BENZIMIDAZOLE DERIVATIVES

Abstract

The invention relates to benzimidazole derivatives which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Claims

1.-20. (canceled)

21. A compound comprising at least one structure of the formula (I): ##STR00270## wherein: R.sup.a, R.sup.b is the same or different at each instance and is N(Ar).sub.2, N(R).sub.2, B(Ar).sub.2, B(R).sub.2, OAr, OR, SAr, SR, S(═O)Ar, S(═O)R, S(═O).sub.2Ar, S(═O).sub.2R, P(═O)(Ar).sub.2, P(═O)(R).sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R radicals; at the same time, two R.sup.a, R.sup.b radicals together may also form a ring system or be bridged to one another by a bridge selected from B(R), C(R).sub.2, Si(R).sub.2, Ge(R).sub.2, C═O, C═NR, C═NAr′, C═C(R).sub.2, O, S, S═O, SO.sub.2, N(R), N(Ar′), P(R) and P(═O)R; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R radicals; the Ar group here may form a ring system with at least one further group; X is N, CR or C if the Ar group forms a ring system via a bond, with the proviso that not more than two of the X groups in any cycle are N; R is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar′).sub.2, N(R.sup.1).sub.2, C(═O)N(Ar′).sub.2, C(═O)N(R.sup.1).sub.2, C(Ar′).sub.3, C(R.sup.1).sub.3, Si(Ar′).sub.3, Si(R.sup.1).sub.3, B(Ar′).sub.2, B(R.sup.1).sub.2, C(═O)Ar′, C(═O)R.sup.1, P(═O)(Ar′).sub.2, P(═O)(R.sup.1).sub.2, P(Ar′).sub.2, P(R.sup.1).sub.2, S(═O)Ar′, S(═O)R.sup.1, S(═O).sub.2Ar′, S(═O).sub.2R.sup.1, OSO.sub.2Ar′, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═Se, C═NR.sup.1, —C(═O)O—, —C(═O)NR.sup.1—, NR.sup.1, P(═O)(R.sup.1), —O—, —S—, SO or SO.sub.2 or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R radicals may also together or with a further group form a ring system; Ar′ is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, it is possible for two Ar′ radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.1), C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, C═NR.sup.1, C═C(R.sup.1).sub.2, O, S, S═O, SO.sub.2, N(R.sup.1), P(R.sup.1) and P(═O)R.sup.1; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar″).sub.2, N(R.sup.2).sub.2, C(═O)Ar″, C(═O)R.sup.2, P(═O)(Ar″).sub.2, P(Ar″).sub.2, B(Ar″).sub.2, B(R.sup.2).sub.2, C(Ar″).sub.3, C(R.sup.2).sub.3, Si(Ar″).sub.3, Si(R.sup.2).sub.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sub.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more, optionally adjacent R.sup.1 radicals together may form a ring system; at the same time, one or more R.sup.1 radicals may form a ring system with a further part of the compound; Ar″ 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.2 radicals; at the same time, it is possible for two Ar″ radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.2), C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, C═C(R.sup.2).sub.2, O, S, S═O, SO.sub.2, N(R.sup.2), P(R.sup.2) and P(═O)R.sup.2; R.sup.2 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more, adjacent substituents R.sup.2 together may form a ring system.

22. A compound as claimed in claim 21, comprising at least one structure of the formulae (IIa), (IIb), (IIc) and (IId): ##STR00271## where X and Ar have the definitions given in claim 21, Y.sup.a is O, S, S═O, SO.sub.2, N(R) or N(Ar′), Y.sup.b is B(R), C(R).sub.2, Si(R).sub.2, Ge(R).sub.2, C═O, C═NR, C═NAr′, C═C(R).sub.2, O, S, S═O, SO.sub.2, N(R), N(Ar′), P(R) or P(═O)R, and W is the same or different at each instance and is NAr, NR, BAr, BR, O, S, P(═O)Ar, P(═O)R, S(═O), S(═O).sub.2.

23. A compound as claimed in claim 21, comprising at least one structure of the formulae (IIIa), (IIIb), (IIIc), (IIId) and (IIIe): ##STR00272## where R and Ar have the definitions given in claim 21, Y.sup.a is O, S, S═O, SO.sub.2, N(R) or N(Ar′), Y.sup.b is B(R), C(R).sub.2, Si(R).sub.2, Ge(R).sub.2, C═O, C═NR, C═NAr′, C═C(R).sub.2, O, S, S═O, SO.sub.2, N(R), N(Ar′), P(R) or P(═O)R, and W is the same or different at each instance and is NAr, NR, BAr, BR, O, S, P(═O)Ar, P(═O)R, S(═O), S(═O).sub.2, the index l is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, and the index j is 0, 1 or 2.

24. A compound as claimed in claim 21, comprising at least one structure of the formulae (IVa), (IVb), (IVc) and (IVd): ##STR00273## where R and Ar have the definitions given in claim 21, Y.sup.a is O, S, S═O, SO.sub.2, N(R) or N(Ar′), Y.sup.b is B(R), C(R).sub.2, Si(R).sub.2, Ge(R).sub.2, C═O, C═NR, C═NAr′, C═C(R).sub.2, O, S, S═O, SO.sub.2, N(R), N(Ar′), P(R) or P(═O)R, and W is the same or different at each instance and is NAr, NR, BAr, BR, O, S, P(═O)Ar, P(═O)R, S(═O), S(═O).sub.2, the index l is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, and the index j is 0, 1 or 2.

25. A compound as claimed in claim 22, wherein at least one of the W radicals represents N(R) or N(Ar).

26. A compound as claimed in claim 22, wherein at least one of the W radicals represents B(R) or B(Ar).

27. A compound as claimed in claim 22, wherein at least one of the W radicals represents O, S, S(═O), S(═O).sub.2.

28. A compound as claimed in claim 22, at least one of the W radicals represents N(R) or N(Ar), and at least one of the W radicals is B(Ar), B(R), O or S.

29. A compound as claimed in claim 22, comprising at least one structure of the formulae (Va) to (Ve): ##STR00274## where Y.sup.a is O, S, S═O, SO.sub.2, N(R) or N(Ar′), Y.sup.b is B(R), C(R).sub.2, Si(R).sub.2, Ge(R).sub.2, C═O, C═NR, C═NAr′, C═C(R).sub.2, O, S, S═O, SO.sub.2, N(R), N(Ar′), P(R) or P(═O)R, and W is the same or different at each instance and is NAr, NR, BAr, BR, O, S, P(═O)Ar, P(═O)R, S(═O), S(═O).sub.2, the index l is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, and the index j is 0, 1 or 2.

30. A compound as claimed in claim 22, comprising at least one structure of the formulae (VIa) to (VId): ##STR00275## where Y.sup.a is O, S, S═O, SO.sub.2, N(R) or N(Ar′), Y.sup.b is B(R), C(R).sub.2, Si(R).sub.2, Ge(R).sub.2, C═O, C═NR, C═NAr′, C═C(R).sub.2, O, S, S═O, SO.sub.2, N(R), N(Ar′), P(R) or P(═O)R, and W is the same or different at each instance and is NAr, NR, BAr, BR, O, S, P(═O)Ar, P(═O)R, S(═O), S(═O).sub.2, the index l is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, and the index j is 0, 1 or 2.

31. A compound as claimed in claim 22, comprising at least one structure of the formulae (VIa-1) to (VIb-13): ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## where Y.sup.a is O, S, S=0, 502, N(R) or N(Ar′), the index l is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, and the index j is 0, 1 or 2.

32. A compound as claimed in claim 21, wherein at least two R radicals form a fused ring together with the further groups to which the two R radicals bind, where the two R radicals form at least one structure of the formulae (RA-1) to (RA-12): ##STR00282## ##STR00283## where R.sup.1 has the definition set out above, the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R radicals bind, and the further symbols have the following definition: Y.sup.c is the same or different at each instance and is C(R.sup.1).sub.2, (R.sup.1).sub.2C—C(R.sup.1).sub.2, (R.sup.1)C═C(R.sup.1), NR.sup.1, NAr′, O or S; R.sup.c is the same or different at each instance and is F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkyl or alkenyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more R.sup.2 radicals, where one or more adjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sub.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, where R.sup.2 has the definition detailed above; at the same time, it is also possible for two R.sup.c radicals together to form a ring system; s is 0, 1, 2, 3, 4, 5 or 6; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

33. A compound as claimed in claim 21, that at least two R radicals form a fused ring together with the further groups to which the two R radicals bind, where the two R radicals form of the structures of the formula (RB): ##STR00284## where R.sup.1 has the definition set out in claim 21, the index m is 0, 1, 2, 3 or 4, and Y.sup.d is C(R.sup.1).sub.2, NR.sup.1, NAr′, BR.sup.1, BAr′, O or S.

34. A compound as claimed in claim 21, wherein compounds of formula A are excluded ##STR00285## where the symbols Ar and R have the definition given in claim 21.

35. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 21, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

36. A formulation comprising at least one compound as claimed in claim 21 and at least one further compound, where the further compound is selected from one or more solvents.

37. A composition comprising at least one compound as claimed in claim 21 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

38. A process for preparing a compound as claimed in claim 21, wherein a base skeleton having two aromatic amino groups is synthesized and this is then converted to a compound of formula (I) by means of a nucleophilic aromatic substitution reaction, a nucleophilic addition reaction or a coupling reaction.

39. The use of a compound as claimed in claim 21 in an electronic device.

40. An electronic device comprising at least one compound as claimed in claim 21, wherein the electronic device is an organic electroluminescent device.

Description

EXAMPLES

[0210] 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. In the case of compounds that can have multiple enantiomeric, diastereomeric or tautomeric forms, one form is shown in a representative manner.

[0211] Synthesis of Synthons S:

Example S1

[0212] ##STR00110##

[0213] Procedure analogous to P.-Y. Gu et al., Dyes and Pigments, 2016, 131, 224.

[0214] A mixture of 15.0 g [100 mmol] of 2,3-dichloropyrazine [4858-85-9] and 54.3 g [300 mmol] of benzophenone imine [1013-88-3] in 500 ml DMSO is stirred at 160° C. for 24 h. The mixture is allowed to cool to 80° C., 20 ml of 10.2 molar aqueous HCl is added, and the mixture is heated again to 160° C. for 40 h. After cooling, the mixture is poured onto 2000 ml of degassed ice-water and stirred briefly, and the solids are filtered off with suction, washed three times with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography, n-heptane/DCM (dichloromethane), Torrent automated column system from A. Semrau. Yield: 15.4 g (56 mmol) 56%; purity about 95% by .sup.1H NMR.

[0215] The following compounds can be prepared analogously:

TABLE-US-00013 Ex. Reactants Product Yield S2 [00111]   [00112] [00113] 50% S3 [00114]   [00115] [00116] 55% S4 [00117]   [00118] [00119] 44% S5 [00120]   [00121] [00122] 60% S6 [00123]   [00124] [00125] 41% S7 [00126]   [00127] [00128] 49% S8 [00129]   [00130] [00131] 32%

Example S50

[0216] ##STR00132##

[0217] A well-stirred mixture of 23.6 g [100 mmol] of o-dibromobenzene [583-53-9], 54.3 g [300 mmol] of benzophenone imine [1013-88-3], 38.4 g [400 mmol] of sodium tert-butoxide [865-48-5], 2.5 g [4 mmol] of BINAP [98327-87-8], 898 mg [4 mmol] of palladium(II) acetate and 500 ml of toluene is heated under reflux for 1 h. After cooling, 500 ml is added, the mixture is stirred for 5 min., and the organic phase is removed, washed three times with 300 ml of water and once with saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off using a Celite bed in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is taken up in 500 ml of DMSO, 20 ml of 10.2 molar aqueous HCl is added, and the mixture is heated to 160° C. for 40 h. After cooling, the mixture is poured onto 2000 ml of degassed ice-water and stirred briefly, and the solids are filtered off with suction, washed three times with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography, n-heptane/DCM (dichloromethane), Torrent automated column system from A. Semrau. Yield: 15.5 g (57 mmol) 57%; purity about 95% by .sup.1H NMR.

[0218] The following compounds can be prepared analogously:

TABLE-US-00014 Ex. Reactants Product Yield S51 [00133]   [00134] [00135] 48% S52 [00136]   [00137] [00138] 60% S53 [00139] [00140] 53% [00141] S54 [00142] [00143] 49% [00144] S55 [00145]   [00146] [00147] 50% S56 [00148]   [00149] [00150] 55% S57 [00151] [00152] 44% [00153] S58 [00154]   [00155] [00156] 56% S59 [00157]   [00158] [00159] 54% S60 [00160]   [00161] [00162] 31% S61 [00163]   [00164] [00165] 20%

Example S100

[0219] ##STR00166##

[0220] A mixture of 26.6 g [100 mmol] of 1,3-dihydro-1,3-diphenyl-2H-benzimidazol-2-one [28386-83-5] and 100 ml of phosphorus oxytrichloride [10025-87-3] is heated under reflux for 16 h. Then the excess phosphorus oxytrichloride is distilled off, the oily residue is taken up in 250 ml of ice-cold methanol, and 200 ml of a saturated aqueous potassium hexafluorophosphate solution is added while stirring. The mixture is stirred for 15 min, 200 ml of ice-water is added dropwise to the suspension with good stirring, and the solids are filtered off with suction, washed three times with 100 ml each time of water, suction-dried and then dried under reduced pressure at 60° C. The 2-chlorobenzimidazolium hexafluorophosphate thus obtained is suspended in 150 ml of acetonitrile, and then 14.1 g [130 mmol] of o-phenylenediamine [95-54-5] and 50 ml of triethylamine are added, and the mixture is stirred at 50° C. for 8 h. The reaction mixture is poured into 500 ml of ice-water with good stirring, and the precipitated solids are filtered off with suction, washed three times with 100 ml of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography, n-heptane/EA (ethyl acetate), Torrent automated column system from A. Semrau. Yield: 12.5 g (33 mmol) 33%; purity about 95% by .sup.1H NMR.

[0221] The following compounds can be prepared analogously:

TABLE-US-00015 Ex. Reactants Product Yield S101 [00167]   [00168] [00169] 40% S102 [00170]   [00171] [00172] 43% S103 [00173]   [00174] [00175] 36% S104 [00176] [00177] 30% [00178] S105 [00179] [00180] 35% [00181] S106 [00182]   [00183] [00184] 45% S107 [00185]   [00186] [00187] 38% A108 [00188]   [00189] [00190] 50%

[0222] By way of clarification, it should be emphasized that the compounds S100 to S107 are encompassed by the scope of protection of the present invention. These compounds are valuable intermediates for production of stable hole conductors, electron conductors and host materials, as set out in detail above. However, compounds having N—H bonds show relatively low stability when used directly in a device. Compound A108 obtained via the above-detailed synthesis route does not have any N—H bond and can thus be used directly for the production of a device.

[0223] Synthesis of the Inventive Compounds A:

Example A1

[0224] ##STR00191##

[0225] A mixture of 27.4 g [100 mmol] of S1, 53.6 g [230 mmol] of 3-bromobiphenyl [2113-57-7], 25.0 g [260 mmol] of sodium tert-butoxide [865-48-5], 607 mg [3 mmol] of tri-tert-butylphosphine [13716-12-6], 584 mg [2.6 mmol] of palladium(II) acetate and 700 ml of toluene is heated under reflux for 16 h. After cooling, the salts are filtered off with suction using a Celite bed in the form of a toluene slurry. The filtrate is washed three times with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off and concentrated, and the crude product is chromatographed, silica gel, n-heptane/EA, Torrent automated column system from A. Semrau. Further purification is effected by recrystallization or continuous hot extraction crystallization (cellulose thimbles from Whatman, initial amount about 300 ml), typically twice from DCM/iso-propanol (1:2, vv) and then three to five times from DCM/acetonitrile (1:2, vv). Finally, the product is sublimed under high vacuum, preferably by zone sublimation, or freed of the solvent and volatile constituents by heat treatment. Yield: 34.2 g (59 mmol), 59%; purity: about 99.9% by HPLC.

[0226] The following compounds can be prepared analogously:

TABLE-US-00016 Ex. Reactants Product Yield A2 [00192] [00193] 55% A3 [00194] [00195] 43% A4 [00196] [00197] 60% A5 [00198] [00199] 72% A6 [00200] [00201] 59% A7 [00202] [00203] 51% A8 [00204] [00205] 17% A50a [00206] [00207] 63% A50b [00208] [00209] 61% A51 [00210] [00211] 57% A52 [00212] [00213] 55% A53 [00214] [00215] 60% A54 [00216] [00217] 62% A55 [00218] [00219] 67% A56 [00220] [00221] 56% A57 [00222] [00223] 64% A58 [00224] [00225] 45% A59 [00226] [00227] 61% A60 [00228] [00229] 59% A61 [00230] [00231] 26% A100 [00232] [00233] 63% A101 [00234] [00235] 66% A102 [00236] [00237] 60% A103 [00238] [00239] 48% A104 [00240] [00241] 57% A105 [00242] [00243] 59% A106a [00244] [00245] A106b [00246] [00247] 72% A107 [00248] [00249] 67%

Example: Production of the OLEDs

[0227] A) Vacuum-Processed Devices:

[0228] OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

[0229] In the examples which follow, the results for various OLEDs are presented. Cleaned glass plates (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 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180° C. for 10 min. These coated glass plates form the substrates to which the OLEDs are applied.

[0230] The OLEDs basically have the following layer structure: substrate/hole injection layer 1 (HIL1) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 1 (HTL1) consisting of HTM1, 170 nm for blue devices, 215 nm for green/yellow devices, 110 nm for red devices/hole transport layer 2 (HTL2)/emission layer (EML)/hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL from ETM2) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm.

[0231] First of all, vacuum-processed OLEDs are described. For this purpose, all the materials 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:Ir(L1) (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 by volume of 35% and Ir(L1) in a proportion by volume 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 4.

[0232] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined. Electroluminescence spectra are determined at a luminance of 1000 cd/m2, and these are used to calculate the CIE 1931 x and y color coordinates.

[0233] Use of Compounds of the Invention as Emitter Materials in Phosphorescent OLEDs

[0234] Among other uses, the compounds of the invention can be used as hole transport material in the HTL, as hole-conducting host material hTMM or electron-conducting host material eTMM in the emission layer EML of a phosphorescent OLED, and as electron transport material in the ETL. The results for the OLEDs are collated in table 2.

TABLE-US-00017 TABLE 1 Structure of the OLEDs HTL2 EML HBL ETL Ex. thickness thickness thickness thickness Blue OLEDs DB1- HTM3 M3:M4:IrB1 ETM1 ETM1:ETM2 Ref 20 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm DB1 A50a M3:M4:IrB1 ETM1 ETM1:ETM2 20 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm DB2 A58 M3:M4:IrB1 ETM1 ETM1:ETM2 20 nm (30%:60%:10%) 10 nm (50%:50%) 30 nm 30 nm Green and yellow OLEDs DG1- P1-1 M1:M2:IrG1 ETM1 ETM1:ETM2 Ref 10 nm (40%:50%:10%) 10 nm (50%:50%) 30 nm 30 nm DG1 A50a M1:M2:IrG1 ETM1 ETM1:ETM2 10 nm (40%:50%:10%) 10 nm (50%:50%) 30 nm 30 nm DG2- HTM2 M1:P1-1:IrG1 ETM1 ETM1:ETM2 Ref 10 nm (60%:25%:15%) 10 nm (50%:50%) 30 nm 30 nm DG3- HTM2 M1:P1-29:IrG1 ETM1 ETM1:ETM2 Ref 10 nm (60%:25%:15%) 10 nm (50%:50%) 30 nm 30 nm DG2 HTM2 M1:A50a:IrG1 ETM1 ETM1:ETM2 10 nm (60%:25%:15%) 10 nm (50%:50%) 30 nm 30 nm DG3 HTM2 M1:A50b:IrG1 ETM1 ETM1:ETM2 10 nm (60%:25%:15%) 10 nm (50%:50%) 30 nm 30 nm DG4 HTM2 M1:A51:IrG1 ETM1 ETM1:ETM2 10 nm (60%:25%:15%) 10 nm (50%:50%) 30 nm 30 nm DG5 HTM2 M1:A52:IrG1 ETM1 ETM1:ETM2 10 nm (60%:25%:15%) 10 nm (50%:50%) 30 nm 30 nm DG6 HTM2 M1:A53:IrG2 ETM1 ETM1:ETM2 10 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm DG7 A58 M1:A58:IrG2 ETM1 ETM1:ETM2 10 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm DG8 A60 M1:A60:IrG2 ETM1 ETM1:ETM2 10 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm DG9 A58 M1:A108:IrG2 ETM1 ETM1:ETM2 10 nm (55%:30%:15%) 10 nm (50%:50%) 30 nm 30 nm DG10 A102 M1:M2:IrG3 ETM1 ETM1:ETM2 10 nm (40%:45%:15%) 10 nm (50%:50%) 30 nm 30 nm DG11 HTM2 M1:A1:IrG3 ETM1 ETM1:ETM2 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm DG12 HTM2 M1:A2:IrG3 ETM1 ETM1:ETM2 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm DG13 HTM2 M1:A3:IrG3 ETM1 ETM1:ETM2 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm DG14 HTM2 M1:M2:IrG3 A5 ETM1:ETM2 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm DG15 HTM2 A55:M2:IrG3 ETM1 ETM1:ETM2 10 nm (50%:40%:10%) 10 nm (50%:50%) 30 nm 30 nm Red OLEDs DR1- HTM2 M5:IrR1 ETM1 ETM1:ETM2 Ref 10 nm (94%:6%) 10 nm (50%:50%) 30 nm 30 nm DR1 HTM2 A57:IrR1 ETM1 ETM1:ETM2 10 nm (94%:6%) 10 nm (50%:50%) 30 nm 30 nm DR2 HTM2 A101:IrR1 ETM1 ETM1:ETM2 10 nm (94%:6%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00018 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Blue OLEDs DB1-Ref 21.3 3.8 0.16/0.36 DB1 22.2 3.6 0.16/0.35 DB2 22.6 3.5 0.16/0.35 Green and yellow OLEDs DG1-Ref 20.6 3.4 0.34/0.61 DG1 22.1 3.1 0.34/0.61 DG2-Ref 20.3 3.5 0.35/0.61 DG3-Ref 20.1 3.4 0.35/0.61 DG2 21.9 3.3 0.35/0.61 DG3 22.3 3.1 0.35/0.61 DG4 22.1 3.2 0.35/0.61 DG5 22.0 3.3 0.35/0.61 DG6 22.2 3.2 0.34/0.64 DG7 22.4 3.0 0.33/0.63 DG8 22.1 3.1 0.33/0.63 DG9 21.8 3.1 0.34/0.63 DG10 28.1 3.1 0.49/0.51 DG11 27.7 3.1 0.49/0.51 DG12 27.5 3.1 0.49/0.51 DG13 28.0 3.0 0.49/0.51 DG14 27.3 3.1 0.48/0.51 DG15 27.5 3.0 0.48/0.51 Red OLEDs DR1-Ref 18.8 3.3 0.70/0.30 DR1 18.6 3.1 0.70/0.30 DR2 19.4 3.1 0.70/0.30

[0235] B) Solution-Processed Devices:

[0236] From Soluble Functional Materials of Low Molecular Weight

[0237] The compounds of the invention may also be processed from solution and lead therein to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have 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). The structure is composed of substrate/ITO/hole injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole blocker layer (10 nm)/electron transport layer (40 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in a cleanroom, a 20 nm hole injection layer (PEDOT:PSS from Clevios™) is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 200° C. for 30 minutes. The interlayer used serves for hole transport, with use of HL-X from Merck in this case. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfill the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the triplet emitters of the invention are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/I when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed devices contain an emission layer Ma:Mb:Ir (w %:x %:z %) or Ma:Mb:Mc:Ir (w %:x %:y %:z %); see table 3. The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160° C. for 10 min. Vapor-deposited above the latter are the hole blocker layer (10 nm ETM1) and the electron transport layer (40 nm ETM1 (50%)/ETM2 (50%)) (vapor deposition systems from Lesker or the like, typical vapor deposition pressure 5×10.sup.−6 mbar). Finally, a cathode of aluminum (100 nm) (high-purity metal from Aldrich) is applied by vapor deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited have not yet been optimized. Table 3 summarizes the data obtained.

TABLE-US-00019 TABLE 3 Results with materials processed from solution EQE Voltage (%) (V) CIE x/y 1000 1000 1000 Ex. Emission layer cd/m.sup.2 cd/m.sup.2 cd/m.sup.2 Sol-Ref M6:M7:IrG-Sol1 22.7 4.5 0.34/0.62 (20%:55%:25%) Sol-D1 M6:M7:A6:IrG-Sol1 22.8 4.3 0.34/0.62 (20%:40%:15%:25%) Sol-D2 M6:M7:A7:IrG-Sol1 22.7 4.3 0.34/0.62 (20%:45%:10%:25%) Sol-D3 M6:M7:A8:IrG-Sol1 22.9 4.2 0.34/0.62 (20%:50%:5%:25%) Sol-D4 M6:M7:A61:IrG-Sol1 22.9 4.3 0.34/0.62 (20%:50%:5%:25%) Sol-D5 M6:M7:A103:IrG-Sol1 22.7 4.2 0.35/0.61 (25%:50%:5%:20%) S0l-D6 M6:M7:A104:IrG-Sol1 23.0 4.2 0.35/0.62 (25%:50%:5%:20%) Sol-D7 M6:M7:A107:IrG-Sol1 23.1 4.2 0.35/0.62 (25%:50%:5%:20%) Sol-D8 A54:M7:IrG-Sol1 22.9 4.2 0.34/0.62 (15%:60%:25%) Sol-D9 A56:M7:IrG-Sol1 23.1 4.3 0.34/0.62 (15%:60%:25%) Sol- A106b:M7:IrG-Sol1 22.9 4.3 0.34/0.62 D10 (40%:35%:25%)

TABLE-US-00020 TABLE 4 Structural formulae of the materials used [00250] [00251] [00252] [00253] [00254] [00255] [00256] [00257] [00258] [00259] [00260] [00261] [00262] [00263] [00264] [00265] [00266] [00267] [00268] [00269]

[0238] The materials of the invention, when used as HTL2=EBL (Electron Blocking Layer), in the emission layer EML and in the hole blocker layer HBL (Hole Blocking Layer), lead to improved EQE (External Quantum Efficacy) in conjunction with reduced voltage and hence improved power efficiency overall.

[0239] The example data demonstrate that the materials claimed lead to an unexpected improvement over the prior art. With regard to the compounds of the invention, it is found that compounds of the formula (IIa) and (IIc) in many cases have slightly better properties than compounds of the formula (IId).

[0240] Moreover, the examples show that the properties resulting from the use of carbazole structures in many cases lead to improvements. Similarly, compounds having triazine and/or pyrimidine groups show improvements. Moreover, compounds having fused cyclic groups as described above as structures (RB) and/or (RA-1) to (RA-12) have very good properties.

[0241] Furthermore, compounds of the formula (IIIe) have advantages over compounds of the formula (IVd), as shown by the comparison of examples DG11 and DG12 with example DG5. Surprisingly, the use of compounds of the formula (IIIe) as hole blocker material leads to excellent device properties, as shown by example DG14.