Derivatives of 2-diarylaminofluorene and organic electronic compounds containing them

Abstract

The present invention relates to certain fluorenes, to the use of the compounds in an electronic device, and to an electronic device comprising at least one of these compounds. The present invention furthermore relates to a process for the preparation of the compounds and to a formulation and composition comprising one or more of the compounds.

Claims

1. An electroluminescent device comprising at least one compound of the general formula (1) ##STR00228## where the following applies to the symbols and indices occurring: Ar.sup.1 and Ar.sup.2 are on each occurrence, identically or differently, an aromatic group having two or more aromatic rings and having 10 to 60 aromatic ring atoms in said aromatic group, which is optionally substituted by one or more radicals R4, which are identical to or different from one another, R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, NO.sub.2, P(═O)(R.sup.5).sub.2, S(═O)R.sup.5, S(═O).sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.5 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═S, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, or a condensed ring system having 9 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, where, in the case of aromatic or heteroaromatic condensed rings, not more than 10 ring atoms is optionally present; the two radicals R.sup.1 may also form a ring closure with one another, so that a spiro compound forms, where no aromatic or heteroaromatic rings are condensed onto the ring formed by the two radicals R.sup.1; R.sup.2, R.sup.3 and R.sup.4 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, NO.sub.2, P(═O)(R.sup.5).sub.2, S(═O)R.sup.5, S(═O).sub.2R.sup.5, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.5 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═S, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5; R.sup.5 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, NO.sub.2, P(═O)(R.sup.6).sub.2, S(═O)R.sup.6, S(═O).sub.2R.sup.6, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.6 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═S, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.6, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6; R.sup.6 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D or F; n is 0, 1, 2, 3 or 4; m is 0, 1, 2 or 3; with the proviso that the compound of the formula (1), besides the one fluorene group and besides the possible condensed or polycyclic groups in position 9 of the fluorene, contains no further polycyclic or condensed groups.

2. The device according to claim 1, wherein the two radicals R.sup.1 in the compound of the formula (1) are identical.

3. The device according to claim 1, wherein m is equal to 1 and n is equal to 0, 1 or 2.

4. The device according to claim 1, wherein it comprises at least one compound of the general formula (2) ##STR00229## where the definitions from claim 1 apply to the symbols.

5. The device according to claim 1, wherein R.sup.3 is equal to H.

6. The device according to claim 2, wherein Ar.sup.1 and Ar.sup.2 are identical or different and are selected from a biphenyl, terphenyl or quaterphenyl group, each of which is optionally substituted by one or more radicals R.sup.4.

7. The device according to claim 1, wherein the two radicals R.sup.1 are identical and are selected from an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, or a condensed ring system having 9 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, where, in the case of aromatic or heteroaromatic condensed rings, not more than 10 ring atoms is optionally present and where R.sup.2 is equal to H.

8. The device according to claim 1, wherein the two radicals R.sup.1 are identical and are selected from a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the groups may each be substituted by one or more radicals R.sup.5 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2 and where R.sup.2 is an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5.

9. The device according to claim 1, wherein it is an organic light-emitting transistor (OLET), an organic field-quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEC or LEEC), an organic laser diode (O-laser) or an organic light-emitting diode (OLED).

10. The device according to claim 1, wherein the device is an organic light-emitting diode (OLED), wherein the compound is employed in one of the following functions: as hole-transport material in a hole-transport or hole-injection layer, as matrix material in an emitting layer, as electron-blocking material or as exciton-blocking material.

11. A compound of the general formula (167) ##STR00230## where the following applies to the symbols used in formula (167): Ar.sup.3 and Ar.sup.4 are on each occurrence, identically or differently, an aromatic group having two or more aromatic rings and having 10 to 60 ring atoms in said aromatic group, which is optionally substituted by one or more radicals R5, which are identical to or different from one another; R.sup.7 is identical on each occurrence and is selected from the group consisting of a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.5 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, where R.sup.5 is defined as indicated above, or a condensed ring system having 9 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, where, in the case of aromatic or heteroaromatic condensed rings, not more than 10 ring atoms is optionally present in the condensed ring system; the two radicals R.sup.7 may also form a ring closure with one another, so that a spiro compound forms, where no aromatic or heteroaromatic rings are condensed onto the ring formed by the two radicals R.sup.7, and where, if R.sup.7 is a straight-chain or branched alkyl group, R.sup.8 is an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, and where R.sup.5 is defined as indicated above; R.sup.8 is H, D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, where R.sup.5 is defined as indicated above and where, if R.sup.8 is equal to H, R.sup.7 is an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.5, where R.sup.5 is defined as indicated above; a is either 1, 2, 3 or 4; with the proviso that the compound of the formula (167), besides the one fluorene group and besides the possible condensed or polycyclic groups in position 9 of the fluorene, contains no further polycyclic or condensed groups and with the proviso that the compound contains no halogens.

12. The compound according to claim 11, wherein the compound has the general formula (168) ##STR00231## where, for the symbols used, Ar.sup.3 and Ar.sup.4 are identical or different on each occurrence and are selected from a biphenyl, terphenyl or quaterphenyl group, which is optionally substituted by one or more radicals R.sup.5; R.sup.7 is identical on each occurrence and is selected from an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, where R.sup.5 is defined as indicated above, or a condensed ring system having 9 to 30 ring atoms, which may in each case be substituted by one or more radicals R.sup.5, where, in the case of aromatic or heteroaromatic condensed rings, not more than 10 ring atoms is optionally present in the condensed ring system.

13. The compound according to claim 11, wherein the compound has the general formula (169) ##STR00232## where, for the symbols used, X is, identically or differently on each occurrence, N or CR.sup.5, preferably X is equal to CR.sup.5; Ar.sup.3 and Ar.sup.4 are identical or different on each occurrence and are selected from a biphenyl, terphenyl and quaterphenyl group, each of which is optionally substituted by one or more radicals R.sup.5; and R.sup.5 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, NO.sub.2, P(═O)(R.sup.6).sub.2, S(═O)R.sup.6, S(═O).sub.2R.sup.6, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.6 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═S, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.6, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.6; R.sup.6 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D or F.

14. A process for the preparation of the compound according to claim 11 by means of one-step Buchwald coupling by reacting a fluorene derivative containing a leaving group with Ar.sup.3—NH—Ar.sup.4.

15. A process for the preparation of the compound according to claim 11 by means of two-step Buchwald coupling by stepwise reacting a phenanthrene derivative containing a leaving group with (1) Ar.sup.3—NH.sub.2 and (2) NH.sub.2—Ar.sup.4.

16. An oligomer, polymer or dendrimer containing one or more compounds according to claim 11, where the bond(s) to the polymer, oligomer or dendrimer is optionally localised at any positions.

17. A composition comprising one or more compounds according to claim 11 and at least one further organically functional material 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-blocking materials and hole-blocking materials.

18. A formulation comprising at least one compound according to claim 11 and at least one solvent.

19. An electronic device comprising at least one compound according to claim 11.

20. The electronic device according to claim 19, wherein the device is selected from the group consisting of organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

21. An organic electroluminescent device which comprises the compound according to claim 11 is employed in one or more of the following functions: as hole-transport material in a hole-transport or hole-injection layer, as matrix material in an emitting layer, as electron-blocking material or as exciton-blocking material.

22. The device according to claim 1, wherein Ar.sup.1 and Ar.sup.2 are selected from the group consisting of radicals having the formulae (5) to (30) ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237##

Description

EXAMPLES

Materials

(1) ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109##

(2) Materials HU, HIL2 (EP 0676461), H1 (WO 2008/145239), ETM1 (WO 2005/053055), SEB1 (WO 2008/006449), LiQ and NPB are well known to the person skilled in the art. Their properties and syntheses are known from the prior art. Compounds (3-3), (3-1), (2-1) and (2-2) and (2-7) are in accordance with the invention.

Example 1

Synthesis of the compound biphenyl-2-ylbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (1-1) and compounds (1-2) to (1-5)

(3) ##STR00110##

(4) 23.5 g of biphenyl-2-ylbiphenyl-4-ylamine (73 mmol) and 20.0 g of 2-bromofluorene (73 mmol) are dissolved in 500 ml of toluene: the solution is degassed and saturated with N.sub.2. 2.52 g (2.93 mmol) of tri-tert-butylphosphine and 0.33 g (1.46 mmol) of palladium(II) acetate are then added. 10.8 g of sodium tert-butoxide (110 mmol) are subsequently added. The reaction mixture is heated at the boil for 6 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After the crude product has been filtered through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 32.0 g (85% of theory).

(5) The following compounds (1-2) to (1-5) are prepared analogously:

(6) TABLE-US-00001 Starting material 1 Starting material 2 Product Yield 78% 92% 88% 0 77%

Example 2

Synthesis of the compound biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (2-1) and compounds (2-2) to (2-10)

(7) ##STR00123##

2-Bromo-9,9-diphenyl-9H-fluorene (2-1)

(8) 30 g (103 mmol) of methyl 4′-bromobiphenyl-2-carboxylate are dissolved in 500 ml of dried THE in a flask which has been dried by heating. The clear solution is cooled to −10° C., and 102 ml (307 mmol) of a freshly prepared 3 M 2-phenylmagnesium bromide solution are then added. The reaction mixture is slowly warmed to room temperature and then quenched using NH.sub.4Cl (500 ml).

(9) The mixture is subsequently partitioned between ethyl acetate and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. 400 ml of acetic acid are carefully added to the residue. 80 ml of fuming HCl are subsequently added. The batch is heated to 75° C. and kept at this temperature for 5 h. A white solid precipitates out during this time. The batch is then cooled to room temperature, and the precipitated solid is filtered off with suction and rinsed with methanol. The residue is dried at 40° C. in vacuo. The yield is 29.4 g (74 mmol) (72% of theory).

(10) The following brominated compounds are prepared analogously:

(11) TABLE-US-00002 Starting material 1 Starting material 2 Product Yield 65% 70% 0 72% 80%

Biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (2-1)

(12) 17 g of biphenyl-2-ylbiphenyl-4-ylamine (53 mmol) and 21 g of 2-bromo-9,9-diphenyl-9H-fluorene (53 mmol) are dissolved in 350 ml of toluene: the solution is degassed and saturated with N.sub.2. 2.1 ml (2.1 mmol) of a 1 M solution of tri-tert-butylphosphine and 0.24 g (1.06 mmol) of palladium(II) acetate are then added, and 12.7 g of sodium tert-butoxide (132 mmol) are subsequently added. The reaction mixture is heated at the boil for 5 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After the crude product has been filtered through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 25 g (74% of theory).

(13) The following compounds (2-2) to (2-10) can be prepared analogously.

(14) TABLE-US-00003 Starting material 1 Starting material 2 Product Yield 72% 0 78% 81% 75% 0 75% 77% 65% 62% 0 70%

Example 3

Synthesis of the compound biphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)amine (3-1) and compounds (3-2) to (3-8)

(15) ##STR00163##

9,9-Dimethyl-7-phenyl-9H-fluorene

(16) 8.9 g (73 mmol) of benzeneboronic acid and 20 g (73 mmol) of 2-bromo-9,9′-dimethyl-9H-fluorene are suspended in 330 ml of dimethoxyethane and 110 ml of 2 M Na.sub.2CO.sub.3 solution. 2.54 g (2.0 mmol) of tetrakis(triphenyl-phosphine)palladium are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the reaction mixture is diluted with ethyl acetate, and the organic phase is separated off, washed three times with 100 ml of water and subsequently evaporated to dryness. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gives 18.8 g (95%) of 9,9-dimethyl-7-phenyl-9H-fluorene.

(17) The following fluorenes are prepared analogously.

(18) TABLE-US-00004 Starting Starting material 1 material 2 Product Yield 90% 93% 0 88% 95% 80%

2-Bromo-9,9-dimethyl-7-phenyl-9H-fluorene

(19) 29.0 g (107 mmol) of 9,9-dimethyl-2-phenyl-9H-fluorene are dissolved in 250 ml of CHCl.sub.3, and 17.2 g (107 mmol) of bromine, dissolved in 50 ml of CHCl.sub.3, are slowly added at −10° C. When the reaction is complete, water is added, and the organic phase is separated off, dried and evaporated. The crude product is subsequently washed a number of times by stirring with hot MeOH/heptane (1:1). The yield is 33.3 g (89% of theory) of the product as a white solid.

(20) The following brominated compounds are prepared analogously.

(21) TABLE-US-00005 Starting material 1 Product Yield 0 80% 75% 72% 65% 80%

Biphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)amine (3-1)

(22) 19.9 g of biphenyl-2-ylbiphenyl-4-ylamine (62 mmol) and 21.6 g of 2-bromo-9,9-dimethyl-7-phenyl-9H-fluorene (62 mmol) are dissolved in 400 ml of toluene. The solution is degassed and saturated with N.sub.2. 3 ml (3 mmol) of a 1 M tri-tert-butylphosphine solution and 0.57 g (2 mmol) of palladium(II) acetate are then added. 14.9 g of sodium tert-butoxide (155 mmol) are subsequently added. The reaction mixture is heated at the boil for 5 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After the crude product has been filtered through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 29.7 g (82% of theory).

(23) Compounds (3-2) to (3-8) are prepared analogously.

(24) TABLE-US-00006 Starting material 1 Starting material 2 Product Yield 0 77% 87% 84% 00 75% 01 02 03 82% 04 05 06 85% 07 08 09 76%

Example 4

Synthesis of Comparative Compounds HTMV1 to HTMV6

(25) The following comparative compounds (HTMV1) to (HTMV6) are also prepared analogously to the synthesis of compound (3-1) described in Example 3.

(26) TABLE-US-00007 Starting material 1 Starting material 2 Product 0 0

Example 5

Characterisation of the Compounds

(27) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 04/058911, which is adapted to the circumstances described here (layer-thickness variation, materials).

(28) The data for various OLEDs are presented in the following examples (see Tables 1, 3 and 2, 4). The substrates used are glass plates which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs basically have the following layer structure: substrate/optional hole-injection layer (HIL1)/hole-transport layer (HTL)/hole-injection layer (HIL2)/electron-blocking layer (EBL)/emission layer (EML)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs is shown in Tables 1 and 3. The materials required for the production of the OLEDs are indicated above.

(29) All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter) with which the matrix material or matrix materials is (are) admixed in a certain proportion by volume by co-evaporation. An expression such as H1:SEB1 (95%:5%) here means that material H1 is present in the layer in a proportion by volume of 95% and SEB1 is present in the layer in a proportion of 5%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(30) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/IN) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics, and the lifetime are determined. The electroluminescence spectra are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The expression EQE @ 1000 cd/m.sup.2 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. LT80 @ 6000 cd/m.sup.2 is the lifetime by which the OLED has dropped from a luminance of 6000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4800 cd/m.sup.2. The data for the various OLEDs are summarised in Tables 2 and 4.

(31) Use of Compounds According to the Invention as Hole-Transport Materials in Fluorescent and Phosphorescent OLEDs

(32) The compounds according to the invention are particularly suitable as HIL, HTL or EBL in OLEDs. They are suitable as a single layer, but also as a mixed component as HIL, HTL, EBL or within the EML.

(33) Compared with NPB reference components (V1, V8), the samples comprising the compounds according to the invention, besides higher efficiencies, also exhibit significantly improved lifetimes both for singlet blue and for triplet green.

(34) Compared with reference materials HTMV1 HTMV6 (V2-V10), the compounds according to the invention have the same or better efficiencies and improved lifetimes.

(35) TABLE-US-00008 TABLE 1 Structure of the OLEDs Layer structure: substrate/HIL1/HTL/HIL2/EBL/EML/ETL/EIL 1 nm LiQ/cathode HIL1 HTL HIL2 EBL EML ETL Ex. Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm V1 HIL1 HIL2 HIL1 NPB H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V2 HIL1 HIL2 HIL1 HTMV1 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V3 HIL1 HIL2 HIL1 HTMV2 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V4 HIL1 HIL2 HIL1 HTMV3 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V5 HIL1 HIL2 HIL1 HTMV4 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V6 HIL1 HIL2 HIL1 HTMV5 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V7 HIL1 HIL2 HIL1 HTMV6 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E1 HIL1 HIL2 HIL1 (3-3) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E2 HIL1 HIL2 HIL1 (3-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E3 HIL1 HIL2 HIL1 (2-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E4 HIL1 HIL2 HIL1 (2-2) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E5 HIL1 HIL2 HIL1 (2-7) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm

(36) TABLE-US-00009 TABLE 2 Data for the OLEDs EQE LT80 @ 1000 @ 6000 cd/m.sup.2 cd/m.sup.2 CIE Ex. % [h] x y V1 4.8 70 0.14 0.17 V2 6.9 120 0.13 0.14 V3 7.0 115 0.13 0.15 V4 6.8 105 0.13 0.15 V5 6.6 105 0.13 0.15 V6 6.6 120 0.13 0.14 V7 7.3 15 0.14 0.15 E1 7.2 140 0.13 0.15 E2 7.0 135 0.13 0.14 E3 6.6 150 0.13 0.15 E4 6.4 145 0.13 0.15 E5 6.6 155 0.13 0.15

(37) TABLE-US-00010 TABLE 3 Structure of the OLEDs Layer structure: substrate/HTL/HIL2/EBL/EML/ETL/cathode HTL HIL2 EBL EML ETL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm V8  HIL2 HIL1 NPB H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V9  HIL2 HIL1 HTMV5 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V10 HIL2 HIL1 HTMV6 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E6  HIL2 HIL1 (2-1) H2(88%);Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E7  HIL2 HIL1 (2-2) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E8  HIL2 HIL1 (2-7) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm

(38) TABLE-US-00011 TABLE 4 Data for the OLEDs LT80 Efficiency @ 8000 @ 1000 cd/m.sup.2 cd/m.sup.2 CIE Ex. % [h] x y V8  13.4 85 0.32 0.63 V9  17.0 155 0.37 0.61 V10 18.1 65 0.37 0.61 E6  17.6 195 0.37 0.61 E7  17.1 185 0.37 0.61 E8  17.5 200 0.37 0.61