Compounds for electronic devices

Abstract

The present invention relates to a compound of a formula (I) or (II), to the use of this compound in an electronic device, and to an electronic device comprising one or more compounds of the formula (I) or (II). The invention furthermore relates to the preparation of the compound of the formula (I) or (II) and to a formulation comprising one or more compounds of the formula (I) or (II).

Claims

1. A compound of formula (I) or (II) ##STR00274## wherein: Y is selected on each occurrence, identically or differently, from BR.sup.1, C(R.sup.1).sub.2, C═O, C═NR.sup.1, C═C(R.sup.1).sub.2, C═S, Si(R.sup.1).sub.2, NR.sup.1, PR.sup.1, P(═O)R.sup.1, O, S, S═O and S(═O).sub.2; L is selected from C═O, C═NR.sup.1, Si(R.sup.1).sub.2, NR.sup.1, P(═O)(R.sup.1), O, S, SO, SO.sub.2, alkylene groups having 1 to 20 C atoms or alkenylene or alkynylene groups having 2 to 20 C atoms, where one or more CH.sub.2 groups in the said groups may be replaced by Si(R.sup.1).sub.2, O, S, C═O, C═NR.sup.1, C(═O)O, (C═O)NR.sup.1, NR.sup.1, P(═O)(R.sup.1), SO or SO.sub.2 and where one or more H atoms in the said groups may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, and aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, and any desired combinations of 1, 2, 3, 4 or 5 identical or different groups selected from the above-mentioned groups; or L is a single bond, where p in this case must be equal to 2; R.sup.1is on each occurrence, identically or differently, H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O) OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.2 and where one or more adjacent or non-adjacent CH.sub.2 groups in the above-mentioned groups may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sup.2, —C(═O)O —, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more H atoms in the above-mentioned groups may be 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.2, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2; 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.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.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, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.3 and where one or more adjacent or non-adjacent CH.sub.2 groups in the above-mentioned groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═Se, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and where one or more H atoms in the above-mentioned groups may be 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 may be substituted by one or more radicals R.sup.3, where two or more radicals R.sup.2 may be linked to one another and may form a ring or a ring system; R.sup.3 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 substituents R.sup.3 here may also be linked to one another and form a ring or a ring system; n is equal to 0 or 1; and p is equal to 2, 3, 4, 5 or 6; where a benzene ring may optionally be condensed on at the positions marked by *, and where the group Y and the nitrogen atom are bonded to the six-membered ring of the carbazole derivative in vicinal positions, and where, in the formulae (I) and (II), furthermore no or 1, 2, 3, 4, 5 or 6 carbon atoms which are constituents of an aromatic or heteroaromatic ring may be replaced by N, and where furthermore the compound of the formula (I) or (II) may be substituted by a radical R.sup.1at one or more positions depicted as unsubstituted; and where, in formula (II), the moieties in square brackets which are bonded to L may be identical or different; and where, in formula (II), the group L may be bonded at any desired position of the moiety in square brackets.

2. Compound according to claim 1, characterised in that n is equal to zero.

3. Compound according to claim 1, characterised in that p is equal to 2.

4. Compound according to claim 1, characterised in that 0 or 1 carbon atom which is constituent of an aromatic or heteroaromatic ring in formula (I) or (II) has been replaced by N.

5. Compound according to claim 1, characterised in that L is selected from a single bond, where p must be ═2, or from C═O, NR.sup.1, O, S, alkylene groups having 1 to 10 C atoms, alkenylene groups having 2 to 10 C atoms, where one or more CH.sub.2 groups in the said groups may be replaced by C═O, NR.sup.1 , P(═O)(R.sup.1), O or S, and arylene or heteroarylene groups having 5 to 20 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or from divalent aromatic or heteroaromatic ring systems of the formula (L-1) ##STR00275## where p is equal to 2 and furthermore: Ar.sup.1is on each occurrence, identically or differently, an aryl or heteroaryl group having 5 to 20 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1; E is on each occurrence, identically or differently, a single bond, C═O, NAr.sup.1, P(═O)(R.sup.1), O, S, SO or SO.sub.2; i is on each occurrence, identically or differently, 0 or 1; k,l are on each occurrence, identically or differently, 0, 1, 2 or 3, where the sum of the values of k and l must be greater than 0; and where furthermore the groups Ar.sup.1may be connected to one another via one or more divalent groups T, where T is selected on each occurrence, identically or differently, from a single bond, BR.sup.1, C(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, C═C(R.sup.1).sub.2, CR.sup.1═CR.sup.1, Si(R.sup.1).sub.2, NR.sup.1, PR.sup.1, P(═O)R.sup.1, O, S, S═O and S(═O).sub.2; and the symbols * mark bonds from the group L to the remainder of the compound.

6. Compound according to claim 1, characterised in that Y is selected on each occurrence, identically or differently, from C(R.sup.1).sub.2, C═O, NR.sup.1, O and S.

7. Compound according to claim 1, characterised in that the compound is selected from the following formulae ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## where no or 1, 2, 3, 4, 5 or 6 carbon atoms which are constituents of an aromatic or heteroaromatic ring in formula (I-1) to (I-27) may be replaced by N, and where the compounds may be substituted by a radical R.sup.1at one or more positions depicted as unsubstituted, and where furthermore the symbols occurring are as defined in claim 1.

8. Compound according to claim 1, characterised in that the compound conforms to one of the formulae (II-A) to (II-D) ##STR00282## where the symbols and indices occurring are as defined in claim 1 for formula (II), and where the representation in formula (II-A) means that the group L is bonded to one of the two six-membered rings of the carbazole.

9. Formulation comprising at least one compound according to claim 1 and at least one solvent.

10. Electronic device comprising at least one compound according to claim 1.

11. Electronic device according to claim 10, wherein the electronic 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).

12. Electronic device according to claim 10, selected from organic electroluminescent devices, characterised in that the at least one compound is present as hole-transport material in a hole-transport layer, as matrix material in an emitting layer and/or as electron-transport material in an electron-transporting layer.

13. Oligomer, polymer or dendrimer containing 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 in formula (I) or (II) that are substituted by R.sup.1 or R.sup.2.

14. Formulation comprising at least one polymer, oligomer or dendrimer according to claim 13 and at least one solvent.

15. Electronic device comprising at least one polymer, dendrimer or oligomer according to claim 13.

16. Electronic device according to claim 15, wherein the electronic 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).

17. Electronic device according to claim 15, selected from organic electroluminescent devices, characterised in that the at least one polymer, dendrimer, or oligomer is present as hole-transport material in a hole-transport layer, as matrix material in an emitting layer and/or as electron-transport material in an electron-transporting layer.

Description

USE EXAMPLES

A) Synthesis Examples

Example Compound 1

(1) ##STR00239##

(2) 1st Step:

(3) 50 g (245 mmol) of 2-methyl indole-2-carboxylate, 161.5 g (571 mmol) of 1-bromo-4-iodobenzene and 108.7 g of K.sub.2CO.sub.3 are suspended in 1 l of dioxane. 21.71 g (114 mmol) of CuI and 10.06 g of N,N′-dimethylene-diamine (114 mmol) are added to this suspension. The reaction mixture is heated under reflux for 48 h. After cooling, the precipitate is filtered off via a fluted filter. The reaction solution is subsequently partitioned between ethyl acetate and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a roray evaporator. The black-green oil remaining is filtered through silica gel with heptane:toluene. The evaporated filtrate residue is recrystallised from methanol. Yield: 43 g of 1-phenyl-1H-indole-2-methylcarboxylate (60%)

(4) 2nd Step:

(5) 32.8 g of anhydrous cerium(III) chloride (133.26 mmol) are initially introduced in 500 ml of dry THF. 40 g (121 mmol) of 1-phenyl-1H-indole-2-methylcarboxylate are metered into this solution in portions, and the mixture is stirred for 1 h. The reaction mixture is cooled, and 121 ml (363.44 mmol) of methylmagnesium chloride solution (3 mol/l in THF) are added dropwise at 5° C. over the course of 40 min. After one hour, the reaction mixture is carefully poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from toluene. Yield: 37.5 g (93.6%)

(6) 3rd Step:

(7) 89 g of polyphosphoric acid (968 mmol) and 59 g of methanesulfonic acid are initially introduced in 600 ml of CH.sub.2Cl.sub.2. 37 g (1123 mmol) of 2-(1-(4-bromophenyl)-1H-indol-2-yl)propan-2-ol in CH.sub.2Cl.sub.2 solution (150 ml) are added dropwise to this solution over the course of 30 min, and the mixture is stirred at 50° C. for 1 h. After this time, the reaction mixture is cooled, carefully poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from toluene. Yield: 30 g of 8-bromo-10,10-dimethyl-10H-indolo[1,2-a]indole (85%)

(8) 4th Step:

(9) 30 g of 8-bromo-10,10-dimethyl-10H-indolo[1,2-a]indole (96 mmol), 10.9 ml of 2-chloroaniline (104 mmol), 0.79 g of DPPF (1.43 mmol), 0.26 g of palladium(II) acetate (1.143 mmol) and 23.8 g of sodium tert-butoxide (248 mmol) are heated at the boil in 600 ml of toluene for 18 h under protective atmosphere. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue which remains is recrystallised from heptane/ethyl acetate. The yield is 27.6 g (77 mmol, 80%).

(10) 5th Step:

(11) 25 g of 2-chlorophenylamine compound (70 mmol), 0.78 g of palladium(II) acetate (3 mmol) and 24 g of potassium carbonate (174 mmol), 5.6 ml of 1 M solution of P(t-Bu).sub.3 in toluene (5.6 mmol) and 5.3 ml of pivalic acid (21 mmol) are set in 500 ml of NMP, and the mixture is stirred at 150° C. for 5 h under nitrogen. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue is recrystallised from toluene/heptane. The yield is 15 g (67%) as mixture of A and B. Compounds A and B are separated via silica gel (eluent heptane/toluene).

(12) ##STR00240##

(13) 6th Step:

(14) 20 g (62 mmol) of carbazole derivative A from the preceding step, 20.6 g (66.8 mmol) of 5′-bromo-[1,1′;3′,1″]-terphenyl and 17.9 g of NaOtBu (186.1 mmol) are suspended in 500 ml of p-xylene. 0.28 g (1.24 mmol) of Pd(OAc).sub.2 and 3.7 ml of a 1M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene and subsequently sublimed in a high vacuum. The purity is 99.9%.

Example Compound 2

(15) ##STR00241##

(16) 1st step: 2-chloro-4,6-diphenylpyrimidine

(17) 75 g (0.41 mmol) of 1,3,5-trichloropyrimidine, 100 g (0.82 mol) of phenylboronic acid and 625 ml of 4 M NaHCO.sub.3 solution are suspended in 2.5 l of ethylene glycol dimethy ether. 2.3 g (10.23 mmol) of Pd(OAc).sub.2 and 10.35 g (34 mmol) of (o-Tol).sub.3P are added to this suspension, and the reaction mixture is heated under reflux for 16 h. The mixture is subsequently partitioned between ethyl acetate and water, the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue which remains is recrystallised from heptane/toluene. The yield is 43 g (0.15 mol, 38%).

(18) 2nd Step:

(19) 2.48 g of 60% NaH in mineral oil (62 mmol) are dissolved in 150 ml of dimethylformamide under protective atmosphere. 20 g (62 mmol)) of the compound from the 5th step of Example 1 are dissolved in 100 ml of DMF and added dropwise to the reaction mixture. After 1 h at room temperature, a solution of 2-chloro-4,6-diphenyl-1,3-pyrimidine (20.2 g, 71.2 mmol) in 100 ml of THF is added dropwise. The reaction mixture is subsequently stirred at room temperature for 12 h. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is extracted with hot toluene, recrystallised from toluene/n-heptane and finally sublimed in a high vacuum. The purity is 99.9%, the yield is 27 g (80%).

Example Compound 3

(20) ##STR00242##

(21) Example compound 3 is synthesised analogously to example compound 2. The purity after sublimation is 99.9%, the yield is 45%.

Example Compound 4

(22) ##STR00243##

(23) 31 g (96 mmol) of the compound from the 5th step of Example 1, 15 g (48 mmol) of 4,4′-dibromobiphenyl and 25.9 g (270 mmol) of NaOtBu are suspended in 800 ml of p-xylene. 0.54 g (2.4 mmol) of Pd(OAc).sub.2 and 4.8 ml of a 1M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene and finally sublimed in a high vacuum. The purity is 99.9%.

Example Compound 5

(24) ##STR00244##

(25) 15 g (47 mmol) of the compound from the 5th step of Example 1, 25.7 g (47 mmol) of bisbiphenyl-4-yl-(4′-bromobiphenyl-4-yl)amine and 13.4 g of NaOtBu (139.6 mmol) are suspended in 400 ml of p-xylene. 0.21 g (0.93 mmol) of Pd(OAc).sub.2 and 0.7 ml (2.79 mmol) of a 1M tri-tert-butyl-phosphine solution are added to this suspension. The reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene and subsequently sublimed in a high vacuum. The purity is 99.9%.

Example Compound 6

(26) ##STR00245##

(27) 1st Step:

(28) 30 g (96 mmol) of the compound from the 3rd step of Example 1, 11 ml of 3-chloro-4-pyridin-4-ylamine (104 mmol), 0.79 g of DPPF (1.43 mmol), 0.26 g of palladium(II) acetate (1.143 mmol) and 23.8 g of sodium tert-butoxide (248 mmol) are heated at the boil in 600 ml of toluene for 18 h under protective atmosphere. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue which remains is recrystallised from heptane/ethyl acetate. The yield is 27.6 g (77 mmol, 80%).

(29) 2nd Step:

(30) 25 g (70 mmol) of the compound from the preceding step, 0.78 g of palladium(II) acetate (3 mmol), 24.07 g of potassium carbonate (174 mmol), 5.6 ml of 1 M solution of (tBu).sub.3P in toluene (5.6 mmol) and 2.1 g of pivalic acid (21 mmol) are set in 300 ml of NMP, and the mixture is stirred at 130° C. for 5 h under nitrogen. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue is recrystallised from toluene/heptane. The yield is 15 g (67%) as mixture of C and D. Compounds C and D are separated via silica gel (eluent heptane/toluene).

(31) ##STR00246##

(32) 3rd Step:

(33) 2.13 g of 60% NaH in mineral oil (53.3 mol) are dissolved in 150 ml of dimethylformamide under protective atmosphere. 15 g (0.31 mol) of compound C from the preceding step are dissolved in 100 ml of DMF and added dropwise to the reaction mixture. After 1 hour at room temperature, a solution of 2-chloro-4,6-diphenyl-1,3-pyrimidine (14.21 g, 53.3 mmol) in 100 ml of THF is added dropwise. The reaction mixture is then stirred at room temperature for 12 h. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is extracted with hot toluene, recrystallised from toluene/n-heptane and subsequently sublimed in a high vacuum. The purity is 99.9%.

Example Compound 7

(34) ##STR00247##

(35) 1st Step:

(36) 50 g (285 mmol) of 2-methyl indole-2-carboxylate, 98.8 g (285 mmol) of 2-bromo-N-Boc-carbazole and 151 g of K.sub.3PO.sub.4 (714 mmol) are suspended in 800 ml of dioxane. 21.7 g (114 mmol) of CuI and 10.06 g of N,N-dimethylenediamine (114 mmol) are added to this suspension. The reaction mixture is heated under reflux for 48 h. After cooling, the precipitate is filtered off via a fluted filter. The reaction solution is subsequently partitioned between ethyl acetate and water, the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The black-green oil remaining is filtered through silica gel with heptane: toluene. The evaporated filtrate residue is recrystallised from methanol. The yield is 72.8 g (58%).

(37) 2nd Step:

(38) 72 g (163.4 mmol) of the compound from the preceding step are dissolved in 500 ml of dichloromethane, and 12.4 ml of trifluoroacetic acid (163.4 mmol) are subsequently added. The mixture is stirred at 40° C. for 3 h and, when the conversion is complete, neutralised using ice-water and 20% NaOH solution. The mixture is extracted with methylene chloride, dried and purified by means of recrystallisation from toluene/heptane, giving 52.8 g (95%) of the product as white solid.

(39) 3rd Step:

(40) 23.9 g of anhydrous cerium(III) chloride (97 mmol) are initially introduced in 300 ml of dry THF. 30 g (88 mmol) of 1-(9H-carbazol-2-yl)-1H-indole-2-methylcarboxylate are metered into this solution in portions and the mixture is stirred for 30 min. The reaction mixture is cooled, and 88 ml (254 mmol) of methylmagnesium chloride solution (3 mol/l in THF) are added dropwise over the course of 30 min at 5° C. After one hour, the reaction mixture is carefully poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from toluene. Yield: 27.5 g (92%).

(41) 4th Step:

(42) 58.7 g of polyphosphoric acid (600 mmol) and 38.9 g of methanesulfonic acid (270 mmol) are initially introduced in 500 ml of CH.sub.2Cl.sub.2. 25 g (73 mmol) of 2-[1-(9H-carbazol-3-yl)-1H-indol-2-yl]propan-2-ol in CH.sub.2Cl.sub.2 solution (150 ml) are added dropwise to this solution over the course of 30 min, and the mixture is stirred at 50° C. for 1 h. After this time, the reaction mixture is cooled, carefully poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from toluene. The yield is 17.8 g of the corresponding cyclised product (75%).

(43) 5th Step:

(44) 15 g (47 mmol) of the compound from the preceding step, 14.4 g (47 mmol) of 5′-bromo-[1,1′;3′,1″]terphenyl and 13.4 g of NaOtBu (139.6 mmol) are suspended in 400 ml of p-xylene. 0.21 g (0.93 mmol) of Pd(OAc).sub.2 and 0.7 ml (2.79 mmol) of a 1M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene and finally sublimed in a high vacuum. The purity is 99.9%.

Example Compound 8

(45) ##STR00248##

(46) 1st Step:

(47) 101.9 g (240 mmol) of 2-methylindole-2-carboxylate, 20 g (114 mmol) of 3,6-dibromo-N-Boc-carbazole and 151 g of K.sub.3PO.sub.4 (714 mmol) are suspended in 1.21 of dioxane. 17.4 g (92 mmol) of CuI and 8 g of N,N-dimethylenediamine (92 mmol) are added to this suspension. The reaction mixture is heated under reflux for 48 h. After cooling, the precipitate is filtered off via a fluted filter. The reaction solution was subsequently partitioned between ethyl acetate and water, the organic phase was washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator organic phase separated off washed three times with 200 ml of water and subsequently evaporated to dryness. The black-green oil which remains is filtered through silica gel with heptane:toluene. The evaporated filtrate residue is recrystallised from methanol. The yield is 49 g (70%).

(48) The further steps are carried out analogously to the synthesis of example compound 1, with bromobenzene being employed instead of bromo-terphenyl in the final step.

B) Device Examples

(49) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

(50) The data for various OLEDs are presented in Examples E1 to E13 below (see Tables 1 and 2). 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/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)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs is shown in Table 1. The materials required for the production of the OLEDs are shown in Table 3.

(51) 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:H4:TER1 (50%:40%:10%) here means that material ST1 is present in the layer in a proportion by volume of 50%, H4 is present in the layer in a proportion of 40% 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.

(52) 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 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) assuming Lambert emission characteristics and the lifetime are determined. The electroluminescence spectra are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931× 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 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. The data for the various OLEDs are summarised in Table 2.

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

(54) Compounds according to the invention are particularly suitable as matrix materials for phosphorescent dopants. They are suitable as single matrix (Examples E6 to E9) or as component in a mixed-matrix system, i.e. in combination with a second matrix material (Examples E1 to E5). Very good values for voltage and efficiency are achieved here. Thus, for example, a voltage of only 3.3 V for 1000 cd/m.sup.2 and an external quantum efficiency of about 16% are obtained on use of H7 in combination with IC2. Good values are also obtained for the lifetime. Thus, for example for Example E1, the drop from a luminous density of 8000 to 6400 cd/m.sup.2 takes about 270 h on operation with constant current density.

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

(56) Compounds according to the invention can furthermore be employed in the hole-transport layer of OLEDs. Good values are obtained here for voltage and in particular also efficiency in blue-fluorescent OLEDs (Examples E11 and E12). The same applies on use in green-phosphorescent OLEDs (Examples E10 and E13). Good lifetimes are again achieved, in Example E10 the luminous density on operation with constant current density drops from 8000 to 6400 cd/m.sup.2 within about 170 h.

(57) TABLE-US-00003 TABLE 1 Structure of the OLEDs HIL HTL IL EBL EML HBL ETL EIL Ex. Thickness Thickness Thickness Thickness Thickness Thickness Thickness Thickness E1 — SpA1 HATCN BPA1 IC1:H1:TEG1 IC1 ST1:LiQ — 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm E2 — SpA1 HATCN BPA1 IC1:H4:TEG1 IC1 ST1:LiQ — 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm E3 — SpA1 HATCN BPA1 IC1:H6:TEG1 IC1 ST1:LiQ — 70 nm 5 nm 90 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm E4 — SpA1 HATCN BPA1 IC2:H7:TEG1 IC1 ST1:LiQ — 70 nm 5 nm 90 nm (25%:65%:10%) 10 nm (50%:50%) 30 nm 30 nm E5 — SpA1 — BPA1 ST1:H4:TER1 ST1 Alq.sub.3 LiF 20 nm 20 nm (50%:40%:10%) 10 nm 20 nm 1 nm 30 nm E6 — SpA1 HATCN BPA1 H2:TEG1 ST1 ST1:LiQ — 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E7 — SpA1 — NPB H2:TER2 — Alq.sub.3 LiF 20 nm 20 nm (85%:15%) 20 nm 1 nm 30 nm E8 — SpA1 HATCN BPA1 H3:TEG1 ST1 ST1:LiQ — 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E9 — SpA1 HATCN BPA1 H5:TEG1 ST1 ST1:LiQ — 70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E10 — SpA1 HATCN HTM1 IC1:TEG1 — ST1:LiQ — 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm E11 HATCN SpA1 — HTM1 M1:D1 — ST2:LiQ — 5 nm 140 nm 20 nm (95%:5%) (50%:50%) 30 nm 20 nm E12 HATCN SpA1 — HTM1 M2:D2 — ST2:LiQ — 5 nm 140 nm 20 nm (98.5%:1.5%) (50%:50%) 30 nm 20 nm E13 — SpA1 HATCN H7 IC1:TEG1 — ST1:LiQ — 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm

(58) TABLE-US-00004 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 E1 3.4 53 49 14.8% 0.36/0.61 E2 3.6 56 49 15.5% 0.36/0.60 E3 3.4 53 49 14.6% 0.36/0.61 E4 3.3 58 55 16.1% 0.37/0.60 E5 4.9 8.7 5.6 12.3% 0.68/0.32 E6 3.3 50 48 13.8% 0.36/0.60 E7 5.8 10.5 5.7 9.7% 0.66/0.33 E8 3.3 51 48 14.0% 0.36/0.60 E9 3.7 44 37 12.2% 0.37/0.60 E10 3.7 54 46 14.9% 0.36/0.60 E11 4.5 8.4 5.8 6.5% 0.14/0.15 E12 4.3 9.3 6.8 7.2% 0.14/0.16 E13 3.8 51 43 14.1% 0.37/0.60

(59) TABLE-US-00005 TABLE 3 Structural formulae of the materials for the OLEDs 0 0 0