MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES
20240357926 ยท 2024-10-24
Inventors
- Amir Parham (Frankfurt am Main, DE)
- Jonas Kroeber (Frankfurt am Main, DE)
- Christian EHRENEICH (Darmstadt, DE)
- Jonas ENGELHART (Darmstadt, DE)
- Christian Eickhoff (Mannheim, DE)
- Jens PFALZGRAF (Otzberg, DE)
Cpc classification
C07D209/00
CHEMISTRY; METALLURGY
H10K85/6574
ELECTRICITY
H10K85/6572
ELECTRICITY
C07D519/00
CHEMISTRY; METALLURGY
H10K85/615
ELECTRICITY
H10K85/6576
ELECTRICITY
International classification
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. Compound of formula (1) ##STR01489## with the proviso that at least one R radical that represents a Y group is present, and where the symbols and indices used are as follows: Y is the same or different at each instance and is a group of the formula (2), ##STR01490## where the dotted bond indicates the linkage of this group in the formula (1); X is the same or different at each instance and is CR or two adjacent X are a group of the formula (3), and the remaining X are the same or different at each instance and are CR, ##STR01491## where the dotted bonds indicate the linkage of this group in the formula (2); V is NR, C(R).sub.2, O or S; L is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R radicals; R, R is the same or different at each instance and is H, D, F, Cl, Br, I, N(Ar).sub.2, N(R.sup.1).sub.2, OAr, SAr, 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, 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, preferably 5 to 40 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, heteroaliphatic, aromatic or heteroaromatic ring system; in addition, two R radicals together may also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; with the proviso that at least one R radical is a Y group; 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 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, COOR.sup.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 each be substituted by one or more R.sup.2 radicals, 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 and where one or more hydrogen atoms in the alkyl, alkenyl or alkynyl group may be replaced by D, F, Cl, Br, I or CN, 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 an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R.sup.2 is the same or different at each instance and is H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; a is 0, 1, 2, 3 or 4; b is the same or different at each instance and is 0, 1, 2 or 3; c is 0, 1, 2, 3 or 4; d is the same or different at each instance and is 0, 1, 2, 3 or 4; with the proviso that a+b+c1; with exclusion of the following compound from the invention: ##STR01492##
2. Compound according to claim 1, selected from the compounds of the formulae (4) to (6) ##STR01493## where the symbols and indices have the definitions given in claim 1 and in addition: e is 0, 1 or 2.
3. Compound according to claim 1, selected from the compounds of the formulae (4a) to (6a) ##STR01494## where the symbols have the definitions given in claim 1.
4. Compound according to claim 1, selected from the compounds of the formulae (4b) to (6b) ##STR01495## where the symbols have the definitions given in claim 1.
5. Compound according to claim 1, wherein exactly one or two R radicals are a Y group.
6. Compound according to claim 1, wherein L is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms and may be substituted by one or more R radicals, where L, when L is a heteroaromatic ring system, does not contain any electron-deficient heteroaryl groups.
7. Compound according to claim 1, wherein L is the same or different at each instance and is selected from the group consisting of benzene, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, phenanthrene, triphenylene or a combination of two or three of these groups, where these groups may each be substituted by one or more R radicals.
8. Compound according to claim 1, wherein the Y group is the same or different at each instance and is selected from the groups of the following formulae (Y-1) to (Y-8): ##STR01496## ##STR01497## where the symbols have the definitions given in claim 1.
9. Compound according to claim 1, wherein the Y group is the same or different at each instance and is selected from the structures of the formulae (Y-1a) to (Y-8a) ##STR01498## ##STR01499## where the symbols have the definitions given in claim 1.
10. Compound according to claim 1, wherein R and R are the same or different at each instance and are selected from the group consisting of H, D, F, N(Ar).sub.2, CN, OR.sup.1, a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the alkyl or alkenyl group may each be substituted by one or more R.sup.1 radicals, but is preferably unsubstituted, and where one or more nonadjacent CH.sub.2 groups may be replaced by O, or an aromatic or heteroaromatic ring system which has 6 to 30 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 ring system; in addition, two R radicals together may also form an aliphatic or aromatic ring system.
11. Process for preparing a compound according to claim 1, characterized by the following synthesis steps: a) synthesizing the lactam base skeleton that bears a reactive leaving group rather than the Y group; and b) introducing the Y group by a coupling reaction.
12. Formulation comprising at least one compound according to claim 1 and at least one further compound and/or at least one solvent.
13. Use of a compound according to claim 1 in an electronic device.
14. Electronic device comprising at least one compound according to claim 1.
15. Electronic device according to claim 14 which is an organic electroluminescent device, wherein the compound according is used in an emitting layer as matrix material for phosphorescent emitters or for emitters that exhibit TADF and/or in an electron transport layer and/or in a hole blocker layer and/or in a hole transport layer and/or in an exciton blocker layer.
Description
EXAMPLES
Synthesis Examples
[0123] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. 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.
Preparation of the Synthons:
[0124] ##STR00581##
[0125] An initial charge of para-anisidine [104-94-9] (136.2 g, 1.11 mol), 1-bromo-2,6-dichlorobenzene [19393-92-1] (250.2 g, 1.11 mol) and sodium tert-butoxide (214.7 g, 2.23 mol) together with toluene (1500 ml) in a 4 l four-neck flask is inertized with argon for 30 min. Subsequently, Pd(dppf)Cl.sub.2DCM [95464-05-4] (4.51 g, 5.53 mmol) is added and the reaction mixture is stirred under reflux for 18 h. The mixture is then worked up by extraction with water and toluene, and the organic phase is dried over Na.sub.2SO.sub.4 and filtered through a silica gel bed. The filtrate is concentrated by rotary evaporation, and the crude product obtained is purified further by vacuum distillation. Yield: 218.3 g (813 mmol, 74%), yellow semicrystalline oily solid.
[0126] In an analogous manner, it is possible to prepare the following compounds: The catalyst system used here, rather than Pd(dppf)Cl.sub.2DCM, may also be Pd(OAc).sub.2/S-Phos [657408-07-6]. Purification can be effected not only by distillation but also using column chromatography, or recrystallization can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc. The yields are typically in the range between 40% and 85%.
TABLE-US-00005 Reactant 1 Reactant 2 Product
##STR00609##
[0127] An initial charge of S1 (217.7 g, 812 mmol) in pyridine (1000 ml) is inertized with argon. Subsequently, benzoyl chloride [98-88-4] (150 ml, 1.29 mol) is added dropwise. After the addition has ended, the mixture is stirred under reflux for 15 h. The mixture is allowed to cool down to room temperature, and the precipitated solids are filtered off with suction and washed four times with water. The crude product is suspended in ethanol and stirred under reflux for 3 h. After cooling, the precipitated solids are filtered off with suction and washed with ethanol. Yield: 284 g (763 mmol, 94%) of white solid, 98% by .sup.1H NMR.
[0128] In an analogous manner, it is possible to prepare the following compounds: Purification can also be effected using column chromatography, or recrystallization can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc. The yields are typically in the range between 40% and 85%.
TABLE-US-00006 Reactant 1 Reactant 2 Product
##STR00649##
[0129] An initial charge of S25 (181.2 g, 486.8 mmol) and potassium carbonate (202.5 g, 1.46 mol) in N,N-dimethylacetamide (1800 ml) is inertized with argon for 30 min. Subsequently, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride [CAS-250285-32-6] (8.55 g, 19.47 mmol) and palladium(II) acetate (2.18 g, 9.69 mmol) are added, and the reaction mixture is heated to reflux and stirred at this temperature for 72 h. After cooling to room temperature, the solvent is drawn off on a rotary evaporator, the residue is stirred with ethanol/water (1:1; 1000 ml), and the solids are filtered off with suction and washed with water and ethanol. The crude product is recrystallized from ethyl acetate. Yield: 49.4 g (165 mmol, 34%) of brown solid; about 95% by .sup.1H NMR.
[0130] In an analogous manner, it is possible to prepare the following compounds: The ligand used here, rather than 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride [CAS-250285-32-6], may also be 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride [141556-45-8], tricyclohexylphosphine [2622-14-2] or tri-tert-butylphosphine [13716-12-6]. Purification can be effected not only by distillation but also using column chromatography, or recrystallization can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc. The yields are typically in the range between 10% and 50%.
TABLE-US-00007 Reactant Product(s)
##STR00676##
[0131] An initial charge of S50 (36.84 g, 123.1 mmol) in a flask under an argon atmosphere in dichloromethane (1200 ml) is cooled in an ice bath to 000. Subsequently, boron tribromide [10294-33-4] (24.0 ml, 252.9 mmol) is added dropwise, and then the mixture is gradually warmed up to room temperature. Subsequently, the mixture is quenched by dropwise addition of methanol and the solvent is drawn off on a rotary evaporator. Methanol (300 ml) is twice added and removed again by rotary evaporation. The brown solids are admixed with 400 ml of methanol and heated under reflux. After cooling, the solids are filtered off with suction and washed with methanol. The crude product is subjected to hot extraction with n-butyl acetate.
[0132] Yield: 28.5 g (100 mmol; 81%) of beige solid; 95% by .sup.1H NMR.
[0133] In an analogous manner, it is possible to prepare the following compounds: Purification can also be effected using column chromatography, or recrystallization can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc. The yields are typically in the range between 50% and 90%.
TABLE-US-00008 Reactant Product(s)
##STR00707##
[0134] An initial charge of S75 (27.84 g, 97.6 mmol) in pyridine (500 ml) is cooled in an ice bath to 0 C. Subsequently, trifluoromethanesulfonic anhydride [358-23-6] (50.4 ml, 293.4 mmol) is gradually added dropwise at such a rate that the internal temperature does not rise above 10 C. Subsequently, the mixture is left to warm up to room temperature overnight. The pyridine is drawn off on a rotary evaporator and the residue is worked up by extraction with dichloromethane and 1 mol/I HCl. The organic phase is washed four times with water, dried over Na.sub.2SO.sub.4 and concentrated to 300 ml. The precipitated solids are filtered off with suction and washed with dichloromethane and ethanol. Yield: 38.7 g (92.7 mmol, 95%) of beige solid, 95% by .sup.1H NMR.
[0135] In an analogous manner, it is possible to prepare the following compounds: Purification can also be effected using column chromatography, or recrystallization can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc. The yields are typically in the range between 55% and 97%.
TABLE-US-00009 Reactant Product(s)
##STR00738##
[0136] An initial charge of S1 (40.2 g, 96.2 mmol), bis(pinacolato)diboron [73183-34-3] (26.93 g, 105.0 mmol) and potassium acetate (28.82 g, 293.6 mmol) in 1,4-dioxane (600 ml) is inertized with argon for 2 min. Subsequently, X-Phos [564483-18-7] (456 mg, 0.96 mmol) and Pd.sub.2(dba).sub.3 [51364-51-3](435 mg, 0.48 mmol) are added and the reaction mixture is stirred under reflux for 16 h. After cooling, the solvent is removed by rotary evaporation and the residue is worked up by extraction with dichloromethane/water. The organic phase is dried over Na.sub.2SO.sub.4, ethyl acetate is added, and the dichloromethane is removed by rotary evaporation on a rotary evaporator down to 500 mbar. The precipitated solids are filtered off with suction and washed with ethyl acetate. Yield: 30.8 g (77.9 mmol, 81%) of beige solid, 98% by .sup.1H NMR.
[0137] In an analogous manner, it is possible to prepare the following compounds: The ligand used here may also be S-Phos rather than X-Phos. Purification can be effected using column chromatography, or recrystallization can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc. The yields are typically in the range between 60% and 95%.
TABLE-US-00010 Reactant Product(s)
##STR00769##
[0138] Under an inert atmosphere, an initial charge of 1-bromo-8-iododibenzofuran [CAS-1822311-11-4] (37.28 g, 100 mmol), carbazole [86-74-8] (16.71 g, 100 mmol) of potassium carbonate (34.55 g, 250 mmol) and copper powder (1.27 g, 20.0 mmol) in DMF (350 ml) is inertized with argon for a further 15 min and then stirred at 130 C. for 32 h. The mixture is left to cool down to room temperature, filtered through a Celite bed and washed through twice with 200 ml of DMF, and the filtrate is concentrated to dryness on a rotary evaporator. The residue is worked up by extraction with dichloromethane/water, and the organic phase is washed twice with water and once with saturated NaCl solution and dried over Na.sub.2SO.sub.4. 150 ml of ethanol are added, dichloromethane is drawn off on a rotary evaporator down to 500 mbar, and the precipitated solids are filtered off with suction and washed with ethanol. Yield: 29.2 g (71.1 mmol, 71%) of grey solid, 97% by .sup.1H NMR.
[0139] In an analogous manner, it is possible to prepare the following compounds: Purification can be effected using column chromatography, or recrystallization can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc. The yields are typically in the range between 20% and 80%.
TABLE-US-00011 Reactant 1 Reactant 2 Product
Preparation of the Products:
[0140] ##STR00908##
[0141] To an initial charge, in a flask, of S100 (15.02 g, 36.0 mmol), 9-phenyl-9-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-9H,9H-[3,3]bicarbazolyl [2088364-11-6] (26.41 g, 43.3 mmol) and tripotassium phosphate (15.54 g) are added tetrahydrofuran (400 ml) and water (100 ml), and the mixture is inertized with argon for 30 min. Subsequently, palladium(II) acetate [3375-31-3] (204.3 mg) and X-Phos [564483-18-7] (905 mg) are added and the mixture is heated under reflux for 20 h. After cooling, the precipitated solids are filtered off with suction and washed twice with water and twice with THF. The crude product is subjected to hot extraction four times with toluene and finally sublimed under high vacuum. Yield: 15.6 g (20.7 mmol, 58%) of yellow solid, purity: >99.9% by HPLC.
[0142] In an analogous manner, it is possible to prepare the following compounds: The phosphine ligand used here may also be S-Phos [657408-07-6] rather than X-Phos, or the catalyst system (palladium source and ligand) used may be bis(triphenylphosphine)palladium chloride [13965-03-2]. Purification can also be effected using column chromatography, or recrystallization or hot extraction using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. The yields are typically in the range between 15% and 75%.
TABLE-US-00012 Reactant 1 Reactant 2 Product S100
##STR01089##
[0143] An initial charge of 5-(9-bromo-2-dibenzofuranyl)-5,7-dihydro-7,7-dimethylindeno[2,1-b]carbazole [2226483-41-4] (21.24 g, 40.2 mmol), S125 (15.89 g, 40.2 mmol) and sodium carbonate (8.51 g, 80.3 mmol) in toluene (200 ml), 1,4-dioxane (200 ml) and water (100 ml) is inertized with argon for 20 min. Subsequently, tetrakis(triphenylphosphine)palladium(0) (928 mg, 0.80 mmol) is added and the reaction mixture is stirred under reflux for 32 h. After cooling, the precipitated solids are filtered off with suction and washed with ethanol. The crude product is twice subjected to hot extraction with toluene, then recrystallized three times from dimethylacetamide and finally sublimed under high vacuum. Yield: 15.8 g (22.1 mmol, 55%) of yellow solid, purity: >99.9% by HPLC.
Catalyst System for the Conversion of Cl Rather than Br:
[0144] For the conversion of Cl rather than bromine, the phosphine ligand used is X-Phos [564483-18-7] or S-Phos [657408-07-6] rather than tetrakis(triphenylphosphine)palladium(0), or the palladium source used is Pd(OAc).sub.2 [3375-31-3] or Pd.sub.2(dba).sub.3 [51364-51-3]. Alternatively, the catalyst system used may also be PdX-Phos-G3 [1445085-55-1]. It may also be advantageous for the conversion of bromine to use one of the latter catalyst systems.
[0145] Purification can also be effected using column chromatography, or recrystallization or hot extraction using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. The yields are typically in the range between 13% and 75%.
TABLE-US-00013 Reactant 1 Reactant 2 Product S125
Production of the OLEDs
[0146] Examples C1 to 118 which follow (see Table 1) present the use of the materials of the invention in OLEDs.
[0147] Pretreatment for Examples C1-118: 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.
[0148] 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 3. The device data of the OLEDs are listed in Table 2. Examples C1 to C4 are comparative examples according to the prior art, examples 11 to 118 show data of OLEDs of the invention.
[0149] 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 SoA1:CoH1:TEG1 (45%:45%:10%) mean here that the material SoA1 is present in the layer in a proportion by volume of 45%, CoH1 in a proportion by volume of 45% and TEG1 in a proportion by volume of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.
[0150] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra and the current efficiency (SE, measured in cd/A) as a function of luminance, calculated from current-voltage-luminance characteristics assuming Lambertian radiation characteristics, and the lifetime are measured. The electroluminescence spectra are determined at a current density of 10 mA/cm.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 in the course of operation with constant current density j.sub.0. A figure of L1=80% in Table 2 means that the lifetime reported in the LT column corresponds to the time after which the luminance falls to 80% of its starting value.
Use of Materials of the Invention in OLEDs
[0151] The materials of the invention can be used in the emission layer in phosphorescent green OLEDs. Inventive compounds P1, P9, P13, P28, P35, P67, P88, P205, P213, P218, P229, P247, P251, P332, P393 with or without CoH1 or CoH2 are used in Examples 11 to 118 as matrix material in the emission layer. The examples are elucidated in detail hereinafter, in order to illustrate the advantages of the OLEDs of the invention.
Use of Materials of the Invention in the Emission Layer of Phosphorescent OLEDs
[0152] The use of the inventive compounds P1 and P9 as matrix material in the emission layer (Examples 11 to 14) can achieve a distinct improvement in lifetime compared to the prior art compounds (Examples C1 to C4). By combination of P1, P9, P13, P28, P35, P67, P88, P205, P213, P218, P229, P247, P251, P332, P393 with CoH1 or with CoH2 and TEG1 or TEG2, it is additionally possible to further distinctly enhance the lifetime.
TABLE-US-00014 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness C1 HATCN SpMA1 SpMA2 SoA1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (88%:12%) 10 nm (50%:50%) 30 nm 30 nm C2 HATCN SpMA1 SpMA2 SoA2:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (88%:12%) 10 nm (50%:50%) 30 nm 30 nm I1 HATCN SpMA1 SpMA2 P1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (88%:12%) 10 nm (50%:50%) 30 nm 30 nm I2 HATCN SpMA1 SpMA2 P9:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (88%:12%) 10 nm (50%:50%) 30 nm 30 nm C3 HATCN SpMA1 SpMA2 SoA1:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm C4 HATCN SpMA1 SpMA2 SoA1:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I3 HATCN SpMA1 SpMA2 P1:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I4 HATCN SpMA1 SpMA2 P9:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I5 HATCN SpMA1 SpMA2 P1:CoH2:TEG2 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm I6 HATCN SpMA1 SpMA2 P13:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I7 HATCN SpMA1 SpMA2 P28:CoH2:TEG2 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm I8 HATCN SpMA1 SpMA2 P35:CoH2:TEG2 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm I9 HATCN SpMA1 SpMA2 P67:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I10 HATCN SpMA1 SpMA2 P88:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I11 HATCN SpMA1 SpMA2 P205:CoH2:TEG2 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm I12 HATCN SpMA1 SpMA2 P213:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I13 HATCN SpMA1 SpMA2 P218:CoH2:TEG2 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm I14 HATCN SpMA1 SpMA2 P229:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I15 HATCN SpMA1 SpMA2 P247:CoH2:TEG2 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm I16 HATCN SpMA1 SpMA2 P251:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm I17 HATCN SpMA1 SpMA2 P332:CoH2:TEG2 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm I18 HATCN SpMA1 SpMA2 P393:CoH1:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 230 nm 20 nm (59%:29%:12%) 10 nm (50%:50%) 30 nm 30 nm
TABLE-US-00015 TABLE 2 Device data of the OLEDs CIE x/y at j0 L1 LT Ex. 10 mA/cm2 (mA/cm.sup.2) (%) (h) C1 0.34/0.62 40 80 100 C2 0.34/0.62 40 80 105 I1 0.34/0.62 40 80 260 I2 0.36/0.61 40 80 130 C3 0.34/0.62 40 80 180 C4 0.35/0.62 40 80 140 I3 0.34/0.62 40 80 400 I4 0.35/0.62 40 80 240 I5 0.35/0.63 40 80 520 I6 0.35/0.62 40 80 220 I7 0.35/0.63 40 80 480 I8 0.35/0.63 40 80 500 I9 0.35/0.62 40 80 210 I10 0.35/0.62 40 80 220 I11 0.35/0.63 40 80 420 I12 0.35/0.62 40 80 205 I13 0.35/0.63 40 80 450 I13 0.35/0.62 40 80 210 I15 0.35/0.63 40 80 495 I16 0.35/0.62 40 80 230 I17 0.35/0.63 40 80 490 I18 0.35/0.62 40 80 210
TABLE-US-00016 TABLE 3 Structural formulae of the materials for the OLEDs