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WO2018108110A1 - Complexe organométallique et son utilisation, mélange et dispositif électronique organique - Google Patents

Complexe organométallique et son utilisation, mélange et dispositif électronique organique Download PDF

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Publication number
WO2018108110A1
WO2018108110A1 PCT/CN2017/115984 CN2017115984W WO2018108110A1 WO 2018108110 A1 WO2018108110 A1 WO 2018108110A1 CN 2017115984 W CN2017115984 W CN 2017115984W WO 2018108110 A1 WO2018108110 A1 WO 2018108110A1
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carbon atoms
group
organic
aromatic
metal organic
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Chinese (zh)
Inventor
潘君友
梁志明
黄宏
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/12—Gold compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals

Definitions

  • the invention relates to the technical field of organic photoelectric materials, in particular to a metal organic complex and an application, a mixture thereof and an organic electronic device.
  • OLED Organic Light-Emitting Diode
  • OLED Organic Light-Emitting Diode
  • various systems based on fluorescent and phosphorescent materials have been developed.
  • An organic light-emitting diode using a fluorescent material has high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electric field excitation.
  • the branch ratio of the singlet excited state and the triplet excited state of the excitons is 1:3, an organic light emitting diode using a phosphorescent material can achieve an internal luminescence quantum efficiency of almost 100%.
  • the triplet excitation is effectively obtained by doping the center of the heavy metal, thereby increasing the spin-orbit coupling, and thus the inter-system to triplet state.
  • Metal ruthenium (III)-based complexes are a class of materials widely used in high-efficiency OLEDs with high efficiency and stability. Baldo et al. reported the use of fac-tris(2-phenylpyridine)ruthenium(III)[Ir(ppy)3] as a phosphorescent material, 4,4'-N,N'-dicarbazole-biphenyl (4 , 4'-N, N'-diarbazole-biphenyl) (CBP) is a high quantum efficiency OLED of matrix material (Appl. Phys. Lett. 1999, 75, 4).
  • a phosphorescent luminescent material is the sky blue complex bis[2-(4',6'-difluorophenyl)pyridine-N,C2]-pyridinium ruthenate (III) (FIrpic), which is doped to high The triplet energy matrix exhibits an extremely high photoluminescence quantum efficiency of approximately 60% in solution and almost 100% in solid film (Appl. Phys. Lett. 2001, 79, 2082).
  • ruthenium (III) systems based on 2-phenylpyridine and its derivatives have been used in large quantities for the preparation of OLEDs, phosphorescent luminescent materials containing other metal centers with these ligands have remained largely unexplored.
  • Yam et al. disclose the synthesis of a series of bis-cyclometalated acetylene fund (III) compounds using various strong ⁇ -donor alkynyl ligands, all of which exhibit in various media at room and low temperatures. Very strong luminescent properties (J. Am. Chem. Soc. 2007, 129, 4350). In addition, the external quantum efficiency of OLEDs prepared using these luminescent gold (III) compounds as phosphorescent dopant materials was 5.5%. These luminescent gold (III) compounds contain a tridentate ligand and at least one strong ⁇ -donor group coordinated to the gold (III) metal center. Since then, Yam et al.
  • the tridentate ligand and the monodentate coordination combine to form a tetradentate ligand with more coordinate bonds to obtain a more stable complex.
  • Tetradentate ligands have been investigated for use in other transition metals such as platinum (II) (US9224963B2), palladium (II) (Chem. Sci. 2016, 7, 6083) and the like. Such tetradentate coordination metal complexes also have good performance in OLED applications.
  • gold (III) which is an electronic structure, this research field is relatively small.
  • the gold (III) complex of the tridentate ligand is a precursor that requires mercury as a precursor (Chem. Commun. 2005, 2906), which is detrimental to the environment.
  • the tetradentate ring metallized gold (III) complex can make the complex more stable, increase the rigidity of the molecule, and make the luminous efficiency higher.
  • the tetradentate ring metallized gold (III) complex does not require the use of a mercury compound as a precursor in the synthesis.
  • M is a metal atom and M is selected from gold or palladium
  • L is selected from the group consisting of two bridges
  • Ar 1 and Ar 2 are independently selected from an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar 1 And Ar 2 independently have a substituent R 1 or R 2 ;
  • Ar 3 and Ar 4 independently have an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar 3 and Ar 4 independently has a substituent R 3 or R 4 ;
  • R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, deuterium, a halogen atom or a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and 1 a linear alkenyl group of -20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a heteroaromatic group of 1 to 20 carbon atoms or a non-aromatic ring system of 1 to 20 carbon atoms.
  • a polymer in which at least one repeating unit comprises the above metal organic complex comprises the above metal organic complex.
  • a mixture comprising at least one organic functional material and the above metal organic or the above polymer;
  • the organic functional material is selected from the group consisting of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, and an empty Hole blocking material, illuminant, host material or doping material.
  • a composition comprising an organic solvent and the above metal organic or the above polymer or a mixture thereof.
  • An organic electronic device comprising the above metal organic complex or the above polymer or a mixture thereof.
  • compositions, printing inks, and inks have the same meaning and are interchangeable.
  • host materials, matrix materials, Host, and Matrix materials have the same meaning and are interchangeable.
  • metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • the structure of the metal organic complex of one embodiment is as shown in the general formula (1):
  • M is a metal atom and M is selected from gold or palladium
  • L is selected from the group consisting of two bridges
  • Ar 1 and Ar 2 are independently selected from an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar 1 And Ar 2 independently have a substituent R 1 or R 2 ;
  • Ar 3 and Ar 4 independently have an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar 3 and Ar 4 independently has a substituent R 3 or R 4 ;
  • R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, deuterium, a halogen atom or a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and 1 a linear alkenyl group of -20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a heteroaromatic group of 1 to 20 carbon atoms or a non-aromatic ring system of 1 to 20 carbon atoms.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 may be the same or different when they occur multiple times independently.
  • R 1 , R 2 , R 3 and R 4 independently may be the same or different when they occur multiple times.
  • R 1 , R 2 , R 3 and R 4 may be bonded at any position of the aromatic ring or the heteroaromatic ring.
  • the metal organic complex is used in an OLED, especially as a light-emitting layer doping material, which can provide higher device light-emitting properties and device lifetime.
  • the novel metal-organic complexes of this type contain coordination bonds to the center of four pairs of metal atoms, so that the entire complex has better chemical, optical, electrical, and thermal stability, and the four coordination bonds increase the entire
  • the rigidity of the complex can effectively improve the light-emitting properties of the complex material, which provides the possibility of improving the photoelectric performance and device stability of the related device.
  • mercury compounds are not required as precursors, thus making the synthesis process simpler and environmentally friendly.
  • changing the concentration of metal complexes in the matrix can achieve the best device performance, easy to achieve high efficiency, high brightness and high stability of OLED devices, providing better material options for full color display and lighting applications. .
  • M is selected from the group consisting of gold.
  • gold Au
  • Au is used as the central metal M of the above metal organic complex. This is because gold is chemically stable and has a significant heavy atomic effect that results in high luminous efficiency.
  • M the same or different is a bridge or a second bridge or a triple bridge or a quad bridge group, which is connected to Ar 1 or Ar 2 or Ar 3 or Ar 4 by a single bond or a double bond.
  • R is selected from an aromatic ring system having 5 to 15 carbon atoms or a heteroaromatic ring system having 4 to 15 carbon atoms.
  • R is selected from the group consisting of an aromatic ring system having 5 to 10 carbon atoms or a heteroaromatic ring system having 4 to 10 carbon atoms.
  • L is selected from the group consisting of a linear alkyl group having 0 to 5 carbon atoms, a branched alkyl group having 0 to 5 carbon atoms, a linear alkenyl group having 0 to 5 carbon atoms, and having A branched alkenyl group of 0 to 5 carbon atoms, an alkyl ether group having 0 to 5 carbon atoms.
  • L is selected from a linear alkyl group having 0 to 2 carbon atoms, a branched alkyl group having 0 to 2 carbon atoms, a linear alkenyl group having 0 to 2 carbon atoms, and having 0 to 2 A branched alkenyl group of a carbon atom, an alkyl ether group having 0 to 2 carbon atoms.
  • L is selected from any of the following groups:
  • R 18 -R 20 are independently selected from H, D, a halogen atom, CN, NO 2 , CF 3 , B(OR) 2 , Si(R) 3 , a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 1 to 20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether having 1 to 20 carbon atoms a group having an aromatic group of 1 to 20 carbon atoms, a heteroaromatic group having 1 to 20 carbon atoms or a non-aromatic ring system having 1 to 20 carbon atoms; the R is selected from the group consisting of hydrogen and hydrogen, a halogen atom,
  • L is selected from any of the following groups.
  • R 3 , R 4 , R 5 and R 6 are the same as defined for R 1 and R 2 described above; the dashed bond represents a bond to Ar 1 or Ar 2 .
  • L is selected from any of the following groups.
  • L is selected from any of the following groups.
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 is selected from the group consisting of a non-aromatic ring system having 5-20 ring atoms which are unsubstituted or substituted by R. It has a triplet energy level that can increase the metal complex, thereby facilitating the technical effect of obtaining a green or blue light emitter.
  • non-aromatic ring systems contain from 1 to 10 carbon atoms in the ring system and include not only saturated but also partially unsaturated cyclic systems which may be unsubstituted or single or multiple by the group R. Instead, the groups R may be the same or different in each occurrence.
  • the non-aromatic ring system contains from 1 to 3 carbon atoms in the ring system.
  • the non-aromatic ring system may also contain one or more heteroatoms.
  • the hetero atom may be selected from one or more of Si, N, P, O, S, and Ge.
  • the hetero atom is selected from one or more of Si, N, P, O, and S.
  • non-aromatic ring system contains from 1 to 6 carbon atoms in the ring system.
  • R is selected from the group consisting of: (1) a C1-C10 alkyl group, wherein the C1-C10 alkyl group may refer to the group: methyl, ethyl, n-propyl, isopropyl, cyclopropane.
  • n-butyl isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl , cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl , hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl (2)
  • C2-C10 aryl or heteroaryl which may be monovalent or divalent depending on the use, and in each case may also be the above-mentioned group, and R 10 may be substituted by any desired position of the aromatic or heteroaromatic group Connection.
  • the C2-C10 aryl or heteroaryl group is selected from the group consisting of benzene, naphthalene, anthracene, quinone, indoline, fluorene, fluorene, fluoranthene, butyl, pentane, benzene.
  • aromatic and heteroaromatic ring systems are considered to be especially in addition to the above-mentioned aryl and heteroaryl groups, but also to biphenylene, benzene terphenyl, anthracene, spirobifluorene, dihydrogen. Phenanthrene, tetrahydroanthracene and cis or trans fluorene.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from an aromatic group having 5 to 20 ring atoms or a heteroaromatic group having 5 to 20 ring atoms. In one embodiment, Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from an aromatic group having 5 to 18 ring atoms or a heteroaromatic group having 5 to 18 ring atoms. In one embodiment, Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from an aromatic group having 5 to 12 ring atoms or a heteroaromatic group having 5 to 12 ring atoms. In one embodiment, at least one of Ar 1 , Ar 2 , Ar 3 and Ar 4 is selected from heteroaromatic groups containing one ring heteroatom N. Further, at least two of Ar 1 , Ar 2 , Ar 3 and Ar 4 are selected from heteroaromatic groups containing one ring hetero atom N.
  • An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • a heteroaromatic group refers to a hydrocarbon group (containing a hetero atom) comprising at least one heteroaromatic ring, including a monocyclic group and a polycyclic ring system.
  • These multi-ring rings can There are two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic.
  • aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units ( ⁇ 10%).
  • Non-H atoms such as C, N or O atoms.
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.
  • a plurality of aryl or heteroaryl groups may also be interrupted by short non-aromatic units (less than 5% non-H atoms).
  • the aromatic group may be selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene or derivatives thereof.
  • heteroaromatic group may include furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, Carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine , pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone or derivatives thereof.
  • Ar 1 -Ar 4 are independently selected from any of the following groups:
  • a 1 -A 8 are independently selected from CR 3 or N;
  • R 3 , R 4 , R 5 are independently selected from H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, and sulfur having 1 to 20 C atoms.
  • Ar 1 -Ar 4 are independently selected from any of the following groups. Among them, H on the ring can be arbitrarily substituted.
  • Ar 1 and Ar 2 are independently selected from any of the following groups:
  • P represents a bond to any position of Ar 3 or Ar 4 ;
  • X 1 -X 18 independently contains at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom;
  • R 5 -R 7 are independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Heteroaromatic group or a non-aromatic ring system having 1-20 carbon atoms;
  • Y is selected from the group consisting of two bridged groups.
  • R is the same or different and is selected from the group consisting of hydrogen, deuterium, a halogen atom, hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and a linear alkenyl group of 1 to 20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, A heteroaromatic group having 1 to 20 carbon atoms or a non-aromatic ring system having 1 to 20 carbon atoms.
  • Y is selected from a non-aromatic group selected from any of the groups recited above for L.
  • Ar 1 and Ar 2 are independently selected from any of the following groups:
  • R 8 - R 10 are independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbons. a linear alkenyl group of an atom, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 A heteroaromatic group of a carbon atom or a non-aromatic ring system having 1 to 20 carbon atoms.
  • Ar 3 and Ar 4 are independently selected from any of the following groups:
  • Q represents Ar 1 or Ar with any of the 2-position is bonded
  • X 19 -X 31 independently comprise at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom;
  • R 11 -R 13 are independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Heteroaromatic groups or non-aromatic ring systems having 1-20 carbon atoms.
  • Ar 3 and Ar 4 are independently selected from any of the following groups:
  • R 11 to R 13 are independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group of an atom, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 A heteroaromatic group of a carbon atom or a non-aromatic ring system having 1 to 20 carbon atoms.
  • the structure of the metal organic complex is as shown in the formula (I-1) or (I-18):
  • R 21 - R 31 are independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms.
  • a linear alkenyl group of an atom a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 a heteroaromatic group of a carbon atom or a non-aromatic ring system having 1 to 20 carbon atoms;
  • R 21 -R 31 may be bonded at any position of an aromatic group or a heteroaromatic group;
  • X 32 -X 38 independently Contains at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom.
  • At least one of X 32 -X 38 is selected from a nitrogen atom.
  • the metal organic complex according to the invention is a luminescent material having an emission wavelength between 300 and 1000 nm. Further, the metal organic complex has an emission wavelength of between 350 and 900 nm. In one embodiment, the metal organic complex has an emission wavelength between 400 and 800 nm.
  • the luminescence referred to herein means photoluminescence or electroluminescence. In one embodiment, the photoluminescence efficiency of the metal organic complex is > 30%. In one embodiment, the photoluminescence efficiency of the metal organic complex is > 40%. In one of the embodiments, the photoluminescence efficiency of the metal organic complex is ⁇ 50%. In one embodiment, the photoluminescence efficiency of the metal organic complex is > 60%.
  • the metal organic complex according to the invention may also be a non-luminescent material.
  • the polymer of one embodiment wherein at least one of the repeating units comprises the above metal organic complex.
  • the polymer is a non-conjugated high polymer in which the structural unit represented by the formula (1) is on the side chain.
  • the polymer is a conjugated polymer.
  • the mixture of an embodiment comprises at least one organic functional material and the above metal organic complex.
  • Organic functional materials are selected from the group consisting of holes (also known as holes) injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injecting or transporting materials (EIM/ETM), electron blocking materials (EBM), organic Host material, singlet emitter (fluorescent emitter), heavy emitter (phosphorescent emitter) or organic thermal excitation delayed fluorescent material (TADF material).
  • the organic thermal excitation delayed fluorescent material may be a light emitting organic metal complex.
  • Various organic functional materials are described in detail in, for example, WO 2010135519 A1, US 2009 0 134 784 A1, and WO 2011110277 A1, the entire contents of each of which are hereby incorporated by reference.
  • the organic functional material may be a small molecule or a high polymer material.
  • small molecule refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules.
  • the molecular weight of the small molecule is ⁇ 3000 g/mol. Further, the molecular weight of the small molecule is ⁇ 2000 g/mol. Further, the molecular weight of the small molecule is ⁇ 1500 g/mol.
  • the high polymer that is, the polymer, contains a homopolymer, a copolymer, and a block copolymer. Further, in the present invention, the high polymer also contains a dendrimer.
  • a dendrimer For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].
  • a conjugated polymer is a high polymer whose backbone is mainly composed of sp2 hybrid orbitals of C atoms. Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene).
  • the C atom in the main chain can also be substituted by other non-C atoms, and is still considered to be a conjugated polymer when the sp 2 hybrid on the main chain is interrupted by some natural defects.
  • the conjugated high polymer further comprises an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.
  • the metal organic complex is present in an amount of from 0.01 to 30% by weight. In one embodiment, the metal organic complex is present in an amount of from 0.1 to 20% by weight. In one embodiment, the metal organic complex is present in an amount of 0.2. Up to 20% by weight. In one embodiment, the metal organic complex is present in an amount from 2 to 15% by weight.
  • the mixture comprises the above metal organic complex and a triplet matrix material.
  • the metal organic complex is used as a guest (phosphorescent emitter), and the weight percentage of the metal organic complex is ⁇ 30% by weight. In one embodiment, the weight percent of the metal organic complex is ⁇ 20 wt%. Further, the weight percentage of the metal organic complex is ⁇ 15% by weight.
  • the mixture comprises the above metal organic complex, one triplet matrix material, and another triplet emitter.
  • the mixture comprises the above metal organic complex and a thermally activated delayed fluorescent luminescent material (TADF).
  • TADF thermally activated delayed fluorescent luminescent material
  • Triplet Host Material (Triplet Host):
  • the example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant.
  • metal complexes that can be used as the triplet host include, but are not limited to, the following general structure:
  • M is a metal
  • (Y 3 -Y 4 ) is a two-dentate ligand, Y 3 and Y 4 are independently selected from C, N, O, P or S
  • L is an ancillary ligand
  • m is an integer, The value is from 1 to the maximum coordination number of this metal; m+n is the maximum coordination number of this metal.
  • the metal complex that can be used as the triplet host has the following form:
  • (O-N) is a two-dentate ligand in which the metal is coordinated to the O and N atoms.
  • M is selected from the group consisting of Ir or Pt.
  • Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, fluorene; or a compound containing an aromatic heterocyclic group such as dibenzothiophene.
  • a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, fluorene
  • a compound containing an aromatic heterocyclic group such as dibenzothiophene.
  • the triplet host material is selected from the group consisting of at least one of the following groups:
  • R 1 -R 7 are independently selected from hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl, when they are aryl or heteroaryl When they are the same as Ar 1 and Ar 2 described above; n is selected from 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 , 14, 15, 16 , 17, 18, 19 or 20; X1-X8 is selected from CH or N, and X 9 is selected from CR 1 R 2 or NR 1 .
  • Triplet emitters are also known as phosphorescent materials.
  • the triplet emitter is a metal complex of the formula M 2 (L)n.
  • M 2 is a metal atom; each occurrence of L may be the same or different, and is an organic ligand which is bonded to the metal atom M by one or more position bonding or coordination; n is a value greater than 1.
  • the metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.
  • the metal atom M 2 is selected from the group consisting of transition metal elements or lanthanides or actinides. In one embodiment, M is selected from the group consisting of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu, or Ag. In one embodiment, M is selected from the group consisting of Os, Ir, Ru, Rh, Re, Pd, or Pt.
  • the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites. In one embodiment, the triplet emitter comprises two or three identical or different bidentate or multidentate ligands. Chelating ligands are beneficial for increasing the stability of metal complexes.
  • organic ligand examples include a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative or a 2-phenylquinoline.
  • a morphine derivative All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may be selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from the group consisting of transition metal elements, lanthanides or actinides.
  • Ar 1 is a cyclic group which may be the same or different at each occurrence, and Ar 1 contains at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group and a metal Coordination linkage;
  • Ar 2 is a cyclic group, which may be the same or different at each occurrence, Ar 2 contains at least one C atom through which a cyclic group is bonded to the metal;
  • Ar 1 and Ar 2 are covalently
  • the linkages are linked together and may each carry one or more substituent groups, which may also be joined together by a substituent group;
  • L may be the same or different at each occurrence, and L is an auxiliary ligand, preferably a double-sided chelate
  • the ligand preferably a monoanionic bidentate chelate ligand;
  • m is selected from 1, 2 or 3;
  • n is selected from 0, 1 or 2.
  • L is a bidentate chelate ligand. In one embodiment, L is a monoanionic bidentate chelate ligand. In one of the embodiments, m is 2 or 3. In one of the embodiments, m is 3. In one of the embodiments, n is 0 or 1. In one of the embodiments, n is zero.
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • TADF materials need to have a small singlet-triplet energy level difference.
  • the TADF material has a relatively small ⁇ Est.
  • TADF has better fluorescence quantum efficiency.
  • TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem.
  • TADF luminescent materials Some examples of suitable TADF luminescent materials are listed in the table below.
  • the metal organic complex is used in an evaporated OLED device.
  • the molecular weight of the metal organic complex is ⁇ 1000 g/mol.
  • the metal organic complex has a molecular weight of ⁇ 900 g/mol.
  • the metal organic complex has a molecular weight of ⁇ 850 g/mol.
  • the metal organic complex has a molecular weight of ⁇ 800 g/mol.
  • the metal organic complex has a molecular weight of ⁇ 700 g/mol.
  • the metal organic complex is used in a printed OLED.
  • the molecular weight of the metal organic complex is ⁇ 700 g/mol.
  • the metal organic complex has a molecular weight of ⁇ 800 g/mol.
  • the metal organic complex has a molecular weight of > 900 g/mol.
  • the metal organic complex has a molecular weight of > 1000 g/mol.
  • the metal organic complex has a molecular weight of > 1100 g/mol.
  • the above metal organic complex has a solubility in toluene of > 5 mg/ml at 25 °C. In one of the examples, the solubility in toluene is > 8 mg/ml. In one of the examples, the solubility in toluene is > 10 mg/ml.
  • the mixture of another embodiment includes the above-mentioned polymer, and the various components and contents of the mixture are as described in the mixture of the above embodiment, and will not be described herein.
  • the composition of an embodiment comprises an organic solvent and the above metal organic complex or polymer or mixture.
  • the composition is an ink.
  • the viscosity and surface tension of the ink are important parameters when the composition is used in a printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.
  • the present invention provides a film prepared from a solution comprising a metal organic complex or polymer according to the present invention.
  • the ink has a surface tension at an operating temperature or at 25 ° C in the range of 19 dyne/cm to 50 dyne/cm. In one of the embodiments, the ink has a surface tension at an operating temperature or at 25 ° C in the range of 22 dyne/cm to 35 dyne/cm. In one of the embodiments, the ink has a surface tension at an operating temperature or at 25 ° C in the range of 25 dyne/cm to 33 dyne/cm.
  • the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 1 cps to 100 cps. In one of the embodiments, the viscosity of the ink at the operating temperature or 25 ° C is in the range of 1 cps to 50 cps, in one of the examples, the viscosity of the ink at the operating temperature or 25 ° C. In one of the embodiments, the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 1.5 cps to 20 cps. In one of the embodiments, the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 4.0 cps to 20 cps. This makes the composition more convenient for ink jet printing.
  • the viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink.
  • An ink containing a metal organic complex or a polymer facilitates the adjustment of the printing ink to an appropriate range in accordance with the printing method used.
  • the weight ratio of the organic functional material contained in the composition is from 0.3% to 30% by weight. In one embodiment, the composition The weight ratio of the organic functional material contained in the material is from 0.5% to 20% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 0.5% to 15% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 0.5% to 10% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 1% to 5% by weight.
  • the organic solvent comprises a first solvent selected from the group consisting of aromatic and/or heteroaromatic based solvents.
  • the first solvent may be an aliphatic chain/ring-substituted aromatic solvent, or an aromatic ketone solvent, or an aromatic ether solvent.
  • Examples of the first solvent are, but not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene.
  • the first solvent may also be selected from aliphatic ketones, for example, 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, 2,6,8 - trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol II Ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether and tetraethylene One or more of the glycerols.
  • aliphatic ketones for example, 2-nonanone, 3-fluorenone, 5-fluor
  • the organic solvent further includes a second solvent selected from the group consisting of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, Anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-benzene Oxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl One or more of a sulfoxide, tetrahydronaphthalene, decalin, and anthracene.
  • a second solvent selected from the group consisting of methanol, ethanol,
  • the composition can be a solution or suspension. This is determined based on the compatibility between the organic mixture and the organic solvent.
  • compositions as a coating or printing ink in the preparation of an organic electronic device are particularly preferred by a printing or coating preparation method.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing or slit-type extrusion coating. Preferred are gravure, inkjet and inkjet printing.
  • the composition may further include a component example, and the cap component is selected from one or more of a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobic agent, and a binder, thereby being used for adjusting viscosity. , film forming properties, improved adhesion and the like.
  • the above metal organic complex or polymer is used in an organic electronic device.
  • the organic electronic device may be selected from an Organic Light-Emitting Diode (OLED), an Organic Photovoltaic (OPV), an Organic Light Emitting Battery (OLEEC), an organic field effect transistor (OFET), and an organic organic device.
  • OLED Organic Light-Emitting Diode
  • OCV Organic Photovoltaic
  • OEEC Organic Light Emitting Battery
  • OFET organic field effect transistor
  • Luminescent field effect transistor organic laser, organic spintronic device, organic sensor or Organic Plasmon Emitting Diode.
  • the organic electronic device is an OLED.
  • the excessive metal complex is used for the light emitting layer of the OLED.
  • the organic electronic device of an embodiment comprises at least one of the above metal organic complexes or polymers or mixtures.
  • the organic electronic device may include a cathode, an anode, and a functional layer between the cathode and the anode, the functional layer comprising the above-mentioned excessive metal complex or the above polymer or the above mixture, or the functional layer is prepared from the above composition.
  • the organic electronic device comprises at least a cathode, an anode and a functional layer between the cathode and the anode, the functional layer comprising at least one of the above organic compounds or the above polymer or the above organic mixture, or the functional layer is prepared from the above composition Made.
  • the functional layer is selected from one or more of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a light emitting layer.
  • the organic electronic device may be selected from an Organic Light-Emitting Diode (OLED), an Organic Photovoltaic (OPV), an Organic Light Emitting Battery (OLEEC), an organic field effect transistor (OFET), and an organic organic device.
  • OLED Organic Light-Emitting Diode
  • OLED Organic Photovoltaic
  • OEEC Organic Light Emitting Battery
  • OFET organic field effect transistor
  • Luminescent field effect transistor organic laser, organic spintronic device, organic sensor or Organic Plasmon Emitting Diode.
  • the organic electronic device is an organic electroluminescent device such as an OLED.
  • the OLED includes a substrate, an anode, a light-emitting layer, and a cathode that are sequentially stacked.
  • the number of layers of the light-emitting layer is at least one layer.
  • the substrate can be opaque or transparent.
  • a transparent substrate can be used to make a transparent luminescent component, see Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can also be plastic, metal, semiconductor wafer or glass.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible, optionally in a polymeric film or plastic, having a glass transition temperature Tg of 150 ° C or higher.
  • the flexible substrate can be poly(ethylene terephthalate) (PET) or polyethylene glycol (2,6-naphthalene) (PEN).
  • the substrate has a glass transition temperature Tg of 200 ° C or higher. In one of the embodiments, the substrate has a glass transition temperature Tg of 250 ° C or higher. In one of the embodiments, the substrate has a glass transition temperature Tg of 300 ° C or higher.
  • the anode can include a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5eV.
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.3 eV.
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.2 eV.
  • anode material examples include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, and aluminum-doped zinc oxide (AZO).
  • the anode material can also be other materials.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned.
  • a patterned ITO conductive substrate is commercially available and can be used to prepare an organic electronic device according to the present embodiment.
  • the cathode can include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the work function of the cathode and the LUMO level or conductance of the illuminant in the luminescent layer or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL)
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the work function of the cathode and the difference in LUMO energy level or conduction band energy level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) in the light-emitting layer The absolute value is less than 0.3 eV.
  • the work function of the cathode and the difference in LUMO energy level or conduction band energy level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) in the light-emitting layer
  • the absolute value is less than 0.2 eV.
  • cathode material of the organic electronic device of the present embodiment.
  • cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, and electron beam (e-beam).
  • the OLED may further include other functional layers such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer. (HBL). Materials suitable for use in these functional layers are described above.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the light-emitting layer comprises a metal-organic complex or polymer according to the invention, which can be prepared by vacuum evaporation or solution processing.
  • the organic electroluminescent device light-emitting device has an emission wavelength between 300 and 1000 nm. In one of the embodiments, the organic electroluminescent device light-emitting device has an emission wavelength between 350 and 900 nm. In one of the embodiments, the organic electroluminescent device light-emitting device has an emission wavelength of between 400 and 800 nm.
  • the above-described organic electronic device is used in an electronic device.
  • the electronic device is selected from a display device, a lighting device, a light source or a sensor.
  • the organic electronic device may be an organic electroluminescent device.
  • An electronic device comprising the above organic electronic device.
  • the energy levels of the metal-organic complexes Au-1, Au-2, Au-3, Au-4 can be obtained by quantum calculations, such as by TD-DFT (time-dependent density functional theory) by Gaussian03W (Gaussian Inc.).
  • the simulation method can be found in WO2011141110. First, use the semi-empirical method "Ground State/Hartree-Fock/Default Spin/LanL2MB" (Charge 0/Spin Singlet) to optimize the molecular geometry. Then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method.
  • HOMO(eV) ((HOMO(Gaussian) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree. The results are shown in Table 1.
  • 6-Bromo-2-pyridinecarboxylic acid (17.5 g, 1 eq) and o-phenylenediamine (10.28 g, 1 eq) were placed in a 500 mL three-necked flask under nitrogen atmosphere, and then acetonitrile (300 mL) was added thereto. And a 37% aqueous solution of hydrogen chloride (30 mL, 3.5 eq), and then a 30% aqueous hydrogen peroxide solution (68 mL, 7 eq) was slowly added dropwise under ice bath (0 ° C) and stirred for 4 hours. It was then mixed with a large amount of water (1000 mL), and the solid was filtered to give a brown solid Intermediate B.
  • 1,3-dibromobenzene (15 g, 1 eq), Pd(PPh 3 ) 4 (1.46 g, 0.02 eq), and potassium carbonate (35 g, 4 eq) were placed in a nitrogen-filled atmosphere. Then, toluene (200 mL) and water (100 mL) were added as a solvent, and the mixture was heated to 120 ° C, and then a solution of bismuth borate (16 g, 0.8 eq) in toluene (150 mL) was added dropwise thereto, followed by stirring at 120 ° C for 24 hours. .
  • 2,6-dibromopyridine (15 g, 1 eq), Pd(PPh 3 ) 4 (1.46 g, 0.02 eq) and potassium carbonate (35 g, 4 eq) were placed in a 1000 mL three-necked flask in a nitrogen-filled atmosphere. Then, toluene (200 mL) and water (100 mL) were added as a solvent, and the mixture was heated to 120 ° C, and then a solution of bismuth borate (16 g, 0.8 eq) in toluene (150 mL) was added dropwise thereto, followed by stirring at 120 ° C for 24 hours. .
  • 6-Bromo-2-pyridinecarboxylic acid (17.5 g, 1 eq) and o-phenylenediamine (10.28 g, 1 eq) were placed in a 500 mL three-necked flask under nitrogen atmosphere, and then acetonitrile (300 mL) was added thereto. And a 37% aqueous solution of hydrogen chloride (30 mL, 3.5 eq), and then a 30% aqueous hydrogen peroxide solution (68 mL, 7 eq) was slowly added dropwise under ice bath (0 ° C) and stirred for 4 hours. It was then mixed with a large amount of water (1000 mL), and the solid was filtered to give a brown solid intermediate J, yield 67%.
  • 2,6-dibromopyridine (15 g, 1 eq), Pd(PPh 3 ) 4 (1.46 g, 0.02 eq) and potassium carbonate (35 g, 4 eq) were placed in a 1000 mL three-necked flask in a nitrogen-filled atmosphere. Then, toluene (200 mL) and water (100 mL) were added as a solvent, and the mixture was heated to 120 ° C, and then a solution of bismuth borate (16 g, 0.8 eq) in toluene (150 mL) was added dropwise thereto, followed by stirring at 120 ° C for 24 hours. .
  • ITO/NPD 60 nm) / 15% Au-1: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode
  • the preparation steps of the OLED device are as follows:
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • HTL 60 nm
  • EML 45 nm
  • ETL 35 nm
  • hot evaporation in high vacuum (1 ⁇ 10 -6 mbar, mbar);
  • cathode LiF / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the current-voltage luminance (JVL) characteristics of OLED devices are characterized by characterization devices while recording important parameters such as efficiency and external quantum efficiency.
  • the maximum external quantum efficiency of the OLED device Au-1 was 5.4%.
  • the OLED device structure can be further optimized, such as the combined optimization of HTM, ETM and host materials, which will further improve device performance, especially efficiency, drive voltage and lifetime.

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Abstract

L'invention concerne un complexe organométallique et son utilisation, un mélange et un dispositif électronique organique. La structure du complexe organométallique est représentée par la formule générale (1), et les définitions des symboles dans la formule générale (I) sont les mêmes que dans la description.
PCT/CN2017/115984 2016-12-13 2017-12-13 Complexe organométallique et son utilisation, mélange et dispositif électronique organique Ceased WO2018108110A1 (fr)

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