MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES
20190378996 · 2019-12-12
Inventors
- Philipp Stoessel (Frankfurt Am Main, DE)
- Amir Parham (Frankfurt am Main, DE)
- Dominik Joosten (Frankfurt am Main, DE)
- Aurélie Ludemann (Frankfurt am Main, DE)
- Tobias Grossmann (Darmstadt, DE)
- Jonas Kroeber (Frankfurt am Main, DE)
Cpc classification
C07D491/052
CHEMISTRY; METALLURGY
C07D471/22
CHEMISTRY; METALLURGY
H10K85/6574
ELECTRICITY
H10K85/626
ELECTRICITY
H10K85/6572
ELECTRICITY
C07D519/00
CHEMISTRY; METALLURGY
International classification
C07D491/052
CHEMISTRY; METALLURGY
C07D519/00
CHEMISTRY; METALLURGY
Abstract
The present invention relates to compounds suitable for use in electronic devices, and to electronic devices, especially organic electroluminescent devices, comprising these compounds.
Claims
1.-15. (canceled)
16. A compound of formula (1) ##STR00199## where the symbols used are as follows: X is the same or different at each instance and is CR or N; Y is NR, BR, O or S; R is the same or different at each instance and is H, D, F, Cl, Br, I, NAr.sub.2, N(R.sup.1).sub.2, CN, NO.sub.2, OR.sup.1, SR.sup.1, COOR.sup.1, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.1).sub.2, CO, NR.sup.1, O, S or CONR.sup.1, 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; at the same time, two R radicals together may also form an aliphatic or heteroaliphatic ring system; R is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, OR.sup.2, SR.sup.2, Si(R.sup.2).sub.3, B(OR.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, OSO.sub.2R.sup.2, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.2 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.2).sub.2, CO, NR.sup.2, O, S or CONR.sup.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; at the same time, two or more R.sup.1 radicals together may form a ring system; R.sup.2 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; with the proviso that the compound of the formula (1) contains at least one substituent R and/or that the compound of the formula (1) contains at least one substituent R selected from the group consisting of NAr.sub.2 and 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.
17. The compound as claimed in claim 16, wherein the compound of formula (1) is a compound of formula (1) or (1) ##STR00200## where the symbols have the definitions given in claim 16 and the compound of the formula (1) has at least one R radical selected from the group consisting of NAr.sub.2 and 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.
18. The compound as claimed in claim 16, wherein not more than one symbol X per ring is N and the remaining symbols X are CR.
19. The compound as claimed in claim 16, wherein the compound of formula (1) is a compound of one of the formulae (2a) to (2h) ##STR00201## ##STR00202## where the symbols have the definitions given in claim 16.
20. The compound as claimed in claim 16 wherein the compound of formula (1) is a compound of one of the formulae (2a) and (2a) ##STR00203## where the symbols have the definitions given in claim 16 and at least one R group in formula (2a) is selected from the group consisting of NAr.sub.2 and 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.
21. The compound as claimed in claim 16, wherein the compound of formula (1) is a compound of the formula (3) ##STR00204## where the symbols have the definitions given in claim 16.
22. The compound as claimed in claim 16, wherein the compound of formula (1) is a compound of one of the formulae (3) and (3) ##STR00205## where the symbols have the definitions given in claim 16 and at least one R group in formula (3) is selected from the group consisting of NAr.sub.2 and 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.
23. The compound as claimed in claim 16, wherein the compound of formula (1) is a compound of formula (4) ##STR00206## where the symbols have the definitions given in claim 16.
24. The compound as claimed in claim 16, wherein the compound of formula (1) is a compound of one of the formulae (4) and (4) ##STR00207## where the symbols have the definitions given in claim 16 and at least one R group in formula (4) is selected from the group consisting of NAr.sub.2 and 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.
25. The compound as claimed in claim 16, wherein R, when it is an aromatic or heteroaromatic ring system, R and/or Ar are selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, phenanthrene, triphenylene or a combination of two or three of these groups, each of which may be substituted by one or more R.sup.1 radicals.
26. A process for preparing the compound as claimed in claim 16, comprising the reaction steps of: a) providing the base skeleton having a reactive leaving group; and b) coupling an aromatic or heteroaromatic ring system or a compound HNAr.sub.2 to the base skeleton with detachment of the leaving group.
27. A formulation comprising at least one compound as claimed in claim 16 and at least one solvent and/or at least one further organic or inorganic compound.
28. An organic electroluminescent device comprising at least one compound as claimed in claim 16.
29. An electronic device comprising at least one compound as claimed in claim 16.
30. An organic electroluminescent device which comprises the compound as claimed in claim 16 is used as matrix material and/or in a hole blocker layer and/or in an electron transport layer.
Description
EXAMPLES
[0097] 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.
Synthons and Inventive Examples S
Example S1
[0098] ##STR00083##
[0099] A mixture of 30.3 g (100 mmol) of 3-chloro-8H-quino[4,3,2-kl]acridine [198025-90-0], 13.4 g (110 mmol) of phenylboronic acid [98-80-6], 69.1 g (300 mmol) of tripotassium phosphate monohydrate, 821 mg (2 mmol) of SPhos [657408-07-6], 225 (1 mmol) of palladium acetate, 50 g of glass beads (diameter 3 mm) and 300 ml of DMSO is heated to 120 C. for 24 h. After cooling, the DMSO is largely removed under reduced pressure, the residue is taken up in 500 ml of dichloromethane (DCM), and the organic phase 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 with suction using a short Celite bed and the filtrate is concentrated to dryness. The crude product is recrystallized from dimethylacetamide. Yield: 24.8 g (72 mmol), 72%; purity: >98% by HPLC.
[0100] In an analogous manner, it is possible to prepare the following compounds:
TABLE-US-00001 Ex. Reactants Product Yield S2 198025-90-0
Example 1
[0101] ##STR00099##
[0102] To a solution of 26.8 g (100 mmol) of 8H-quino[4,3,2-kl]acridine [111180-95-5] and 26.8 g (100 mmol) of chlorodiphenyltriazine [3842-55-5] in 300 ml of dimethylacetamide (DMAC) are added 2.4 g (100 mmol) of sodium hydride in portions at room temperature (caution: evolution of hydrogen!). After the addition has ended, the mixture is heated gradually to 140 C. and stirring is continued until the reactants have been consumed (about 2 h). After cooling, the yellow acicular solids are filtered off with suction and washed once with 100 ml of DMAC and three times with 100 ml each time of ethanol, and then dried under reduced pressure. The crude product thus obtained is recrystallized five times from DMAC and then fractionally sublimed twice (p about 10.sup.5 mbar, T=about 320 C.). Yield: 26.0 g (52 mmol), 52%; purity: >99.99% by HPLC.
[0103] In an analogous manner, it is possible to prepare the following compounds:
TABLE-US-00002 Ex. Reactants Product Yield 2 111180-95-5
Example 100
[0104] ##STR00154##
[0105] A mixture of 26.8 g (100 mmol) of 8H-quino[4,3,2-kl]acridine [111180-95-5], 35.6 g (100 mmol) of 5-iodo-1,1:3,1-terphenyl [87666-86-2], 27.6 g (200 mmol) of potassium carbonate, 28.4 g (200 mmol) of sodium sulfate, 1.3 g (20 mmol) of copper powder, 100 g of glass beads (diameter 3 mm) and 300 ml of nitrobenzene is heated under reflux with good stirring for 16 h. After cooling, 1000 ml of methanol are added, and the solids are filtered off with suction and washed three times with 300 ml each time of methanol. The solids are subjected to hot extraction by stirring in 1000 ml of water, filtered off with suction and then washed twice with 200 ml each time of hot water and three times with 200 ml each time of methanol, and then dried under reduced pressure. The crude product thus obtained is hot extracted five times with o-xylene (amount initially charged 250 ml) and then fractionally sublimed twice (p about 10.sup.5 mbar, T about 310 C.). Yield: 28.3 g (57 mmol), 57%; purity: >99.99% by HPLC.
[0106] In an analogous manner, it is possible to prepare the following compounds:
TABLE-US-00003 Ex. Reactants Product Yield 101 87666-86-2
[0107] Production of the OLEDs
[0108] Examples I1 to I22 which follow present the use of various materials of the invention in OLEDs.
Pretreatment for Examples I1-I22
[0109] Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plaques form the substrates to which the OLEDs are applied.
[0110] 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 aluminum 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.
[0111] All 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 IC5:IC3:TEG2 (55%:35%:10%) mean here that the material IC5 is present in the layer in a proportion by volume of 55%, IC3 in a proportion of 35% and TEG2 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.
[0112] 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 lm/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. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom.
[0113] Use of Mixtures of the Invention in the Emission Layer of Phosphorescent OLEDs
[0114] The materials of the invention can be used in the emission layer in phosphorescent red OLEDs. The inventive material EG1 is used in Example I1 as matrix material in combination with the phosphorescent emitter TEG5. At a luminance of 1000 cd/m.sup.2, the OLED from I1 has a voltage of 3.8 V, an EQE of 21% and color coordinates of CIEx=0.67 and CIEy=0.33.
[0115] In examples I2 to I16 too, the OLED emits light with the color coordinates CIEx=0.67 and CIEy=0.33. This shows that the inventive compounds IV1-IV16 are suitable for use as matrix material in OLEDs.
[0116] Use of Mixtures of the Invention in the Electron Transport Layer of Phosphorescent OLEDs
[0117] The materials of the invention can also be used in the electron transport layer in OLEDs. In Examples I17 to I22, the inventive materials IV17 to IV22 are used in the electron transport layer. In examples I17 to I22, the OLED emits light with the color coordinates CIEx=0.67 and CIEy=0.33. This shows that the inventive compounds IV17 to IV22 are suitable for use as electron transport material in OLEDs.
TABLE-US-00004 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness I1 HATCN SpMA1 SpMA3 IV1:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I2 HATCN SpMA1 SpMA3 IV2:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I3 HATCN SpMA1 SpMA3 IV1:IV3:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (85% 10%:5%) 40 nm 35 nm I4 HATCN SpMA1 SpMA3 IV1:IV4:TER5 ST2:LiQ (50%.50%) 5 nm 125 nm 10 nm (85% 10%:5%) 40 nm 35 nm I5 HATCN SpMA1 SpMA3 IV5:TER5 ST2:LiQ (50%.50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I6 HATCN SpMA1 SpMA3 IV6:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (96%:5%)40 nm 35 nm I7 HATCN SpMA1 SpMA3 IV7:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I8 HATCN SpMA1 SpMA3 IV8:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35nm I9 HATCN SpMA1 SpMA3 IV9:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I10 HATCN SpMA1 SpMA3 IV10:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35nm I11 HATCN SpMA1 SpMA3 IV11:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35nm I12 HATCN SpMA1 SpMA3 IV12:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35nm I13 HATCN SpMA1 SpMA3 IV1:IV13:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (85% 10%:5%) 35nm I14 HATCN SpMA1 SpMA3 IV1:IV14:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (85% 10%:5%) 40 nm 35nm I15 HATCN SpMA1 SpMA3 IV1:IV15:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (85% 10%:5%) 40 nm 35nm I16 HATCN SpMA1 SpMA3 IV1:IV16:TER5 ST2:LiQ (50%:50%) 5 nm 125 nm 10 nm (85% 10%:5%) 40 nm 35nm I17 HATCN SpMA1 SpMA3 IV1:TER5 ST2 ST2:IV17 (50%:50%) LiQ 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 30 nm 3 nm I18 HATCN SpMA1 SpMA3 IV1.TER5 ST2 ST2:IV18 (50%:50%) LiQ 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 30 nm 3 nm I19 HATCN SpMA1 SpMA3 IV1:TER5 ST2 ST2:IV19 (50%:50%) LiQ 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 30 nm 3 nm I20 HATCN SpMA1 SpMA3 IV1:TER5 ST2 ST2:IV20 (50%:50%) LiQ 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 30 nm 3 nm I21 HATCN SpMA1 SpMA3 IV1:TER5 ST2 ST2:IV21 (50%:50%) LiQ 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 30 nm 3 nm I22 HATCN SpMA1 SpMA3 IV1:TER5 ST2 ST2:IV22 (50%:50%) LiQ 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 30 nm 3 nm
TABLE-US-00005 TABLE 2 Structural formulae of the materials for the OLEDs