NITROGEN-CONTAINING HETEROCYCLES FOR USE IN OLEDS

Abstract

The present invention describes nitrogen-containing heterocycles substituted by carbazole groups, especially for use in electronic devices. The invention further relates to a process for preparing the compounds of the invention and to electronic devices comprising these.

Claims

1. Compound comprising at least one structure of the formula (I): ##STR00382## where the symbols used are as follows: X is the same or different at each instance and is N or CR.sup.1 or C-(CAB); W.sup.1 is O, S, SO, SO.sub.2, SiR.sup.1.sub.2 or CO; 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.sup.1).sub.2, N(R.sup.2).sub.2, OAr.sup.1, OR.sup.2, SAr.sup.1, SR.sup.2, C(O)Ar.sup.1, C(O)R.sup.2, P(O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, Si(Ar.sup.1).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, and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CS, CNR.sup.2, C(O)O, C(O)NR.sup.2, NR.sup.2, P(O)(R.sup.2), O, S, SO or SO.sub.2 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 40 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 40 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 40 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 R.sup.1 substituents together may also form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same 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, CO, CNR.sup.2, CC(R.sup.2).sub.2, O, S, SO, 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 H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, OR.sup.3, SR.sup.3, NO.sub.2, C(O)R.sup.3, CR.sup.3C(R.sup.3).sub.2, C(O)OR.sup.3, C(O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.13).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(O)R.sup.3, S(O).sub.2R.sup.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, each of which may be substituted by one or more R.sup.3 radicals, and where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CS, CNR.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 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 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more R.sup.2 substituents together may also form a mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.3 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 having 5 to 30 aromatic ring atoms 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, it is possible for two or more R.sup.3 substituents together to form a mono- or polycyclic, aliphatic ring system; with the proviso that at least one X group is N which is adjacent to a group in which X is C-(CAB) in which CAB is a group of the formula (CAB-1) ##STR00383## in which X.sup.1 is the same or different at each instance and is CR.sup.1 or N and the dotted line represents the bond to the carbon atom of the aromatic ring to which the group of the formula (CAB-1) is bonded.

2. Compound according to claim 1, comprising at least one structure of the formula (IIa), (IIb), (IIc) or (IId) ##STR00384## where the symbols W.sup.1 and X used have the definition given in claim 1 and X.sup.1 is the same or different and is N or CR.sup.1, where at least one X.sup.1 group adjacent to the carbon atom to which the (aza)carbazole group is bonded is N.

3. Compound according to claim 2, comprising at least one structure of the formula (IIIa), (IIIb), (IIIc) or (IIId) ##STR00385## where m is the same or different and is 0, 1, 2, 3 or 4 and X.sup.1 is N or CR.sup.1, where at least one X.sup.1 group is N.

4. Compound according to claim 3, comprising at least one structure of the formula (IVa), (IVb), (IVc) or (IVd) ##STR00386## where m is the same or different and is 0, 1, 2, 3 or 4, n is the same or different and is 0, 1, 2 or 3, and X.sup.1 is N or CR.sup.1, where at least one X.sup.1 group is N.

5. Compound according to claim 4, comprising at least one structure of the formula (Va), (Vb), (Vc) or (Vd) ##STR00387## where m is the same or different and is 0, 1, 2, 3 or 4, and n is 0, 1, 2 or 3.

6. Compound according claim 1, characterized in that two adjacent R.sup.1 radicals form a ring of the formula (DB-1), (DB-2) or (DB-3) ##STR00388## where X.sup.2 is the same or different at each instance and is N or CR.sup.2, Y.sup.1 and Y.sup.2 independently at each instance are O, S, C(R.sup.2).sub.2 or NR.sup.2 and the dotted lines represent the bond to the aryl or heteroaryl group, where R.sup.2 has the definition given in claim 1.

7. Compound according to claim 6, comprising at least one structure of the formula (VIa), (VIb), (VIc), (VId), (IXa), (IXb), (IXc), (IXd), (XIIa), (XIIb), (XIIc) or (XIId) ##STR00389## ##STR00390## ##STR00391## where the symbols Y.sup.1, Y.sup.2 and X.sup.2 have the definition given in claim 6, l is 0, 1 or 2, m is 0, 1, 2, 3 or 4 and X.sup.1 is N or CR.sup.1, where at least one X.sup.1 group adjacent to the carbon atom to which the carbazole derivative group is bonded is N.

8. Compound according to claim 7, comprising at least one structure of the formula (VIIa), (VIIb), (VIIc), (VIId), (Xa), (Xb), (Xc), (Xd), (XIIIa), (XIIIb), (XIIIc) or (XIIId) ##STR00392## ##STR00393## ##STR00394## where m is the same or different and is 0, 1, 2, 3 or 4, and X.sup.1 is N or CR.sup.1, where at least one X.sup.1 group is N.

9. Compound according to claim 8, comprising at least one structure of the formula (VIIIa), (VIIIb), (VIIIc), (VIIId), (XIa), (XIb), (XIc), (XId), (XIVa), (XIVb), (XIVc) or (XIVd) ##STR00395## ##STR00396## ##STR00397## where l is 0, 1 or 2, n is 0, 1, 2 or 3 and m is the same or different and is 0, 1, 2, 3 or 4.

10. Compound according to claim 2, characterized in that not more than four X groups are N.

11. Oligomer, polymer or dendrimer containing one or more compounds according to claim 1, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

12. Composition comprising at least one compound according to claim 1 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.

13. Formulation comprising at least one compound according to claim 1 and at least one solvent.

14. Use of a compound according to claim 1, in an electronic device.

15. Process for preparing a compound according to claim 1, characterized in that, in a coupling reaction, a compound comprising at least one nitrogen-containing heterocyclic group is joined a compound comprising at least one carbazole group.

16. Electronic device comprising at least one compound according to claim 1, wherein the electronic device is 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, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells and organic laser diodes.

Description

EXAMPLES

[0179] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The reactants can be sourced from ALDRICH. The numbers for the reactants known from the literature, some of which are stated in square brackets, are the corresponding CAS numbers.

SYNTHESIS EXAMPLES

a) (9-Oxo-9H-xanthen-1-yl)urea

[0180] ##STR00103##

[0181] To a degassed solution of 51.1 g (244 mmol) of 1-aminoxanthen-9-one in 1300 ml of AcOH are added 27 g (319 mmol) of KOCN in portions over a period of 5 h at room temperature. The solvent is removed under reduced pressure, then CH.sub.2Cl.sub.2 and then water are added. After phase separation, the product is purified by chromatography (90:3, CH.sub.2Cl.sub.2/MeOH). Yield: 38 g (150 mmol), 62% of theory; purity: 93% by HPLC.

[0182] The following compounds can be prepared in an analogous manner.

TABLE-US-00001 Reactant 1 Product Yield 1a [00104] [00105] 59% 2a [00106] [00107] 61% 3a [00108] [00109] 60% 4a [00110] [00111] 63%

b) 3H-7-Oxa-1,3-diazabenzo[de]anthracen-2-one

[0183] ##STR00112##

[0184] To a solution of 21 g (86 mmol) of (9-oxo-9H-xanthen-1-yl)urea in 1500 ml of EtOH are added 11.7 g (190 mmol) of KOH and the mixture is heated to boiling for 40 min. Cooling is followed by addition of CH.sub.2Cl.sub.2 to the mixture, which is filtered and admixed with water. Phase separation is followed by recrystallization from acetone. Yield: 17.5 g (74 mmol) of 3H-7-oxa-1,3-diaza-benzo[de]anthracen-2-one, 90% of theory; purity: 93% by HPLC.

[0185] The following compounds can be prepared in an analogous manner:

TABLE-US-00002 Reactant 1 Product Yield 1b [00113] [00114] 87% 2b [00115] [00116] 91% 3b [00117] [00118] 88% 4b [00119] [00120] 87%

c) 2-Chloro-7-oxa-1,3-diazabenzo[de]anthracene

[0186] ##STR00121##

[0187] 14.1 g (60 mmol) of 3H-7-oxa-1,3-diazabenzo[de]anthracen-2-one are stirred in 200 ml of POCl.sub.3 at 85 C. for 5 h. Then the POCl.sub.3 is removed under reduced pressure, and the pH is adjusted to 7 by adding 1 N NaOH. Then extraction is effected with CH.sub.2Cl.sub.2. The solvent is drawn off under reduced pressure, and the product is recrystallized from hexane under protective gas. Yield: 14.7 g (58 mmol), 97% of theory; purity: 93% by HPLC.

[0188] The following compounds can be prepared in an analogous manner:

TABLE-US-00003 Reactant 1 Product Yield 1c [00122] [00123] 87% 2c [00124] [00125] 91% 3c [00126] [00127] 88% 4c [00128] [00129] 87%

d) 2-Chloro-4-(2-methylsulfanylphenyl)quinazoline

[0189] ##STR00130##

[0190] 73 g (370 mmol) of 2,4-dichloroquinazoline, 58 g (350 mmol) of 2-methylsulfanylphenylboronic acid and 100 g (475 mmol) of K.sub.2CO.sub.3 are suspended in 400 ml of THF and 400 ml of water, the mixture is saturated with N.sub.2, 1.6 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0) are added and the mixture is heated to boiling for 2 h. The mixture is poured into 1 l of a mixture of water/MeOH/6 M HCl 1:1:1, and the beige precipitate is filtered off with suction, washed with water and dried. Yield: 86 g (300 mmol), 82% of theory; purity: 95% by HPLC.

[0191] The following compounds can be prepared in an analogous manner:

TABLE-US-00004 Reactant 1 Reactant 2 Product Yield 1d [00131] [00132] [00133] 89% 2d [00134] [00135] [00136] 90% 3d [00137] [00138] [00139] 91% 4d [00140] [00141] [00142] 92% 5d [00143] [00144] [00145] 95% 6d [00146] [00147] [00148] 91% 7d [00149] [00150] [00151] 90% 8d [00152] [00153] [00154] 87% 9d [00155] [00156] [00157] 95% 10d [00158] [00159] [00160] 85% 11d [00161] [00162] [00163] 87% 12d [00164] [00165] [00166] 91%

e) 2-Chloro-4-(2-methanesulfinylphenyl)quinazoline

[0192] ##STR00167##

[0193] Under protective gas, an initial charge of 86 g (300 mmol) of 2-chloro-4-(2-methylsulfanylphenyl)quinazoline in 1.1 l of glacial acetic acid and 125 ml of dichloromethane is cooled to 0 C. To this solution are added dropwise 500 ml (309 mmol) of 30% H.sub.2O.sub.2 solution, and the mixture is stirred overnight. The mixture is admixed with Na.sub.2SO.sub.3 solution, the phases are separated and the solvent is removed under reduced pressure. Yield: 86 g (285 mmol), 80% of theory; purity: 96% by HPLC.

[0194] The following compounds can be prepared in an analogous manner:

TABLE-US-00005 Reactant 1 Product Yield 1e [00168] [00169] 78% 2e [00170] [00171] 75% 3e [00172] [00173] 77% 4e [00174] [00175] 76% 5e [00176] [00177] 78% 6e [00178] [00179] 76% 7e [00180] [00181] 68% 8e [00182] [00183] 88% 9e [00184] [00185] 82% 10e [00186] [00187] 84% 11e [00188] [00189] 80% 12e [00190] [00191] 87% 13e [00192] [00193] 88% 14e [00194] [00195]

f) 2-Chloro-7-thia-1,3-diazabenzo[de]anthracene

[0195] ##STR00196##

[0196] A mixture of 85 g (280 mmol) of 2-chloro-4-(2-methanesulfinylphenyl)quinazoline and 737 ml (8329 mmol) of trifluoromethanesulfonic acid is stirred at 5 C. for 48 h. Subsequently, the mixture is admixed with 2.4 l of water/pyridine 5:1 and heated under reflux for 20 min. After cooling to room temperature, 500 ml of water and 1000 ml of dichloromethane are added cautiously. The organic phase is washed with 450 ml of H.sub.2O and dried over MgSO.sub.4, and the solvents are removed under reduced pressure. The pure product is obtained by recrystallization from toluene. Yield: 72 g (267 mmol), 95% of theory; purity: 95% by HPLC.

[0197] The following compounds can be prepared in an analogous manner:

TABLE-US-00006 Reactant 1 Product Yield 1f [00197] [00198] 91% 2f [00199] [00200] 79% 3f [00201] [00202] 87% 4f [00203] [00204] 85% 5f [00205] [00206] 91% 6f [00207] [00208] 87% 7f [00209] [00210] 89% 8f [00211] [00212] 92% 9f [00213] [00214] 85% 10f [00215] [00216] 87% 11f [00217] [00218] 76% 12f [00219] [00220] 91% 13f [00221] [00222] 89%

g) 4-(7-Thia-1,3-diazabenzo[de]anthracen-2-yl)-14H-13-thia-14-azabenzo[c]indeno[2,1-a]fluorene

[0198] ##STR00223##

[0199] 16.2 g (60 mmol) of 14H-13-thia-14-azabenzo[c]indeno[2,1-a]fluorene are dissolved in 300 ml of dimethylformamide under a protective gas atmosphere, and 3 g of NaH (75 mmol), 60% in mineral oil, are added.

[0200] After 1 h at room temperature, a solution of 16.7 g (62 mmol) of 2-chloro-7-thia-1,3-diazabenzo[de]anthracene in 150 ml of dimethylformamide is added dropwise. The reaction mixture is stirred at room temperature for 12 h, then poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated. The residue is recrystallized with toluene and finally fractionally sublimed twice (p about 10.sup.6 mbar, T=375-390 C.). Yield: 26.7 g (47 mmol), 80% of theory; purity: 99.9% by HPLC.

[0201] The following compounds can be prepared in an analogous manner:

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield 1g [00224] [00225] [00226] 76% 2g [00227] [00228] [00229] 80% 3g [00230] [00231] [00232] 86% 4g [00233] [00234] [00235] 81% 5g [00236] [00237] [00238] 82% 6g [00239] [00240] [00241] 78% 7g [00242] [00243] [00244] 75% 8g [00245] [00246] [00247] 77% 9g [00248] [00249] [00250] 80% 10g [00251] [00252] [00253] 84% 11g [00254] [00255] [00256] 89% 12g [00257] [00258] [00259] 85% 13g [00260] [00261] [00262] 84% 14g [00263] [00264] [00265] 83% 15g [00266] [00267] [00268] 9{circumflex over ()}1% 16g [00269] [00270] [00271] 83% 17g [00272] [00273] [00274] 85% 18g [00275] [00276] [00277] 84% 19g [00278] [00279] [00280] 73% 20g [00281] [00282] [00283] 74% 21g [00284] [00285] [00286] 81% 22g [00287] [00288] [00289] 85% 23g [00290] [00291] [00292] 77% 24g [00293] [00294] [00295] 87% 25g [00296] [00297] [00298] 88% 26g [00299] [00300] [00301] 76% 27g [00302] [00303] [00304] 75% 28g [00305] [00306] [00307] 76% 29g [00308] [00309] [00310] 77% 30g [00311] [00312] [00313] 80% 31g [00314] [00315] [00316] 72% 32g [00317] [00318] [00319] 70% 33g [00320] [00321] [00322] 73% 34g [00323] [00324] [00325] 69% 35g [00326] [00327] [00328] 87% 36g [00329] [00330] [00331] 72% 37g [00332] [00333] [00334] 70% 38g [00335] [00336] [00337] 81% 39g [00338] [00339] [00340] 78% 40g [00341] [00342] [00343] 76% 41g [00344] [00345] [00346] 77% 42g [00347] [00348] [00349] 71% 43g [00350] [00351] [00352] 69% 44g [00353] [00354] [00355] 60% 45g [00356] [00357] [00358] 74% 46g [00359] [00360] [00361] 72% 47g [00362] [00363] [00364] 70% 48g [00365] [00366] [00367] 67%

Production of the OLEDs

[0202] Examples I1 to I8 which follow (see Table 1) present the use of the materials of the invention in OLEDs.

Pretreatment for Examples I1 to I8:

[0203] Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating, first with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plaques form the substrates to which the OLEDs are applied.

[0204] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 1. The materials required for production of the OLEDs are shown in Table 2.

[0205] 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 IC1:IC2:TER1 (50%:45%:5%) mean here that the material IC1 is present in the layer in a proportion by volume of 50%, IC2 in a proportion of 45% and TER1 in a proportion of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0206] The OLEDs are characterized in a standard manner. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom.

Use of Mixtures of the Invention in OLEDs

[0207] The materials of the invention can be used in the emission layer in phosphorescent red OLEDs. The inventive compounds EG1 to EG6 are used in Examples 11 to 18 as matrix material in the emission layer. The colour coordinates of the electroluminescence spectra of the OLEDs are CIEx=0.67 and CIEy=0.33. The materials are thus suitable for use in the emission layer of red-phosphorescing OLEDs.

[0208] In addition, the materials of the invention can be used successfully in the hole blocker layer (HBL) or electron blocker layer (EBL). This is shown in Examples 17 and 18. Here too, the colour coordinates of the spectrum of the OLED are CIEx=0.67 and CIEy=0.33.

TABLE-US-00008 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL thick- thick- thick- thick- thick- thick- thick- Ex. ness ness ness ness ness ness ness I1 HATCN SpMA1 SpMA2 IC2:EG1:TER1 ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I2 HATCN SpMA1 SpMA2 EG2:TER1 ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I3 HATCN SpMA1 SpMA2 IC1:EG3:TER1 ST1:LiQ 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm (50%:50%) 35 nm I4 HATCN SpMA1 SpMA2 EG4:TER1 ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I5 HATCN SpMA1 SpMA2 IC2:EG5:TER1 ST1:LiQ 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm (50%:50%) 35 nm I6 HATCN SpMA1 SpMA2 IC2:EG6:TER1 ST1:LiQ 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm (50%:50%) 35 nm I7 HATCN SpMA1 SpMA2 EG4:TER1 EG4 ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 30 nm I8 HATCN SpMA1 EG4 EG4:TER1 ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm

TABLE-US-00009 TABLE 2 Structural formulae of the materials for the OLEDs [00368] [00369] [00370] [00371] [00372] [00373] [00374] [00375] [00376] [00377] [00378] [00379] [00380] [00381]