Formulations and electronic devices

Abstract

A formulation comprising at least one solvent and at least two different functional compounds of formula (I)
AB].sub.k(I) wherein A is a functional structural element, the structural element serving as host material, as a unit that has hole-injection and/or hole-transport properties, as a unit t at has electron-injection and/or electron-transport properties, as a unit which has light-emitting properties, or as a unit which improves the transfer from the singlet state to the triplet state of light-emitting compounds; B is a solubility-promoting structural element; and k is an integer in the range from 1 to 20; the molecular weight of the functional compound is at least 550 g/mol, and the solubility-promoting structural element B conforms to the general formula (L-I) ##STR00001##

Claims

1. A formulation comprising at least one solvent and at least two different functional compounds of formula (I)
AB].sub.k(I) wherein A is a functional structural element, the structural element serving as a host material, as a unit that has hole-injection and/or hole-transport properties, as a unit that has electron-injection and/or electron-transport properties, as a unit which has light-emitting properties, or as a unit which improves the transfer from the singlet state to the triplet state of light-emitting compounds; B is a solubility-promoting structural element; and k is an integer in the range from 1 to 20; the molecular weight of the functional compound is at least 550 g/mol, and the solubility-promoting structural element B conforms to the general formula (L-I) ##STR00125## wherein Ar.sup.1 and Ar.sup.2 are each, independently of one another, an optionally substituted aryl or heteroaryl group; X is, in each case, independently of one another, N or CR.sup.2; with the proviso that in each case at least one X is N; R.sup.1 and R.sup.2 are each, independently of one another, hydrogen, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or is a silyl group or a substituted keto group having 1 to 40 C atoms, an alkoxycarbonyl group having 2 to 40 C atoms, an aryloxycarbonyl group having 7 to 40 C atoms, a cyano group CN, a carbamoyl group C(O)NH.sub.2, a haloformyl group C(O)X, wherein X is a halogen atom, a formyl group C(O)H, an isocyano group, an isocyanate group, a thiocyanate group or a thioisocyanate group, a hydroxyl group, a nitro group, a CF.sub.3 group, Cl, Br, F, a crosslinkable group or an optionally substituted aromatic or heteroaromatic ring system having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems, wherein one or more of the groups R.sup.1 and/or R.sup.2 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another and/or with the ring to which the group R.sup.1 is bonded; and l is 0, 1, 2, 3 or 4; the dashed bond indicates the bond to the functional structural element A.

2. The formulation of claim 1, wherein the functional structural element A in formula (I) serves as host material.

3. The formulation of claim 1, wherein the functional structural element A in formula (I) is a unit that has hole-injection and/or hole-transport properties.

4. The formulation of claim 1, wherein the functional structural element A in formula (I) is a unit that has electron-injection and/or electron-transport properties.

5. The formulation of claim 1, wherein the functional structural element A in formula (I) is a unit which has light-emitting properties.

6. The formulation of claim 1, wherein the formulation comprises at least one functional compound in which the functional structural element A in formula (I) is a unit having phosphorescent properties.

7. The formulation of claim 6, wherein the formulation comprises at least one functional compound in which the functional structural element A in formula (I) is a unit which includes at least one heavy atom having an atomic number of greater than 36.

8. The formulation of claim 1, wherein the functional structural element A in formula (I) is a unit which improves the transfer from the singlet state to the triplet state of light-emitting compounds.

9. The formulation of claim 1, wherein the formulation comprises at least one functional compound in which the functional structural element A in formula (I) is a unit which has light-emitting properties, and at least one functional compound in which the functional structural element A in formula (I) is a unit which can serve as host material.

10. The formulation of claim 1, wherein the formulation comprises at least two functional compounds in which the functional structural element A in formula (I) is a unit which can serve as host material.

11. The formulation of claim 1, wherein the formulation comprises at least one functional compound in which the functional structural element A in formula (I) is a unit which can serve as host material, where the functional structural element A has at least one nitrogen atom.

12. The formulation of claim 1, wherein the formulation comprises at least one functional compound which comprises no solubility-promoting structural element B of the general formula (L-I).

13. The formulation of claim 1, wherein the proportion of functional compounds in the formulation which comprise no solubility-promoting structural element B of the general formula (L-I) is at most 50% by weight, based on the total weight of the functional compounds.

14. The formulation of claim 1, wherein the formulation comprises at least 80% by weight of aromatic or heteroaromatic solvent.

15. The formulation of claim 1, wherein the index k in formula (I) is an integer greater than or equal to 2.

16. The formulation of claim 1, wherein the molecular weight of the functional compound of the general formula (I) is at least 800 g/mol.

17. The formulation of claim 1, wherein the functional compound of the general formula (I) has a glass-transition temperature of at least 70 C.

18. The formulation of claim 1, wherein the weight ratio of structural element A to structural element B in formula (I) is in the range from 2:1 to 1:20.

19. An electronic device produced from the formulation of claim 1.

20. The electronic device of claim 19, wherein the at least two functional compounds of the general formula (I) is present in the device as hole-transport, hole-injection, emitter, electron-transport, electron-injection, charge-blocking and/or charge-generation layer.

21. The electronic device of claim 19, wherein the electronic device is an organic electroluminescent device, a polymeric electroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell, or an organic laser diode.

22. A process for producing an electronic device comprising (1) applying the formulation of claim 1 to a substrate and (2) drying the applied formulation.

23. The formulation of claim 1, wherein X is, in each case, N.

Description

WORKING EXAMPLES

Example 1: Synthesis of Compounds 3 and 4

(1) ##STR00098##
Synthesis of Compound 3

(2) 40.0 g (146 mmol) of 3-borono-[3,1;5,1]terphenyl 2, 18.8 g (146 mmol) of 1-iodo-3-bromophenyl (1) and 109.3 g (730 mmol) of potassium carbonate are suspended in 1350 ml of toluene and 1150 ml of water. 844 mg (0.73 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is separated off, washed three times with 200 ml of water, dried using sodium sulfate and subsequently evaporated to dryness. The residue is washed with ethanol and recrystallised from ethyl acetate and finally dried under reduced pressure. The yield is 47.6 g (123 mmol), corresponding to 84.5% of theory.

(3) Synthesis of Compound 4

(4) 40.0 g (104 mmol) of 1-bromo-3-([3,1;5,1]terphen-1-yl)phenyl 3, 29.0 g (114 mmol) of bispinacolatodiboron, 29.5 g (301 mmol) of potassium acetate are suspended in 800 ml of dimethyl sulfoxide. 4.24 g (5.2 mmol) of 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride DCM are added to this suspension, and the reaction mixture is heated under reflux for 16 hours. After cooling, 600 ml of ethyl acetate and 400 ml of water are added, and the organic phase is separated off, washed three times with 200 ml of water, dried using sodium sulfate and subsequently evaporated to dryness. The crude product is recrystallised from heptane and finally dried under reduced pressure. The yield is 34.5 g (80 mmol), corresponding to 46.1% of theory.

Example 2

(5) Synthesis of Compound 5

(6) ##STR00099##

(7) 74.7 g (150 mmol) of bis(3,5-dibromophenyl) ketone, 109.7 g (900 mmol) of phenylboronic acid, 267.5 g (1162 mmol) of tripotassium phosphate mono-hydrate, 5.5 g (18 mmol) of tri-o-tolylphosphine and 673.5 mg (3 mmol) of palladium(II) acetate are suspended in a mixture of 600 ml of toluene, 300 ml of dioxane and 750 ml of water and heated under reflux for 72 hours. After cooling, the organic phase is separated off, washed three times with water and dried over sodium sulfate. The mixture is subsequently filtered through aluminium oxide, evaporated to about 200 ml, and 500 ml of ethanol are added, whereupon the crude product precipitates. The solid is filtered off with suction and washed with 100 ml of ethanol, then dissolved in boiling toluene and re-precipitated by addition of hot ethanol. The yield is 44.0 g (90 mmol), corresponding to 60.2% of theory.

Example 3: Synthesis of Compound 6

(8) ##STR00100##

(9) The synthesis is carried out analogously to compound 5, with phenylboronic acid being replaced by 1-bromo-3-([3,1;5,1]-terphen-1-yl)phenyl 3. The yield is 123.2 g (88 mmol), corresponding to 58.7% of theory.

Example 4: Synthesis of Compound 7

(10) ##STR00101##

(11) 28.0 g (50.0 mmol) of spiro-9,9-bifluorene-2-boronic acid, 14.7 g (55.0 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 44.6 g (210.0 mmol) of tripotassium phosphate are suspended in 500 ml of toluene, 500 ml of dioxane and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene and finally sublimed in high vacuum. The yield is 38 g (41.5 mmol), corresponding to 95.0% of theory.

Example 5: Synthesis of Compound 8

(12) ##STR00102##

a) Synthesis of 2-chloro-4,6-bis(3-([3,1;5,1]terphen-1-yl)phen-1-yl)-1,3,5-triazine

(13) 80.2 ml of a 2.0 molar solution of n-butyllithium in hexane were slowly added dropwise to a solution, cooled to 78 C., of 43.88 g (143 mmol) of 1-bromo-3-([3,1;5,1 ]terphen-1-yl)phenyl in 250 ml of abs. tetrahydrofuran, and the mixture is stirred for 15 minutes. The reaction solution is slowly added dropwise to a solution, cooled to 78 C., of 10.0 g (45 mmol) of cyanuric chloride in 400 ml of abs. tetrahydrofuran, and the cooling is removed. When room temperature has been reached, the precipitated product is filtered off. The yield is 6.3 g (9.0 mmol), corresponding to 23.3% of theory.

b) Synthesis of 2-(4,6-bis(3-([3,1;5,1]terphen-1-yl)phen-1-yl)-1,3,5-triazin-2-yl)spiro-9,9-bifluorene

(14) The synthesis is carried out analogously to compound 7 with 4.07 g (11.3 mmol) of spiro-9,9-bifluorene-2-boronic acid, with 2-chloro-4,6-diphenyl-1,3,5-triazine being replaced by 6.3 g (9.0 mmol) of 2-chloro-4,6-bis-(3-([3,1;5,1]-terphen-1-yl)phen-1-yl)-1,3,5-triazine. The yield is 4.9 g (4.8 mmol), corresponding to 56.3% of theory.

Example 6: Synthesis of Compound 9

(15) ##STR00103##

(16) 8 g (28.2 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene are dissolved in 225 ml of dimethylformamide under a protective-gas atmosphere, and 1.5 g of NaH, 60% in mineral oil (37.5 mmol), are added. After 1 hour at room temperature, a solution of 2-chloro-4,6-diphenyl-1,3,5-triazine (8.5 g, 31.75 mmol) in 75 ml of dimethylformamide is added dropwise. The reaction mixture is then stirred at room temperature for 12 hours. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is extracted with hot toluene. The yield is 12 g (23 mmol), corresponding to 83% of theory.

Example 7: Synthesis of Compound 10

(17) ##STR00104##

(18) 8.0 g (28 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene are dissolved in 210 ml of dimethylformamide under a protective-gas atmosphere, and 1.4 g of NaH 60% in mineral oil (35 mmol), are added. After 1 hour at room temperature, a solution of 2-chloro-[4,6-bis-5-(3-bromophenyl)-[1,1;3,1 ]terphenyl-5-yl]-1,3,5-triazine (22.5 g, 31 mmol) in 250 ml of dimethylformamide is added dropwise. The reaction mixture is stirred at room temperature for 12 hours. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from heptane/toluene. The yield is 12.2 g (13 mmol), corresponding to 44% of theory.

Example 8: Synthesis of Compound 11

(19) ##STR00105##

(20) 25.0 g (42.1 mmol) of 7-bromo-10-(4,6-diphenyl-1,3,5-triazin-2-yl)-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene and 19.9 g of 1-pinacolylboronato-3-([3, 1;5,1]terphen-1-yl)phenyl (46.3 mmol) are dissolved in 80 ml of toluene and degassed. 281 ml of degassed 2 M K.sub.2CO.sub.3 and 2.4 g (2.1 mmol) of Pd(PPh.sub.3).sub.4 are added. The reaction mixture is subsequently stirred at 80 C. for 48 hours under a protective-gas atmosphere. Toluene is added to the cooled solution, and the mixture is washed a number of times with water, dried and evaporated. The residue is recrystallised from heptane/toluene. The yield is 21.8 g (26.6 mmol), corresponding to 63.2% of theory.

Example 9: Synthesis of Compound 12

(21) ##STR00106##

(22) Compound 12 is prepared as described in WO 2008/086851 A1.

Example 10: Synthesis of Compound

(23) ##STR00107##

(24) Compound 13 is prepared as described in WO 2009/124627.

Example 11: Synthesis of Compound 14

(25) ##STR00108##

(26) 1.7 g (2.0 mmol) of fac-tris[2-(2-pyridinyl-N)(5-bromophenyl)-C]-iridium(III), 7.42 g (17 mmol) of 1-pinacolylboronato-3-([3,1;5,1]terphen-1-yl)benzene, 2.51 g (12 mmol) of potassium phosphate are suspended in 100 ml of toluene, 100 ml of dioxane and 111 ml of water. 4 mg (0.1 mmol) of palladium(II) acetate and 35 mg (0.2 mmol) of tri-o-tolylphosphine are added to this suspension, and the reaction mixture is heated under reflux for 24 hours. After cooling, the organic phase is separated off, washed three times with 200 ml of water, filtered through silica gel, dried using sodium sulfate and subsequently evaporated to dryness. The residue is recrystallised from dioxane/ethanol and finally dried under reduced pressure. The yield is 2.42 g (1.6 mmol), corresponding to 80.9% of theory.

Example 12: Synthesis of Compound 15

(27) ##STR00109##

a) Synthesis of 2-(3-pinacolylboronatophenyl)-4,6-diphenyl-1,3,5-triazine (compound 4a)

(28) The synthesis is carried out analogously to the synthesis of compound 4. The yield is 31.9 g (73 mmol), corresponding to 81.3% of theory.

b) Synthesis of fac-tris[2-(2-pyridinyl-N)(5-(3-phenyl (4,6-diphenyl-1,3,5-triazine)phenyl)-C]iridium(III) (compound 15)

(29) The synthesis is carried out analogously to the synthesis of compound 14. The yield is 1.5 g (0.95 mmol), corresponding to 55.6% of theory.

Example 13: Synthesis of Compound 16

fac-Tris[2-(1-isoquinolinyl-N)(5-(3-([3,1;5,1]terphen-1-yl)-phenyl)phenyl)-C]iridium(III)

(30) ##STR00110##

(31) The synthesis is carried out analogously to the synthesis of compound 14. The yield is 6.52 g (3.8 mmol), corresponding to 65.6% of theory.

Example 14: Synthesis of Compound 22

(32) ##STR00111##
a) Synthesis of Compound 18

(33) ##STR00112##

(34) 52 ml (130 mmol) of n-butyllithium (2.5 M in n-hexane) are added dropwise to a suspension of 30.7 g (100 mmol) of 4-bromobenz[a]anthracene (17) in 1000 ml of THF at 78 C. with vigorous stirring, and the mixture is stirred for a further 2 hours. 16.7 ml (150 mmol) of trimethyl borate are added in one portion to the red solution with vigorous stirring, the mixture is stirred at 78 C. for a further 30 minutes and then warmed to room temperature over the course of 3 hours, 300 ml of water are added, and the mixture is stirred for 30 minutes. The organic phase is separated off and evaporated to dryness in vacuo. The solid is taken up in 100 ml of n-hexane, filtered off with suction, washed once with 100 ml of n-hexane and dried in vacuo. Yield: 23.7 g (87.0 mmol), 87.0%, purity about 90.0% (NMR) of the boronic acid, with varying amounts of the boronic anhydride and borinic acid. The boronic acid can be used in this form without further purification.

(35) b) Synthesis of Compound 20

(36) ##STR00113##

(37) 25.0 g (97.2 mmol) of 9-bromoanthracene (19), 27.0 g (99.2 mmol) of benz[a]anthracene-4-boronic acid (18) and 44.5 g (210 mmol) of tripotassium phosphate are suspended in 500 ml of toluene, 600 ml of water and 100 ml of dioxane. 1.83 g (6.01 mmol) of tri-o-tolylphosphine and then 225 mg (1.00 mmol) of palladium(II) acetate are added to this suspension, and the mixture is subsequently heated under reflux for 16 hours. After cooling, the organic phase is separated off, washed three times with 500 ml of water, dried using sodium sulfate and subsequently evaporated to dryness. The solid is recrystallised from 300 ml of toluene and finally dried under reduced pressure. The yield is 26.2 g (64.8 mmol), corresponding to 64.8% of theory.

(38) c) Synthesis of Compound 21

(39) ##STR00114##

(40) 1.30 g (8.02 mmol) of iron(III) chloride and then 13.3 g (74.7 mmol) of N-bromosuccinimide are added to a suspension, cooled to 0 C., of 26.0 g (64.3 mmol) of of compound (20) in 600 ml of chloroform, and the mixture is stirred at 0 C. for 4 hours. After the mixture has warmed to room temperature, 400 ml of water are added, and the organic phase is separated off, washed three times with 300 ml of water, dried using sodium sulfate and subsequently evaporated to dryness. The orange solid obtained is recrystallised from toluene and finally dried under reduced pressure. The yield is 23.7 g (49.0 mmol), corresponding to 76.6% of theory.

(41) d) Synthesis of Compound 22

(42) ##STR00115##

(43) 2.0 g (4.14 mmol) of compound (21), 2.00 g (4.63 mmol) of 1-boronyl-3-([3,1;5,1]terphen-1-yl)phenyl (4) and 1.70 g (16.0 mmol) of sodium carbonate are suspended in 30 ml of toluene, 7 ml of water and 30 ml of ethanol. 70 mg (0.061 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the mixture is subsequently heated under reflux for 16 hours. After cooling, the precipitated solid is filtered off with suction, extracted twice with 250 ml of hot toluene and subsequently sublimed. The yield is 2.72 g (3.84 mmol), corresponding to 93.8% of theory.

Example 15: Synthesis of Compound

(44) ##STR00116##

(45) Compound 23 is prepared as described in WO 2009/100925.

Example 16: Synthesis of Compound 28

(46) ##STR00117## ##STR00118##
a) Synthesis of Compound 24

(47) ##STR00119##

(48) 40.0 g (156 mmol) of 9-bromoanthracene (19), 74.0 g (171 mmol) of compound (4) and 58.0 g (547 mmol) of sodium carbonate are suspended in 900 ml of toluene, 900 ml of ethanol and 210 ml of water. 1.80 g (1.56 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the mixture is subsequently heated under reflux for 16 hours. After cooling, the solid is filtered off with suction, taken up in 500 ml of dichloromethane, the organic phase is washed three times with 100 ml of water each time, dried using sodium sulfate and subsequently evaporated to dryness. The yield is 70.2 g (145 mmol), corresponding to 92.9% of theory.

(49) b) Synthesis of Compound 25

(50) ##STR00120##

(51) 2.5 g (15.4 mmol) of iron(III) chloride and then 31.0 g (174 mmol) of N-bromosuccinimide are added to a suspension, cooled to 0 C., of 70.0 g (145 mmol) of compound (24) in 1.4 l of chloroform, and the mixture is stirred at 0 C. for 2 hours. After warming to room temperature, 1000 ml of water are added, the organic phase is separated off, washed three times with 500 ml of water, dried using sodium sulfate and subsequently evaporated to dryness. The solid obtained is recrystallised from a heptane/ethyl acetate mixture and finally dried under reduced pressure. The yield is 56.7 g (101 mmol), corresponding to 69.7% of theory.

(52) c) Synthesis of Compound 27

(53) ##STR00121##

(54) 35.6 g (138 mmol) of 3-bromophenanthrene (26), 42.0 g (165 mmol) of bispinacolatodiboron and 46.0 g (469 mmol) of potassium acetate are suspended in 500 ml of dimethyl sulfoxide. 3.50 g (4.29 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II)*DCM are added to this suspension, and the reaction mixture is stirred at 80 C. for 6 hours. After cooling, 1000 ml of ethyl acetate and 1000 ml of water are added, the organic phase is separated off, washed three times with 300 ml of water each time, dried using sodium sulfate and subsequently evaporated to dryness. The crude product is passed through silica gel in a column with a heptane/ethyl acetate mixture (10:1), corresponding fractions are evaporated and finally dried under reduced pressure. The yield is 38.5 g (127 mmol), corresponding to 92.0% of theory.

(55) d) Synthesis of Compound 28

(56) ##STR00122##

(57) 13.3 g (23.7 mmol) of compound (25), 7.80 g (25.6 mmol) of compound (27) and 8.80 g (83.0 mmol) of sodium carbonate are suspended in 140 ml of toluene, 140 ml of ethanol and 35 ml of water. 300 mg (260 mol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the mixture is subsequently heated under reflux for 16 hours. After cooling, the solid is filtered off with suction and extracted with 500 ml of hot toluene. The residue is recrystallised three times from heptane/toluene and sublimed. The yield is 13.1 g (19.9 mmol), corresponding to 84.0% of theory.

(58) ##STR00123##
are commercially available and comprise no solubility-promoting structural elements of the formula (I).

(59) ##STR00124##
is prepared as described in WO 2008/006449.
Production and Characterisation of Organic Electroluminescent Devices

(60) Materials to be employed in accordance with the invention are used from solution, where they result in simple devices having surprisingly good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887 A2). In the present case, the compounds according to the invention are dissolved in toluene or chlorobenzene. The concentration employed in the examples given here is 20% by weight of the emitter (compounds 14, 15, 16, 19 and 20) and 80% by weight of the matrix materials (compounds 5 to 13, 17 and 18). The typical solids content of such solutions is between 16 and 25 g/l if, as here, the typical layer thickness of 80 nm for a device is to be achieved by means of spin coating.

(61) FIG. 1 shows the typical structure of a device of this type. The EML comprises the jointly dissolved matrix materials and the emitter in the form of an amorphous layer. Structured ITO substrates and the material for the so-called buffer layer (PEDOT, actually PEDOT:PSS) are commercially available (ITO from Technoprint and others, PEDOT:PPS as Clevios P aqueous dispersion from H.C. Starck). The Interlayer used (HIL-012 from Merck) serves for hole injection. The emission layer is applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 160 C. or 180 C. for 10 minutes. Finally, a cathode comprising barium and aluminium is applied by vacuum vapour deposition. The HBL and ETL layers used in the above-mentioned examples can also be applied by vapour deposition between the EML and the cathode, the interlayer can also be replaced by one or more layers, which merely have to satisfy the condition of not being detached again by the subsequent processing step of EML deposition from solution.

(62) The devices processed from solution were characterised by standard methods, the OLED examples given were not optimised. Table 1 shows the results.

(63) TABLE-US-00001 TABLE 1 Results of the device configuration in accordance with FIG. 1 Max. Voltage [V] Lifetime [h], EML eff. at 1000 CIE initial luminance Ex. 80 nm [cd/A] cd/m.sup.2 (x, y) 1000 cd/m.sup.2 Cmpn. Cpd. 5: cpd. 31 27 5.0 0.35/0.61 3200 Cpd. 6: cpd. 14 40 4.9 0.34/0.62 10500 Cpd. 6: cpd. 15 36 4.9 0.34/0.62 8500 Cmpn. Cpd. 5: cpd. 29: cpd. 31 33 4.7 0.34/0.62 12000 Cpd. 6: cpd. 12: cpd. 31 38 4.7 0.34/0.62 18000 Cpd. 6: cpd. 29: cpd. 14 40 4.7 0.34/0.62 20000 Cpd. 6: cpd. 29: cpd. 15 41 4.7 0.34/0.62 23000 Cpd. 5: cpd. 12: cpd. 14 38 4.7 0.34/0.62 21000 Cpd. 5: cpd. 12: cpd. 15 39 4.7 0.34/0.62 25000 Cpd. 6: cpd. 12: cpd. 14 41 4.7 0.34/0.62 22000 Cpd. 6: cpd. 12: cpd. 15 41 4.7 0.34/0.62 25000 Cmpn. Cpd. 5: cpd. 30: cpd. 31 25 6.5 0.33/0.63 6000 Cpd. 6: cpd. 13: cpd. 31 32 6.7 0.33/0.63 13000 Cpd. 6: cpd. 30: cpd. 14 30 6.7 0.33/0.63 18000 Cpd. 6: cpd. 30: cpd. 15 29 6.7 0.33/0.63 19000 Cpd. 5: cpd. 13: cpd. 14 30 6.7 0.33/0.63 14000 Cpd. 5: cpd. 13: cpd. 15 32 6.7 0.33/0.63 15000 Cpd. 6: cpd. 13: cpd. 14 35 6.7 0.33/0.63 24000 Cpd. 6: cpd. 13: cpd. 15 34 6.7 0.33/0.63 25000 Cmpn. Cpd. 7: cpd. 29: cpd. 31 24 5.3 0.34/0.62 12000 Cpd. 8: cpd. 12: cpd. 31 30 5.3 0.34/0.62 38000 Cpd. 8: cpd. 29: cpd. 14 33 5.2 0.34/0.62 45000 Cpd. 8: cpd. 29: cpd. 15 34 5.1 0.34/0.62 43000 Cpd. 7: cpd. 12: cpd. 14 32 5.2 0.34/0.62 35000 Cpd. 7: cpd. 12: cpd. 15 31 5.2 0.34/0.62 32000 Cpd. 8: cpd. 12: cpd. 14 37 5.1 0.34/0.62 48000 Cpd. 8: cpd. 12: cpd. 15 35 5.1 0.34/0.62 46000 Cmpn. Cpd. 7: cpd. 30: cpd. 31 20 4.8 0.33/0.63 9000 Cpd. 8: cpd. 13: cpd. 31 34 5.1 0.34/0.62 20000 Cpd. 8: cpd. 30: cpd. 14 28 5.1 0.33/0.62 16000 Cpd. 8: cpd. 30: cpd. 15 30 5.0 0.33/0.62 17000 Cpd. 7: cpd. 13: cpd. 14 23 3.6 0.33/0.63 17000 Cpd. 7: cpd. 13: cpd. 15 31 5.0 0.33/0.63 22000 Cpd. 8: cpd. 13: cpd. 14 29 5.3 0.33/0.62 34000 Cpd. 8: cpd. 13: cpd. 15 30 5.2 0.33/0.62 36000 Cmpn. Cpd. 9: cpd. 29: cpd. 31 21 6.0 0.34/0.62 6000 Cpd. 11: cpd. 12: cpd. 31 35 5.8 0.34/0.62 24000 Cpd. 10: cpd. 12: cpd. 31 36 5.9 0.34/0.62 28000 Cpd. 11: cpd. 29: cpd. 14 38 5.7 0.34/0.62 26000 Cpd. 10: cpd. 29: cpd. 14 39 5.8 0.34/0.62 25000 Cpd. 11: cpd. 29: cpd. 15 39 5.9 0.34/0.62 24000 Cpd. 10: cpd. 29: cpd. 15 40 5.8 0.34/0.62 25000 Cpd. 9: cpd. 12: cpd. 14 33 5.7 0.34/0.62 28000 Cpd. 9: cpd. 12: cpd. 15 34 5.8 0.34/0.62 29000 Cpd. 11: cpd. 12: cpd. 14 40 5.8 0.33/0.63 50000 Cpd. 10: cpd. 12: cpd. 14 41 5.9 0.34/0.62 53000 Cpd. 11: cpd. 12: cpd. 15 39 5.7 0.34/0.62 48000 Cpd. 10: cpd. 12: cpd. 15 40 5.8 0.34/0.62 49000 Cmpn. Cpd. 9: cpd. 30: cpd. 31 23 5.9 0.34/0.62 12000 Cpd. 11: cpd. 13: cpd. 31 32 5.2 0.33/0.62 24000 Cpd. 10: cpd. 13: cpd. 31 32 6.0 0.34/0.62 24000 Cpd. 11: cpd. 30: cpd. 14 33 6.1 0.34/0.62 22000 Cpd. 10: cpd. 30: cpd. 14 34 6.2 0.34/0.62 21000 Cpd. 11: cpd. 30: cpd. 15 32 6.0 0.34/0.62 22000 Cpd. 10: cpd. 30: cpd. 15 34 6.1 0.34/0.62 23000 Cpd. 9: cpd. 13: cpd. 14 35 6.0 0.34/0.62 25000 Cpd. 9: cpd. 13: cpd. 15 34 6.1 0.34/0.62 24000 Cpd. 11: cpd. 13: cpd. 14 38 6.1 0.34/0.62 33000 Cpd. 10: cpd. 13: cpd. 14 37 6.0 0.34/0.62 32000 Cpd. 11: cpd. 13: cpd. 15 39 6.1 0.33/0.62 31000 Cpd. 10: cpd. 13: cpd. 15 40 6.1 0.33/0.62 34000 Cmpn. Cpd. 5: cpd. 29: cpd. 31: cpd. 32 6 6.4 0.65/0.35 4000 Cpd. 6: cpd. 12: cpd. 31: cpd. 32 9 6.5 0.65/0.35 16000 Cpd. 6: cpd. 12: cpd. 31: cpd. 16 10 6.3 0.65/0.35 22000 Cpd. 5: cpd. 12: cpd. 31: cpd. 16 8 6.3 0.65/0.35 18000 Cpd. 6: cpd. 29: cpd. 31: cpd. 16 9 6.5 0.65/0.35 20000

(64) As can be seen from the results, the formulations according to the invention represent a significant improvement over the comparable compositions in accordance with the prior art with respect to operating voltage, lifetime and efficiency of the electronic devices obtained therefrom.

(65) Production and Characterisation of Organic Electroluminescent Devices Comprising Compounds 22 and 28 According to the Invention

(66) The materials to be employed in accordance with the invention are, as described above, dissolved in toluene or chlorobenzene. However, the concentration employed in the examples given here is 5% by weight of the emitter (cpd. 33) and 95% by weight of the matrix materials. The typical solids content of such solutions is between 10 and 15 g/l if, as here, the typical layer thickness of 50 nm for a device is to be achieved by means of spin coating.

(67) The devices are characterised by standard methods, the OLED examples given have not yet been optimised. Table 2 summarises the data obtained.

(68) TABLE-US-00002 TABLE 2 Results with materials processed from solution in the device configuration of FIG. 1. Voltage Lifetime [h], Max. [V] initial EML eff. at 1000 CIE luminance Ex. 50 nm [cd/A] cd/m.sup.2 (x, y) 1000 cd/m.sup.2 Cmpn. Cpd. 23: cpd. 33 4.8 5.0 0.14, 0.17 400 Cmpn. Cpd. 28: cpd. 33 5.3 4.9 0.14, 0.17 300 Cmpn. Cpd. 23: cpd. 33 6.1 4.9 0.14, 0.17 500 Cmpn. Cpd. 23: cpd. 28: 6.1 4.8 0.14, 0.17 800 cpd. 33 Cmpn. Cpd. 23: cpd. 22: 6.1 4.8 0.14, 0.17 700 cpd. 33 Cpd. 28: cpd. 22: 6.2 4.8 0.14, 0.17 1000 cpd. 33