MATERIALS FOR ELECTRONIC DEVICES

Abstract

The invention relates to propellane compounds according to defined formula, to the use of said compounds in electronic devices, and to electronic devices containing one or more of the known propellane compounds. The invention also relates to methods for producing the known propellane compounds.

Claims

1. A compound of the formula (I), (II), (III) or (IV) ##STR00506## where the variables that occur are as follows: Z is the same or different at each instance and is selected from N and CR.sup.1 or C, where a Z group is C in the specific case when a Y group is bonded to it; Y is the same or different at each instance and is selected from BR.sup.2, C(R.sup.2).sub.2, Si(R.sup.2).sub.2, NR.sup.2, P(O)R.sup.2, O, S, SO, SO.sub.2; n is the same or different at each instance and is 0 or 1; R.sup.1, R.sup.2 are the same or different at each instance and are selected from H, D, F, CN, Si(R.sup.3).sub.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, and aromatic ring systems having 6 to 40 aromatic ring atoms; where two or more R.sup.1 and/or R.sup.2 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems mentioned may each be substituted by one or more R.sup.3 radicals; where an indole ring may be fused in each case to one or more of the six-membered rings in formula (I) to (IV) and may in turn be substituted by R.sup.3 radicals; R.sup.3 is the same or different at each instance and is selected from H, D, F, CN, Si(R.sup.4).sub.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, and aromatic ring systems having 6 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems mentioned may each be substituted by one or more R.sup.4 radicals; R.sup.4 is the same or different at each instance and is selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, and aromatic ring systems having 6 to 40 aromatic ring atoms; where two or more R.sup.4 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic ring systems mentioned may be substituted by F or CN; characterized in that at least one Z group per formula selected from the formulae (I), (II), (III) and (IV) is CR.sup.1; and further characterized in that exactly one R.sup.1 group per formula (I) is replaced by a group of the formula (A) or a group of the formula (H) ##STR00507## and further characterized in that exactly one R.sup.1 group per formula selected from the formulae (II), (II) and (IV) is replaced by a group of the formula (A), where: L.sup.1 is the same or different at each instance and is an aromatic ring system having 6 to 24 aromatic ring atoms or a heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more R.sup.5 radicals; k is 0, 1, 2 or 3; Ar.sup.1 is the same or different at each instance and is an aromatic ring system having 6 to 24 aromatic ring atoms or a heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more R.sup.5 radicals; Ar.sup.2 is a heteroaromatic ring system which has 5 to 24 aromatic ring atoms and may be substituted by one or more R.sup.5 radicals; R.sup.5 is the same or different at each instance and is selected from H, D, F, C(O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(O)(R.sup.6).sub.2, OR.sup.6, S(O)R.sup.6, S(O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by R.sup.6CCR.sup.6, CC, Si(R.sup.6).sub.2, CO, CNR.sup.6, C(O)O, C(O)NR.sup.6, NR.sup.6, P(O)(R.sup.6), O, S, SO or SO.sub.2; R.sup.6 is the same or different at each instance and is selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.6 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; where the group of the formula (A) or the group of the formula (H) is bonded via the bond marked *.

2. A compound as claimed in claim 1, characterized in that formula (I) conforms to one of the formulae (I-H-1) to (I-H-7) and (I-A-1) to (I-A-7) ##STR00508## ##STR00509## ##STR00510## ##STR00511## and/or in that formula (II) conforms to one of the formulae (II-A-1) to (II-A-3) ##STR00512## and/or in that formula (III) conforms to one of the formulae (III-A-1) to (III-A-3) ##STR00513## and/or in that formula (IV) conforms to one of the formulae (IV-A-1) to (IV-A-3) ##STR00514## where the groups that occur are as defined in claim 1, and where formula (A) is a group of the formula (A) as defined in claim 1, and where formula (H) is a group of the formula (H) as defined in claim 1.

3. The compound as claimed in claim 1, wherein Z is CR.sup.1 or C, where Z is C in the specific case when a Y group is bonded to it.

4. The compound as claimed in claim 1, wherein Y is the same or different at each instance and is selected from O and NR.sup.2.

5. The compound as claimed in claim 1, wherein the sum total of the indices n in a compound of the formula (II) is 1 or 0, and/or in that the sum total of the indices n in a compound of the formula (III) is 0.

6. The compound as claimed in claim 1, wherein the index n is 0.

7. The compound as claimed in claim 1, wherein the Y group is bonded to that six-membered ring which bears a group of the formula (A) or (H).

8. The compound as claimed in claim 1, wherein R.sup.1 is the same or different at each instance and is selected from H, D, straight-chain or branched alkyl groups having up to 12 carbon atoms, and aromatic ring systems having 6 to 24 aromatic ring atoms; where the alkyl groups mentioned and the aromatic ring systems mentioned may each be substituted by one or more R.sup.3 radicals.

9. The compound as claimed in claim 1, wherein R.sup.2 is selected from straight-chain or branched alkyl groups having up to 12 carbon atoms, and aromatic ring systems having 6 to 24 aromatic ring atoms, where two R.sup.2 radicals that bind to the same carbon atom in a C(R.sup.2).sub.2 group and are alkyl groups or aryl groups may be joined to one another to give a cyclic alkyl group or to give a fluorene group.

10. The compound as claimed in claim 1, wherein R.sup.3 is the same or different at each instance and is selected from H, D, F, CN, straight-chain alkyl groups having 1 to 12 carbon atoms, branched or cyclic alkyl groups having 3 to 12 carbon atoms, and aromatic ring systems having 6 to 24 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; and where the alkyl groups mentioned and the aromatic ring systems mentioned may each be substituted by one or more R.sup.4 radicals.

11. The compound as claimed in claim 1, wherein R.sup.4 is the same or different at each instance and is selected from H, D, F, CN, straight-chain alkyl groups having 1 to 12 carbon atoms, branched or cyclic alkyl groups having 3 to 12 carbon atoms, and aromatic ring systems having 6 to 24 aromatic ring atoms; where two or more R.sup.4 radicals may be joined to one another and may form a ring; and where the alkyl groups mentioned and the aromatic ring systems mentioned may be substituted by F or CN.

12. The compound as claimed in claim 1, wherein exactly one R.sup.1 group per formula (I) has been replaced by a group of the formula (A).

13. The compound as claimed in claim 1, wherein L.sup.1 is a divalent group selected from phenylene, biphenylene, terphenylene, naphthylene, dibenzofuran, dibenzothiophene, carbazole and fluorene, where the divalent group may be substituted by one or more R.sup.5 radicals.

14. The compound as claimed in claim 1, wherein Ar.sup.1 is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, spirobifluorenyl, pyridyl, pyrimidyl, triazinyl, dibenzofuranyl, benzofused dibenzofuranyl, dibenzothiophenyl, benzofused dibenzothiophenyl, carbazolyl, and benzofused carbazolyl, and combinations of two, three or four of these groups, where the groups mentioned may each be substituted by one or more R.sup.5 radicals.

15. The compound as claimed in claim 1, wherein L.sup.1 is a divalent group selected from phenylene, biphenylene, terphenylene, naphthylene, dibenzofuran, dibenzothiophene, carbazole and fluorene, where the divalent group may be substituted by one or more R.sup.5 radicals.

16. The compound as claimed in claim 1, wherein Ar.sup.2 is the same or different at each instance and is selected from groups of the following formulae: ##STR00515## where the variables that occur are defined as follows: V is the same or different at each instance and is N or CR.sup.5, where at least one V group in each of formulae (Ar.sup.2-A) and (Ar.sup.2-D) is N; W is the same or different at each instance and is N or CR.sup.5; U is NR.sup.5; where one R.sup.5 group per formula is replaced by the bond to the L.sup.1 group or the propellane group.

17. The compound as claimed in claim 1, wherein Ar.sup.2 is selected from pyridine, pyrimidine, pyridazine, pyrazine, triazine, carbazole, imidazole, pyrazole, triazole, benzimidazole, benzimidazobenzimidazole, quinoline, quinazoline, phenanthroline, phenanthridine, diazaphenanthrene, and acridine, each of which may be substituted by one or more R.sup.5 radicals.

18. The compound as claimed in claim 1, wherein R.sup.5 is selected from H, D, F, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl and alkoxy groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl or alkoxy groups mentioned may be replaced by CC, R.sup.6CCR.sup.6, Si(R.sup.6).sub.2, CO, CNR.sup.6, NR.sup.6, O, S, C(O)O or C(O)NR.sup.6.

19. A process for preparing the compound as claimed in claim 1 which comprises the alkoxy-substituted base skeleton is first prepared and is then converted in a further step to a reactive compound, preferably to a triflate derivative, which is converted in a further step by transition metal-catalyzed coupling reaction, preferably Hartwig-Buchwald, Suzuki, Stille, or Negishi coupling, to the compound as claimed in one or more of claims 1 to 18.

20. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.1, R.sup.2 or R.sup.5.

21. A formulation comprising one or more compounds as claimed claim 1 and at least one solvent.

22. An electronic device selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs), comprising at least one compound as claimed in claim 1.

23. The device as claimed in claim 22, wherein the device is an electroluminescent device comprising anode, cathode and at least one organic layer, wherein the compound is present in a hole-transporting layer, as matrix material in an emitting layer, or in an electron-transporting layer.

24. (canceled)

Description

EXAMPLES

A) Synthesis Examples

[0128] 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. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

[0129] Hereinafter, the [4.4.4]-propellanes, for the sake of clarity, are shown in the form of a Newman projection, as is also customary in the literature; see, for example, M. Kimura et al., Bull. Chem. Soc. Jpn., 2006, 79, 11, 1793.

A: Synthesis of the Synthons

Example S1

[0130] ##STR00232##

[0131] A mixture of 31.3 g (100 mmol) of 1-bromo-2-iodo-6-methoxybenzene [74128-84-0], 12.2 g (100 mmol) of benzeneboronic acid [98-80-6], g (300 mmol) of tripotassium phosphate, g (1 mmol) of tetrakis(triphenylphosphino)palladium(0), 200 ml of toluene, 80 ml of dioxane and 200 ml of water is heated under reflux for 16 h. After cooling, the aqueous phase is removed and the organic phase is washed three times with 200 ml each time of water and once with 200 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off, the organic phases concentrated to dryness and the remaining oil is subjected to kugelrohr distillation under high vacuum, Yield: 16.1 g (61 mmol), 61%; purity: 97% by .sup.1H NMR.

Example S10

[0132] ##STR00233##

[0133] A solution, cooled to 78 C., of 26.3 g (100 mmol) of S1 in 1000 ml of diethyl ether and 40 ml (100 mmol) of n-butyllithium, 2.5 M in n-hexane, are used to prepare the corresponding lithium reagent. With good stirring, 34.4 g (100 mmol) of spiro[9H-fluorene-9,9(10H)-phenanthrene]-10-one [1749-36-6] are added, the mixture is stirred at 70 C. for a further 30 minutes, then the mixture is allowed to warm up to room temperature and stirred for a further 24 h. The reaction is stopped by adding 200 ml of water and 200 ml of saturated ammonium chloride solution, and the organic phase is removed and dried over magnesium sulfate. The desiccant is filtered off, the solvent is removed under reduced pressure, and the residue is taken up in 500 ml of glacial acetic acid and homogenized while heating. Then 1 conc. sulfuric acid and 20 g of phosphorus pentoxide are added with good stirring, and the mixture is heated under reflux for 2 h. The mixture is left to cool to 80 C., then 400 ml of water are gradually added dropwise without further heating, and the precipitated solids are filtered off with suction, washed three times with 200 ml each time of water and once with 100 ml of methanol, and dried under reduced pressure. Yield: 38.9 g (76 mmol), 76%; purity: 97% by .sup.1H NMR.

[0134] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00003 Ex. Bromide Product Yield S11 [00234] [00235] 84% S12 [00236] [00237] 80% S13 [00238] [00239] 73% S14 [00240] [00241] 38% S15 [00242] [00243] 43% S16 [00244] [00245] 45% S17 [00246] [00247] 48% S18 [00248] [00249] 43%

Example S30

[0135] ##STR00250##

[0136] A mixture of 3.1 g (10 mmol) of 3-methoxyacenaphth[1,2-a]acenaphthylene [1088585-98-1], 20.4 g (100 mmol) of iodobenzene [591-50-4], 11.1 g (80 mmol) of potassium carbonate, 6.5 g (20 mmol) of tetra-n-butylammonium bromide and 112 mg (0.5 mmol) of palladium(II) acetate in 100 ml of DMF is stirred at 120 C. in a stirred autoclave under argon for 10 days. After cooling, the reaction mixture is diluted with 1000 ml of dichloromethane and filtered through a silica gel bed in the form of a slurry. The filtrate is freed of the dichloromethane under reduced pressure and then of the excess iodobenzene under high vacuum. The residue is separated by flash chromatography on an automated column system (Torrent from A. Semrau). Yield: 2.6 g (5.6 mmol), 56%; purity: 95% by .sup.1H NMR.

Example S50

[0137] ##STR00251##

[0138] A mixture of 51.2 g (100 mmol) of S10 and 250 g of pyridinium hydrochloride is heated to 200 C. for 6 h. The reaction mixture is left to cool to 100 C., and 1000 ml of water and then 50 ml of 2 N hydrochloric acid are cautiously added dropwise with good stirring without further heating. After cooling to about 30 C., the precipitated solids are filtered off with suction and washed three times with 200 ml each time of water and once with 100 ml of methanol, and dried under reduced pressure. Yield: 38.8 g (73 mmol), 73%; purity: 97% by .sup.1H NMR.

[0139] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00004 Ex. Reactant Product Yield S51 S11 [00252] 87% S52 S12 [00253] 85% S53 S13 [00254] 79% S54 S14 [00255] 80% S55 S15 [00256] 87% S56 S16 [00257] 85% S57 S30 [00258] 90% S58 S17 [00259] 88% S59 S18 [00260] 94%

Example S100

[0140] ##STR00261##

[0141] To a mixture, cooled to 0 C., of 49.7 g (100 mmol) of S50 and 24.2 ml (300 mmol) of pyridine are added dropwise, over the course of 1 h, 25.2 ml (150 mol) of trifluoromethanesulfonic anhydride O(Tf).sub.2 [358-23-6]. The mixture is stirred at 0 C. for a further 1 h, then allowed to warm up to room temperature and stirred for a further 12 h. The reaction mixture is poured into 1 l of ice-water with very good stirring, stirred for a further 10 min and extracted three times with 300 ml each time of dichloromethane. The combined organic phases are washed once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate. After the desiccant has been filtered off and the solvent removed, the residue is recrystallized from acetonitrile. 50.3 g (80 mmol), 80%; purity: 97% by .sup.1H NMR.

[0142] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00005 Ex. Bromide Product Yield S101 S51 [00262] 93% S102 S52 [00263] 90% S103 S53 [00264] 85% S104 S54 [00265] 70% S105 S55 [00266] 87% S106 S56 [00267] 85% S107 S57 [00268] 92% S108 S58 [00269] 77% S109 S59 [00270] 87%

Example S150

[0143] ##STR00271##

[0144] 23.8 g (100 mmol) of 1-bromonaphthalene [90-11-9] and 2.4 g (100 mmol) of magnesium turnings in 800 ml of THF are used to prepare the corresponding Grignard reagent. 13.1 g (50 mmol) of 3-bromo-1,2-acenaphthylenedione [21170-55-8] are added with good stirring and the mixture is stirred at 50 C. for a further 4 h. After cooling to room temperature, the mixture is quenched by cautiously adding 20 ml of water. The THF is largely removed under reduced pressure, and the residue is taken up in 1500 ml of toluene and washed twice with water and once with saturated sodium chloride solution. For drying, 500 ml of toluene are removed on a water separator, then 10 ml of trifluoromethanesulfonic acid are added with good stirring and the reaction mixture is heated on a water separator for a further 16 h. Then a further 800 ml of toluene are distilled off, the mixture is allowed to cool to about 50 C., 500 ml of methanol are added dropwise, the mixture is stirred for a further 30 min, and the solids are filtered off with suction, washed three times with 100 ml each time of methanol and dried under reduced pressure. Yield: 8.2 g (17 mmol), 34%; purity: 97% by .sup.1H NMR.

[0145] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00006 Ex. Reactant Product Yield S151 [00272] [00273] 44% S152 [00274] [00275] 46% S153 [00276] [00277] [00278] 44%

B: Compounds of the Invention

Example H1

[0146] ##STR00279##

[0147] A mixture of 62 0.8 g (100 mmol) of S100, 18.6 g (110 mmol) of diphenylamine, 13.5 g (120 mmol) of sodium tert-butoxide, 449 mg (2 mmol) of palladium acetate, 1230 mg (3 mmol) of SPhos and 800 ml of toluene is heated under reflux for 16 h. 1 ml of hydrazine hydrate is added and the mixture is heated under reflux for 1 h. 400 ml of water are added to the reaction mixture at 50 C. while stirring, then the organic phase is separated off and filtered while still warm through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to about 100 ml and then 200 ml of methanol are added to the filtrate while hot with good stirring. The mixture is left to cool while stirring, and the crystallized product is filtered off and washed three times with 100 ml each time of methanol. Further purification is effected by hot extraction five times with toluene (amount initially charged 250 ml) and subsequent double fractional sublimation under reduced pressure (T about 300 C., p about 10.sup.6 mbar). Yield: 45.0 g (68 mmol), 68%; purity: about 99.9% by HPLC.

[0148] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00007 Ex. Reactants Product Yield H2 [00280] [00281] 55% H3 [00282] [00283] 46% H4 [00284] [00285] 43% H5 [00286] [00287] 48% H6 [00288] [00289] 40% H7 [00290] [00291] 52% H8 [00292] [00293] 49% H9 [00294] [00295] 75% H10 [00296] [00297] 73% H11 [00298] [00299] 75% H12 [00300] [00301] 70% H13 [00302] [00303] 68% H14 [00304] [00305] 74% H15 [00306] [00307] 70% H16 [00308] [00309] 71% H17 [00310] [00311] 69% H18 [00312] [00313] 76% H19 [00314] [00315] 70% H20 [00316] [00317] 78% H21 [00318] [00319] 75% H22 [00320] [00321] 73% H23 [00322] [00323] 70% H24 [00324] [00325] 74% H25 [00326] [00327] 71% H26 [00328] [00329] 68% H27 [00330] [00331] 65% H28 [00332] [00333] 67% H29 [00334] [00335] 63% H30 [00336] [00337] 65% H31 [00338] [00339] 66% H32 [00340] [00341] 65% H33 [00342] [00343] 67% H34 [00344] [00345] 62% H35 [00346] [00347] 46% H36 [00348] [00349] 39% H37 [00350] [00351] 41% H38 [00352] [00353] 65% H39 [00354] [00355] 69% H40 [00356] [00357] 65% H41 [00358] [00359] 62% H42 [00360] [00361] 68% H43 [00362] [00363] 67% H44 [00364] [00365] 69% H45 [00366] [00367] 66% H46 [00368] [00369] 67% H47 [00370] [00371] 65% H48 [00372] [00373] 40% H49 [00374] [00375] 39% H50 [00376] [00377] 42% H51 [00378] [00379] 68% H52 [00380] [00381] 72% H53 [00382] [00383] 70% H54 [00384] [00385] 67% H55 [00386] [00387] 65% H56 [00388] [00389] 65% H57 [00390] [00391] 53% H58 [00392] [00393] 68% H59 [00394] [00395] 67% H60 [00396] [00397] 37% H61 [00398] [00399] 87%

Example H100

[0149] ##STR00400##

[0150] A mixture of 62.8 g (100 mmol) of S100, 37.1 g (110 mmol) of N,N-diphenylamino-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene [267221-88-5], 63.7 g (300 mmol) of tripotassium phosphate, 820 mg (2 mmol) of SPhos, 225 mg (1 mmol) of palladium acetate, 400 ml of toluene, 200 ml of dioxane and 400 ml of water is heated under reflux for 20 h. 1 ml of hydrazine hydrate is added and the mixture is heated under reflux for 1 h. The mixture is left to cool to 60 C., the aqueous phase is separated off, and the organic phase is washed twice with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, and filtered while still hot through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to about 100 ml and then 200 ml of methanol are added to the filtrate while hot with good stirring. The mixture is left to cool while stirring, and the crystallized product is filtered off and washed three times with 100 ml each time of methanol. Further purification is effected by hot extraction five times with butyl acetate (amount initially charged 250 ml) and subsequent double fractional sublimation under reduced pressure (T about 310 C., p about 10.sup.5 mbar). Yield: 31.9 g (44 mmol), 44%; purity: about 99.9% by HPLC.

[0151] In an analogous manner, it is possible to prepare the following compounds:

TABLE-US-00008 Ex. Reactants Product Yield H101 [00401] [00402] 40% H102 [00403] [00404] 45% H103 [00405] [00406] 73% H104 [00407] [00408] 70% H105 [00409] [00410] 70% H106 [00411] [00412] 74% H107 [00413] [00414] 72% H108 [00415] [00416] 70% H109 [00417] [00418] 58% H110 [00419] [00420] 63% H111 [00421] [00422] 60% H112 [00423] [00424] 61% H113 [00425] [00426] 66% H114 [00427] [00428] 63% H115 [00429] [00430] 58% H116 [00431] [00432] 68% H117 [00433] [00434] 65% H118 [00435] [00436] 66% H119 [00437] [00438] 64% H120 [00439] [00440] 38% H121 [00441] [00442] 41% H122 [00443] [00444] 70% H123 [00445] [00446] 68% H124 [00447] [00448] 73% H125 [00449] [00450] 70% H126 [00451] [00452] 67% H127 [00453] [00454] 65% H128 [00455] [00456] 69% H129 [00457] [00458] 49% H130 [00459] [00460] 33% H131 [00461] [00462] 71%

Example E1

[0152] ##STR00463##

[0153] A mixture of 62.8 g (100 mmol) of S100, 47.9 g (110 mmol) of 2,4-diphenyl-6-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine [1219956-23-6], 63.7 g (300 mmol) of tripotassium phosphate, 820 mg (2 mmol) of SPhos, 225 mg (1 mmol) of palladium acetate, 400 ml of toluene, 200 ml of dioxane and 400 ml of water is heated under reflux for 20 h. The mixture is left to cool to 60 C., the aqueous phase is separated off, and the organic phase is washed twice with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, and filtered while still hot through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to about 100 ml and then 200 ml of methanol are added to the filtrate while hot with good stirring. The mixture is left to cool while stirring, and the crystallized product is filtered off and washed three times with 100 ml each time of methanol. Further purification is effected by hot extraction five times with toluene (amount initially charged 250 ml) and subsequent double fractional sublimation under reduced pressure (T about 320 C., p about 10.sup.5 mbar). Yield: 38.6 g (49 mmol), 49%; purity: about 99.9% by HPLC.

[0154] In an analogous manner, its possible to pre are the following compounds:

TABLE-US-00009 Ex Reactants Product Yield E2 [00464] [00465] 46% E3 [00466] [00467] 72% E4 [00468] [00469] 70% E5 [00470] [00471] 68% E6 [00472] [00473] 75% E7 [00474] [00475] 77 & E8 [00476] [00477] 64% E9 [00478] [00479] 67% E10 [00480] [00481] 63% E11 [00482] [00483] 60% E12 [00484] [00485] 63% E13 [00486] [00487] 61% E14 [00488] [00489] 67% E15 [00490] [00491] 65% E16 [00492] [00493] 38% E17 [00494] [00495] 69%

B) Device Examples

1) General Description of the Production and Analysis of the OLEDs

[0155] In the examples which follow, the production and device data of various OLEDs are presented.

[0156] The OLEDs can be produced as follows: Cleaned glass plaques (cleaning in Miele laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 30 min, for improved processing, coated with 25 nm of PEDOT:PSS (purchased as CLEVIOS P VP Al 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution), and then baked at 180 C. for 10 min. These coated glass plaques form the substrates to which the OLEDs are applied.

[0157] The OLEDs have the following layer structure: substrate/hole transport layer 1 (HTL1) consisting of the compound HTM (see table 3) doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 2 (HTL2)/optional electron blocker layer (EBL)/emission layer (EML)/hole blocker layer (HBL)/electron transport layer (ETL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm. The exact composition of layers HTL1, EBL (if present), EML, HBL and ETL is shown in the tables which follow.

[0158] For production of the OLEDs, the materials used correspondingly in one layer are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as M1:M2:Ir1 (55%:35%:10%) mean here that the material M1 is present in the layer in a proportion by volume of 55%, M2 in a proportion of 35% and Ir1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in table 1. The materials used for production of the OLEDs are shown in table 3.

[0159] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, and the lifetime are determined. 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. The parameter U1000 in table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

[0160] The lifetime LD80 is defined as the time after which the luminance drops to 80% of the starting luminance in the course of operation with a constant current of 40 mA/cm.sup.2.

2) Use of the Compounds of the Invention in a Hole Transport Layer

[0161] The examples which follow show that the compounds of the invention can be used as hole transport materials in a hole transport layer.

[0162] In examples D1 to D11 and D14, the inventive compounds H3, H5, H6, H9, H10, H13, H26 and H104 are used as hole transport materials in green-emitting triplet OLEDs (emitter Ir1 or Ir2 in each case).

[0163] In examples D18 to D24, the inventive compounds H9, H37, H47, H49 and H131 are used as hole transport materials in yellow-emitting triplet OLEDs (emitter Ir3 or Ir4 in each case).

TABLE-US-00010 HTL2 EML HBL ETL Ex. thickness thickness thickness thickness D1 H9 M1:Ir1 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D2 M1:Ir2 (85%:15%) 30 nm D3 M1:M2:Ir1 (45%:45%:10%) 30 nm D4 M1:M2:Ir2 (45%:45%:10%) 30 nm D5 H3 M1:M2:Ir1 40 nm (45%:45%:10%) 30 nm D6 H5 40 nm D7 H6 40 nm D8 H10 M1:M2:Ir1 40 nm (35%:55%:10%) 30 nm D9 H13 M1:M2:Ir1 40 nm (45%:40%:15%) 30 nm D10 H20 M1:M2:Ir2 40 nm (40%:45%:15%) 30 nm D11 H26 40 nm D14 H104 40 nm D18 H9 M1:Ir3 40 nm (80%:20%) 30 nm D19 M1:Ir4 (85%:15%) 30 nm D20 H131 M1:Ir3 40 nm (80%:20%) 30 nm D22 H37 M1:Ir4 40 nm (85%:15%) 30 nm D23 H47 M1:Ir4 40 nm (85%:15%) 30 nm D24 H49 M1:Ir4 40 nm (85%:15%) 30 nm

[0164] Excellent performance data are measured for the OLEDs in question, which are shown below:

TABLE-US-00011 Ex. EQE1000 (%) U1000 (V) CIE x/y LT80 (h) D1 20.3 3.1 0.33/0.64 120 D2 19.2 3.1 0.36/0.62 150 D3 20.5 3.0 0.33/0.64 140 D4 19.5 3.0 0.36/0.62 180 D5 20.7 3.0 0.33/0.64 240 D6 20.4 2.9 0.33/0.64 230 D7 20.9 3.0 0.33/0.64 210 D8 20.5 3.0 0.33/0.64 240 D9 20.1 3.1 0.33/0.63 260 D10 19.3 3.0 0.36/0.62 430 D11 19.7 3.0 0.36/0.62 470 D14 19.7 3.1 0.37/0.62 460 D18 17.0 2.9 0.39/0.59 300 D19 19.1 3.0 0.46/0.53 360 D20 17.6 3.0 0.40/0.58 520 D22 19.0 2.8 0.46/0.52 380 D23 19.5 2.9 0.46/0.53 370 D24 19.7 2.9 0.46/0.53 410

3) Use of the Compounds of the Invention in a Hole Transport Layer and as Matrix Material in an Emitting Layer

[0165] The examples which follow show that the compounds of the invention can be used as hole transport materials in a hole transport layer and additionally, in the same OLED, also as matrix materials in an emitting layer.

[0166] In each of examples D12 and D13, the inventive compound H26 is used. In addition, the inventive compound H32 or H34 is present in the emitting layer as co-host (h-type TMM) together with the further matrix material M1. The triplet emitter used in each case is the green emitter Ir-2.

TABLE-US-00012 HTL2 EML HBL ETL Ex. thickness thickness thickness thickness D12 H26 M1:H32:Ir2 ETM1 ETM1:ETM2 40 nm (40%:45%:15%) 10 nm (50%:50%) 30 nm 30 nm D13 M1:H34:Ir2 (40%:45%:15%) 30 nm

[0167] Excellent performance data are measured for the OLEDs in question, which are shown below:

TABLE-US-00013 Ex. EQE1000 (%) U1000 (V) CIE x/y LT80 (h) D12 19.8 2.9 0.37/0.62 450 D13 19.4 3.1 0.36/0.62 480

4) Use of the Compounds of the Invention in the Hole Blocker Layer and the Electron Transport Layer, and in Some Cases Additionally Also in the Emitting Layer, the Electron Blocker Layer and the Hole Transport Layer

[0168] Example D15 shows that the compounds of the invention can be used as materials in the hole blocker layer and additionally, in the same OLED, also as materials in the electron transport layer.

[0169] In example D15, the inventive compound E3 is used as hole blocker material in each case. In addition, the same compound E3 is present in the electron transport layer in a mixture with the further electron transport material ETM2. The triplet emitter used is the green emitter Ir-2.

TABLE-US-00014 HTL2 EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness D15 HTM M1:M2:Ir2 E3 E3:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm

[0170] Excellent performance data are measured for the OLED in question, which are shown below:

TABLE-US-00015 Ex. EQE1000 (%) U1000 (V) CIE x/y LT80 (h) D15 19.9 2.9 0.37/0.62 390

[0171] In examples D16, D17 and D21, inventive compounds are additionally used in the hole transport layer (D16, D17). In example D21, inventive compounds are actually present in all layers of the OLED from HTL to ETL:

TABLE-US-00016 HTL2 EBL EML HBL ETL EX. thickness thickness thickness thickness thickness D16 H26 M1:M2:Ir2 E3 E3:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D17 H26 M1:M2:Ir2 E8 E8:ETM2 40 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm D21 H26 H131 M1:H34:Ir3 E8 E8:ETM2 30 nm 10 nm (40%:50%:10%) 10 nm (50%:50%) 30 nm 30 nm

[0172] Excellent performance data are measured for the OLED in question, which are shown below:

TABLE-US-00017 Ex. EQE1000 (%) U1000 (V) CIE x/y LT80 (h) D16 19.5 3.0 0.37/0.62 430 D17 19.6 3.1 0.36/0.62 450 D21 18.2 3.0 0.40/0.58 550
6) Comparison of the Inventive Compounds H9 with the Compound HTM-Ref

[0173] The performance of OLEDs comprising the material H9 is compared with reference OLEDs comprising the material HTM-Ref in various device constructions.

[0174] Six different device constructions a) to f) are used:

a) D-Ref1 vs. D1
b) D-Ref2 vs. D2
c) D-Ref3 vs. D3
e) D-Ref4 vs. D4
e) D-Ref5 vs. D18
f) D-Ref6 vs. D19

[0175] The exact device constructions comprising constructions with different triplet emitters and different matrix materials are as follows:

TABLE-US-00018 HTL2 EML HBL ETL Ex. thickness thickness thickness thickness D-Ref1 HTM-Ref M1:Ir1 ETM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D1 H9 40 nm D-Ref2 HTM-Ref M1:Ir2 40 nm (85%:15%) 30 nm D2 H9 40 nm D-Ref3 HTM-Ref M1:M2:Ir1 40 nm (45%:45%:10%) 30 nm D3 H9 40 nm D-Ref4 HTM-Ref M1:M2:Ir1 40 nm (45%:45%:10%) 30 nm D4 H9 40 nm D-Ref5 HTM-Ref M1:Ir3 40 nm (80%:20%) 30 nm D18 H9 40 nm D-Ref6 HTM-Ref M1:Ir4 40 nm (85%:15%) 30 nm D19 H9 40 nm

[0176] The measurement data obtained for efficiency and lifetime inter alia are shown in the following table:

TABLE-US-00019 Ex. EQE1000 (%) U1000 (V) CIE x/y LT80 (h) D-Ref1 19.2 3.0 0.33/0.63 70 D1 20.3 3.1 0.33/0.64 120 D-Ref2 18.7 3.1 0.36/0.62 95 D2 19.2 3.1 0.36/0.62 150 D-Ref3 19.4 3,0 0.33/0.63 90 D3 20.5 3.0 0.33/0.64 140 D-Ref4 19.0 2.9 0.36/0.62 130 D4 19.5 3.0 0.36/0.62 180 D-Ref5 16.7 2.9 0.40/0.58 130 D18 17.0 2.9 0.39/0.59 300 D-Ref6 18.8 3.0 0.46/0.53 160 D19 19.1 3.0 0.46/0.53 360

[0177] As apparent from the measurement data, in all direct comparisons between H9 and HTM-Ref, lifetime and efficiency are greatly improved, with comparable CIE coordinates and voltage.

TABLE-US-00020 TABLE 3 Structural formulae of the materials used and CAS numbers [00496] HTM [00497] M1 [00498] M2 [00499] ETM1 [00500] ETM2 [00501] Ir1 [00502] Ir2 [00503] Ir3 [00504] Ir4 [00505] HTM-Ref