Heterocyclic compounds for use in electronic devices

Abstract

The invention relates to heterocyclic compounds, particularly for use in electronic devices. The invention further relates to a method for producing the compounds according to the invention, and to electronic devices comprising same.

Claims

1. A compound comprising at least one structure of the formula (I) and/or (II): ##STR00395## where the symbols used are as follows: X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, X.sup.9, X.sup.10, X.sup.11, X.sup.12, X.sup.13, X.sup.14, X.sup.15, X.sup.16, X.sup.17, X.sup.18, X.sup.19, X.sup.20, X.sup.21, X.sup.22, X.sup.23, X.sup.24 is N or CR.sup.1, Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; Ar.sup.10 is the same or different at each instance and is of the formula (H-1) ##STR00396## Ar.sup.2 is an aromatic or heteroaromatic ring system which has 5 to 14 aromatic or heteroaromatic ring atoms, which may be substituted by one or more R.sup.21 radicals; p is 0 or 1, Ar.sup.3 and Ar.sup.4 are the same or different at each instance and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more R.sup.21 radicals; R.sup.1 is the same or different at each instance and is 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 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 may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 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, NR.sup.2, P(═O)(R.sup.2), —C(═O)O—, —C(═O)NR.sup.2—, —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; or a combination of these systems; at the same time, two or more R.sup.1 radicals together may form a ring system; R.sup.2 is the same or different at each instance and is 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, 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 may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, 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, NR.sup.3, P(═O)(R.sup.3), —C(═O)O—, —C(═O)NR.sup.3—, —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more R.sup.2 substituents together may also form a ring system; R.sup.21 is the same or different at each instance and is 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, 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 may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, 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, P(═O)(R.sup.3), —C(═O)O—, —C(═O)NR.sup.3—, —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals and with the proviso that the aromatic or heteroaromatic ring system does not contain triarylamine; R.sup.3 is the same or different at each instance and is H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, in which hydrogen atoms may also be replaced by F; at the same time, two or more R.sup.3 substituents together may also form a ring system.

2. A compound as claimed in claim 1, comprising at least one structure of the formula (III) and/or (IV) ##STR00397## where the symbols R.sup.1, Ar.sup.10 and Ar used have the definition given in claim 1 and m at each instance is in each case independently 0, 1, 2, 3 or 4, and n at each instance is in each case independently 0, 1, 2 or 3.

3. A compound as claimed in claim 1, comprising at least one structure of the formula (V) and/or (VI) ##STR00398## where R.sup.a is 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 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 may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 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, NR.sup.2, P(═O)(R.sup.2), —C(═O)O—, —C(═O)NR.sup.2—, —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; or a combination of these systems; at the same time, the R.sup.a radical may form a ring system together with an R.sup.1 radical or with the ring to which it is bonded; the symbols X.sup.1, X.sup.2, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, X.sup.9, X.sup.10, X.sup.11, X.sup.12, X.sup.13, X.sup.14, X.sup.15, X.sup.16, X.sup.17, X.sup.18, X.sup.19, X.sup.20, X.sup.21, X.sup.22, X.sup.23, X.sup.24, R.sup.1, R.sup.2, Ar.sup.10 and Ar used to have the definition given in claim 1.

4. A compound as claimed in claim 3, comprising at least one structure of the formula (V-3) and/or (VI-3) ##STR00399## where the symbols R.sup.1, Ar.sup.10 and Ar have the definition given in claim 1, and the symbol R.sup.a has the definition given in claim 3, and R.sup.b, R.sup.c and R.sup.d are as defined for R.sup.a, and m at each instance is in each case independently 0, 1, 2, 3 or 4, and n at each instance is in each case independently 0, 1, 2 or 3.

5. A compound as claimed in claim 1, characterized in that the R.sup.1 radical comprises a group, selected from the group consisting of the formulae (H-4) to (H-26) ##STR00400## ##STR00401## ##STR00402## ##STR00403## where Y.sup.1 represents O, S, C(R.sup.2).sub.2 or NAr.sup.1, the dotted bond marks the attachment position, e is 0, 1 or 2, j is 0, 1, 2 or 3, h is 0, 1, 2, 3 or 4, p is 0 or 1, Ar.sup.1 represents an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, an aryloxy group which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aralkyl group which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, where it is optionally possible for two or more R.sup.2 substituents to form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.3 radicals and Ar.sup.2 are each independently an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals; and R.sup.2 has the definition given in claim 1 and R.sup.3 is the same or different at each instance and is H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, in which hydrogen atoms may also be replaced by F; at the same time, two or more R.sup.3 substituents together may also form a ring system.

6. A compound as claimed in claim 1, characterized in that, in the structure of formula (I), (II), (III), (IV), (V), (VI), (V-3), (VI-3) and/or (H4) to (H-26), ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## ##STR00409## at least one R.sup.1 radical comprises a group selected from the formulae (R.sup.1-1) to (R.sup.1-95) ##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## ##STR00422## ##STR00423## where the symbols used are as follows: Y is O, S or NR.sup.2; i at each instance is independently 0, 1 or 2; j independently at each instance is 0, 1, 2 or 3; h independently at each instance is 0, 1, 2, 3 or 4; g independently at each instance is 0, 1, 2, 3, 4 or 5; the dotted bond marks the position of attachment; and R.sup.2 has the definition given in claim 1.

7. A compound as claimed in claim 1, characterized in that the R.sup.1 radical comprises a group, selected from the group consisting of the formulae (H-1′) to (H-3′) ##STR00424## where the dotted bond marks the attachment position and Ar.sup.21, Ar.sup.31, Ar.sup.41 are each independently an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals; p is 0 or 1 and Z is a bond, C(R.sup.2).sub.2, C═O, N—Ar.sup.1, O or S, where the R.sup.2 radical has the definition given in claim 1 and Ar.sup.1 represents an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, an aryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl group which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals; where it is optionally possible for two or more, R.sup.2 substituents to form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.3 radicals.

8. A compound as claimed in claim 1, characterized in that, in the structure of the formula (I) or (II), not more than 2 of the symbols X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, X.sup.9, X.sup.10, X.sup.11, X.sup.12, X.sup.13, X.sup.14, X.sup.15, X.sup.16 are not CH or CD or, in the structures of the formula (II), not more than 4 of the symbols X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5, X.sup.6, X.sup.7, X.sup.8, X.sup.9, X.sup.10, X.sup.11, X.sup.12, X.sup.13, X.sup.14, X.sup.15, X.sup.16 X.sup.17, X.sup.18, X.sup.19, X.sup.20, X.sup.21, X.sup.22, X.sup.23, X.sup.24 are not CH or CD.

9. A compound as claimed in claim 1, characterized in that the R.sup.1 radicals that are not H or D.

10. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

11. A composition comprising at least one compound as claimed in 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.

12. A formulation comprising at least one compound as claimed in claim 1 and at least one solvent.

13. An electronic device comprising at least one compound as claimed in claim 1, 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.

14. A compound as claimed in claim 1, characterized in that the Ar radical is selected from the structures of the formula (H-1) and the Ar.sup.3 and Ar.sup.4 radicals are selected from groups of the formulae (R.sup.1-1) to (R.sup.1-95), ##STR00425## ##STR00426## ##STR00427## ##STR00428## ##STR00429## ##STR00430## ##STR00431## ##STR00432## ##STR00433## ##STR00434## ##STR00435## ##STR00436## ##STR00437## ##STR00438## ##STR00439## where the symbols used are as follows: Y is O, S or NR.sup.2; i at each instance is independently 0, 1 or 2; j independently at each instance is 0, 1, 2 or 3; h independently at each instance is 0, 1, 2, 3 or 4; g independently at each instance is 0, 1, 2, 3, 4 or 5; the dotted bond marks the position of attachment; and R.sup.2 has the definition given in claim 1 and the Ar.sup.2 radical is selected from the groups of the formulae (L.sup.1-1) to (L.sup.1-108) ##STR00440## ##STR00441## ##STR00442## ##STR00443## ##STR00444## ##STR00445## ##STR00446## ##STR00447## ##STR00448## ##STR00449## ##STR00450## ##STR00451## ##STR00452## ##STR00453## ##STR00454## ##STR00455## ##STR00456## where the dotted bonds in each case mark the attachment positions, the index k is 0 or 1, the index l is 0, 1 or 2, the index j at each instance is independently 0, 1, 2 or 3; the index h at each instance is independently 0, 1, 2, 3 or 4, the index g is 0, 1, 2, 3, 4 or 5; the symbol Y is O, S or NR.sup.2; and the symbol R.sup.2 has the definition given in claim 1.

15. A compound as claimed in claim 7, characterized in that, the Ar.sup.2 group is a group selected from the formulae (L.sup.1-1) to (L.sup.1-108) ##STR00457## ##STR00458## ##STR00459## ##STR00460## ##STR00461## ##STR00462## ##STR00463## ##STR00464## ##STR00465## ##STR00466## ##STR00467## ##STR00468## ##STR00469## ##STR00470## ##STR00471## where the dotted bonds in each case mark the attachment positions, the index k is 0 or 1, the index l is 0, 1 or 2, the index j at each instance is independently 0, 1, 2 or 3; the index h at each instance is independently 0, 1, 2, 3 or 4, the index g is 0, 1, 2, 3, 4 or 5; the symbol Y is O, S or NR.sup.2; and the symbol R.sup.2 has the definition given in claim 1.

16. A compound as claimed in claim 1, characterized in that Z is a bond, C(R.sup.2).sub.2, C═O, N—Ar.sup.1, O or S, where the R.sup.2 radical has the definition given in claim 1 and Ar.sup.1 represents an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, an aryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl group which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals; where it is optionally possible for two or more, adjacent R.sup.2 substituents to form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.3 radicals.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The reactants can be sourced from ALDRICH. The numbers for the reactants known from the literature, some of which are stated in square brackets, are the corresponding CAS numbers.

Synthesis Examples

(2) Stage 1:

(3) ##STR00297##
Variant A:

(4) 18.0 g (37.6 mmol, 1.0 eq) of 3-bromo-N-(3-bromo[1,1′-biphenyl]-4-yl)-[1,1-biphenyl]-4-amine [1388152-32-6] 1a, together with 15.3 g (37.6 mmol, 1.0 eq) of 2,2′-[1,1′-biphenyl]-2,2′-diylbis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane [398128-09-1] 2a, are dissolved in 200 ml each of toluene and 1,4-dioxane, and 100 ml of water are added. The mixture is degassed with argon for 30 minutes. Subsequently, 12.0 g (106 mmol, 3.0 eq) of sodium carbonate and 2.17 g (1.88 mmol, 0.05 eq) of tetrakis(triphenylphosphine) are added and the mixture is stirred at 100° C. for two days. After the reaction has ended, the aqueous phase is removed and extracted twice with toluene, and the combined organic phases are washed once again with water. This is followed by drying over sodium sulfate and removal of the solvents on a rotary evaporator. The residue is recrystallized from toluene/heptane. 7.27 g (15.4 mmol, 41%) of the desired product 3a are obtained.

(5) Variant B:

(6) 0.02 eq of palladium(II) acetate, 0.05 eq of tri-o-tolylphosphine, 2.25 eq of potassium phosphate; in toluene/dioxane/water 2:2:1 as solvent

(7) Variant C:

(8) 0.03 eq of palladium(II) acetate, 0.05 eq of tri-t-butylphosphine, 3.0 eq of potassium fluoride anhydr.; in THF as solvent

(9) The following are prepared analogously:

(10) TABLE-US-00008 Entry Reactant 1 Reactant 2 Product 3 Yield Variant 3b 00 34% C 3c 01 02 03 55% B 3d 04 05 06 28% C
Stage 2:

(11) ##STR00307##
Variant A:

(12) 10.0 g (21.2 mmol, 1.0 eq) of the prepared compound 3a together with 4.00 g (25.4 mmol, 1.2 eq) of bromobenzene [108-86-1] 4a are dissolved in 200 ml of toluene and degassed with argon for 30 minutes. Subsequently, 4.07 g (42.4 mmol, 2.0 eq) of sodium t-butoxide, 238 mg (1.06 mmol, 0.05 eq) of palladium(II) acetate and 2.1 ml (2.12 mmol, 0.10 eq) of tri-t-butylphosphine (1.0M in toluene) are added and the mixture is stirred under reflux overnight. After the reaction has ended, 200 ml of water are added to the mixture, and the organic phase is removed and extracted twice with water. The organic phase is dried over sodium sulfate and concentrated to about 80 ml on a rotary evaporator. The precipitated solids are filtered off with suction and purified by means of hot extraction in toluene. The product is recrystallized three times with toluene/heptane and then sublimed. 6.59 g (12.0 mmol, 57%) of the desired target compound 5a are obtained with an HPLC purity of >99.9%.

(13) Variant B:

(14) 0.05 eq of tris(dibenzylideneacetone)dipalladium(0), 0.10 eq of dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine/S-Phos, 2.0 eq sodium t-butoxide; in toluene as solvent

(15) Variant C:

(16) 0.05 eq of 1,1′-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with dichloromethane, 2.0 eq of sodium t-butoxide; in toluene as solvent

(17) The following are prepared analogously:

(18) TABLE-US-00009 Yield Entry Reactant 3 Reactant 4 Product 5 [%] Variant 5b 08 09 0 31 A 5c 56 C 5d 45 A 5e 41 B 5f 0 66 B 5g 38 B 5h 46 B 5i 0 71 A 5j 54 B 5k 33 B 5l 0 41 A 5m 21 B 5n 52 C 5o 39 A 5p 0 11 C 5q 53 B 5r 31 B 5s 0 13 B
Stage 3:

(19) ##STR00362##
Variant A:

(20) A solution of 8.0 g (17 mmol, 1.0 eq) of 3a in 75 ml of dried DMF is slowly added dropwise to a suspension of 820 mg (20.4 mmol, 1.2 eq) of sodium hydride (60% suspension in mineral oil) in 50 ml of dried DMF and stirred for two hours. Subsequently, 7.9 g (20 mmol, 1.2 eq) of 2-(3-bromophenyl)-4,6-diphenyl-[1,3,5]triazine 6a in 50 ml of dried THF are added dropwise and the mixture is stirred at room temperature overnight. After the reaction has ended, the mixture is added to 300 ml of a 1:1 water/ice mixture and the resultant solids are filtered off with suction. The crude product is purified by means of hot extraction from toluene and recrystallization three times from heptane/toluene and sublimed twice. 8.2 g (10.5 mmol, 62%) of the desired product 7a are obtained with an HPLC purity of >99%.

(21) Variant B:

(22) 5.0 eq of cesium carbonate in dimethylacetamide

(23) The following are prepared analogously:

(24) TABLE-US-00010 Yield Entry Reactant 3 Reactant 6 Product 7 [%] Variant 7b 73 A 7c 65 A 7d 0 69 A 7e 44 B 7f 52 B 7g 0 38 A
Production of the OLEDs

(25) OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

(26) In the examples which follow, the results for various OLEDs are presented. Glass plaques with structured ITO (50 nm, indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate/hole transport layer 1 (HTL1) consisting of HTM doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 2 (HTL2)/optional electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm.

(27) First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapor 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 M3:M2:Ir(L1).sub.3 (55%:35%:10%) mean here that the material M3 is present in the layer in a proportion by volume of 55%, M2 in a proportion of 35% and Ir(L1).sub.3 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 1. The materials used for production of the OLEDs are shown in Table 3.

(28) The OLEDs are characterized in a standard manner. The lifetime is defined as the time after which the luminance has fallen from a particular starting luminance to a certain proportion. The figure LT50 means that the lifetime specified is the time at which the luminance has dropped to 50% of the starting luminance, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.2. According to the emission color, different starting brightnesses are chosen. The values for the lifetime can be converted to a figure for other starting luminances with the aid of conversion formulae known to those skilled in the art. In this context, the lifetime for a starting luminance of 1000 cd/m.sup.2 is a standard figure.

(29) The compounds of the invention can be used inter alia as hole conductor (HTL) and as hole-conducting material (h-TMM) in the emission layer in OLEDs (see table 1). The results for the OLEDs are collated in Table 2.

(30) TABLE-US-00011 TABLE 1 Structure of the OLEDs HTL2 EBL EML HBL ETL thick- thick- thick- thick- thick- Ex. ness ness ness ness ness Red OLEDs D-R1 5b — M5:M6:Ir-R1 — ETM1:ETM2 280 nm (65%:30%:5%) (50%:50%) 35 nm 40 nm D-R2 HTM — M5:5c:Ir-R1 — ETM1:ETM2 280 nm (60%:35%:5%) (50%:50%) 35 nm 40 nm D-R3 5b — M5:5c:Ir-R1 — ETM1:ETM2 280 nm (60%:35%:5%) (50%:50%) 35 nm 40 nm D-R4 5l — 7d:Ir-R1 — ETM1:ETM2 280 nm (60%:35%:5%) (50%:50%) 35 nm 40 nm Yellow OLEDs D-Y1 5b — M5:M6:Ir-Y1 — ETM1:ETM2 250 nm (62%:30%:8%) (50%:50%) 30 nm 45 nm D-Y2 5c — M5:5c:Ir-Y1 — ETM1:ETM2 250 nm (60%:30%:10%) (50%:50%) 30 nm 45 nm Green OLEDs D-G1 HTM 5c M5:5c:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-G2 5c 5c M5:5c:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-G3 HTM 5a M5:M6:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (45%:40%:15%) 10 nm (50%:50%) 30 nm 35 nm D-G4 HTM 5b M5:M6:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (45%:40%:15%) 10 nm (50%:50%) 30 nm 35 nm D-G5 HTM 5c M5:5e:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (55%:30%:15%) 10 nm (50%:50%) 30 nm 35 nm D-G6 HTM 5g M5:5f:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (65%:20%:15%) 10 nm (50%:50%) 30 nm 35 nm D-G7 HTM 5g M5:5k:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (45%:40%:15%) 10 nm (50%:50%) 30 nm 35 nm D-G8 5i 5c M5:M6:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (55%:30%:15%) 10 nm (50%:50%) 30 nm 35 nm D-G9 HTM 5c M5:5q:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (55%:30%:15%) 10 nm (50%:50%) 30 nm 35 nm D-G10 HTM 5c 7f:Ir-G1 HBM2 ETM1:ETM2 220 nm 10 nm (80%:20%) 10 nm (50%:50%) 30 nm 35 nm Blue OLEDs D-B1 5b EBM M1:M4:Ir-B1 HBM1 ETM1:ETM2 190 nm 10 nm (60%:35%:5%) 10 nm (50%:50%) 25 nm 15 nm D-B2 5c EBM M2:M4:Ir-B1 HBM1 ETM1:ETM2 190 nm 10 nm (60%:35%:5%) 10 nm (50%:50%) 25 nm 15 nm D-B3 5m EBM M2:M4:Ir-B1 HBM1 ETM1:ETM2 190 nm 10 nm (60%:35%:5%) 10 nm (50%:50%) 25 nm 15 nm D-B4 5l EBM M2:M4:Ir-B1 HBM1 ETM1:ETM2 190 nm 10 nm (60%:30%:10%) 10 nm (50%:50%) 25 nm 15 nm

(31) TABLE-US-00012 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 LT80 (h) 1000 cd/m.sup.2 Red OLEDs D-R1 15.3 3.0 0.67/0.33 15000 D-R2 16.2 3.1 0.67/0.33 16000 D-R3 15.9 3.0 0.67/0.33 14500 D-R4 15.9 2.9 0.67/0.33 18000 Yellow OLEDs D-Y1 22.7 3.1 0.44/0.55 73000 D-Y2 23.1 3.2 0.48/0.51 62000 Green OLEDs D-G1 20.6 3.3 0.32/0.64 33000 D-G2 19.0 3.2 0.33/0.63 35000 D-G3 19.5 3.2 0.32/0.64 41000 D-G4 19.8 3.1 0.32/0.64 38000 D-G5 20.2 3.3 0.33/0.63 35000 D-G6 19.2 3.2 0.33/0.63 26000 D-G7 19.6 3.2 0.33/0.63 36000 D-G8 19.4 3.3 0.32/0.64 38000 D-G9 20.0 3.2 0.32/0.64 40000 D-G10 19.8 3.1 0.32/0.64 32000 Blue OLEDs LT50 (h) 1000 cd/m.sup.2 D-B1 22.3 4.4 0.16/0.33 900 D-B2 17.8 4.5 0.15/0.34 1100 D-B3 18.8 4.8 0.15/0.33 1000 D-B4 19.4 4.4 0.15/0.33 1100

(32) TABLE-US-00013 TABLE 3 Structural formulae of the materials used 0