Phenanthrene compounds for organic electronic devices

Abstract

The invention relates to specific phenanthrenes, the use of the compound in an electronic device, and an electronic device containing at least one of said compounds. The invention further relates to a method for producing the compound and a formulation and composition containing one or more of the compounds.

Claims

1. A compound of the general formula (1) ##STR00204## where the following applies to the symbols and indices occurring: X is on each occurrence, identically or differently, N and CR.sup.1, where a maximum of 2 of the X is optionally equal to N; L is a single bond or a divalent aryl or heteroaryl group having 12 to 40 ring atoms, which is optionally substituted by one or more radicals R.sup.2, where, if L is a single bond, the nitrogen is bonded directly to position 3 of the phenanthrene; Ar.sup.1 is selected from formulae (37)-(57): ##STR00205## ##STR00206## ##STR00207## Ar.sup.2 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, where the ring or ring system is optionally substituted by one or more radicals R.sup.4, where, if both Ar.sup.1 and also Ar.sup.2 are phenyl radicals, at least one R.sup.4 on the phenyl radicals is not equal to H and this at least one radical R.sup.4 optionally contains one or more aromatic or heteroaromatic rings; R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, NO.sub.2, P(═O)(R.sup.2).sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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.2 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C≡NR.sup.2, —C(O)O—, —C(═O)NR.sup.2—, P(═O)(R.sup.2), —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 ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, where two or more radicals R.sup.1 is optionally linked to one another and may form a ring; R.sup.4 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, NR.sup.2, NO.sub.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, 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.2 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.2C═CR.sup.2—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, P(═O)(R.sup.2), —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, CN or NO.sub.2, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, where two or more radicals R.sup.4 is optionally linked to one another and may form a ring; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R.sup.3, CN, Si(R.sup.3).sub.3, NO.sub.2, P(═O)(R.sup.3).sub.2, S(═O)R.sup.3, S(═O).sub.2R.sup.3, 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.3 and where one or more CH.sub.2 groups in the above-mentioned groups is optionally replaced by —R.sup.3C═CR.sup.3—, Si(R.sup.3).sub.2, CO, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, P(═O)(R.sup.3), —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.3, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, where two or more radicals R.sup.2 is optionally linked to one another and optionally form a ring; R.sup.3 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; two or more substituents R.sup.3 here is optionally linked to one another and optionally form a ring; where the compound of the formula (1), besides the phenanthrene, contains no further condensed aromatic or heteroaromatic ring having more than 10 ring atoms and where the radicals R.sup.1 on the phenanthrene in formula (1) contain no further amine groups.

2. The compound according to claim 1, wherein the compound is of the general formula ##STR00208## where the definitions from claim 1 apply to the symbols used.

3. The compound according to claim 1, wherein L is an aromatic ring system selected from the group consisting of biphenylenes, terphenylenes and the compounds of the formula (101a) and (101b), ##STR00209## where Y is equal to C(R.sup.2).sub.2, NR.sup.2, O, Si(R.sup.2).sub.2 or S.

4. The compound according to claim 3, wherein Y is C(R.sup.2).sub.2 or NR.sup.2.

5. The compound according to claim 1, wherein L is a single bond, so that the amine group is bonded directly to the phenanthrene.

6. The compound according to claim 1, wherein the compound contains in total at least 26 ring atoms.

7. The compound according to claim 1, wherein the compound contains only one amine group.

8. A process for the preparation of the compound according to claim 1 which comprises a one-step Buchwald coupling by reaction of a phenanthrene derivative which contains a leaving group with Ar.sup.2—NH—Ar.sup.1.

9. A process for the preparation of the compound according to claim 1 which comprises a two-step Buchwald coupling by stepwise reaction of a phenanthrene derivative which contains a leaving group with (1) Ar.sup.2—NH.sub.2 and (2) NH.sub.2—Ar.sup.1.

10. An oligomer, polymer or dendrimer containing one or more claim 1 compounds according to claim 1, where the bond(s) to the polymer, oligomer or dendrimer is optionally localised at any desired positions in formula (1) which are substituted by R.sup.1, R.sup.4 or R.sup.2.

11. A composition comprising one or more compound according to claim 1 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.

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

13. An electronic device comprising at least one compound according to claim 1.

14. The electronic device according to claim 13, wherein the device is selected from 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).

15. An electronic device which is selected from the group of organic electroluminescent devices, which comprises the compound according to claim 1 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, as exciton-blocking material.

16. The compound according to claim 1, wherein the compound is of the formula ##STR00210## wherein L, Ar.sup.1, Ar.sup.2, and R.sup.1 are defined in claim 1.

17. The compound according to claim 1, wherein the compound is of the formula ##STR00211## wherein L, Ar.sup.1 and Ar.sup.2 are defined in claim 1.

Description

EXAMPLES

(1) Materials

(2) ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104##

(3) Materials HIL1, 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 (1-9), (1-1), (1-11), (1-12), (2-6) (1-2) and (4-1) are according to the invention.

Example 1

Synthesis of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)phenanthren-3-ylamine (1-1)

(4) ##STR00105##

Synthesis of Starting Material 3-bromophenanthrene

(5) ##STR00106##

Synthesis of 3-aminophenanthrene

(6) 50 g (227 mmol) of 3-acetyiphenenthrene and 63.8 ml of pyridine (790 mmol) and 42 g (592 mmol) of hydroxylammonium chloride are dissolved in 300 ml of EtOH. The batch is heated to 75° C. After reaction for 1 h, the batch is cooled. The mixture is subsequently partitioned between ethyl acetate and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated in a rotary evaporator. 300 ml of polyphosphoric acid are carefully added to the concentrated solution, and the mixture is heated at 75° C. for 1 h. The batch is then cooled to room temperature, and carefully poured with ice-water (300 ml). The precipitated solid is filtered off with suction and rinsed with methanol. Finally, 800 ml of MeOH and 70 ml of conc. HCl are added to the solid. The reaction mixture is heated at the boil for 8 h. The mixture is subsequently neutralised using sodium hydroxide solutions, partitioned between etyl acetate and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. The residue was dried at 40° C. in vacuo. Yield 35.5 g (184 mmol) (81% of theory)

Synthesis of 3-bromophenanthrene

(7) 30 g (155 mmol) of 3-aminophenanthrene and 36.7 g of CuBr.sub.2 (155 mmol) are dissolved in 300 ml of dried acetonitrile. 40.4 ml of tert-butyl nitrite (535 mmol) are added in portions at 0° C. The suspension is stirred for a further 1 h and then poured onto 400 ml of ice-water and stirred for about 20 min. The precipitated solid is filtered off with suction, dissolved in dichloromethane and washed a number of times with water. The organic phase is evaporated in a rotary evaporator and recrystallised from toluene/heptane. Yield: 21.9 g (85 mmol) (55% of theory)

(8) Other halogenated phenanthrenes as starting compounds can be prepared analogously.

(9) TABLE-US-00001 Starting material 1 Starting material 2 Product Yield 07 CuI.sub.2 08 45% 09 CuCl.sub.2 0 50%

Synthesis of Compound (1-1)

(10) 28.1 g (78 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amines, 20.0 g (78 mol) of 3-bromophenanthrenes are dissolved in 600 ml of toluene: The solution is degassed and saturated with N.sub.2. 3.1 ml (3.11 mmol) of a tri-tert-butylphosphine solution and 0.35 g (1.56 mmol) of palladium(II) acetate are then added, and 11.6 g of sodium tert-butoxide (116.7 mmol) are subsequently added. The reaction mixture is heated at the boil under a protective atmosphere for 5 h. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum, purity is 99.9% (HPLC). The yield of compound (1-1) is 29.6 g (71% of theory).

Examples 2-12

Synthesis of Compounds (1-2) to (1-12)

(11) The following compounds (1-2) to (1-12) are also prepared analogously to the synthesis of compound (1-1) described in Example 1.

(12) TABLE-US-00002 Starting material Starting material 1 2 Product Yield 1-2  78% 1-3  82% 1-4  88% 1-5  0 67% 1-6  76% 1-7  80% 1-8  0 75% 1-9  70% 1-10 67% 1-11 0 72% 1-12 65%

(13) The following comparative compounds (HTMV1) to (HTMV3) and (HTMV6) to (HTMV7) are also prepared analogously to the synthesis of compound (1-1) described in Example 1.

(14) TABLE-US-00003 Starting Starting material 1 material 2 Product HTMV1 HTMV2 HTMV3 0   (2 eq.) HTMV6 HTMV7

Examples 13

Synthesis of the compound N*4′*-biphenyl-4-yl-N*4′*-dibenzofuran-4-yl-N*4*-phenanthren-3-yl-N*4*-phenylbiphenyl-4,4′-diamine (2-1)

(15) ##STR00159##

(16) 10 g of phenanthren-3-ylphenylamines (37 mmol), 21 g. of biphenyl-4-yl-(4′-bromobiphenyl-4-yl)dibenzofuran-4-ylamines (37 mol) are dissolved in 500 ml of toluene: The solution is degassed and saturated with N.sub.2. 1.5 ml (1.5 mmol) of a tri-tert-butylphosphine solution and 0.17 g (0.74 mmol) of palladium(II) acetate are then added, and 5.6 g of sodium tert-butoxide (56 mmol) are subsequently added. The reaction mixture is heated at the boil under a protective atmosphere for 3 h. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum, purity is 99.9% (HPLC). The yield is 16.8 g (60% of theory).

Examples 14-18

Synthesis of Compounds (2-2) to (2-6)

(17) The following compounds (2-2) to (2-6) are also prepared analogously to the synthesis of compound (2-1) described in Example 13.

(18) TABLE-US-00004 Starting Starting material 1 material 2 Product Yield 2-2 0 55% 2-3 62% 2-4 65% 2-5 0 65% 2-6 60%

(19) The comparative compound (HTMV5) is also prepared analogously to the synthesis of compound (2-1) described in Example 13.

(20) TABLE-US-00005 Starting Starting material 1 material 2 Product HTMV5   (2 eq)

Examples 19

Synthesis of the compound biphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenanthren-3-yl-9H-fluoren-2-yl)amine (3-1)

(21) ##STR00178##

3-(7-Bromo-9,9-dimethyl-9H-1-fluoren-2-yl)phenanthrene

(22) 52 g (164 mmol) of 7-bromo(9,9-dimethyllfluoren-2-yl)boronic acid (CAS No.: 1213768-48-9), 50 g (164 mmol) of 3-iodophenanthrene and 205 ml of a 2 M NaHCO.sub.3 aqueous solution (327 mmol) are suspended in 800 ml of dimethoxyethane. 3.8 g (3.3 mmol) of tetrakis(triphenyl)phosphinepalladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 300 ml of water and subsequently evaporated to dryness. Filtration of the crude product through silica gel with heptane/ethyl acetate (20:1) gave 55 g (75%) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)phenanthrenes.

Biphenyl-4-ylbiphenyl-2-yl-(9,9-dimethyl-7-phenanthren-3-yl-9H-fluoren-2-yl)amines

(23) 19.2 g of biphenyl-4-biphenyl-2-ylamine (60 mmol), 26.9 g of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)phenanthrenes (60 mol) are dissolved in 500 ml of toluene: The solution is degassed and saturated with N.sub.2. 3.2 g (3.9 mmol) of a tri-tert-butylphosphine solution and 0.27 g (1.2 mmol) of palladium(II) acetate are then added, and 8.9 g of sodium tert-butoxide (90 mmol) are subsequently added. The reaction mixture is heated at the boil under a protective atmosphere for 4 h. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum, purity is 99.9%. The yield is 28 g (68% of theory.

Examples 20-22

Synthesis of Compounds (3-2) to (3-4)

(24) The starting compounds are prepared analogously to the synthesis described in Example 18.

(25) TABLE-US-00006 Starting Starting material 1 material 2 Product Yield 0   CAS No.: 1177264-88-8 78%   CAS No.: 1030620-82-6 70%

(26) Compounds (3-2) to (3-4) are prepared analogously to the synthesis of compound (3-1) described in Example 19.

(27) TABLE-US-00007 Starting material Starting material 1 2 Product Yield 3-2 65% 3-3 0 75% 3-4 78%

(28) The comparative compound (V4) is also prepared analogously to the synthesis of compound (3-1) described in Example 19.

(29) TABLE-US-00008 Starting Starting material 1 material 2 Product HTMV4

Examples 23-25

Synthesis of the compounds (9,9-dimethyl-9H-fluoren-2-yl)-(9,9-diphenyl-9H-fluoren-4-yl)phenanthren-3-ylamine (4-1), (4-2 and (4-3)

(30) ##STR00197##

(9,9-Dimethyl-9H-fluoren-2-yl)phenanthren-3-ylamine

(31) 18.4 g (95.29 mmol) of 3-aminophenanthrene, 26 g (95.4 mmol) of 2-bromofluorene and 18.3 g (190 mmol) of sodium tert-butoxide are suspended in 350 ml of toluene. 1.07 g (4.76 mmol) of palladium acetate and 2.64 g of 1,1-bis(diphenylphosphino)ferrocene (4.76 mmol) are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene (31 g, 85% yield).

(9,9-Dimethyl-9H-fluoren-2-yl)-(9,9-diphenyl-9H-fluoren-4-yl)phenanthren-3-ylamine (4-1)

(32) 13.1 g of (9,9-dimethyl-9H-fluoren-2-yl)phenanthren-3-ylamine (34 mmol), 13.5 g of 4-bromo-9,9-diphenyl-9H-fluorene (34 mol) are dissolved in 300 ml of toluene: The solution is degassed and saturated with N.sub.2. 1.4 ml (0.68 mmol) of a 1 M tri-tert-butylphosphine solution and 0.153 g (0.68 mmol) of palladium(II) acetate are then added, and 6.5 g of sodium tert-butoxide (68 mmol) are subsequently added. The reaction mixture is heated at the boil under a protective atmosphere for 4 h. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and evaporated in a rotary evaporator. After filtration of the crude product through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum, purity is 99.9%. The yield is 14.3 g (60% of theory).

(33) The following compounds are prepared analogously:

(34) TABLE-US-00009 Starting Starting material 1 material 2 Product Yield 4-2   2 eq 00 65% 4-3 01 02   2 eq 03 58%

Example 26

(35) Characterisation of the Compounds

(36) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials etc.).

(37) The data of various OLEDs are shown in the following examples (see Tables 1 and 2). The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs have in principle the following layer structure: substrate/hole-injection layer (HIL1)/hole-transport layer (HIL2)/hole-injection layer (HIL3)/electron-blocking layer (EBL)/emission layer (EML)/electron-transport layer (ETL)/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 revealed by Table 1. The materials required for the production of the OLEDs are shown above.

(38) 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), which is admixed with the matrix material or matrix materials 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.

(39) 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 Im/W) 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 term 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/m2 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 of the various OLEDs are summarised in Table 2.

(40) Use of Compounds According to the Invention as Matrix Materials in Fluorescent OLEDs

(41) 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 mixed component as HIL, HTL, EBL or within the EML.

(42) Compared with NPB reference components (V1), all samples comprising the compounds according to the invention exhibit both higher efficiencies and also significantly improved lifetimes in singlet blue.

(43) Compared with the reference material HTMV1-HTMV5 (V2-V6), the compound (1-9), (1-1) and (1-11) according to the invention have better efficiencies and improved lifetimes. Compared with HTMV6 and HTMV7 (V7 and V8), the compound (1-1) according to the invention has a significantly improved lifetime.

(44) TABLE-US-00010 TABLE 1 Structure of the OLEDs IL (5 nm HIL1)/HTL (150 nm HIL2)/IL(5 nm HIL1)/EBL/EML/ETL EBL EML ETL Ex. Thickness/nm Thickness/nm Thickness/nm V1 NPB H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V2 HTMV1 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V3 HTMV2 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V4 HTMV3 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V5 HTMV4 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V6 HTMV5 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V7 HTMV6 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm V8 HTMV7 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E0 HTMV8 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E1 (1-9) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E2 (1-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E3  (1-11) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E4  (1-12) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E5 (2-6) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E6 (1-2) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm E7 (4-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 20 nm 20 nm 30 nm

(45) TABLE-US-00011 TABLE 2 Data of the OLEDs EQE LT80 @ 1000 @ 6000 cd/M2 cd/m.sup.2 CIE Ex. % [h] x y V1 4.8 70 0.14 0.17 V2 6.4 20 0.13 0.16 V3 5.4 25 0.13 0.15 V4 6.6 65 0.13 0.15 V5 5.6 80 0.13 0.15 V6 5.0 60 0.13 0.16 V7 6.8 100 0.14 0.14 V8 6.9 110 0.14 0.15 E0 6.8 115 0.13 0.16 E1 6.7 125 0.13 0.15 E2 7.0 155 0.13 0.15 E3 6.9 135 0.13 0.15 E4 6.8 120 0.13 0.15 E5 5.0 80 0.13 0.16 E6 7.1 125 0.13 0.15 E7 7.1 120 0.13 0.15

(46) Example E0 exhibits a significantly improved LT50 value compared with Comparative Examples V1 to V8. Further, significant improvements compared both with the comparative examples and also compared with E0 can be achieved by the phenanthrene, apart from position 3, having no further aromatic and/or heteroaromatic substitution (E1 to E7), Compound (2-6) (E5) can be compared directly with NPB (V1). It can be seen that compound (2-6) results in devices having significantly improved EQE values and in particular in improved LT80 values.