Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.

Claims

1. A compound of the formula (1), ##STR00393## where the following applies to the symbols and indices used: Ar.sup.4 stands for a group of formula (Ar4-1), ##STR00394##  where the dashed bond in formula (Ar4-1) indicates the bonding to the structure of formula (1); G is a condensed aryl group having 10 to 50 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.2; Ar.sup.1, Ar.sup.2 and Ar.sup.3 stand on each occurrence, identically or differently, for Ar.sup.4, or for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.3; Ar.sup.S is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can in each case also be substituted by one or more radicals R.sup.3; Ar.sup.5, Ar.sup.6 stand on each occurrence, identically or differently, for an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.4; X stands for CR.sup.1 or nitrogen; or X stands for carbon, if it is bonded to Ar.sup.5, Ar.sup.6, R.sup.4 or to an adjacent fluorene derivative unit; R, R.sup.0, R.sup.1, R.sup.2, R.sup.3, R.sup.4 stand on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, CHO, C≡N, N(Ar.sup.7).sub.2, C(═O)Ar.sup.7, P(═O)(Ar.sup.7).sub.2, S(═O)Ar.sup.7, S(═O).sub.2Ar.sup.7, NO.sub.2, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 carbon atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.5, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by R.sup.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.5), SO, SO.sub.2, O, S or CONR.sup.5 and where one or more H atoms can be replaced by deuterium, fluorine, chlorine, bromine, iodine, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.5, or an aryloxy groups having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R.sup.5, where two adjacent substituents R, two adjacent substituents R.sup.0, two adjacent substituents R.sup.1, two adjacent substituents R.sup.2, two adjacent substituents R.sup.3 and/or two adjacent substituents R.sup.4, can form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more radicals R.sup.5; R.sup.5 stands on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, CHO, C≡N, N(Ar.sup.7).sub.2, C(═O)Ar.sup.7, P(═O)(Ar.sup.7).sub.2, S(═O)Ar.sup.7, S(═O).sub.2Ar.sup.7, NO.sub.2, Si(R.sup.6).sub.3, B(OR.sup.6).sub.2, OSO.sub.2R.sup.6, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.6, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by R.sup.6C═CR.sup.6, C≡C, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.6), SO, SO.sub.2, O, S or CONR.sup.6 and where one or more hydrogen atoms can be replaced by deuterium, fluorine, chlorine, bromine, iodine, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.6, or an aryloxy group having 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R.sup.6, where two adjacent substituents R.sup.5 can form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more radicals R.sup.6; Ar.sup.7 is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can in each case also be substituted by one or more radicals R.sup.6; R.sup.6 stands on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C≡N, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 carbon atoms, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by SO, SO.sub.2, O, S and where one or more hydrogen atoms can be replaced by deuterium, fluorine, chlorine, bromine or iodine, or an aromatic or heteroaromatic ring system having 5 to 24 carbon atoms; n is equal to 0 or 1; r is equal to 0, 1 or 2; m, q are, identically or differently, an integer selected from 1 to 10; p, s are on each occurrence, identically or differently, an integer selected from 0 to 10; with the proviso that, if the group G is a pyrene group, then the compound of formula (1) bears at least one group R, R.sup.0, R.sup.2 or R.sup.3, which stands for a straight-chain alkyl group having 3 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.6.

2. The compound according to claim 1, wherein s is an integer selected from 1 to 10.

3. The compound according to claim 1, selected from compounds of formulae (2) to (5), ##STR00395## where the symbols and indices have the same meaning as in claim 1.

4. The compound according to claim 1, wherein Ar.sup.5 and Ar.sup.6 are selected, identically or differently, from the group consisting of the groups of formulae (Ar5-1) to (Ar5-26), ##STR00396## ##STR00397## ##STR00398## ##STR00399## where the dashed bonds indicate the bonding to the adjacent groups as depicted in formula (1); the groups of formulae (Ar5-1) to (Ar5-26) can be substituted at each free position by a group R.sup.4, which has the same meaning as in claim 1; and E.sup.1 is selected from —B(R.sup.0—), —C(R.sup.0).sub.2—, —C(R.sup.0).sub.2—C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —C(═NR.sup.0)—, —C═(C(R.sup.0)).sub.2—, —O—, —S—, —S(═O)—, —SO.sub.2—, —N(R.sup.0)—, —P(R.sup.0)—, and —P((═O)R.sup.0—, where the substituent R.sup.0 has the same meaning as in claim 1.

5. The compound according to claim 1, wherein Ar.sup.5 and Ar.sup.6 are selected, identically or differently, from the group consisting of the groups of formulae (Ar5-27) to (Ar5-35), ##STR00400## ##STR00401## where the dashed bonds indicate the bonding to the adjacent groups depicted in formula (1); the groups of formulae (Ar5-27) to (Ar5-35) can be substituted at each free position by a group R.sup.4, which has the same meaning as in claim 1; and the substituent E.sup.1 in formulae (Ar5-28) to (Ar5-30) is selected from —B(R.sup.0—), —C(R.sup.0).sub.2—, —C(R.sup.0).sub.2—C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —C(═NR.sup.0)—, —C═(C(R.sup.0)).sub.2—, —O—, —S—, —S(═O)—, —SO.sub.2—, —N(R.sup.0)—, —P(R.sup.0)— and —P((═O)R.sup.0)—.

6. The compound according to claim 1, wherein the group Ar.sup.4 is selected from the groups of formula (Ar4-2) to (Ar4-6), ##STR00402## where the dashed bond indicate the bonding to the structure of formula (1) and where the symbols and indices X, R, R.sup.0, R.sup.4, Ar.sup.6, m, p, q and s have the same meaning as in claim 1 and the symbol E.sup.1 is selected from —B(R.sup.0—), —C(R.sup.0).sub.2—, —C(R.sup.0).sub.2—C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —C(═NR.sup.0)—, —C═(C(R.sup.0)).sub.2—, —O—, —S—, —S(═O)—, —SO.sub.2—, —N(R.sup.0)—, —P(R.sup.0)— and —P((═O)R.sup.0)—.

7. The compound according to claim 1, wherein m and q are on each occurrence, identically or differently, equal to 1, 2 or 3.

8. The compound according to claim 1, wherein the group G is selected from the group consisting of naphthalene, anthracene, phenanthrene, tetracene, chrysene, benzophenanthracene, pyrene, perylene, triphenylene, benzopyrene, fluoranthene, each of which can be substituted by one or more radicals R.sup.2 at any free positions.

9. The compound according to claim 1, wherein n is equal to 1 and the group G is selected from the group consisting of the groups of formulae (G-1) to (G-11), ##STR00403## ##STR00404## where the dashed bonds indicate the bonding to the adjacent groups as depicted in formula (1); and the groups of formulae (G-1) to (G-11) can be substituted at each free position by a group R.sup.2, which has the same meaning as in claim 1.

10. The compound according to claim 9, wherein the group G is selected from the groups of formulae (G-12) to (G-23), ##STR00405## ##STR00406## ##STR00407## where the dashed bonds indicate the bonding to adjacent groups as depicted in formula (1) and where R.sup.2 has the same meaning as in claim 1.

11. The compound according to claim 9, wherein the group G is selected from the groups of formulae (G-24) to (G-39), ##STR00408## ##STR00409## ##STR00410## where the dashed bonds indicate the bonding to the adjacent group as depicted in formula (1) and where R.sup.2 has the same meaning as in claim 1.

12. The compound according to claim 1, wherein R.sup.2 stands on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, a straight-chain alkyl group having 1 to 10 carbon atoms or branched or a cyclic alkyl groups having 3 to 10 carbon atoms, each of which can be substituted by one or more radicals R.sup.5, an aromatic ring systems having 5 to 30 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.5, where two adjacent substituents R.sup.2 can form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more radicals R.sup.5, where R.sup.5 has the same meaning as in claim 1.

13. The compound according to claim 1, wherein Ar.sup.5 is selected from benzene, biphenyl, naphthalene, fluorene, dibenzofuran, dibenzothiophene or carbazole, each of which can be substituted by one or more radicals R.sup.3.

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

15. An electronic device comprising at least one compound according to claim 1, 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, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

16. The electronic device according to claim 15, which is an organic electroluminescent device, wherein the compound according to claim 1 is a fluorescent emitter or a matrix material for fluorescent emitters.

17. The compound of the formulae (2) to (5), ##STR00411## where the following applies to the symbols and indices used: Ar.sup.4 stands for a group of formula (Ar4-1), ##STR00412##  where the dashed bond in formula (Ar4-1) indicates the bonding to the structure of formula (1); G is a condensed aryl group having 10 to 50 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.2; Ar.sup.1 and Ar.sup.3 stand on each occurrence, identically or differently, for Ar.sup.4, or for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.3; Ar.sup.S is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can in each case also be substituted by one or more radicals R.sup.3; Ar.sup.5, Ar.sup.6 stand on each occurrence, identically or differently, for an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.4; X stands for CR.sup.1 or nitrogen; or X stands for carbon, if it is bonded to Ar.sup.5, Ar.sup.6, R.sup.4 or to an adjacent fluorene derivative unit; R, R.sup.0, R.sup.1, R.sup.2, R.sup.3, R.sup.4 stand on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, CHO, C≡N, N(Ar.sup.7).sub.2, C(═O)Ar.sup.7, P(═O)(Ar.sup.7).sub.2, S(═O)Ar.sup.7, S(═O).sub.2Ar.sup.7, NO.sub.2, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 carbon atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.5, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by R.sup.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.5), SO, SO.sub.2, O, S or CONR.sup.5 and where one or more hydrogen atoms can be replaced by deuterium, fluorine, chlorine, bromine, iodine, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.5, or an aryloxy groups having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R.sup.5, where two adjacent substituents R, two adjacent substituents R.sup.0, two adjacent substituents R.sup.1, two adjacent substituents R.sup.2, two adjacent substituents R.sup.3 and/or two adjacent substituents R.sup.4, can form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more radicals R.sup.5; R.sup.5 stands on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, CHO, C≡N, N(Ar.sup.7).sub.2, C(═O)Ar.sup.7, P(═O)(Ar.sup.7).sub.2, S(═O)Ar.sup.7, S(═O).sub.2Ar.sup.7, NO.sub.2, Si(R.sup.6).sub.3, B(OR.sup.6).sub.2, OSO.sub.2R.sup.6, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.6, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by R.sup.6C═CR.sup.6, C≡C, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.6), SO, SO.sub.2, O, S or CONR.sup.6 and where one or more hydrogen atoms can be replaced by deuterium, fluorine, chlorine, bromine, iodine, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.6, or an aryloxy group having 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R.sup.6, where two adjacent substituents R.sup.5 can form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more radicals R.sup.6; Ar.sup.7 is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can in each case also be substituted by one or more radicals R.sup.6; R.sup.6 stands on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C≡N, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 carbon atoms, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by SO, SO.sub.2, O, S and where one or more hydrogen atoms can be replaced by deuterium, fluorine, chlorine, Br or iodine, or an aromatic or heteroaromatic ring system having 5 to 24 carbon atoms; n is equal to 0 or 1; r is equal to 0, 1 or 2; m, q are, identically or differently, an integer selected from 1 to 10; p is on each occurrence, identically or differently, an integer selected from 0 to 10; s is on each occurrence, identically or differently, an integer selected from 1 to 10; with the proviso that, if the group G is a pyrene group, then the compound of formula (1) bears at least one group R, R.sup.0, R.sup.2 or R.sup.3, which stands for a straight-chain alkyl group having 3 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.6.

18. The compound according to claim 17, wherein the group Ar4 is selected from the groups of formula (Ar4-2) to (Ar4-6), ##STR00413## where the dashed bond indicate the bonding to the structure of formula (1) and where the symbol E.sup.1 is selected from —B(R.sup.0—), —C(R.sup.0).sub.2—, —C(R.sup.0).sub.2—C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —C(═NR.sup.0)—, —C═(C(R.sup.0)).sub.2—, —O—, —S—, —S(═O)—, —SO.sub.2—, —N(R.sup.0)—, —P(R.sup.0)— and —P((═O)R.sup.0)—.

19. The compound of the formula (1), ##STR00414## where the following applies to the symbols and indices used: Ar.sup.4 stands for a group of formula (Ar.sup.4-1), ##STR00415##  where the dashed bond in formula (Ar4-1) indicates the bonding to the structure of formula (1); G is selected from the group consisting of the groups of formulae (G-1) to (G-11), ##STR00416## ##STR00417## where the dashed bonds indicate the bonding to the adjacent groups as depicted in formula (1); and the groups of formulae (G-1) to (G-11) can be substituted at each free position by a group R.sup.2; Ar.sup.1, Ar.sup.2 and Ar.sup.3 stand on each occurrence, identically or differently, for Ar.sup.4, or for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.3; Ar.sup.S is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can in each case also be substituted by one or more radicals R.sup.3; Ar.sup.5, Ar.sup.6 stand on each occurrence, identically or differently, for an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.4; X stands for CR.sup.1 or nitrogen; or X stands for carbon, if it is bonded to Ar.sup.5, Ar.sup.6, R.sup.4 or to an adjacent fluorene derivative unit; R, R.sup.0, R.sup.1, R.sup.3, R.sup.4 stand on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, CHO, C≡N, N(Ar.sup.7).sub.2, C(═O)Ar.sup.7, P(═O)(Ar.sup.7).sub.2, S(═O)Ar.sup.7, S(═O).sub.2Ar.sup.7, NO.sub.2, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 carbon atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.5, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by R.sup.5C═CR.sup.5, C≡C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.5), SO, SO.sub.2, O, S or CONR.sup.5 and where one or more hydrogen atoms can be replaced by deuterium, fluorine, chlorine, bromine, iodine, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.5, or an aryloxy groups having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R.sup.5, where two adjacent substituents R, two adjacent substituents R.sup.0, two adjacent substituents R.sup.1, two adjacent substituents R.sup.2, two adjacent substituents R.sup.3 and/or two adjacent substituents R.sup.4, can form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more radicals R.sup.5; R.sup.2 stands on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, a straight-chain alkyl group having 1 to 10 carbon atoms or branched or a cyclic alkyl groups having 3 to 10 carbon atoms, each of which can be substituted by one or more radicals R.sup.5, an aromatic ring systems having 5 to 30 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.5, where two adjacent substituents R.sup.2 can form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more radicals R.sup.5; R.sup.5 stands on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, CHO, C≡N, N(Ar.sup.7).sub.2, C(═O)Ar.sup.7, P(═O)(Ar.sup.7).sub.2, S(═O)Ar.sup.7, S(═O).sub.2Ar.sup.7, NO.sub.2, Si(R.sup.6).sub.3, B(OR.sup.6).sub.2, OSO.sub.2R.sup.6, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.6, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by R.sup.6C═CR.sup.6, C≡C, Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C═O, C═S, C═Se, P(═O)(R.sup.6), SO, SO.sub.2, O, S or CONR.sup.6 and where one or more hydrogen atoms can be replaced by deuterium, fluorine, chlorine, bromine, iodine, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which can in each case be substituted by one or more radicals R.sup.6, or an aryloxy group having 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R.sup.6, where two adjacent substituents R.sup.5 can form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more radicals R.sup.6; Ar.sup.7 is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can in each case also be substituted by one or more radicals R.sup.6; R.sup.6 stands on each occurrence, identically or differently, for hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C≡N, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 carbon atoms, where in each case one or more non-adjacent CH.sub.2 groups can be replaced by SO, SO.sub.2, O, S and where one or more hydrogen atoms can be replaced by deuterium, fluorine, chlorine, bromine or iodine, or an aromatic or heteroaromatic ring system having 5 to 24 carbon atoms; n is equal to 0 or 1; r is equal to 0, 1 or 2; m, q are, identically or differently, an integer selected from 1 to 10; p, s are on each occurrence, identically or differently, an integer selected from 0 to 10; with the proviso that, if the group G is a pyrene group, then the compound of formula (1) bears at least one group R, R.sup.0, R.sup.2 or R.sup.3, which stands for a straight-chain alkyl group having 3 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which can be substituted by one or more radicals R.sup.6.

20. The compound of claim 19, wherein Ar.sup.S is selected from benzene, biphenyl, naphthalene, fluorene, dibenzofuran, dibenzothiophene or carbazole, each of which can be substituted by one or more radicals R.sup.3.

Description

A) SYNTHESES EXAMPLES

(1) Following Building blocks can be used to synthesize compounds according to the invention:

(2) ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235##

(3) Synthesis of Compound BB-001

(4) ##STR00236##

(5) 30 g (97.5 mmol) 2-Bromo-7-Chloro-9,9-dimethyl-9H-fluorene (see JP 2003277305 A), 25.5 g (107.3 mmol) (9,9-dimethylfluoren-2-yl)boronic acid 90 g (390 mmol) potassium phosphate monohydrate, 0.9 g (4 mmol) palladium(II)acetate and 3.6 g (11.7 mmol) tri(o-tolyl)-phosphine are dissolved in 1 l toluene, dioxane, water (1:1:1) and stirred at reflux overnight. After cooling to room temperature 200 mL toluene is added and the organic phase is separated and washed with water (2×200 ml). The combined organic phases are concentrated under reduced pressure. The residue is purified by recrystallization from toluene/heptane.

(6) Yield: 39.1 g (93 mmol; 96%)

(7) The following compounds can be synthesized in an analogous manner:

(8) TABLE-US-00002 Compound Boronates Compound structure BB-002

(9) Compound BB-003

(10) ##STR00239##

(11) 40 g (95 mmol) BB-001, 38.6 g (152 mmol) bis-(pinacolato)-diboron, 4.2 g (5.7 mmol) trans-dichloro(tricyclohexylphosphine)palladium(II) and 28 g (285 mmol) potassium acetate are dissolved in 400 ml dioxane and stirred for 16 h at reflux. The reaction mixture is allowed to cool to room temperature and 400 ml toluene are added. The organic phase is separated, washed with water (2×200 mL) and filtered through Celite. The solution is concentrated to dryness under reduced pressure. The residue is purified by recrystallization from toluene/heptane.

(12) Yield: 36 g (70 mmol; 74%)

(13) The following compound can be synthesized in an analogous manner:

(14) TABLE-US-00003 Starting Compound material Compound structure BB-004 BB-002 0

(15) Compound BB-005

(16) ##STR00241##

(17) 5.5 g (17.8 mmol) 2-Bromo-5-iodo-1,3-dimethylbenzene, 6.5 g (12.7 mmol) BB-003, 366 mg (0.3 mmol) tetrakis(triphenylphosphin)-palladium(0) and 2.7 g (13 mmol) sodium carbonate are dissolved in 200 ml toluene, ethanol and water (2:1:1) and stirred for 16 hours at 90° C. After cooling to room temperature, 100 ml toluene are added, the organic phase is separated and washed with water (2×50 ml). The organic phase is concentrated to dryness under reduced pressure. The residue is purified by recrystallization from toluene/heptane.

(18) Yield: 6.2 g (11 mmol; 86%)

(19) The following compound can be synthesized in an analogous manner:

(20) TABLE-US-00004 Compound Educt A Educt B Product BB-006 BB-002 CAS 844856-42-4 BB-015 BB-004 CAS 23055-77-8 BB-016 BB-002 CAS 106-40-1

(21) Compound BB-007:

(22) The following compound can be synthesized in an analogous manner to BB-005:

(23) TABLE-US-00005 Compound Educt A Educt B Product BB-007 CAS 1679-18-1 BB-004

(24) Compounds BB-008 to BB-009:

(25) Compounds BB-008 to BB-009 can be synthesized in an analogous manner to BB-003:

(26) TABLE-US-00006 Compound Reactant Compound structure BB-008 BB-006 BB-009 BB-007

(27) Compound BB-010:

(28) ##STR00248##

(29) 12.2 g (37.3 mmol) bis-(4-bromo-phenyl)-amine, 55.5 g (78.4 mmol) BB-004, 37.8 g (164.2 mmol) potassiumphosphate monohydrate and 1.2 g (1.5 mmol) XPhos Pd Gen 3 (CAS 1445085-55-1) are added to 600 mL THF/water (2:1) and stirred at 65° C. After 16 h the mixture is cooled to room temperature diluted with toluene and H2O. The organic phase is collected, the aqueous phase extracted further with toluene. The combined organics are washed with brine, collected, dried with Na2SO4, filtered and concentrated. The resulting residue is deposited in 1 L EtOH and stirred vigorously until a free flowing precipitate is formed. The precipitate is collected by filtration, washing with EtOH. The material is taken up in DCM and filtered through SiO.sub.2. The filtrate is concentrated to dryness.

(30) Yield: 44.7 g (33.6 mmol; 90%)

(31) The following compounds BB-011 to BB-012 can be synthesized in analogous manner:

(32) TABLE-US-00007 Educt 1 Educt 2 Compound structure BB-011 BB-003 0 CAS 1383254-17-8 BB-012 BB-003 CAS 27996-13-0 BB-013 BB-008 CAS 16929-17-4 BB-014 BB-009 CAS 16929-17-4 BB-017 BB-016 CAS 106-40-1 BB-018 BB-004 CAS 1863111-68-5

(33) Synthesis of Compounds According to the Invention:

(34) Sample Synthesis of P-001

(35) ##STR00260##

(36) 25.5 g (27.2 mmol) BB-010, 5.0 g (12.95 mmol) BB-500, 1.3 ml (1.3 mmol) tri-tert-butylphosphine (1M in toluene), 3.72 g (22.3 mmol) sodium-tert-butylate and 250.5 mg (1.11 mmol) palladium(II)diacetate are added to 750 ml toluene and stirred at 100° C. After 16 h the reaction mixture is allowed to cool down to room temperature, diluted with toluene and H2O. The organic phase are collected, the aqueous phase extracted further with toluene. The combined organic phases are washed with brine, collected, dried with Na.sub.2SO.sub.4, filtered and concentrated. The resulting residue is dissolved in toluene and filtered through silica and concentrated. The precipitate is further purified by recrystallisation from toluene/heptane and tempering (250° C., <10.sup.−4 mbar).

(37) Yield: 10.1 g (4.79 mmol; 37%)

(38) The following compounds can be synthesized in analogous manner:

(39) TABLE-US-00008 Educt A Educt B Compound structure Comp. BB-500 BB-011 P-001 BB-500 BB-012 P-002 BB-500 BB-013 P-003 BB-500 BB-014 P-004 BB-501 BB-011 P-005 BB-501 BB-012 P-006 BB-501 BB-013 P-007 BB-501 BB-014 P-008 BB-502 BB-011 P-009 BB-502 BB-012 0 P-010 BB-502 BB-013 P-011 BB-502 BB-014 P-012 BB-503 BB-011 P-013 BB-503 BB-012 P-014 BB-503 BB-013 P-015 BB-503 BB-014 P-016 BB-504 BB-011 P-017 BB-504 BB-012 P-018 BB-504 BB-013 P-019 BB-504 BB-014 0 P-020 BB-505 BB-011 P-021 BB-505 BB-012 P-022 BB-505 BB-013 P-023 BB-505 BB-014 P-024 BB-506 BB-011 P-025 BB-506 BB-012 P-026 BB-506 BB-013 P-027 BB-506 BB-014 P-028 BB-507 BB-013 P-031 BB-508 BB-013 0 P-035 BB-509 BB-013 P-039 BB-510 BB-013 P-043 BB-511 BB-013 P-047 BB-511 BB-014 P-048 BB-512 BB-013 P-051 BB-513 BB-013 P-055 BB-514 BB-013 P-059 BB-515 BB-013 P-063 BB-516 BB-013 P-067 BB-517 BB-013 00 P-071 BB-518 BB-011 01 P-073 BB-518 BB-012 02 P-074 BB-518 BB-013 03 P-075 BB-518 BB-014 04 P-076 BB-519 BB-011 05 P-077 BB-519 BB-012 06 P-078 BB-519 BB-013 07 P-079 BB-519 BB-014 08 P-080 BB-520 BB-011 09 P-081 BB-520 BB-012 0 P-082 BB-520 BB-013 P-083 BB-520 BB-014 P-084 BB-521 BB-011 P-085 BB-521 BB-012 P-086 BB-521 BB-013 P-087 BB-521 BB-014 P-088 BB-522 BB-011 P-089 BB-522 BB-012 P-090 BB-522 BB-013 P-091 BB-522 BB-014 0 P-092 BB-523 BB-011 P-093 BB-523 BB-012 P-094 BB-523 BB-013 P-095 BB-523 BB-014 P-096 BB-524 BB-011 P-097 BB-524 BB-012 P-098 BB-524 BB-013 P-099 BB-524 BB-014 P-100 BB-525 BB-011 P-101 BB-525 BB-012 0 P-102 BB-525 BB-013 P-103 BB-525 BB-014 P-104 BB-526 BB-011 P-105 BB-526 BB-012 P-106 BB-526 BB-013 P-107 BB-526 BB-014 P-108 BB-527 BB-011 P-109 BB-527 BB-012 P-110 BB-527 BB-013 P-111 BB-527 BB-014 0 P-112 BB-528 BB-011 P-113 BB-528 BB-012 P-114 BB-528 BB-013 P-115 BB-528 BB-014 P-116 BB-550 BB-018 P-155

(40) Synthesis of P-117

(41) ##STR00346##

(42) 5.0 g (12.2 mmol) BB-529, 15.8 g (26.8 mmol) BB-002, 1.35 ml (1.35 mmol) tri-tert-butylphosphine (1M in toluene), 7.73 g (80.4 mmol) sodium-tert-butylate and 150.5 mg (0.67 mmol) palladium(II)-diacetate are added to 450 ml toluene and stirred at 100° C. After 16 h the reaction mixture is allowed to cool down to room temperature, diluted with toluene and H2O. The organic phase is collected, the aqueous phase extracted further with toluene. The combined organic phases are washed with brine, collected, dried with Na2SO4, filtered and concentrated. The resulting residue is dissolved in toluene and filtered through silica and concentrated. The precipitate is further purified by recrystallization from toluene/heptane and tempering (250° C., <10.sup.−4 mbar).

(43) Yield: 4.2 g (3.5 mmol; 29%)

(44) The following compounds can be synthesized in analogous manner:

(45) TABLE-US-00009 Educt A Educt B Compound structure Comp. BB-529 BB-002 P-117 BB-530 BB-002 P-118 BB-531 BB-002 P-119 BB-532 BB-002 0 P-120 BB-533 BB-002 P-121 BB-534 BB-002 P-122 BB-535 BB-002 P-123 BB-536 BB-002 P-124 BB-537 BB-002 P-125 BB-529 BB-005 P-126 BB-530 BB-005 P-127 BB-531 BB-005 P-128 BB-533 BB-005 P-130 BB-534 BB-005 0 P-131 BB-535 BB-005 P-132 BB-536 BB-005 P-133 BB-537 BB-005 P-134 BB-529 BB-006 P-135 BB-530 BB-006 P-136 BB-531 BB-006 P-137 BB-532 BB-006 P-138 BB-533 BB-006 P-139 BB-534 BB-006 P-140 BB-535 BB-006 0 P-141 BB-536 BB-006 P-142 BB-537 BB-006 P-143 BB-529 BB-007 P-144 BB-530 BB-007 P-145 BB-531 BB-007 P-146 BB-533 BB-007 P-148 BB-534 BB-007 P-149 BB-535 BB-007 P-150 BB-536 BB-007 P-151 BB-537 BB-007 0 P-152 BB-539 BB-015 P-153 BB-540 BB-017 P-154

B) FABRICATION OF OLEDS

(46) The production of solution-based OLEDs has already been described many times in the literature, for example in WO 2004/037887 and WO 2010/097155. The process is adapted to the circumstances described below (layer-thickness variation, materials).

(47) The inventive material combinations are used in the following layer sequence: substrate, ITO (50 nm), Buffer (20 nm), hole transport layer (20 nm), emission layer (EML) (40 nm), electron-transport layer (ETL) (20 nm), electron injection layer (EIL) (3 nm), cathode (Al) (100 nm).

(48) Glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm serve as substrate. These are coated with the buffer (PEDOT) Clevios P VP AI 4083 (Heraeus Clevios GmbH, Leverkusen). The spin coating of the buffer is carried out from water in air. The layer is subsequently dried by heating at 180° C. for 10 minutes. The hole transport layers and the emission layers are applied to the glass plates coated in this way.

(49) The hole-transport layer is the polymer of the structure shown in Table 1, which was synthesised based on monomers in accordance with CAS 374934-77-7, WO2013156130 and WO2010/097155. The polymer is dissolved in toluene, so that the solution typically has a solid content of approx. 5 g/l if, as here, the layer thickness of 20 nm which is typical for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 220° C. for 30 min.

(50) The emission layer is composed of the matrix material (host material) H1 and the emitting dopant (emitter) D1. Both material are present in the emission layer in a proportion of 97% by weight H1 and 3% by weight D1. The mixture for the emission layer is dissolved in toluene. The solids content of such solutions is about 14 mg/ml if, as here, the layer thickness of 40 nm which is typical for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, and dried by heating at 120° C. for 10 minutes. The materials used in the present case are shown in table 1.

(51) TABLE-US-00010 TABLE 1 Structural formulae of the materials used for the OLEDs   HTL   H1   SdT1   SdT2   SdT3   D1 P-154   D2 P-155 0   D3 P-153

(52) The materials for the electron-transport layer and the electron injection layer are likewise applied by thermal vapour deposition in a vacuum chamber and are shown in table 2. The electron-transport layer consists of the material ETM and the electron injection layer consists of LiQ. The cathode is formed by the thermal evaporation of an aluminium layer with a thickness of 100 nm.

(53) TABLE-US-00011 TABLE 2 ETL and EIL materials used ETM LiQ

(54) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra are recorded, the current efficiency (measured in cd/A) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density assuming Lambert emission characteristics are calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines). The electroluminescence spectra are recorded at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated from this data. The term EQE1000 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2.

(55) The properties of the various OLEDs are summarised in table 3. Example V01, V02 and V03 are the comparative examples for the state-of-the-art, whereas E1, E2 and E3 show properties of OLEDs containing materials of the present invention.

(56) TABLE-US-00012 TABLE 3 Device data of solution processed OLEDs EML EML Example host dopant EQE1000 [%] CIE x/y V01 H1 SdT1 3.8 0.14/0.10 V02 H1 SdT2 3.7 0.14/0.14 V03 H1 SdT3 3.0 0.17/0.15 E01 H1 D1 4.7 0.15/0.11 E02 H1 D2 4.7 0.14/0.15 E03 H1 D3 4.4 0.17/0.15

(57) Table 3 shows, that use of materials (D1, D2 and D3) according to the present invention give rise to improvements over the prior art (SdT, SdT2 and SdT3) when used as fluorescent blue emitters, in particular with respect to efficiency.