WO2011099718A1 - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent device using the same Download PDF

Info

Publication number
WO2011099718A1
WO2011099718A1 PCT/KR2011/000652 KR2011000652W WO2011099718A1 WO 2011099718 A1 WO2011099718 A1 WO 2011099718A1 KR 2011000652 W KR2011000652 W KR 2011000652W WO 2011099718 A1 WO2011099718 A1 WO 2011099718A1
Authority
WO
WIPO (PCT)
Prior art keywords
substituent
aryl
alkyl
organic electroluminescent
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2011/000652
Other languages
French (fr)
Inventor
Hee Choon Ahn
Nam Kyun Kim
Young Jun Cho
Hyuck Joo Kwon
Bong Ok Kim
Sung Min Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Specialty Materials Korea Ltd
Original Assignee
Rohm and Haas Electronic Materials Korea Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Electronic Materials Korea Ltd filed Critical Rohm and Haas Electronic Materials Korea Ltd
Publication of WO2011099718A1 publication Critical patent/WO2011099718A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • 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 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
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • 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
    • 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
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • 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
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • 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
    • C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
    • 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
    • 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • 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
    • 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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Definitions

  • the present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device using the same, more particularly, to novel organic electroluminescent compounds used as an electroluminescent material and an organic electroluminescent device using the same as host.
  • An organic EL device is a device wherein, when charge is applied to an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode), an electron and a hole form a pair and then become extinct with emitting light.
  • a device can be formed on a transparent flexible substrate such as plastics. The device can be operated at a lower voltage (not more than 10 V) with relatively lower power consumption but excellent color purity, as compared to a plasma display panel or an inorganic EL display. Since the organic electroluminescent (EL) devices can develop three colors (green, blue and red), they have been focused as full colored display devices for next generation.
  • the electroluminescent materials may be divided into host materials and dopant materials.
  • an electroluminescent layer prepared by doping a dopant in a host is known to provide superior EL property.
  • development of an organic EL device having high efficiency and long operation life is becoming an imminent task.
  • development of materials which are much superior to existing electroluminescent materials is urgently needed.
  • an object of the present invention is to provide an organic electroluminescent compound 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 an organic electroluminescent device employing the organic electroluminescent compound as an electroluminescent material.
  • the present invention provides an organic electroluminescent compound represented by Chemical Formula 1 and an organic electroluminescent device using the same.
  • the organic electroluminescent compound according to the present invention may be used to manufacture an OLED device having very superior operation life.
  • a 1 through A 4 independently represent CR 3 or N;
  • X represents -N(R 10 )-, -S-, -O- or -Si(R 11 )(R 12 )-;
  • Y represents CR 4 or N
  • Ar 1 and Ar 2 independently represent (C6-C30)arylene with or without substituent(s) or (C3-C30)heteroarylene with or without substituent(s), and Ar 3 represents (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s);
  • R 1 through R 4 and R 10 through R 12 independently represent hydrogen, deuterium, halogen, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), substituted or unsubstituted (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl(s) with or without substituent(s), (C3-C30)heteroaryl with or without substituent(s), 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), cyano, nitro, NR 21 R 22 , BR 23 R 24 , PR 25
  • a ring and B ring independently represent (C5-C30)cycloalkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s),(C6-C30)heteroaryl with or without substituent(s);
  • R 21 through R 32 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s);
  • z represents S or O
  • R 41 through R 43 and R 51 through R 58 are the same as R 1 through R 3 ;
  • n an integer from 0 to 2;
  • a and b independently represent an integer from 0 to 4; and they may be identical or different when a and b are larger than 2.
  • alkyl in the present invention, “alkyl”, “alkoxy” and other substituents containing “alkyl” moiety include both linear and branched species.
  • the cycloalkyl includes hydrocarbon such as adamantyl or bicycloalkyl of a polycyclic ring as well as a monocyclic ring.
  • * marked in the chemical structure of the present invention means a portion linked inside the structure.
  • 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 aryls linked by chemical bond(s).
  • 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.
  • heteroaryl 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 includes more than one heteroaryls linked by chemical bond(s).
  • 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.
  • heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzo
  • 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 term 'substituted' means being further substituted by an unsubstituted substituent.
  • the substituent further substituted by the Ar 1 and Ar 3 , R 1 through R 4 , R 10 through R 12 , R 21 through R 32 , R 41 through R 43 and R 51 through R 58 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, halogen, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl, (C6-C30)aryl with or without (C6-C30)aryl substituent(s), (C6-C30)aryl with or without (C6-C30)heteroaryl substituent(s), (C3-C30)heteroaryl with or without (C6-C30)aryl substituent(s), (C3-C30)heteroaryl with or without (C6-C30)aryl substituent(s), (C3-C
  • R 61 through R 72 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl;
  • Z represents S or O
  • R 73 and R 74 independently represent (C1-C30)alkyl, (C1-C30)alkoxy, (C6-C30)aryl or (C6-C30)aryloxy.
  • organic electroluminescent compound according to the present invention is selected from the following compounds, but is not limited thereto
  • Ar 1 through Ar 3 , Y, R 1 , R 2 , R 10 through R 12 , a and b are the same as defined in Chemical Formula 1 of claim 1.
  • The is selected from the following structures but are not limited thereto.
  • R 1 and R 2 are independently selected from the following structures, but are not limited thereto.
  • the organic electroluminescent compound may be exemplified as the following compounds but the present invention is not limited by the compounds.
  • the organic electroluminescent compound according to the present invention may be prepared as shown in following Scheme 1.
  • a 1 through A 4 , X, Y, Ar 1 through Ar 3 , R 1 , R 2 , a and b are the same as defined in the 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 organic electroluminescent compound(s) represented by Chemical Formula 1.
  • the organic layer comprises an electroluminescent layer, which includes one or more dopants with one or more organic electroluminescent compounds of Chemical Formula 1 as a host.
  • the 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 2.
  • M 1 is selected from the group consisting of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, Group 15 and Group 16 metals, and ligands L 101 , L 102 and L 103 are independently selected from the following structures:
  • R 201 through R 203 independently represent hydrogen, (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, (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(
  • 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 dopant compounds of the Chemical Formula 2 may be exemplified by the compounds having following structures but are not limited thereto.
  • the organic layer may further include, in addition to the organic electroluminescent compound 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 organic electroluminescent compound 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 organic electroluminescent compound 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 compound 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 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, SiO x (1 ⁇ x ⁇ 2) , AlOx (1 ⁇ x ⁇ 1.5), SiON, SiAlON, etc.
  • 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 organic electroluminescent compound 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.
  • An OLED device was manufactured using the electroluminescent material 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.
  • an electroluminescent layer was formed thereon as follows.
  • Compound 30 was placed in a cell of a vacuum vapor deposition apparatus as a host, and Ir(ppy) 3 [tris(2-phenylpyridine)iridium] 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 10 wt%.
  • Each compound used in the OLED was purified by vacuum sublimation at 10 -6 torr.
  • An OLED device was manufactured as in Example 1 except that Compound 34 was added as a host material on the electroluminescent layer and Ir(ppy) 3 [tris(2-phenylpyridine)iridium] was used as an electroluminescent dopant.
  • An OLED device was manufactured as in Example 1 except that Compound 51 was added as a host material on the electroluminescent layer and Ir(ppy) 3 [tris(2-phenylpyridine)iridium] was used as an electroluminescent dopant.
  • An OLED device was manufactured as in Example 1 except that Compound 13 was added as a host material on the electroluminescent layer and (piq) 2 Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] was used as an electroluminescent dopant.
  • An OLED device was manufactured as in Example 1 except that Compound 34 was added as a host material on the electroluminescent layer and (piq) 2 Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] was used as an electroluminescent dopant.
  • An OLED was manufactured in the same manner as Example 1 except that 4,4'-bis(carbazol-9-yl)biphenyl(CBP) instead of the compounds of the present invention as a host material at one cell of the vacuum vapor deposition apparatus, Ir(ppy) 3 [tris(2-phenyl pyridine)iridium] as a dopant and Bis(2-methyl-8-quinolinato)( p- phenyl-phenolato)aluminum(III) (BAlq) as a hole blocking layer were used.
  • An OLED was manufactured in the same manner as Example 1 except that 4,4'-bis(carbazol-9-yl)biphenyl(CBP) instead of the compounds of the present invention as a host material at one cell of the vacuum vapor deposition apparatus,(piq) 2 Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] as a dopant and Bis(2-methyl-8-quinolinato)( p- phenyl-phenolato)aluminum(III) (BAlq) as a hole blocking layer were used.
  • the organic electroluminescent compounds according to the present invention have excellent properties compared with the conventional material.
  • the device using the organic electroluminescent compound according to the present invention as host material has excellent electroluminescent properties and drops driving voltage, thereby increasing power efficiency and improving power consumption.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

Provided are novel organic electroluminescent compounds and an organic electroluminescent device using the same. Since the organic electroluminescent compound exhibits good luminous efficiency and excellent life property compared to the existing host material, it may be used to manufacture OLED devices having very superior operation life and consuming less power due to improved power efficiency.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device using the same, more particularly, to novel organic electroluminescent compounds used as an electroluminescent material and an organic electroluminescent device using the same as host.
An organic EL device is a device wherein, when charge is applied to an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode), an electron and a hole form a pair and then become extinct with emitting light. A device can be formed on a transparent flexible substrate such as plastics. The device can be operated at a lower voltage (not more than 10 V) with relatively lower power consumption but excellent color purity, as compared to a plasma display panel or an inorganic EL display. Since the organic electroluminescent (EL) devices can develop three colors (green, blue and red), they have been focused as full colored display devices for next generation.
In an organic light-emitting diode (OLED), the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. In functional aspect, the electroluminescent materials may be divided into host materials and dopant materials. In general, an electroluminescent layer prepared by doping a dopant in a host is known to provide superior EL property. Recently, development of an organic EL device having high efficiency and long operation life is becoming an imminent task. Especially, considering the level of EL performance required for medium-to-large sized OLED panels, development of materials which are much superior to existing electroluminescent materials is urgently needed.
Accordingly, an object of the present invention is to provide an organic electroluminescent compound 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 an organic electroluminescent device employing the organic electroluminescent compound as an electroluminescent material.
In one general aspect, the present invention provides an organic electroluminescent compound represented by Chemical Formula 1 and an organic electroluminescent device using the same. With superior luminescence efficiency and excellent life property, the organic electroluminescent compound according to the present invention may be used to manufacture an OLED device having very superior operation life.
[Chemical Formula 1]
Figure PCTKR2011000652-appb-I000001
wherein
A1 through A4 independently represent CR3 or N;
X represents -N(R10)-, -S-, -O- or -Si(R11)(R12)-;
Y represents CR4 or N;
Ar1 and Ar2 independently represent (C6-C30)arylene with or without substituent(s) or (C3-C30)heteroarylene with or without substituent(s), and Ar3 represents (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s);
R1 through R4 and R10 through R12 independently represent hydrogen, deuterium, halogen, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), substituted or unsubstituted (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl(s) with or without substituent(s), (C3-C30)heteroaryl with or without substituent(s), 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), cyano, nitro, NR21R22, BR23R24, PR25R26, P(=O)R27R28, R29R30R31Si-, R32Z-, (C6-C30)ar(C1-C30)alkyl with or without substituent(s), (C2-C30)alkenyl with or without substituent(s), (C2-C30)alkynyl with or without substituent(s),
Figure PCTKR2011000652-appb-I000002
,
Figure PCTKR2011000652-appb-I000003
or
Figure PCTKR2011000652-appb-I000004
or each of them may be linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicylic ring, a mono- or polycyclic aromatic ring or a mono- or polycyclic heteroaromatic ring;
A ring and B ring independently represent (C5-C30)cycloalkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s),(C6-C30)heteroaryl with or without substituent(s);
R21 through R32 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s);
z represents S or O;
W represents -(CR51R52)m-, -(R51)C=C(R52)-, -N(R53)-, -S-, -O-, -Si(R54)(R55)-, -P(R56)-, -P(=O)(R57)-, -C(=O)- or -B(R58)-;
R41 through R43 and R51 through R58 are the same as R1 through R3;
the heterocycloalkyl, heteroaryl or heteroaromatic ring may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P;
m represents an integer from 0 to 2; and
a and b independently represent an integer from 0 to 4; and they may be identical or different when a and b are larger than 2.
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 hydrocarbon such as adamantyl or bicycloalkyl of a polycyclic ring as well as a monocyclic ring. Also, * marked in the chemical structure of the present invention means a portion linked inside the structure.
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 aryls linked by chemical bond(s). 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. Further, the heteroaryl includes more than one heteroaryls linked by chemical bond(s). 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 heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, carborinyl, 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.
In the term 'substituted or unsubstituted (or with or without) substituent(s)' described herein, the term 'substituted' means being further substituted by an unsubstituted substituent. The substituent further substituted by the Ar1 and Ar3, R1 through R4, R10 through R12, R21 through R32, R41 through R43 and R51 through R58 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, halogen, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl, (C6-C30)aryl with or without (C6-C30)aryl substituent(s), (C6-C30)aryl with or without (C6-C30)heteroaryl substituent(s), (C3-C30)heteroaryl with or without (C6-C30)aryl substituent(s), (C3-C30)heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s), (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more aromatic ring(s), NR61R62, BR63R64, PR65R66, P(=O)R67R68, R69R70R71Si-, R72Z-, R73C(=O)-, R74C(=O)O-, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, carboxyl, nitro and hydroxyl, or may be linked to an adjacent substituent to form a ring;
R61 through R72 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl;
Z represents S or O; and
R73 and R74 independently represent (C1-C30)alkyl, (C1-C30)alkoxy, (C6-C30)aryl or (C6-C30)aryloxy.
More specifically, organic electroluminescent compound according to the present invention is selected from the following compounds, but is not limited thereto
Figure PCTKR2011000652-appb-I000005
wherein
Ar1 through Ar3, Y, R1, R2, R10 through R12, a and b are the same as defined in Chemical Formula 1 of claim 1.
The
Figure PCTKR2011000652-appb-I000006
is selected from the following structures but are not limited thereto.
Figure PCTKR2011000652-appb-I000007
Figure PCTKR2011000652-appb-I000008
Figure PCTKR2011000652-appb-I000009
Also, the R1 and R2 are independently selected from the following structures, but are not limited thereto.
Figure PCTKR2011000652-appb-I000010
The organic electroluminescent compound may be exemplified as the following compounds but the present invention is not limited by the compounds.
Figure PCTKR2011000652-appb-I000011
Figure PCTKR2011000652-appb-I000012
Figure PCTKR2011000652-appb-I000013
Figure PCTKR2011000652-appb-I000014
Figure PCTKR2011000652-appb-I000015
Figure PCTKR2011000652-appb-I000016
Figure PCTKR2011000652-appb-I000017
Figure PCTKR2011000652-appb-I000018
Figure PCTKR2011000652-appb-I000019
Figure PCTKR2011000652-appb-I000020
Figure PCTKR2011000652-appb-I000021
Figure PCTKR2011000652-appb-I000022
Figure PCTKR2011000652-appb-I000023
Figure PCTKR2011000652-appb-I000024
Figure PCTKR2011000652-appb-I000025
Figure PCTKR2011000652-appb-I000026
Figure PCTKR2011000652-appb-I000027
The organic electroluminescent compound according to the present invention may be prepared as shown in following Scheme 1.
[Scheme 1]
Figure PCTKR2011000652-appb-I000028
Wherein
A1 through A4, X, Y, Ar1 through Ar3, R1, R2, a and b are the same as defined in the 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 organic electroluminescent compound(s) represented by Chemical Formula 1. The organic layer comprises an electroluminescent layer, which includes one or more dopants with one or more organic electroluminescent compounds of Chemical Formula 1 as a host. The 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 2.
[Chemical Formula 2]
M1L101L102L103
Wherein
M1 is selected from the group consisting of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, Group 15 and Group 16 metals, and ligands L101, L102 and L103 are independently selected from the following structures:
Figure PCTKR2011000652-appb-I000029
Figure PCTKR2011000652-appb-I000030
Figure PCTKR2011000652-appb-I000031
Figure PCTKR2011000652-appb-I000032
wherein
R201 through R203 independently represent hydrogen, (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, (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 PCTKR2011000652-appb-I000033
,
Figure PCTKR2011000652-appb-I000034
or
Figure PCTKR2011000652-appb-I000035
, 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 dopant compounds of the Chemical Formula 2 may be exemplified by the compounds having following structures but are not limited thereto.
Figure PCTKR2011000652-appb-I000036
Figure PCTKR2011000652-appb-I000037
Figure PCTKR2011000652-appb-I000038
Figure PCTKR2011000652-appb-I000039
Figure PCTKR2011000652-appb-I000040
Figure PCTKR2011000652-appb-I000041
Figure PCTKR2011000652-appb-I000042
In the organic electronic device of the present invention, the organic layer may further include, in addition to the organic electroluminescent compound 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 organic electroluminescent compound 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 organic electroluminescent compound 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 compound 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 organic electroluminescent compound 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 organic electroluminescent compounds 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 2
Figure PCTKR2011000652-appb-I000043
Preparation of Compound 1-1
After 3-bormothiophene (50 g, 306 mmol) was dissolved in THF (300 mL) and toluen (1,200 mL), the mixture was cooled to -78 ℃, and n-BuLi (150 mL, 2.5M in hexane, 367 mmol) was added thereto. After stirring the mixture for 1 hour, triisopropylborate (112 mL, 490 mmol) was added while maintaining temperature at -78 ℃. The mixture was stirred for 10 minutes. Upon completion of the reaction, H2O was added and the mixture was extracted with EA/H2O. After removing moisture with MgSO4 and performing distillation under reduced pressure, Compound 1-1 (24 g, 60%) was obtained by column (methylene chloride (MC)/Hexane) separation.
Preparation of Compound 1-2
After Compound 1-1 (20.6 g, 161 mmol), 2-bromonitrobenzene (25 g, 124 mmol), Pd2dba3 (1.1 g, 1.2 mmol),X-phos (2.4 g, 5 mmol), and K3PO4 (79 g, 370 mmol) were dissolved in 1,4-dioxane (300 mL), the mixture was stirred under reflux for one day. Upon completion of the reaction, the mixture was cooled at room temperature and extracted with EA/H2O. After removing moisture with MgSO4 and performing distillation under reduced pressure, Compound 1-2 (23.5 g, 92%) was obtained by column(MC/Hexane) separation.
Preparation of Compound 1-3
After Compound 1-2 (22.5 g, 110 mmol) was dissolved in P(OEt)3 (500 mL) and was stirred under reflux for 4 hours, P(OEt)3 was removed by distillation to give a red liquid. Compound 1-3 (6 g, 31%) was obtained by performing column(EA/Hexane) separation on the red liquid.
Preparation of Compound 1-4
2,4,6-trichloropyrimidine (10 g, 54.51 mmol), phenylboronic acid (16.6 g, 136,29 mmol), Pd(PPh3)4 (3.15 g, 2.72 mmol), 2M K2CO3 (50 mL), toluen (100 mL) and ethanol (30 mL) were stirred under reflux. 4 hours later, the mixture was cooled to room temperature and extracted with EA after adding distilled water. After drying with MgSO4 and distillation under reduced pressure, Compound 1-4 (7 g, 48.%) was obtained by column separation.
Preparation of Compound 2
NaH (1.57 g, 39.36 mmol, 60% in mineral oil) was added to DMF (70 mL), and Compound 1-4 (7 g, 26.24 mmol) was dissolved in DMF (60 mL). 1 hour later, Compound 1-3 (3.8 g, 21.87 mmol) was dissolved in DMF (70 mL). After stirring the mixture for 10 hours, distilled water was added and the mixture was extracted with EA. After drying with MgSO4 and distillation under reduced pressure, Compound 2 (7 g, 56%) was obtained by column separation.
[Preparation Example 2] Preparation of Compound 17
Figure PCTKR2011000652-appb-I000044
Preparation of Compound 2-1
After Compound 1-3 (5.3 g, 30.6mmol), 4-iodobromobenzene (17.3 g, 61 mmol), Cu (2.9 g, 46mmol), 18-crown-6 (0.8 g, 3 mmol) and K2CO3 (12 g, 72 mmol) were dissolved in 1,2-dichlorobenzene (350 mL), the mixture was stirred under reflux for one day. Upon completion of the reaction, Cu and base were removed using cellite and the solution was extracted with EA/H2O. After drying with MgSO4 and distillation under reduced pressure, Compound 2-1 (5 g, 50%) was obtained by column(MC/Hexane) separation.
Preparation of Compound 2-2
After Compound 2-1 (4 g, 12 mmol) was dissolved in THF (60 mL), the mixture was cooled to -78 ℃, and n-BuLi (5.8 mL, 2.5M in hexane, 14.4 mmol) was slowly added thereto. After stirring the mixture for 1 hour, triisopropylborate (4 mL, 19.2 mmol) was added. After slowly increasing temperature, the mixture was stirred at room temperature for one day. Upon completion of the reaction, 2M HCl was added and the mixture was extracted with EA/H2O. After removing moisture with MgSO4 and performing distillation under reduced pressure, Compound 2-2 (2.1 g, 60%) was obtained by column(MC/Hexane) separation.
Preparation of Compound 2-3
After 1,3-dibromobenzene (11.2 g, 47 mmol) was dissolved in THF (200 mL), the mixture was cooled to -78 ℃. After slowly adding n-BuLi (19 mL, 2.5M in hexane, 70.5 mmol), the mixture was stirred for 1 hour. Solution that TPS-Cl (20 g, 56.8 mmol) was dissolved in THF (25 mL) was slowly added. After slowly increasing temperature, the mixture was stirred at room temperature for one day. Upon completion of the reaction, H2O was added and the mixture was extracted with EA/H2O. After removing moisture with MgSO4 and performing distillation under reduced pressure, Compound 2-3 (17 g, 87%) was obtained by column(MC/Hexane) separation.
Preparation of Compound 2-4
After Compound 2-3 (17.3 g, 41.8 mmol) was dissolved in THF (200 mL), the mixture was cooled to -78 ℃. After slowly adding n-BuLi (20 mL, 2.5M in hexane, 50 mmol), the mixture was stirred for 1 hour. Trimethyl borate (7 mL, 67 mmol) was slowly added thereto and temperature was slowly increased. The mixture was stirred at room temperature for one day. Upon completion of the reaction, 2M HCl was added and the mixture was extracted with EA/H2O. After removing moisture with MgSO4 and performing distillation under reduced pressure, Compound 2-4 (10.5 g, 66%) was obtained by column(MC/Hexane) separation.
Preparation of Compound 2-5
After Compound 2-4 (5 g, 13 mmol), 2,4-dichloropyrimidine (1.8 g, 12 mmol), Pd(PPh3)4 (0.7 g, 0.6 mmol) and Na2CO3 (2.5 g, 24 mmol) were dissolved in toluen (90 mL), EtOH (30 mL), and H2O (12 mL), the mixture was stirred at 80 ℃ for 1.5 hours. Upon completion of the reaction, the mixture was extracted with EA/H2O. After removing moisture with MgSO4 and performing distillation under reduced pressure, Compound 2-5 (5 g, 93%) was obtained by column (MC/Hexane) separation.
Preparation of Compound 17
After Compound 2-2 (2 g, 6.8 mmol), Compound 2-5 (2.8 g, 6.2 mmol), Pd(PPh3)4 (0.3 g, 0.3 mmol) and Na2CO3 (1.4 g, 12.5 mmol) were dissolved in toluen (50 mL), EtOH (15 mL), and H2O (6 mL), the mixture was stirred at 100 ℃ for one day. Upon completion of the reaction, the mixture was extracted with EA/H2O. After removing moisture with MgSO4 and performing distillation under reduced pressure, Compound 17 (2 g, 60%) was obtained by column(MC/Hexane) separation.
Compounds 1 to 68 were prepared according to the procedure of Preparation Examples 1 and 2. 1H NMR and MS/FAB data of thus prepared organic electroluminescent compounds are given in Tables 1 to 8.
Table 1
1H NMR(CDCl3, 200 MHz) MS/FAB
compound found calculated
1 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41(2H, m), 7.51~7.52(8H, m), 7.88(1H, m), 7.94(1H, m), 8.05(2H, m), 8.55(1H, m) 401.52 401.12
2 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41(2H, m), 7.51(4H, m), 7.94(1H, m), 8.28(4H, m), 8.55(1H, m) 404.49 404.11
3 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.32(1H, s), 7.33(1H, m), 7.41(2H, m), 7.51(4H, m), 7.79(2H, m), 7.94(1H, m), 8.28(2H, m), 8.55(1H, m) 403.50 403.11
4 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41(2H, m), 7.51(4H, m), 7.79(4H, m), 7.94(1H, m), 8.55(1H, m), 8.63(1H, s), (H, ) 403.50 403.11
5 δ = 6.96~7(3H, m), 7.2~7.26(4H, m), 7.33(1H, m), 7.51(2H, m), 7.94(1H, m), 8.5~8.55(3H, m), 8.62(2H, m), 8.9(1H, m) 403.50 403.11
6 δ = 6.96(1H, m), 7.11(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41~7.54(8H, m), 7.94(1H, m), 8.3(2H, m), 8.55~8.6(2H, m) 402.51 402.12
7 δ = 6.96(1H, m), 7.2~7.25(10H, m), 7.33(1H, m), 7.41(2H, m), 7.51~7.52(8H, m), 7.88(1H, m), 7.94(1H, m), 8.05(2H, m), 8.55(1H, m) 553.71 553.19
8 δ = 1.72(12H, s), 6.96(1H, m), 7.2~7.38(7H, m), 7.55(2H, m), 7.63(2H, m), 7.77(2H, m), 7.87~7.94(6H, m), 8.05(2H, m), 8.55(1H, m) 633.84 633.25
9 δ = 1.72(6H, s), 6.96(1H, m), 7.17~7.25(3H, m), 7.33~7.34(2H, m), 7.41(2H, m), 7.51~7.56(5H, m), 7.63(1H, m), 7.87~7.94(3H, m), 8.28(4H, m), 8.55(1H, m) 596.74 596.20
10 δ = 6.96(1H, m), 7.2~7.25(4H, m), 7.33(1H, m), 7.41(2H, m), 7.51(4H, m), 7.68(2H, m), 7.79~7.85(8H, m), 7.94(1H, m), 8.23(1H, s), 8.55(1H, m) 555.69 555.18
Table 2
1H NMR(CDCl3, 200 MHz) MS/FAB
compound found calculated
11 δ = 6.96(1H, m), 7.2~7.26(3H, m), 7.33~7.41(3H, m), 7.5~7.52(5H, m), 7.88(2H, m), 7.94(1H, m), 8.55(1H, m), 8.81(2H, m) 402.51 402.12
12 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41(1H, m), 7.51~7.52(4H, m), 7.6(1H, m), 7.62(1H, s), 7.78(1H, m), 7.88(2H, m), 7.94~7.98(2H, m), 8.22(1H, m), 8.55(1H, m), 8.81(2H, m) 452.57 452.13
13 δ = 6.96(1H, m), 7.2~7.25(4H, m), 7.33(1H, m), 7.41(1H, m), 7.51~7.52(4H, m), 7.8~7.85(3H, m), 7.94(1H, m), 8.05~8.06(2H, m), 8.16(1H, m), 8.55(1H, m) 453.56 453.13
14 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33~7.37(7H, m), 7.46~7.55(14H, m), 7.89~7.94(3H, m), 8.09(1H, m), 8.55(1H, m) 583.82 583.18
15 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33~7.37(7H, m), 7.46~7.55(11H, m), 7.89~7.96(4H, m), 8.55~8.57(2H, m) 585.79 585.17
16 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33~7.55(21H, m), 7.89~7.94(3H, m), 8.28(2H, m), 8.55(1H, m) 662.88 662.20
17 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33~7.46(14H, m), 7.55~7.61(5H, m), 7.68(2H, m), 7.76~7.79(3H, m), 7.89~7.94(2H, m), 8.29(1H, m), 8.55(1H, m) 661.89 661.20
18 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33~7.41(3H, m), 7.51(2H, m), 7.85(1H, m), 7.94(1H, m), 8.28(2H, m), 8.38(1H, m), 8.55~8.59(2H, m) 405.47 405.10
19 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.55(4H, m), 7.61(2H, m), 7.94~7.95(3H, m), 8.04~8.08(4H, m), 8.55(3H, m) 504.60 504.14
20 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.59(4H, m), 7.92~8(7H, m), 8.49(2H, m), 8.55(1H, m), 9.09(2H, m) 504.60 504.14
Table 3
1H NMR(CDCl3, 200 MHz) MS/FAB
compound found calculated
21 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.6(2H, m), 7.78(2H, m), 7.94~7.98(3H, m), 8.06(2H, m), 8.22(2H, m), 8.55~8.57(3H, m) 506.58 506.13
22 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.67(4H, m), 7.8(4H, m), 7.94(1H, m), 8.55(1H, m), 8.7(2H, s), (H, ) 508.56 508.12
23 δ = 6.96(1H, m), 7.2~7.33(4H, m), 7.41~7.51(10H, m), 7.67(1H, m), 7.94(1H, m), 8.06(1H, m), 8.55(1H, m) 453.56 453.13
24 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41(2H, m), 7.51(4H, m), 7.68(2H, m), 7.79(6H, m), 7.94(1H, m), 8.23(1H, s), 8.55(1H, m) 479.59 479.15
25 δ = 7.25(2H, s), 7.25(0H, m), 7.33(1H, m), 7.41(3H, m), 7.51(6H, m), 7.79(2H, m), 7.94(1H, m), 8.28(4H, m), 8.55(1H, m) 480.58 480.14
26 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41(2H, m), 7.51~7.52(8H, m), 7.66(3H, m), 7.94(1H, m), 8.55(1H, m), 9.42(2H, m) 479.59 479.15
27 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.36(1H, s), 7.41~7.42(3H, m), 7.51~7.52(4H, m), 7.62(4H, m), 7.71(1H, m), 7.94(1H, m), 8.17(1H, m), 8.55(1H, m) 440.56 440.13
28 δ = 6.96(1H, m), 7.2~7.29(4H, m), 7.32(1H, s), 7.33(2H, m), 7.41(1H, m), 7.5~7.51(3H, m), 7.63~7.68(3H, m), 7.79(4H, m), 7.94(2H, m), 8.12(1H, m), 8.55(2H, m) 568.69 568.17
29 δ = 6.96(1H, m), 7.2~7.25(3H, m), 7.33(2H, m), 7.63~7.67(4H, m), 7.8(1H, m), 7.94(2H, m), 8.05~8.06(2H, m), 8.16(2H, m), 8.54~8.55(3H, m) 516.61 516,.14
Table 4
1H NMR(CDCl3, 200 MHz) MS/FAB
compound found calculated
30 δ = 6.96(1H, m), 7.16(1H, s), 7.2~7.33(9H, m), 7.5(2H, m), 7.63~7.68(4H, m), 7.79(2H, m), 7.94(3H, m), 8.12(2H, m), 8.55(3H, m) 657.78 657.20
31 δ = 6.96(1H, m), 7.2~7.33(6H, m), 7.45~7.5(7H, m), 7.58~7.63(5H, m), 7.69(1H, m), 7.77(2H, m), 7.87~7.88(2H, m), 7.94~8.05(5H, m), 8.12(1H, m), 8.18(1H, m), 8.55(2H, m) 731.90 731.24
32 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.57(1H, m), 7.67(4H, m), 7.8(1H, m), 7.94~7.96(3H, m), 8.05~8.16(6H, m), 8.51~8.55(3H, m) 566.67 566.16
33 δ = 6.96(1H, m), 7.2(1H, m), 7.41(3H, m), 7.51~7.52(8H, m), 7.68(2H, m), 7.77~7.79(7H, m), 8(1H, m), 8.18(1H, m), 8.23(1H, s), (H, ) 555.69 555.18
34 δ = 6.96(1H, m), 7.2~7.33(4H, m), 7.41(2H, m), 7.5~7.51(5H, m), 7.62~7.68(4H, m), 7.79(6H, m), 7.94~7.98(3H, m), 8.12(1H, m), 8.23(1H, s), 8.55(1H, m) 644.78 644.20
35 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41~7.51(8H, m), 7.79(4H, m), 7.94(1H, m), 8.09(1H, m), 8.23(1H, s), 8.28(1H, m), 8.55(1H, m) 479.59 479.15
36 δ = 1.48(6H, m), 1.73(4H, m), 2.72(1H, m), 6.95~6.96(2H, m), 7.2(1H, m), 7.41(2H, m), 7.51(4H, m), 7.68(2H, m), 7.79(6H, m), 7.86(1H, m), 8.23(1H, s), 8.79(1H, m) 561.74 561.22
37 δ = 6.96(1H, m), 7.06(1H, m), 7.2(1H, m), 7.41(2H, m), 7.51(4H, m), 7.68(2H, m), 7.79(6H, m), 7.92(1H, m), 8.22(1H, m), 8.23(1H, s), (H, ) 497.58 497.14
Table 5
1H NMR(CDCl3, 200 MHz) MS/FAB
compound found calculated
38 δ = 3.05(2H, m), 4.14(2H, m), 6.06(1H, m), 6.55(1H, m), 6.72(1H, m), 6.96(1H, m), 7.05~7.07(2H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.68(2H, m), 7.79~7.83(3H, m), 7.94(1H, m), 8.55(1H, m) 444.55 444.14
39 δ = 6.96(2H, m), 7.2~7.25(4H, m), 7.33(2H, m), 7.68(4H, m), 7.79(4H, m), 7.94(2H, m), 8.55(2H, m) 496.64 496.11
40 δ = 1.72(6H, s), 6.55(2H, m), 6.69~6.73(4H, m), 6.96~7.05(5H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.54(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(1H, m), 8.55(1H, m) 532.70 532.20
41 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41~7.52(8H, m), 7.58(2H, m), 7.68(2H, m), 7.79(2H, m), 7.92~7.94(2H, m), 8.07(1H, m), 8.28(1H, m), 8.55(1H, m) 517.64 517.16
42 δ = 0.66(6H, s), 6.69~6.73(6H, m), 6.96(1H, m), 7.2~7.33(7H, m), 7.54(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(1H, m), 8.55(1H, m) 548.77 548.17
43 δ = 1.16(2H, m), 1.48(2H, m), 1.58(2H, m), 1.73(2H, m), 2.95(2H, m), 6.52(1H, m), 6.66~6.69(3H, m), 6.96(1H, m), 7.05~7.08(2H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.57(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(1H, m), 8.55(1H, m) 496.66 496.20
44 δ = 6.96(1H, m), 7.2~7.25(3H, m), 7.33(1H, m), 7.67~7.68(6H, m), 7.79(4H, m), 7.94~7.97(4H, m), 8.16(1H, m), 8.43(1H, m), 8.54~8.55(2H, m) 541.66 541.16
45 δ = 6.59(2H, m), 6.69(2H, m), 6.77(2H, m), 6.89~6.96(5H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.54(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(1H, m), 8.55(1H, m) 506.62 506.15
Table 6
1H NMR(CDCl3, 200 MHz) MS/FAB
compound found calculated
46 δ = 6.69(2H, m), 6.96~6.97(3H, m), 7.16~7.25(8H, m), 7.33(1H, m), 7.54(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(1H, m), 8.55(1H, m) 522.68 522.18
47 δ = 6.38(4H, m), 6.56(4H, m), 6.63(2H, m), 6.69(2H, m), 6.81(1H, m), 6.96(1H, m), 7.2~7.25(4H, m), 7.33(1H, m), 7.54(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(1H, m), 8.55(1H, m) 581.73 581.19
48 δ = 2.88(4H, m), 6.58(2H, m), 6.69(2H, m), 6.76(2H, m), 6.96~7.04(5H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.54(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(1H, m), 8.55(1H, m) 518.67 518.18
49 δ = 6.63(2H, m), 6.69(2H, m), 6.81(2H, m), 6.96~7.05(5H, m), 7.2~7.25(4H, m), 7.33(1H, m), 7.54(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(1H, m), 8.55(1H, m) 516.65 516.17
50 δ = 6.69(4H, m), 6.87(2H, m), 6.96(1H, m), 7.16~7.25(4H, m), 7.33(1H, m), 7.47(2H, m), 7.54(4H, m), 7.68(2H, m), 7.79~7.85(4H, m), 7.94(1H, m), 8.55(1H, m) 566.71 566.18
51 δ = 6.96(1H, m), 7.2~7.33(6H, m), 7.46~7.52(4H, m), 7.63~7.68(3H, m), 7.79(2H, m), 7.94(2H, m), 8.09~8.12(2H, m), 8.55(2H, m) 490.62 490.15
52 δ = 6.96(1H, m), 7.2~7.25(7H, m), 7.33(2H, m), 7.45~7.5(3H, m), 7.58(2H, m), 7.68~7.69(3H, m), 7.77~7.79(3H, m), 7.87(1H, m), 7.94(2H, m), 8.55(2H, m) 566.71 566.18
Table 7
1H NMR(CDCl3, 200 MHz) MS/FAB
compound found calculated
53 δ = 6.96(1H, m), 7.2~7.33(6H, m), 7.41(1H, m), 7.5~7.51(3H, m), 7.63~7.68(5H, m), 7.79(6H, m), 7.94(2H, m), 8.12(1H, m), 8.23(1H, s), 8.55(2H, m) 644.78 644.20
54 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41(2H, m), 7.48~7.51(5H, m), 7.57(1H, m), 7.68~7.7(3H, m), 7.79(2H, m), 7.94(1H, m), 8.24~8.28(5H, m), 8.55(1H, m) 556.68 556.17
55 δ = 6.96(1H, m), 7.2~7.25(2H, m), 7.33(1H, m), 7.41(3H, m), 7.51~7.52(8H, m), 7.66~7.68(5H, m), 7.79(4H, m), 7.94(1H, m), 8.23(1H, s), 8.28(2H, m), 8.55(1H, m) 631.79 631.22
56 δ = 7.25(1H, m), 7.33(1H, m), 7.41~7.42(3H, m), 7.51(4H, m), 7.79(4H, m), 7.94(1H, m), 8.13(1H, m), 8.55(1H, m), 8.63(1H, s), (H, ) 387.43 387.14
57 δ = 7.25(1H, m), 7.33~7.55(19H, m), 7.89~7.96(4H, m), 8.13(1H, m), 8.55~8.57(2H, m) 569.73 569.19
58 δ = 7.25(3H, m), 7.33(1H, m), 7.41~7.42(3H, m), 7.51(4H, m), 7.68(2H, m), 7.79~7.85(8H, m), 7.94(1H, m), 8.13(1H, m), 8.23(1H, s), 8.55(1H, m) 539.62 539.20
59 δ = 0.14(6H, s), 5.2(1H, m), 6.6(1H, m), 7.25(2H, m), 7.41(2H, m), 7.51~7.54(5H, m), 7.68(2H, m), 7.79(6H, m), 8.23(1H, s), 8.4(1H, m) 505.68 505.20
60 δ = 0.14(6H, s), 5.2(1H, m), 6.6(1H, m), 7.25(2H, m), 7.41(2H, m), 7.48~7.57(7H, m), 7.68~7.7(3H, m), 7.79(2H, m), 8.24~8.28(5H, m), 8.4(1H, m) 582.77 582.22
61 δ = 0.14(6H, s), 5.2(1H, m), 6.6(1H, m), 7.25(2H, m), 7.41(2H, m), 7.51~7.54(9H, m), 7.85(4H, m), 8.3(4H, m), 8.4(1H, m), 8.63(1H, s), (H, ) 581.78 581.23
Table 8
1H NMR(CDCl3, 200 MHz) MS/FAB
compound found calculated
62 δ = 6.19(1H, m), 7.25~7.26(2H, m), 7.33(1H, m), 7.41~7.51(9H, m), 7.58(2H, m), 7.79(4H, m), 7.94(1H, m), 8.55(1H, m), 8.63(1H, s), (H, ) 462.54 462.18
63 δ = 6.19(1H, m), 7.25~7.26(2H, m), 7.33(1H, m), 7.41~7.52(14H, m), 7.58(2H, m), 7.66~7.68(5H, m), 7.79(4H, m), 7.94(1H, m), 8.23(1H, s), 8.28(2H, m), 8.55(1H, m) 690.83 690.28
64 δ = 6.19(1H, m), 7.25~7.26(2H, m), 7.33(1H, m), 7.41~7.51(9H, m), 7.58(2H, m), 7.68(2H, m), 7.79(6H, m), 7.94(1H, m), 8.23(1H, s), 8.55(1H, m) 538.64 538.22
65 δ = 6.19(1H, m), 7.25~7.26(7H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58(4H, m), 7.68~7.69(3H, m), 7.77~7.79(3H, m), 7.87(1H, m), 7.94(2H, m), 8.55(2H, m) 625.76 625.25
66 δ = 2.06(3H, m), 7.25(1H, m), 7.33(1H, m), 7.41~7.52(12H, m), 7.58(2H, m), 7.66~7.68(5H, m), 7.79(4H, m), 7.94(1H, m), 8.23(1H, s), 8.24~8.28(4H, m), 8.55(1H, m) 705.85 705.29
67 δ = 2.06(3H, m), 7.25(1H, m), 7.33(1H, m), 7.41~7.51(7H, m), 7.58(2H, m), 7.68(2H, m), 7.79(6H, m), 7.94(1H, m), 8.23(1H, s), 8.24(2H, m), 8.55(1H, m) 553.65 553.23
68 δ = 2.06(3H, m), 7.25(6H, m), 7.33(2H, m), 7.4~7.5(5H, m), 7.58(2H, m), 7.68~7.69(3H, m), 7.77~7.79(3H, m), 7.87(1H, m), 7.94(2H, m), 8.42(2H, m), 8.55(2H, m) 641.76 641.26
[Example 1] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured using the electroluminescent material 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(--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.
After forming the hole injection layer and the hole transport layer, an electroluminescent layer was formed thereon as follows. Compound 30 was placed in a cell of a vacuum vapor deposition apparatus as a host, and Ir(ppy)3[tris(2-phenylpyridine)iridium] 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 10 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) of a following structure 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.
Each compound used in the OLED was purified by vacuum sublimation at 10-6torr.
As a result, it was confirmed that current of 3.7 mA/cm2 flows at voltage of 6.8 V and a green light of 1060 cd/m2 was emitted.
[Example 2]
An OLED device was manufactured as in Example 1 except that Compound 34 was added as a host material on the electroluminescent layer and Ir(ppy)3[tris(2-phenylpyridine)iridium] was used as an electroluminescent dopant.
As a result, it was confirmed that current of 3.5 mA/cm2 flows at voltage of 6.5 V and a green light of 1075 cd/m2 was emitted.
[Example 3]
An OLED device was manufactured as in Example 1 except that Compound 51 was added as a host material on the electroluminescent layer and Ir(ppy)3[tris(2-phenylpyridine)iridium] was used as an electroluminescent dopant.
As a result, it was confirmed that current of 3.9 mA/cm2 flows at voltage of 6.9 V and a green light of 1070 cd/m2 was emitted.
[Example 4]
An OLED device was manufactured as in Example 1 except that Compound 13 was added as a host material on the electroluminescent layer and (piq)2Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] was used as an electroluminescent dopant.
As a result, it was confirmed that current of 13.8 mA/cm2 flows at voltage of 7.0 V and a red light of 1120 cd/m2 was emitted.
[Example 5]
An OLED device was manufactured as in Example 1 except that Compound 34 was added as a host material on the electroluminescent layer and (piq)2Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] was used as an electroluminescent dopant.
As a result, it was confirmed that current of 14.2 mA/cm2 flows at voltage of 6.8 V and a red light of 1095 cd/m2 was emitted.
[Comparative Example 1]
An OLED was manufactured in the same manner as Example 1 except that 4,4'-bis(carbazol-9-yl)biphenyl(CBP) instead of the compounds of the present invention as a host material at one cell of the vacuum vapor deposition apparatus, Ir(ppy)3[tris(2-phenyl pyridine)iridium] as a dopant and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III) (BAlq) as a hole blocking layer were used.
As a result, it was confirmed that current of 3.8 mA/cm2 flows at voltage of 7.5 V and a green light of 1000 cd/m2 was emitted.
[Comparative Example 2]
An OLED was manufactured in the same manner as Example 1 except that 4,4'-bis(carbazol-9-yl)biphenyl(CBP) instead of the compounds of the present invention as a host material at one cell of the vacuum vapor deposition apparatus,(piq)2Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] as a dopant and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III) (BAlq) as a hole blocking layer were used.
As a result, it was confirmed that current of 15,3 mA/cm2 flows at voltage of 7.5 V and a red light of 1000 cd/m2 was emitted.
The organic electroluminescent compounds according to the present invention have excellent properties compared with the conventional material. In addition, the device using the organic electroluminescent compound according to the present invention as host material has excellent electroluminescent properties and drops driving voltage, thereby increasing power efficiency and improving power consumption.

Claims (10)

  1. An organic electroluminescent compound represented by Chemical Formula 1:
    Figure PCTKR2011000652-appb-I000045
    (1)
    wherein
    A1 through A4 independently represent CR3 or N;
    X represents -N(R10)-, -S-, -O- or -Si(R11)(R12)-;
    Y represents CR4 or N;
    Ar1 and Ar2 independently represent (C6-C30)arylene with or without substituent(s) or (C3-C30)heteroarylene with or without substituent(s), and Ar3 represents (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s);
    R1 through R4 and R10 through R12 independently represent hydrogen, deuterium, halogen, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), substituted or unsubstituted (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl(s) with or without substituent(s), (C3-C30)heteroaryl with or without substituent(s), 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), cyano, nitro, NR21R22, BR23R24, PR25R26, P(=O)R27R28, R29R30R31Si-, R32Z-, (C6-C30)ar(C1-C30)alkyl with or without substituent(s), (C2-C30)alkenyl with or without substituent(s), (C2-C30)alkynyl with or without substituent(s),
    Figure PCTKR2011000652-appb-I000046
    ,
    Figure PCTKR2011000652-appb-I000047
    or,
    Figure PCTKR2011000652-appb-I000048
    or each of them may be linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicylic ring, a mono- or polycyclic aromatic ring or a mono- or polycyclic heteroaromatic ring;
    A ring and B ring independently represent (C5-C30)cycloalkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s),(C6-C30)heteroaryl with or without substituent(s);
    R21 through R32 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s);
    Z represents S or O;
    W represents -(CR51R52)m-, -(R51)C=C(R52)-, -N(R53)-, -S-, -O-, -Si(R54)(R55)-, -P(R56)-, -P(=O)(R57)-, -C(=O)- or -B(R58)-;
    R41 through R43 and R51 through R58 are the same as R1 through R3;
    the heterocycloalkyl, heteroaryl or heteroaromatic ring may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P;
    m represents an integer from 0 to 2; and
    a and b independently represent an integer from 0 to 4; and they may be identical or different when a and b are larger than 2.
  2. The organic electroluminescent compound according to claim 1, which is selected from the following compounds:
    Figure PCTKR2011000652-appb-I000049
    wherein
    Ar1 through Ar3, Y, R1, R2, R10 through R12, a and b are the same as defined in Chemical Formula 1 of claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein the substituent further substituted by the Ar1 and Ar3, R1 through R4, R10 through R12, R21 through R32, R41 through R43 and R51 through R58 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, halogen, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl, (C6-C30)aryl with or without (C6-C30)aryl substituent(s), (C6-C30)aryl with or without (C6-C30)heteroaryl substituent(s), (C3-C30)heteroaryl with or without (C6-C30)aryl substituent(s), (C3-C30)heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s), (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more aromatic ring(s), NR61R62, BR63R64, PR65R66, P(=O)R67R68, R69R70R71Si-, R72Z-, R73C(=O)-, R74C(=O)O-, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, carboxyl, nitro and hydroxyl, or may be linked to an adjacent substituent to form a ring;
    R61 through R72 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl;
    Z represents S or O; and
    R73 and R74 independently represent (C1-C30)alkyl, (C1-C30)alkoxy, (C6-C30)aryl or (C6-C30)aryloxy.
  4. The organic electroluminescent compound according to claim 1, wherein
    Figure PCTKR2011000652-appb-I000050
    is selected from the following structures:
    Figure PCTKR2011000652-appb-I000051
    Figure PCTKR2011000652-appb-I000052
  5. The organic electroluminescent compound according to claim 1, wherein R1 and R2 are independently selected from the following structures:
    Figure PCTKR2011000652-appb-I000053
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to any of claims 1 to 5.
  7. The organic electroluminescent device according to claim 6, 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 organic electroluminescent compound(s) according to any of claims 1 to 5 and one or more dopant(s) represented by Chemical Formula 2:
    M1L101L102L103 (2)
    wherein
    M1 is selected from the group consisting of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, Group 15 and Group 16 metals, and ligands L101, L102 and L103 are independently selected from the following structures:
    Figure PCTKR2011000652-appb-I000054
    Figure PCTKR2011000652-appb-I000055
    Figure PCTKR2011000652-appb-I000056
    Figure PCTKR2011000652-appb-I000057
    wherein
    R201 through R203 independently represent hydrogen, (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, (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 PCTKR2011000652-appb-I000058
    ,
    Figure PCTKR2011000652-appb-I000059
    or
    Figure PCTKR2011000652-appb-I000060
    , 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.
  8. The organic electroluminescent device according to claim 7, wherein the organic layer further comprises one or more amine compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds, or 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.
  9. The organic electroluminescent device according to claim 7, wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
  10. The organic electroluminescent device according to claim 7, which is a white light-emitting electroluminescent device wherein the organic layer further comprises one or more organic electroluminescent layer(s) emitting blue, red or green light.
PCT/KR2011/000652 2010-02-11 2011-01-31 Novel organic electroluminescent compounds and organic electroluminescent device using the same Ceased WO2011099718A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2010-0012861 2010-02-11
KR1020100012861A KR20110093055A (en) 2010-02-11 2010-02-11 Novel organic light emitting compound and organic electroluminescent device employing the same

Publications (1)

Publication Number Publication Date
WO2011099718A1 true WO2011099718A1 (en) 2011-08-18

Family

ID=44367938

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/000652 Ceased WO2011099718A1 (en) 2010-02-11 2011-01-31 Novel organic electroluminescent compounds and organic electroluminescent device using the same

Country Status (2)

Country Link
KR (1) KR20110093055A (en)
WO (1) WO2011099718A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012165844A1 (en) * 2011-05-30 2012-12-06 Rohm And Haas Electronic Materials Korea Ltd. Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2013069762A1 (en) * 2011-11-11 2013-05-16 東ソー株式会社 Cyclic azine compound having nitrogen-containing fused aromatic group, method for producing same, and organic electroluminescent element using same as constituent component
WO2013068376A1 (en) 2011-11-10 2013-05-16 Basf Se 4h-imidazo[1,2-a]imidazoles for electronic applications
WO2014088290A1 (en) * 2012-12-04 2014-06-12 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2015081282A1 (en) * 2013-11-27 2015-06-04 Redwood Bioscience, Inc. Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
US9620724B2 (en) 2012-07-10 2017-04-11 Udc Ireland Limited Benzimidazo[1,2-A]benzimidazole derivatives for electronic applications
US9666809B2 (en) 2013-12-03 2017-05-30 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
CN106986879A (en) * 2015-10-01 2017-07-28 环球展览公司 Organic Electroluminescent Materials and Devices
US9806270B2 (en) 2011-03-25 2017-10-31 Udc Ireland Limited 4H-imidazo[1,2-a]imidazoles for electronic applications
CN107759593A (en) * 2017-11-08 2018-03-06 长春海谱润斯科技有限公司 A kind of electroluminescent organic material and its organic luminescent device
JP2019505478A (en) * 2015-12-08 2019-02-28 ヒソン・マテリアル・リミテッドＨｅｅｓｕｎｇ Ｍａｔｅｒｉａｌ Ｌｔｄ． Heterocyclic compound and organic light emitting device using the same
US12102689B2 (en) 2015-11-09 2024-10-01 R.P. Scherer Technologies, Llc Anti-CD22 antibody-maytansine conjugates and methods of use thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102220954B1 (en) * 2013-02-14 2021-02-26 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
CN112300052B (en) * 2019-07-23 2025-03-14 北京鼎材科技有限公司 A compound and its application, and an organic electroluminescent device containing the same
KR102201473B1 (en) * 2020-09-08 2021-01-11 최돈수 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
WO2023027220A1 (en) * 2021-08-27 2023-03-02 최돈수 Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070196687A1 (en) * 2004-03-31 2007-08-23 Konica Minolta Holding, Inc. Organic Electroluminescence Element Material, Organic Electroluminescence Element,Display Device And Illumination Device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070196687A1 (en) * 2004-03-31 2007-08-23 Konica Minolta Holding, Inc. Organic Electroluminescence Element Material, Organic Electroluminescence Element,Display Device And Illumination Device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ACKERMANN, L. ET AL.: "Domino N-H/C-H borid activation: palladium-catalyzed synthesis of annulated heterocycles using dichloro(hetero)arenes", ANGEWANDTE CHEMIE, INTERNATIONAL EDITION, vol. 46, no. 10, 2007, pages 1627 - 1629 *
BOEINI, H. Z.: "Highly efficient synthesis of thieno[2,3-b]indole derivatives", HELVETICA CHIMICA ACTA, vol. 92, no. 7, 2009, pages 1268 - 1272 *

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12538704B2 (en) 2011-03-25 2026-01-27 Udc Ireland Limited 4H-imidazo[1,2-a]imidazoles for electronic applications
US10431750B2 (en) 2011-03-25 2019-10-01 Udc Ireland Limited 4H-imidazo[1,2-a]imidazoles for electronic applications
US11450812B2 (en) 2011-03-25 2022-09-20 Udc Ireland Limited 4H-imidazo[1,2-a]imidazoles for electronic applications
US9806270B2 (en) 2011-03-25 2017-10-31 Udc Ireland Limited 4H-imidazo[1,2-a]imidazoles for electronic applications
WO2012165844A1 (en) * 2011-05-30 2012-12-06 Rohm And Haas Electronic Materials Korea Ltd. Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2013068376A1 (en) 2011-11-10 2013-05-16 Basf Se 4h-imidazo[1,2-a]imidazoles for electronic applications
US9502664B2 (en) 2011-11-10 2016-11-22 Udc Ireland Limited 4H-imidazo[1,2-a]imidazoles for electronic applications
WO2013069762A1 (en) * 2011-11-11 2013-05-16 東ソー株式会社 Cyclic azine compound having nitrogen-containing fused aromatic group, method for producing same, and organic electroluminescent element using same as constituent component
JP2014111548A (en) * 2011-11-11 2014-06-19 Tosoh Corp Cyclic azine compounds having nitrogen-containing condensed cyclic aromatic group and its manufacturing method, and organic electroluminescent element containing the same as constitutional component
CN104039773A (en) * 2011-11-11 2014-09-10 东曹株式会社 Cyclic azine compound having nitrogen-containing ring-condensed aromatic group, method for producing the same, and organic electroluminescent device comprising the cyclic azine compound as a constituent
US9252368B2 (en) 2011-11-11 2016-02-02 Tosoh Corporation Cyclic azine compound having nitrogen-containing condensed aromatic group, method for producing same, and organic electroluminescent device comprising same as constituent component
TWI609862B (en) * 2011-11-11 2018-01-01 東曹股份有限公司 Cyclic azine compound having nitrogen-containing condensed ring aromatic group, process for producing same, organic electroluminescent device comprising same as constituent
CN104039773B (en) * 2011-11-11 2016-08-24 东曹株式会社 Cyclic azine compound having nitrogen-containing ring-condensed aromatic group, method for producing the same, and organic electroluminescent device comprising the cyclic azine compound as a constituent
US11744152B2 (en) 2012-07-10 2023-08-29 Udc Ireland Limited Benzimidazo[1,2-a]benzimidazole derivatives for electronic applications
US10862051B2 (en) 2012-07-10 2020-12-08 Udc Ireland Limited Benzimidazo[1,2-a]benzimidazole derivatives for electronic applications
US9620724B2 (en) 2012-07-10 2017-04-11 Udc Ireland Limited Benzimidazo[1,2-A]benzimidazole derivatives for electronic applications
US10243150B2 (en) 2012-07-10 2019-03-26 Udc Ireland Limited Benzimidazo[1,2-a]benzimidazole derivatives for electronic applications
WO2014088290A1 (en) * 2012-12-04 2014-06-12 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and organic electroluminescent device comprising the same
KR102320019B1 (en) 2013-11-27 2021-11-01 레드우드 바이오사이언스 인코포레이티드 Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
US11180451B2 (en) 2013-11-27 2021-11-23 Redwood Bioscience, Inc. Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
WO2015081282A1 (en) * 2013-11-27 2015-06-04 Redwood Bioscience, Inc. Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
US12215080B2 (en) 2013-11-27 2025-02-04 Redwood Bioscience, Inc. Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
US10464894B2 (en) 2013-11-27 2019-11-05 Redwood Biosciences, Inc. Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
AU2014354643B2 (en) * 2013-11-27 2020-03-05 Redwood Bioscience, Inc. Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
KR20160091963A (en) * 2013-11-27 2016-08-03 레드우드 바이오사이언스 인코포레이티드 Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
US10604483B2 (en) 2013-11-27 2020-03-31 Redwood Bioscience, Inc. Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
US9493413B2 (en) 2013-11-27 2016-11-15 Redwood Bioscience, Inc. Hydrazinyl-pyrrolo compounds and methods for producing a conjugate
US9666809B2 (en) 2013-12-03 2017-05-30 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
CN106986879A (en) * 2015-10-01 2017-07-28 环球展览公司 Organic Electroluminescent Materials and Devices
US10593892B2 (en) 2015-10-01 2020-03-17 Universal Display Corporation Organic electroluminescent materials and devices
CN117285541A (en) * 2015-10-01 2023-12-26 环球展览公司 Organic electroluminescent material and device
US12063853B2 (en) 2015-10-01 2024-08-13 Universal Display Corporation Organic electroluminescent materials and devices
US12102689B2 (en) 2015-11-09 2024-10-01 R.P. Scherer Technologies, Llc Anti-CD22 antibody-maytansine conjugates and methods of use thereof
JP2019505478A (en) * 2015-12-08 2019-02-28 ヒソン・マテリアル・リミテッドＨｅｅｓｕｎｇ Ｍａｔｅｒｉａｌ Ｌｔｄ． Heterocyclic compound and organic light emitting device using the same
EP3392246A4 (en) * 2015-12-08 2019-10-30 Heesung Material Ltd. HETEROCYCLIC COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
CN107759593A (en) * 2017-11-08 2018-03-06 长春海谱润斯科技有限公司 A kind of electroluminescent organic material and its organic luminescent device

Also Published As

Publication number Publication date
KR20110093055A (en) 2011-08-18

Similar Documents

Publication Publication Date Title
WO2011099718A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011126224A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011019156A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011132866A1 (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2011055911A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2012050371A1 (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2011055912A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011010843A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011071255A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011136520A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011132865A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010126270A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2012050347A1 (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2010126234A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011010842A2 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011010839A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010114264A2 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010151006A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010114256A2 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010151011A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010114253A2 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011126225A1 (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2011136484A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2012011756A1 (en) Novel organic electroluminescent compounds and organic electroluminescent devices including the same
WO2011010840A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11742410

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11742410

Country of ref document: EP

Kind code of ref document: A1