm/W 15.5% 0.37/0.60 450 h C22 3.9 V 46 cd/A 38 lm/W 12.9% 0.36/0.60 360 h I13 4.7 V 61 cd/A 41 lm/W 17.0% 0.36/0.61 460 h I14 4.5 V 59 cd/A 41 lm/W 16.4% 0.37/0.60 440 h I15 3.7 V 56 cd/A 48 lm/W 15.7% 0.37/0.60 670 h I16 4.4 V 63 cd/A 45 lm/W 17.5% 0.36/0.61 510 h I17 4.6 V 61 cd/A 43 lm/W 16.9% 0.37/0.61 500 h I18 3.9 V 62 cd/A 50 lm/W 17.4% 0.37/0.60 570 h I19 3.7 V 64 cd/A 54 lm/W 17.9% 0.36/0.60 520 h I20 4.0 V 60 cd/A 47 lm/W 16.7% 0.37/0.60 540 h I21 3.7 V 65 cd/A 52 lm/W 18.2% 0.37/0.60 550 h I22 3.7 V 58 cd/A 49 lm/W 16.3% 0.36/0.60 490 h I23 3.8 V 56 cd/A 46 lm/W 15.7% 0.36/0.61 470 h I24 3.5 V 57 cd/A 51 lm/W 16.0% 0.36/0.60 510 h I27 3.2 V 56 cd/A 55 lm/W 15.8% 0.36/0.61 710 h I28 3.1 V 49 cd/A 50 lm/W 13.8% 0.36/0.61 630 h I29 4.0 V 46 cd/A 36 lm/W 12.9% 0.36/0.60 640 h I30 3.3 V 54 cd/A 52 lm/W 15.2% 0.36/0.61 680 h I31 3.1 V 50 cd/A 51 lm/W 13.9% 0.36/0.61 590 h I32 4.1 V 48 cd/A 37 lm/W 13.5% 0.36/0.60 620 h I33 3.3 V 56 cd/A 53 lm/W 15.7% 0.38/0.61 640 h I35 3.3 V 54 cd/A 52 lm/W 15.3% 0.36/0.61 660 h I36 3.5 V 50 cd/A 45 lm/W 14.0% 0.36/0.61 620 h I41 3.9 V 60 cd/A 49 lm/W 16.7% 0.36/0.60 640 h I43 3.8 V 56 cd/A 46 lm/W 15.5% 0.36/0.60 610 h I44 3.6 V 61 cd/A 53 lm/W 16.8% 0.36/0.60 520 h I46 3.8 V 60 cd/A 49 lm/W 16.5% 0.36/0.60 650 h I50 3.8 V 62 cd/A 51 lm/W 17.2% 0.36/0.60 500 h I51 3.8 V 63 cd/A 52 lm/W 17.4% 0.36/0.60 560 h I52 3.7 V 60 cd/A 50 lm/W 16.6% 0.36/0.60 510 h I53 3.9 V 55 cd/A 45 lm/W 15.3% 0.36/0.60 450 h I56 3.7 V 49 cd/A 42 lm/W 13.7% 0.37/0.61 540 h I57 4.0 V 57 cd/A 45 lm/W 15.8% 0.37/0.60 420 h I58 3.4 V 54 cd/A 49 lm/W 14.8% 0.36/0.61 710 h I60 3.8 V 51 cd/A 42 lm/W 14.0% 0.37/0.61 660 h

(163) TABLE-US-00009 TABLE 4 Structural formulae of the materials used HIL1 HTM1 (prior art) NPB (prior art) EBM1 (prior art) 0 HTM11 (prior art) HTM12 (prior art) Alq.sub.3 H1 H2 D1 D2 ETM1 ETM2 CBP (prior art) 0 Ket1 TCTA (prior art) DAP1 FTPh (prior art) H3 H4 LIQ TEG1 TER1 HTM2 0 H5 H7 HTM3 H8 HTM4 HTM5 HTM6 HTM7 HTM8 H9 0 HTM9 HTM10 H10 HTM13 HTM14 HTM15 HTM16 HTM17 HTM18 HTM19 00 HTM20 01 HTM21 02 HTM22 03 HTM23 04 HTM24 05 HTM25 06 HTM26 07 H11 08 H12 09 H14 0 H16 H17