MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present invention relates to compounds of the formula (I), to the use of compounds of the formula (I) in electronic devices and electronic devices comprising one or more compounds of the formula (I). The invention furthermore relates to the preparation of the compounds of the formula (I) and to formulations comprising one or more compounds of the formula (I).

Claims

1-14. (canceled)

15. An organic electroluminescent device comprising at least one compound of the formula (I) ##STR00302## where the following applies to the symbols and indices occurring: X.sup.1, X.sup.2 and X.sup.3 are on each occurrence, identically or differently, C(R.sup.2).sub.2, CO, CNR.sup.2, Si(R.sup.2).sub.2, NR.sup.1, PR.sup.1, P(O)R.sup.1, O, S, SO or S(O).sub.2; Z is on each occurrence, identically or differently, CR.sup.2 or N, where not more than two adjacent groups Z may simultaneously be equal to N; R.sup.1 is on each occurrence, identically or differently, C(O)R.sup.3, CR.sup.3C(R.sup.3).sub.2, C(O)OR.sup.3, C(O)NR.sup.3.sub.2, P(O)(R.sup.3).sub.2, OR.sup.3, S(O)R.sup.3, S(O).sub.2R.sup.3, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which optionally in each case be substituted by one or more radicals R.sup.3, or a combination of these systems, where two or more radicals R.sup.1 is optionally linked to one another and may form an aliphatic or aromatic ring; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(O)R.sup.3, CR.sup.3C(R.sup.3).sub.2, CN, C(O)OR.sup.3, C(O)NR.sup.3.sub.2, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, NO.sub.2, P(O)(R.sup.3).sub.2, OS(O).sub.2R.sup.3, OH, S(O)R.sup.3, S(O).sub.2R.sup.3, 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, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3 and where one or more non-adjacent CH.sub.2 groups in the above-mentioned groups is optionally 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, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), O, S, SO or S(O).sub.2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or a combination of these systems, where two or more radicals R.sup.2 is optionally linked to one another and may form an aliphatic or aromatic ring; R.sup.3 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, B(OR.sup.4).sub.2, CHO, C(O)R.sup.4, CR.sup.4C(R.sup.4).sub.2, CN, C(O)OR.sup.4, C(O)NR.sup.42, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, NO.sub.2, P(O)(R.sup.4).sub.2, OS(O).sub.2R.sup.4, OH, S(O)R.sup.4, S(O).sub.2R.sup.4, 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, where the above-mentioned groups may each be substituted by one or more radicals R.sup.4 and where one or more non-adjacent CH.sub.2 groups in the above-mentioned groups is optionally 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, C(O)O, C(O)NR.sup.4, NR.sup.4, P(O)(R.sup.4), O, S, SO or S(O).sub.2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.4, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.4, or a combination of these systems, where two or more radicals R.sup.3 is optionally linked to one another and may form an aliphatic or aromatic ring; R.sup.4 is, identically or differently on each occurrence, 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 is optionally replaced by D or F; two or more substituents R.sup.4 here may also be linked to one another and form an aliphatic or aromatic ring; and n has a value of 0, 1 or 2; where the case where all groups X.sup.1, X.sup.2 and X.sup.3 are identical is excluded.

16. The device according to claim 15, wherein n is equal to 0 or 1.

17. The device according to claim 15, wherein at least one of the groups X.sup.1, X.sup.2 and X.sup.3 represents a group NR.sup.1.

18. The device according to claim 15, wherein 0, 1 or 2 groups Z per aromatic or heteroaromatic six-membered ring are equal to N.

19. The device according to claim 15, wherein the groups X.sup.1, X.sup.2 and X.sup.3 are selected, identically or differently, from C(R.sup.2).sub.2, CO, Si(R.sup.2).sub.2, NR, PR.sup.1, P(O)R.sup.1, O and S.

20. The device according to claim 15, wherein R.sup.1 represents on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which optionally in each case be substituted by one or more radicals R.sup.3.

21. The device according to claim 15, wherein at least one group is present as substituent R.sup.1 or R.sup.2 which is selected from electron-deficient heteroaryl groups, aromatic or heteroaromatic ring systems having 10 to 30 aromatic ring atoms and from arylamine groups, each of which is optionally substituted by one or more radicals as defined in claim 15.

22. The device according to claim 15, wherein the compound of formula (I) conforms to the compounds of one of the following formulae ##STR00303## ##STR00304## ##STR00305## ##STR00306## where the groups Z and R.sup.1 are as defined in claim 15.

23. A process for the preparation of the compound of the formula (I) as defined in claim 15 which comprises ring-closure reacting one or more condensed heteroaromatic five-membered rings.

24. An oligomer, polymer or dendrimer comprising one or more compounds of the formula (I) as defined in claim 15, where the bond(s) to the polymer, oligomer or dendrimer is optionally localised at any position in formula (I) substituted by R.sup.1 or R.sup.2.

25. A formulation comprising at least one compound of the formula (I) as defined in claim 15 and at least one solvent.

26. A formulation comprising at least one polymer, oligomer or dendrimer according to claim 24 and at least one solvent.

27. The organic electroluminescent device according to claim 15 which comprises the compound according to formula (I) as hole-transport material in a hole-transport layer or hole-injection layer and/or is employed as matrix material in an emitting layer and/or as electron-transport material in an electron-transport layer.

28. An organic electroluminescent device which comprises the polymer, oligomer or dendrimer according to claim 24 is employed as hole-transport material in a hole-transport layer or hole-injection layer and/or is employed as matrix material in an emitting layer and/or as electron-transport material in an electron-transport layer.

Description

USE EXAMPLES

A) Synthesis Examples

[0130] The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. Benzo[b]thiophene and solvents can be purchased commercially, for example from ALDRICH.

1) Synthesis of compound 1: 6-o-Biphenylbis[1]benzothieno[2,3-b:3,2-d]-pyrrole

[0131] Scheme for the Synthesis of Compounds 1 and 2

##STR00264##

Step 1-a: 3-Bromobenzo[b]thiophene

[0132] ##STR00265##

[0133] 100 g (745 mmol) of benzo[b]thiophene are suspended in 1000 ml of chloroform and 1000 ml of glacial acetic acid with 145 g (815 mmol) of NBS and stirred at room temperature for 24 h. After a TLC check, the batch is evaporated under reduced pressure. The purification is carried out by distillation of the product and gives a red oil (111 g; 73%).

Step 1-b: [3,3]-Bisbenzo[b]thiophenyl

[0134] ##STR00266##

[0135] 3000 ml of THF, 40 g (61 mmol) of bis(triphenylphosphine)nickel(II) chloride, 34.3 g (524.6 mmol) of zinc and 101.6 g (275 mmol) of n-Bu.sub.4NI are added to 50 g (235 mmol) of the compound from the preceding step. The batch is heated at 70 C. for 20 h, then cooled to room temperature, and 400 ml of water are added. The mixture is extracted with ethyl acetate, the combined organic phases are then dried over sodium sulfate and evaporated under reduced pressure. The purification is carried out by recrystallisation (heptane/MeOH) and gives a white solid (22 g, 71.7 mmol, 61%).

Step 1-c: 2,2-Dibromo-[3,3]-bisbenzo[b]thiophenyl

[0136] ##STR00267##

[0137] 10 g (37.5 mmol) of the compound from the preceding step are initially introduced in 250 ml of acetic acid. With exclusion of light, a solution of 8 ml (24 g, 150 mmol) of Br.sub.2 in 10 ml of acetic acid is added dropwise at 5 C. The mixture is subsequently allowed to come to room temperature and is stirred at this temperature for a further 24 h. 150 ml of water are then 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. Yield: 14 g (33 mmol), 83.5%. Purity according to .sup.1H-NMR about 98%.

Compound 1: 6-o-Biphenylbis-[1]benzothieno[2,3-b:3,2-d]pyrrole

[0138] ##STR00268##

[0139] 500 ml of toluene, 2.3 g (2.5 mmol) of tris(dibenzylideneacetone)dipalladium, 10 ml of 1 M t-Bu.sub.3P in toluene and 11.5 g (120 mmol) of sodium tertbutoxide are added to 21.2 g (50 mmol) of the compound from the preceding step. 6.8 g (40 mmol) of 2-aminobiphenyl are subsequently added. The batch is heated at 110 C. for 20 h, then cooled to room temperature, and 400 ml of water are added. The mixture is extracted with ethyl acetate, the combined organic phases are then dried over sodium sulfate and evaporated under reduced pressure. 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 10.6 g (24.5 mmol), corresponding to 49% of theory.

2) Synthesis of compound 2: 2,4,6-Trimethylphenylbis[1]benzothieno[2,3-b:3,2-d]pyrrole

[0140] ##STR00269##

[0141] 500 ml of toluene, 2.3 g (2.5 mmol) of tris(dibenzylideneacetone)dipalladium, 10 ml of 1 M t-Bu.sub.3P in toluene and 11.5 g (120 mmol) of sodium tertbutoxide are added to 21.2 g (50 mmol) of the compound from step 1-c. 5.4 g (40 mmol) of 2,4,6-trimethylaniline are subsequently added. The batch is heated at 110 C. for 20 h, then cooled to room temperature, and 400 ml of water are added. The mixture is extracted with ethyl acetate, the combined organic phases are then dried over sodium sulfate and evaporated under reduced pressure. The residue is recrystallised from toluene and from heptane/methanol and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 11.5 g (29 mmol), corresponding to 58% of theory.

3) Synthesis of compound 3: 2,4,6-Triphenylpyrimidinylbis[1]benzothieno[2,3-b:3,2-d]pyrrole

[0142] Scheme for the Synthesis of Compound 3

##STR00270##

Step 3-a: 2-Nitro-3,3-bisbenzo[b]thiophene

[0143] ##STR00271##

[0144] 12.6 g (47 mmol) of 3,3-dibenzo(b)thiophene are initially introduced in 1000 ml of glacial acetic acid. The batch is warmed to a bath temperature of 60 C., and a mixture of 4 ml of conc. HNO.sub.3 and 200 ml of glacial acetic acid is added. The mixture is subsequently stirred at 65 C. for 1 h and poured into ice-water. The yellow solid formed in the process is filtered off with suction. The product is washed by stirring with hot hexane and filtered off with suction. Yield: 13.5 g (43 mmol), 96% of theory, purity according to .sup.1H-NMR about 98%.

Step 3-b: 6H-Bis[1]benzothieno[2,3-b:3,2-d]pyrrole

[0145] ##STR00272##

[0146] 11.7 g (42 mmol) of the compound from the preceding step and 29 ml (165 mmol) of triethyl phosphite are dissolved in 350 ml of 1,2-dichlorobenzene and stirred at 150 C. for 24 h. After cooling, the solvent is distilled off. The purification is carried out by recrystallisation (heptane) and gives a colourless solid (3.5 g, 12.6 mmol, 30%). Purity according to .sup.1H-NMR about 90%.

Step 3-c: 5-Bromo-2,4,6-triphenylpyrimidine

[0147] ##STR00273##

[0148] 50 g (177 mmol) of trifluoromethanesulfonic anhydride and 36.5 g (354 mmol) of benzonitrile are dissolved in 300 ml of dichloromethane. A solution of dichloromethane and 35.2 g (177 mmol) of 2-bromoacetophenone is added dropwise to this solution at room temperature. The reaction mixture is left to stir at RT for 24 h. The batch is washed with aqueous NaHCO.sub.3 solution, and the organic phase is dried using MgSO.sub.4 and evaporated to dryness in a rotary evaporator. The product is washed by stirring with hot ethanol and filtered off with suction. Yield: 33.5 g (86.5 mmol), 49% of theory, purity according to .sup.1H-NMR about 98%.

Compound 3: 2,4,6-Triphenylpyrimidinylbis[1]benzothieno[2,3-b:3,2-d]-pyrrole

[0149] ##STR00274##

[0150] 9.1 g (23.5 mmol) of the compound from the preceding step, 13.11 g (47 mmol) of 6H-bis[1]benzothieno[2,3-b:3,2-d]pyrrole and 29.2 g of Rb.sub.2CO.sub.3 are suspended in 250 ml of p-xylene. 0.95 g (4.2 mmol) of Pd(OAc).sub.2 and 12.6 ml of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 24 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 three times from toluene and finally sublimed in a high vacuum, giving 5.6 g (9.7 mmol) of the product, corresponding to 41% of theory. The purity is 99.9%.

4) Synthesis of compound 4: 3-((Z)-Buta-1,3-dienyl)-1-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-2-methyl-1H-benzo[4,5]thieno[2,3-b]pyrrole

[0151] Scheme for the Synthesis of Compound 4

##STR00275##

Step 4-a: 2-Benzo[b]thiophen-3-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0152] ##STR00276##

[0153] 1600 ml of THF, 145 g (568 mmol) of bis(pinacolato)diborane and 142 g (1.45 mol) of potassium acetate are added to 111 g (516 mmol) of 3-bromobenzo-[b]thiophene. 10 g (12 mmol) of 1,1-bis(diphenylphosphino)ferrocene-palladium(II) chloride (complex with dichloromethane (1:1), Pd 13%) are subsequently added. The batch is heated at 70 C. for 16 h, then cooled to room temperature, and 400 ml of water are added. The mixture is extracted with ethyl acetate, the combined organic phases are then dried over sodium sulfate and evaporated under reduced pressure. The purification is carried out by recrystallisation (heptane/MeOH) and gives a brown solid (78 g, 58.3%).

Step 4-b: 2-Nitrophenylbenzo[b]thiophene

[0154] ##STR00277##

[0155] 56 g (0.225 mol) of the compound from the preceding step, 70.2 g (1.2 molar equivalents, 0.270 mol) of 1-iodonitrobenzene and 286 g (1.345 mol) of tripotassium phosphate are suspended in 700 ml of toluene, 700 ml of dioxane and 700 ml of water. 0.684 g (2.25 mmol) of tri-o-tolylphosphine and then 2.53 g (11.2 mmol) of palladium(II) acetate are added to this suspension, and the reaction mixture is heated under reflux for 21 h. After cooling, the organic phase is separated off. The aqueous phase is extracted with dichloromethane, the combined organic phases are then dried over sodium sulfate, filtered and evaporated under reduced pressure. The residue is chromatographed over silica gel. The yield is 39 g (152 mmol), corresponding to 68% of theory.

Step 4-c: 6H-[1]Benzothieno[2,3-b]indole

[0156] ##STR00278##

[0157] 32 g (0.124 mol) of the compound from the preceding step and 86 ml (0.495 mol) of triethyl phosphite are dissolved in 1000 ml of 1,2-dichlorobenzene and stirred at 150 C. for 72 h. After cooling, the solvent is distilled off. The purification is carried out by recrystallisation (heptane) and gives a colourless solid (12 g, 45.3%).

Compound 4: 3-((Z)-Buta-1,3-dienyl)-1-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-2-methyl-1H-benzo[4,5]thieno[2,3-b]pyrrole

[0158] ##STR00279##

[0159] 9.1 g (23.5 mmol) of 5-bromo-2,4,6-triphenylpyrimidine, 13.11 g (47 mmol) of 6H-[1]benzothieno[2,3-b]indole and 29.2 g of Rb.sub.2CO.sub.3 are suspended in 250 ml of p-xylene. 0.95 g (4.2 mmol) of Pd(OAc).sub.2 and 12.6 ml of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 24 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 and recrystallised three times from toluene and finally sublimed in a high vacuum, giving 5.6 g (9.7 mmol) corresponding to 41% of theory, the purity is 99.9%.

5) Synthesis of Compound 5

[0160] Scheme for the Synthesis of Compound 5

##STR00280##

Step 5-a: 5-Bromobenzo[b]thiophene

[0161] ##STR00281##

[0162] 97.2 g (351 mmol) of 1-bromo-4-[(2,2-dimethoxyethyl)sulfanyl]benzene and 100 g of polyphosphoric acid are dissolved in 2000 ml of chlorobenzene and stirred at 135 C. for 4 h. After cooling, the solvent is distilled off. The residue is extracted with dichloromethane, and the organic phase is washed three times with 200 ml of water. The combined organic phases are then dried over sodium sulfate, filtered and evaporated under reduced pressure. The purification is carried out by recrystallisation (heptane) and gives a colourless solid (60.3 g, 283 mmol, 80.1%).

Step 5-b: Benzo[b]thiophene-5-carbonitrile

[0163] ##STR00282##

[0164] 45 g (211 mmol) of the compound from the preceding step, 26.18 g (295 mmol) of copper(I) cyanide and 25 ml of pyridine are dissolved in 500 ml of N,N-dimethylformamide and stirred at 130 C. for 24 h. After cooling, the solvent is distilled off. The residue is extracted with dichloromethane, and the organic phase is washed three times with 200 ml of water. The combined organic phases are then dried over sodium sulfate, filtered and evaporated under reduced pressure. The residue is chromatographed over silica gel. The purification is carried out by recrystallisation (heptane) and gives a colourless solid (18.9 g, 118.2 mmol, 56%).

Step 5-c: 3-Bromo-1-benzothiophene-6-carbonitrile

[0165] ##STR00283##

[0166] 23.7 g (149 mmol) of the compound from the preceding step are suspended in 200 ml of chloroform and 200 ml of glacial acetic acid with 29 g (163 mmol) of NBS and stirred at RT for 24 hrs. After a TLC check, the batch is evaporated under reduced pressure. The purification is carried out by distillation of the product and gives a red oil (12.5 g, 52.15 mmol, 35% of theory).

Step 5-d

[0167] ##STR00284##

[0168] 16.4 g (56.25 mmol) of 3-bromo-1-benzothiophene-6-carbonitrile, 17.55 g (67.5 mmol) of 2-benzo[b]thiophen-3-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 71.5 g (6.0 molar equivalents, 0.335 mol) of tripotassium phosphate are suspended in 500 ml of toluene, 500 ml of dioxane and 250 ml of water. 0.180 g (0.56 mmol) of tri-o-tolylphosphine and then 0.63 g (2.8 mmol) of palladium(II) acetate are added to this suspension, and the reaction mixture is heated under reflux for 24 h. After cooling, the organic phase is separated off. The aqueous phase is extracted with dichloromethane, the combined organic phases are then dried over sodium sulfate, filtered and evaporated under reduced pressure. The residue is chromatographed over silica gel. The yield is 7.4 g (25.3 mmol), corresponding to 45% of theory.

Step 5-e

[0169] ##STR00285##

[0170] 11.06 g (37.5 mmol) of the compound from the preceding step is initially introduced in 250 ml of acetic acid. A solution of 8 ml (24 g, 150 mmol) of Br.sub.2 in 10 ml of acetic acid is subsequently added dropwise with exclusion of light at 5 C., the mixture is allowed to come to RT and is stirred further at this temperature for 24 h. 150 ml of water are then 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. Yield: 10.11 g (22.5 mmol), 60.5% of theory, purity according to .sup.1H-NMR about 98%.

Step 5-f

[0171] ##STR00286##

[0172] 200 ml of toluene are added to 8.98 g (20 mmol) of the compound from the preceding step, 0.95 g (1 mmol) of tris(dibenzylideneacetone)dipalladium, 4 ml of 1M t-Bu.sub.3P solution in toluene and 4.6 g (48 mmol) of sodium tertbutoxide. 1.8 g (16 mmol) of aniline are subsequently added. The batch is heated at 110 C. for 20 h, then cooled to room temperature, and 100 ml of water are added. The mixture is extracted with ethyl acetate, the combined organic phases are then dried over sodium sulfate and evaporated under reduced pressure. The residue is recrystallised from toluene and from heptane/methanol. The yield is 3.3 g (8.64 mmol), corresponding to 48% of theory. Purity according to .sup.1H-NMR about 96%.

Compound 5

[0173] ##STR00287##

[0174] Ethanol (50 ml) and sodium hydroxide solution (20 ml) are added to 3.3 g (8.64 mmol) of the compound from the preceding step. The reaction mixture is stirred under reflux for 6 h. After cooling to 25 C., the solution is evaporated in vacuo. 50 ml of 5M HCl are subsequently added slowly. The precipitated solid is filtered off and washed with water. The yield is 3.1 g (7.8 mmol), corresponding to 91% of theory. Purity according to .sup.1H-NMR about 95%.

[0175] Thionyl chloride (50 ml) is added to the carboxylic acid obtained (3.1 g, 7.8 mmol). The reaction mixture is warmed to 80 C. and heated under reflux for 2 h. The solvent is then removed in vacuo. The carboxylic acid chloride is obtained in a yield of 2.9 g (7.7 mmol, 98% of theory).

[0176] 1.0 g (7.6 mmol) of aluminium trichloride, 2.9 g (7.7 mmol) of the carboxylic acid chloride, 0.18 ml (2.3 mmol) of thionyl chloride and 1.6 ml (15.8 mmol) of benzonitrile are dissolved in 80 ml of 1,2-dichlorobenzene. The batch is firstly warmed to 110 C., and 0.8 g (15.2 mmol) of ammonium chloride is then added. The batch is subsequently heated at 110 C. for 20 h, then cooled to room temperature, and 100 ml of methanol are added. The solid is filtered off with suction and washed with ethanol. The residue is chromatographed over silica gel, extracted with hot toluene, recrystallised three times from toluene and finally sublimed in a high vacuum, giving 2.2 g (3.9 mmol), corresponding to 29% of theory. The purity is 99.9%.

B) Device Examples

[0177] 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).

[0178] In Examples V1 to E8 below (see Tables 1 and 2), the data for various OLEDs are presented. 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 basically have 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) 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.

[0179] 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), to which the matrix material or materials is (are) admixed by co-evaporation in a certain proportion by volume. An expression such as ST1:HTM4:TEG1 (30%:60%:10%) here means that the material ST1 is present in the layer in a proportion by volume of 30%, HTM4 is present in the layer in a proportion of 60% and TEG1 is present in the layer in a proportion of 10%.

[0180] Analogously, the electron-transport layer may also consist of a mixture of two materials.

[0181] The OLEDs are characterised by standard methods. To this end, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/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), 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 expression 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 is 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 has dropped from the initial luminous density L0 to a certain proportion L1 on operation at constant current. The expression L0=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 of the corresponding OLED has dropped from 4000 cd/m.sup.2 to 3200 cd/m.sup.2. The values for the lifetime can be converted into a value 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 the usual figure quoted here.

[0182] The data for the various OLEDs are summarised in Table 2. Examples V1 and V2 are comparative examples in accordance with the prior art, while Examples E1 to E8 show data for OLEDs comprising materials according to the invention.

[0183] 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 Table 2.

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

[0184] On use of materials HTM1 and HTM2 in accordance with the prior art in green-phosphorescent OLEDs, good efficiency and also operating voltage are obtained. However, the lifetime on use of the compounds is very short (Ex. V1, V2). By contrast, with materials HTM3 and HTM4 according to the invention, good efficiency and voltage are likewise obtained, but a good lifetime is also obtained (Ex. E1, E2).

Use of Compounds According to the Invention as Matrix Materials in Phosphorescent OLEDs

[0185] If materials HTM3 and HTM4 according to the invention are used as second component in a mixed matrix, good efficiency, lifetime and also voltage are obtained (Ex. E3, E4).

[0186] Furthermore, the triazine- or pyrimidine-substituted compounds M2-M4 according to the invention can also be employed as individual matrix materials, where good efficiencies, lifetimes and operating voltages are again obtained (Ex. E5 to E8).

TABLE-US-00006 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness Thickness V1 SpA1 HATCN HTM1 IC1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 30 nm 70 nm 5 nm 90 nm 30 nm 10 nm V2 SpA1 HATCN HTM2 IC1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 30 nm 70 nm 5 nm 90 nm 30 nm 10 nm E1 SpA1 HATCN HTM3 IC1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 30 nm 70 nm 5 nm 90 nm 30 nm 10 nm E2 SpA1 HATCN HTM4 IC1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 30 nm 70 nm 5 nm 90 nm 30 nm 10 nm E3 SpA1 HATCN BPA1 ST1:HTM3:TEG1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 30 nm E4 SpA1 HATCN BPA1 ST1:HTM4:TEG1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 30 nm E5 SpA1 HATCN BPA1 M2:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 30 nm 70 nm 5 nm 90 nm 30 nm 10 nm E6 SpA1 HATCN BPA1 M3:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 30 nm 70 nm 5 nm 90 nm 30 nm 10 nm E7 SpA1 HATCN BPA1 M3:TEG1 (90%:10%) ST1:LiQ (50%:50%) 30 nm 70 nm 5 nm 90 nm 30 nm E8 SpA1 HATCN BPA1 M4:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 30 nm 70 nm 5 nm 90 nm 30 nm 10 nm

TABLE-US-00007 TABLE 2 Data for the OLEDs CIE x/y at L0 U1000 CE1000 PE1000 EQE 1000 (cd/ L1 LT Ex. (V) (cd/A) (lm/W) 1000 cd/m.sup.2 m.sup.2) % (h) V1 3.7 54 46 14.9% 0.36/0.60 4000 80 45 V2 3.9 48 39 13.4% 0.36/0.60 4000 80 30 E1 3.6 49 43 13.6% 0.36/0.60 4000 80 360 E2 3.8 56 46 15.4% 0.36/0.60 4000 80 385 E3 3.9 52 42 14.4% 0.37/0.61 4000 80 460 E4 3.8 54 45 15.1% 0.37/0.61 4000 80 480 E5 3.7 47 40 13.0% 0.36/0.60 4000 80 340 E6 3.4 54 50 15.5% 0.37/0.59 4000 80 305 E7 3.5 56 51 15.7% 0.38/0.59 4000 80 280 E8 3.5 53 47 14.8% 0.36/0.60 4000 80 260

TABLE-US-00008 TABLE 3 Structural formulae of the materials for the OLEDs [00288] [00289] [00290] [00291] [00292] [00293] [00294] [00295] [00296] [00297] [00298] [00299] [00300] [00301]