Organic electroluminescent device

Abstract

The present invention relates to the use of aromatic boronic acid or borinic acid derivatives in organic electronic devices, in particular electroluminescent devices.

Claims

1. A compound of formulae (9), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), or (26) ##STR00102## ##STR00103## ##STR00104## wherein said compounds of formulae (9), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), or (26) are optionally substituted by R.sup.1, wherein B is a boron atom; X is, identically or differently on each occurrence, OR.sup.2, SR.sup.2, N(R.sup.2).sub.2, NHR.sup.2, or OBAr.sub.2; Y is, identically or differently on each occurrence, Ar or X; R.sup.1 is, identically or differently on each occurrence, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy, or thioalkoxy chain having up to 40 C atoms optionally substituted by R.sup.3, or a branched or cyclic alkyl, alkoxy, or thioalkoxy chain having 3 to 40 C atoms, optionally substituted by R.sup.3, wherein one or more non-adjacent C atoms of said straight-chain, branched, or cyclic alkyl, alkoxy, or thioalkoxy chain is optionally replaced by NR.sup.3, O, S, CO, OCOO, COO, CR.sup.3?CR.sup.3, or C?Cand wherein one or more H atoms of said straight-chain, branched, or cyclic alkyl, alkoxy, or thioalkoxy chain is optionally replaced by F, Cl, Br, I, CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms optionally substituted by one or more R.sup.3, or a combination of two, three or four of these systems; and wherein two or more R.sup.1 optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; R.sup.3 is, identically or differently on each occurrence, H or an aliphatic or aromatic hydrocarbon radical having up to 20 C atoms. Ar.sup.1 is, identically or differently on each occurrence, an aryl or heteroaryl group having 5 to 40 aromatic ring atoms, which may be substituted by R.sup.1; G is, identically or differently on each occurrence, CH, CR.sup.1, CBXY, or N; J is, identically or differently on each occurrence, CH, CR.sup.1, or CBXY; v is, identically or differently on each occurrence, 0 or 1; R.sup.2 is, identically or differently on each occurrence, a straight-chain alkyl chain having up to 40 C atoms optionally substituted by R.sup.3 or a branched or cyclic alkyl chain having 3 to 40 C atoms optionally substituted by R.sup.3; wherein one or more non-adjacent C atoms is optionally replaced by NR.sup.3, O, S, CO, OCOO, COO, CR.sup.3?CR.sup.3, or C?C, with the proviso that a heteroatom is not bonded directly to the oxygen or sulfur or nitrogen of the group X or Y; and wherein one or more H atoms is optionally replaced by F, Cl, Br, I, CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, or a combination of two, three or four of these systems; and wherein two or more radicals R.sup.2 optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; with the proviso when X is OR.sup.2 and Y is OR.sup.2 in formulae (24) and (25), the two R.sup.2 define an aromatic ring system, and with the proviso that the following compounds are excluded: ##STR00105## ##STR00106##

2. A compound of formulae (27), (27a), or (28) ##STR00107## wherein B is a boron atom; X is, identically or differently on each occurrence, OR.sup.2, SR.sup.2, N(R.sup.2).sub.2, NHR.sup.2, or OBAr.sub.2; Y is, identically or differently on each occurrence, Ar or X; Ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms optionally substituted by one or more R.sup.1; Ar.sup.1 is, identically or differently on each occurrence, an aryl or heteroaryl group having 5 to 40 aromatic ring atoms, which may be substituted by R.sup.1; R.sup.1 is, identically or differently on each occurrence, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy, or thioalkoxy chain having up to 40 C atoms optionally substituted by R.sup.3, or a branched or cyclic alkyl, alkoxy, or thioalkoxy chain having 3 to 40 C atoms, optionally substituted by R.sup.3, wherein one or more non-adjacent C atoms of said straight-chain, branched, or cyclic alkyl, alkoxy, or thioalkoxy chain is optionally replaced by NR.sup.3, O, S, CO, OCOO,COO, CR.sup.3?CR.sup.3, or C?Cand wherein one or more H atoms of said straight-chain, branched, or cyclic alkyl, alkoxy, or thioalkoxy chain is optionally replaced by F, Cl, Br, I, CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms optionally substituted by one or more R.sup.3, or a combination of two, three or four of these systems; and wherein two or more R.sup.1 optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; R.sup.3 is, identically or differently on each occurrence, H or an aliphatic or aromatic hydrocarbon radical having up to 20 C atoms. v is, identically or differently on each occurrence, 0 or 1; Z is, identically or differently on each occurrence, O, S, NR.sup.2, or NH; L is, identically or differently on each occurrence, an organic group having 4 to 60 C atoms, to which at least four groups Z are bonded in such a way that they are able, with the boron atom, to form a cyclic system; R.sup.2 is, identically or differently on each occurrence, a straight-chain alkyl chain having up to 40 C atoms optionally substituted by R.sup.3 or a branched or cyclic alkyl chain having 3 to 40 C atoms optionally substituted by R.sup.3; wherein one or more non-adjacent C atoms is optionally replaced by NR.sup.3, O, S, CO, OCOO, COO, CR.sup.3?CR.sup.3, or C?Cwith the proviso that a heteroatom is not bonded directly to the oxygen or sulfur or nitrogen of the group X or Y; and wherein one or more H atoms is optionally replaced by F, Cl, Br, I, CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, or a combination of two, three or four of these systems; and wherein two or more radicals R.sup.2 optionally define a mono- or polycyclic, aliphatic, or aromatic ring system; Ar.sup.2 is, identically or differently on each occurence, a fused aryl or heteroaryl group having 9 to 20 C atoms; Ar.sup.3 is, identically or differently on each occurence, a flourene or spirobiflourene group optionally substituted by R.sup.1; Q is, identically or differently on each occurrence, a divalent unit selected from Ar, O, S, SO, SO.sub.2, Se, SeO, SeO.sub.2, Te, TeO, TeO.sub.2, NAr, PAr, P(?O)Ar, AsAr, As(?O)Ar, SbAr, Sb(?O)Ar, C(R.sup.1).sub.2, C?O, Si(R.sup.1).sub.2, and OBArO; p is, identically or differently on each occurrence, 1, 2, 3, 4, 5, or 6; is 0 or 1; t is 1, 2, 3, 4, or 5; w is, identically or differently on each occurrence, 1, 2, 3, 4, 5, or 6; with the proviso that Ar.sup.2 in formula (27) is not naphthyl on each occurrence if all p equal 1 and at the same time s equals 0 and t equals 1, and with the proviso that boronic acid esters of formula (28) formed with pinacol, 1,2-ethanediol, 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, and isopropanol are excluded.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The absorption and photoluminescence spectrum of anthracene-9,10-bis(boronic acid glycol ester) is shown in FIG. 1.

EXAMPLES

(2) The following syntheses are carried out under a protective-gas atmosphere, unless indicated otherwise. The starting materials (9-bromoanthracene, 4-methylnaphth-1-ylboronic acid, 9,10-dibromoanthracene, ethylene glycol, pinacol, hexafluoro-2,3-bis(trifluoromethyl)butane-2,3-diol, pinacolborane, 1,4-dibromonaphthalene, p-xylene diethyl phosphonate, N,N,N,N-tetraphenylbenzidine, 4-bromobenzoyl chloride, DPEPhos, inorganics, solvents) can be obtained from ALDRICH, Lancaster, Sensient, Strem or ABCR. Dibromopyrene (isomer mixture) can be prepared by the method of Minabe et al., Bull. Chem. Soc. Jpn. 1994, 67(1), 172, 2,6-dibromoanthraquinone can be prepared by the method of Lee et al., Org. Lett. 2005, 7(2), 323, bis(4-bromophenyl)methyl diethyl phosphonate can be prepared in accordance with JP 09003079, bis(4-bromophenyl)(4-formylphenyl)amine can be prepared by the method of Holmberg et al., Poly. Mat. Sci. Engen. 2001, 84, 717, 4-bromophenylphosphorus dibromide can be prepared by the method of Hinke et al., Phos. Sulf. Rel. El. 1983, 15(1), 93; fac-tris[2-(2-pyridinyl-?N)(5-bromophenyl)-?C]-iridium(III), fac-tris[2-(2-pyridinyl-?N)(4-fluoro-5-bromophenyl)-?C]-iridium(III) and fac-tris[2-(1-isoquinolinyl-?N)(5-bromophenyl)-?C]-iridium(III) are prepared in accordance with/analogously to WO 02/068435 (Example 4).

Example 1

Synthesis of anthracene-9,10-bis(boronic acid glycol ester)

(3) ##STR00047##

(4) 428.0 ml (1.07 mol) of n-butyllithium (2.5M in n-hexane) are added over the course of 20 min. to a vigorously stirred suspension, cooled to ?78? C., of 150.0 g (446 mmol) of 9,10-dibromoanthracene in 2000 ml of diethyl ether, and the mixture is subsequently stirred at ?78? C. for 30 min. The suspension is allowed to warm to 20? C. over the course of 2 h, stirred at 20? C. for a further 2 h and re-cooled to ?78? C. 199.0 ml (1.78 mol) of trimethyl borate are added over the course of 5 min. with vigorous stirring, and the suspension is allowed to re-warm to 20? C. After 15 h at 20? C., a mixture of 67.0 ml (1.12 mol) of acetic acid in 300 ml of water is added, and the mixture is stirred at room temperature for a further 5 h. After the water phase has been separated off, the organic phase is evaporated to dryness under reduced pressure. 500 ml of n-hexane are added to the slurry which remains, and the mixture is stirred vigorously for 1 h. The solid formed is subsequently filtered off with suction, washed twice with 200 ml of n-hexane and sucked dry. The solid is suspended in 500 ml of toluene, 60 ml of ethylene glycol are added, and the mixture is boiled on a water separator for 5 h. The crystals deposited after cooling of the toluene solution are filtered off with suction, recrystallised a further twice from toluene and subsequently sublimed (T=240? C., p=5?10.sup.?5 mbar). Yield: 71.3 g (50.3% of theory), 99.9% according to .sup.1H-NMR. The absorption and photoluminescence spectrum of anthracene-9,10-bis(boronic acid glycol ester) is shown in FIG. 1. As can clearly be seen, the compound exhibits a very small Stokes shift.

Example 2

Synthesis of 10-(4-methylnaphth-1-yl)anthracene-9-boronic acid pinacol ester

a) 9-(4-Methylnaphth-1-yl)anthracene

(5) ##STR00048##

(6) 3.6 g (11.7 mmol) of tri-o-tolylphosphine and then 437 mg (1.9 mmol) of palladium(II) acetate are added with vigorous stirring to a suspension of 93.0 g (500 mmol) of 4-methylnaphthalene-1-boronic acid, 100.0 g (389 mmol) of 9-bromoanthracene, 212.3 g (1 mol) of tripotassium phosphate in a mixture of 400 ml of dioxane, 600 ml of toluene and 1000 ml of water, and the mixture is refluxed for 16 h. After the reaction mixture has been cooled, the organic phase is separated off and washed three times with 500 ml of water. The organic phase is subsequently filtered through silica gel and evaporated to dryness. The oil which remains is taken up in 1000 ml of ethanol and dissolved under reflux. After cooling, the colourless solid is filtered off with suction, again washed by stirring with 1000 ml of ethanol and finally dried under reduced pressure. Yield: 103.0 g (83.1% of theory), about 96% according to .sup.1H-NMR.

b) 9-Bromo-10-(4-methylnaphth-1-yl)anthracene

(7) ##STR00049##

(8) A mixture of 18.0 ml (352 mmol) of bromine in 100 ml of dichloromethane is added dropwise with vigorous stirring to a solution of 102.0 g (320 mmol) of 9-(4-methylnaphth-1-yl)anthracene in 2000 ml of dichloromethane at ?5? C., and the mixture is stirred at room temperature for 12 h. The suspension is subsequently diluted with 1000 ml of ethanol. The precipitated solid is filtered off with suction, washed with 500 ml of a mixture of water and ethanol (1:1, v:v) and three times with 200 ml of ethanol. After washing twice with 1000 ml of boiling ethanol each time, the solid is dried under reduced pressure. Yield: 108.0 g (84.9% of theory), about 97% according to .sup.1H-NMR.

c) 10-(4-Methylnaphth-1-yl)anthracene-9-boronic acid pinacol ester

(9) ##STR00050##

(10) 44.0 ml (110 mmol) of n-butyllithium (2.5M in n-hexane) are added over the course of 20 min. to a vigorously stirred suspension, cooled to ?78? C., of 39.7 g (100 mmol) of 9-bromo-10-(4-methylnaphth-1-yl)anthracene in 1000 ml of diethyl ether, and the mixture is subsequently stirred at ?78? C. for 30 min. The suspension is allowed to warm to 20? C. over the course of 2 h, is stirred at 20? C. for a further 2 h and re-cooled to ?78? C. 28.0 ml (250 mol) of trimethyl borate are added over the course of 5 min. with vigorous stirring, and the suspension is allowed to re-warm to 20? C. After 15 h at 20? C., a mixture of 15.0 ml (250 mol) of acetic acid in 200 ml of water is added, and the mixture is stirred at room temperature for a further 5 h. After the water phase has been separated off, the organic phase is evaporated to dryness under reduced pressure. 300 ml of n-hexane are added to the slurry which remains, and the mixture is stirred vigorously for 1 h. The solid formed is subsequently filtered off with suction, washed twice with 100 ml of n-hexane and sucked dry. The solid is suspended in 150 ml of toluene, 13.0 g (110 mmol) of pinacol are added, and the mixture is boiled on a water separator for 5 h. The crystals deposited after cooling of the toluene solution are filtered off with suction, recrystallised twice from DMSO and subsequently sublimed (T=350? C., p=5?10.sup.?5 mbar); yield: 30.4 g (68.4% of theory), 99.9% according to .sup.1H-NMR.

Example 3

Synthesis of 9,10-bis(phenyl-2-boronic acid pinacol ester)anthracene

a) 9,10-Bis(2-bromophenyl)anthracene

(11) ##STR00051##

(12) 6.7 g (5.8 mmol) of tetrakis(triphenylphosphino)palladium(0) are added to a solution of 149.0 ml (1.2 mol) of 1,2-dibromobenzene, 98.0 g (308 mmol) of 9,10-anthracenediboronic acid ethylene glycol ester and 179.0 g (3.1 mol) of potassium fluoride (anhydrous, spray-dried) in a mixture of 1300 ml of dioxane, 350 ml of ethanol and 950 ml of water, and the mixture is refluxed for 120 h. After cooling, the precipitated solid is filtered off with suction, washed three times with 100 ml of water each time and three times with 100 ml of ethanol each time and dried under reduced pressure. Yield: 64.3 g (132 mmol), 42.8% of theory; purity 98% according to .sup.1H-NMR, atropisomerically pure.

b) Synthesis of 9,10-bis(phenyl-2-boronic acid pinacol ester)anthracene

(13) ##STR00052##

(14) 40.0 ml of n-BuLi (2.5M in hexane) are added to a suspension of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene in 1000 ml of diethyl ether, and the mixture is stirred at room temperature for 6 h. The reaction mixture is subsequently cooled to ?78? C., and 26.8 ml (240 mmol) of trimethyl borate are added rapidly with vigorous stirring. After slow warming to room temperature, a mixture of 8 ml of acetic acid and 300 ml of water and then 500 ml of ethyl acetate are added, the mixture is stirred at room temperature for a further 1 h, and the organic phase is separated off, washed twice with 500 ml of water and evaporated under reduced pressure. 300 ml of toluene and 10.6 g (90 mmol) of pinacol are added to the residue, and the mixture is heated on a water separator. When the separation of water is complete, 250 ml of toluene are distilled off, and 300 ml of ethanol are added. After cooling, the colourless solid is filtered off with suction, recrystallised three times from toluene and dried under reduced pressure. Sublimation, p=1?10.sup.?5 mbar, T=260? C. Yield: 10.6 g (18 mmol), 45.5% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 4

Synthesis of 1,2-bis(anthracen-9-yl-10-boronic acid pinacol ester)benzene

a) 1,2-Bis(anthracen-9-yl)benzene

(15) ##STR00053##

(16) Procedure analogous to Example 3a. Instead of 149.0 ml (1.2 mol) of 1,2-dibromobenzene and 98.0 g (308 mmol) of 9,10-anthracenediboronic acid ethylene glycol ester, 12.1 ml (100 mmol) of dibromobenzene and 68.0 g (306 mmol) of 9-anthraceneboronic acid are used. After cooling, the solid is filtered off with suction, washed three times with 100 ml of ethanol each time and then washed twice by stirring with 1000 ml of refluxing acetic acid each time (1 h) and each time filtered off with suction after cooling to 90? C. The mother liquor is discarded in each case. The solid is finally washed once with boiling ethanol. Yield: 33.0 g (76 mmol), 76.6% of theory; purity: 98% according to .sup.1H-NMR.

b) 1,2-Bis(10-bromoanthracen-9-yl)benzene

(17) ##STR00054##

(18) 142.4 g (800 mmol) of N-bromosuccinimide are added with exclusion of light to a suspension of 86.1 g (200 mmol) of 1,2-bis(anthracen-9-yl)benzene and 500 g of glass beads (diameter 4 mm) in 2000 ml of THF, stirred by a precision glass stirrer. The mixture is stirred at room temperature for 24 h, then the glass beads are filtered off via a sieve and washed with THF, and the solid is filtered off from the THF, washed three times with 200 ml of ethanol each time and then dried under reduced pressure. Yield: 114.1 g (194 mmol), 97.0% of theory; purity: 97% according to .sup.1H-NMR.

c) 1,2-Bis(anthracen-9-yl-10-boronic acid pinacol ester)benzene

(19) ##STR00055##

(20) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 23.5 g (40 mmol) of 1,2-bis(10-bromoanthracen-9-yl)benzene are used. Sublimation at p=1?10.sup.?5 mbar, T=310? C. Yield: 17.1 g (25 mmol), 62.6% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 5

Synthesis of 1,4-bis(anthracen-9-yl-10-boronic acid pinacol ester)naphthalene

a) 1,4-Bis(anthracen-9-yl)naphthalene

(21) ##STR00056##

(22) Procedure analogous to Example 3a. Instead of 149.0 ml (1.2 mol) of 1,2-dibromobenzene and 98.0 g (308 mmol) of 9,10-anthracenediboronic acid ethylene glycol ester, 28.6 g (100 mmol) of 1,4-dibromonaphthalene and 68.0 g (306 mmol) of 9-anthraceneboronic acid are used. After cooling, the solid is filtered off with suction and washed twice with 500 ml of boiling ethanol each time. Yield: 33.0 g (69 mmol), 68.7% of theory; purity: 98% according to .sup.1H-NMR.

b) 1,4-Bis(10-bromoanthracen-9-yl)naphthalene

(23) ##STR00057##

(24) Procedure analogous to Example 4b. Instead of 86.0 g (200 mmol) of 1,2-bis(anthracen-9-yl)benzene and 142.4 g (800 mmol) of N-bromosuccinimide, 96.1 g (200 mmol) of 1,4-bis(anthracen-9-yl)naphthalene and 42.7 g (240 mmol) of N-bromosuccinimide are used. Yield: 109.2 g (171 mmol), 85.5% of theory; purity: 97% according to .sup.1H-NMR.

c) 1,4-Bis(anthracen-9-yl-10-boronic acid pinacol ester)naphthalene

(25) ##STR00058##

(26) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 25.5 g (40 mmol) of 1,4-bis(10-bromoanthracen-9-yl)naphthalene are used. Sublimation at p=1?10.sup.?5 mbar, T=300? C. Yield: 12.1 g (16.5 mmol), 41.3% of theory; purity: 99.8% according to .sup.1H-NMR.

Example 6

Synthesis of 9,10-bis(naphth-1-yl)anthracene-2,6-bis-(boronic acid pinacol ester)

a) 2,6-Dibromo-9,10-bis(naphth-1-yl)anthracene

(27) ##STR00059##

(28) The corresponding Grignard reagent is prepared from 30.5 ml (220 mmol) of 1-bromonaphthalene and 5.5 g (225 mmol) of magnesium in 500 ml of THF. 36.6 g (100 mmol) of 2,6-dibromoanthraquinone are added to this Grignard reagent, the mixture is refluxed for 6 h and allowed to cool, 15 ml of acetic acid are added, the mixture is evaporated to dryness, the residue is taken up in 500 ml of DMF, 56.9 g (300 mmol) of tin(II) chloride are added, and the mixture is refluxed for 5 h. After cooling, 200 ml of 2N hydrochloric acid are added, the mixture is stirred for a further 1 h, the solid is filtered off with suction, washed three times with 200 ml of 2N hydrochloric acid each time, three times with 300 ml of water each time, and three times with 200 ml of ethanol each time, dried under reduced pressure and recrystallised once from DMF. Yield: 48.9 g (83 mmol), 83.1% of theory; purity: 98% according to .sup.1H-NMR.

b) 9,10-Bis(naphth-1-yl)anthracene-2,6-bis(boronic acid pinacol ester)

(29) ##STR00060##

(30) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 23.5 g (40 mmol) of 2,6-dibromo-9,10-bis-(naphth-1-yl)anthracene are used. Recrystallisation twice from both toluene and then dioxane. Sublimation at p=1?10.sup.?5 mbar, T=270? C. Yield: 14.6 g (21 mmol), 53.5% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 7

Synthesis of 9,10-bis(naphth-1-yl-4-boronic acid pinacol ester)anthracene

a) 9,10-Bis(4-bromonaphth-1-yl)anthracene

(31) ##STR00061##

(32) 48.0 ml (120 mmol) of n-butyllithium (2.5M in hexane) are added at ?78? C. with vigorous stirring to a solution of 31.9 g (120 mmol) of 1,4-dibromonaphthalene in 1000 ml of THF. The mixture is stirred at ?78? C. for 1 h, then allowed to warm to 0? C., 10.4 g (50 mmol) of anthraquinone are added, and the mixture is stirred at 0? C. for a further 3 h. After 15 ml of acetic acid have been added, the mixture is evaporated to dryness, the residue is taken up in 500 ml of DMF, 28.4 g (150 mmol) of tin(II) chloride are added, and the mixture is refluxed for 5 h. After cooling, 200 ml of 2N hydrochloric acid are added, the mixture is stirred for a further 1 h, the solid is filtered off with suction, washed three times with 200 ml of 2N hydrochloric acid each time, three times with 300 ml of water each time and three times with 200 ml of ethanol each time, dried under reduced pressure and recrystallised from NMP. Yield: 25.9 g (44 mmol), 88.0% of theory; purity: 98% according to .sup.1H-NMR.

b) 9,10-Bis(4-bromonaphth-1-yl)anthracene

(33) ##STR00062##

(34) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 23.5 g (40 mmol) of 9,10-bis(4-bromonaphth-1-yl)anthracene are used. Owing to the poor solubility of the 9,10-bis(4-bromonaphth-1-yl)anthracene, 200 g of glass beads (diameter 4 mm) are added to the batch, the stirring is carried out using a mechanical paddle stirrer, and the reaction time for the lithiation is increased to 24 h. Recrystallisation four times from dioxane. Sublimation at p=1?10.sup.?5 mbar, T=290? C. Yield: 17.6 g (26 mmol), 64.5% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 8

Synthesis of 1,6-bis(2,5-dimethylphenyl)pyrene-3,8-bis(boronic acid pinacol ester)

a) 1,6-Bis(2,5-dimethylphenyl)pyrene

(35) ##STR00063##

(36) 7.2 g (20 mmol) of tri-o-tolylphosphine and 740 mg (3.3 mmol) of palladium(II) acetate are added to a vigorously stirred suspension of 76.0 g (211 mmol) of dibromopyrene (isomer mixture), 72.9 g (486 mmol) of 2,5-dimethylphenylboronic acid and 222.4 g (966 mmol) of potassium phosphate monohydrate in a mixture of 500 ml of toluene, 500 ml of dioxane and 100 ml of water, and the mixture is refluxed for 12 h. After cooling to room temperature, the precipitated solid is filtered off with suction, washed with 200 ml of ethanol and dissolved in 500 ml of dichloromethane with warming, the solution is filtered through silica gel, the filtrate is evaporated to 1000 ml under reduced pressure, and 300 ml of ethanol are added. After standing for 2 h, the colourless crystals are filtered off with suction, washed with 100 ml of ethanol and dried under reduced pressure. Yield: 32.5 g (79 mmol), 37.5% of theory; purity 98% according to .sup.1H-NMR.

b) 1,6-Bis(2,5-dimethylphenyl)-3,8-dibromopyrene

(37) ##STR00064##

(38) A suspension of 25.8 g (63 mmol) of 1,6-bis(2,5-dimethylphenyl)pyrene and 24.8 g (139 mmol) of N-bromosuccinimide in 800 ml of THF is stirred at room temperature with exclusion of light for 16 h. The reaction mixture is evaporated to 100 ml under reduced pressure, and 200 ml of ethanol and 200 ml of water are added. The precipitate is filtered off with suction, washed three times with 100 ml of ethanol, dried under reduced pressure and recrystallised twice from chlorobenzene. Yield: 26.0 g (46 mmol), 72.6% of theory; purity 97% according to .sup.1H-NMR.

c) 1,6-Bis(2,5-dimethylphenyl)pyrene-3,8-bis(boronic acid pinacol ester)

(39) ##STR00065##

(40) Procedure analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 22.7 g (40 mmol) of 1,6-bis(2,5-dimethylphenyl)-3,8-dibromopyrene are employed. The recrystallisation is carried out from dioxane. Sublimation, p=1?10.sup.?5 mbar, T=290? C. Yield: 11.5 g (17 mmol), 43.3% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 9

Synthesis of 1,4-bis(anthracen-9-yl-10-boronic acid pyrocatechol ester)naphthalene

(41) ##STR00066##

(42) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 25.5 g (40 mmol) of 1,4-bis(10-bromoanthracen-9-yl)naphthalene are used, and instead of 10.6 g (90 mmol) of pinacol, 9.9 g (90 mmol) of pyrocatechol are used. Sublimation at p=1?10.sup.?5 mbar, T=330? C. Yield: 17.7 g (25 mmol), 61.8% of theory; purity: 99.7% according to .sup.1H-NMR.

Example 10

Synthesis of 9,10-bis(naphth-1-yl)anthracene-3,8-bis-(boronic acid pyrocatechol ester)

(43) ##STR00067##

(44) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 23.5 g (40 mmol) of 2,6-dibromo-9,10-bis-(naphth-1-yl)anthracene are used, and instead of 10.6 g (90 mmol) of pinacol, 9.9 g (90 mmol) of pyrocatechol are used. Sublimation at p=1?10.sup.?5 mbar, T=305? C. Yield: 9.2 g (14 mmol), 34.5% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 11

2,4,6-Tris[10-(4-methylnaphth-1-yl)anthracen-9-yl]-cyclotriboroxane

(45) ##STR00068##

(46) Preparation analogous to Example 2c. After isolation of the boronic acid, it is suspended in 300 ml of acetonitrile and boiled on a water separator for 5 h, during which the azeotrope is removed continuously down to 50 ml. After addition of 300 ml of ethanol and cooling, the deposited crystals are filtered off with suction, recrystallised four times from dioxane and subsequently sublimed (T=370? C., p=5?10.sup.?5 mbar); yield: 15.8 g (18 mmol), 45.9% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 12

9,10-Bis(naphth-1-yl)anthracene-3,8-bis(boronic acid hexafluoro-2,3-bis(trifluoromethyl)but-2,3-yl ester)

(47) ##STR00069##

(48) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 23.5 g (40 mmol) of 2,6-dibromo-9,10-bis-(naphth-1-yl)anthracene are used. Instead of 10.6 g (90 mmol) of pinacol, 30.1 g (90 mmol) of hexafluoro-2,3-bis(trifluoromethyl)butane-2,3-diol are used. Recrystallisation five times from toluene/acetonitrile. Sublimation at p=1?10.sup.?5 mbar, T=280? C. Yield: 18.1 g (16 mmol), 40.6% of theory; purity: 99.8% according to .sup.1H-NMR.

Example 13

Synthesis of 9,10-bis(naphth-1-yl)anthracene-3,8-bis(2-(3-methyl-2,3-dihydrobenzo-1,3,2-oxazaborole)

(49) ##STR00070##

(50) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 23.5 g (40 mmol) of 2,6-dibromo-9,10-bis-(naphth-1-yl)anthracene are used. Instead of 10.6 g (90 mmol) of pinacol, 11.1 g (90 mmol) of 2-methylaminophenol are used. Recrystallisation four times from DMF. Sublimation at p=1?10.sup.?5 mbar, T=280? C. Yield: 14.9 g (21.5 mmol), 53.8% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 14

Synthesis of tris((4-(2,2-di(4-phenylboronic acid pinacol ester)vinyl)phen-1-yl)amine

a) Tris((4-(2,2-di(4-bromophenyl)vinyl)phen-1-yl)amine

(51) ##STR00071##

(52) A solution of 184.8 g (400 mmol) of bis(4-bromophenyl)methyl diethylphosphonate in 200 ml of DMF is added to a suspension, cooled to 0? C., of 76.9 g (800 mmol) of sodium tert-butoxide in 1000 ml of anhydrous DMF. After the mixture has been stirred for a further 30 min., a solution of 32.9 g (100 mmol) of tris(4-formyl)amine in 300 ml of DMF is added over the course of 30 min., the mixture is stirred at 0? C. for a further 4 h, then 1000 ml of 1N hydrochloric acid and 500 ml of ethanol are added. The solid is filtered off with suction, washed three times with 300 ml of water and three times with 200 ml of ethanol and dried under reduced pressure. The product is subsequently recrystallised from DMF, filtered off with suction, washed three times with 200 ml of ethanol and dried under reduced pressure. Yield: 109.4 g (87 mmol), 87.3% of theory; purity: 99% according to .sup.1H-NMR.

b) Tris((4-(2,2-di(4-phenylboronic acid pinacol ester)vinyl)phen-1-yl)amine

(53) ##STR00072##

(54) 65 ml of n-BuLi (2.5M in hexane) are added to a suspension of 31.3 g (25 mmol) of tris((4-(2,2-di(4-bromophenyl)vinyl)phen-1-yl)amine in 1000 ml of diethyl ether, and the mixture is stirred at room temperature for 6 h. The reaction mixture is subsequently cooled to ?78? C., and 44.5 ml (450 mmol) of trimethyl borate are added rapidly with vigorous stirring. After slow warming to room temperature, a mixture of 15 ml of acetic acid and 500 ml of water and then 500 ml of ethyl acetate are added, the mixture is stirred at room temperature for a further 1 h, and the organic phase is separated off, washed twice with 500 ml of water and evaporated under reduced pressure. 500 ml of toluene and 18.9 g (160 mmol) of pinacol are added to the residue, and the mixture is heated on a water separator.

(55) When the separation of water is complete, 400 ml of toluene are distilled off, and 300 ml of ethanol are added. After cooling, the yellow solid is filtered off with suction, recrystallised five times from dioxane/ethanol (1:3, v:v) and sublimed under reduced pressure (p=1?10.sup.?5 mbar, T=330? C.). Yield: 14.5 g (9 mmol), 37.7% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 15

Synthesis of 1,4-bis(4-di(4-phenylboronic acid pinacol ester)aminostyryl)benzene

a) 1,4-Bis(4-di(4-bromophenyl)aminostyryl)benzene

(56) ##STR00073##

(57) A solution of 37.8 g (100 mmol) of p-xylene diethylphosphonate in 200 ml of DMF is added to a suspension, cooled to 0? C., of 38.5 g (400 mmol) of sodium tert-butoxide in 1000 ml of anhydrous DMF. After the mixture has been stirred for a further 30 min., a solution of 90.5 g (210 mmol) of bis(4-bromophenyl)(4-formylphenyl)amine in 300 ml of DMF is added over the course of 30 min., the mixture is stirred at 0? C. for a further 4 h, and then 500 ml of 1N hydrochloric acid and 300 ml of ethanol are added. The solid is filtered off with suction, washed three times with 300 ml of water and three times with 200 ml of ethanol and dried under reduced pressure. The product is subsequently recrystallised from DMF, filtered off with suction, washed three times with 200 ml of ethanol and dried under reduced pressure. Yield: 86.1 g (92 mmol), 92.3% of theory; purity: 99% according to .sup.1H-NMR.

b) 1,4-Bis(4-di(4-phenylboronic acid pinacol ester)aminostyryl)benzene

(58) ##STR00074##

(59) Preparation analogous to Example 14b. Instead of 31.3 g (25 mmol) of tris((4-(2,2-di(4-bromophenyl)vinyl)phen-1-yl)amine, 34.5 g (37 mmol) of 1,4-bis(4-di(4-bromophenyl)aminostyryl)benzene are used. Sublimation, p=1?10.sup.?5 mbar, T=310? C. Yield: 18.9 g (17 mmol), 45.6% of theory; purity: 99.7% according to .sup.1H-NMR.

Example 16

Synthesis of N,N,N,N-tetrakis(4-1,3,2-dioxaborolan-2-ylphenyl)biphenyl-4,4-diamine

a) N,N,N,N-tetra(4-bromophenyl)benzidine

(60) ##STR00075##

(61) 74.8 g (420 mmol) of N-bromosuccinimide are added in portions to a solution of 48.9 g (100 mmol) of N,N,N,N-tetraphenylbenzidine in 500 ml of THF at 40? C. with vigorous stirring, and the mixture is stirred for 16 h. The mixture is subsequently transferred onto 2000 g of ice, and the resultant precipitate is filtered off with suction, washed three times with 300 ml of water and twice with 200 ml of ethanol and then recrystallised from DMF. Yield: 73.5 g (91 mmol), 91.4% of theory; purity 98% according to .sup.1H-NMR.

b) N4,N4,N4,N4-tetrakis(4-1,3,2-dioxaborolan-2-ylphenyl)biphenyl-4,4-diamine

(62) ##STR00076##

(63) Preparation analogous to Example 15b. Instead of 34.5 g (37 mmol) of 1,4-bis(4-di(4-bromophenyl)aminostyryl)benzene, 29.8 g (37 mmol) of N,N,N,N-tetra(4-bromophenyl)benzidine are used, and instead of 18.9 g (160 mmol) of pinacol, 9.0 ml (160 mmol) of ethylene glycol are used. Recrystallisation from toluene. Sublimation, p=1?10.sup.?5 mbar, T=250? C. Yield: 21.3 g (28 mmol), 75.0% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 17

Synthesis of 2,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)spiro-9,9-bifluorene

a) 2,2-Bis(4-bromobenzoyl)spiro-9,9-bifluorene

(64) ##STR00077##

(65) A solution of 24.1 g (110 mmol) of 4-bromobenzoyl chloride in 100 ml of 1,2-dichloroethane is added dropwise to a suspension of 16.0 g (120 mmol) of aluminium chloride in 300 ml of 1,2-dichloroethane. A solution of 15.8 g (50 mmol) of spiro-9,9-bifluorene in 200 ml of 1,2-dichloroethane is added dropwise to this mixture. The mixture is subsequently stirred at room temperature for a further 4 hours and poured into a mixture of 1000 g of ice and 200 ml of 2N hydrochloric acid with vigorous stirring, and the precipitated solid is filtered off with suction. The solid is washed three times with 500 ml of water and three times with 200 ml of ethanol and dried under reduced pressure. Yield: 29.2 g (43 mmol), 85.6% of theory; purity: 98% according to .sup.1H-NMR.

b) 2,2-Bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-spiro-9,9-bifluorene

(66) ##STR00078##

(67) The preparation is carried out by the method of Melaimi et al., J. Organomet. Chem. 2004, 689(19), 2988, analogously to the preparation of 2-(4-acetylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. Instead of 4-acetylbromobenzene, 17.1 g (25 mmol) of 2,2-bis(4-bromobenzoyl)spiro-9,9-bifluorene are employed. Sublimation, p=1?10.sup.?5 mbar, T=265? C. Yield: 8.4 g (11 mmol), 43.2% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 18

Synthesis of 2-bis(spiro-9,9-bifluorene)-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide

a) 2-Bis(spiro-9,9-bifluorene)-(4-bromophenyl))phosphine oxide

(68) ##STR00079##

(69) Preparation analogous to WO 05/003253, Example 1. Instead of dichlorophenylphosphine, 41.6 g (120 mmol) of 4-bromophenylphosphorus dibromide are used. Recrystallisation twice from chlorobenzene. Yield: 71.0 g (71 mmol), 71.0% of theory; purity: 98% according to .sup.1H-NMR.

b) 2-Bis(spiro-9,9-bifluorene)-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide

(70) ##STR00080##

(71) Preparation analogous to Example 17b. Instead of 17.1 g (25 mmol) of 2,2-bis(4-bromobenzoyl)spiro-9,9-bifluorene, 20.8 g (25 mmol) of 2-bis-(spiro-9,9-bifluorene)-(4-bromophenyl))phosphine oxide are employed. Sublimation, p=1?10.sup.?5 mbar, T=310? C. Yield: 8.0 g (9 mmol), 36.3% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 19

Synthesis of 4,4-bis(4,4-bis(1,3,2-dioxaborolan-2-yl)-carbazolyl)biphenyl

a) 4,4-Bis(4,4-bisbromocarbazolyl)biphenyl

(72) ##STR00081##

(73) 74.8 g (420 mmol) of N-bromosuccinimide are added in portions to a solution of 48.5 g (100 mmol) of biscarbazolylbiphenyl in 1000 ml of THF at 40? C. with vigorous stirring, and the mixture is then stirred for 16 h. The mixture is subsequently transferred onto 2000 g of ice, and the resultant precipitate is filtered off with suction, washed three times with 300 ml of water and twice with 200 ml of ethanol and recrystallised from DMF. Yield: 74.3 g (93 mmol), 92.8% of theory; purity 98% according to .sup.1H-NMR.

b) 4,4-Bis(4,4-bis(1,3,2-dioxaborolan-2-yl)carbazolyl)biphenyl

(74) ##STR00082##

(75) Preparation analogous to Example 16b. Instead of 29.8 g (37 mmol) of N,N,N,N-tetra(4-bromophenyl)benzidine, 29.6 g (37 mmol) of 4,4-bis-(4,4-bisbromocarbazolyl)biphenyl are used, and instead of 18.9 g (160 mmol) of pinacol, 9.0 ml (160 mmol) of ethylene glycol are used. Recrystallisation from dioxane. Sublimation, p=1?10.sup.?5 mbar, T=270? C. Yield: 21.3 g (28 mmol), 75.3% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 20

Synthesis of 1,6-bis((4-methylphenyl)amino)pyrene-3,8-bis(boronic acid pinacol ester)

a) 1,6-Bis((4-methylphenyl)amino)pyrene

(76) ##STR00083##

(77) 1.05 ml (5.2 mmol) of di-tert-butylphosphine chloride and then 898 mg (4.0 mmol) of palladium(II) acetate are added to a vigorously stirred suspension of 76.0 g (211 mmol) of dibromopyrene (isomer mixture), 94.7 g (480 mmol) of bis(4-methylphenyl)amine and 50.0 g (520 mmol) of sodium tert-butoxide in 1000 ml of toluene, and the mixture is refluxed for 5 h. After cooling to room temperature, 1000 ml of water are added, and the precipitated solid is filtered off with suction, washed with 200 ml of ethanol and dried under reduced pressure. Recrystallisation, three times from DMF. Yield: 41.4 g (70 mmol), 33.1% of theory; purity 99% according to .sup.1H-NMR.

b) 1,6-Bis((4-methylphenyl)amino)-3,8-dibromopyrene

(78) ##STR00084##

(79) Preparation analogous to Example 8b. Instead of 25.8 g (63 mmol) of 1,6-bis(2,5-dimethylphenyl)pyrene, 29.6 g (50 mmol) of 1,6-bis((4-methyl-phenyl)amino)pyrene are used, and instead of 24.8 g (139 mmol) of N-bromosuccinimide, 19.6 g (110 mmol) of N-bromosuccinimide are used. Yield: 27.4 g (36.5 mmol), 73.0% of theory; purity 99% according to .sup.1H-NMR.

c) 1,6-Bis((4-methylphenyl)amino)pyrene-3,8-bis(boronic acid pinacol ester)

(80) ##STR00085##

(81) Procedure analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 30.0 g (40 mmol) of 1,6-bis((4-methyl-phenyl)amino)-3,8-dibromopyrene are employed. The recrystallisation is carried out from chlorobenzene. Sublimation, p=1?10.sup.?5 mbar, T=285? C. Yield: 13.8 g (16 mmol), 40.8% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 21

Synthesis of 9,10-bis((bis-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amino)anthracene

a) 9,10-Bis(diphenylamino)anthracene

(82) ##STR00086##

(83) Preparation analogous to Example 20a. Instead of 76.0 g (211 mmol) of dibromopyrene (isomer mixture) and 94.7 g (480 mmol) of bis(4-methyl-phenyl)amine, 70.9 g (211 mmol) of 9,10-dibromoanthracene and 81.2 g (480 mmol) of diphenylamine are used. Yield: 86.2 g (168 mmol), 79.7% of theory; purity 99% according to .sup.1H-NMR.

b) 9,10-Bis-N,N-(di(4-bromophenyl)amino)anthracene

(84) ##STR00087##

(85) Preparation analogous to Example 16a. Instead of 48.9 g (100 mmol) of N,N,N,N-tetraphenylbenzidine, 51.3 g (100 mmol) of 9,10-bis(diphenylamino)anthracene are used. Yield: 70.8 g (85 mmol), 85.5% of theory; purity 98% according to .sup.1H-NMR.

c) 9,10-Bis((bis-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl)amino)anthracene

(86) ##STR00088##

(87) Preparation analogous to Example 3b. Instead of 19.5 g (40 mmol) of 9,10-bis(2-bromophenyl)anthracene, 16.6 g (20 mmol) of 9,10-bis(di(4-bromo-phenyl)amino)anthracene are used. The recrystallisation is carried out from chlorobenzene. Sublimation, p=1?10.sup.?5 mbar, T=285? C. Yield: 9.9 g (9.7 mmol), 48.7% of theory; purity 99.8% according to .sup.1H-NMR.

Example 22

Synthesis of fac-tris[2-(2-pyridinyl-?N)(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-?C]-iridium(III)

(88) ##STR00089##

(89) The preparation is carried out by the method of Broutin et al., Org. Lett. 2004, 6(24), 4419 analogously to the general preparation procedure for phenylboronates. 892 mg (1 mmol) of fac-tris[2-(2-pyridinyl-?N)(5-bromo-phenyl)-?C]iridium(III) in 10 ml of dioxane and 1.3 g (10 mmol) of pinacolborane are employed, and the reaction time is 16 h. Chromatographic purification on deactivated silica gel (5% of triethylamine), eluent dichloromethane:n-hexane (1:10, v:v). Sublimation, p=1?10.sup.?5 mbar, T=295? C. Yield: 325 mg (315 ?mol), 31.5% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 23

Synthesis of fac-tris[2-(2-pyridinyl-?N)(4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-?C]iridium(III)

(90) ##STR00090##

(91) The preparation is carried out by the method of Broutin et al., Org. Lett. 2004, 6(24), 4419 analogously to the general preparation procedure for phenylboronates. 946 mg (1 mmol) of fac-tris[2-(2-pyridinyl-?N)(4-fluoro-5-bromophenyl)-?C]iridium(III) in 10 ml of dioxane and 1.3 g (10 mmol) of pinacolborane are employed, and the reaction time is 16 h. Chromatographic purification on deactivated silica gel (5% of triethylamine), eluent dichloromethane:n-hexane (1:10, v:v). Sublimation, p=1?10.sup.?5 mbar, T=280? C. Yield: 324 mg (298 ?mol), 29.8% of theory; purity: 99.8% according to .sup.1H-NMR.

Example 24

Synthesis of fac-tris[2-(1-isoquinolinyl-?N)(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-?C]-iridium(III)

(92) ##STR00091##

(93) The preparation is carried out by the method of Broutin et al., Org. Lett. 2004, 6(24), 4419 analogously to the general preparation procedure for phenylboronates. 1042 mg (1 mmol) of fac-tris[2-(1-isoquinolinyl-?N)(5-bromophenyl)-?C]iridium(III) in 10 ml of dioxane and 1.3 g (10 mmol) of pinacolborane are employed, and the reaction time is 16 h. Chromatographic purification on deactivated silica gel (5% of triethylamine), eluent dichloromethane:n-hexane (1:10, v:v). Sublimation, p=1?10.sup.?5 mbar, T=340? C. Yield: 485 mg (410 ?mol), 41.0% of theory; purity: 99.9% according to .sup.1H-NMR.

Example 25

Production of OLEDs Comprising the Materials According to the Invention According to Examples 1 to 13

(94) OLEDs are produced by a general process in accordance with WO 04/058911, which is adapted in individual cases to the particular circumstances (for example layer-thickness variation in order to achieve optimum efficiency or colour).

(95) The results for various OLEDs are presented in Examples 26 to 39 below. The basic structure and the materials used (apart from the emitting layer) are identical in the examples for better comparability. OLEDs having the following structure are produced analogously to the above-mentioned general process:

(96) TABLE-US-00001 Hole-injection 20 nm PEDOT (spin-coated from water; from layer (HIL) H. C. Starck, Goslar, Germany; poly(3,4- ethylenedioxy-2,5-thiophene)) Hole-transport 30 nm 4,4,4-tris(N-1-naphthyl-N-phenyl- layer (HTL) amino)triphenylamine (abbreviated to NaphDATA, purchased from SynTec) Hole-transport 30 nm NPB (N-naphthyl-N-phenyl-4,4- layer (HTL) diaminobiphenyl) Emission 30 nm layer of the host materials in accor- layer (EML) dance with Examples 1 to 13 (see table), doped with 5% of tris[4-(2,2-diphenyl-vinyl)- phenyl]amine as dopant (abbreviated to D1, vapour-deposited, synthesised in accordance with WO 06/000388) OR: as comparative example 30 nm 9,10-bis(1- naphthylanthracene) as host material (abbre- viated to H), doped with 5% of tris[4-(2,2-di- phenylvinyl)phenyl]amine as dopant (abbre- viated to D1) Electron 20 nm AlQ.sub.3 (purchased from SynTec, conductor (ETC) tris(quinolinato)aluminium(III)) Cathode 1 nm LiF, 150 nm Al on top

(97) These OLEDs are characterised by standard methods; the electroluminescence spectra, the efficiency (measured in cd/A), the power efficiency (measured in lm/W) as a function of the brightness, calculated from current/voltage/brightness characteristic lines (IUL characteristic lines), are determined for this purpose.

(98) Table 1 shows the results for some OLEDs (Examples 26 to 39).

(99) The host material employed for the comparative example is 9,10-bis(1-naphthyl)anthracene; the dopant employed in all examples is D1. Both are prepared as follows:

(100) ##STR00092##

(101) As can be seen from the examples in Table 1, OLEDs comprising the host materials according to Examples 1 to 13 according to the invention exhibit lower operating voltages. Besides significantly improved power efficiencies, equivalent to lower power consumption for the same operating brightnesses, this also results in improved lifetimes.

(102) TABLE-US-00002 TABLE 1 Voltage Max. (V) at efficiency 1000 Example EML (cd/A) cd/m.sup.2 CIE Example 26 Host H 7.9 6.6 x = 0.17; (Comparison) Dopant D1 y = 0.31 Example 27 Host acc. to Ex. 1 8.2 5.3 x = 0.16; Dopant D1 y = 0.28 Example 28 Host acc. to Ex. 2 8.3 5.2 x = 0.16; Dopant D1 y = 0.29 Example 29 Host acc. to Ex. 3 8.2 5.3 x = 0.16; Dopant D1 y = 0.29 Example 30 Host acc. to Ex. 4 8.0 5.4 x = 0.16; Dopant D1 y = 0.30 Example 31 Host acc. to Ex. 5 8.5 5.0 x = 0.16; Dopant D1 y = 0.28 Example 32 Host acc. to Ex. 6 8.6 4.9 x = 0.16; Dopant D1 y = 0.29 Example 33 Host acc. to Ex. 7 8.7 4.7 x = 0.15; Dopant D1 y = 0.27 Example 34 Host acc. to Ex. 8 8.5 4.9 x = 0.16; Dopant D1 y = 0.28 Example 35 Host acc. to Ex. 9 8.3 5.0 x = 0.17; Dopant D1 y = 0.29 Example 36 Host acc. to Ex. 10 8.4 5.1 x = 0.16; Dopant D1 y = 0.29 Example 37 Host acc. to Ex. 11 8.7 5.4 x = 0.15; Dopant D1 y = 0.27 Example 38 Host acc. to Ex. 12 8.6 5.5 x = 0.16; Dopant D1 y = 0.28 Example 39 Host acc. to Ex. 13 7.9 5.3 x = 0.16; Dopant D1 y = 0.29

Example 40

Production of OLEDs Comprising the Host Materials According to Examples 5 to 8 or Host H and the Emitters According to Examples 14 and 15

(103) The results for various OLEDs are presented in Examples 41 to 51 below. The basic structure and the materials used (apart from the emitting layer) are identical in the examples for better comparability. OLEDs having the following structure are produced analogously to the above-mentioned general process:

(104) TABLE-US-00003 Hole-injection 20 nm PEDOT (spin-coated from water; from layer (HIL) H. C. Starck, Goslar, Germany; poly(3,4- ethylenedioxy-2,5-thiophene)) Hole-transport 30 nm 4,4,4-tris(N-1-naphthyl-N-phenyl- layer (HTL) amino)triphenylamine (abbreviated to NaphDATA, purchased from SynTec) Hole-transport 30 nm NPB (N-naphthyl-N-phenyl-4,4-di- layer (HTL) aminobiphenyl) Emission 30 nm layer of the host materials in accor- layer (EML) dance with Examples 5, 6, 7, 8 (see table), doped with 5% of dopant according to Exam- ple 14 or 15 OR: as comparative example 9,10-bis(1-naphthyl- anthracene) as host material (abbreviated to H), doped with 5% of tris[4-(2,2-diphenyl- vinyl)phenyl]amine as dopant (abbreviated to D1), vapour-deposited, synthesised in accor- dance with WO 06/000388 or doped with 5% of 1,4-bis(4-di(3-methyl- phenyl)aminostyryl)benzene as dopant (ab- breviated to D2), vapour-deposited, synthe- sised in accordance with JP 06001973 Electron 20 nm AlQ.sub.3 (purchased from SynTec, conductor (ETC) tris(quinolinato)aluminium(III)) Cathode 1 nm LiF, 150 nm Al on top

(105) These OLEDs are characterised by standard methods; the electroluminescence spectra, the efficiency (measured in cd/A), the power efficiency (measured in lm/W) as a function of the brightness, calculated from current/voltage/brightness characteristic lines (IUL characteristic lines), are determined for this purpose.

(106) Table 2 shows the results for some OLEDs (Examples 41 to 51). The host material for the comparative examples is 9,10-bis(1-naphthyl)anthracene (see above), and the dopants employed for the comparative examples are D1 (see above) and D2.

(107) ##STR00093##

(108) As can be seen from the examples in Table 2, OLEDs comprising the host materials according to the invention exhibit significantly improved efficiencies at the same time as comparable colour coordinates and improved lifetimes.

(109) In addition, the considerably improved thermal stability of the dopant according to Example 15 according to the invention compared with dopant D2, which is structurally analogous, but is not substituted by 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl groups, should again be pointed out at this point. This improved stability is of crucial importance, in particular on industrial use, since dopants in industrial use must have lifetimes of several days to weeks at high temperatures.

(110) TABLE-US-00004 TABLE 2 Voltage Max. (V) at efficiency 1000 Example EML (cd/A) cd/m.sup.2 CIE Example 41 Host H 7.9 6.6 x = 0.17; (comparison) Dopant D y = 0.31 Example 42 Host H 9.8 5.1 x = 0.19; Dopant acc. to Ex. 14 y = 0.31 Example 43 Host H 12.3 5.0 x = 0.21; Dopant acc. to Ex. 15 y = 0.33 Example 44 Host acc. to Ex. 5 10.2 5.0 x = 0.17; Dopant acc. to Ex. 14 y = 0.31 Example 45 Host acc. to Ex. 6 10.3 4.9 x = 0.18; Dopant acc. to Ex. 14 y = 0.32 Example 46 Host acc. to Ex. 7 9.9 5.2 x = 0.18; Dopant acc. to Ex. 14 y = 0.32 Example 47 Host acc. to Ex. 8 10.6 4.9 x = 0.18; Dopant acc. to Ex. 14 y = 0.32 Example 48 Host acc. to Ex. 5 13.2 5.0 x = 0.19; Dopant acc. to Ex. 15 y = 0.32 Example 49 Host acc. to Ex. 6 13.0 4.9 x = 0.19; Dopant acc. to Ex. 15 y = 0.32 Example 50 Host acc. to Ex. 7 12.9 5.2 x = 0.19; Dopant acc. to Ex. 15 y = 0.32 Example 51 Host acc. to Ex. 8 12.7 4.9 x = 0.19; Dopant acc. to Ex. 15 y = 0.32

Example 52

Production of OLEDs Comprising the Hole-Transport Material According to Example 16

(111) The results for various OLEDs are presented in Examples 53 and 54 below. The basic structure and the materials used (apart from the emitting layer) are identical in the examples for better comparability. OLEDs having the following structure are produced analogously to the above-mentioned general process:

(112) TABLE-US-00005 Hole-injection 20 nm PEDOT (spin-coated from water; from layer (HIL) H. C. Starck, Goslar, Germany; poly(3,4- ethylenedioxy-2,5-thiophene)) Hole-transport 30 nm layer of the hole-transport material layer (HTL) according to Example 16 OR: as comparative example 30 nm layer of N,N,N,N-tetraphenyl-[1,1-biphenyl]-4,4- diamine (abbreviated to TAD; purchased from SynTec) Hole-transport 30 nm NPB (N-naphthyl-N-phenyl-4,4- layer (HTL) diaminobiphenyl) Emission 30 nm layer of the host material according to layer (EML) Example 8 (see table), doped with 5% of dopant according to Example 14 Electron 20 nm AlQ.sub.3 (purchased from SynTec, tris- conductor (ETC) (quinolinato)aluminium(III)) Cathode 1 nm LiF, 150 nm Al on top

(113) These OLEDs are characterised by standard methods; the electroluminescence spectra, the efficiency (measured in cd/A), the power efficiency (measured in lm/W) as a function of the brightness, calculated from current/voltage/brightness characteristic lines (IUL characteristic lines), are determined for this purpose.

(114) Table 3 shows the results for two OLEDs (Examples 53 and 54). As can be seen from the examples in Table 3, OLEDs comprising the hole-transport material according to Example 16 according to the invention exhibit significantly improved efficiencies at the same time as comparable colour coordinates and improved lifetimes.

(115) TABLE-US-00006 TABLE 3 Max. Voltage efficiency (V) at Example HTL (cd/A) 1000 cd/m.sup.2 CIE Example 53 TAD 9.0 5.6 x = 0.19; (comparison) y = 0.33 Example 54 HTL acc. to Ex. 16 10.8 4.7 x = 0.18; y = 0.32

Example 55

Production of OLEDs Comprising Matrix Materials According to Examples 17, 18 and 19 and Emitters According to Examples 22, 23 and 24

(116) OLEDs are produced by a general process in accordance with WO 04/93207, which is adapted in individual cases to the particular circumstances (for example layer-thickness variation in order to achieve optimum efficiency or colour).

(117) The results for various OLEDs are compared here. The basic structure, such as the materials used, degree of doping and their layer thicknesses, is identical in the example experiments for better comparability. Only the host material in the emitter layer is exchanged, and the examples are carried out with different triplet emitters.

(118) The first example describes a comparison standard in accordance with the prior art in which the emitter layer consists of the matrix material CBP.

(119) Furthermore, OLEDs comprising an emitter layer consisting of the matrix materials according to Examples 17, 18 and 19 according to the invention are described.

(120) Green- and red-emitting OLEDs having the following structure are produced analogously to the above-mentioned general process:

(121) TABLE-US-00007 PEDOT 60 nm (spin-coated from water; purchased from H. C. Starck; poly [3,4-ethylenedioxy-2,5- thiophene]) NaphDATA 20 nm (vapour-deposited; NaphDATA pur- chased from SynTec; 4,4,4-tris(N-1- naphthyl-N-phenylamino)triphenylamine S-TAD 20 nm (vapour-deposited; S-TAD prepared in accordance with WO99/12888; 2,2,7,7- tetrakis(diphenylamino)spirobifluorene) Emitter 20 nm of the matrix material according to layer: Example 17, 18 or 19 in each case doped with 10% of E1 (synthe- sised in accordance with WO 04/085449) or E2 (synthesised in accordance with US 2003/0068526) OR: 20 nm of the matrix material according to Example 17, 18 or 19 in each case doped with 10% of the emitter in accordance with Example 22, 23 or 24 OR: as comparative example 20 nm CBP (vapour- deposited; CBP purchased from ALDRICH and purified further, finally sublimed twice; 4,4-bis(N-carbazolyl)biphenyl) (comparison standard), doped with 10% of E1 (synthe- sised in accordance with WO 04/085449) or E2 (synthesised in accordance with US 2003/0068526) Bathocuproin (BCP) 10 nm (vapour-deposited; BCP purchased from ABCR, used as supplied; 2,9-dimethyl- 4,7-diphenyl-1,10-phenanthroline); not used in all examples AlQ.sub.3 10 nm (vapour-deposited; AlQ.sub.3 purchased from SynTec; tris(quinolinolato)alumin- ium(III)), not used in all examples Ba/Al 3 nm Ba, 150 nm Al on top as cathode

(122) These OLEDs are characterised by standard methods; the electroluminescence spectra, the efficiency (measured in cd/A), the power efficiency (measured in lm/W) as a function of the brightness, calculated from current/voltage/brightness characteristic lines (IUL characteristic lines), and the lifetime are determined for this purpose. The lifetime is defined as the time after which the initial brightness of 1000 cd/m.sup.2 has dropped to half. For an overview, the triplet emitters used and the host materials used are shown below:

(123) ##STR00094##

(124) TABLE-US-00008 TABLE 4 Max. efficiency Max. power efficiency Lifetime (h) at Experiment EML HBL ETL (cd/A) (lm/W) x, y (CIE) 1000 cd/cm.sup.2 Example 56 CBP BCP AlQ.sub.3 25.0 12.2 0.33, 0.61 400 (comparison) E1 (10 nm) (10 nm) Example 57 Matrix acc. to Ex. 17 BCP AlQ.sub.3 32.2 26.7 0.32, 0.60 1050 E1 (10 nm) (10 nm) Example 58 Matrix acc. to Ex. 18 BCP AlQ.sub.3 43.0 36.5 0.32, 0.60 1200 E1 (10 nm) (10 nm) Example 59 Matrix acc. to Ex. 19 BCP AlQ.sub.3 33.9 17.4 0.31, 0.61 650 E1 (10 nm) (10 nm) Example 60 CBP BCP AlQ.sub.3 20.9 17.2 0.31, 0.63 900 (Comparison) Emitter acc. to Ex. 22 (10 nm) (10 nm) Example 61 Matrix acc. to Ex. 17 BCP AlQ.sub.3 34.8 28.8 0.30, 0.62 2200 Emitter acc. to Ex. 22 (10 nm) (10 nm) Example 62 Matrix acc. to Ex. 18 BCP AlQ.sub.3 47.2 36.8 0.30, 0.62 2600 Emitter acc. to Ex. 22 (10 nm) (10 nm) Example 63 Matrix acc. to Ex. 19 BCP AlQ.sub.3 35.0 19.1 0.30, 0.61 1750 Emitter acc. to Ex. 22 (10 nm) (10 nm) Example 64 Matrix acc. to Ex. 17 42.0 34.6 0.31, 0.62 2000 Emitter acc. to Ex. 22 Example 65 Matrix acc. to Ex. 18 56.4 46.8 0.31, 0.62 2100 Emitter acc. to Ex. 22 Example 66 Matrix acc. to Ex. 18 59.2 51.9 0.30, 0.61 1550 Emitter acc. to Ex. 22 Example 67 Matrix acc. to Ex. 18 45.2 33.2 0.38, 0.52 1550 Emitter acc. to Ex. 23 Example 68 CBP 6.5 4.8 0.68, 0.32 5000 (Comparison) E2 (extrapolated) Example 69 Matrix acc. to Ex. 17 7.7 6.7 0.69, 0.31 25000 E2 (extrapolated) Example 70 Matrix acc. to Ex. 18 8.1 7.6 0.68, 0.32 27000 E2 (extrapolated) Example 71 Matrix acc. to Ex. 19 7.2 5.4 0.68, 0.32 8000 E2 (extrapolated) Example 72 CBP 13.4 9.0 0.66, 0.34 11000 Emitter acc. to Ex. 24 (extrapolated) Example 73 Matrix acc. to Ex. 17 14.3 11.5 0.67, 0.33 32000 Emitter acc. to Ex. 24 (extrapolated) Example 74 Matrix acc. to Ex. 18 14.7 12.2 0.66, 0.34 27000 Emitter acc. to Ex. 24 (extrapolated) Example 75 Matrix acc. to Ex. 19 14.1 10.1 0.66, 0.34 15000 Emitter acc. to Ex. 24 (extrapolated)
Electroluminescence Spectra:

(125) The OLEDs, both from the comparative examples and also the OLEDs comprising the matrices and emitters according to the invention, exhibit comparable colour coordinates, where the emitters according to Examples 22, 23 and 24 according to the invention, which carry 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl groups, have somewhat hypsochromically shifted emission.

(126) Efficiency:

(127) OLEDs produced using the matrix materials according to Example 17, 18 or 19 according to the invention and comprising the emitters according to Examples 22, 23 and 24 exhibit both significantly better photometric efficiency and also better power efficiencies compared with the matrix material in accordance with the prior art. This applies, in particular, to the power efficiency, which is crucial from a technical point of view, due to the lower operating voltages on use of the matrix materials according to the invention.

(128) Lifetime:

(129) The lifetime achieved on use of the matrix materials 17, 18 and 19 according to the invention and emitters 22, 23 and 24 considerably exceeds that of the comparative examples comprising the matrix material CBP.

(130) Layer Simplification:

(131) As can be seen from Examples 64, 65 and 66, it is possible using the matrix materials according to the invention to produce OLEDs which comprise neither a hole-blocking layer nor an electron-conductor layer without thereby impairing the overall electro-optical property profile. This is a considerable advantage from a production point of view.

(132) Thermal Stability:

(133) The emitters according to Examples 22, 23 and 24 have significantly higher thermal stability compared with the compounds which are structural analogous, but are not substituted by boronic acid ester groups. This improved stability is of crucial importance, in particular on industrial use, since dopants in industrial use must have lifetimes of from several days to weeks at high temperatures.

Example 76

Production of OLEDs Comprising the Electron-Transport Materials According to Examples 17, 18 and 19

(134) OLEDs are produced by a general process in accordance with WO 04/058911, which is adapted in individual cases to the particular circumstances (for example layer-thickness variation in order to achieve optimum efficiency or colour).

(135) The results for various OLEDs are presented in Examples 77 to 79 below. The basic structure and the materials used (apart from the electron-transport layer) are identical in the examples for better comparability. OLEDs having the following structure are produced analogously to the above-mentioned general process:

(136) TABLE-US-00009 Hole-injection 20 nm PEDOT (spin-coated from water; from layer (HIL) H. C. Starck, Goslar, Germany; poly(3,4- ethylenedioxy-2,5-thiophene)) Hole-transport 30 nm 4,4,4-tris(N-1-naphthyl-N-phenyl- layer (HTL) amino)triphenylamine (abbreviated to NaphDATA, purchased from SynTec) Hole-transport 30 nm NPB (N-naphthyl-N-phenyl-4,4- layer (HTL) diaminobiphenyl) Emission 30 nm doped layer of 9,10-bis(1-naphthyl- layer (EML) anthracene) as host material (abbreviated to H), doped with 5% of tris[4-(2,2-diphenyl- vinyl)phenyl]amine as dopant (abbreviated to D1), vapour-deposited Electron 20 nm of the electron conductor according to conductor (ETC) Example 17 or 18 OR: as comparative example 20 nm AlQ.sub.3 (purchased from SynTec, tris(quinolinato)-aluminium(III)) Cathode 1 nm LiF, 150 nm Al on top

(137) These OLEDs are characterised by standard methods; the electroluminescence spectra, the efficiency (measured in cd/A), the power efficiency (measured in lm/W) as a function of the brightness, calculated from current/voltage/brightness characteristic lines (IUL characteristic lines), are determined for this purpose.

(138) Table 5 shows the results for some OLEDs (Examples 79 and 80) in which the electron-transport layer (ETL) consists of the compounds 17 or 18 according to the invention. The comparative material used in the comparative example is AlQ.sub.3 in accordance with the prior art.

(139) As can be seen from Examples 77 to 79 in Table 5, OLED devices comprising the electron-transport materials according to Examples 17 and 18 according to the invention exhibit a significantly lower operating voltage at 1000 cd/m.sup.2, which is evident from better power efficiencies.

(140) TABLE-US-00010 TABLE 5 Max. Voltage efficiency (V) at Example ETL (cd/A) 1000 cd/m.sup.2 CIE Example 77 AlQ.sub.3 7.9 6.6 x = 0.17; (comparison) y = 0.31 Example 78 ETL acc. to Ex. 17 8.0 5.1 x = 0.16; y = 0.31 Example 79 ETL acc. to Ex. 18 8.0 5.0 x = 0.16; y = 0.31

Example 80

Production of OLEDs Comprising the Emitter Materials According to Examples 20 and 21

(141) OLEDs are produced by a general process in accordance with WO 04/058911, which is adapted in individual cases to the particular circumstances (for example layer-thickness variation in order to achieve optimum efficiency or colour).

(142) The results for various OLEDs are presented in Examples 81 and 82 below. The basic structure and the materials used (apart from the electron-transport layer) are identical in the examples for better comparability. OLEDs having the following structure are produced analogously to the above-mentioned general process:

(143) TABLE-US-00011 Hole-injection 20 nm PEDOT (spin-coated from water; from layer (HIL) H. C. Starck, Goslar, Germany; poly(3,4- ethylenedioxy-2,5-thiophene)) Hole-transport 30 nm 4,4.sup.,4-tris(N-1-naphthyl-N-phenyl- layer (HTL) amino)triphenylamine (abbreviated to NaphDATA, purchased from SynTec) Hole-transport 30 nm NPB (N-naphthyl-N-phenyl-4,4- layer (HTL) diaminobiphenyl) Emission 30 nm doped layer of 9,10-bis(1-naphthyl- layer (EML) anthracene) as host material (abbreviated to H), doped with 5% of the emitter materials according to Example 20 or 21 Electron 20 nm AlQ.sub.3 (purchased from SynTec, tris- conductor (ETC) (quinolinato)aluminium(III)) Cathode 1 nm LiF, 150 nm Al on top

(144) These OLEDs are characterised by standard methods; the electroluminescence spectra, the efficiency (measured in cd/A), the power efficiency (measured in lm/W) as a function of the brightness, calculated from current/voltage/brightness characteristic lines (IUL characteristic lines), are determined for this purpose.

(145) Table 6 shows the results for some OLEDs (Examples 81 and 82) in which the emitter materials consist of compounds 20 and 21 according to the invention.

(146) As can be seen from Examples 81 and 82 in Table 6, OLED devices comprising the emitter materials according to Examples 20 and 21 according to the invention exhibit efficient green emission.

(147) TABLE-US-00012 TABLE 6 Max. Voltage efficiency (V) at Example EML (cd/A) 1000 cd/m.sup.2 CIE Example 81 Emitter acc. 21.0 5.1 x = 0.27; to Ex. 20 y = 0.62 Example 82 Emitter acc. 18.2 5.0 x = 0.24; to Ex. 21 y = 0.58

Example 83

Sublimation Temperatures

(148) In Table 7 below, the sublimation temperatures (at a pressure of 1?10.sup.?5 mbar) of some compounds which are described in the preceding examples are compared with the sublimation temperatures of compounds which have the same basic structure, but are not substituted by boronic acid esters. It can be seen from the examples given that the sublimation temperature of the corresponding boronic esters is in all cases lower than that of the unsubstituted compounds. This is a considerable industrial advantage since temperature-sensitive parts of the vapour-deposition apparatus, such as, for example, shadow masks, are thus only heated to a smaller extent.

(149) It is furthermore evident that some of the compounds which, as unsubstituted compound, exhibit decomposition during sublimation can be sublimed without decomposition if they are substituted by boronic acid ester groups. This is a considerable industrial advantage.

(150) TABLE-US-00013 TABLE 7 Compound T.sub.sublimation Comparison T.sub.sublimation from Example 6 270? C. stable 360? C. stable from Example 7 290? C. stable 360? C. stable from Example 14 300? C. stable 315? C. stable from Example 17 265? C. stable 290? C. stable from Example 18 310? C. stable 385? C. stable from Example 22 295? C. stable 00 340? C. little decomposition from Example 24 340? C. stable 01 385? C. strong decomposi- tion