Compounds with diazadibenzofurane or diazadibenzothiophene structures

Abstract

The present invention describes diazadibenzofuran or diazadibenzothiophene derivatives substituted by carbazole, fluorene, phenanthrene, benzofuran and/or benzothiophene groups, especially for use in electronic devices. The invention further relates to a process for preparing the compounds of the invention and to electronic devices comprising these.

Claims

1. A compound of formula (A): ##STR00475## wherein Y.sup.1 is O or S; Y.sup.2 is C(R.sup.1).sub.2, or —R.sup.1C═CR.sup.1—; W is the same or different in each instance and is N or CR.sup.1, with the proviso that not more than two W in one cycle are N, wherein the R.sup.1 radicals in the W groups do not form a fused heteroaromatic ring system; L.sup.1 is a bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more R.sup.1 radicals; A is the same or different in each instance and is N, CAr.sup.a, or CAr.sup.b, wherein exactly two A are N separated by at least one CAr.sup.a or CAr.sup.b group, with the proviso that A is CAr.sup.b if two N are adjacent to this A; Ar is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more radicals R.sup.1; Ar.sup.a is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more radicals R′; Ar.sup.b is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more radicals R′; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, Si(Ar.sup.1).sub.3, Si(R.sup.2).sub.3, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.2C═CR.sup.2—, Si(R.sup.2).sub.2, C═O, C═S, 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 wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which is optionally substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or a combination of these systems; and wherein two or more R.sup.1 together optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; Ar.sup.1 is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more nonaromatic R.sup.2 radicals; and wherein two Ar.sup.1 bonded to the same silicon atom, nitrogen atom, phosphorus atom, or baron atom are optionally also joined together via a single bond or a bridge selected from the group consisting of B(R.sup.2), C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, C═C(R.sup.2).sub.2, O, S, S═O, SO.sub.2, N(R.sup.2), P(R.sup.2), and P(═O)R.sup.2; R.sup.2 is the same or different in each instance and is H, D, F, Cl, Br, I, CN, B(OR?.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.13).sub.2, 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 thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.3 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, Si(R.sup.3).sub.2, C═O, C═S, 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 wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.3 R.sup.3 radicals, or a combination of these systems; and wherein two or more adjacent R.sup.2 together optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; R.sup.3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein hydrogen atoms are also optionally replaced by F; and wherein two or more adjacent R.sup.3 together optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; n is 0, 1, 2, or 3.

2. The compound of claim 1, wherein the compound comprises a compound of formula (I), (II), or (III): ##STR00476##

3. The compound of claim 1, wherein the compound is a compound of formulae (Ia), (IIa), or (IIIa): ##STR00477##

4. The compound of claim 1, wherein the compound is a compound of formulae (Ib), (IIb), or (IIIb): ##STR00478##

5. The compound of claim 1, wherein the compound is a compound of formulae (Ic), (IIc), or (IIc): ##STR00479##

6. The compound of claim 1, wherein the compound is a compound of formulae (Id), (IId), or (IIId): ##STR00480##

7. The compound of claim 1, wherein the compound is a compound of formulae (Ie), (IIe), or (IIIe): ##STR00481##

8. The compound of claim 1, wherein the compound is a compound of formulae (If), (IIf), or (IIIf): ##STR00482##

9. The compound of claim 1, wherein the compound is a compound of formulae (Ig), (IIg), or (IIIg): ##STR00483##

10. The compound of claim 1, wherein the compound is a compound of formulae (Ih), (IIh), or (IIIh): ##STR00484##

11. The compound of claim 1, wherein Y.sup.2 is C(R.sup.1).sub.2 and R.sup.1 is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which are optionally substituted in each case by one or more R.sup.2 radicals.

12. The compound of claim 1, wherein Y.sup.2 is a group of formula (Y.sup.2-2): ##STR00485## wherein the dotted lines denote the bonds to the adjacent atoms and m is 0, 1, 2, 3, or 4.

13. The compound of claim 1, wherein Ar.sup.b is a group of formula (Ar.sup.b-1): ##STR00486## wherein L.sup.2 is a bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more R.sup.1 radicals; m is 0, 1, 2, 3, or 4; and the dotted line denotes the bond.

14. An oligomer, polymer, or dendrimer comprising one or more compounds according to claim 1, wherein one or more bonds of the compound to the polymer, oligomer, or dendrimer are present.

15. A composition comprising at least one compound of claim 1 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials.

16. A composition comprising at least one oligomer, polymer, or dendrimer of claim 14 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials.

17. A formulation comprising at least one compound of claim 1 and at least one solvent.

18. A formulation comprising at least one oligomer, polymer, or dendrimer of claim 14 and at least one solvent.

19. A formulation comprising at least one composition of claim 15 and at least one solvent.

20. A formulation comprising at least one composition of claim 16 and at least one solvent.

21. A process for preparing the compound of claim 1, comprising joining a compound comprising at least one diazadibenzofuran or diazadibenzothiophene group to a group comprising at least one, fluorene, and/or phenanthrene radical in a coupling reaction.

22. A process for preparing an oligomer, polymer, or dendrimer of claim 14, comprising joining a compound comprising at least one diazadibenzofuran or diazadibenzothiophene group to a group comprising at least one and/or phenanthren radical in a coupling reaction.

23. An electronic device comprising at least one compound of claim 1.

24. An electronic device comprising at least one oligomer, polymer, or dendrimer of claim 14.

25. The electronic device of claim 23, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

26. The electronic device of claim 24, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

27. A compound of formula (A): ##STR00487## wherein Y.sup.1 is O or S; Y.sup.2 is N(Ar), O, C(R.sup.1).sub.2, or —R.sup.1C═CR.sup.1—; W is the same or different in each instance and is N or CR.sup.1, with the proviso that not more than two W in one cycle are N, wherein the R.sup.1 radicals in the W groups do not form a fused heteroaromatic ring system; L.sup.1 is a bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more R.sup.1 radicals; A is the same or different in each instance and is N, CAr.sup.a, or CAr.sup.b, wherein exactly two A are N separated by at least one CAr.sup.a or CAr.sup.b group, with the proviso that A is CAr.sup.b if two N are adjacent to this A; Ar is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more radicals R.sup.1; Ar.sup.a is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more radicals R′; Ar.sup.b is a group of formula (Ar.sup.b-1): ##STR00488## wherein L.sup.2 is a bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more R.sup.1 radicals; m is 0, 1, 2, 3, or 4; and the dotted line denotes the bond, R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, Si(Ar.sup.1).sup.3, Si(R.sup.2).sub.3, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.2C═CR.sup.2—, Si(R.sup.2).sub.2, C═O, C═S, 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 wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which is optionally substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.2 radicals, or a combination of these systems; and wherein two or more R.sup.1 together optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; Ar.sup.1 is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and which is optionally substituted by one or more nonaromatic R.sup.2 radicals; and wherein two Ar.sup.1 bonded to the same silicon atom, nitrogen atom, phosphorus atom, or baron atom are optionally also joined together via a single bond or a bridge selected from the group consisting of B(R.sup.2), C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, C═C(R.sup.2).sub.2, O, S, S═O, SO.sub.2, N(R.sup.2), P(R.sup.2), and P(═O)R.sup.2; R.sup.2 is the same or different in each instance and is H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, —CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.13).sub.2, 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 thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each of which is optionally substituted by one or more R.sup.3 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by —R.sup.3C═CR.sup.3—, Si(R.sup.3).sub.2, C═O, C═S, 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 wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which is optionally substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and which is optionally substituted by one or more R.sup.3 radicals, or a combination of these systems; and wherein two or more adjacent R.sup.2 together optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; R.sup.3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein hydrogen atoms are also optionally replaced by F; and wherein two or more adjacent R.sup.3 together optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; n is 0, 1, 2, or 3; with the proviso that, if Y.sup.2 is N(Ar) or O, Ar.sup.a does not comprise any carbazole group, including any R.sup.1, R.sup.2, and R.sup.3 substituents bonded to Ar.sup.a.

28. The compound of claim 27, wherein the compound comprises a compound of formula (I), (II), or (III): ##STR00489##

29. The compound of claim 27, wherein the compound is a compound of formulae (Ia), (IIa), or (IIIa): ##STR00490##

30. The compound of claim 27, wherein the compound is a compound of formulae (Ib), (IIb), or (IIIb): ##STR00491##

31. The compound of claim 27, wherein the compound is a compound of formulae (Ic), (IIc), or (IIIc): ##STR00492##

32. The compound of claim 27, wherein the compound is a compound of formulae (Id), (IId), or (IIId): ##STR00493##

33. The compound of claim 27, wherein the compound is a compound of formulae (Ie), (IIe), or (IIIe): ##STR00494##

34. The compound of claim 27, wherein the compound is a compound of formulae (If), (IIf), or (IIIf) ##STR00495##

35. The compound of claim 27, wherein the compound is a compound of formulae (Ig), (IIg), or (IIIg): ##STR00496##

36. The compound of claim 27, wherein the compound is a compound of formulae (Ih), (IIh), or (IIIh): ##STR00497##

37. The compound of claim 27, wherein Y.sup.2 is C(R.sup.1).sub.2 and R.sup.1 is the same or different in each instance and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which are optionally substituted in each case by one or more R.sup.2 radicals.

38. The compound of claim 27, wherein Y.sup.2 is a group of formula (Y.sup.2-2): ##STR00498## wherein the dotted lines denote the bonds to the adjacent atoms and m is 0, 1, 2, 3, or 4.

39. An oligomer, polymer, or dendrimer comprising one or more compounds according to claim 27, wherein one or more bonds of the compound to the polymer, oligomer, or dendrimer are present.

40. A composition comprising at least one compound of claim 27 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials.

41. A composition comprising at least one oligomer, polymer, or dendrimer of claim 39 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials.

42. A formulation comprising at least one compound of claim 27 and at least one solvent.

43. A formulation comprising at least one oligomer, polymer, or dendrimer of claim 39 and at least one solvent.

44. A formulation comprising at least one composition of claim 40 and at least one solvent.

45. A formulation comprising at least one composition of claim 41 and at least one solvent.

46. A process for preparing a compound of claim 27, comprising joining a compound comprising at least one diazadibenzofuran or diazadibenzothiophene group to a group comprising at least one carbazole, fluorene, phenanthrene and/or benzofuran radical in a coupling reaction.

47. A process for preparing an oligomer, polymer, or dendrimer of claim 39, comprising joining a compound comprising at least one diazadibenzofuran or diazadibenzothiophene group to a group comprising at least one carbazole, fluorene, phenanthrene, and/or benzofuran radical in a coupling reaction.

48. An electronic device comprising at least one compound of claim 27.

49. An electronic device comprising at least one oligomer, polymer, or dendrimer of claim 39.

50. The electronic device of claim 48, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

51. The electronic device of claim 49, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells, and organic laser diodes.

52. A process for preparing the compound of claim 2, comprising joining a compound comprising at least one diazadibenzofuran or diazadibenzothiophene group to a group comprising at least one, fluorene, and/or phenanthrene radical in a coupling reaction.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The compounds of the invention can be prepared by means of synthesis methods known to those skilled in the art.

Synthesis Examples

a) 2,4-Diphenylbenzo[4,5]furo[3,2-cl]pyrimidine

(2) ##STR00243##

(3) 13 g (110.0 mmol) of phenylboronic acid, 13 g (55 mmol) of 2,4-dichlorobenzo[4,5]furo[3,2-d]pyrimidine and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. Added to this suspension are 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/heptane. Yield: 15 g (47 mmol), 87% of theory.

(4) The following compounds are prepared in an analogous manner:

(5) TABLE-US-00005 Reactant 1 Reactant 2  2a  3a  4a  5a 0  6a  7a  8a  9a 10a 0 11a 12a 13a 14a 15a 0 16a Product Yield  2a 89%  3a 70%  4a 77%  5a 76%  6a 77%  7a 74%  8a 0 76%  9a 69% 10a 75% 11a 73% 12a 75% 13a 76% 14a 68% 15a 71% 16a 73%

(6) The product 9a and 13a is purified via column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed under high vacuum (p=5×10.sup.−7 mbar) (99.9% purity).

b) 8-Bromo-2,4-diphenylbenzo[4,5]furo[3,2-d]pyrimidine

(7) ##STR00289##

(8) 61 g (190.0 mmol) of 2,4-diphenylbenzo[4,5]furo[3,2-d]pyrimidine are suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulphuric acid (95-98%). 34 g (190 mmol) of NBS are added to this suspension in portions and the mixture is stirred in the dark for 2 hours. Thereafter, water/ice is added and solids are removed and washed with ethanol. The residue is recrystallized in toluene. The yield is 65 g (163 mmol), corresponding to 86% of theory.

(9) The following compounds are prepared in an analogous manner:

(10) TABLE-US-00006 Reactant 1 Product Yield  2b 0 85%  3b 84%  4b 85%  5b 79%  6b 70%  7b 00 01 73%  8b 02 03 80%  9b 04 05 85% 10b 06 07 69% 11b 08 09 71% 12b 0 74% 13b 67% 14b 56%

c) 2,4-Diphenyl-8-(9-phenyl-9H-carbazol-3-yl)-benzo[4,5]furo[3,2-d]pyrimidine

(11) ##STR00316##

(12) 62 g (156 mmol) of 8-bromo-2,4-diphenylbenzo[4,5]furo[3,2-d]pyrimidine, 50 g (172 mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol diamine ether and 280 ml of water. To this suspension are added 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0), and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel and then concentrated to dryness. The product is purified via column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed under high vacuum (p=5×10.sup.−7 mbar) (purity 99.9%). The yield is 60 g (106 mmol), corresponding to 69% of theory.

(13) In an analogous manner, the following compounds are prepared:

(14) TABLE-US-00007 Reactant 1 Reactant 2  1c  2c 0  3c  4c  5c  6c  7c 0  8c  9c 10c 11c 12c 0 13c 14c 15c 16c 17c 0 18c 19c 20c 21c 22c 0 23c 24c Product Yield  1c 65%  2c 68%  3c 65%  4c 65%  5c 71%  6c 0 76%  7c 74%  8c 71%  9c 69% 10c 70% 11c 77% 12c 60% 13c 56% 14c 64% 15c 65% 16c 0 67% 17c 68% 18c 66% 19c 77% 20c 75% 21c 80% 22c 64% 23c 61% 24c 62%

(15) In an analogous manner, 11c-17c and also 12c-18c and 22c-24c are used to prepare the following compounds:

(16) TABLE-US-00008 Reactant 1 Reactant 2 25c 0 26c 27c 28c 29c 30c 00 31c 01 02 32c 03 04 33c 05 06 34c 07 08 35c 09 0 36c 37c 38c 39c 40c 0 Product Yield 25c 72% 26c 74% 27c 68% 28c 66% 29c 64% 30c 72% 31c 73% 32c 71% 33c 75% 34c 0 75% 35c 76% 36c 63% 37c 75% 38c 73% 39c 76% 40c 78%

d) 2,4-Bis(carbazol-9-yl)-8-[2-eth-(Z)-ylidene-3,3-dimethyl-1-prop-2-en-(Z)-ylideneindan-4-yl]benzo[4,5]furo[3,2-d]pyrimidine

(17) ##STR00437##

(18) A degassed solution of 53 g (147 mmol) of 2,4-dichloro-8-(9,9-dimethyl-9H-fluoren-1-yl)benzo[4,5]furo[3,2-d]pyrimidine and 24 g (147 mmol) of 9H-carbazole in 600 ml of toluene is saturated with N2 for 1 h. Added to the solution thereafter are first 2.09 ml (8.6 mmol) of P(tBu).sub.3, then 1.38 g (6.1 mmol) of palladium(II) acetate, and then 17.7 g (185 mmol) of NaOtBu are added in the solid state. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 ml of water are added cautiously. The aqueous phase is washed with 3×50 ml of toluene, dried over MgSO.sub.4, and the solvent is removed under reduced pressure. Thereafter, the crude product is purified by chromatography using silica gel with heptane/ethyl acetate (20/1). The residue is recrystallized from toluene and finally sublimed under high vacuum (p=5×10.sup.−6 mbar).

(19) The yield is 67 g (95 mmol), corresponding to 78% of theory.

(20) In an analogous manner, it is possible to obtain the following compounds:

(21) TABLE-US-00009 Reactant 1 Reactant 2 1d 2d 0 3d Product Yield 1d 75% 2d 70% 3d 73%

e) 4-Phenyl-2,8-bis-(9-phenyl-9H-carbazol-3-yl)benzo[4,5]thieno[3,2-d]-pyrimidine (Ie)

(22) ##STR00447##

(23) 2,4-Dichlorobenzo[4,5]thieno[3,2-d]pyrimidine is brominated analogously to method b, then reacted with phenylcarbazoleboronic acid via Suzuki analogously to method c and then reacted, again analogously to method c, first with phenylboronic acid and finally with phenylcarbazoleboronic acid.

f) 4-(6-Dibenzofuran-4-yl-pyridin-2-yl)-2,8-di(pyridin-2-yl)-benzo[4,5]thieno[3,2-d]pyrimidine (If)

(24) ##STR00448##

(25) The preparation is effected according to the method detailed above under e).

g) 2,2′-Bis(carbazol-9-yl-4,4′-diphenyl-[8,8]bi[benzo[4,5]thieno[3,2-d]pyrimidinyl])

(26) ##STR00449##

(27) 2,4-Dichlorobenzo[4,5]thieno[3,2-d]pyrimidine is brominated analogously to method b, then converted to the corresponding boronic acid with BuLi and triethyl borate. Then the coupling is effected analogously to method c to give the corresponding dimer and then, in turn, first reacted with phenylboronic acid analogously to method c and finally converted to the target molecule by reaction with NaH and carbazole via nucleophilic substitution.

j) 2-Carbazol-9-yl-8-dibenzothiophen-2-yl-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine

(28) ##STR00450##

(29) The preparation is conducted according to the procedure set out above under g).

(30) Production of the OLEDs

(31) In examples C1 to I13 which follow (see Tables 1 and 2), the data of various OLEDs are presented.

Pretreatment for Examples C1-I13

(32) Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plaques form the substrates to which the OLEDs are applied.

(33) The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 1. The materials required for production of the OLEDs are shown in Table 3.

(34) All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as IC5:IC3:TEG2 (55%: 35%:10%) mean here that the material 105 is present in the layer in a proportion by volume of 55%, 103 in a proportion of 35% and TEG2 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(35) The OLEDs are characterized in a standard manner. 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 luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined.

(36) The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 in the course of operation with constant current. Figures of L0;j0=4000 cd/m.sup.2 and L1=70% in Table 2 mean that the lifetime given in the column LT corresponds to the time after which the starting luminance drops from 4000 cd/m.sup.2 to 2800 cd/m.sup.2. Analogously, L0;j0=20 mA/cm.sup.2 and L1=80% means that the luminance in the course of operation at 20 mA/cm.sup.2 drops to 80% of its starting value after the time LT.

(37) The data for the various OLEDs are collated in Table 2. Examples C1-C4 are comparative examples according to the prior art; examples I1-I13 show data of OLEDs of the invention.

(38) Some of the examples are elucidated in detail hereinafter, in order to illustrate the advantages of the OLEDs of the invention.

(39) Use of Materials of the Invention in Phosphorescent OLEDs

(40) The materials of the invention, when used in the emission layer (EML) in OLEDs, give significant improvements over the prior art, particularly with regard to lifetime.

(41) Through use of the inventive compounds 3d,1e,1f and 15a, it is possible to achieve an increase in the lifetime by about 20-30% compared to the prior art (comparison of example I1 with C1; comparison of example I2 with C2; comparison of example I3 with C3; comparison of example I4 with C4).

(42) TABLE-US-00010 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness C1 HATCN SpMA1 SpMA3 PA1:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm C2 HATCN SpMA1 SpMA3 PA2:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm C3 HATCN SpMA1 SpMA3 PA3:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm C4 HATCN SpMA1 SpMA3 PA4:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I1 HATCN SpMA1 SpMA3 3d:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I2 HATCN SpMA1 SpMA3 1e:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I3 HATCN SpMA1 SpMA3 1f:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I4 HATCN SpMA1 SpMA3 15a:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I5 HATCN SpMA1 SpMA3 11a:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I6 HATCN SpMA1 SpMA3 12a:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I7 HATCN SpMA1 SpMA3 9c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I8 HATCN SpMA1 SpMA3 1c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I9 HATCN SpMA1 SpMA3 39c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I10 HATCN SpMA1 SpMA3 19c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I11 HATCN SpMA1 SpMA3 27c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I12 HATCN SpMA1 SpMA3 30c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I13 HATCN SpMA1 SpMA3 9c:IC3:TEG2 — ST2:LiQ — 5 nm 235 nm 20 nm (45%:45%:10%) (50%:50%) 30 nm 40 nm

(43) TABLE-US-00011 TABLE 2 Data of the OLEDs U1000 EQE CIE x/y at L1 LD Ex. (V) 1000 1000 cd/m.sup.2 L.sub.0; j.sub.0 % (h) C1 3.5 22.2% 0.67/0.33 50 mA/cm.sup.2 95 45 C2 3.6 21.6% 0.67/0.33 50 mA/cm.sup.2 95 40 C3 3.7 22.2% 0.67/0.33 50 mA/cm.sup.2 95 5 C4 3.7 22.4% 0.67/0.33 50 mA/cm.sup.2 95 45 I1 3.6 21.8% 0.67/0.33 50 mA/cm.sup.2 95 60 I2 3.7 22.4% 0.67/0.33 50 mA/cm.sup.2 95 50 I3 3.6 22.1% 0.67/0.33 50 mA/cm.sup.2 95 10 I4 3.7 22.3% 0.67/0.33 50 mA/cm.sup.2 95 55 I5 3.7 22.2% 0.67/0.33 50 mA/cm.sup.2 95 50 I6 3.8 22.4% 0.67/0.33 50 mA/cm.sup.2 95 45 I7 3.7 22.5% 0.67/0.33 50 mA/cm.sup.2 95 50 I8 3.6 22.2% 0.67/0.33 50 mA/cm.sup.2 95 60 I9 3.8 22.0% 0.67/0.33 50 mA/cm.sup.2 95 50 I10 3.8 22.2% 0.67/0.33 50 mA/cm.sup.2 95 55 I11 3.8 22.4% 0.67/0.33 50 mA/cm.sup.2 95 60 I12 3.4 21.8% 0.67/0.33 50 mA/cm.sup.2 95 45 I13 3.4 20.2% 0.33/0.63 40 mA/cm.sup.2 80 120

(44) TABLE-US-00012 TABLE 3 Structural formulae of the materials for the OLEDs 0 3d 1e 1f 15a 11a 12a 9c 0 1c 39c 19c 27c 30c