WO2011136483A1 - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents

Novel compounds for organic electronic material and organic electroluminescent device using the same Download PDF

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WO2011136483A1
WO2011136483A1 PCT/KR2011/002525 KR2011002525W WO2011136483A1 WO 2011136483 A1 WO2011136483 A1 WO 2011136483A1 KR 2011002525 W KR2011002525 W KR 2011002525W WO 2011136483 A1 WO2011136483 A1 WO 2011136483A1
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alkyl
aryl
heteroaryl
organic
cycloalkyl
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Seok-Keun Yoon
Young Jun Cho
Hyuck Joo Kwon
Bong Ok Kim
Sung Min Kim
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/14—Ortho-condensed systems
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Definitions

  • the present invention relates to novel compounds for organic electronic materials and an organic electroluminescent device using the same.
  • electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices.
  • Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [ Appl. Phys. Lett. 51, 913, 1987].
  • an organic EL device when a charge is applied to an organic layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode), an electron and a hole are paired and exciton is generated. Light is emitted by using electroluminescence (phosphorescence or fluorescence) in a state that the exciton is inactivated.
  • the organic EL device emits polarization of light at voltage of about 10V and high brightness of about 100 ⁇ 10,000cd/m2.
  • the organic EL device has a feature in that light is emitted in a spectrum ranging from blue color to red color by simply selecting a fluorescent material.
  • the organic EL device is advantageous in that it can be formed on a flexible transparent substrate such as plastic, is operable with relatively low voltage (10 V or lower) as compared to plasma display panels or inorganic EL displays, consumes less power, and provides excellent color.
  • the electroluminescent material In an organic EL device, the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. Some requirements of the electroluminescent material include high electroluminescence quantum yield in solid state, high electron and hole mobility, resistance to decomposition during vacuum deposition, ability to form uniform film and stability.
  • Organic electroluminescent materials are generally classified into high-molecular materials and low-molecular materials.
  • the low-molecular materials include metal complexes and thoroughly organic electroluminescent materials which do not contain metal, from the aspect of molecular structure.
  • Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives and oxadiazole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained.
  • electroluminescent materials for red, green and blue
  • OLED organic light-emitting diode
  • the important issue is to develop red, green and blue electroluminescent materials with high efficiency and long life, in order to enhance the overall feature of the organic electroluminescent (EL) devices.
  • the EL materials are classified into host materials and dopant materials. It is generally known that a device structure having the most excellent EL properties can be fabricated with an EL layer prepared by doping a dopant to a host.
  • the desired properties for the host material are high purity and appropriate molecular weight to enable vapor-deposition in vacuo.
  • glass transition temperature and thermal decomposition temperature should be high enough to ensure thermal stability.
  • the host material should have high electrochemical stability for providing long life. It is to be easy to form an amorphous thin film, with high adhesiveness to other adjacent materials but without interlayer migration.
  • the organic EL device When the organic EL device is fabricated by doping technology, a ratio of energy transferred from host molecule to dopant in an excited state does not achieve 100% and a host material as well as dopant emits light. In particular, since the host material emits light in a range of wavelength having larger visibility than the dopant in case of a red light emitting device, color purity is deteriorated due to dull light emission of the host material. If the technology is actually applied, it is required to increase luminescence life and improve durability.
  • CBP is most widely known as a host material for a phosphorescent material.
  • High-efficiency OLEDs using a hole blocking layer comprising BCP, BAlq, etc. are reported.
  • High-performance OLEDs using BAlq derivatives as a host were reported by Pioneer (Japan) and others.
  • an object of the present invention is to provide compounds for organic electronic materials having luminescence efficiency and device operation life improved over existing materials and having superior backbone with appropriate color coordinates in order to solve the aforesaid problems.
  • Another object of the present invention is to provide a highly efficient organic electroluminescent device having long operation life by employing the compounds for organic electronic materials as an electroluminescent material.
  • compounds for organic electronic materials represented by Chemical Formula 1 and an organic electroluminescent device using the same.
  • the compounds for organic electronic materials according to the present invention may be used to manufacture an OLED device having very superior operation life.
  • L represents a single bond, (C6-C30)arylene or (C3-C30)heteroarylene;
  • R 1 represents (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C1-C30)alkoxy, (C1-C30)alkylthio, (C6-C30)aryloxy, (C6-C30)arylthio, -SiR 2 R 3 R 4 , -NR 5 R 6 , (C2-C30)alkenyl, (C2-C30)alkynyl, adamantyl, (C6-C30)aryl or (C3-C30)heteroaryl;
  • R 2 through R 6 independently represent (C1-C30)alkyl or (C6-C30)aryl;
  • Ar 1 through Ar 4 independently represent hydrogen, deuterium, (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl or (C3-C30)heteroaryl, and at least one of Ar 1 through Ar 4 is linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring, and -CH 2 - of the alkylene is substituted by -CR 11 R 12 -, -NR 13 -, -SiR 14 R 15 -, -O-, -S- or -Se-;
  • R 11 through R 15 independently represent (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C6-C30)aryl or (C3-C30)heteroaryl, or are linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
  • arylene and heteroarylene of the L alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R 1 , alkyl and aryl of R 2 through R 6 , alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of Ar 1 through Ar 4 , and alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R 11 through R 15 are further substituted by one or more selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl,
  • alkyl in the present invention, “alkyl”, “alkoxy” and other substituents containing “alkyl” moiety include both linear and branched species.
  • the "cycloalkyl” includes polycyclic hydrocarbon ring such as adamantyl with or without substituent(s) or (C7-C30)bicycloalkyl with or without substituent(s) as well as a monocyclic hydrocarbon ring.
  • aryl means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and may include a 4- to 7-membered, particularly 5- or 6-membered, single ring or fused ring, including a plurality of aryl groups having single bond(s) therebetween.
  • Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., but are not limited thereto.
  • the naphthyl includes 1-naphthyl and 2-naphthyl.
  • the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
  • the heteroaryl also includes heteroaryl groups having single bond(s) therebetween.
  • the heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt.
  • Specific examples include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothi
  • the “(C1-C30)alkyl” groups described herein may include (C1-C20)alkyl or (C1-C10)alkyl and the "(C6-C30)aryl” groups include (C6-C20)aryl or (C6-C12)aryl.
  • the "(C3-C30)heteroaryl” groups include (C3-C20)heteroaryl or (C3-C12)heteroaryl and the "(C3-C30)cycloalkyl” groups include (C3-C20)cycloalkyl or (C3-C7)cycloalkyl.
  • the "(C2-C30)alkenyl or alkynyl” group include (C2-C20)alkenyl or alkynyl, (C2-C10)alkenyl or alkynyl.
  • the compounds for organic electronic materials according to the present invention may be represented by Chemical Formula 2 or 3:
  • L represents a single bond, (C6-C30)arylene or (C3-C30)heteroarylene;
  • R 1 represents (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C6-C30)arylthio, -SiR 2 R 3 R 4 , -NR 5 R 6 , (C2-C30)alkenyl, (C2-C30)alkynyl, adamantyl, (C6-C30)aryl or (C3-C30)heteroaryl;
  • R 2 through R 6 independently represent (C1-C30)alkyl or (C6-C30)aryl;
  • Ar 3 , Ar 4 and R 21 and R 22 independently represent hydrogen, deuterium, (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl or (C3-C30)heteroaryl;
  • X and Y independently represent -CR 11 R 12 -, -NR 13 -, -SiR 14 R 15 -, -O-, -S- or -Se-;
  • R 11 through R 15 are the same as defined in Chemical Formula 1;
  • arylene and heteroarylene of the L cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R 1 , alkyl and aryl of R 2 through R 6 , and alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of Ar 3 through Ar 4 may be further substituted by one or more selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (
  • the may be selected from the following structures but is not limited thereto.
  • the may be selected from the following structures but is not limited thereto.
  • the compounds for organic electronic materials according to the present invention may be exemplified by the following compounds but are not limited thereto.
  • the compounds for organic electronic materials according to the present invention may be prepared as represented by following Scheme 1.
  • X 1 through X 3 represnet halogen; L, R 1 and Ar 1 through Ar 4 are the same as defined in Chemical Formula 1.
  • an organic electroluminescent device which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more compound(s) for organic electronic material represented by Chemical Formula 1.
  • the organic layer comprises an electroluminescent layer, in which the compounds for organic electronic material of Chemical Formula 1 are used as a host material.
  • the phosphorescent dopant used in the organic electroluminescent device of the present invention is not particularly limited, but may be selected from the compounds represented by Chemical Formula 4:
  • M 1 is a metal selected from the group consisting of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 15 and Group 16 metals, and ligands L 101 , L 102 and L 103 are independently selected from the structures:
  • R 201 through R 203 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl with or without (C1-C30)alkyl substituent(s) or halogen;
  • R 204 through R 219 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C1-C30)alkoxy with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C2-C30)alkenyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), mono- or di(C1-C30)alkylamino with or without substituent(s), mono- or di(C6-C30)arylamino with or without substituent(s), SF 5 , tri(C1-C30)alkylsilyl with or without substituent(s), di(C1-C30)alkyl(C6-C30)arylsilyl with or without substituent(s), tri(C6-C30)arylsilyl with or without substituent(s), cyano or halogen;
  • R 220 through R 223 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s) or (C6-C30)aryl with or without (C1-C30)alkyl substituent(s);
  • R 224 and R 225 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen, or R 224 and R 225 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
  • R 226 represents (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), (C5-C30)heteroaryl with or without substituent(s) or halogen;
  • R 227 through R 229 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen;
  • R 231 through R 242 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s), (C1-C30)alkoxy, halogen, (C6-C30)aryl with or without substituent(s), cyano or (C5-C30)cycloalkyl with or without substituent(s), or each of them may be linked to an adjacent substituent via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked to R 207 or R 208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
  • the phosphorescent dopant compound of Chemical Formula 4 may be exemplified as the compound having following structures but are not limited thereto:
  • the organic layer may further include, in addition to the compound for organic electric material represented by Chemical Formula 1, one or more compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds, at the same time.
  • the arylamine compounds or styrylarylamine compounds are exemplified in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
  • the organic layer may further include, in addition to the compounds for organic electronic materials represented by Chemical Formula 1, one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s).
  • the organic layer may include an electroluminescent layer and a charge generating layer.
  • the organic layer may include, in addition to the compound for organic electric material of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device.
  • the compounds emitting blue, green or red light may be exemplified by the compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
  • a layer (hereinafter referred to as "surface layer" selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom.
  • the metal halide may be, for example, LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.
  • the metal oxide may be, for example, Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • the organic electroluminescent device it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant.
  • a mixed region of an electron transport compound and a reductive dopant or a mixed region of a hole transport compound and an oxidative dopant.
  • the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated.
  • the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated.
  • Preferable oxidative dopants include various Lewis acids and acceptor compounds.
  • Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. Further, a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.
  • the compounds for organic electronic material according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.
  • the present invention is further described with respect to the compounds for organic electronic materials according to the present invention, processes for preparing the same, and luminescence properties of devices employing the same.
  • the following examples are provided for illustrative purposes only and they are not intended to limit the scope of the present invention.
  • 2,4-dichloropyrimidine (10 g, 67.1 mmol) and phenylboronic acid (8.18 g, 67.1 mmol) were dissolved in a mixture solvent of toluene (200 mL), ethanol (50 mL) and distilled water (50 mL).
  • Pd(PPh 3 ) 4 (3.88 g, 3.36 mmol) and Na 2 CO 3 (21.34 g, 201.3 mmol) were added thereto.
  • the mixture solution was stirred at 120 °C for 4 hours and cooled to room temperature.
  • An OLED device was manufactured using the compound for organic electronic materials according to the present invention.
  • a transparent electrode ITO thin film (15 ⁇ / ⁇ ) obtained from a glass for OLED (produced by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use.
  • an ITO substrate was equipped in a substrate folder of a vacuum vapor deposition apparatus, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum vapor deposition apparatus, which was then ventilated up to 10 -6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate 2-TNATA, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • 2-TNATA 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine
  • N , N '-bis( ⁇ -naphthyl)- N , N '-diphenyl-4,4'-diamine (NPB) was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • the compound (e.g. Compound 1) purified by vacuum sublimation at 10 -6 torr was placed in a cell of a vacuum vapor deposition apparatus as a host, and an electroluminescent dopant (e.g., (piq) 2 Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate]) was placed in another cell as a dopant.
  • the two materials were evaporated at different rates such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer through doping at 4 to 20 wt%.
  • An OLED device was manufactured as in Example 1 except that 4,4 -bis(carbazol-9-yl)biphenyl (CBP) instead of the compounds according to the present invention was used as a host material at one cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III) (BAlq) was used as a hole blocking layer.
  • CBP 4,4 -bis(carbazol-9-yl)biphenyl
  • BAlq Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III)
  • the driving voltage and the luminous efficiencies of the OLED comprising the compound for organic electronic materials according to the present invention in the Examples 1-6 or the conventional electroluminescent compound in Comparative Example 1 were measured at 1,000 cd/m 2 , respectively, and the results are shown in Table 2.
  • the compounds for organic electronic material developed in the present invention as a red light-emitting material showed the same or superior luminous property than that of the convention electroluminescent material.
  • the device using the compounds for organic electronic material of the present invention as a host material shows the excellent luminous property, reduces driving voltage and consumes less power due to improved power efficiency without using the hole blocking layer in the conventional device structure.
  • the compounds for organic electronic material according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.

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Abstract

Provided are novel compounds for organic electronic material and an organic electrolu¬ minescent device using the same. The compound for organic electronic material is used as a host material of the organic electroluminescent material in an OLED device. Since the compound for organic electronic material exhibits good luminous efficiency in red color and excellent life property, it may be used to manufacture OLED devices having very superior operation life.

Description

NOVEL COMPOUNDS FOR ORGANIC ELECTRONIC MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel compounds for organic electronic materials and an organic electroluminescent device using the same.
Among display devices, electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices. In 1987, Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [Appl. Phys. Lett. 51, 913, 1987].
In an organic EL device, when a charge is applied to an organic layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode), an electron and a hole are paired and exciton is generated. Light is emitted by using electroluminescence (phosphorescence or fluorescence) in a state that the exciton is inactivated. The organic EL device emits polarization of light at voltage of about 10V and high brightness of about 100∼10,000cd/㎡. The organic EL device has a feature in that light is emitted in a spectrum ranging from blue color to red color by simply selecting a fluorescent material. The organic EL device is advantageous in that it can be formed on a flexible transparent substrate such as plastic, is operable with relatively low voltage (10 V or lower) as compared to plasma display panels or inorganic EL displays, consumes less power, and provides excellent color.
In an organic EL device, the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. Some requirements of the electroluminescent material include high electroluminescence quantum yield in solid state, high electron and hole mobility, resistance to decomposition during vacuum deposition, ability to form uniform film and stability.
Organic electroluminescent materials are generally classified into high-molecular materials and low-molecular materials. The low-molecular materials include metal complexes and thoroughly organic electroluminescent materials which do not contain metal, from the aspect of molecular structure. Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives and oxadiazole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained.
Three electroluminescent materials (for red, green and blue) are employed to realize a full-colored organic light-emitting diode (OLED) display. The important issue is to develop red, green and blue electroluminescent materials with high efficiency and long life, in order to enhance the overall feature of the organic electroluminescent (EL) devices. From the aspect of function, the EL materials are classified into host materials and dopant materials. It is generally known that a device structure having the most excellent EL properties can be fabricated with an EL layer prepared by doping a dopant to a host. Recently, development of organic EL devices with high efficiency and long life comes to the fore as an urgent subject, and particularly urgent is development of a material with far better EL properties as compared to conventional EL materials as considering EL properties required for a medium to large sized OLED panel.
From this point of view, development of a host material is one of the most important issues to be settled. The desired properties for the host material (serving as a solvent and energy conveyer in solid state) are high purity and appropriate molecular weight to enable vapor-deposition in vacuo. In addition, glass transition temperature and thermal decomposition temperature should be high enough to ensure thermal stability. Further, the host material should have high electrochemical stability for providing long life. It is to be easy to form an amorphous thin film, with high adhesiveness to other adjacent materials but without interlayer migration.
When the organic EL device is fabricated by doping technology, a ratio of energy transferred from host molecule to dopant in an excited state does not achieve 100% and a host material as well as dopant emits light. In particular, since the host material emits light in a range of wavelength having larger visibility than the dopant in case of a red light emitting device, color purity is deteriorated due to dull light emission of the host material. If the technology is actually applied, it is required to increase luminescence life and improve durability.
At present, CBP is most widely known as a host material for a phosphorescent material. High-efficiency OLEDs using a hole blocking layer comprising BCP, BAlq, etc. are reported. High-performance OLEDs using BAlq derivatives as a host were reported by Pioneer (Japan) and others.
Figure PCTKR2011002525-appb-I000001
Although these materials provide good electroluminescence characteristics, they are disadvantageous in that degradation may occur during the high-temperature deposition process in vacuum because of low glass transition temperature and poor thermal stability. Since the power efficiency of an OLED is given by (π / voltage) × current efficiency, the power efficiency is inversely proportional to the voltage. High power efficiency is required to reduce the power consumption of an OLED. Actually, OLEDs using phosphorescent materials provide much better current efficiency (cd/A) than those using fluorescent materials. However, when the existing materials such as BAlq, CBP, etc. are used as a host of the phosphorescent material, there is no significant advantage in power efficiency (lm/W) over the OLEDs using fluorescent materials because of high driving voltage. Further, the OLED devices do not have satisfactory operation life. Therefore, development of more stable, higher-performance host materials is required.
Accordingly, an object of the present invention is to provide compounds for organic electronic materials having luminescence efficiency and device operation life improved over existing materials and having superior backbone with appropriate color coordinates in order to solve the aforesaid problems. Another object of the present invention is to provide a highly efficient organic electroluminescent device having long operation life by employing the compounds for organic electronic materials as an electroluminescent material.
Provided are compounds for organic electronic materials represented by Chemical Formula 1 and an organic electroluminescent device using the same. With superior luminescence efficiency and excellent life property, the compounds for organic electronic materials according to the present invention may be used to manufacture an OLED device having very superior operation life.
[Chemical Formula 1]
Figure PCTKR2011002525-appb-I000002
wherein
L represents a single bond, (C6-C30)arylene or (C3-C30)heteroarylene;
R1 represents (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C1-C30)alkoxy, (C1-C30)alkylthio, (C6-C30)aryloxy, (C6-C30)arylthio, -SiR2R3R4, -NR5R6, (C2-C30)alkenyl, (C2-C30)alkynyl, adamantyl, (C6-C30)aryl or (C3-C30)heteroaryl;
R2 through R6 independently represent (C1-C30)alkyl or (C6-C30)aryl;
Ar1 through Ar4 independently represent hydrogen, deuterium, (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl or (C3-C30)heteroaryl, and at least one of Ar1 through Ar4 is linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring, and -CH2- of the alkylene is substituted by -CR11R12-, -NR13-, -SiR14R15-, -O-, -S- or -Se-;
R11 through R15 independently represent (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C6-C30)aryl or (C3-C30)heteroaryl, or are linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
arylene and heteroarylene of the L, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R1, alkyl and aryl of R2 through R6, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of Ar1 through Ar4, and alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R11 through R15 are further substituted by one or more selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono or di(C1-C30)alkylamino, mono or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro and hydroxyl; and
the heterocycloalkyl and heteroaryl may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P.
In the present invention, "alkyl", "alkoxy" and other substituents containing "alkyl" moiety include both linear and branched species. In the present invention, the "cycloalkyl" includes polycyclic hydrocarbon ring such as adamantyl with or without substituent(s) or (C7-C30)bicycloalkyl with or without substituent(s) as well as a monocyclic hydrocarbon ring.
In the present invention, "aryl" means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and may include a 4- to 7-membered, particularly 5- or 6-membered, single ring or fused ring, including a plurality of aryl groups having single bond(s) therebetween. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., but are not limited thereto. The naphthyl includes 1-naphthyl and 2-naphthyl. The anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. In the present invention, "heteroaryl" means an aryl group containing 1 to 4 heteroatom(s) selected from B, N, O, S, P(=O), Si and P as aromatic ring backbone atom(s), other remaining aromatic ring backbone atoms being carbon. It may be 5- or 6-membered monocyclic heteroaryl or polycyclic heteroaryl resulting from condensation with a benzene ring, and may be partially saturated. The heteroaryl also includes heteroaryl groups having single bond(s) therebetween.
The heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt. Specific examples include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, etc., an N-oxide thereof (e.g., pyridyl N-oxide, quinolyl N-oxide, etc.), a quaternary salt thereof, etc., but are not limited thereto.
The "(C1-C30)alkyl" groups described herein may include (C1-C20)alkyl or (C1-C10)alkyl and the "(C6-C30)aryl" groups include (C6-C20)aryl or (C6-C12)aryl. The "(C3-C30)heteroaryl" groups include (C3-C20)heteroaryl or (C3-C12)heteroaryl and the "(C3-C30)cycloalkyl" groups include (C3-C20)cycloalkyl or (C3-C7)cycloalkyl. The "(C2-C30)alkenyl or alkynyl" group include (C2-C20)alkenyl or alkynyl, (C2-C10)alkenyl or alkynyl.
The compounds for organic electronic materials according to the present invention may be represented by Chemical Formula 2 or 3:
[Chemical Formula 2]
Figure PCTKR2011002525-appb-I000003
[Chemical Formula 3]
Figure PCTKR2011002525-appb-I000004
wherein
L represents a single bond, (C6-C30)arylene or (C3-C30)heteroarylene;
R1 represents (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C6-C30)arylthio, -SiR2R3R4, -NR5R6, (C2-C30)alkenyl, (C2-C30)alkynyl, adamantyl, (C6-C30)aryl or (C3-C30)heteroaryl;
R2 through R6 independently represent (C1-C30)alkyl or (C6-C30)aryl;
Ar3, Ar4 and R21 and R22 independently represent hydrogen, deuterium, (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl or (C3-C30)heteroaryl;
X and Y independently represent -CR11R12-, -NR13-, -SiR14R15-, -O-, -S- or -Se-;
R11 through R15 are the same as defined in Chemical Formula 1; and
arylene and heteroarylene of the L, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R1, alkyl and aryl of R2 through R6, and alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of Ar3 through Ar4 may be further substituted by one or more selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono or di(C1-C30)alkylamino, mono or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro or hydroxyl.
More specifically, the
Figure PCTKR2011002525-appb-I000005
may be selected from the following structures but is not limited thereto.
Figure PCTKR2011002525-appb-I000006
Figure PCTKR2011002525-appb-I000007
Figure PCTKR2011002525-appb-I000008
Figure PCTKR2011002525-appb-I000009
Figure PCTKR2011002525-appb-I000010
Also, the
Figure PCTKR2011002525-appb-I000011
may be selected from the following structures but is not limited thereto.
Figure PCTKR2011002525-appb-I000012
More specifically, the compounds for organic electronic materials according to the present invention may be exemplified by the following compounds but are not limited thereto.
Figure PCTKR2011002525-appb-I000013
Figure PCTKR2011002525-appb-I000014
Figure PCTKR2011002525-appb-I000015
Figure PCTKR2011002525-appb-I000016
Figure PCTKR2011002525-appb-I000017
Figure PCTKR2011002525-appb-I000018
Figure PCTKR2011002525-appb-I000019
Figure PCTKR2011002525-appb-I000020
Figure PCTKR2011002525-appb-I000021
The compounds for organic electronic materials according to the present invention may be prepared as represented by following Scheme 1.
[Scheme 1]
Figure PCTKR2011002525-appb-I000022
wherein
X1 through X3 represnet halogen; L, R1 and Ar1 through Ar4 are the same as defined in Chemical Formula 1.
Provided is an organic electroluminescent device, which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more compound(s) for organic electronic material represented by Chemical Formula 1. The organic layer comprises an electroluminescent layer, in which the compounds for organic electronic material of Chemical Formula 1 are used as a host material.
When the compounds for organic electronic material of Chemical Formula 1 are used as a host, one or more phosphorescent dopant(s) is included. The phosphorescent dopant used in the organic electroluminescent device of the present invention is not particularly limited, but may be selected from the compounds represented by Chemical Formula 4:
[Chemical Formula 4]
M1L101L102L103
M1 is a metal selected from the group consisting of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 15 and Group 16 metals, and ligands L101, L102 and L103 are independently selected from the structures:
Figure PCTKR2011002525-appb-I000023
Figure PCTKR2011002525-appb-I000024
Figure PCTKR2011002525-appb-I000025
Figure PCTKR2011002525-appb-I000026
wherein
R201 through R203 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl with or without (C1-C30)alkyl substituent(s) or halogen;
R204 through R219 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C1-C30)alkoxy with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C2-C30)alkenyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), mono- or di(C1-C30)alkylamino with or without substituent(s), mono- or di(C6-C30)arylamino with or without substituent(s), SF5, tri(C1-C30)alkylsilyl with or without substituent(s), di(C1-C30)alkyl(C6-C30)arylsilyl with or without substituent(s), tri(C6-C30)arylsilyl with or without substituent(s), cyano or halogen;
R220 through R223 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s) or (C6-C30)aryl with or without (C1-C30)alkyl substituent(s);
R224 and R225 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen, or R224 and R225 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
R226 represents (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), (C5-C30)heteroaryl with or without substituent(s) or halogen;
R227 through R229 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen; and
Q represents
Figure PCTKR2011002525-appb-I000027
,
Figure PCTKR2011002525-appb-I000028
or
Figure PCTKR2011002525-appb-I000029
, wherein R231 through R242 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s), (C1-C30)alkoxy, halogen, (C6-C30)aryl with or without substituent(s), cyano or (C5-C30)cycloalkyl with or without substituent(s), or each of them may be linked to an adjacent substituent via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked to R207 or R208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
The phosphorescent dopant compound of Chemical Formula 4 may be exemplified as the compound having following structures but are not limited thereto:
Figure PCTKR2011002525-appb-I000030
Figure PCTKR2011002525-appb-I000031
Figure PCTKR2011002525-appb-I000032
Figure PCTKR2011002525-appb-I000033
Figure PCTKR2011002525-appb-I000034
Figure PCTKR2011002525-appb-I000035
Figure PCTKR2011002525-appb-I000036
In the organic electronic device of the present invention, the organic layer may further include, in addition to the compound for organic electric material represented by Chemical Formula 1, one or more compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds, at the same time. The arylamine compounds or styrylarylamine compounds are exemplified in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
Further, in the organic electroluminescent device of the present invention, the organic layer may further include, in addition to the compounds for organic electronic materials represented by Chemical Formula 1, one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s). The organic layer may include an electroluminescent layer and a charge generating layer.
Further, the organic layer may include, in addition to the compound for organic electric material of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device. The compounds emitting blue, green or red light may be exemplified by the compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
In the organic electroluminescent device of the present invention, a layer (hereinafter referred to as "surface layer" selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom.
The chalcogenide may be, for example, SiOx (1 = x = 2), AlOx (1 = x = 1.5), SiON, SiAlON, etc. The metal halide may be, for example, LiF, MgF2, CaF2, a rare earth metal fluoride, etc. The metal oxide may be, for example, Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant. In that case, since the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated. In addition, since the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated. Preferable oxidative dopants include various Lewis acids and acceptor compounds. Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. Further, a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.
Since the compounds for organic electronic material according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.
The present invention is further described with respect to the compounds for organic electronic materials according to the present invention, processes for preparing the same, and luminescence properties of devices employing the same. However, the following examples are provided for illustrative purposes only and they are not intended to limit the scope of the present invention.
[Preparation Example 1] Preparation of Compound 19
Figure PCTKR2011002525-appb-I000037
Preparation of Compound A
After isatine (20 g, 0.13 mol) and indole (17.5 g, 0.143 mol) were dissolved in ethanol (200 mL), diethylamine (1.4 mL, 0.013 mol) was added thereto. After stirring the reaction mixture for 2 hours at 45 ℃, the mixture was cooled to room temperature and filtered. A filtered solid was washed with distilled water (50 mL) twice and washed again with methanol (10 mL) once. An obtained solid was dried in a vacuum to obtain Compound A (26 g, 76%).
Preparation of Compound B
After Compound A (26 g, 98.4 mmol) and NaBH4 (11.2 g, 295.2 mmol) were dissolved in dimethoxyethane (400 mL), a trifluoroborane diethylether complex diluted in dimethoxyethane (10 mL) was added at 0℃. The reaction mixture was slowly heated at 100℃ and stirred for 1 hour. After cooling a reactant to room temperature, the reaction was completed with 6N-hydrochloric acid solution (50 mL). After the mixture was extracted with ethylacetate (1 L), an obtained organic layer was washed with distilled water (200 mL). After drying the organic layer with anhydrous magnesium sulfate and removing an organic solvent under reduced pressure, Compound B (20 g, 80%) was obtained by purifying an obtained solid via column chromatography using silica gel.
Preparation of Compound C
Compound B (20 g, 86 mmol) was dissolved in toluene (400 mL). Then, bromobenzene (40.5 g, 258 mmol), Pd(OAc)2 (956 mg, 4.3 mmol), 50% solution P(t-Bu)3 (5.8 mL, 8.6 mmol) and t-BuONa (33.1 g, 344 mmol) were added thereto. The mixture was stirred for 5 hours at 120 ℃, and then cooled to room temperature. After completing the reaction by adding saturated ammonium chloride solution (100 mL) to the mixture, the reaction mixture was extracted with ethylacetate (1 L) and an organic layer was washed with distilled water (200 mL). After drying the organic layer with anhydrous magnesium sulfate and removing an organic solvent under reduced pressure, Compound C (20 g, 60%) was obtained by purifying an obtained solid via column chromatography using silica gel.
Preparation of Compound D
After Compound C (20 g, 52 mmol) and maleimide (10 g, 104 mmol) were dissolved in acetic acid (500 mL), the mixture was stirred for 5 days at 100 ℃. The mixture was cooled to room temperature and filtered. An obtained solid was washed with ethyl acetate (EA) (50 mL) and dried to obtain Compound D (9 g, 36%).
Preparation of Compound E
2,4-dichloropyrimidine (10 g, 67.1 mmol) and phenylboronic acid (8.18 g, 67.1 mmol) were dissolved in a mixture solvent of toluene (200 mL), ethanol (50 mL) and distilled water (50 mL). Pd(PPh3)4 (3.88 g, 3.36 mmol) and Na2CO3 (21.34 g, 201.3 mmol) were added thereto. The mixture solution was stirred at 120 ℃ for 4 hours and cooled to room temperature. After completing the reaction by adding saturated ammonium chloride solution (50 mL) to the mixture, the reaction mixture was extracted with EA (500 mL) and an obtained organic layer was washed with distilled water (100 mL). After drying an organic layer with anhydrous magnesium sulfate and removing an organic solvent under reduced pressure, Compound E (10 g, 78%) was obtained by purifying an obtained solid via column chromatography using silica gel.
Preparation of Compound 19
Compound D (9 g, 19 mmol) and Compound E (5.4 g, 28.5 mmol) were dissolved in toluene (150 mL). Then, Pd(OAc)2 (216 mg, 1 mmol), 50% solution P(t-Bu)3 (1.3 mL, 1.9 mmol) and t-BuONa (3.64 g, 38 mmol) were added thereto. The mixture was stirred at 120 ℃ for 20 hours and cooled to room temperature. After completing the reaction by adding saturated ammonium chloride solution (30 mL) to the mixture, the reaction mixture was extracted with ethyl acetate (300 mL) and an obtained organic layer was washed with distilled water (100 mL). After drying the organic layer with anhydrous magnesium sulfate and removing an organic solvent under reduced pressure, Compound 19 (4 g, 70%) was obtained by purifying an obtained solid via column chromatography using silica gel.
[Preparation Example 2] Preparation of Compound 23
Figure PCTKR2011002525-appb-I000038
Preparation of Compound F
Compound D (9 g, 19 mmol) and 1-bromo-4-iodobenzene (8.06 g, 28.5 mmol) were dissolved in toluene (150 mL). Then, Pd(OAc)2 (216 mg, 1 mmol), 50% solution P(t-Bu)3 (1.3 mL, 1.9 mmol) and t-BuONa (3.64 g, 38 mmol) were added thereto. The mixture was stirred at 120 ℃ for 20 hours and cooled to room temperature. After completing the reaction by adding saturated ammonium chloride solution (30 mL) to the mixture, the reaction mixture was extracted with ethyl acetate (300 mL) and an obtained organic layer was washed with distilled water (100 mL). After drying the organic layer with anhydrous magnesium sulfate and removing an organic solvent under reduced pressure, Compound F (10 g, 83%) was obtained by purifying an obtained solid via column chromatography using silica gel.
Preparation of Compound G
Compound F (10 g, 15.8 mmol) was dissolved in THF (200 mL) and cooled to -78℃. 2.5 M n-BuLi (in hexane) (7.6 mL, 19 mmol) was slowly added the solution at -78℃. After stirring the mixture solution at 78℃ for 1 hour, B(OCH3)3 (2.64 mL, 23.7 mmol) was slowly added thereto at -78℃. The mixture was stirred at -78℃ for 1 hour and cooled to room temperature. After completing the reaction by adding saturated ammonium chloride solution (30 mL) to the mixture, the reaction mixture was extracted with EA (300 mL) and an obtained organic layer was washed with distilled water (100 mL). After drying the organic layer with anhydrous magnesium sulfate and removing an organic solvent under reduced pressure, Compound G (8.7 g, 92%) was obtained by purifying an obtained solid.
Preparation of Compound 23
Compound G (8.7 g, 14.56 mmol) and Compound E (2.52 g, 13.2 mmol) were dissolved in a mixture solvent of toluene (100 mL), ethanol (25 mL) and distilled water (25 mL). Pd(PPh3)4 (763 mg, 0.66 mmol) and Na2CO3 (4.2 g, 39.6 mmol) were added to the mixture. The mixture was stirred at 120 ℃ for 4 hours and cooled to room temperature. After completing the reaction by adding saturated ammonium chloride solution (20 mL) to the mixture, the reaction mixture was extracted with EA (200 mL) and an obtained organic layer was washed with distilled water (30 mL). After drying the organic layer with anhydrous magnesium sulfate and removing an organic solvent under reduced pressure, Compound 23 (8.5 g, 91%) was obtained by purifying an obtained solid via column chromatography using silica gel.
Compounds for organic electronic material 1 to 38 were prepared according to Preparation Example 1. Table 1 shows 1H NMR and MS/FAB of the prepared compounds for organic electronic material.
Table 1
Comp. 1H NMR(CDCl3, 200 MHz) MS/FAB
found calculated
1 δ= 6.3(1H, m), 6.48(1H, m), 7.07(1H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.58(13H, m), 7.94(2H, m), 8.3(2H, m), 8.55(2H, m) 630.69 630.21
2 δ= 6.44(1H, m), 7.14(1H, m), 7.25~7.26(3H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.7(1H, m), 7.94(2H, m), 8.52~8.55(4H, m), 9.3(1H, m) 631.68 631.20
3 δ= 1.48(6H, m), 1.73(4H, m), 2.72(1H, m), 6.42(1H, m), 6.55(1H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.58(11H, m), 7.94(2H, m), 8.55(2H, m) 636.74 636.25
4 δ= 1.35(9H, s), 6.3(1H, m), 6.48(1H, m), 7.07(1H, m), 7.25(2H, m), 7.33(2H, m), 7.41~7.5(8H, m), 7.58(4H, m), 7.94(2H, m), 8.22(2H, m), 8.55(2H, m) 686.80 686.27
5 δ= 0.33(9H, s), 6.68(1H, m), 6.82(1H, m), 7.25(2H, m), 7.33(3H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.94(2H, m), 8.55(2H, m) 626.78 626.21
6 δ= 6.8(1H, m), 6.88(1H, m), 7.25(2H, m), 7.33~7.37(8H, m), 7.45~7.58(20H, m), 7.94(2H, m), 8.55(2H, m) 812.99 812.26
7 δ= 2.05(3H, m), 6.59~6.67(4H, m), 7.21~7.25(3H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.94(2H, m), 8.55(2H, m) 594.66 594.21
8 δ= 1.8(3H, m), 6.17(1H, m), 6.68(1H, m), 7.25(2H, m), 7.32~7.33(3H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.94(2H, m), 8.55(2H, m) 592.64 592.19
9 δ= 6.3(1H, m), 6.48(1H, m), 7.07(1H, m), 7.25(2H, m), 7.33(2H, m), 7.41~7.52(11H, m), 7.58(4H, m), 7.88(2H, m), 7.94(2H, m), 8.55(2H, m), 8.81(2H, m) 706.79 706.24
10 δ= 6.3(1H, m), 6.48(1H, m), 7.07(1H, m), 7.25(2H, m), 7.33(2H, m), 7.43~7.5(7H, m), 7.58~7.62(5H, m), 7.94~7.97(3H, m), 8.24(1H, m), 8.55(2H, m) 709.59 708.12
11 δ= 6.3(1H, m), 6.48(1H, m), 7.07(1H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.72(1H, m), 7.94(3H, m), 8.24(1H, m), 8.55~8.58(3H, m) 655.70 655.20
12 δ= 6.3(1H, m), 6.48(1H, m), 7.07(1H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.5(7H, m), 7.58~7.64(5H, m), 7.94(2H, m), 8.3(1H, m), 8.55(2H, m), 8.69(1H, m) 698.69 698.19
13 δ= 5.92(2H, m), 6.63(4H, m), 6.81(2H, m), 7.04(1H, m), 7.2~7.25(6H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.94(2H, m), 8.55(2H, m) 721.80 721.25
14 δ= 6.5(1H, m), 7.12(1H, m), 7.23~7.39(9H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.94(2H, m), 8.05(1H, m), 8.55(2H, m) 662.76 662.18
15 δ= 3.83(3H, m), 6.85(1H, m), 6.98(1H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.71(1H, m), 7.94(2H, m), 8.55(2H, m) 584.62 584.18
16 δ= 6.85(1H, m), 6.95~7.01(4H, m), 7.25~7.33(6H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.71(1H, m), 7.94(2H, m), 8.55(2H, m) 646.69 646.20
17 δ= 6.3(1H, m), 6.48(1H, m), 7.07(1H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.83(1H, m), 7.9~7.94(3H, m), 8.55(2H, m), 8.65(1H, m), 8.78(1H, m) 659.69 659.20
18 δ= 5.35(1H, s), 6.3(1H, m), 6.48(1H, m), 6.89(2H, m), 7.07(1H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.94~8(4H, m), 8.55(2H, m) 646.69 646.20
19 δ= 7.18(1H, m), 7.25(2H, m), 7.33(2H, m), 7.41~7.51(9H, m), 7.58(4H, m), 7.79(2H, m), 7.94(2H, m), 8.09(1H, m), 8.55(2H, m) 631.68 631.20
20 δ= 7.18(1H, m), 7.25(2H, m), 7.33(2H, m), 7.41~7.52(11H, m), 7.58(4H, m), 7.85(2H, m), 7.94(2H, m), 8.09(1H, m), 8.3(2H, m), 8.55(2H, m) 707.78 707.23
21 δ= 3.57(4H, m), 3.65(4H, m), 5.68(1H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58~7.63(5H, m), 7.94(2H, m), 8.55(2H, m) 640.69 640.22
22 δ= 1.71(6H, m), 1.99~2.02(9H, m), 7.25(2H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.94(2H, m), 8.55~8.58(4H, m) 689.80 689.28
23 δ= 7.25(2H, m), 7.32~7.33(4H, m), 7.41~7.58(14H, m), 7.79(2H, m), 7.94(2H, m), 8.13(2H, m), 8.54~8.55(3H, m) 707.78 707.23
24 δ= 2.34(3H, m), 7.18(1H, m), 7.25~7.33(6H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.67(2H, m), 7.94(2H, m), 8.09(1H, m), 8.55(2H, m) 645.71 645.22
25 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.51(12H, m), 7.58(4H, m), 7.94(2H, m), 8.28(4H, m), 8.55(2H, m) 708.76 708.23
26 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.51(9H, m), 7.58(4H, m), 7.94(2H, m), 8.11(1H, s), 8.28(2H, m), 8.55(2H, m) 632.67 632.20
27 δ= 7.25(2H, m), 7.32~7.33(4H, m), 7.41~7.51(12H, m), 7.58(4H, m), 7.94(2H, m), 8.13(2H, m), 8.28(4H, m), 8.55(2H, m) 784.86 784.26
28 δ= 7.25(2H, m), 7.33~7.36(3H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.85(1H, m), 7.94(2H, m), 8.3(1H, s), 8.38(1H, m), 8.55~8.59(3H, m) 633.66 633.19
29 δ= 6.3(1H, m), 6.48(1H, m), 7.07(1H, m), 7.25(1H, m), 7.33(1H, m), 7.41~7.51(12H, m), 7.94(1H, m), 8.21~8.26(2H, m), 8.33(1H, m), 8.55(2H, m) 541.60 541.18
30 δ= 7.18(1H, m), 7.25(1H, m), 7.33(1H, m), 7.41~7.5(12H, m), 7.7~7.75(2H, m), 7.94(1H, m), 8.09(1H, m), 8.33(1H, m), 8.55(2H, m) 542.59 542.17
31 δ= 7(1H, m), 7.25~7.26(2H, m), 7.33(1H, m), 7.45~7.51(4H, m), 7.58~7.6(3H, m), 7.94(1H, m), 8.11(1H, s), 8.21~8.33(4H, m), 8.5~8.55(3H, m) 544.56 544.16
32 δ= 7.25(1H, m), 7.33(1H, m), 7.41~7.51(9H, m), 7.58(2H, m), 7.79(2H, m), 7.94(1H, m), 8.11(1H, s), 8.28(2H, m), 8.55(1H, m), 8.84(1H, s) 543.57 543.17
33 δ= 7.41~7.52(11H, m), 7.58(2H, m), 7.77(1H, m), 8(1H, m), 8.11(1H, s), 8.18(1H, m), 8.28~8.33(3H, m), 8.55(1H, m) 543.57 543.17
34 δ= 7.25~7.33(7H, m), 7.45~7.5(7H, m), 7.58~7.63(7H, m), 7.81(2H, m), 7.94(3H, m), 8.12(1H, m), 8.55(3H, m) 718.80 718.24
35 δ= 7.25(3H, m), 7.33(3H, m), 7.45~7.5(6H, m), 7.58~7.67(10H, m), 7.81(2H, m), 7.94(3H, m), 8.16(1H, m), 8.54~8.55(4H, m) 768.86 768.25
36 δ= 1.72(6H, s), 7.25~7.38(8H, m), 7.45~7.63(12H, m), 7.77(3H, m), 7.87~7.94(4H, m), 8.55(2H, m) 745.86 745.27
37 δ= 7.25~7.33(7H, m), 7.45~7.5(10H, m), 7.58~7.63(7H, m), 7.77(3H, m), 7.94~8(3H, m), 8.12(1H, m), 8.18(1H, m), 8.55(2H, m) 794.89 794.27
38 δ= 7.25(2H, m), 7.32~7.33(4H, m), 7.45~7.52(8H, m), 7.58(5H, m), 7.77(2H, m), 7.94~7.98(3H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.55(2H, m) 735.85 735.20
[Examples 1-6] Manufacture of OLED device using compound for organic electronic materials according to the present invention
An OLED device was manufactured using the compound for organic electronic materials according to the present invention. First, a transparent electrode ITO thin film (15 Ω/□) obtained from a glass for OLED (produced by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use. Then, an ITO substrate was equipped in a substrate folder of a vacuum vapor deposition apparatus, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum vapor deposition apparatus, which was then ventilated up to 10-6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate 2-TNATA, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
Then, N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
The compound (e.g. Compound 1) purified by vacuum sublimation at 10-6torr was placed in a cell of a vacuum vapor deposition apparatus as a host, and an electroluminescent dopant (e.g., (piq)2Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate]) was placed in another cell as a dopant. The two materials were evaporated at different rates such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer through doping at 4 to 20 wt%.
Subsequently, tris(8-hydroxyquinoline)-aluminum(III) (Alq) was vapor-deposited with a thickness of 20 nm as an electron transport layer on the electroluminescent layer. Then, after vapor-depositing lithium quinolate (Liq) with a thickness of 1 to 2 nm as an electron injection layer, an Al cathode having a thickness of 150 nm was formed using another vacuum vapor deposition apparatus to manufacture an OLED.
[Comparative Example 1] Manufacture of OLED device using conventional electroluminescent materials
An OLED device was manufactured as in Example 1 except that 4,4 -bis(carbazol-9-yl)biphenyl (CBP) instead of the compounds according to the present invention was used as a host material at one cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III) (BAlq) was used as a hole blocking layer.
The driving voltage and the luminous efficiencies of the OLED comprising the compound for organic electronic materials according to the present invention in the Examples 1-6 or the conventional electroluminescent compound in Comparative Example 1 were measured at 1,000 cd/m2, respectively, and the results are shown in Table 2.
Table 2
Host material Electroluminescent material Hole blocking layer @1,000cd/m2 color
Driving voltage(V) Luminous efficiency(cd/A)
Example 1 Compound 1 (piq)2Ir(acac) - 6.7 6.8 Red
Example 2 Compound 6 (piq)2Ir(acac) - 7.1 6.8 Red
Example 3 Compound 13 (piq)2Ir(acac) - 6.3 7.1 Red
Example 4 Compound 19 (piq)2Ir(acac) - 6.5 6.9 Red
Example 5 Compound 25 (piq)2Ir(acac) - 6.2 7.3 Red
Example 6 Compound 37 (piq)2Ir(acac) - 6.4 6.9 Red
Comparative Example 1 CBP (piq)2Ir(acac) BAlq 7.5 2.6 Red
As shown in Table 2, the compounds for organic electronic material developed in the present invention as a red light-emitting material showed the same or superior luminous property than that of the convention electroluminescent material.
The device using the compounds for organic electronic material of the present invention as a host material shows the excellent luminous property, reduces driving voltage and consumes less power due to improved power efficiency without using the hole blocking layer in the conventional device structure.
Since the compounds for organic electronic material according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.

Claims (10)

  1. An compounds for organic electronic material represented by Chemical Formula 1:
    [Chemical Formula 1]
    Figure PCTKR2011002525-appb-I000039
    wherein
    L represents a single bond, (C6-C30)arylene or (C3-C30)heteroarylene;
    R1 represents (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C1-C30)alkoxy, (C1-C30)alkylthio, (C6-C30)aryloxy, (C6-C30)arylthio, -SiR2R3R4, -NR5R6, (C2-C30)alkenyl, (C2-C30)alkynyl, adamantyl, (C6-C30)aryl or (C3-C30)heteroaryl;
    R2 through R6 independently represent (C1-C30)alkyl or (C6-C30)aryl;
    Ar1 through Ar4 independently represent hydrogen, deuterium, (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl or (C3-C30)heteroaryl, and at least one of Ar1 through Ar4 is linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring, and -CH2- of the alkylene is substituted by -CR11R12-, -NR13-, -SiR14R15-, -O-, -S- or -Se-;
    R11 through R15 independently represent (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C6-C30)aryl or (C3-C30)heteroaryl, or are linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
    arylene and heteroarylene of the L, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R1, alkyl and aryl of R2 through R6, alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of Ar1 through Ar4, and alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R11 through R15 are further substituted by one or more selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono or di(C1-C30)alkylamino, mono or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro and hydroxyl; and
    the heterocycloalkyl and heteroaryl may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P.
  2. The compounds for organic electronic material according to claim 1, which is represented by Chemical Formula 2 or 3:
    [Chemical Formula 2]
    Figure PCTKR2011002525-appb-I000040
    [Chemical Formula 3]
    Figure PCTKR2011002525-appb-I000041
    wherein
    L represents a single bond, (C6-C30)arylene or (C3-C30)heteroarylene;
    R1 represents (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C6-C30)arylthio, -SiR2R3R4, -NR5R6, (C2-C30)alkenyl, (C2-C30)alkynyl, adamantyl, (C6-C30)aryl or (C3-C30)heteroaryl;
    R2 through R6 independently represent (C1-C30)alkyl or (C6-C30)aryl;
    Ar3, Ar4 and R21 and R22 independently represent hydrogen, deuterium, (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl or (C3-C30)heteroaryl;
    X and Y independently represent -CR11R12-, -NR13-, -SiR14R15-, -O-, -S- or -Se-;
    R11 through R15 are the same as defined in Claim 1; and
    arylene and heteroarylene of the L, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R1, alkyl and aryl of R2 through R6, and alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of Ar3 through Ar4 may be further substituted by one or more selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono or di(C1-C30)alkylamino, mono or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro or hydroxyl.
  3. The compounds for organic electronic material according to claim 2, wherein
    Figure PCTKR2011002525-appb-I000042
    is selected from the following structures:
    Figure PCTKR2011002525-appb-I000043
    Figure PCTKR2011002525-appb-I000044
    Figure PCTKR2011002525-appb-I000045
    Figure PCTKR2011002525-appb-I000046
    Figure PCTKR2011002525-appb-I000047
  4. The compounds for organic electronic material according to claim 1, wherein
    Figure PCTKR2011002525-appb-I000048
    is selected from the following structures:
    Figure PCTKR2011002525-appb-I000049
  5. An organic electroluminescent device comprising the compounds for organic electronic material according to any one of claims 1 to 4.
  6. The organic electroluminescent device according to claim 5, which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more compound(s) for organic electronic material according to any of claims 1 to 4 and one or more phosphorescent dopant(s).
  7. The organic electroluminescent device according to claim 6, wherein the organic layer further comprises one or more amine compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds.
  8. The organic electroluminescent device according to claim 6, wherein the organic layer further comprises one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s).
  9. The organic electroluminescent device according to claim 6, wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
  10. The organic electroluminescent device according to claim 6, which is a white-light emitting organic electroluminescent device wherein the organic layer further comprises one or more organic electroluminescent layer(s) emitting blue, red or green light.
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WO2014061546A1 (en) * 2012-10-18 2014-04-24 東レ株式会社 Benzindolocarbazole derivative, light-emitting element material produced using same, and light-emitting element
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US11236103B2 (en) 2018-07-27 2022-02-01 Biotheryx, Inc. Bifunctional compounds
US11897930B2 (en) 2020-04-28 2024-02-13 Anwita Biosciences, Inc. Interleukin-2 polypeptides and fusion proteins thereof, and their pharmaceutical compositions and therapeutic applications

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