CN115637146A - Phosphorescent material composition and organic electroluminescent device comprising same - Google Patents
Phosphorescent material composition and organic electroluminescent device comprising same Download PDFInfo
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- CN115637146A CN115637146A CN202211192152.7A CN202211192152A CN115637146A CN 115637146 A CN115637146 A CN 115637146A CN 202211192152 A CN202211192152 A CN 202211192152A CN 115637146 A CN115637146 A CN 115637146A
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- 229910052805 deuterium Inorganic materials 0.000 claims description 19
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
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- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical group C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
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- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HCAUQPZEWLULFJ-UHFFFAOYSA-N benzo[f]quinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=N1 HCAUQPZEWLULFJ-UHFFFAOYSA-N 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
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- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
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- DHFABSXGNHDNCO-UHFFFAOYSA-N dibenzoselenophene Chemical compound C1=CC=C2C3=CC=CC=C3[se]C2=C1 DHFABSXGNHDNCO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 239000007850 fluorescent dye Substances 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
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- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical compound C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention relates to the technical field of organic electroluminescent display, and particularly discloses a phosphorescent material composition which comprises a first metal complex and a second metal complex, wherein the first metal complex and the second metal complex are respectively and independently selected from compounds shown in a formula (I), the first metal complex and the second metal complex are different from each other, and the weight ratio of the first metal complex to the second metal complex is 1: (0.01-99); the invention also discloses an organic electroluminescent device containing the composition, which has the superior performances of high purity, high brightness and high efficiency.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent display, in particular to a phosphorescent material composition and an organic electroluminescent device comprising the same.
Background
Organic electronic devices include, but are not limited to, the following classes: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), organic Light Emitting Transistors (OLETs), organic photovoltaics (COPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LEGS), organic laser diodes, and organic plasma light emitting devices.
In 1987, tang et al from Ishmann Kodak company in USA reported for the first time a green electroluminescent device made of a double-layer organic film, the device uses Indium Tin Oxide (ITO) as an anode, an amorphous pinhole-free aromatic diamine film with a thickness of 75nm is evaporated on the anode for hole transport, then an 8-hydroxyquinoline aluminum film with a thickness of 60nm is further coated on the aromatic diamine film for an electron transport layer and a light emitting layer, and a magnesium-silver alloy is used as a cathode, the double-layer film structure successfully reduces the starting voltage to 5.5V, and high-radiation light emission is realized (high-radiation light emission is realized: (A)>1000cd·m -2 ) The wavelength is 550nm, the external quantum efficiency reaches 1.0 percent, and the method has great practical significance. In 1994, KH1do et al from japan produced white light-emitting organic electroluminescent devices for the first time. The fluorescent dyes with 3 colors of blue, green and orange are doped in a poly (N-vinyl carbazole) (PVK) film to be used as a hole transport layer and an emission layer, 1,2, 4-triazole derivative (TAZ) is used as a hole blocking layer, 8-hydroxyquinoline aluminum (Alq 3) is used as an electron transport layer, the device is composed of a glass substrate/ITO/PVK/TAZ/Alq 3/Mg: ag multilayer structure, under the drive voltage of 14V, white light emission which covers a wide visible light region and has the brightness of 3400 cd-m & lt-2 & gt is obtained, and the high-brightness white emission is realized by doping fluorescent compounds with multiple colors in a polymer film to form a single light-emitting layer. This discovery by KIdo et al adds a heavy jet of color to the organic electroluminescent applicationThe pen opens the door of the organic light-emitting device in the field of illumination, and promotes the further development of the organic light-emitting device.
Light emitted from the organic electroluminescent device is also classified into fluorescence and phosphorescence, and light emitted by energy possessed by singlet excitons is fluorescence, while light emitted by energy possessed by singlet and triplet excitons is phosphorescence. Since the number of singlet and triplet states formed by excitons has a fixed value of 1:3, the internal quantum efficiency of a fluorescent device using only singlet excitons is theoretically only 25% at the highest, whereas the internal quantum efficiency when phosphorescence is emitted can reach 100%.
At present, both an organometallic complex having phosphorescent emission and an organic electroluminescent device are reported, but in many applications such as TV and lighting, the OLED lifetime is insufficient and there is still a need for higher efficiency OLEDs. Typically, the higher the luminance of an OLED, the shorter the lifetime of the OLED. Therefore, for a display that is used for a long time and has high resolution, an OLED having high luminous efficiency or long lifetime is required.
In the prior art, a large number of phosphorescent light-emitting materials are disclosed, and when the materials are applied to an organic electroluminescent device, some materials have longer service life and some materials have higher external quantum efficiency, but the materials often cannot have both the service life and the efficiency, so that the materials need to be selected according to requirements in practical application.
The present inventors have found, through intensive studies, that an organic electroluminescent device having significantly improved overall properties can be obtained by using at least two light-emitting guest materials of specific structures in a light-emitting layer at the same time.
Disclosure of Invention
The invention aims to provide a phosphorescent material composition which comprises at least two phosphorescent materials and can be used for preparing a novel organic electroluminescent device with excellent performances of high purity, high brightness, high efficiency and the like.
Specifically, in a first aspect, the present invention provides a phosphorescent material composition comprising a first metal complex and a second metal complex, each of which is independently selected from compounds represented by formula (I), and the first metal complex and the second metal complex are different from each other,
wherein:
r is selected from hydrogen atom, substituted or unsubstituted straight-chain or branched-chain alkyl with 1-20 carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 carbon atoms, and substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 3 ～C 30 Said substitution using a substituent selected from C 1 ～C 5 Linear or branched alkyl, C 3 ～C 6 Cycloalkyl group of (2), halogen atom, C 1 ～C 5 Linear or branched deuterated alkyl of (1), C 6 ～C 20 Aryl of, C 3 ～C 20 The heteroaryl group of (a);
R 1 ～R 11 each independently is optionally substituted or unsubstituted C 1 ～C 20 Linear or branched alkyl, substituted or unsubstituted C 1 ～C 20 Linear or branched deuterated alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 1 ～C 20 Alkylamino, substituted or unsubstituted C 1 ～C 20 Alkylthio group, halogen atom, substituted or unsubstituted C 6 ～C 40 And substituted or unsubstituted C 3 ～C 40 The substituent adopted by the substitution is selected from C 1 ～C 5 Linear or branched alkyl, C 3 ～C 6 Cycloalkyl group of (2), halogen atom, C 1 ～C 5 Linear or branched deuterated alkyl of (1), C 6 ～C 20 Aryl of (C) 3 ～C 20 And/or R 1 ～R 11 Any two or more groups in (b) form a fused ring structure by bridging;
l is a monovalent bidentate anionic ligand, wherein the bonding atoms X, Y are independently selected from the group consisting of oxygen atom, nitrogen atom and carbon atom;
n is 1,2 or 3;
the weight ratio of the first metal complex to the second metal complex is 1: (0.01-99).
In one embodiment of the present invention, L is phenylpyridyl, substituted phenylpyridyl, acetylacetonate or substituted acetylacetonate.
Preferably, L is a group of formula L1 or formula L2:
in the formula L1, R 12 ～R 19 Each independently selected from hydrogen atom, deuterium atom, substituted or unsubstituted C 1 ～C 20 Linear or branched alkyl, substituted or unsubstituted C 1 ～C 20 Deuterated alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 1 ～C 20 Alkylamino, substituted or unsubstituted C 1 ～C 20 Alkylthio group, halogen atom, trifluoromethyl group, substituted or unsubstituted C 6 ～C 30 And substituted or unsubstituted C 3 ～C 30 And/or R 12 ～R 19 Two or more of which form a fused ring structure by bridging;
in the formula L2, R 20 ～R 26 Each independently selected from hydrogen atom, deuterium atom, substituted or unsubstituted C 1 ～C 20 Linear or branched alkyl, substituted or unsubstituted C 1 ～C 20 Deuterated alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 1 ～C 20 Alkylamino, substituted or unsubstituted C 1 ～C 20 Alkylthio group, halogen atom, trifluoromethyl group, substituted or unsubstituted C 6 ～C 30 And substituted or unsubstituted C 3 ～C 30 And/or R 20 ～R 26 Two or more of which form a fused ring structure by bridging.
As a preferred embodiment of the present invention, L is optionally selected from the following groups:
as a preferred embodiment of the present invention, the compound represented by the formula (I) has a structure represented by the following formula (I-1) or formula (I-2) or formula (I-3):
wherein m is 1 or 2 1 ～R 26 And R is as previously defined.
As a preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R is optionally selected from substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 3 ～C 12 Heteroaryl, substituted or unsubstituted C 1 ～C 5 And a substituted or unsubstituted C 3 ～C 6 Wherein the substituents are optionally selected from: c 1 ～C 5 Linear or branched alkyl, C 3 ～C 6 Cycloalkyl group of (2), halogen atom, deuterated C 1 ～C 5 The linear chain or branched chain-containing alkyl, phenyl, biphenyl, monocyclic aryl, benzo, pyrido, phenanthro, naphtho, indo, benzothiopheno and benzofuro, wherein the number of the substituent groups is an integer of 1 to 5.
As a preferred embodiment of the present inventionIn the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R is optionally selected from substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl and C 1 ～C 5 Such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and neopentyl, wherein the substituents are optionally selected from C 1 ～C 5 Linear or branched alkyl group, halogen atom, deuterated C 1 ～C 5 The number of the substituents is an integer of 1 to 3.
As a more preferred embodiment of the present invention, in said formula (I) or formula (I-1) or formula (I-2) or formula (I-3), R is optionally selected from the group consisting of phenyl, methyl-substituted phenyl, difluorophenyl, deuterated methyl-substituted phenyl and pyridyl.
As a preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R 1 ～R 11 Each independently selected from hydrogen atom, deuterium atom, and C 1 ～C 5 Linear or branched alkyl, deuterated C 1 ～C 5 A straight chain or branched alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkylamino group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 3 ～C 12 Said substituted substituent is selected from C 1 ～C 5 Linear or branched alkyl group, halogen atom, C 1 ～C 5 Linear or branched deuterated alkyl of (a); and/or, R 1 ～R 11 Any two or more groups form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted five-membered ring, a substituted or unsubstituted six-membered ring, a substituted or unsubstituted five-membered heterocyclic ring and a substituted or unsubstituted six-membered heterocyclic ring, and the substituent adopted by the substitution is a halogen atom, C 1 ～C 5 Straight-chain or branched alkyl, phenyl, deuterated C 1 ～C 5 Linear or branched alkyl, benzo, substituted phenyl, substituted benzo ofThe five-membered heterocyclic ring or the six-membered heterocyclic ring contains at least one heteroatom, which is optionally selected from an oxygen atom, a sulfur atom and a nitrogen atom. The fused ring structure may be a benzo ring, a furo ring, a thieno ring, or the like. The fused ring structure may be further substituted with a substituent, such as substituted with a benzo group, substituted with an alkyl group (e.g., methyl-substituted benzo group, ethyl-substituted benzo group, propyl-substituted benzo group), substituted with a deuterated alkyl group (e.g., deuterated methyl-substituted benzo group, deuterated propyl-substituted benzo group), or the like.
As a preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R 1 ～R 11 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Linear or branched alkyl, deuterated C 1 ～C 5 The linear or branched alkyl group, halogen atom, trifluoromethyl group, phenyl group, pyridyl group, substituted phenyl group, substituted pyridyl group, the substituted substituent is selected from C 1 ～C 5 Linear or branched alkyl group, halogen atom, C 1 ～C 5 Linear or branched deuterated alkyl groups of (a); and/or, R 1 ～R 11 Wherein two or more groups form a fused ring structure through bridging, the fused ring structure is a substituted or unsubstituted benzene ring, and the substituent adopted by the substitution is a halogen atom and C 1 ～C 5 Linear or branched alkyl, deuterated C 1 ～C 5 Linear or branched alkyl groups of (1).
As a more preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), the R 1 ～R 11 Independently selected from hydrogen atom, methyl, ethyl, fluorine atom, isopropyl, deuterated methyl, phenyl, pyridyl, n-butyl, isobutyl, sec-butyl and tert-butyl; and/or, R 1 ～R 11 Any two or more of them form a fused ring structure by bridging, the fused ring structure is a substituted or unsubstituted benzene ring, and the substituent employed for the substitution is a fluorine atom, an isopropyl group, or a deuterated methyl group.
As a preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R 12 ～R 19 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Linear or branched alkyl, deuterated C 1 ～C 5 A straight chain or branched alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkylamino group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a trifluoromethyl group, a substituted or unsubstituted C 6 ～C 12 Aryl of (2) such as phenyl or substituted phenyl, substituted or unsubstituted C 3 ～C 12 The heteroaryl group of (a); and/or, R 12 ～R 19 Any two or more groups form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted five-membered ring, a substituted or unsubstituted six-membered ring, a substituted or unsubstituted five-membered heterocyclic ring and a substituted or unsubstituted six-membered heterocyclic ring, and a substituent adopted by substitution is C 1 ～C 5 Alkyl group, halogen atom, phenyl group, benzo group, pyrido group, C 1 ～C 5 Alkyl-substituted pyrido group of (1), C 1 ～C 5 The deuterated alkyl-substituted pyrido group of (a), wherein the five-membered heterocyclic ring or the six-membered heterocyclic ring contains at least one heteroatom, and the heteroatom is optionally selected from an oxygen atom, a sulfur atom and a nitrogen atom.
As a preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R 12 ～R 19 Each independently selected from hydrogen atom, deuterium atom, and C 1 ～C 5 Linear or branched alkyl, deuterated C 1 ～C 5 The linear or branched alkyl group of (1), a halogen atom, a phenyl group, a substituted phenyl group, a pyridyl group, a substituted pyridyl group.
As a more preferred embodiment of the present invention, said R 12 ～R 19 Each independently selected from hydrogen atom, methyl, deuterated methyl, fluorine atom, phenyl, pyridyl and isopropyl.
As a preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R 20 ～R 26 Each independently selected from a hydrogen atom, a deuterium atom, C 1 ～C 10 Linear or branched alkyl, C 1 ～C 10 Linear or branched deuterated alkyl, halogen atom, C 1 ～C 10 Alkoxy group of (1), C 1 ～C 10 Alkylamino group of (2), C 1 ～C 10 Alkylthio and trifluoromethyl.
As a preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R 20 ～R 26 Each independently selected from hydrogen atom, deuterium atom, and C 1 ～C 5 Linear or branched alkyl, deuterated C 1 ～C 5 A straight-chain or branched alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkylamino group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, and a trifluoromethyl group.
As a more preferred embodiment of the present invention, in the formula (I) or the formula (I-1) or the formula (I-2) or the formula (I-3), R 20 ～R 26 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Linear or branched alkyl, deuterated C 1 ～C 5 And a straight or branched alkyl group and a halogen atom.
As a further preferred embodiment of the present invention, in said formula (I) or formula (I-1) or formula (I-2) or formula (I-3), R 20 ～R 26 Each independently selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.
As a preferred embodiment of the present invention, the first metal complex and the second metal complex are optionally selected from compounds represented by the following structural formula:
as a preferable embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-1).
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Is the same, e.g. R, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Any one or any two or any three or any four or any five or any six or any seven or any eight or any nine or any ten or any eleven of the same or any three or the same or any four or the same or any five or any six or any seven or the same or any eight or any nine or any ten or any eleven or the same.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least two of which are identical.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected fromR and R of the first metal complex from the compound shown in the formula (I-1) 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least three of which are identical.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least four of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least five of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least six of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least seven of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least eight of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least nine of which are identical.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least ten of which are identical.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-1), and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 Any one of which is different and each is independently selected from a hydrogen atom, a methyl group, an ethyl group, a fluorine atom, an isopropyl group, a deuterated methyl group, a phenyl group, a pyridyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group, and the remaining 11 are the same. In some more preferred embodiments, R of the first metal complex 7 R with the second metal complex 7 Different from each other and each independently selected from a hydrogen atom, a methyl group, an ethyl group, a fluorine atom, an isopropyl group, a deuterated methyl group, a phenyl group, a pyridyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group, and the remaining groups are the same.
As a preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-2).
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are both selected from the compounds represented by the formula (I-2), and m of the first metal complex is the same as m of the second metal complex, for example, m of the first metal complex and m of the second metal complex are both 1 or m of the first metal complex and m of the second metal complex are both 2.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from the group consisting of compounds represented by the formula (I-2), and the first metal complex and the second metal complex are each selected from the group consisting ofM of the metal complex is the same as m of the second metal complex, R and R of the first metal complex 1 ～R 19 With R, R of the second metal complex 1 ～R 19 At least one of which is the same.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-2), m of the first metal complex is the same as m of the second metal complex, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Is the same, e.g. R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Any one or any two or any three or any four or any five or any six or any seven of the same or the same.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-2), m of the first metal complex is the same as m of the second metal complex, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 At least two of which are identical.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-2), m of the first metal complex is the same as m of the second metal complex, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 At least three of which are identical.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-2), m of the first metal complex is the same as m of the second metal complex, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 12 ～R 19 With R of said second metal complex 12 ～R 19 At least four of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-2), m of the first metal complex is the same as m of the second metal complex, and R, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 12 ～R 19 With R of said second metal complex 12 ～R 19 At least five of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-2), m of the first metal complex is the same as m of the second metal complex, and R, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 12 ～R 19 With R of said second metal complex 12 ～R 19 At least six of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from the group consisting of compounds represented by the formula (I-2), and the first metal complexM of the first metal complex is the same as m of the second metal complex, R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least one of the same, e.g. R, of said first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Any one and the same or any two and the same or any three and the same or any four and the same or any five and the same or any six and the same or any seven and any eight and the same or any nine and the same or any ten and the same or any eleven and the same. In some embodiments, R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least two are identical. In some embodiments, R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least three are identical. In some embodiments, R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least four are identical. In some embodiments, R of the first metal complex 12 ～R 19 With R of said second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 And said firstR, R of a bimetallic complex 1 ～R 11 At least five are identical. In some embodiments, R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least six are identical. In some embodiments, R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least seven are identical. In some embodiments, R of the first metal complex 12 ～R 19 R with the second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least eight of which are identical. In some embodiments, R of the first metal complex 12 ～R 19 With R of said second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least nine are identical. In some embodiments, R of the first metal complex 12 ～R 19 With R of said second metal complex 12 ～R 19 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least ten are identical.
As a preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-3).
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from the group consisting of compounds represented by the formula (I-3) and R, R of the first metal complex 1 ～R 11 、R 20 ～R 26 With R, R of the second metal complex 1 ～R 11 、R 20 ～R 26 Is the same.
As a more preferred embodiment of the present invention, both the first metal complex and the second metal complex are selected from the compounds represented by the formula (I-3) and R, R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Is the same, e.g. R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Any one or any two of the same or any three of the same or any four of the same or any five of the same or any six of the same.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from the group consisting of compounds represented by the formula (I-3) and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 At least two of which are identical.
As a more preferred embodiment of the present invention, the first metal complex and the second metal complex are each selected from compounds represented by the formula (I-3) and R, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 Are all the same, and R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 At least three of which are identical.
As one of the present inventionIn a preferred embodiment, both the first metal complex and the second metal complex are selected from compounds represented by the formula (I-3) and R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least one of the same, e.g. R, of said first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 Any one and the same or any two and the same or any three and the same or any four and the same or any five and the same or any six and the same or any seven and any eight and the same or any nine and the same or any ten and the same or any eleven and the same. In some embodiments, R of the first metal complex 20 ～R 26 With R of said second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least two are identical. In some embodiments, R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least three are identical. In some embodiments, R of the first metal complex 20 ～R 26 With R of said second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least four are identical. In some embodiments, R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Are all the same, and the firstR, R of metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least five are identical. In some embodiments, R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least six are identical. In some embodiments, R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least seven are identical. In some embodiments, R of the first metal complex 20 ～R 26 R with the second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 With R, R of the second metal complex 1 ～R 11 At least eight of which are identical. In some embodiments, R of the first metal complex 20 ～R 26 With R of said second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least nine are identical. In some embodiments, R of the first metal complex 20 ～R 26 With R of said second metal complex 20 ～R 26 Are all the same, and R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least ten are identical.
As a preferred embodiment of the present invention, in the composition, the weight ratio of the first metal complex to the second metal complex is 1: (0.25 to 4), preferably 1: (0.5 to 2), more preferably 1: (0.8-1.3).
In a second aspect, the invention provides the use of said composition in an organic electroluminescent device.
Preferably, the composition is used as a light emitting material in a light emitting layer in an organic electroluminescent device.
In a third aspect, the present invention provides an OLED light-emitting layer comprising a composition according to the first aspect of the present invention.
Preferably, the light-emitting layer further comprises at least one host material comprising at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.
Preferably, the composition is doped in the at least one host material.
Preferably, the sum of the weight of the first metal complex and the second metal complex in the composition accounts for 2% to 12%, preferably 4% to 10%, of the total weight of the light-emitting layer.
Preferably, the weight ratio of the first metal complex to the second metal complex is 1: (0.01 to 99), for example, 1:0.02, 1:0.05, 1:0.08, 1:0.1, 1:0.2, 1:0.25, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1. 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.8, 1:1.9, 1: 2. 1: 3. 1: 4. 1: 5. 1: 8. 1: 10. 1: 20. 1: 30. 1: 40. 1: 50. 1: 60. 1: 70. 1: 80. 1:90.
preferably, the weight ratio of the first metal complex to the second metal complex is 1: (0.25-4).
Preferably, the weight ratio of the first metal complex to the second metal complex is 1: (0.5-2).
Preferably, the weight ratio of the first metal complex to the second metal complex is 1: (0.8-1.3).
In a fourth aspect, the present invention provides an organic electroluminescent device comprising an anode layer, a cathode layer and a light-emitting layer according to the third aspect of the present invention.
Preferably, the electroluminescent device comprises an anode layer, a cathode layer and an organic layer arranged between the anode layer and the cathode layer.
Preferably, the organic layer is a light-emitting layer comprising the composition of the second aspect of the present invention.
Preferably, the organic electroluminescent device further comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
Preferably, the electroluminescent device emits green or yellow light.
Preferably, the difference between the evaporation temperatures of the first metal complex and the second metal complex during the device fabrication process is less than 15 ℃.
Preferably, the difference between the evaporation temperatures of the first metal complex and the second metal complex during the device fabrication process is less than 5 ℃.
In a fifth aspect, the present invention provides a display device or a lighting device comprising the electroluminescent device according to the fourth aspect of the present invention.
The invention has the beneficial effects that: the phosphorescent material composition provided by the invention combines two different metal complexes with similar structures according to a specific dosage ratio, and can be used in a light-emitting layer of an electroluminescent device, so that the electroluminescent device can obtain lower voltage, higher efficiency and longer service life, and the performance of the device is obviously improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and do not constitute any limitation on the invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure.
It is to be understood that, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood in the art to which this invention belongs.
The "containing 1 to n C atoms" and the "C" of the present invention 1 ～C n "has the same meaning and n represents the number of carbon atoms contained in the group.
Said C of the invention 1 ～C 5 The straight-chain or branched-chain alkyl group of (2) may be a methyl group, an ethyl group, a propyl group (e.g., n-propyl group, isopropyl group), a butyl group (e.g., n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), a pentyl group (e.g., n-pentyl group, neopentyl group) or the like.
Deuterated C described herein 1 ～C 5 The straight-chain or branched alkyl group of (1) means an alkyl group in which a part of hydrogen atoms is substituted by deuterium, and may be, for example, deuterated methyl, deuterated isopropyl, deuterated pentyl, deuterated neopentyl, deuterated butyl (e.g., deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl), etc.
C of the invention 1 ～C 20 Alkoxy of (C) n H 2n+1 O-, and n is 1 to 20. The alkoxy containing 1 to 5C atoms is C n H 2n+1 O-, wherein n is 1 to 5. The alkoxy group having 1 to 5 carbon atoms may be a methoxy group, an ethoxy group or the like.
C of the invention 1 ～C 20 Alkylthio of C n H 2n+1 S-, wherein n is 1 to 20.
Said C of the invention 1 ～C 20 The alkylamino group of (A) is amino-NH 2 One H or two H by C 1 ～C 20 The resulting group is substituted with the alkyl group of (a).
The halogen atom in the invention is fluorine atom, chlorine atom, bromine atom and the like.
OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. The OLED has multiple layers including a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. Can be fabricated by depositing the described layers sequentially. The nature and function of the various layers and exemplary materials are described in more detail in U.S. Pat. No. 7,279,704B 2 at columns 6-10, which are incorporated herein by reference in their entirety.
There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50 4 m-MTDATA of TCNQ, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg: ag and an overlying layer of transparent, conductive, sputter-deposited ITO. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implant layers are provided in U.S. patent application publication No. 2004/0174H6, which is incorporated by reference in its entirety. A description of a protective layer can be found in U.S. patent application publication No. 2004/0174H6, which is incorporated by reference in its entirety.
The function of the OLED may be achieved by combining the various layers described above, or some layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sub-layers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.
Devices manufactured according to embodiments of the present invention may be incorporated into various consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet phones, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, microdisplays, 3-D displays, vehicle displays, and taillights.
The materials and structures described herein may also be used in other organic electronic devices as previously listed.
As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed on" a second layer, the first layer is disposed farther from the substrate. Other layers may be present between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode can be described as being "disposed on" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive properties of the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.
The particular materials described herein for use in organic light emitting devices can be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application US2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that can be used in combination.
Materials described herein as being useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the compounds disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application US2015/0349273A1, paragraphs 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that can be used in combination.
In the examples of material synthesis, all reactions were carried out under nitrogen unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. The synthesis product was structurally validated and characterized using one or more equipment conventional in the art (including but not limited to Agilent's liquid chromatograph, liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, fluorescence spectrophotometer, electrochemical workstation, sublimator, etc.) in a manner well known to those skilled in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, an evaporator manufactured by Nanjing Mike, an optical test system manufactured by Fushida, suzhou, an optical life test system, an ellipsometer manufactured by Wuhan Yingshi, etc.) in a manner well known to those skilled in the art. Since the relevant contents of the above-mentioned device usage, testing method, etc. are known to those skilled in the art, the inherent data of the sample can be obtained with certainty and without being affected, and therefore, the relevant contents are not described in detail in this patent.
Material synthesis:
the preparation method of the first metal complex and the second metal complex selected by the invention is not limited, and the following compounds are typically but not limited to, and the synthetic route and the preparation method are as follows:
synthesis example 1: synthesis of Compound I-1
The reaction formula is as follows:
the specific experimental steps are as follows: ir (acac) was added sequentially to a 250ml three-necked flask equipped with a magnetic stirring and reflux condenser 3 (10mmol, 4.9 g), ligand P1 (40mmol, 15.7 g), and 150mL of glycerol. Vacuumizing and filling N 2 Repeating the above steps for 5 times to remove oxygen in the system. N is a radical of 2 Heated to reflux in an oil bath at 190 ℃ for 24 hours with protection. Naturally cooling to room temperature, filtering, washing with water, normal hexane and diethyl ether in sequence, and drying to obtain a yellow crude product. By CH 2 Cl 2 Column separation after dissolution, eluent CH 2 Cl 2 Washing and solvent suction drying gave 6.2 g of yellow powder with a yield of 45.4%.
Product MS (m/e): 1366.26; elemental analysis (C) 75 H 48 IrN 6 O 3 P 3 ): theoretical value C:65.87%, H:3.51%, N:6.15 percent; measured value C:65.92%, H:3.46%, N:6.34 percent.
Synthesis example 2: synthesis of Compound II-1
The reaction formula is as follows:
the specific experimental steps are as follows:
(1) Is provided with a mechanical stirring and reflux condensing device and a nitrogen protectorIn a three-necked flask of 100mL equipped with a guard ring, phenylpyridine (15mmol, 2.5mL), iridium trichloride hydrate (6mmol, 2.01 g), ethylene glycol monoethyl ether (45 mL) and distilled water (15 mL) were added in this order. Vacuumizing and filling N 2 Repeating the steps for five times to remove oxygen in the system. Heated to 110 ℃ under reflux for 24 hours. After natural cooling, 10mL of distilled water is added, and the mixture is shaken, filtered, washed with water and washed with ethanol. Vacuum drying gave 2.6 g of crude M8 as a yellow solid in 81.0% yield.
(2) In a 500mL three-necked flask equipped with a nitrogen blanket, dichloro-bridged intermediate M8 (10.7 g, 10 mmol) was sequentially added, 150mL of dichloromethane was added, and the mixture was sufficiently stirred, then 200mL of a methanol solution of silver trifluoromethanesulfonate (6.4 g, 25 mmol) was added, and the mixture was stirred for 24 hours in the dark, cooled to room temperature, then the generated AgCl was filtered off with celite, and the filtrate was dried by spinning to obtain an earth-yellow solid powder. The solid was used in the next reaction without further treatment.
(3) The solid yellowish brown (5.3 g, 7.1 mmol) obtained in step (2) and the ligand P1 (8.2 g, 21 mmol) were added to a 250ml three-necked flask, then 100ml of ethanol was added, the mixture was heated under reflux for 36 hours, the reaction was cooled to room temperature, the resulting yellow solid was filtered, the solid was dissolved in dichloromethane and separated by column chromatography to give 3.98 g of a bright yellow solid, which was 63.2% yield in two steps.
Product MS (m/e): 892.19; elemental analysis (C) 47 H 32 IrN 4 OP): theoretical value C:63.22%, H:3.59%, N:6.28 percent; measured value C:63.39%, H:3.47%, N:6.43 percent.
Synthetic example 3: synthesis of Compound III-21
The reaction formula is as follows:
the specific experimental steps are as follows:
(1) A500 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser and a nitrogen gas protector was charged with ligand P1 (25mmol, 9.8 g), iridium trichloride hydrate (10mmol, 3.25 g), 90mL of ethylene glycol monoethyl ether and 30mL of distilled water in this order. Vacuumizing and filling N 2 Repeating the steps for 5 times to remove oxygen in the system. Heated to 110 ℃ and refluxed for 24 hours. After natural cooling, 10mL of distilled water is added, and the mixture is shaken, filtered, washed with water and washed with ethanol. Drying in vacuo afforded 7.94 g of crude M7, a yellow solid, 78% yield.
(2) To a 250mL three-necked flask equipped with a magnetic stirring and reflux condenser, the above intermediate M7 (5 mmol,10.18 g), acetylacetone (25mmol, 2.5 g, 2.6 mL), and anhydrous Na were added in this order 2 CO 3 (22mmol, 2.35 g) and 100mL of ethylene glycol monoethyl ether. Vacuumizing and filling N 2 Repeating the above steps for 5 times to remove oxygen in the system. N is a radical of 2 Heated to reflux for 24 hours in an oil bath at 120 ℃ under protection. Naturally cooling to room temperature, filtering, washing with water, normal hexane and diethyl ether in sequence, and drying to obtain a yellow crude product. By CH 2 Cl 2 Column separation after dissolution, eluent CH 2 Cl 2 Washing and solvent suction drying gave 7.36 g of yellow powder in 68.5% yield.
Product MS (m/e): 1074.21; elemental analysis (C) 55 H 39 IrN 4 O 4 P 2 ): theoretical value C:61.44%, H:3.63%, N:5.21 percent; measured value C:61.52%, H:3.74%, N:5.31 percent.
Other compounds such as compounds I-6, II-4 and III-1 refer to patent CN 112321648A.
It will be appreciated by those skilled in the art that the above preparation method is only an illustrative example, and that those skilled in the art will be able to modify it to obtain other compound structures of the present invention.
Device embodiments
The method of fabricating the organic electroluminescent device is not particularly limited, and the method of fabricating the following example is only an example and should not be construed as a limitation. The preparation of the following examples can be reasonably modified by one skilled in the art based on the prior art. For example, the ratio of each material in the light emitting layer is not particularly limited, and those skilled in the art can reasonably select the material within a certain range according to the prior art. For example, the host material may be 88% to 98%, and the first metal complex and the second metal complex may be 2% to 12% or preferably 4% to 10% based on the total weight of the light-emitting layer material.
Device example 1
First, a glass substrate, having an Indium Tin Oxide (ITO) anode 120nm thick, was cleaned and then treated with UV ozone and oxygen plasma. After the treatment, the substrate was dried in a glove box filled with nitrogen gas to remove moisture, and then the substrate was mounted on a substrate holder and loaded into a vacuum chamber. The organic layer specified below was in a vacuum of about 10 degrees -8 In the case of Torr
The rate of (a) was successively evaporated on the ITO anode by thermal vacuum. Compounds HT and NDP-9 (95
The compound HT is used as Hole Transport Layer (HTL) with a thickness of
The compound TAPC is used as an Electron Blocking Layer (EBL) with a thickness of
Then, the compound I-6 as a host compound DIC-TRZ and the compound I-1 as a first dopant and the compound I-6 as a second dopant were co-evaporated to be used as an emission layer (EML) with a thickness of
Wherein the compound DIC-TRZ accounts for 96% of the total weight of the light-emitting layer, the compound I-1 accounts for 2% of the total weight of the light-emitting layer, and the compound I-6 accounts for 2% of the total weight of the light-emitting layer. The compound TPBI is used as a Hole Blocking Layer (HBL) with a thickness of
On the hole-blocking layer, compound ET01 and 8-hydroxyquinoline-lithium (Liq) were co-evaporated as an electron-transporting layer (ETL) with a thickness of
Wherein compounds ET01 and Liq each comprise 50% of the total weight of the electron transport layer. Finally, evaporation
LiF in thickness as Electron Injection Layer (EIL) and evaporated
As a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid to complete the device.
Device example 2
Device example 2 was prepared the same as device example 1 except that in the light emitting layer (EML), compound I-6 accounted for 4% of the total weight of the light emitting layer and the host material weight accounted for 94% of the total weight of the light emitting layer.
Device example 3
Device example 3 was prepared the same as device example 1 except that in the light emitting layer (EML), compound I-6 was 8% by weight of the total weight of the light emitting layer and the host material was 90% by weight of the total weight of the light emitting layer.
Device example 4
Device example 4 was prepared the same as device example 1 except that compound II-1 was used as the second dopant instead of I-6 in the light emitting layer (EML).
Device example 5
Device example 5 was prepared the same as device example 1 except that compound III-1 was used as the second dopant instead of compound I-6 in the light emitting layer (EML).
Device example 6
Device example 6 was prepared the same as device example 1 except that compound II-1 was used instead of compound I-1 as the first dopant and compound III-1 was used instead of I-6 as the second dopant in the light emitting layer (EML).
Device example 7
Device example 7 was prepared the same as device example 1 except that compound II-1 was used instead of compound I-1 as the first dopant and compound II-4 was used instead of I-6 as the second dopant in the light emitting layer (EML).
Device example 8
Device example 8 was prepared the same as device example 1 except that compound II1-1 was used instead of compound I1 as the first dopant and compound III-21 was used instead of compound I-6 as the second dopant in the light emitting layer (EML).
Device comparative example 1
Device comparative example 1 was prepared the same as device example 1 except that compound I-1 was used as the first and second dopants in the light emitting layer (EML).
Device comparative example 2
Device comparative example 2 was prepared the same as device example 1 except that compound II-1 was used as the first and second dopants in the light emitting layer (EML).
Device comparative example 3
Device comparative example 3 was prepared the same as device example 1 except that compound III-1 was used as the first and second dopants in the light emitting layer (EML).
The detailed device layer structure and thickness are shown in table 1 below. In which more than one layer of the materials used is obtained by doping different compounds in the stated weight proportions.
TABLE 1 device structures of device examples and comparative examples
The material structures used in the devices are as follows:
the current density at 20mA/cm is shown in Table 2 2 Under the conditions, the Voltage (Voltage, V), current Efficiency (CE) and device Lifetime (LT) of device examples 1 to 8 and device comparative examples 1 to 3 were measured 97 ) And (4) data.
TABLE 2
From the device data we can find that: examples 1-8 the use of the combinations of the present invention as dopants, regardless of voltage, current efficiency or lifetime, was improved over the use of a single metal complex as dopant, compared to the device data of comparative examples 1-3, providing unexpected results in device performance.
As can be seen from the device data of examples 1 to 3, the obtained device data are also different by changing the ratio of the two dopants to the total weight of the light emitting layer, and when the doping ratio of the compound I-1 and the compound I-6 is 1.
It can be seen from the comparison of examples 1, 7, 8 and 4, 5, 6 that the more similar the structures of the two compounds are, the better the performance of the device prepared by using the double dopant, especially in example 1, the difference between the ligand structures of the two doped compounds is only one isopropyl group, the current efficiency of the device prepared by the combination of the two doped compounds is obviously improved, and the service life is more unexpected. The similar coordination modes of the double-dopant structure in example 8 are the same, and the similar coordination modes of the double-dopant structure in example 7 are different, so that the effect of example 8 is improved better than that of example 7.
In summary, the combination of the first metal complex and the second metal complex disclosed in the present invention can show excellent overall device performance in devices, such as lower driving voltage, higher efficiency and ultra-long device lifetime, because the two compounds can be well matched with each other in terms of energy.
It should be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the invention. Thus, the invention as claimed may include variations from the specific embodiments and preferred embodiments described herein, as will be apparent to those skilled in the art. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present invention. It should be understood that various theories as to why the present invention works are not intended to be limiting.
Claims (10)
1. A phosphorescent material composition comprises a first metal complex and a second metal complex, wherein the first metal complex and the second metal complex are respectively and independently selected from compounds shown in a formula (I), and the first metal complex and the second metal complex are different from each other,
in the formula (I), R is selected from hydrogen atom and substituted or unsubstituted C 1 ～C 20 Linear or branched alkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 6 ～C 30 Aryl, substituted or unsubstituted C 3 ～C 30 Said substituted substituent is selected from C 1 ～C 5 Linear or branched alkyl, C 3 ～C 6 Cycloalkyl group of (2), halogen atom, C 1 ～C 5 Linear or branched deuterated alkyl of (1), C 6 ～C 20 Aryl of (C) 3 ～C 20 The heteroaryl group of (a);
R 1 ～R 11 each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C 1 ～C 20 Linear or branched alkyl, substituted or unsubstituted C 1 ～C 20 Linear or branched deuterated alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 1 ～C 20 Alkylamino, substituted or unsubstituted C 1 ～C 20 Alkylthio group, halogen atom, substituted or unsubstituted C 6 ～C 40 And substituted or unsubstituted C 3 ～C 40 The substituted substituent is selected from C 1 ～C 5 Linear or branched alkyl, C 3 ～C 6 Cycloalkyl group of (2), halogen atom, C 1 ～C 5 Linear or branched deuterated alkyl of (1), C 6 ～C 20 Aryl of (C) 3 ～C 20 And/or R 1 ～R 11 Any two or more groups in (b) form a fused ring structure by bridging;
l is a monovalent bidentate anionic ligand in which the bonding atoms X, Y are each independently selected from the group consisting of an oxygen atom, a nitrogen atom and a carbon atom;
n is 1,2 or 3;
wherein the weight ratio of the first metal complex to the second metal complex is 1: (0.01-99).
2. The composition of claim 1, wherein L is phenylpyridyl, substituted phenylpyridyl, acetylacetonate, or substituted acetylacetonate; preferably, L is selected from a group represented by formula L1 or formula L2:
in the formula L1, R 12 ～R 19 Each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C 1 ～C 20 Linear or branched alkyl, substituted or unsubstitutedC 1 ～C 20 Deuterated alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 1 ～C 20 Alkylamino, substituted or unsubstituted C 1 ～C 20 Alkylthio group, halogen atom, trifluoromethyl group, substituted or unsubstituted C 6 ～C 30 And substituted or unsubstituted C 3 ～C 30 And/or R 12 ～R 19 Two or more of which form a fused ring structure by bridging; and/or
In the formula L2, R 20 ～R 26 Each independently selected from hydrogen atom, deuterium atom, substituted or unsubstituted C 1 ～C 20 Linear or branched alkyl, substituted or unsubstituted C 1 ～C 20 Deuterated alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 1 ～C 20 Alkylamino, substituted or unsubstituted C 1 ～C 20 Alkylthio group, halogen atom, trifluoromethyl group, substituted or unsubstituted C 6 ～C 30 And substituted or unsubstituted C 3 ～C 30 And/or R 20 ～R 26 Two or more of which form a fused ring structure by bridging;
preferably, the compound represented by the formula (I) has a structure represented by the formula (I-1) or the formula (I-2) or the formula (I-3):
wherein R, R 1 ～R 11 Is defined by the formula (I), R 12 ～R 19 Is as defined in formula L1, R 20 ～R 26 Wherein m is 1 or 2.
3. The composition of claim 1 or 2, wherein R is selected from substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 3 ～C 12 Heteroaryl, substituted or unsubstituted C 1 ～C 5 And substituted or unsubstituted C 3 ～C 6 Wherein said substituted substituent is optionally selected from C 1 ～C 5 Linear or branched alkyl, C 3 ～C 6 Cycloalkyl group of (2), halogen atom, C 1 ～C 5 The linear or branched chain-containing deuterated alkyl, phenyl, biphenyl, benzo, pyrido, phenanthro, naphtho, indo, benzothieno and benzofuro, wherein the number of the substituent groups is an integer from 1 to 5; preferably, R is optionally selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl and C 1 ～C 5 Wherein said substituted substituent is optionally selected from the group consisting of C 1 ～C 5 A straight-chain or branched alkyl group, a halogen atom, C 1 ～C 5 The number of the substituent groups is selected from an integer between 1 and 3; more preferably, R is selected from phenyl, methyl-substituted phenyl, difluorophenyl, deuterated methyl-substituted phenyl, and pyridyl; and/or the presence of a gas in the gas,
R 1 ～R 11 each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Linear or branched alkyl, C 1 ～C 5 Linear or branched deuterated alkyl, halogen atom, trifluoromethyl, C 1 ～C 5 Alkoxy group of (C) 1 ～C 5 Alkylamino group of (C) 1 ～C 5 Alkylthio, substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 3 ～C 12 Said substituted substituent is selected from C 1 ～C 5 Linear or branched alkyl group, halogen atom, C 1 ～C 5 Linear or branched deuterated alkyl groups of (a); and/or, R 1 ～R 11 Any two or more of them form a fused ring structure by bridging, the fused ring structure being a substituted or unsubstituted five-membered ring, a substituted or unsubstituted six-membered ring, a substituted or unsubstituted five-membered heterocyclic ring and a fused ringSubstituted or unsubstituted six-membered heterocycle, wherein the substituent for substitution is halogen atom, C 1 ～C 5 Linear or branched alkyl, phenyl, C 1 ～C 5 The straight-chain or branched-chain deuterated alkyl, the benzo group, the substituted phenyl and the substituted benzo group, wherein the heteroatom contained in the five-membered heterocyclic ring or the six-membered heterocyclic ring is selected from oxygen atom, sulfur atom and nitrogen atom; preferably, said R is 1 ～R 11 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Linear or branched alkyl, C 1 ～C 5 The linear or branched deuterated alkyl group, the halogen atom, the trifluoromethyl group, the phenyl group, the pyridyl group, the substituted phenyl group and the substituted pyridyl group are selected from C 1 ～C 5 A straight-chain or branched alkyl group, a halogen atom, C 1 ～C 5 Linear or branched deuterated alkyl of (a); and/or, R 1 ～R 11 Any two or more of them form a fused ring structure by bridging, the fused ring structure is a substituted or unsubstituted benzene ring, and the substituent for substitution is a halogen atom, C 1 ～C 5 Linear or branched alkyl, deuterated C 1 ～C 5 Linear or branched alkyl groups of (a); more preferably, said R 1 ～R 11 Independently selected from hydrogen atom, methyl, ethyl, fluorine atom, isopropyl, deuterated methyl, phenyl, pyridyl, n-butyl, isobutyl, sec-butyl and tert-butyl; and/or, R 1 ～R 11 Any two or more of them form a fused ring structure by bridging, the fused ring structure being a substituted or unsubstituted benzene ring, the substitution employing a substituent selected from the group consisting of a fluorine atom, an isopropyl group and a deuterated methyl group.
4. The composition of claim 2 or 3, wherein R in formula L1 is 12 ～R 19 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Linear or branched alkyl, C 1 ～C 5 Linear or branched deuterated alkyl, halogen atom, C 1 ～C 5 Alkoxy group of (C) 1 ～C 5 Alkylamino group of (C) 1 ～C 5 Alkylthio, substituted or unsubstituted C 6 ～C 12 Aryl, substituted or unsubstituted C 3 ～C 12 Heteroaryl, trifluoromethyl of (a); and/or, R 12 ～R 19 Any two or more groups form a fused ring structure through bridging, the fused ring structure is any one of a substituted or unsubstituted five-membered ring, a substituted or unsubstituted six-membered ring, a substituted or unsubstituted five-membered heterocyclic ring and a substituted or unsubstituted six-membered heterocyclic ring, and a substituent adopted by substitution is C 1 ～C 5 Alkyl group, halogen atom, phenyl group, benzo group, pyrido group, C 1 ～C 5 Alkyl-substituted pyrido group of (1), C 1 ～C 5 The deuterated alkyl-substituted pyrido group of (a), the heteroatom in the five-or six-membered heterocycle being selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom; preferably, R 12 ～R 19 Each independently selected from hydrogen atom, deuterium atom, C 1 ～C 5 Linear or branched alkyl, C 1 ～C 5 The linear or branched deuterated alkyl group of (1), a halogen atom, a phenyl group, a substituted phenyl group, a pyridyl group, a substituted pyridyl group; more preferably, R 12 ～R 19 Each independently selected from the group consisting of a hydrogen atom, a methyl group, an isopropyl group, a deuterated methyl group, a fluorine atom, a phenyl group, and a pyridyl group; and/or
In the formula L2, R 20 ～R 26 Each independently selected from a hydrogen atom, a deuterium atom, C 1 ～C 10 Linear or branched alkyl, C 1 ～C 10 Linear or branched deuterated alkyl, halogen atom, C 1 ～C 10 Alkoxy group of (1), C 1 ～C 10 Alkylamino group of (C) 1 ～C 10 Alkylthio and trifluoromethyl of (a); preferably, R 20 ～R 26 Each independently selected from a hydrogen atom, a deuterium atom, C 1 ～C 5 Linear or branched alkyl, C 1 ～C 5 A linear or branched deuterated alkyl group of (a) and a halogen atom; more preferably, R 20 ～R 26 Each independently selected from a hydrogen atom,Methyl and ethyl;
further preferably, the ligand L is selected from the group consisting of:
5. the composition of any one of claims 1 to 4, wherein the first metal complex and the second metal complex are selected from the following structures:
6. composition according to any one of claims 1 to 5, characterized in that the first metal complex and the second metal complex are each chosen from compounds of formula (I-1), preferablyR, R of the first metal complex 1 ～R 11 R, R with the second metal complex 1 ～R 11 At least one of the same; or alternatively
The first metal complex and the second metal complex are both selected from compounds shown as a formula (I-2), m of the first metal complex is the same as m of the second metal complex, and preferably R and R of the first metal complex 1 ～R 19 R, R with the second metal complex 1 ～R 19 At least one of the same; or
The first metal complex and the second metal complex are both selected from compounds shown as a formula (I-3), and preferably R and R of the first metal complex 1 ～R 11 、R 20 ～R 26 R, R with the second metal complex 1 ～R 11 、R 20 ～R 26 At least one of which is the same.
7. Use of a composition according to any one of claims 1 to 6 for the preparation of an organic electroluminescent device; preferably, the composition is used as a light emitting material in a light emitting layer in an organic electroluminescent device.
8. An OLED light-emitting layer comprising the composition of any one of claims 1 to 6, preferably the sum of the weights of the first metal complex and the second metal complex in the composition is from 2% to 12%, preferably from 4% to 10%, of the total weight of the light-emitting layer;
and/or the weight ratio of the first metal complex to the second metal complex is 1: (0.25 to 4), preferably 1: (0.5-2).
9. An organic electroluminescent device comprising an anode layer, a cathode layer and the light-emitting layer according to claim 8;
preferably, the organic electroluminescent device further comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
10. A display apparatus or a lighting apparatus comprising the organic electroluminescent device according to claim 9.
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| US20210104687A1 (en) * | 2019-10-02 | 2021-04-08 | Arizona Board Of Regents On Behalf Of Arizona State University | Green and red organic light-emitting diodes employing excimer emitters |
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| US20210104687A1 (en) * | 2019-10-02 | 2021-04-08 | Arizona Board Of Regents On Behalf Of Arizona State University | Green and red organic light-emitting diodes employing excimer emitters |
| CN112321648A (en) * | 2020-11-05 | 2021-02-05 | 北京燕化集联光电技术有限公司 | P-containing organic electrophosphorescent material and application thereof |
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