MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices, which comprise these compounds.

##STR00001##

Claims

1. Compound of the formula (1), ##STR00462## where: L is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R; G is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; or G is a group N(Ar.sup.3).sub.2; Ar, Ar.sup.2 are, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; Ar.sup.1 is an aryl or heteroaryl group having 6 to 10 aromatic ring atoms, which may be substituted by one or more radicals R; Ar.sup.3 is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where two groups Ar.sup.3 present in a group N(Ar.sup.3).sub.2 are allowed to be connected via a single bond or a divalent bridge; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar.sup.4).sub.2, C(O)Ar.sup.4, P(O)(Ar.sup.4).sub.2, S(O)Ar.sup.4, S(O).sub.2Ar.sup.4, (R)CC(R)Ar.sup.4, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, B(R.sup.1).sub.2, B(N(R.sup.1).sub.2).sub.2, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more CH.sub.2 groups may be replaced by (R.sup.1)CC(R.sup.1), CC, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, CO, CS, CSe, P(O)(R.sup.1), SO, SO.sub.2, N(R.sup.1), O, S or CON(R.sup.1) and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, where optionally two adjacent substituents R can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; Ar.sup.4 is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(R.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, (R.sup.2)CC(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, B(R.sup.2).sub.2, B(N(R.sup.2).sub.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.2, where one or more CH.sub.2 groups may be replaced by (R.sup.2)CC(R.sup.2), CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, P(O)(R.sup.2), SO, SO.sub.2, N(R.sup.2), O, S or CON(R.sup.2) and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, where optionally two adjacent substituents R.sup.1 can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, CN, NO.sub.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms; where optionally two adjacent substituents R.sup.2 can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; n is 1, 2 or 3; with the proviso that, if L is a single bond, then G does not stand for benzene.

2. Compound according to claim 1 selected from the compounds of formula (1-1), ##STR00463## where m is 0, 1, 2 or 3 and where the other symbols and indices used have the same meanings as given in claim 1.

3. Compound according to claim 1, characterized in that L is a single bond or an aromatic or heteroaromatic ring system selected from benzene, naphthalene, biphenyl, terphenyl, fluorene, spirobifluorene, dibenzofuran, dibenzothiophene, carbazole or benzocarbazole, each of which may be substituted by one or more radicals R.

4. Compound according to claim 1, characterized in that G is an aromatic or heteroaromatic ring system selected from naphthalene, anthracene, fluoranthene, biphenyl, terphenyl, fluorene, furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, carbazole, benzocarbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, pyridazine, benzopyridazine, benzimidazole, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, azacarbazole, benzocarboline, phenanthroline, 1,3,5-triazine, 1,2,4-triazine or 1,2,3-triazine, each of which may be substituted by one or more radicals R.

5. Compound according to claim 1, characterized in that G is an aromatic or heteroaromatic ring system selected from the groups of formulae (G-1) to (G-10), ##STR00464## where the dashed bond indicates the bonding to the group L or, if L is a single bond, to the group Ar.sup.1 as depicted in formula (1); and where X is on each occurrence, identically or differently, CR or N; where X is a C atom when a group L or Ar.sup.1 is bonded to X, where there are maximum three X groups per 6-membered ring, which stand for N, and two X groups per 5-membered ring, which stand for N; with the proviso that, in formula (G-1), at least one X stands for N; V is on each occurrence, identically or differently, CR or N; V is a C atom when a group L or Ar.sup.1 is bonded to V; or two adjacent groups V form together a group of formula (V-1) or (V-2), ##STR00465## where the dashed bonds in formula (V-1) and (V-2) indicate the bonding to the structures depicted in formulae (G-5) to (G-10); W is on each occurrence, identically or differently, CR or N; wherein there are maximum three X groups per 6-membered ring, which stand for N; E is O, S, N(R.sup.N), C(R.sup.C).sub.2; R.sup.N, R.sup.C are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar.sup.4).sub.2, C(O)Ar.sup.4, P(O)(Ar.sup.4).sub.2, S(O)Ar.sup.4, S(O).sub.2Ar.sup.4, (R)CC(R)Ar.sup.4, CN, NO.sub.2, Si(R).sub.3, B(OR.sup.1).sub.2, B(R.sup.1).sub.2, B(N(R.sup.1).sub.2).sub.2, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more CH.sub.2 groups may be replaced by (R.sup.1)CC(R.sup.1), CC, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, CO, CS, CSe, P(O)(R.sup.1), SO, SO.sub.2, N(R.sup.1), O, S or CON(R.sup.1) and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, where optionally two adjacent substituents R.sup.C can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.

6. Compound according to claim 1, characterized in that G is an aromatic or heteroaromatic ring system selected from the groups of formulae (G-11) to (G-64), ##STR00466## ##STR00467## ##STR00468## ##STR00469## ##STR00470## ##STR00471## ##STR00472## ##STR00473## ##STR00474## where the dashed bond indicates the bonding to the group L or, if L is a single bond, to the diazaphosphole moiety depicted in formula (1); the symbols R.sup.C, R.sup.N and E have the same meaning as in claim 5; and the groups of formulae (G-11) to (G-64) are optionally substituted by one or more radicals R at any free positions, where R has the same meaning as in claim 1.

7. Compound according to claim 1, characterized in that G stands for a group N(Ar.sup.3).sub.2, where Ar.sup.3 is selected on each occurrence, identically or differently, from benzene, naphthalene, fluoranthene, biphenyl, terphenyl, fluorene, spirobifluorene, cis- or trans-indenofluorene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, carbazole, benzocarbazole, indolocarbazole and indenocarbazole, which may be: substituted by one or more radicals R, and where two groups Ar.sup.3 present in a group N(Ar.sup.3).sub.2 are allowed to be connected via a single bond or a divalent bridge.

8. Compound according to claim 7, characterized in that G stands for a group N(Ar.sup.3).sub.2, where Ar.sup.3 is selected on each occurrence, identically or differently, from the groups of the following formulae (A-1) to (A-48), ##STR00475## ##STR00476## ##STR00477## ##STR00478## ##STR00479## ##STR00480## ##STR00481## ##STR00482## ##STR00483## ##STR00484## ##STR00485## where the dashed bonds indicate the bonds to the nitrogen atom, where the groups of formulae (A-1) to (A-48) may further be substituted at each free position by a group R as in claim 1 and where the groups R.sup.C, in formulae (A-31) to (A-34), (A-41), (A-42) and (A-44) are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar.sup.4).sub.2, C(O)Ar.sup.4, P(O)(Ar.sup.4).sub.2, S(O)Ar.sup.4, S(O).sub.2Ar.sup.4, (R)CC(R)Ar.sup.4, CN, NO.sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, B(R.sup.1).sub.2, B(N(R).sub.2).sub.2, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more CH.sub.2 groups may be replaced by (R.sup.1)CC(R.sup.1), CC, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, CO, CS, CSe, P(O)(R.sup.1), SO, SO.sub.2, N(R.sup.1), O, S or CON(R.sup.1) and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, where optionally two adjacent substituents R.sup.C can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.

9. Compound according to claim 7, characterized in that G stands for a group N(Ar.sup.3).sub.2, where the two groups Ar.sup.3 are connected via a single bond or a divalent bridge and form a group selected from formulae (E-1) to (E-24), ##STR00486## ##STR00487## ##STR00488## ##STR00489## ##STR00490## where the dashed bond indicates the bonding to the group L or, if L is a single bond, to the diazaphosphole moiety depicted in formula (1); and where the groups (E-1) to (E-24) may be substituted at each free position by a group R.

10. Compound according to claim 1, characterized in that the compounds of formula (1) comprise at least one group Ar, Ar.sup.2, R or R.sup.N, which is selected from substituted or non-substituted triazine, pyrimidine, pyrazine, pyridazine, pyridine, imidazole, pyrazole, oxazole, oxadiazole, triazole, thiazole, thiadiazole, benzimidazole, quinolone, isoquinoline and quinoxaline.

11. Compound according to claim 1, characterized in that the compounds of formula (1) comprise at least one group Ar, Ar.sup.2, R or R.sup.N, which is selected from substituted or non-substituted pyrrole, furan, thiophene, benzothiophene, benzofuran, indole, carbazole, dibenzothiophene, dibenzofuran and azacarbazole.

12. Process for the preparation of a compound according to claim 1, in which a group selected from an aromatic or heteroaromatic ring system, an arylamino group or a carbazole derivative, is connected to the phenyl ring condensed on the diazaphosphole moiety of a diazaphosphole derivative via a CN or a CC coupling.

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

14. An electronic device comprising at least one compound according to claim 1, selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

15. An organic electroluminescent device, characterised in that the compound according claim 1 is employed as one or more of a matrix material for phosphorescent or fluorescent emitters, an electron-blocking or exciton-blocking material, a hole-blocking material, or an electron-transport material.

Description

A) SYNTHESES EXAMPLES

[0113] The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The corresponding CAS numbers are also indicated in each case from the compounds known from the literature.

Example A: Synthesis of Phenylphosphoric Acid

[0114] ##STR00086##

[0115] 47.7 g (223 mmol) of benzophosphoric acid are dissolved in 250 ml of concentrated HCl. The mixture is heated during 12 h at 100 C. After cooling, the solid is filtered and washed with some HCl and toluene and then dried. The product is then recrystallized from ethyl acetate/heptane 1:4.

[0116] Yield: 21 g (136 mmol), 62%.

[0117] The following compounds are prepared analogously:

TABLE-US-00001 Reactant 1 Product Yield A1 [00087] [00088] 67% A2 [00089] [00090] 70% A3 [00091] [00092] 65% A4 [00093] [00094] 60% A5 [00095] [00096] 74% A6 [00097] [00098] 70%

Example B: Synthesis of Phenylphosphoric Dichloride

[0118] ##STR00099##

[0119] 39 g (250 mmol) of phenylphosphoric acid are dissolved in 1500 ml of methylene chloride, in which 10 drops of DMF are added. Afterwards, 90 ml (1030 mmol) of oxalyl chloride are added dropwise at room temperature in 400 ml of methylene chloride and the mixture is then stirred at 45 C. during 5 hours. The solvent is removed under vacuum and the product is recrystallized from hexane under a protective gas.

[0120] Yield: 46 g (239 mmol), 96%.

[0121] The following compounds are prepared analogously:

TABLE-US-00002 Reactant 1 Product Yield B1 [00100] [00101] 67% B2 [00102] [00103] 70% B3 [00104] [00105] 65% B4 [00106] [00107] 60% B5 [00108] [00109] 74% B6 [00110] [00111] 77% B7 [00112] [00113] 79%

Example C: General Synthesis of N,N-Diaryl-1,2-benzodiamine

[0122] ##STR00114##

[0123] 1.06 g (4.75 mmol) of Pd(OAc).sub.2 and 14.46 ml (14.46 mmol) of tri-tert-butylphosphine (1M solution in toluene) are added to 660 ml of degassed toluene and the mixture is stirred during 5 min. Then, 240 mmol of 1,2-dibromobenzene derivative, 505 mmol of the arylamine and 67.22 g (700 mmol) of sodium tert-butylate are added to the reaction mixture, which is degassed and then stirred at 140 C. during 10 h under an inert gas. After cooling, the solution is mixed with 600 ml of a NH.sub.4Cl solution and 150 ml of ethyl acetate, the phases are separated, washed with water, dried over MgSO.sup.4 and concentrated. The solid is dissolved in toluene and filtered through Celite. The crude product is stirred with hot heptane. This gives 65 g (223 mmol) of a crystalline solid. The yield is 93%.

[0124] The following compounds are prepared analogously:

TABLE-US-00003 Reactant 1 Reactant 2 Product Yield C1 [00115] [00116] [00117] 83% C2 [00118] [00119] [00120] 87% C3 [00121] [00122] [00123] 86% C4 [00124] [00125] [00126] 80% C5 [00127] [00128] [00129] 72% C6 [00130] [00131] [00132] 75%

Example D: Synthesis of N-biphenyl-4-yl-N-phenyl-1,2-phenyldiamine

[0125] ##STR00133##

[0126] 0.35 g (1.58 mmol) of Pd(OAc).sub.2 and 4.8 ml (4.86 mmol) of tri-tert-butylphosphine (1M solution in toluene) are added to 660 mL of degassed toluene and the mixture is stirred during 5 minutes. Then, the solution is treated with 37.2 g (160 mmol) 4-bromobiphenyl, 29.4 g (160 mmol) of N-phenyl-o-phenylenediamine and 22.4 g (233 mmol) of sodium tert-butoxide, the mixture is then degassed and stirred under an inert gas at 140 C. for 10 h. After cooling, the solution is mixed with 200 ml of a NH.sub.4Cl solution and 50 ml of ethyl acetate, the phases are separated, washed with water, dried over MgSO.sub.4 and concentrated. The solid is dissolved in toluene and filtered through Celite. The crude product is stirred with hot heptane and washed with MeOH. This gives 47 g (140 mmol) of a crystalline solid. The yield is 80%.

[0127] The following compounds are prepared analogously:

TABLE-US-00004 Reactant 1 Reactant 2 Product Yield D1 [00134] [00135] [00136] 62% D2 [00137] [00138] [00139] 77% D3 [00140] [00141] [00142] 67% D4 [00143] [00144] [00145] 75% D5 [00146] [00147] [00148] 71% D6 [00149] [00150] [00151] 83% D7 [00152] [00153] [00154] 80% D8 [00155] [00156] [00157] 76% D9 [00158] [00159] [00160] 79% D10 [00161] [00162] [00163] 64%

Example E: Synthesis of 1,2,3-triphenyl-1,3-dihydro-benzo[1,3,2]diazaphosphole 2-oxide

[0128] ##STR00164##

[0129] 41 g (158 mmol) of N,N-diaryl-1,2-phenyldiamine is dissolved in 500 ml of pyridine and cooled down to 0 C. A solution comprising 30 g (158 mmol) of phenyl phosphoric dichloride dissolved in 1000 ml of toluene is added dropwise to the reaction mixture at 0 C. The mixture is stirred during 1 hour and then heated under reflux during 24 h. The solvent is evaporated under vacuum, the solid is boiled in ethyl acetate, filtered off, washed once with 100 ml acetic acid ester and then recrystallized from dioxane.

[0130] Yield: 41 g (106 mmol), 69%.

[0131] The following compounds are prepared analogously:

TABLE-US-00005 Reactant 1 Reactant 2 Product Yield E1 [00165] [00166] [00167] 70% E2 [00168] [00169] [00170] 72% E3 [00171] [00172] [00173] 74% E4 [00174] [00175] [00176] 78% E5 [00177] [00178] [00179] 70% E6 [00180] [00181] [00182] 76% E7 [00183] [00184] [00185] 81% E8 [00186] [00187] [00188] 80% E9 [00189] [00190] [00191] 79% E10 [00192] [00193] [00194] 73% E11 [00195] [00196] [00197] 85% E12 [00198] [00199] [00200] 81% E13 [00201] [00202] [00203] 74% E14 [00204] [00205] [00206] 78% E15 [00207] [00208] [00209] 84% E16 [00210] [00211] [00212] 72% E17 [00213] [00214] [00215] 71% E19 [00216] [00217] [00218] 76% E20 [00219] [00220] [00221] 78% E21 [00222] [00223] [00224] 76% E22 [00225] [00226] [00227] 75%

Example F: Synthesis of 5-Bromo-1,2,3-triphenyl-1,3-dihydro-benzo[1,3,2]-diazaphosphole 2-oxide

[0132] ##STR00228##

[0133] 48 g (125 mmol) of 1,2,3-triphenyl-1,3-dihydro-benzo[1,3,2]diazaphosphole 2-oxide are suspended in 1000 ml of chloroform and mixed slowly with 48 g (275 mmol) of N-bromosuccinimide at room temperature. The mixture is then stirred during 16 h. Afterwards, the reaction mixture is mixed with a solution of Na.sub.2SO.sub.4, the phases are then separated and evaporated. The product is dried, concentrated, and then recrystallized from dichloromethane to a purity of 99.0%. Yield: 52 g (113 mmol), 90% of the product as a white solid.

[0134] The following compounds are prepared analogously:

TABLE-US-00006 Reactant 1 Product Yield F1 [00229] [00230] 83% F2 [00231] [00232] 86% F3 [00233] [00234] 72% F4 [00235] [00236] 88% F5 [00237] [00238] 53% F6 [00239] [00240] 46% F7 [00241] [00242] 54% F8 [00243] [00244] 50% F9 [00245] [00246] 51% F10 [00247] [00248] 55% F11 [00249] [00250] 49% F12 [00251] [00252] 57% F13 [00253] [00254] 61% F14 [00255] [00256] 60% F15 [00257] [00258] 85% F16 [00259] [00260] 83% F17 [00261] [00262] 80% F18 [00263] [00264] 75% F19 [00265] [00266] 82% F20 [00267] [00268] 83% F21 [00269] [00270] 57% F22 [00271] [00272] 67%

Example G: Synthesis of 1,2,3-triphenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1,3-dihydro-benzo[1,3,2]diazaphosphole 2-oxide

[0135] ##STR00273##

[0136] In a 2 L four-necked flask, 50 g (105 mmol) of 5-bromo-1,2,3-triphenyl-1,3-dihydro-benzo[1,3,2]-diazaphosphole 2-oxide, 29.9 g (115 mmol) of bispinacolatodiborane (73183-34-3), 30.9 g (315 mmol) of potassium acetate and 2.25 g (3.1 mmol) of bis(triphenylphosphine)-palladium(II) chloride are mixed with 750 mL of anhydrous dioxane during 3 hours under reflux, until the reaction is complete. After cooling to room temperature, the organic phase is added to ethyl acetate and washed three times with 300 ml of water and dried with sodium sulfate. The combined organic phases are then concentrated by rotary evaporation until dryness. After recrystallization from heptane, the product is obtained as a solid. The yield is 49 g (96 mmol; 90%).

[0137] The following compounds are prepared analogously:

TABLE-US-00007 Reactant 1 Product Yield G1 [00274] [00275] 86% G2 [00276] [00277] 84% G3 [00278] [00279] 80%

Example H: Synthesis of 3-(2-oxo-1,2,3-triphenyl-2,3-dihydro-benzo[1,3,2]diazaphosphol-5-yl)-9-phenyl-9H-carbazole

[0138] ##STR00280##

[0139] 71.9 g (156 mmol) of 5-bromo-1,2,3-triphenyl-1,3-dihydro-benzo [1,3,2]-diazaphosphole 2-oxide, 50 g (172 mmol) of N-phenyl-carbazol-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 mL of ethylene glycol dimethyl ether and 280 mL of water. Then, 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)-palladium (0) are added to this suspension and the reaction mixture is heated under reflux during 16 h. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200 mL water and then concentrated to dryness. The product is purified via column chromatography on silica gel with toluene/heptane (1:2) and finally sublimated in high vacuum (p=510.sup.7 mbar) (purity 99.9%). The yield is 72 g (115 mmol), corresponding to 67% of theory.

[0140] The following compounds are prepared analogously:

TABLE-US-00008 Reactant 1 Reactant 2 Product Yield H1 [00281] [00282] [00283] 77% [1257220-44-2] H2 [00284] [00285] [00286] 81% H3 [00287] [00288] [00289] 78% H4 [00290] [00291] [00292] 61% [1001911-63-2] H5 [00293] [00294] [00295] 74% [1476799-10-6] H6 [00296] [00297] [00298] 78% [1361094-91-8] H7 [00299] [00300] [00301] 72% [1247092-44-9] H8 [00302] [00303] [00304] 63% [854952-58-2] H9 [00305] [00306] [00307] 61% [1361094-91-8] H10 [00308] [00309] [00310] 64% [1547492-13-6] H11 [00311] [00312] [00313] 56% [1493715-37-9] H12 [00314] [00315] [00316] 54% [1369369-44-7] H13 [00317] [00318] [00319] 68% [1656982-96-5] H14 [00320] [00321] [00322] 65% [854952-58-2] H15 [00323] [00324] [00325] 66% [1572537-61-1] H16 [00326] [00327] [00328] 58% [1628066-19-2] H17 [00329] [00330] [00331] 62% [1346010-98-7] H18 [00332] [00333] [00334] 56% 1493716-02-1] H19 [00335] [00336] [00337] 57% [1616729-22-6] H20 [00338] [00339] [00340] 62% [854952-58-2] H21 [00341] [00342] [00343] 58% H22 [00344] [00345] [00346] 54% [854952-58-2] H23 [00347] [00348] [00349] 68% [854952-58-2] H25 [00350] [00351] [00352] 63% [854952-58-2] H26 [00353] [00354] [00355] 60% [1377576-69-6] H27 [00356] [00357] [00358] 57% [854952-58-2] H28 [00359] [00360] [00361] 65% [1825379-39-2] H29 [00362] [00363] [00364] 63% [1821457-68-4] H30 [00365] [00366] [00367] 74% [1702361-93-0] H31 [00368] [00369] [00370] 70% [1792219-03-4] H32 [00371] [00372] [00373] 74% [1612243-82-9] H33 [00374] [00375] [00376] 69% [1251825-65-6] H34 [00377] [00378] [00379] 78% [1616632-72-4] H35 [00380] [00381] [00382] 82% ]359012-63-8] H24 [00383] [00384] [00385] 76% [597554-03-5] H25 [00386] [00387] [00388] 80% [162607-19-4]

Example I: Synthesis of 9-(2-oxo-1,2,3-triphenyl-2,3-dihydro-1H-benzo[1,3,2]diazaphosphol-5-yl)-3-phenyl-9H-carbazole

[0141] ##STR00389##

[0142] A degassed solution of 69 g (150 mmol) of 5-bromo-1,2,3-triphenyl-1,3-dihydro-benzo[1,3,2]-diazaphosphole 2-oxide and 36.5 g (150 mmol) of 3-phenyl-9H-carbazole in 600 mL toluene is saturated with N.sub.2 during 1 h. Afterwards, this solution is mixed with 2.09 mL (8.6 mmol) of P(tBu).sub.3, then with 1.38 g (6.1 mmol) of palladium(II)acetate and finally, 17.7 g (185 mmol) of NaOtBu in the solid state is added to the solution. The reaction mixture is heated under reflux during 1 h. After cooling to room temperature, 500 ml of water are carefully added to the reaction mixture. The aqueous phase is washed with 350 ml of toluene, dried over MgSO.sub.4 and the solvent removed under vacuum. Thereafter, the crude product is purified by chromatography on silica gel with heptane/acetic ester (20:1). The residue is recrystallized from toluene (5p=10.sup.6 mbar) and sublimated under high vacuum. The yield is 79 g (127 mmol), corresponding to 85% of theory.

[0143] The following compounds are prepared analogously:

TABLE-US-00009 Reactant 1 Reactant 2 Product Yield I1 [00390] [00391] [00392] 85% [1257220-47-5] I2 [00393] [00394] [00395] 84% [1060735-14-9] I3 [00396] [00397] [00398] 54% [1024598-06-8] I4 [00399] [00400] [00401] 72% [1257220-47-5] I5 [00402] [00403] [00404] 71% [1373281-72-1] I6 [00405] [00406] [00407] 74% [1316311-27-9] I7 [00408] [00409] [00410] 65% [1260228-95-2] I8 [00411] [00412] [00413] 76% [1199350-22-5] I9 [00414] [00415] [00416] 61% [1447708-58-8] I10 [00417] [00418] [00419] 70% [1257248-14-8] I11 [00420] [00421] [00422] 83% [1361126-04-6] I12 [00423] [00424] [00425] 76% [1257220-47-5]

Example J: Synthesis of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)-(2-oxo-1,2,3-triphenyl-2,3-dihydro-1H-benzo[1,3,2]diazaphosphol-5-yl)-amine

[0144] ##STR00426##

[0145] A mixture of 9.3 g (26 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl) amine, 11.9 g (26 mmol) of 5-bromo-1,2,3-triphenyl-1,3-dihydro-benzo [1,3,2]-diazaphosphole 2-oxide, 7.7 g (80 mmol) of sodium tert-butylate, 2.6 ml (78 mmol) of tri-tert-butylphosphine (1M, toluene), 224 mg (2.6 mmol) of palladium(II)acetate and 300 ml of mesitylene are heated during 24 h under reflux. After cooling, 200 ml of water are added to the mixture, which is stirred during 30 minutes. Then, the organic phase is separated, filtered on Celite and the solvent is removed in vacuum. The residue is recrystallized from DMF five times, and finally sublimated (p=10.sup.6 mbar, T=340-350 C.).

[0146] Yield: 13.8 g (18.6 mmol), 72% of theory: 99.9% after HPLC.

[0147] The following compounds are prepared analogously:

TABLE-US-00010 Reactant 1 Reactant 2 Product Yield J1 [00427] [00428] [00429] 61% J2 [00430] [00431] [00432] 65% J3 [00433] [00434] [00435] 66% 1454679-22-1 J4 [00436] [00437] [00438] 69% [1548450-93-6] J5 [00439] [00440] [00441] 64% [1579281-06-3] J6 [00442] [00443] [00444] 70% [1776969-70-0]

B) FABRICATION OF OLEDS

[0148] The following examples V1 to E7 (see Table 1 and 2) show data of various OLEDs.

[0149] Substrate Pre-Treatment of Examples V1-E7:

[0150] Glass plates with structured ITO (50 nm, indium tin oxide) form the substrates on which the OLEDs are processed. Before evaporation of the OLED materials, the substrates are cleaned in a wet process (using filtered deionized water and the detergent Extran of Merck KGaA). Subsequently the clean and dry substrates are exposed to a UV-Ozone plasma and then coated with a layer of 20 nm PEDOT:PSS (Poly(3,4-ethylendioxythiophen) poly(styrolsulfonate), by using an aqueous solution of CLEVIOS P VP AI 4083 purchased from Heraeus Precious Metals GmbH, Germany, for better processing. Before evaporating OLED materials onto the glass substrates,

[0151] The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The exact layer structure is denoted in Table 1 (ITO, PEDOT:PSS and Aluminium layers are omitted for clarity). The materials used for the OLED fabrication are presented in Table 3.

[0152] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as IC1:M1:TEG1 (55%:35%:10%) here means that material IC1 is present in the layer in a proportion by volume of 55%, M1 is present in the layer in a proportion of 35% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

[0153] The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE1000, measured in % at 1000 cd/m.sup.2) and the voltage (U1000, measured at 1000 cd/m.sup.2 in V) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines) assuming a Lambertian emission profile. Lifetime LT is defined as the time in hours (h), after which the starting brightness is reduced to a certain level L1 in % of the starting brightness. Here L0;j0=4000 cd/m.sup.2 and L1=70% in table 2 means, that the starting brightness is reduced from 4000 cd/m.sup.2 to 2800 cd/m.sup.2 after the time in hours (h) of column LT. Analogously, L0;j0=20 mA/cm.sup.2, L1=80% means, that the starting brightness at a current density of 20 mA/cm.sup.2 after the time LT in hours (h), is reduced to 80% of it's starting value.

[0154] The device data of various OLEDs is summarized in Table 2. The examples V1-V3 are comparison examples according to the state-of-the-art. The examples E1-E7 show data of OLEDs according to the invention. In the following section several examples are described in more detail to show the advantages of the inventive OLEDs.

[0155] Use of Inventive Compounds as Host Material in Phosphorescent OLEDs

[0156] The use of the inventive compounds as host material results in significantly improved OLED device data compared to state-of-the-art materials, especially with respect to lifetime.

[0157] The use of the inventive materials Inv1-Inv7 as host materials in phosphorescent green OLEDs results in a 15-40% improved lifetime compared to devices with the materials SdT1-SdT3 (comparison of examples V1 and V2 with E1, E2 and E4-E7 and the comparison of V3 with E3, respectively).

TABLE-US-00011 TABLE 1 OLED layer structure HIL IL HTL EML HBL ETL Bsp. Dicke Dicke Dicke Dicke Dicke Dicke V1 SpA1 HATCN SpMA1 IC5:SdT1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm V2 SpA1 HATCN SpMA1 IC5:SdT2:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm V3 SpA1 HATCN SpMA1 IC5:SdT3:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm E1 SpA1 HATCN SpMA1 IC5:Inv1:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm E2 SpA1 HATCN SpMA1 IC5:Inv2:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm E3 SpA1 HATCN SpMA1 IC5:Inv3:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm E4 SpA1 HATCN SpMA1 IC5:Inv4:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm E5 SpA1 HATCN SpMA1 IC5:Inv5:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm E6 SpA1 HATCN SpMA1 IC5:Inv6:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm E7 SpA1 HATCN SpMA1 IC5:Inv7:TEG1 ST2 ST2:LiQ (50%:50%) 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm 30 nm 30 nm

TABLE-US-00012 TABLE 2 OLED device data U1000 EQE L.sub.1 LT Bsp. (V) 1000 L.sub.0; j.sub.0 % (h) V1 3.4 15.3% 20 mA/cm.sup.2 80 140 V2 3.5 15.4% 20 mA/cm.sup.2 80 120 V3 3.6 15.3% 20 mA/cm.sup.2 80 100 E1 3.5 15.3% 20 mA/cm.sup.2 80 175 E2 3.4 15.5% 20 mA/cm.sup.2 80 190 E3 3.6 15.4% 20 mA/cm.sup.2 80 130 E4 3.3 15.6% 20 mA/cm.sup.2 80 165 E5 3.3 15.5% 20 mA/cm.sup.2 80 170 E6 3.5 16.1% 20 mA/cm.sup.2 80 175 E7 3.5 15.4% 20 mA/cm.sup.2 80 180

TABLE-US-00013 Tabelle 3 Chemical structures of the OLED materials [00445] HATCN [00446] SpA1 [00447] SpMA1 [00448] LiQ [00449] TEG1 [00450] ST2 [00451] IC5 [00452] SdT1 [00453] SdT2 [00454] SdT3 [00455] Inv1 [00456] Inv2 [00457] Inv3 [00458] Inv4 [00459] Inv5 [00460] Inv6 [00461] Inv7