MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present application relates to spirobifluorene derivatives of a formula (I), to the use thereof in electronic devices, and to processes for preparing said derivatives.

Claims

1.-21. (canceled)

22. A compound of the formula (I) ##STR00376## which has a group of the formula (T) ##STR00377## bonded at two adjacent positions marked by * to the base structure of formula (I), where the condensation is such that any bond marked by * in formula (T) is attached at a position marked by * to the base structure of formula (I); which may be substituted at one or more positions shown as unsubstituted in the base structure of formula (I) and the group of the formula (T) by an R.sup.1 radical; and which has the following definitions of the variables: A is the same or different at each instance and is a group of the formula (A1), (A2) or (A3) which is bonded via the bond marked with # and may be substituted at one or more positions shown as unsubstituted by an R.sup.2 radical; ##STR00378## Ar.sup.1 is the same or different at each instance and is a single bond or an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; Ar.sup.2 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; X is the same or different at each instance and is a single bond or a group selected from BR.sup.2, C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C═O, O, S, S═O, SO.sub.2, NR.sup.2, PR.sup.2 and P(═O)R.sup.2; Y is selected from O, S and Se; Z is selected from O, S, Se and a single bond, where Z is not a single bond when Y is O; R.sup.0 is the same or different at each instance and is 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, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; 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.3 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.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2; R.sup.1 is the same or different at each instance and is selected from H, D, F, C(═O)R.sup.3, CN, Si(R.sup.3).sub.3, P(═O)(R.sup.3).sub.2, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, 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.1 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.3 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.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2; R.sup.2 is the same or different at each instance and is selected from H, D, F, C(═O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, P(═O)(R.sup.3).sub.2, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.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, 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.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 and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.3 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.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2; R.sup.3 is the same or different at each instance and is selected from H, D, F, C(═O)R.sup.4, CN, Si(R.sup.4).sub.3, N(R.sup.4).sub.2, P(═O)(R.sup.4).sub.2, OR.sup.4, S(═O)R.sup.4, S(═O).sub.2R.sup.4, 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.1 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 and heteroaromatic ring systems mentioned may each be substituted by one or more R.sup.4 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.4C═CR.sup.4—, —C≡C—, Si(R.sup.4).sub.2, C═O, C═NR.sup.4, —C(═O)O—, —C(═O)NR.sup.4—, NR.sup.4, P(═O)(R.sup.4), —O—, —S—, SO or SO.sub.2; R.sup.4 is the same or different at each instance and is selected from H, D, F, CN, alkyl groups having 1 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.4 radicals may be joined to one another and may form a ring; and where the alkyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by F or CN; q is the same or different at each instance and is 0 or 1, where at least one q in formula (A2) is 1; i, k, m, n and p are the same or different at each instance and are 0 or 1, where at least one of these indices is 1.

23. The compound according to claim 22, wherein it corresponds to one of the following formulae: ##STR00379## ##STR00380## ##STR00381## where the symbols that occur are as defined in claim 22, and the compounds may be substituted at positions shown as unsubstituted by R.sup.1 radicals.

24. The compound according to claim 22, wherein A is a group of the formula (A-1).

25. The compound according to claim 22, wherein Ar.sup.1 is the same or different at each instance and is selected from a single bond and a divalent group derived from benzene, biphenyl, terphenyl, fluorene, spirobifluorene, indenofluorene, carbazole, dibenzofuran or dibenzothiophene, each optionally substituted by R.sup.2 radicals, or a combination of two or more of these groups, but not more than 30 aromatic ring atoms may be present in Ar.sup.1.

26. The compound according to claim 22, wherein Ar.sup.2 is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, fluorenyl, spirobifluorenyl, indenofluorenyl, naphthyl, phenanthrenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, indolocarbazolyl and indenocarbazolyl, each of which may be substituted by one or more R.sup.2 radicals.

27. The compound according to claim 22, wherein X is a single bond.

28. The compound according to claim 22, wherein R.sup.0 is H.

29. The compound according to claim 22, wherein R.sup.1 and R.sup.2 are the same or different at each instance and are H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic or heteroaromatic ring system having 6 to 25 aromatic ring atoms, where said alkyl and alkoxy groups and said aromatic or heteroaromatic ring systems may each be substituted by one or more R.sup.3 radicals.

30. The compound according to claim 22, wherein p is 1, and in that all the other indices k, i, m and n are 0, or wherein k is 1, and in that all the other indices i, m, n and p are 0.

31. The compound according to claim 22, wherein the sum total of the indices i, k, m, n and p is 1.

32. The compound according to claim 22, wherein the Y group is S, and the Z group is O, S or a single bond.

33. The compound according to claim 22, wherein the Y group is S, and the Z group is a single bond.

34. A process for preparing a compound according to claim 22, comprising either A) first preparing the spirobifluorene base skeleton substituted by a reactive group by reacting a dibenzothiophenyl derivative with a fluorenone derivative bearing the reactive group and, in a later step, via an organometallic coupling reaction, a diarylamino or carbazole group or an aryl or heteroaryl group substituted by a diarylamino or carbazole group is introduced at the position of the reactive group, or B) reacting a dibenzothiophenyl derivative with a fluorenone bearing a diarylamino or carbazole group or an aryl or heteroaryl group substituted by a diarylamino or carbazole group is involved, or C) first preparing a spirobifluorene base skeleton by reacting a dibenzothiophenyl derivative with a fluorenone derivative, then the latter is functionalized with a reactive group and, in a later step, via an organometallic coupling reaction, a diarylamino or carbazole group or an aryl or heteroaryl group substituted by a diarylamino or carbazole group is introduced at the position of the reactive group.

35. An oligomer, polymer or dendrimer containing one or more compounds of the formula (I) according to claim 22, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.0, R.sup.1 or R.sup.2 in formula (I).

36. A formulation comprising at least one compound according to claim 22, or at least one polymer, oligomer or dendrimer according to claim 35, and at least one solvent.

37. A method comprising utilizing the compound according to claim 22, or the oligomer, polymer or dendrimer according to claim 35, in an electronic device.

38. An electronic device comprising at least one compound according to claim 22 or at least one oligomer, polymer or dendrimer according to claim 35.

39. The electronic device according to claim 38, 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).

40. The electronic device according to claim 39, wherein the at least one compound or the at least one oligomer, polymer or dendrimer is present in a layer selected from hole transport layers and emitting layers.

41. The electronic device according to claim 40, wherein the at least one compound or the at least one oligomer, polymer or dendrimer is present in an emitting layer together with one or more phosphorescent emitters.

42. The electronic device according to claim 40, wherein the at least one compound or the at least one oligomer, polymer or dendrimer is present in a hole transport layer together with one or more p-dopants.

Description

WORKING EXAMPLES

A) Synthesis Examples

Example 1: Synthesis of Compounds (1-1) to (1-14)

[0125] ##STR00098##

Synthesis of 4-(2-bromophenyl)dibenzothiophene A-1

[0126] 80 g (351 mmol) of dibenzothiophene-4-boronic acid (CAS: 108847-20-7), 83 g (351 mmol) of 1,2-dibromobenzene and 8.2 g (7.02 mmol) of Pd(Ph.sub.3P).sub.4 are suspended in 700 ml of dioxane. Added gradually to this suspension are 440 ml (877 mmol) of potassium carbonate solution (2 M), and the reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The residue is purified by chromatography on silica gel. Yield: 95 g (280 mmol), 80% of theory, purity by HPLC >97%.

[0127] In a manner analogous to the synthesis of compound A-1 described, the following compounds are prepared:

TABLE-US-00001 Reactant 1 Reactant 2 Product Yield A-2 [00099] [00100] [00101] 73% A-3 [00102] [00103] [00104] 61% A-4 [00105] [00106] [00107] 78% A-5 [00108] [00109] [00110] 83% A-6 [00111] [00112] [00113] 75%

Synthesis of Intermediate B-1

[0128] 56.3 g (166 mmol) of 4-(2-bromophenyl)dibenzothiophene A-1 are initially charged in 700 ml of THF at −78° C. At this temperature, 70 ml of BuLi (2.5 M in hexane) are added dropwise. After 1 hour, 45.2 g (174 mmol) of fluoren-9-one in 200 ml of THF are added dropwise. The mixture is left to stir at room temperature overnight, added to ice-water and extracted with dichloromethane. The combined organic phases are washed with water and dried over sodium sulphate. The solvent is removed under reduced pressure and the residue, without further purification, is heated with 90 ml of HCl and 1 l of AcOH at 75° C. overnight. After cooling, the precipitated solid is filtered off with suction and washed twice with 150 ml of water and three times with 150 ml each time of ethanol, and finally recrystallized from heptane. Yield: 54 g (107 mmol), 65%; purity about 98% by .sup.1H NMR.

[0129] In a manner analogous to the synthesis of compound B-1 described, the following compounds are prepared:

TABLE-US-00002 Reactant 1 Reactant 2 Product Yield B-2 [00114] [00115] [00116] 70% B-3 [00117] [00118] [00119] 62% B-4 [00120] [00121] [00122] 75% B-5 [00123] [00124] [00125] 68% B-6 [00126] [00127] [00128] 70% B-7 [00129] [00130] [00131] 65% B-8 [00132] [00133] [00134] 80% B-9 [00135] [00136] [00137] B-10 [00138] [00139] [00140] 64% B-11 [00141] [00142] [00143] 71% B-12 [00144] [00145] [00146] 70% B-13 [00147] [00148] [00149] 56% B-14 [00150] [00151] [00152] 72%

Synthesis of Compound (1-1)

[0130] 14.3 g (39.5 mmol) of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amine and 19.8 g (39.5 mol) of the bromo-spiro derivative B-1 are dissolved in 350 ml of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 1.55 ml (1.55 mmol) of a 1 M tri-tert-butylphosphine solution and 173 mg (1.44 mmol) of Pd(AcO).sub.2 are added thereto, and then 9.5 g of sodium tert-butoxide (98.7 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 4 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene and finally sublimed under high vacuum. The purity is 99.9% (HPLC). The yield of compound (1-1) is 22 g (73% of theory).

Synthesis of compounds (1-2) to (1-14)

[0131] In a manner analogous to the synthesis of compound (1-1) described in Example 1, the following compounds (1-2) to (1-14) are also prepared:

TABLE-US-00003 Reactant 1 Reactant 2 Product Yield 1-2 [00153] [00154] [00155] 78% 1-3 [00156] [00157] [00158] 78% 1-4 [00159] [00160] [00161] 83% 1-5 [00162] [00163] [00164] 66% 1-6 [00165] [00166] [00167] 67% 1-7 [00168] [00169] [00170] 79% 1-8 [00171] [00172] [00173] 77% 1-9 [00174] [00175] [00176] 72% 1-10 [00177] [00178] [00179] 68% 1-11 [00180] [00181] [00182] 68% 1-12 [00183] [00184] [00185] 74% 1-13 [00186] [00187] [00188] 67% 1-14 [00189] [00190] [00191] 71%

Example 2: Synthesis of Compounds (2-1) to (2-12)

[0132] ##STR00192##

Synthesis of Intermediate C-1

[0133] 18 g (44 mmol) of the starting compound are dissolved in 200 ml of acetonitrile, and 7.5 g (42 mmol) of N-bromosuccinimide are added in portions at room temperature. On completion of conversion, water and ethyl acetate are added thereto, and the organic phase is removed, dried and concentrated. The crude product is subsequently stirred repeatedly with hot MeOH. Yield: 16.13 g (75%) of the bromo-spiro derivative C-1.

[0134] In an analogous manner, the following brominated compounds are prepared:

TABLE-US-00004 Brominating Reactant 1 reagent Product Yield C-2 [00193] NBS [00194] 68% C-3 [00195] 1) nBuLi, −78° C. 2) BrCH.sub.2—CH.sub.2Br [00196] 50% C-4 [00197] 1) nBuLi, −78° C. 2) I.sub.2 [00198] 45% C-5 [00199] 1) nBuLi, −78° C. 2) BrCH.sub.2—CH.sub.2Br [00200] 40% C-6 [00201] 1) nBuLi, −78° C. 2) BrCH.sub.2—CH.sub.2Br [00202] 40% C7 [00203] NBS [00204] 66% C-8 [00205] 1) nBuLi, −78° C. 2) BrCH.sub.2—CH.sub.2Br [00206] 50% C-9 [00207] 1) nBuLi, −78° C. 2) BrCH.sub.2—CH.sub.2Br [00208] 48% C-10 [00209] NBS [00210] 61% C-11 [00211] NBS [00212] 60%

Synthesis of compounds (2-1) to (2-12)

[0135] In a manner analogous to the synthesis of compound (1-1) described in Example 1, the following compounds (2-1) to (2-12) are also prepared:

TABLE-US-00005 Reactant 1 Reactant 2 Product Yield 2-1 [00213] [00214] [00215] 76% 2-2 [00216] [00217] [00218] 80% 2-3 [00219] [00220] [00221] 71% 2-4 [00222] [00223] [00224] 78% 2-5 [00225] [00226] [00227] 82% 2-6 [00228] [00229] [00230] 77% 2-7 [00231] [00232] [00233] 75% 2-8 [00234] [00235] [00236] 81% 2-9 [00237] [00238] [00239] 83% 2-10 [00240] [00241] [00242] 75% 2-11 [00243] [00244] [00245] 75% 2-12 [00246] [00247] [00248] 79%

Example 3: Synthesis of Compounds 3-1 to 3-11

[0136] ##STR00249##

Spirofluorene-Boronic Ester Derivative (D-1)

[0137] 25 g (49.9 mmol) of the spirofluorene-bromo derivative, 14 g (55 mmol) of bis(pinacolato)diborane and 14.7 g (150 mmol) of potassium acetate are suspended in 400 ml of DMF. To this suspension is added 1.22 g (1.5 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with DCM. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, washed three times with 400 mL of water and then concentrated to dryness. The residue is recrystallized from toluene (25 g, 92% yield).

[0138] In a manner analogous thereto, the following compounds are prepared:

TABLE-US-00006 Reactant 1 Product Yield D-2 [00250] [00251] 80% D-3 [00252] [00253] 83% D-4 [00254] [00255] 88% D-5 [00256] [00257] 88% D-6 [00258] [00259] 76%

Biphenyl-2-yl(biphenyl-4-yl)(4-chlorophenyl)amine (E-1)

[0139] ##STR00260##

[0140] 23.8 g of biphenyl-2-yl(biphenyl-4-yl)amine (74 mmol) and 21.2 g of 4-chloroiodobenzene (89 mmol) are dissolved in 500 ml of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 3 ml (3 mmol) of a 1 M tri-tert-butylphosphine solution and 0.33 g (1.48 mmol) of palladium(II) acetate are added thereto, and then 10.7 g of sodium tert-butoxide (111 mmol) are added.

[0141] The reaction mixture is heated to boiling under a protective atmosphere for 12 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The yield is 29 g (90% of theory).

[0142] In a manner analogous thereto, the following compounds are prepared:

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield E-2 [00261] [00262] [00263] 78% E-3 [00264] [00265] [00266] 80% E-4 [00267] [00268] [00269] 81% E-5 [00270] [00271] [00272] 92% E-6 [00273] [00274] [00275] 85% E-7 [00276] [00277] [00278] 75%

Synthesis of Compound (3-1)

[0143] 19.05 g (35 mmol) of spirofluorene pinacolboronic ester derivative D-1 and 19.0 g (35 mmol) of chloro derivative E-1 are suspended in 300 ml of dioxane and 10.6 g of caesium fluoride (69.4 mmol). 1.3 g (1.73 mmol) of bis(tricyclohexylphosphine)palladium dichloride are added to this suspension, and the reaction mixture is heated under reflux for 24 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 100 ml of water and then concentrated to dryness. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene and finally sublimed under high vacuum. The purity is 99.9%. The yield is 21.3 g (75% of theory).

Synthesis of Compounds (3-2) to (3-11)

[0144] In a manner analogous to the synthesis of compound (3-1) described in Example 1, the following compounds (3-2) to (3-11) are also prepared:

TABLE-US-00008 Reactant 1 Reactant 2 Product Yield 3-2 [00279] [00280] [00281] 78% 3-3 [00282] [00283] [00284] 71% 3-4 [00285] [00286] [00287] 82% 3-5 [00288] [00289] [00290] 89% 3-6 [00291] [00292] [00293] 69% 3-7 [00294] [00295] [00296] 75% 3-8 [00297] [00298] [00299] 72% 3-9 [00300] [00301] [00302] 63% 3-10 [00303] [00304] [00305] 75% 3-11 [00306] [00307] [00308] 77%

Example 4: Synthesis of Compounds 4-1 to 4-9

[0145] ##STR00309## ##STR00310##

Synthesis of compounds F-1 to F-5

[0146] 27 g (85 mmol) of bis(biphenyl)amine and 22.0 g (85 mmol) of 1-bromofluorenone are dissolved in 170 ml of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 4 ml (1.7 mmol) of a 10% tri-tert-butylphosphine solution and 0.2 g (0.89 mmol) of Pd(AcO).sub.2 are added thereto, and then 12.2 g of sodium tert-butoxide (127 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 12 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The yield of compound F-1 is 34 g (80% of theory).

TABLE-US-00009 Reactant 1 Reactant 2 Product Yield F-2 [00311] [00312] [00313] 67% F-3 [00314] [00315] [00316] 75% F-4 [00317] [00318] [00319] 80% F-5 [00320] [00321] [00322] 78%

Synthesis of Compounds F-6 to F-8

[0147] In a manner analogous to the synthesis of compound (3-1) described in Example 1, the following compounds (F-6) to (F-8) are also prepared:

TABLE-US-00010 Reactant 1 Reactant 2 Product Yield F-6 [00323] [00324] [00325] 89% F-7 [00326] [00327] [00328] 85% F-8 [00329] [00330] [00331] 75%

Synthesis of Compounds 4-1 to 4-9

[0148] 30 g (88 mmol) of 4-(2-bromophenyl)dibenzothiophene are initially charged in 300 ml of THF at −78° C. At this temperature, 39 ml of BuLi (2.5 M in hexane) are added dropwise. After 1 hour, 44 g (88 mmol) of fluorenone F-1 in 200 ml of THF are added dropwise. The mixture is left to stir at room temperature overnight, added to ice-water and extracted with dichloromethane. The combined organic phases are washed with water and dried over sodium sulphate. The solvent is removed under reduced pressure and the residue, without further purification, is heated under reflux with 100 ml of HCl and 1200 ml of AcOH at 75° C. overnight. After cooling, the precipitated solid is filtered off with suction and washed once with 100 ml of water and three times with 100 ml each time of ethanol, recrystallized from heptane and finally sublimed under high vacuum. Yield: 40 g (53 mmol), 60%; purity: about 99.9% by HPLC.

[0149] In an analogous manner, it is possible to prepare the further compounds 4-2 to 4-9:

TABLE-US-00011 Reactant 1 Reactant 2 Product Yield 4-2 [00332] [00333] [00334] 50% 4-3 [00335] [00336] [00337] 61% 4-4 [00338] [00339] [00340] 48% 4-5 [00341] [00342] [00343] 49% 4-6 [00344] [00345] [00346] 45% 4-7 [00347] [00348] [00349] 60% 4-8 [00350] [00351] [00352] 52% 4-9 [00353] [00354] [00355] 60%

Example 5: Synthesis of Compounds 5-1 to 5-3

[0150] ##STR00356##

[0151] 10.5 g (43 mmol) of 3-phenylcarbazole and 18 g (36 mmol) of the bromo-spiro derivative are dissolved in 30 ml of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 1.44 ml (1.44 mmol) of a 1 M tri-tert-butylphosphine solution and 660 mg (0.72 mmol) of Pd.sub.2(dba).sub.3 are added thereto, and then 5.28 g of sodium tert-butoxide (53.8 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 24 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene and finally sublimed under high vacuum. The purity is 99.9% (HPLC). The yield of compound (5-1) is 14 g (60% of theory).

Synthesis of Compounds (5-2) and (5-3)

[0152] In a manner analogous to the synthesis of compound (5-1) described in Example 1, the following compounds (5-2) and (5-3) are also prepared:

[0153] In an analogous manner, the following compounds are obtained:

TABLE-US-00012 Reactant 1 Reactant 2 Product Yield 5-2 [00357] [00358] [00359] 50% 5-3 [00360] [00361] [00362] 45%

B) Device Examples

[0154] OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 04/058911, which is adapted to the circumstances described here (e.g. materials).

[0155] In the inventive examples which follow, the data for various OLEDs are presented. Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. The OLEDs have the following layer structure: substrate/p-doped hole transport layer (HIL1)/hole transport layer (HTL)/p-doped hole transport layer (HTL2)/electron blocker layer (EBL)/emission layer (EML)/electron transport layer (ETL)/electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The materials required for production of the OLEDs are shown in Table 1.

[0156] All materials are applied by thermal vapour 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 H1:SEB(5%) mean here that the material H1 is present in the layer in a proportion by volume of 95% and SEB in a proportion by volume of 5%. In an analogous manner, the electron transport layers or the hole injection layers may also consist of a mixture of two or more materials.

[0157] The OLEDs are characterized in a standard manner. For this purpose, the external quantum efficiency (EQE, measured in percent) is determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, and the lifetime. The parameter EQE @ 10 mA/cm.sup.2 refers to the external quantum efficiency at a current density of 10 mA/cm.sup.2. LD80 @ 60 mA/cm.sup.2 is the lifetime before the OLED, given a starting brightness at constant current of 60 mA/cm.sup.2, has fallen to 80% of the starting intensity.

TABLE-US-00013 TABLE 1 Structures of the materials used [00363] F4TCNQ [00364] HIM [00365] H1 [00366] SEB [00367] H2 [00368] TEG [00369] ETM [00370] LiQ [00371] HTM1 [00372] HTM2 [00373] HTM3 [00374] HTMv1 [00375] HTMv2

Example 1

[0158] The inventive compound HTM1 and the comparative compound HTMv1 are compared with one another in a blue-emitting OLED stack. The structure of the stack is as follows: HIM:F4TCNQ(5%)(20 nm)/HIM(155 nm)/HTM1:F4TCNQ(5%)(20 nm)/HTM1(20 nm)/H1:SEB(5%)(20 nm)/ETM:LiQ(50%)(30 nm)/LiQ(1 nm). In the comparative example, rather than HTM1, HTMv1 is used in all relevant layers.

[0159] The evaluation of the external quantum efficiencies at 10 mA/cm.sup.2 for the experiments conducted shows the following results: HTM1 achieves 7.7% EQE, whereas HTMv1 achieves only 7.0%. The lifetimes of the devices produced until a drop to 80% of the starting intensity at a constant current of 60 mA/cm.sup.2 show the advantage of compound HTM1 even more clearly. These extend to 380 hours in the case of HTM1, whereas HTMv1 achieves only 270 hours.

Example 2

[0160] The same two materials as in Example 1 are used to produce a triplet green component having the following structure: HIM:F4TCNQ(5%)(20 nm)/HIM(210 nm)/HTM1:F4TCNQ(5%)(20 nm)/HTM1(20 nm)/H2:TEG(10%)(30 nm)/ETM:LiQ(50%)(40 nm)/LiQ(1 nm). In the comparative example, HTM1 is replaced by HTMv1.

[0161] The external quantum efficiencies show a similar trend to that in the blue-emitting OLED of Example 1. The external quantum efficiency for HTM1 at 2 mA/cm.sup.2 in this experiment is 19.4%. The component comprising HTMv1 achieves 19.1%. The lifetime of HTM1 here too is much higher than for the comparative HTM. HTM1 at 20 mA/cm.sup.2 has a lifetime before a drop to 80% of the starting intensity of 160 hours. HTMv1 has an LT80 of 110 hours.

Example 3

[0162] In a further experiment, the compounds HTM2 and HTMv2 are compared. Here, the different performance data are even more dearly distinguishable. Again, the blue singlet stack (cf. Example 1) with the following structure is used: HIM:F4TCNQ(5%)(20 nm)/HIM(155 nm)/HTM2:F4TCNQ(5%)(20 nm)/HTM2(20 nm)/H1:SEB(5%)(20 nm)/ETM:LiQ(50%)(30 nm)/LiQ(1 nm), with insertion of HTMv2 rather than HTM2 at all appropriate points in the stack in the comparative experiment.

[0163] In the evaluation of the experimental data, the experiment comprising HTM2 shows an external quantum efficiency at 10 mA/cm.sup.2 of 7.9%, whereas HTMv2 shows only 7.3%. The lifetimes show a dear difference between the two materials. The stack comprising HTM2 has a lifetime LT80 at 60 mA/cm.sup.2 of 330 hours. HTMv2 under the same conditions achieves only 190 hours.

Example 4

[0164] Similar trends are seen as well in the triplet green component tested. The stack is analogous to the above-described green-emitting OLED stack (cf. example 3): HIM:F4TCNQ(5%)(20 nm)/HIM(210 nm)/HTM2:F4TCNQ(5%)(20)/HTM2(20)/H2:TEG(10%)(30 nm)/ETM:LiQ(50%)(40 nm)/LiQ(1 nm). In the comparative experiment, again, HTM2 is replaced by HTMv2.

[0165] The external quantum efficiency at 2 mA/cm.sup.2 for HTM2 is 19.2%; HTMv2 achieves only 17.7%. The LT80 @ 20 mA/cm.sup.2 in the HTM2 stack is 170 hours, and in the comparative structure comprising HTMv2 100 hours.

Example 5

[0166] Finally, the compound HTM3 is also tested in a singlet blue stack. This has the following structure: (HIM:F4TCNQ(5%)(20 nm)/HIM(155 nm)/HTM3:F4TCNQ(5%)(20 nm)/HTM3 (20 nm)/H1:SEB(5%)(20 nm)/ETM:UQ(50%)(30 nm)/LiQ(1 nm)). The compound HTM3 here exhibits an external quantum efficiency at 10 mA/cm.sup.2 of 7.6%. The lifetime to 80% and 60 mA/cm.sup.2 is 340 hours.

Example 6

[0167] In a triplet green component having the following structure: HIM:F4TCNQ(5%)(20 nm)/HIM(210 nm)/HTM3:F4TCNQ(5%)(20 nm)/HTM3(20 nm)/H2:TEG(10%)(30 nm)/ETM:LiQ(50%)(40 nm)/LiQ(1 nm), the compound HTM3 shows an external quantum efficiency at 2 mA/cm.sup.2 of 17.8% and a lifetime LT80 @ 20 mA/cm.sup.2 of 150 hours.

[0168] In summary, the device examples show that excellent performance data are achieved in OLEDs with the inventive compounds, especially excellent lifetime and quantum efficiency, both in systems comprising fluorescent emitters and in systems comprising phosphorescent emitters.

[0169] Substitution by an arylamino group in the specific position on the spirobifluorene as present in the compounds HTM1 to HTM3 additionally leads to much improved device performance compared to substitution in the 2 and 3 positions as exists in comparative examples HTMv1 and HTMv2.