Materials for electronic devices

Abstract

The present application relates to a compound of a formula (I) which comprises a benzene group that is substituted with a group selected from carbazole derivatives and bridged amines and with an electron attracting group, wherein the two groups are located in the ortho-position in relation to one another. The present application further relates to the use of the compound of the formula (I) in an electronic device, and to a method of producing the compound of the formula (I).

Claims

1. A compound of the formula (I) ##STR00367## or a compound containing exactly two or three units of the formula (I) joined to one another via a single bond or an L group, where: L is any divalent or trivalent organic group; A is a group of the formula (A) ##STR00368## bonded via the dotted bond; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; Y is the same or different at each instance and is a single bond, BR.sup.1, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, NR.sup.1, PR.sup.1, P(?O)R.sup.1, O, S, S?O or S(?O).sub.2; B is the same or different at each instance and is selected from H, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which may be substituted by one or more R.sup.1 radicals, or an aryl group having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more R.sup.1 radicals; R.sup.A is the same or different at each instance and is CF.sub.3, CN, and an E group, which is an aryl or heteroaryl group which has 6 to 14 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, and which contains one or more V groups as constituents of the aromatic ring, where the V groups are the same or different at each instance and are selected from ?N, ?C(F), ?C(CN) and ?C(CF.sub.3), and where the heteroaryl group is not bonded via a nitrogen atom; R.sup.B is selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals, and an aryl group having 6 to 14 aromatic ring atoms, which may be substituted by one or more R.sup.1 radicals; R.sup.1 is the same or different at each instance and is H, D, F, C(?O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(?O)(R.sup.2).sub.2, OR.sup.2, S(?O)R.sup.2, S(?O).sub.2R.sup.2, a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, where the abovementioned groups may each be substituted by one or more R.sup.2 radicals and where one or more CH.sub.2 groups in the abovementioned groups may be replaced by R.sup.2C?CR.sup.2, C?C,Si(R.sup.2).sub.2, C?O, C?NR.sup.2, C(?O)O, C(?O)NR.sup.2, NR.sup.2, P(?O)(R.sup.2), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, where two or more R.sup.1 radicals may be joined to one another and may form a ring; R.sup.2 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D or F; at the same time, two or more R.sup.2 substituents may be joined to one another and may form a ring.

2. The compound as claimed in claim 1, wherein the L group is a divalent group selected from alkylene groups having 1 to 20 carbon atoms, in which one or more CH.sub.2 groups may be replaced by Si(R.sup.1).sub.2, O, S, C?O, C?NR.sup.1, C?OO, C?ONR.sup.1, NR.sup.1, P(?O)(R.sup.1), SO or SO.sub.2 and which may be substituted by one or more R.sup.1 radicals, or aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R.sup.1 radicals, or is a trivalent group selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R.sup.1 radicals.

3. The compound as claimed in claim 1, wherein Ar.sup.1 is the same or different at each instance and is an aromatic ring system which has 6 to 20 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals.

4. The compound as claimed in claim 1, wherein the Y group is the same or different at each instance and is a single bond, C(R.sup.1).sub.2, NR.sup.1, O or S.

5. The compound as claimed in claim 1, wherein the B group is the same or different at each instance and is H.

6. The compound as claimed in claim 1, wherein the two R.sup.A radicals are the same or different and are CN.

7. The compound as claimed in claim 1, wherein R.sup.B is the same or different at each instance and is H.

8. The compound as claimed in claim 1, wherein the compound of the formula (I) corresponds to formula (I-3) ##STR00369## where the A and R.sup.A groups are each as defined in claim 1.

9. A process for preparing the compound of formula (I) as claimed in claim 1, which comprises introducing at least one carbazole derivative by nucleophilic aromatic substitution or Buchwald coupling, or in that at least one electron-deficient heteroaryl group is introduced by Suzuki coupling.

10. An oligomer containing one or more compounds of formula (I) as claimed in claim 1, wherein the bond(s) to the oligomer may be localized at any positions substituted by R.sup.1 or R.sup.2 in formula (I).

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

12. An electronic device comprising at least one oligomer as claimed in claim 10.

13. An organic electroluminescent device comprising anode, cathode and at least one emitting layer, wherein at least one organic layer in the device, selected from emitting layers, comprises at least one compound as claimed in claim 1.

14. An organic electroluminescent device comprising anode, cathode and at least one emitting layer, wherein at least one organic layer in the device, selected from emitting layers, comprises at least one oligomer as claimed in claim 10.

15. The compound as claimed in claim 1, wherein at least one R.sup.A radical is CN.

16. The compound as claimed in claim 1, wherein Ar.sup.1 is phenyl, which may be substituted by one or more radicals R.sup.1.

17. The compound as claimed in claim 1, wherein R.sup.B is H and B is H.

18. The compound as claimed in claim 1, wherein R.sup.A is CN, R.sup.B is H, B is H and Ar.sup.1 is phenyl, which may be substituted by one or more radicals R.sup.1.

19. A compound of the formula (I) ##STR00370## where: A is a group of the formula (A) ##STR00371## bonded via the dotted bond; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; Y is the same or different at each instance and is a single bond, BR.sup.1, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, NR.sup.1, PR.sup.1, P(?O)R.sup.1, O, S, S?O or S(?O).sub.2; B is the same or different at each instance and is selected from H, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which may be substituted by one or more R.sup.1 radicals, or an aryl group having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more R.sup.1 radicals; R.sup.A is the same or different at each instance and is CF.sub.3, CN, and an E group, which is an aryl or heteroaryl group which has 6 to 14 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, and which contains one or more V groups as constituents of the aromatic ring, where the V groups are the same or different at each instance and are selected from ?N, ?C(F), ?C(CN) and ?C(CF.sub.3), and where the heteroaryl group is not bonded via a nitrogen atom; R.sup.B is selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals, and an aryl group having 6 to 14 aromatic ring atoms, which may be substituted by one or more R.sup.1 radicals; R.sup.1 is the same or different at each instance and is H, D, F, C(?O)R.sup.2, CN, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, P(?O)(R.sup.2).sub.2, OR.sup.2, S(?O)R.sup.2, S(?O).sub.2R.sup.2, a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, where the abovementioned groups may each be substituted by one or more R.sup.2 radicals and where one or more CH.sub.2 groups in the abovementioned groups may be replaced by R.sup.2C?CR.sup.2, C?C, Si(R.sup.2).sub.2, C?O, C?NR.sup.2, C(?O)O, C(?O)NR.sup.2, NR.sup.2, P(?O)(R.sup.2), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, where two or more R.sup.1 radicals may be joined to one another and may form a ring; and R.sup.2 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D or F; at the same time, two or more R.sup.2 substituents may be joined to one another and may form a ring.

Description

WORKING EXAMPLES

(1) A) Synthesis Examples:

(2) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR.

(3) I) Synthesis of Compounds of the Invention:

Example S1

1,3,5-Triscyano-2,4,6-tris(N-carbazolyl)benzene

(4) ##STR00107##
Variant A:

(5) To a well-stirred suspension of 16.0 g (400 mmol) of sodium hydride, 60% by weight dispersion in mineral oil, in 500 mL of THF are added in portions while cooling with ice, at about +10? C., 66.9 g (400 mmol) of carbazole [51555-21-6]Caution! Evolution of hydrogen! Foaming! After the addition has ended, the mixture is stirred for a further 30 min and then 20.7 g (100 mmol) of 1,3,5-tricyano-2,4,6-trifluorobenzene [363897-9] are added in portions while cooling with ice in such a way that the temperature does not exceed +20? C. After the addition has ended, the mixture is stirred at +10? C. for a further 2 h, then the cooling bath is removed, and the mixture is allowed to warm to 20-25? C., stirred for a further 2 h and then heated to 40? C. for another 12 h. After cooling to room temperature, the reaction is ended by dropwise addition of 30 mL of MeOH and the reaction mixture is concentrated almost to dryness under reduced pressure. The residue is subjected to hot extractive stirring twice with 600 mL each time of a mixture of 400 mL of methanol and 200 mL of water and then once with 500 mL of methanol. Purification is effected by recrystallization from dioxane (about 5 mL/g) three times, then recrystallization from DMF (about 2.5 mL/g) five times and fractional sublimation twice (p about 1?10.sup.?5 mbar, T about 310-320? C.). Yield: 23.6 g (36.3 mmol) 36%. Purity: 99.9% by HPLC.

(6) Variant B:

(7) Procedure analogous to variant A, except that the carbazole is initially charged in the THF, and then 160 mL (400 mmol) of n-BuLi, 2.5 molar in n-hexane, are added dropwise.

(8) Yield: 19.0 g (29.3 mmol) 29%. Purity: 99.9% by HPLC.

(9) Variant C:

(10) A well-stirred suspension of 66.9 g (400 mmol) of carbazole [51555-21-6], 20.7 g (100 mmol) of 1,3,5-tricyano-2,4,6-trifluorobenzene, 106.1 g (500 mmol) of tripotassium phosphate (anhydrous) and 200 g of glass beads is stirred in 500 mL of dimethylacetamide at 160? C. for 16 h. After cooling, 1000 mL of water are added, the precipitated solids are filtered off, and these are washed twice with 300 mL each time of water and twice with 200 mL each time of methanol, and then dried under reduced pressure. Further purification analogously to variant A. Yield: 20.5 g (31.6 mmol) 31%. Purity: 99.9% by HPLC.

(11) In an analogous manner, it is possible to prepare the following compounds:

(12) TABLE-US-00001 Ex. Variant Reactants Product Yield S2 08 09 30% S3 0 33% S4 36% S5 32% S6 37% S7 28% S8 0 29% S9 34% S10 28% S11 30% S12 31% S13 0 26% S14 35% S15 34% S16 32% S17 23% S18 0 25% S19 26% S20 30% S21 21% S22 45% S23 0 40% S24 41% S25 38% S26 39% S27 34% S28 0 35% S29 33% S30 16% S31 15% S32 17% S33 0 13% S34 36% S35 35% S36 31% S37 34% S38 0 33% S39 29% S40 30% S41 26% S42 28% S43 0 32% S44 31% S45 24% S46 19% S47 18% S48 00 01 20% S49 02 03 19% S50 04 05 53% S51 06 07 13% S52 08 09 32% S53 0 34% S54 28% S55 33% S56 28% S57 30% S58 0 18% S59 16% S60 22% S61 21% S62 28% S63 0 13%

Example S64

1,3,5-Triscyano-2-(N-carbazolyl)-4,6-bis-(N-3,6-diphenylcarbazolyl)benzene, S64

(13) ##STR00232##

(14) To a well-stirred suspension of 4.0 g (100 mmol) of sodium hydride, 60% by weight dispersion in mineral oil, in 500 mL of THF are added in portions while cooling with ice, at about +10? C., 16.7 g (100 mmol) of carbazole [51555-21-6]Caution! Evolution of hydrogen! Foaming! After the addition has ended, the mixture is stirred for a further 30 min and then 20.7 g (100 mmol) of 1,3,5-tricyano-2-fluoro-4,6-dichlorobenzene [25751-93-7] are added in portions while cooling with ice in such a way that the temperature does not exceed +20? C. After the addition has ended, the mixture is stirred at +10? C. for a further 2 h, then the cooling bath is removed, and the mixture is allowed to warm to 20-25? C., stirred for a further 2 h and then heated to 40? C. for another 6 h. After cooling to room temperature, 12.0 g (300 mmol) of sodium hydride, 60% by weight dispersion in mineral oil, are added, the reaction mixture is cooled to +10? C., and then 95.8 g (300 mmol) of 3,6-diphenylcarbazole [56525-79-2] are added in portionsCaution! Evolution of hydrogen! Foaming! After the addition has ended, the mixture is stirred at +10? C. for a further 2 h, then the cooling bath is removed, and the mixture is allowed to warm to 20-25? C., stirred for a further 2 h and then heated to 60? C. for another 16 h. After cooling to room temperature, the reaction is ended by dropwise addition of 30 mL of MeOH and the reaction mixture is then concentrated almost to dryness under reduced pressure. The residue is subjected to hot extractive stirring twice with 600 mL each time of a mixture of 400 mL of methanol and 200 mL of water and then once with 500 mL of methanol. Purification is effected by recrystallization from dioxane (about 3.5 mL/g) three times, then recrystallization from DMF (about 2 mL/g) five times and fractional sublimation twice (p about 1?10.sup.?5 mbar, T about 330-340? C.). Yield: 22.9 g (24.0 mmol) 24%. Purity: 99.9% by HPLC.

(15) In an analogous manner, the following compounds are prepared:

(16) TABLE-US-00002 Ex. Reactants Product Yield S65 56525-79-2 1246891 20% S66 42448-04-4 37500-95-1 19% S67 37500-95-1 0 42448-04-4 21% S68 37500-95-1 1335126-51-6 24% S69 64677-58-3 1335126-51-6 17% S70 42448-04-4 91944-01-3 0 18% S71 56525-79-2 17966-00-6 20%
II) Synthesis of Precursors

Example S72-V

9-(2,6-Dibromophenyl)-9H-carbazole

(17) ##STR00254##

(18) A well-stirred suspension of 66.9 g (400 mmol) of carbazole [51555-21-6], 25.4 g (100 mmol) of 1,3-dibromo-2-fluorobenzene [363897-9], 106.1 g (500 mmol) of tripotassium phosphate (anhydrous) and 200 g of glass beads is stirred in 500 mL of dimethylacetamide at 160? C. for 16 h. After cooling, 1000 mL of water are added, the precipitated solids are filtered off, and these are washed twice with 300 mL each time of water and twice with 200 mL each time of methanol, and then dried under reduced pressure. After a single recrystallization from toluene/heptane, 18.9 g (47.2 mmol, 47%) are obtained and then converted further.

(19) The following are converted analogously:

(20) TABLE-US-00003 Ex. Reactants Product Yield S73-V 28%

Example S74-V

9-[2-Bromo-6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolanyl)phenyl]-9H-carbazole

(21) ##STR00257##

(22) 18.5 (46.1 mmol, 1 eq) of S72-V are initially charged together with 14.1 g (55.3 mmol, 1.2 eq) of bis(pinacolato)diborane (CAS 73183-34-3) and 15.8 g (161 mmol, 3.5 eq) of potassium acetate (CAS 127-08-2) in 100 mL of THF and, after degassing, 2.26 g (0.06 eq) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with DCM (CAS 95464-05-4) are added. The mixture is heated at reflux for 14 h and, after the reaction has ended, water is added. The organic phase is removed and the aqueous phase is extracted repeatedly with dichloromethane. The combined organic phases are dried over sodium sulfate and the solvent is removed under reduced pressure. 15.3 g (34.1 mmol, 74%) of the product S74-V are obtained.

(23) The following are converted analogously:

(24) TABLE-US-00004 Ex. Reactants Product Yield S75-V 67%

Example S76-V

9-[2-Bromo-6-(4,6-diphenyl-[1,3,5]triazin-2-yl)phenyl]-9H-carbazole S76-V

(25) ##STR00260##
Variant A

(26) 15.0 g (33.5 mmol) of S74-V, 11.6 g (43.5 mmol, 1.3 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (CAS 3842-55-5) and 5.3 g of sodium carbonate are suspended in 200 mL of dioxane, 200 mL of toluene and 100 mL of water. To this suspension are added 1.94 g (1.68 mmol, 0.05 eq.) of Pd(PPh.sub.3).sub.4. The reaction mixture is heated under reflux overnight. After cooling, the precipitated solids are filtered off with suction, washed with water and ethanol, and dried. The residue is subjected to hot extraction with toluene and recrystallized from toluene/heptane. 7.23 g (13.1 mmol, 39%) of the product S76-V are obtained.

(27) The following are converted analogously:

(28) TABLE-US-00005 Ex. Variant Reactants Product Yield S77-V 39%
III) Synthesis of Compounds of the Invention and Precursors:

Example S78

9-[3-(4,6-Diphenyl-[1,3,5]triazin-2-yl)-biphenyl-2-yl]-9H-carbazole

(29) ##STR00263##

(30) 7.1 g (12.8 mmol) of S76-V, 1.72 g (14.1 mmol, 1.1 eq) of phenylboronic acid (CAS 98-80-6) and 5.45 g (25.7 mmol, 2 eq) of tripotassium phosphate are dissolved in 100 mL of dioxane, 100 mL of toluene and 50 mL of water, and degassed for 30 minutes. Subsequently, 86 mg (0.38 mmol, 0.03 eq.) of palladium(II) acetate and 230 mg (0.77 mmol, 0.06 eq.) of tri-o-tolylphosphine are added and the mixture is heated to reflux. After the reaction has ended, the mixture is cooled, and the aqueous phase is removed and extracted repeatedly with toluene. The combined organic phases are washed with water and dried over sodium sulfate, and the solvent is removed under reduced pressure. The residue is subjected to hot extraction with toluene and recrystallized from toluene/heptane. After sublimation, 4.1 g (7.4 mmol, 58%) of the desired product S78 are obtained with an HPLC purity of >99.9%.

(31) TABLE-US-00006 Ex. Variant Reactants Product Yield S79 37% S80 64%
IV) Synthesis of Precursors:

Example S81-V

4-Bromo-2,3,4,5,6-pentafluoro-3,5-bis(trifluoromethyl)biphenyl

(32) ##STR00268##

(33) To a solution of 11.4 g (30 mmol) of 2,3,4,5,6-pentafluoro-3,5-bis(trifluoromethyl)biphenyl [1363958-46-6] in 300 mL of dichloromethane is added dropwise, with exclusion of light, a mixture of 1.7 mL (32 mmol) of bromine and 20 mL of chloroform. After stirring at 40? C. for 16 h, 200 mL of ethanol and then 50 mL of saturated sodium sulfite solution are added. The colorless solid is filtered off with suction, washed three times with 200 mL of water and three times with 100 mL of ethanol, dried under reduced pressure and then separated from isomers by recrystallizing in DMF and toluene. Yield: 4.1 g (9 mmol), 30% of theory

(34) In an analogous manner, it is possible to obtain the following compounds:

(35) TABLE-US-00007 Ex. Reactant 1 Product Yield S82-V [1261665-44-4] 0 32% S83-V [1363958-46-6] 69% S84-V [1261886-30-9] 31% S85-V [1261805-15-5] 27% S86-V [1261494-38-5] 55% S87-V [1261494-38-5] 0 30% S88-V [56880-53-6] 29% S89-V [54826-31-2] 27% S90-V [61371-30-0] 37%
V) Synthesis of Compounds of the Invention:

Example S91

9-(2,6-Dimethylphenyl)-9H-[3,9]bicarbazolyl

(36) ##STR00287##

(37) 12.6 g (38.32 mmol) of 9H-[3,9]bicarbazolyl [18628-07-4], 7 g (38.32 mmol) of 2-bromo-1,3-ditrifluoromethylbenzene [118527-30-3] and 16 g of K.sub.2CO.sub.3 are suspended in 300 mL of p-xylene. To the suspension are added 0.86 g (3.84 mmol) of Pd(OAc).sub.2 and 7.6 mL of a 1M tri-tert-butylphosphine solution. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, washed three times with 200 mL of water and then concentrated to dryness. The residue is subjected to hot extraction with toluene, recrystallized from toluene and finally sublimed under high vacuum. Yield: 14.5 g (35 mmol), 87% of theory; purity 99.9%

(38) In an analogous manner, it is possible to obtain the following compounds:

(39) TABLE-US-00008 Reactant 1 Reactant 1 Product Yield S92 0 77% S93 68% S94 76% S95 69% S96 00 01 02 81% S97 03 04 05 63% S98 06 07 08 59% S99 09 0 52% S100 48% S101 [95606-57-8] [1257220-47-5] 79% S102 [1231208-09-5] 0 74% S103 [92-84-2] 76% S104 [6267-02-3] 71% S105 [1257220-47-5] 75%
VI) Synthesis of Precursors:

Example S106-V

2,3,4,5,6-Pentafluoro-3-trifluoromethylbiphenyl-2-ylamine

(40) ##STR00330##

(41) 294 mL of concentrated hydrochloric acid, 700 mL of ethanol and 38 g (126 mmol) of 2,3,4,5,6-pentafluoro-2-nitro-3-trifluoromethylbiphenyl [1261680-28-7] are initially charged, and 35 g (294 mmol) of tin powder are added in portions at room temperature. After the addition, the mixture is stirred at room temperature for 3 h. Thereafter, the reaction mixture is adjusted to pH=12 by addition of NaOH (solid) while cooling with ice. The residue is filtered off, washed with dichloromethane and recrystallized from heptane. This gives 22 g (79 mmol) of a white solid, corresponding to 63% of theory.

(42) In an analogous manner, it is possible to obtain the following compounds with 2 eq. of tin powder:

(43) TABLE-US-00009 Reactant 1 Product Yield S107-V 61% S108-V 68%
VII) Synthesis of Compounds of the Invention:

Example S109

9-(3,2,3,4,5,6-Hexafluorobiphenyl-2-yl)-9H-carbazole

(44) ##STR00335##

(45) 15.6 g (50 mmol) of 2,2-dibromobiphenyl are admixed with 500 mL of toluene, 2.3 g (2.5 mmol) of tris(dibenzylideneacetone)dipalladium(0), 10 mL of 1M t-Bu.sub.3P in toluene and 11.5 g (120 mmol) of sodium tert-butoxide. Subsequently, 11.8 g (40 mmol) of 2,3,4,5,6-pentafluoro-3-trifluoromethylbiphenyl-2-ylamine are added. The mixture is heated to 110? C. for 20 h, then cooled to room temperature, and 400 mL of water are added. The mixture is extracted with ethyl acetate, then the combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is recrystallized from toluene and from dichloromethane/isopropanol and finally sublimed under high vacuum. The purity is 99.9%. The yield is 10 g (23 mmol), corresponding to 59% of theory.

(46) In an analogous manner, it is possible to obtain the following compounds:

(47) TABLE-US-00010 Reactant 1 Product Yield S110 [88301-98-8] [13029-09-9] 67% S111 [58458-14-3] 0 [13029-09-9] 67% S112 [313-13-3] [13029-09-9] 59% S113 [1214363-65-1] [13029-09-9] 58% S114 [13029-09-9] 0 68% S115 [1261616-30-1] [13029-09-9] 63% S116 [1261759-86-7] [13029-09-9] 55% S117 [264926-99-0] [13029-09-9] 46% S118 0 [264926-99-0] [13029-09-9] 52% S119 [13029-09-9] 43%
B) Device Examples

(48) In the examples which follow, the results of various OLEDs in which the compounds of the invention are used as emitting compounds are presented.

(49) Glass plaques which have been coated with structured ITO (indium tin oxide) are the substrates for the OLEDs. The substrates are subjected to wet cleaning (cleaning machine, detergent: Merck Extran), then baked at 250? C. for 15 min and, prior to the coating, treated with an oxygen plasma.

(50) All materials are applied by thermal vapor deposition in a vacuum chamber. The emission layer always consists of a matrix material and the emitting material. The latter is added to the matrix material in a particular proportion by volume by coevaporation.

(51) The OLEDs are characterized in a standard manner. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. In addition, the voltage which is required for a luminance of 1000 cd/m.sup.2 is determined. Table 1 additionally reports the external quantum efficiency which is achieved at an operating luminance of 1000 cd/m.sup.2. This is determined assuming Lambertian radiation characteristics.

(52) Type 1

(53) Substrate:

(54) ITO, 50 nm

(55) Hole Injection Layer/Hole Transport Layer:

(56) 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, ?-NPD, [123847-85-8], 90 nm

(57) Emission Layer:

(58) 4,4-bis(N-carbazole)biphenyl CBP, [58328-31-7], as matrix material, doped with 5% by volume of the compound of the invention (see table 1) as dopant, 15 nm

(59) Electron Transport Layer:

(60) 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene TPBi, [192198-85-9], 50 nm

(61) Electron Injection Layer:

(62) LiF, 1 nm

(63) Cathode:

(64) Al, 100 nm

(65) Type 1a

(66) Same construction as type 1, except that an ?-NPD layer of thickness 120 rather than 90 nm and a TPBI layer of thickness 60 rather than 50 nm is used.

(67) Type 2

(68) Substrate:

(69) ITO, 50 nm

(70) Hole Injection Layer/Hole Transport Layer:

(71) 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, ?-NPD, [123847-85-8], 80 nm

(72) Hole Transport Layer:

(73) 1,3-bis(9-carbazolyl)benzene, mCP, [550378-78-4], 10 nm

(74) Emission Layer:

(75) 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene, PPT, [1019842-99-9], as matrix material, doped with 5% by volume of the compound of the invention (see table 1) as dopant, 20 nm

(76) Electron Transport Layer:

(77) 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene, PPT, [1019842-99-9], 50 nm

(78) Electron Injection Layer:

(79) LiF, 1 nm

(80) Cathode:

(81) Al, 100 nm

(82) Use of Compounds of the Invention as Emitter Materials in OLEDs

(83) The compounds of the invention can especially be used as emitter materials in the emission layer of OLEDs. The values measured for power efficiency, voltage and color coordinates are summarized in table 1.

(84) TABLE-US-00011 TABLE 1 EQE (%) Voltage (V) CIE x/y Ex. Emitter Type 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 P1 S1 2 14.0 7.3 0.42/0.56 P2 S6 1 12.8 7.1 0.45/0.55 P3 S23 1 12.1 5.7 0.41/0.57 P4 S32 1 13.0 6.3 0.36/0.59 P5 S36 2 14.4 7.7 0.40/0.57 P6 S47 2 15.5 8.3 0.14/0.19 P7 S49 1 18.5 5.8 0.23/0.54 P8 S52 2 16.8 6.6 0.15/0.28 P9 S54 1 17.2 4.7 0.22/0.52 P10 S61 2 13.8 7.6 0.15/0.27 P11 S64 .sup.1a 13.8 6.3 0.59/0.41 P-V1 Comp. 1 2 1.8 4.6 0.14/0.06 P-V2 Comp. 2 1 1.3 3.7 0.69/0.31

(85) The OLEDs produced exhibit excellent values for power efficiency. By using different emitters, it is possible to obtain light having different color coordinates.

(86) The comparison with compounds according to the prior art (Comp. 1 and Comp. 2 in P-V1 and P-V2) shows an outstanding improvement in power efficiency at similar voltages through replacement of these compounds with the compounds of the invention.

(87) Compounds of comparative examples P-1 and P-V2:

(88) ##STR00366##