WO2023025230A1 - 一种金属配合物、有机电致发光元件及消费型产品 - Google Patents

一种金属配合物、有机电致发光元件及消费型产品 Download PDF

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WO2023025230A1
WO2023025230A1 PCT/CN2022/114702 CN2022114702W WO2023025230A1 WO 2023025230 A1 WO2023025230 A1 WO 2023025230A1 CN 2022114702 W CN2022114702 W CN 2022114702W WO 2023025230 A1 WO2023025230 A1 WO 2023025230A1
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metal complex
group
present
organic
layer
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French (fr)
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赵雷
韩洪波
曹建华
唐怡杰
刘殿君
边坤
郭文龙
何连贞
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上海八亿时空先进材料有限公司
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C—CHEMISTRY; METALLURGY
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F15/0086—Platinum compounds
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/348—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising osmium
    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

Definitions

  • the invention belongs to the technical field of luminescent materials, and in particular relates to a metal complex, an organic electroluminescent element and a consumer product.
  • organic optoelectronic devices utilizing organic materials are becoming increasingly popular, and many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost advantages over inorganic devices.
  • the inherent properties of organic materials such as their flexibility, may make them more suitable for certain applications, such as fabrication on flexible substrates.
  • organic optoelectronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors.
  • OLEDs organic light emitting diodes/devices
  • organic phototransistors organic phototransistors
  • organic photovoltaic cells organic photovoltaic cells
  • organic photodetectors organic photodetectors
  • OLEDs utilize thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for applications such as flat panel displays, lighting and backlighting.
  • OLEDs can be designed to emit white light.
  • absorption filters are used to filter the emission from the white backlight to produce red, green and blue emissions.
  • white OLEDs can be single emissive layer (EML) devices or stacked structures. CIE coordinates well known in the art can be used to measure color, but the luminescent materials in the prior art have poor luminous stability and low luminous efficiency.
  • the present invention provides a metal complex, as well as organic electroluminescent elements and consumer products containing the metal complex.
  • the metal complex of the present invention is used in OLEDs, Especially when used in the green to red emission region, an enhanced phosphorescent quantum yield is exhibited.
  • the first object of the present invention is to provide a metal complex with stable electroluminescence and high luminous efficiency.
  • the second object of the present invention is to provide an organic electroluminescent element containing the metal complex.
  • the third object of the present invention is to provide a consumer product made of the organic electroluminescent element.
  • a kind of metal complex, described metal complex comprises the ligand shown in formula LA:
  • R x , R 1 to R 13 are identically or differently selected from hydrogen, deuterium, halogen atoms, alkanyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkane, Oxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfur A group consisting of group, sulfinyl group, sulfonyl group and phosphino group; and any two or more adjacent substituents are optionally bonded or fused together to form a five-membered ring, a six-membered ring or a polycyclic ring ;
  • R is selected at each occurrence identically or differently from hydrogen, deuterium, halogen atom, alkanyl, cycloalkyl, heteroalkyl, heterocycloalkyl, silyl, alkenyl, cycloalkenyl, heteroalkene
  • R 1 is 1, 2 or 3;
  • the ligand LA is coordinated through the metal M to form a five-membered chelate ring;
  • M can be coordinated with other ligands; and the ligand LA can be connected with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;
  • the M is selected from one of Os, Ir, Pd, Pt, Cu, Ag and Au.
  • the LA is mainly selected from one of the following structures:
  • Each R, R 14 , R 15 , R 16 is independently selected from hydrogen, deuterium, halogen atom, alkanyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryl Oxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl A group consisting of acyl, sulfonyl and phosphino; and any two or more adjacent substituents are arbitrarily bonded or fused together to form a five-membered ring, a six-membered ring or a polycyclic ring.
  • R, R 14 , R 15 , and R 16 are each independently selected from the group consisting of hydrogen, deuterium, fluorine, alkanyl, cycloalkyl, heteroalkyl, silyl, aryl, and heteroaryl.
  • Halo in the sense of the present invention are used interchangeably and refer to fluorine, chlorine, bromine or iodine.
  • Acyl in the sense of the present invention refers to substituted carbonyl groups (COR).
  • Ester in the sense of the present invention refers to a substituted oxycarbonyl group (-OCOR or CO2R ).
  • Sulphinyl in the sense of the present invention refers to a -SOR group.
  • “Sulfonyl” in the sense of the present invention refers to a -SO2R group.
  • a "phosphino" in the sense of the present invention refers to a -PR 3 group, where each R may be the same or different.
  • a “silyl group” in the sense of the present invention refers to a -SiR3 group, where each R may be the same or different.
  • Each R mentioned above is preferably selected from the group consisting of alkyl, cycloalkyl, aryl and heteroaryl.
  • Alkyl in the sense of the present invention is preferably taken to mean the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl Cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl
  • Alkoxy in the sense of the present invention is preferably an alkoxy group having 1 to 40 carbon atoms and is considered to be methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy Cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.
  • cycloalkyl refers to and includes monocyclic, polycyclic and spiroalkyl groups.
  • Preferred cycloalkyl groups are those containing from 3 to 15 ring carbon atoms and may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl , cycloheptyl, cycloheptenyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc., wherein one or more -CH 2 - groups
  • the groups can be replaced by the groups mentioned above; moreover, one or more hydrogen atoms can also be replaced by deuterium atoms, halogen atoms or nitrile groups.
  • Heteroalkyl or “heterocycloalkyl” in the sense of the present invention refers to an alkyl or cycloalkyl group, preferably an alkyl or cycloalkyl group with 1 to 40 carbon atoms, and refers to a single hydrogen atom or A -CH 2 - group may be a group substituted by oxygen, sulfur, a halogen atom, nitrogen, phosphorus, boron, silicon or selenium, preferably a group substituted by oxygen, sulfur or nitrogen. Additionally, a heteroalkyl or heterocycloalkyl group can be optionally substituted.
  • Heteroalkenyl or “heterocycloalkenyl” in the sense of the present invention refers to an alkenyl or cycloalkenyl group in which at least one carbon atom is replaced by a heteroatom.
  • said at least one heteroatom is selected from oxygen, sulfur, nitrogen, phosphorus, boron, silicon or selenium, preferably oxygen, sulfur or nitrogen.
  • Preferred alkenyl, cycloalkenyl groups are those containing 3 to 15 carbon atoms.
  • heteroalkenyl, heterocycloalkenyl may be optionally substituted.
  • Alkyl or arylalkyl in the sense of the present invention are used interchangeably and refer to an alkyl group substituted with an aryl group.
  • aralkyl groups can be optionally substituted.
  • Aryl refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems.
  • a polycyclic ring may have two or more rings in which two carbons are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, such as other ring Can be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl.
  • Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Especially preferred are aryl groups having six, ten or twelve carbons.
  • Suitable aryl groups include phenyl, biphenyl, terphenylene, triphenylene, tetraphenylene, naphthalene, anthracene, anthracene, phenanthrene, fluorene, pyrene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene.
  • aryl groups can be optionally substituted.
  • Heteroaryl in the sense of the present invention refers to monocyclic aromatic radicals and polycyclic aromatic ring systems comprising at least one heteroatom. Heteroatoms include, but are not limited to, oxygen, sulfur, nitrogen, phosphorus, boron, silicon, or selenium. Oxygen, sulfur or nitrogen are preferred heteroatoms in many cases. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings may have from one to six heteroatoms.
  • a heteropolycyclic ring system may have two or more rings in which two atoms are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is heteroaryl, for example Other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic and/or heteroaryl.
  • Heteropolycyclic aromatic ring systems can have from one to six heteroatoms on each ring of the polycyclic aromatic ring system.
  • Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms.
  • Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl Indole, pyrrolobipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, Oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, Quinazoline, qui
  • typical substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, The group consisting of cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl and phosphino.
  • a combination thereof or “group” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can conceive from the applicable list.
  • alkyl and deuterium can be combined to form partially or fully deuterated alkyl
  • halogen and alkyl can be combined to form haloalkyl substituents, such as trifluoromethyl, etc.
  • halogen, alkyl and aryl can be combined to form Haloaralkyl.
  • substitution includes combinations of two to four of the listed groups.
  • substitution includes combinations of two to three groups.
  • substitution includes a combination of two groups.
  • Preferred combinations of substituents are those containing up to fifty atoms other than hydrogen or deuterium, or combinations comprising up to forty atoms other than hydrogen or deuterium, or comprising up to thirty atoms other than hydrogen or deuterium The combination. In many cases, preferred combinations of substituents will include up to twenty atoms other than hydrogen or deuterium.
  • each of R, R 0 , R x , R 1 to R 16 is independently selected from the group consisting of hydrogen atom, deuterium atom, R A1 to R A56 , R B1 to R B45 , R C1 to R C295 ;
  • R A1 to R A56 are as follows:
  • R B1 ⁇ R B45 The structural formulas of R B1 ⁇ R B45 are as follows:
  • R C1 ⁇ R C295 The structural formula of R C1 ⁇ R C295 is as follows:
  • the chemical formula of the metal complex is Ir(LA)(LB) 2 , Ir(LA) 2 (LB), Ir(LA) 2 (LC), Ir(LA) 3 , wherein LB is mainly selected from The group consisting of LB1 ⁇ LB432, the specific structure of LB1 ⁇ LB432 is as follows:
  • LC is mainly selected from the group consisting of LC1-LC56, and the specific structural formulas of LC1-LC56 are as follows:
  • R x , R 1 to R 13 are identically or differently selected from hydrogen, deuterium, alkanyl, cycloalkyl, heteroalkyl, heterocycloalkyl, silyl at each occurrence , a group consisting of nitrile groups; and any two or more adjacent substituents are optionally bonded or fused together to form a five-membered ring, a six-membered ring or a polycyclic ring;
  • R is selected at each occurrence, identically or differently, from the group consisting of hydrogen, deuterium, alkanyl, cycloalkyl, heteroalkyl, heterocycloalkyl, silyl and nitrile;
  • R 1 is 1, 2 or 3;
  • the ligand LA is coordinated through the metal M to form a five-membered chelate ring;
  • M can be coordinated with other ligands; and the ligand LA can be connected with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;
  • the M is selected from one of Ir, Pd or Pt.
  • LA is mainly selected from one of LA1-LA188, and the specific structure of LA1-LA188 is as follows:
  • the chemical formula of the metal complex is Ir(LAi) 2 (LBj), Ir(LAi)(LBj) 2 , Ir(LAi) 2 (LCt) or Ir(LAi) 3 ;
  • i is an integer of 1-188
  • j is an integer of 1-432
  • t is an integer of 1-56
  • LA1-LA188, LB1-LB432, LC1-LC56 have the same meaning as above.
  • the organic electroluminescent material of the present invention includes one or more of the metal complexes of the present invention.
  • the organic electroluminescent material of the present invention may consist of only one or more of the metal complexes of the present invention, or may contain other materials other than the metal complexes of the present invention.
  • an organic electroluminescent material with high luminous efficiency can be obtained with green, yellow or red electroluminescence.
  • the organic electroluminescent material of the present invention is an organic electroluminescent material with good thermal stability.
  • the present invention also provides an organic electroluminescence element, which comprises a first electrode, a second electrode and an organic layer placed between the first electrode and the second electrode, and the organic layer includes the metal complex.
  • the organic layer also includes a host material, and the host material mainly includes a group consisting of the following chemical groups: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenium phen, azatriphenylene, azacarbazole, azadibenzothiophene, azadibenzofuran and azadibenzoselenophene, indolocarbazole, 5,9-dioxa-13b- Boronaphtho[3,2,1-de]anthracene, azaindolocarbazole and aza-(5,9-dioxa-13b-bororaphtho[3,2,1-de]anthracene) .
  • the host material mainly includes a group consisting of the following chemical groups: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenium phen, azatriphenylene, azac
  • one layer may contain the metal complex of the present invention, or two or more layers may contain the metal complex of the present invention.
  • the organic layer can be an emissive layer and the metal complex as described herein can be an emissive dopant or a non-emissive dopant.
  • the invention also provides a consumer product made of the organic electroluminescent element.
  • a consumer product as described in this invention may be one of the following: flat panel displays, computer monitors, medical monitors, televisions, signage, lamps for interior or exterior lighting and/or signaling, head-up Displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearables, laptops, digital cameras, video cameras, viewfinders , microdisplays with a diagonal of less than 2 inches, 3-D displays, virtual or augmented reality displays, vehicles, video walls containing multiple displays tiled together, theater or stadium screens, light therapy devices, and signage.
  • the metal complex described in the present invention is used as a luminescent material to obtain a green to red phosphorescent material with high luminous efficiency, and the prepared luminescent material has good thermal stability, and the organic electroluminescent element prepared in the present invention emits green to red phosphorescence and is High luminous efficiency and good thermal stability; the electronic device of the present invention contains the organic electroluminescent element of the present invention, thereby being able to obtain consumer products whose electroluminescence is green to red phosphorescence and whose luminous efficiency is improved.
  • Fig. 1 is a kind of organic electroluminescent element schematic diagram of the present invention
  • Fig. 2 is a schematic diagram of an inverted organic electroluminescent element of the present invention.
  • the composition of the layer other than the layer containing the metal complex of the present invention there is no limitation on the composition of the layer other than the layer containing the metal complex of the present invention, and those skilled in the art can determine the organic electroluminescent element according to the need based on the general technical knowledge in the field.
  • the composition of the other layers of the component there is no limitation on the composition of the layer other than the layer containing the metal complex of the present invention, and those skilled in the art can determine the organic electroluminescent element according to the need based on the general technical knowledge in the field.
  • Fig. 1 On the substrate 110, there are anode layer 115, hole injection layer 120, hole transport layer 125, electron blocking layer 130, organic light-emitting layer 135, hole blocking layer 140, electron transport layer 145, electron Injection layer 150 , protective layer 155 , cathode layer 160 and encapsulation layer 170 .
  • the metal complex of the present invention is contained in the aforementioned organic light-emitting layer.
  • the organic electroluminescent device of the present invention is connected to an external power source and applied with voltage, the metal complex in the organic light emitting layer 135 electroluminescently emits light with a wavelength range of 520-650 nm.
  • Cathode layer 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164 . The device can be fabricated by sequentially depositing the layers described.
  • FIG. 2 includes a substrate 110 , a cathode 160 , an organic light emitting layer 135 , a hole transport layer 125 and an anode layer 115 .
  • the device can be fabricated by sequentially depositing layers. Since the most common OLED configuration has a cathode disposed above the anode, and the present device has a cathode layer 160 disposed below the anode layer 115, the present device may be referred to as inverted. Materials similar to those described for the present device may be used in the corresponding layers of the present device.
  • FIG. 2 provides an example of how some layers may be omitted from the structure of the FIG. 1 device.
  • the hole transport layer 125 transports holes and injects holes into the organic light emitting layer 135, and may be described as a hole transport layer or a hole injection layer.
  • an OLED can be described as having an organic layer disposed between a cathode and an anode. This organic layer may comprise a single layer or may further comprise multiple layers of different organic materials as described for example in FIGS. 1 and 2 .
  • OLEDs comprising polymeric materials.
  • OLEDs with a single organic layer or multiple stacks can be used.
  • OLED structures can depart from the simple layered structure illustrated in FIGS. 1 and 2 .
  • the substrate may include angled reflective surfaces to improve light coupling.
  • any of the layers of the various embodiments may be deposited by any suitable method.
  • preferred methods comprise thermal evaporation, organic vapor deposition methods or the application of one or more layers by means of sublimation of a carrier gas, wherein the material is applied at a pressure between 10 ⁇ 5 mbar and 1 bar.
  • a particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is thus structured.
  • Other suitable deposition methods include, for example, by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithographic printing, photoinduced thermography, thermal transfer printing, inkjet printing or nozzle printing, to produce a or multiple layers.
  • Soluble compounds for example, can be obtained by appropriately substituting the metal complexes provided by the present invention. These methods are also particularly suitable for oligomers, dendrimers and polymers. Also possible are hybrid methods in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
  • Devices fabricated according to embodiments of the present invention may further optionally include a barrier layer.
  • a barrier layer One purpose of the barrier layer is to protect the electrodes and organic layers from damage due to exposure to harmful substances in the environment, including moisture, vapors and/or gases, and the like.
  • the barrier layer may be deposited on, under, or next to the substrate, electrode, or on any other portion of the device, including the edges.
  • the barrier layer may comprise a single layer or a plurality of layers.
  • the barrier layer can be formed by various known chemical vapor deposition techniques, and can include compositions with a single phase as well as compositions with multiple phases. Any suitable material or combination of materials can be used for the barrier layer.
  • the barrier layer can incorporate inorganic or organic compounds or both.
  • the barrier layer comprises a mixture of polymeric and non-polymeric materials.
  • the aforementioned polymeric and non-polymeric materials making up the barrier layer should be deposited under the same conditions and/or at the same time.
  • the weight ratio of polymeric material to non-polymeric material may be in the range of 95/5 to 5/95.
  • the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.
  • the hydrogen atoms may be partially or fully deuterated.
  • any specifically listed substituents such as, but not limited to, methyl, phenyl, pyridyl, etc. may be in their non-deuterated, partially deuterated, and fully deuterated forms.
  • substituent classes eg, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc. may also be in their non-deuterated, partially deuterated and fully deuterated forms.
  • the materials and structures described herein can be applied in devices other than OLEDs.
  • other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures.
  • organic devices such as organic transistors may use the materials and structures.
  • novel ligands for metal complexes are disclosed.
  • the present inventors have discovered that the introduction of these ligands unexpectedly narrows the emission spectrum, lowers the sublimation temperature, and increases the luminous efficiency of the device.
  • Examples of the method for preparing the organic electroluminescent element of the present invention include the following methods, but are not limited thereto, and those skilled in the art can make various changes based on common technical knowledge in the field.
  • the aforementioned preparation method comprises the following steps:
  • Cleaning process use cleaning agent, deionized water, organic solvent, etc. to clean the glass substrate with ITO;
  • a hole injection layer forming material containing the metal complex of the present invention is vapor-deposited on the aforementioned anode layer by vacuum evaporation, thereby forming holes containing the metal complex of the present invention on the aforementioned substrate.
  • the process of forming a hole transport layer forming a hole transport layer on the aforementioned hole injection layer by vacuum evaporation;
  • an electron transport layer forming material containing the metal complex of the present invention is vacuum-deposited on the organic light-emitting layer to form an electron transport layer containing the metal complex of the present invention on the organic light-emitting layer ;
  • the process of forming the cathode layer vapor-depositing, sputtering or spin-coating a cathode-forming material on the electron transport layer to form the cathode layer.
  • the performance detection conditions of the prepared electroluminescent device are as follows:
  • Luminance and chromaticity coordinates tested using spectral scanner PhotoResearch PR-715;
  • the first step preparation of compound Int-1
  • the third step the preparation of compound Ir(LA16)(LB105) 2
  • LA ligands LA1-LA38, LA40-LA55, and LA57-LA96 were prepared by referring to the above-mentioned synthesis method similar to Example 1 and Example 2.
  • the third step preparation of compound Int-10
  • the Int-12 of 10.0mmol is dissolved in the DMF of 50mL, the PdCl 2 (dppf) DCM catalyst of the anhydrous potassium acetate of the diboronic acid pinacol ester of 12.0mmol, 15.0mmol and 0.1mmol is added, under nitrogen protection, the temperature is raised to Stir the reaction at 100°C for 10 hours, cool down to room temperature, add 150mL of water, extract with ethyl acetate, dry the organic phase, filter, concentrate the filtrate to dryness under reduced pressure, separate and purify with a silica gel column to obtain compound Int-13, a colorless oil , yield 87%.
  • LA ligands LA97-LA110, LA112-LA188 were prepared by referring to the similar synthesis method of the above-mentioned Examples 1-4.
  • the first step preparation of compound Int-15
  • the second step the preparation of the metal complex Ir(LA37) 2 (LB105)
  • i is an integer ranging from 1 to 188, wherein LA1 to LA188 have the same meanings as above.
  • Example 10 prepare the compound represented by the formula Ir(LAi) 2 (LCt), wherein i is an integer of 1 to 188, t is an integer of 1 to 56, and LA1 to LA188, LC1 to LC56 have the same meanings as above same.
  • the glass substrate coated with the ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonicated in acetone/ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, and then cleaned with ultraviolet light.
  • the light washer was irradiated for 10 minutes and the surface was bombarded with a beam of low-energy cations.
  • vapor-deposited EBM is used as an electron blocking layer, and the thickness of the vapor-deposited film is
  • the light-emitting layer contains H1 as the main body and 5% by mass of the metal complex prepared by the present invention as a doping material, and the evaporated film thickness is
  • metal aluminum is vapor-deposited on the above-mentioned electron injection layer as the cathode layer of the element, and the thickness of the vapor-deposited film is
  • Example 12 The compound shown in GD-1 was used to replace the metal complex in Example 12, and the other steps were the same as in Example 12 to produce a comparative element 1.
  • Example 12 use the metal complex of the present invention as the dopant material of the organic light-emitting layer to make an organic electroluminescent element, and its structure and performance data are summarized in Table 1, and the * data in the table are relative to the comparison Instance normalization.
  • the metal complex of the present invention is used as the doping material of the light-emitting layer, and the driving voltage is lower than that of Comparative Example 1, especially the external quantum efficiency has obvious advantages compared with Comparative Example 1, and the element's LT95% life is also very ideal.

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Abstract

本发明涉及一种金属配合物、有机电致发光元件及消费型产品，本发明所述的金属配合物用作发光材料能够获得发光效率高的绿色至红色磷光材料，且制备的发光材料的热稳定性好，本发明制备的有机电致发光元件发绿色至红色磷光且发光效率高，热稳定性好；本发明的电子设备通过含有本发明的有机电致发光元件，从而能够获得电致发光为绿色至红色磷光且发光效率提高的消费型产品。

Description

一种金属配合物、有机电致发光元件及消费型产品 技术领域
本发明属于发光材料技术领域，具体涉及一种金属配合物、有机电致发光元件及消费型产品。
背景技术
目前，利用有机材料的光电装置变得越来越受欢迎，且用于制造所述装置的许多材料相对较为便宜，因此有机光电装置具有优于无机装置的成本优势的潜力。另外，有机材料的固有性质(例如其柔性)可以使其较适用于特定应用，如在柔性衬底上的制造。有机光电装置的实例包括有机发光二极管/装置(OLED)、有机光电晶体管、有机光伏电池和有机光电检测器。对于OLED，有机材料可以具有优于常规材料的性能优势。
OLED利用有机薄膜，其在电压施加于装置上时会发射光。OLED正成为用于如平板显示器、照明和背光的应用中的日益受关注的技术。
磷光发射分子的一个应用是全色显示器。针对此类显示器的行业标准需要适合于发射特定颜色的像素。具体来说，这些标准需要饱和红色、绿色和蓝色像素。或者，OLED可经设计以发射白光。在常规液晶显示器中，使用吸收滤光器过滤来自白色背光的发射以产生红色、绿色和蓝色发射。相同技术也可以用于OLED。白色OLED可以是单发射层(EML)装置或堆叠结构。可以使用所属领域中所熟知的CIE坐标来测量色彩，现有技术中的发光材料发光稳定性不好，发光效率低。
鉴于以上原因，特提出本发明。
发明内容
为了解决现有技术存在的以上问题，本发明提供了一种金属配合物，以及含有所述金属配合物的有机电致发光元件及消费型产品，本发明的金属配合物用于OLED中时，尤其用于绿色至红色发射区域中时，展现增强的磷光量子产率。
本发明的第一目的，提供了一种电致发光稳定，发光效率高的金属配合物。
本发明的第二目的，提供了一种含有所述金属配合物的有机电致发光元件。
本发明的第三目的，提供了一种由所述的有机电致发光元件制成的消费型产品。
为了实现上述目的，本发明采用如下技术方案：
一种金属配合物，所述的金属配合物包含式LA所示的配体：
Figure PCTCN2022114702-appb-000001
其中，R x、R 1～R 13在每次出现时相同或不同地选自由氢、氘、卤原子、链烷基、环烷基、杂烷基、杂环烷基、芳烷基、烷氧基、芳氧基、氨基、硅烷基、链烯基、环烯基、杂烯基、炔基、芳基、杂芳基、酰基、羧酸基、醚、酯、腈、异腈、硫基、亚磺酰基、磺酰基和膦基组成的群组；且任何两个或多个相邻的取代基之间任选地接合或稠合在一起形成五元环、六元环或多环；
R 0在每次出现时相同或不同地选自由氢、氘、卤原子、链烷基、环烷基、杂烷基、杂环烷基、硅烷基、链烯基、环烯基、杂烯基、炔基和腈基组成的群 组；
R 1为1个、2个或3个；
所述配体LA经由金属M配位形成五元螯合环；
M能够与其它配体配位；并且所述配体LA能够与其它配体连接以构成三齿、四齿、五齿或六齿配体；
所述M选自Os、Ir、Pd、Pt、Cu、Ag和Au中的一种。
进一步的，所述LA主要选自以下结构中的一种：
Figure PCTCN2022114702-appb-000002
其中所用符号的含义如上述所定义。
进一步的，所述的金属配合物的化学式为M(LA) p(LB) q(LC) r，其中，LB和LC为二齿配体，p为1、2或3，q为0、1或2，r为0、1或2，且p+q+r＝金属M的氧化态，LB和LC各自选自以下结构中的一种：
Figure PCTCN2022114702-appb-000003
其中，Y 1～Y 13各自独立地选自N或CR，T 1选自BR 14、NR 15、PR 16、O、S、Se、C＝O、S＝O、SO 2、CR 14R 15、SiR 14R 15和GeR 14R 15中的一种，R 14和R 15可以任意接合或稠合形成环；
每个R、R 14、R 15、R 16各自独立地选自由氢、氘、卤原子、链烷基、环烷基、杂烷基、杂环烷基、芳烷基、烷氧基、芳氧基、氨基、硅烷基、链烯基、环烯基、杂烯基、炔基、芳基、杂芳基、酰基、羧酸基、醚、酯、腈、异腈、硫基、亚磺酰基、磺酰基和膦基组成的群组；且任何两个或多个相邻的取代基之间任意地接合或稠合在一起形成五元环、六元环或多环。
进一步的，R、R 14、R 15、R 16各自独立的选自由氢、氘、氟、链烷基、环烷基、杂烷基、硅烷基、芳基、杂芳基组成的群组。
本发明意义上的“卤”、“卤素”、“卤原子”、“卤基”可互换地使用并且指氟、氯、溴或碘。
本发明意义上的“酰基”是指被取代的羰基(COR)。
本发明意义上的“酯”是指被取代的氧基羰基(-OCOR或CO 2R)。
本发明意义上的“醚”是指-OR基团。
本文中所述的“硫基”或“硫醚”可互换地使用并且指-SR基团。
本发明意义上的“亚磺酰基”是指-SOR基团。
本发明意义上的“磺酰基”是指-SO 2R基团。
本发明意义上的“膦基”是指-PR 3基团，其中每个R可以相同或不同。
本发明意义上的“硅烷基”是指-SiR 3基团，其中每个R可以相同或不同。
上述的每一个R，优选的选自由烷基、环烷基、芳基、杂芳基组成的群组。
本发明意义上的“烷基”、“烯基”或“炔基”优选被认为是指如下基团：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、新戊基、环戊基、正己基、新己基、环己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、环己烯基、庚烯基、环庚烯基、辛烯基、环辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基、庚炔基或辛炔基。
本发明意义上的“烷氧基”优选具有1～40个碳原子的烷氧基，被认为是指甲氧基、三氟甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、仲戊氧基、2-甲基丁氧基、正己氧基、环己氧基、正庚氧基、环庚氧基、正辛氧基、环辛氧基、2-乙基己氧基、五氟乙氧基和2,2,2-三氟乙氧基。
一般来说，根据本发明的“环烷基”、“环烯基”是指并且包括单环、多环和螺烷基。优选的环烷基为含有3到15个环碳原子的环烷基，可为环丙基、环丁基、环戊基、环己基、环丁烯基、环戊烯基、环己烯基、环庚基、环庚烯基、 双环[3.1.1]庚基、螺[4.5]癸基、螺[5.5]十一烷基、金刚烷基等，其中一个或多个-CH 2-基团可被上述基团代替；此外，一个或多个氢原子还可被氘原子、卤素原子或腈基代替。
本发明意义上的“杂烷基”或“杂环烷基”分别指烷基或环烷基，优选具有1～40个碳原子的烷基或环烷基，是指其中单独的氢原子或-CH 2-基团可被氧、硫、卤素原子、氮、磷、硼、硅或硒取代的基团，优选地被氧、硫或氮取代的基团。另外，杂烷基或杂环烷基可以任选地被取代。
本发明意义上的“杂烯基”或“杂环烯基”是指至少一个碳原子被杂原子置换的烯基或环烯基。任选地，所述至少一个杂原子选自氧、硫、氮、磷、硼、硅或硒，优选地是氧、硫或氮。优选的烯基、环烯基是含有3～15个碳原子的那些。另外，杂烯基、杂环烯基可以任选地被取代。
本发明意义上的“芳烷基”或“芳基烷基”可互换地使用，并且是指被芳基取代的烷基。另外，芳烷基可以任选地被取代。
根据本发明的“芳基”是指并且包括单环芳香族烃基和多环芳香族环系统。多环可以具有其中两个碳为两个邻接环(所述环是“稠合的”)共用的两个或更多个环，其中所述环中的至少一个是芳香族烃基，例如其它环可以是环烷基、环烯基、芳基、杂环和/或杂芳基。优选的芳基是含有6～30个碳原子、优选6～20个碳原子、更优选6～12个碳原子的芳基。尤其优选的是具有六个碳、十个碳或十二个碳的芳基。合适的芳基包括苯基、联苯、联三苯、三亚苯、四亚苯、萘、蒽、萉、菲、芴、芘、苝、
Figure PCTCN2022114702-appb-000004
和薁，优选苯基、联苯、联三苯、三亚苯、芴和萘。另外，芳基可以任选地被取代。
本发明意义上的“杂芳基”是指包括至少一个杂原子的单环芳香族基团和多环芳香族环系统。杂原子包括但不限于氧、硫、氮、磷、硼、硅或硒。在许多情况下，氧、硫或氮是优选的杂原子。单环杂芳香族系统优选是具有5或6个环原子的单环，并且环可以具有一到六个杂原子。杂多环系统可以具有其中两个原子为两个邻接环(所述环是“稠合的”)共用的两个或更多个环，其中所 述环中的至少一个是杂芳基，例如其它环可以是环烷基、环烯基、芳基、杂环和/或杂芳基。杂多环芳香族环系统可以在多环芳香族环系统的每个环上具有一到六个杂原子。优选的杂芳基是含有三到三十个碳原子、优选三到二十个碳原子、更优选三到十二个碳原子的杂芳基。合适的杂芳基包括二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚并咔唑、吡啶基吲哚、吡咯并二吡啶、吡唑、咪唑、三唑、噁唑、噻唑、噁二唑、噁三唑、二噁唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、噁嗪、噁噻嗪、噁二嗪、吲哚、苯并咪唑、吲唑、吲噁嗪、苯并噁唑、苯并异噁唑、苯并噻唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、萘啶、酞嗪、喋啶、氧杂蒽(xanthene)、吖啶、吩嗪、吩噻嗪、吩噁嗪、苯并呋喃并吡啶、呋喃并二吡啶、苯并噻吩并吡啶、噻吩并二吡啶、苯并硒吩并吡啶和硒吩并二吡啶，优选二苯并噻吩、二苯并呋喃、二苯并硒吩、咔唑、吲哚并咔唑、咪唑、吡啶、三嗪、苯并咪唑、1,2-氮杂硼烷、1,3-氮杂硼烷、1,4-氮杂硼烷、硼氮炔和其氮杂类似物。另外，杂芳基可以任选地被取代。
在许多情况下，一般取代基选自由氘、卤素、烷基、环烷基、杂烷基、杂环烷基、芳烷基、烷氧基、芳氧基、氨基、硅烷基、烯基、环烯基、杂烯基、炔基、芳基、杂芳基、酰基、羧酸、醚、酯、腈、异腈、硫基、亚磺酰基、磺酰基和膦基组成的群组。
如本文所使用，“其组合”或“群组”表示适用清单的一或多个成员被组合以形成本领域普通技术人员能够从适用清单中设想的已知或化学稳定的布置。举例来说，烷基和氘可以组合形成部分或完全氘化的烷基；卤素和烷基可以组合形成卤代烷基取代基，例如三氟甲基等；并且卤素、烷基和芳基可以组合形成卤代芳烷基。
在一个实例中，术语取代包括两到四个列出的基团的组合。
在另一个实例中，术语取代包括两到三个基团的组合。在又一实例中，术语取代包括两个基团的组合。取代基的优选组合是含有多达五十个不是氢或氘 的原子的组合，或包括多达四十个不是氢或氘的原子的组合，或包括多达三十个不是氢或氘的原子的组合。在许多情况下，取代基的优选组合将包括多达二十个不是氢或氘的原子。
进一步的，所述R、R 0、R x、R 1～R 16各自独立地选自由氢原子、氘原子、R A1～R A56、R B1～R B45、R C1～R C295组成的群组；
其中，R A1～R A56结构式如下：
Figure PCTCN2022114702-appb-000005
Figure PCTCN2022114702-appb-000006
R B1～R B45结构式如下：
Figure PCTCN2022114702-appb-000007
Figure PCTCN2022114702-appb-000008
R C1～R C295结构式如下：
Figure PCTCN2022114702-appb-000009
Figure PCTCN2022114702-appb-000010
Figure PCTCN2022114702-appb-000011
Figure PCTCN2022114702-appb-000012
Figure PCTCN2022114702-appb-000013
Figure PCTCN2022114702-appb-000014
进一步的，所述的金属配合物的化学式为Ir(LA)(LB) 2、Ir(LA) 2(LB)、Ir(LA) 2(LC)、Ir(LA) 3，其中，LB主要选自LB1～LB432组成的群组，LB1～LB432的具体结构如下所示：
Figure PCTCN2022114702-appb-000015
Figure PCTCN2022114702-appb-000016
Figure PCTCN2022114702-appb-000017
Figure PCTCN2022114702-appb-000018
Figure PCTCN2022114702-appb-000019
Figure PCTCN2022114702-appb-000020
Figure PCTCN2022114702-appb-000021
Figure PCTCN2022114702-appb-000022
Figure PCTCN2022114702-appb-000023
Figure PCTCN2022114702-appb-000024
Figure PCTCN2022114702-appb-000025
Figure PCTCN2022114702-appb-000026
Figure PCTCN2022114702-appb-000027
Figure PCTCN2022114702-appb-000028
Figure PCTCN2022114702-appb-000029
LC主要选自由LC1～LC56组成的群组，LC1～LC56的具体结构式如下：
Figure PCTCN2022114702-appb-000030
Figure PCTCN2022114702-appb-000031
Figure PCTCN2022114702-appb-000032
Figure PCTCN2022114702-appb-000033
进一步的，式(LA)中R x、R 1～R 13在每次出现时相同或不同地选自由氢、氘、链烷基、环烷基、杂烷基、杂环烷基、硅烷基、腈基组成的群组；且任何两个或多个相邻的取代基之间任选地接合或稠合在一起形成五元环、六元环或多环；
R 0在每次出现时相同或不同地选自由氢、氘、链烷基、环烷基、杂烷基、杂环烷基、硅烷基和腈基组成的群组；
R 1为1个、2个或3个；
所述配体LA经由金属M配位形成五元螯合环；
M能够与其它配体配位；并且所述配体LA能够与其它配体连接以构成三齿、四齿、五齿或六齿配体；
所述M选自Ir、Pd或Pt中的一种。
进一步的，所述的式(LA)主要选自LA1～LA188中的一种，LA1～LA188具体结构如下所示：
Figure PCTCN2022114702-appb-000034
Figure PCTCN2022114702-appb-000035
Figure PCTCN2022114702-appb-000036
Figure PCTCN2022114702-appb-000037
Figure PCTCN2022114702-appb-000038
Figure PCTCN2022114702-appb-000039
Figure PCTCN2022114702-appb-000040
进一步的，所述的金属配合物化学式为Ir(LAi) 2(LBj)、Ir(LAi)(LBj) 2、Ir(LAi) 2(LCt)或Ir(LAi) 3；
其中i为1～188的整数，j为1～432的整数，t为1～56的整数，LA1～LA188、LB1～LB432、LC1～LC56与上述含义相同。
本发明的有机电致发光材料中包括本发明的金属配合物中的一种或多种。本发明的有机电致发光材料可以仅由本发明的金属配合物的一种或多种形成，也可以含有本发明的金属配合物之外的其他材料。
通过在本发明的有机电致发光材料中含有前述的本发明的金属配合物，能够获得电致发光为绿色、黄色或红色发光，发光效率高的有机电致发光材料。 另外，本发明的有机电致发光材料为热稳定性好的有机电致发光材料。
本发明还提供了一种有机电致发光元件，包括第一电极、第二电极和置于第一电极和第二电极之间的有机层，所述的有机层包括所述的金属配合物。
进一步的，所述的有机层还包括主体材料，所述的主体材料主要包括由以下化学基团组成的群组：三亚苯、咔唑、二苯并噻吩、二苯并呋喃、二苯并硒吩、氮杂三亚苯、氮杂咔唑、氮杂二苯并噻吩、氮杂二苯并呋喃和氮杂二苯并硒吩、吲哚并咔唑、5,9-二氧杂-13b-硼萘并[3,2,1-de]蒽、氮杂吲哚并咔唑和氮杂-(5,9-二氧杂-13b-硼萘并[3,2,1-de]蒽)。
其中所述主体中的任何取代基是独立地选自由以下组成的群组的非稠合取代基：C nH 2n+1、OC nH 2n+1、OAr 1、N(C nH 2n+1) 2、N(Ar 1)(Ar 2)、CH＝CH-C nH 2n+1、C≡CC nH 2n+1、Ar 1、Ar 1-Ar 2、C nH 2n-Ar 1或无取代基，其中n是1～10的整数；并且其中Ar 1与Ar 2独立地选自由以下组成的群组：苯、联苯、萘、三亚苯、咔唑和其杂芳香族类似物。
本发明的有机电致发光元件中，可以是其中一层为含有本发明的金属配合物的层，也可以在二层以上的多层中含有本发明的金属配合物。
有机层可以是发射层并且如本文所述的金属配合物可以是发射掺杂剂或非发射掺杂剂。
本发明还提供了一种由所述的有机电致发光元件制成的消费型产品。
本发明中所述的消费型产品可以是以下产品中的一种：平板显示器、计算机监视器、医疗监视器、电视机、告示牌、用于内部或外部照明和/或发信号的灯、平视显示器、全透明或部分透明的显示器、柔性显示器、激光打印机、电话、蜂窝电话、平板电脑、平板手机、个人数字助理(PDA)、可佩戴装置、膝上型计算机、数码相机、摄像机、取景器、对角线小于2英寸的微型显示器、3-D显示器、虚拟现实或增强现实显示器、交通工具、包含多个平铺在一起的显示器的视频墙、剧院或体育馆屏幕、光疗装置和指示牌。
与现有技术相比，本发明的有益效果为：
本发明所述的金属配合物用作发光材料能够获得发光效率高的绿色至红色磷光材料，且制备的发光材料的热稳定性好，本发明制备的有机电致发光元件发绿色至红色磷光且发光效率高，热稳定性好；本发明的电子设备通过含有本发明的有机电致发光元件，从而能够获得电致发光为绿色至红色磷光且发光效率提高的消费型产品。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明的一种有机电致发光元件示意图；
图2是本发明的一种倒转的有机电致发光元件示意图；
附图标记
110-衬底、115-阳极层、120-空穴注入层、125-空穴传输层、130-电子阻挡层、135-有机发光层、140-空穴阻挡层、145-电子传输层、150-电子注入层、155-保护层、160-阴极层、162-第一导电层、164-第二导电层、170-封装层。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明的技术方案进行详细的描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施方式，都属于本发明所保护的范围。
本发明的有机电致发光元件中，作为含有本发明的金属配合物的层之外的层的构成，没有任何限定，本领域技术人员能够根据本领域的技术常识根据需要来决定有机电致发光元件的其他层的构成。
其中，图1中在衬底110上依次有阳极层115、空穴注入层120、空穴传输 层125、电子阻挡层130、有机发光层135、空穴阻挡层140、电子传输层145、电子注入层150、保护层155、阴极层160和封装层170。在前述的有机发光层中含有本发明的金属配合物。当本发明的有机电致发光器件在与外接电源连接而被施加电压时，有机发光层135中的金属配合物电致发光，发出光的波长范围为520～650nm。阴极层160是具有第一导电层162和第二导电层164的复合阴极。本装置可通过按顺序沉积所述层来制造。
图2中包括衬底110、阴极160、有机发光层135、空穴传输层125和阳极层115。本装置可通过按顺序沉积各层来制造。因为最常见的OLED配置具有安置于阳极上方的阴极，并且本装置具有安置于阳极层115下的阴极层160，所以本装置可以被称为倒置式。可以在本装置的对应层中使用与本装置所述的材料类似的材料。图2提供如何可以从图1装置的结构省去一些层的一个实例。
图1和图2中所说明的简单分层结构是作为非限制实例而提供，且应当理解，可结合各种各样的其它结构使用本发明的实施例。所描述的特定材料和结构本质上是示范性的，且可使用其它材料和结构。可基于设计、性能和成本因素，通过以不同方式组合所描述的各个层来实现功能性OLED，或可完全省略若干层。还可包含未具体描述的其它层。可使用不同于具体描述的材料。尽管本文所提供的实例中的许多实例将各种层描述为包括单一材料，但将理解，可使用材料的组合，例如基质与掺杂剂的混合物，或更一般来说，混合物。并且，所述层可具有各种子层。本文中给予各个层的名称不意欲为严格限制性的。举例来说，图2中，空穴传输层125传输空穴并将空穴注入到有机发光层135中，且可被描述为空穴传输层或空穴注入层。在一个实施例中，可将OLED描述为具有安置在阴极与阳极之间的有机层。此有机层可包括单个层或可进一步包括如例图1和图2所描述的不同有机材料的多个层。
还可使用未具体描述的结构和材料，例如包含聚合物材料的PLED。作为另一实例，可使用具有单个有机层的OLED或多个堆叠。OLED结构可脱离图1和图2中所说明的简单分层结构。举例来说，衬底可包含有角度的反射表面以改进光耦合。
除非另有指定，否则可通过任何合适方法来沉积各种实施例的层中的任一者。对于有机层，优选方法包含热蒸发、有机气相沉积方法或借助于载气升华来施加一个或多个层，其中，在10 -5毫巴至1巴之间的压力下施加所述材料。该方法的特别的例子是有机蒸汽喷印方法，其中所述材料通过喷嘴直接施加，并且因此是结构化的。其它合适沉积方法包含例如通过旋涂，或借助于任何所希望的印刷方法例如丝网印刷、柔性版印刷、平版印刷、光引发热成像、热转印、喷墨印刷或喷嘴印刷，来产生一个或多个层。可溶性化合物，例如通过适当的取代本发明提供的金属配合物获得可溶性化合物。这些方法也特别适于低聚物、树枝状大分子和聚合物。此外可行的是混合方法，其中例如从溶液中施加一个或多个层并且通过气相沉积施加一个或多个另外的层。
根据本发明实施例制造的装置可进一步任选地包括障壁层。障壁层的一个用途是保护电极和有机层免于因暴露于环境中的有害物质，包括水分、蒸气和/或气体等而受损。障壁层可沉积在衬底、电极上、沉积在衬底、电极下或沉积在衬底、电极旁，或沉积在装置的任何其它部分，包含边缘上。障壁层可包括单个层或多个层。障壁层可通过各种己知化学气相沉积技术形成，且可包含具有单一相的合成物以及具有多个相的合成物。任何合适材料或材料组合均可用于障壁层。障壁层可并入无机或有机化合物或两者。优选的，障壁层包括聚合材料与非聚合材料的混合物。为了被视为混合物，组成障壁层的前述聚合物和非聚合物材料应在相同条件下和/或在同时沉积。聚合材料对非聚合材料的重量比可在95/5～5/95的范围内。在一个实例中，聚合材料与非聚合材料的混合物本质上由聚合硅和无机硅组成。
在上述OLED装置的每个层中所用的任何上文所提及的化合物中，氢原子可以部分或完全氘化。因此，任何具体列出的取代基，如(但不限于)甲基、苯基、吡啶基等可以是其非氘化、部分氘化以及和完全氘化形式。类似地，取代基类别(例如(但不限于)烷基、芳基、环烷基、杂芳基等)还可以是其非氘化、部分氘化和完全氘化形式。
本文所述的材料和结构可应用于不同于OLED的装置中。举例来说，例如 有机太阳能电池和有机光电检测器等其它光电子装置可使用所述材料和结构。进一步来说，例如有机晶体管等有机装置可使用所述材料和结构。
这些方法是本领域普通技术人员通常已知的，并且他们可以在不付出创造性劳动的情况下将其应用于包含根据本发明的化合物的有机电致发光器件。
根据一个实施例，公开金属络合物新颖的配体。本发明者己发现这些配体的引入出乎意料地使发射光谱变窄，降低升华温度、并提高装置的发光效率。
作为本发明的有机电致发光元件的制备方法，可以列举出下述的制备方法，但是并不限于此，本领域技术人员能够根据本领域的技术常识进行各种改变。前述的制备方法包括以下工序：
清洗工序：使用清洗剂、去离子水、有机溶剂等清洗带有ITO的玻璃基片；
形成空穴注入层的工序：通过真空蒸镀在前述的阳极层上蒸镀含有本发明的金属配合物的空穴注入层形成材料，从而在前述基板上形成包含本发明的金属配合物的空穴注入层；
形成空穴传输层的工序：通过真空蒸镀在前述的空穴注入层上形成空穴传输层；
形成有机发光层的工序：在前述的空穴传输层上通过真空蒸镀包含本发明材料的有机发光层形成材料从而在前述空穴传输层上形成含有本发明的金属配合物的有机发光层；
形成电子传输层的工序：在前述有机发光层上通过真空蒸镀包含本发明的金属配合物的电子传输层形成材料，从而在前述有机发光层上形成含有本发明的金属配合物的电子传输层；
形成阴极层的工序：在前述电子传输层上蒸镀、溅射或者旋涂阴极形成材料从而形成阴极层。
本发明的实施例中，制备得到的电致发光器件的性能检测条件如下：
亮度和色度坐标：使用光谱扫描仪PhotoResearch PR-715测试；
电流密度和起亮电压：使用数字源表Keithley 2420测试；
功率效率：使用NEWPORT 1931-C测试。
实施例1
金属配合物Ir(LA39)(LB105) 2的制备：
第一步：化合物Int-1的制备
Figure PCTCN2022114702-appb-000041
10.0mmol的1,3-二苯基-1,3-丙二酮(CAS:120-46-7)溶解在50mL的乙腈中，加入10.0mmol的邻溴苯甲醛(CAS:6630-33-7)、1.0mmol的哌啶，在氮气保护下，升温回流反应12小时，冷却到室温，减压浓缩干燥，用硅胶柱分离纯化，得到化合物Int-1，黄色固体，收率67％。
第二步：化合物Int-2的制备
Figure PCTCN2022114702-appb-000042
10.0mmol的Int-1溶解在40mL的二氯甲烷中，在氮气保护下，用液氮降温至-78℃，加入35.0mL的0.4M水合氯化铈甲醇溶液，再加入21.0mmol的硼氢化钠固体，搅拌反应30分钟，升到室温反应1小时，加入30mL的0.5M稀盐酸水溶液，用二氯甲烷萃取，收集有机相干燥，过滤，滤液减压浓缩干燥，用硅胶柱分离纯化，得到化合物Int-2，白色固体，收率91％。
第三步：化合物Int-3的制备
Figure PCTCN2022114702-appb-000043
25.3mmol的中间体Int-2溶解在60mL干燥的氯苯中，加入4.8g的多聚磷酸，在氮气保护下，升温至130℃搅拌反应24小时，冷却到室温，加入150mL的冰水，用二氯甲烷萃取，收集有机相，干燥，过滤，滤液用硅胶柱分离纯化，得到化合物Int-3，白色固体，收率30％。
第四步：化合物Int-4的制备
Figure PCTCN2022114702-appb-000044
20.0mmol的中间体Int-3溶解在60mL的DMF中，加入24.0mmol的联硼酸频那醇酯、30.0mmol的无水醋酸钾和0.2mmol的PdCl 2(dppf)催化剂，在氮气保护下，升温至90℃搅拌反应14小时，冷却到室温，加入150mL的冰水，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液用硅胶柱分离纯化，得到化合物Int-4，无色油状物，收率89％。
第五步：化合物Int-5的制备
Figure PCTCN2022114702-appb-000045
12.0mmol的中间体Int-4溶解在40mL的甲苯、20mL的乙醇和20mL的水中，加入10.0mmol的2-溴-4-(甲基-d3)-吡啶(CAS:1185311-65-2)、30.0mmol的无水碳酸钾和0.01mmol的Pd132催化剂，在氮气保护下，升温回流搅拌反 应12小时，冷却到室温，加入100mL的水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液用硅胶柱分离纯化，得到化合物Int-5，黄色固体，收率87％。
第六步：化合物LA39的制备
Figure PCTCN2022114702-appb-000046
10.0mmol的中间体Int-5溶解在50mL的氘甲醇中，加入30.0mmol的甲醇钠，在氮气保护下，升温回流搅拌反应2天，冷却到室温，减压浓缩干，加入100mL的水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液用硅胶柱分离纯化，得到化合物LA39，黄色固体，收率100％。
第七步：化合物Int-6的制备
Figure PCTCN2022114702-appb-000047
10.0g的化合物LB105和9.5g的IrCl 3·3H 2O分散在150mL的乙二醇乙醚和50mL水中，在氮气保护下，升温回流反应24小时，冷却到室温，过滤，滤饼用水洗、乙醇洗，真空干燥，得14.8g的黄色固体，将获得的黄色固体溶解于250mL的二氯甲烷和25mL的甲醇中，加入6.5g的三氟甲磺酸银，搅拌反应24小时，过滤，滤液减压浓缩干燥，得到化合物Int-6，收率83％。
第八步：化合物Ir(LA39)(LB105) 2的制备
Figure PCTCN2022114702-appb-000048
4.7mmol的化合物LA39和2.3mmol的中间体Int-6分散在50mL的乙二醇乙醚和50mL的DMF中，在氮气保护下，升温至100℃搅拌反应7天，冷却到室温，减压浓缩干燥，用硅胶柱分离纯化，二氯甲烷-正己烷洗脱，得到化合物Ir(LA39)(LB105) 2，褐色固体，收率38％。
实施例2
金属配合物Ir(LA16)(LB105) 2的制备：
第一步：化合物Int-7的制备
Figure PCTCN2022114702-appb-000049
参照实施例1第五步的合成方法，仅将实施例1第五步的2-溴-4-(甲基-d3)-吡啶替换为2-溴吡啶，制备化合物Int-7，收率86％。
第二步：化合物LA16的制备
Figure PCTCN2022114702-appb-000050
10.0mmol的化合物Int-7和32.0mmol的NBS分散在250mL的四氯化碳中，再加入0.1mmol的AIBN，在氮气保护下，升温回流搅拌反应5小时，冷却到室温，过滤，滤液用饱和亚硫酸氢钠水溶液洗、水洗，有机相干燥， 减压浓缩干，残余物用100mL的苯溶解，滴加入27mL的2M三甲基铝甲苯溶液，升温至50℃搅拌反应8小时，降到室温，加入50mL的饱和氯化铵水溶液，用甲苯萃取，有机相用饱和盐水洗、水洗，收集有机相干燥，减压浓缩干，用硅胶柱分离纯化，得到化合物LA16，黄色固体，收率55％。
第三步：化合物Ir(LA16)(LB105) 2的制备
Figure PCTCN2022114702-appb-000051
5.0mmol的化合物LA16和2.5mmol实施例1第七步制备的中间体Int-6分散在50mL的乙二醇乙醚和50mL的DMF中，在氮气保护下，升温至100℃搅拌反应7天，冷却到室温，减压浓缩干，用硅胶柱分离纯化，二氯甲烷-正己烷洗脱，得到化合物Ir(LA16)(LB105) 2，褐色固体，收率42％。
实施例3
参照上述实施例1和实施例2类似的合成方法，制备LA配体：LA1～LA38、LA40～LA55、LA57～LA96。
实施例4
金属配合物Ir(LA111)(LB105) 2的制备：
第一步：化合物Int-8的制备
Figure PCTCN2022114702-appb-000052
15.0mmol的2-(甲基-d3)-1,3-茚二酮和15.1mmol的(2-甲氧基苯基)苯基甲醇(CAS:22788-49-4)分散在150mL的甲苯中，再加入5.0mmol的对甲苯磺酸， 升温回流搅拌反应24小时，并通过分水器除去反应生成的水，冷却到室温，加入50mL的饱和碳酸钾水溶液，用乙酸乙酯萃取，有机相干燥，减压浓缩干燥，用硅胶柱分离纯化，得到化合物Int-8，白色固体，收率75％。
第二步：化合物Int-9的制备
Figure PCTCN2022114702-appb-000053
25.0mmol的氢化铝锂分散在80mL干燥的THF中，在氮气保护下，降温至0℃，滴加入10.0mmol的Int-8溶于THF的溶液，升到室温搅拌反应5小时，降温至0℃，滴加入5mL的25％氢氧化钠水溶液和1mL水，过滤，滤饼用乙酸乙酯洗，收集滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-9，无色油状物，收率86％。
第三步：化合物Int-10的制备
Figure PCTCN2022114702-appb-000054
5.0mL的多聚磷酸和50mL干燥的氯苯混合，在氮气保护下，滴加入10.0mmol的Int-9溶于氯苯的溶液，升温回流搅拌反应20小时，降至室温，将反应液倒入200mL的饱和碳酸氢钠水溶液中，分出有机相，水相用乙酸乙酯萃取，有机相合并干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-10，无色油状物，收率38％。
第四步：化合物Int-11的制备
Figure PCTCN2022114702-appb-000055
10.0mmol的Int-10溶解于80mL干燥的二氯甲烷，在氮气保护下，降温至-5℃，滴加入15.0mmol的三溴化硼溶于二氯甲烷的溶液，搅拌反应2小时，升至室温，加入150mL的饱和碳酸氢钠水溶液，分出有机相，水相用二氯甲烷萃取，有机相合并干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-11，无色油状物，收率98％。
第五步：化合物Int-12的制备
Figure PCTCN2022114702-appb-000056
10.0mmol的Int-11溶解于80mL干燥的二氯甲烷，加入20.0mmol的吡啶，在氮气保护下，降温至0℃，滴加入12.0mmol的三氟甲磺酸酐，搅拌反应2小时，升至室温，加入50mL的1N稀盐酸水溶液，分出有机相，水相用二氯甲烷萃取，有机相合并干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-12，无色油状物，收率88％。
第六步：化合物Int-13的制备
Figure PCTCN2022114702-appb-000057
10.0mmol的Int-12溶解于50mL的DMF中，加入12.0mmol的联硼酸频那醇酯、15.0mmol的无水醋酸钾和0.1mmol的PdCl 2(dppf)DCM催化剂，在 氮气保护下，升温至100℃搅拌反应10小时，降至室温，加入150mL的水，用乙酸乙酯萃取，有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Int-13，无色油状物，收率87％。
第七步：化合物Int-14的制备
Figure PCTCN2022114702-appb-000058
参照实施例2第一步的合成方法，仅将实施例2第一步的Int-4替换为Int-13，制备化合物Int-14，黄色固体，收率88％。
第八步：化合物LA111的制备
Figure PCTCN2022114702-appb-000059
参照实施例1第六步的合成方法，仅将实施例1第六步的Int-5替换为Int-14，制备化合物LA111，黄色固体，收率100％。
第九步：化合物Ir(LA111)(LB105) 2的制备
Figure PCTCN2022114702-appb-000060
5.0mmol的化合物LA111和2.5mmol实施例1第七步制备的中间体Int-6分散在50mL的乙二醇乙醚和50mL的DMF中，在氮气保护下，升温至100℃搅拌反应7天，冷却到室温，减压浓缩干，用硅胶柱分离纯化，二氯甲烷-正 己烷洗脱，得到化合物Ir(LA111)(LB105) 2，褐色固体，收率36％。
实施例5
参照上述实施例1～实施例4类似的合成方法，制备LA配体：LA97～LA110、LA112～LA188。
实施例6
金属配合物Ir(LA37) 2(LB105)的制备：
第一步：化合物Int-15的制备
Figure PCTCN2022114702-appb-000061
参照实施例1第七步的制备方法，仅将实施例1第七步的LB105替换为LA37，并根据摩尔量更改该化合物的质量用量，其他实验参数根据实际需要进行相应的调整，制备化合物Int-15，黄色固体，收率82％。
第二步：金属配合物Ir(LA37) 2(LB105)的制备
Figure PCTCN2022114702-appb-000062
5.0mmol的化合物LB105和2.5mmol的中间体Int-15分散在50mL的乙二醇乙醚和50mL的DMF中，在氮气保护下，升温至100℃搅拌反应7天，冷却到室温，减压浓缩干，用硅胶柱分离纯化，二氯甲烷-石油醚洗脱，得到化合物Ir(LA37) 2(LB105)，褐色固体，收率28％。
实施例7
参照实施例1～6的合成方法，制备化合物式Ir(LAi)(LBj) 2和Ir(LAi) 2(LBj)所示化合物，其中，i为1～188的整数，j为1～432的整数，LA1～LA188、LB1～LB432与上述含义相同。
实施例8
金属配合物Ir(LA1) 3的制备：
第一步：化合物Int-16的制备
Figure PCTCN2022114702-appb-000063
10.0mmol的化合物LA1和5.0mmol的IrCl 3·3H 2O分散在90mL的乙二醇乙醚和30mL水中，在氮气保护下，升温回流反应24小时，冷却到室温，过滤，滤饼用水洗、乙醇洗，真空干燥，得化合物Int-16，褐色固体，收率58％。
第二步：化合物Ir(LA1) 3的制备
Figure PCTCN2022114702-appb-000064
5.0mmol第一步制备的Int-16、10.0mmol的三氟甲磺酸银和12.0mmol的LA1分散在20mL的乙二醇乙醚中，在氮气保护下，升温回流搅拌反应24小时，冷却到室温，过滤，滤饼用二氯甲烷溶解，经硅胶柱分离纯化，得到化合物Ir(LA1) 3，深黄色固体，收率47％。
实施例9
参照实施例8的合成方法，适当的调整各试验参数及条件，制备金属配合 物Ir(LAi) 3，i为1～188的整数，其中LA1～LA188与上述含义相同。
实施例10
化合物Ir(LA125) 2(LC7)的制备：
第一步：化合物Int-17的制备
Figure PCTCN2022114702-appb-000065
参照实施例8第一步的制备方法，仅将实施例8第一步的LA1替换为LA125，并根据摩尔量更改该化合物的质量用量，其他实验参数根据实际需要进行相应的调整，制备化合物Int-17，黄色固体，收率55％。
第二步：化合物Ir(LA125) 2(LC7)的制备
Figure PCTCN2022114702-appb-000066
5.0mmol第一步制备的Int-17、50.0mmol的无水碳酸钾和15.0mmol的LC7分散在40mL的乙二醇乙醚中，在氮气保护下，升温回流搅拌反应24小时，冷却到室温，将反应液倒入150mL的冰水中，用二氯甲烷萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物Ir(LA125) 2(LC7)，黄色固体，收率54％。
实施例11
参照实施例10的合成方法，制备式Ir(LAi) 2(LCt)所示化合物，其中，i为1～188的整数，t为1～56的整数，LA1～LA188、LC1～LC56与上述含义相同。
实施例12有机电致发光元件的制备
将涂布了ITO导电层的玻璃基片在清洗剂中超声处理30分钟，在去离子 水中冲洗，在丙酮/乙醇混合溶剂中超声30分钟，在洁净的环境下烘烤至完全干燥，用紫外光清洗机照射10分钟，并用低能阳离子束轰击表面。
把上述处理好的ITO玻璃基片置于真空腔内，抽真空至1×10 -5～9×10 -3Pa，在上述阳极层膜上继续分别蒸镀化合物HATCN作为空穴注入层，蒸镀膜厚为
Figure PCTCN2022114702-appb-000067
在上述空穴注入层膜上继续蒸镀HTM为空穴传输层，蒸镀膜厚为
Figure PCTCN2022114702-appb-000068
在前述空穴传输层上蒸镀EBM作为电子阻挡层，蒸镀膜厚为
Figure PCTCN2022114702-appb-000069
在前述电子阻挡层上蒸镀有机发光层，发光层含有H1作为主体和5％质量的本发明制备的金属配合物为掺杂材料，蒸镀膜厚为
Figure PCTCN2022114702-appb-000070
在上述有机发光层上再继续蒸镀一层LiQ和ETM作为元件的电子传输层，其中LiQ为ETM质量的60％，蒸镀膜厚为
Figure PCTCN2022114702-appb-000071
在上述发光层上继续蒸镀一层LiF作为器件的电子注入层，蒸镀膜厚为
Figure PCTCN2022114702-appb-000072
最后，在上述电子注入层之上蒸镀金属铝作为元件的阴极层，蒸镀膜厚为
Figure PCTCN2022114702-appb-000073
对比例1
采用GD-1所示的化合物代替实施例12中的金属配合物，其他步骤与实施例12相同，制作对比元件1。
前述的HATCN、HTM、EBM、H1、LiQ、GD-1、ETM的结构式如下所示：
Figure PCTCN2022114702-appb-000074
按照与实施例12相同的方法，使用本发明的金属配合物作为有机发光层的掺杂材料制作有机电致发光元件，其结构和性能数据汇总于表1中，表内*数据 是相对于比较实例的归一化。
表1
Figure PCTCN2022114702-appb-000075
Figure PCTCN2022114702-appb-000076
Figure PCTCN2022114702-appb-000077
Figure PCTCN2022114702-appb-000078
Figure PCTCN2022114702-appb-000079
从表1中可以看出，本发明的金属配合物作为发光层的掺杂材料，驱动电压相较于对比例1偏低，尤其是外量子效率比对比例1具有明显的优势，而且元件的LT95％寿命也非常的理想。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (10)

  1. 一种金属配合物，其特征在于，所述的金属配合物包含式LA所示的配体：
    Figure PCTCN2022114702-appb-100001
    其中，R x、R 1～R 13在每次出现时相同或不同地选自由氢、氘、卤原子、链烷基、环烷基、杂烷基、杂环烷基、芳烷基、烷氧基、芳氧基、氨基、硅烷基、链烯基、环烯基、杂烯基、炔基、芳基、杂芳基、酰基、羧酸基、醚、酯、腈、异腈、硫基、亚磺酰基、磺酰基和膦基组成的群组；且任何两个或多个相邻的取代基之间任选地接合或稠合在一起形成五元环、六元环或多环；
    R 0在每次出现时相同或不同地选自由氢、氘、卤原子、链烷基、环烷基、杂烷基、杂环烷基、硅烷基、链烯基、环烯基、杂烯基、炔基和腈基组成的群组；
    R 1为1个、2个或3个；
    所述配体LA经由金属M配位形成五元螯合环；
    M能够与其它配体配位；并且所述配体LA能够与其它配体连接以构成三齿、四齿、五齿或六齿配体；
    所述M选自Os、Ir、Pd、Pt、Cu、Ag和Au中的一种。
  2. 根据权利要求1所述的金属配合物，其特征在于，所述的LA选自以下结构中的一种：
    Figure PCTCN2022114702-appb-100002
    其中，各符号的含义与权利要求1相同。
  3. 根据权利要求1或2所述的金属配合物，其特征在于，所述的金属配合物的化学式为M(LA) p(LB) q(LC) r，其中，LB和LC为二齿配体，p为1、2或3，q为0、1或2，r为0、1或2，且p+q+r＝金属M的氧化态，LB和LC各自选自以下结构中的一种：
    Figure PCTCN2022114702-appb-100003
    Figure PCTCN2022114702-appb-100004
    其中，Y 1～Y 13各自独立地选自N或CR，T 1选自BR 14、NR 15、PR 16、O、S、Se、C＝O、S＝O、SO 2、CR 14R 15、SiR 14R 15和GeR 14R 15中的一种，R 14和R 15可以任意接合或稠合形成环；
    每个R、R 14、R 15、R 16各自独立地选自由氢、氘、卤原子、链烷基、环烷基、杂烷基、杂环烷基、芳烷基、烷氧基、芳氧基、氨基、硅烷基、链烯基、环烯基、杂烯基、炔基、芳基、杂芳基、酰基、羧酸基、醚、酯、腈、异腈、硫基、亚磺酰基、磺酰基和膦基组成的群组；且任何两个或多个相邻的取代基之间任意地接合或稠合在一起形成五元环、六元环或多环。
  4. 根据权利要求1～3任一项所述的金属配合物，其特征在于，所述R、R x、R 0、R 1～R 16各自独立地选自由氢原子、氘原子、R A1～R A56、R B1～R B45、R C1～R C295组成的群组；
    其中，R A1～R A56结构式如下：
    Figure PCTCN2022114702-appb-100005
    Figure PCTCN2022114702-appb-100006
    R B1～R B45结构式如下：
    Figure PCTCN2022114702-appb-100007
    Figure PCTCN2022114702-appb-100008
    R C1～R C295结构式如下：
    Figure PCTCN2022114702-appb-100009
    Figure PCTCN2022114702-appb-100010
    Figure PCTCN2022114702-appb-100011
    Figure PCTCN2022114702-appb-100012
    Figure PCTCN2022114702-appb-100013
    Figure PCTCN2022114702-appb-100014
    Figure PCTCN2022114702-appb-100015
  5. 根据权利要求1～4任一项所述的金属配合物，其特征在于，所述的金属配合物的化学式为Ir(LA)(LB) 2、Ir(LA) 2(LB)、Ir(LA) 2(LC)或Ir(LA) 3，其中，LB选自LB1～LB432组成的群组，LB1～LB432的具体结构如下所示：
    Figure PCTCN2022114702-appb-100016
    Figure PCTCN2022114702-appb-100017
    Figure PCTCN2022114702-appb-100018
    Figure PCTCN2022114702-appb-100019
    Figure PCTCN2022114702-appb-100020
    Figure PCTCN2022114702-appb-100021
    Figure PCTCN2022114702-appb-100022
    Figure PCTCN2022114702-appb-100023
    Figure PCTCN2022114702-appb-100024
    Figure PCTCN2022114702-appb-100025
    Figure PCTCN2022114702-appb-100026
    Figure PCTCN2022114702-appb-100027
    Figure PCTCN2022114702-appb-100028
    Figure PCTCN2022114702-appb-100029
    LC选自LC1～LC56组成的群组，具体结构式如下：
    Figure PCTCN2022114702-appb-100030
    Figure PCTCN2022114702-appb-100031
    Figure PCTCN2022114702-appb-100032
    Figure PCTCN2022114702-appb-100033
  6. 根据权利要求1～5任一项所述的金属配合物，其特征在于，所述的式(LA) 选自LA1～LA188中的一种，LA1～LA188具体结构如下所示：
    Figure PCTCN2022114702-appb-100034
    Figure PCTCN2022114702-appb-100035
    Figure PCTCN2022114702-appb-100036
    Figure PCTCN2022114702-appb-100037
    Figure PCTCN2022114702-appb-100038
    Figure PCTCN2022114702-appb-100039
    Figure PCTCN2022114702-appb-100040
  7. 根据权利要求1～6任一项所述的金属配合物，其特征在于，所述的金属配合物为Ir(LAi) 2(LBj)、Ir(LAi)(LBj) 2、Ir(LAi) 2(LCt)或Ir(LAi) 3；
    其中i为1～188的整数，j为1～432的整数，t为1～56的整数，所述LA1～LA188、LB1～LB432、LC1～LC56的含义与权利要求1～6相同。
  8. 一种有机电致发光元件，包括第一电极、第二电极和置于第一电极和第二电极之间的有机层，其特征在于，所述的有机层包括权利要求1-7任意一项所述的金属配合物。
  9. 根据权利要求8所述的有机电致发光元件，其特征在于，所述的有机层还包括主体材料，所述的主体材料主要包括以下化学基团组成的群组：三亚苯、 咔唑、二苯并噻吩、二苯并呋喃、二苯并硒吩、氮气三亚苯、氮杂咔唑、氮杂二苯并噻吩、氮杂二苯并呋喃和氮杂二苯并硒吩。
  10. 一种由权利要求8或9所述的有机电致发光元件制成的消费型产品。
PCT/CN2022/114702 2021-08-26 2022-08-25 一种金属配合物、有机电致发光元件及消费型产品 WO2023025230A1 (zh)

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Publication number Priority date Publication date Assignee Title
CN113773336B (zh) * 2021-08-26 2024-06-11 上海八亿时空先进材料有限公司 一种金属配合物、有机电致发光元件及消费型产品
CN114409709A (zh) * 2022-01-14 2022-04-29 上海八亿时空先进材料有限公司 一种金属配合物、有机电致发光元件及消费型产品

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012180335A (ja) * 2011-02-07 2012-09-20 Tosoh Corp アリールアミン化合物及びその製造法、並びにその用途
CN104710478A (zh) * 2013-12-11 2015-06-17 江南大学 一种含氟的绿色磷光铱配合物
JP2016074625A (ja) * 2014-10-06 2016-05-12 東ソー株式会社 アリールアミン化合物、及びその用途
CN112940048A (zh) * 2021-03-01 2021-06-11 北京八亿时空液晶科技股份有限公司 金属配合物、有机电致发光材料、有机电致发光元件及电致设备
CN113004339A (zh) * 2021-03-01 2021-06-22 北京八亿时空液晶科技股份有限公司 金属配合物、有机电致发光材料、有机电致发光元件及电致设备
CN113004340A (zh) * 2021-03-16 2021-06-22 北京八亿时空液晶科技股份有限公司 金属配合物，有机电致发光材料和包含该金属配合物的有机电致发光元件
CN113773336A (zh) * 2021-08-26 2021-12-10 上海八亿时空先进材料有限公司 一种金属配合物、有机电致发光元件及消费型产品

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113214326B (zh) * 2021-05-20 2022-04-01 北京八亿时空液晶科技股份有限公司 一种金属配合物、有机电致发光装置及应用
CN113278037B (zh) * 2021-06-04 2023-01-24 北京八亿时空液晶科技股份有限公司 一种金属化合物、有机电致发光元件及消费型产品

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012180335A (ja) * 2011-02-07 2012-09-20 Tosoh Corp アリールアミン化合物及びその製造法、並びにその用途
CN104710478A (zh) * 2013-12-11 2015-06-17 江南大学 一种含氟的绿色磷光铱配合物
JP2016074625A (ja) * 2014-10-06 2016-05-12 東ソー株式会社 アリールアミン化合物、及びその用途
CN112940048A (zh) * 2021-03-01 2021-06-11 北京八亿时空液晶科技股份有限公司 金属配合物、有机电致发光材料、有机电致发光元件及电致设备
CN113004339A (zh) * 2021-03-01 2021-06-22 北京八亿时空液晶科技股份有限公司 金属配合物、有机电致发光材料、有机电致发光元件及电致设备
CN113004340A (zh) * 2021-03-16 2021-06-22 北京八亿时空液晶科技股份有限公司 金属配合物，有机电致发光材料和包含该金属配合物的有机电致发光元件
CN113773336A (zh) * 2021-08-26 2021-12-10 上海八亿时空先进材料有限公司 一种金属配合物、有机电致发光元件及消费型产品

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