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WO2011055911A1 - 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

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Publication number
WO2011055911A1
WO2011055911A1 PCT/KR2010/006796 KR2010006796W WO2011055911A1 WO 2011055911 A1 WO2011055911 A1 WO 2011055911A1 KR 2010006796 W KR2010006796 W KR 2010006796W WO 2011055911 A1 WO2011055911 A1 WO 2011055911A1
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Prior art keywords
substituent
alkyl
organic electroluminescent
aryl
group
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PCT/KR2010/006796
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French (fr)
Inventor
Chi Sik Kim
Young Gil Kim
Young Jun Cho
Hyuck Joo Kwon
Bong Ok Kim
Sung Min Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Publication of WO2011055911A1 publication Critical patent/WO2011055911A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B17/00—Azine dyes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • 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 radiating surfaces
    • H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
    • 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
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • 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
    • H10K85/657—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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than 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.
  • the electroluminescent material The most important factor that determines luminous efficiency of an OLED is the electroluminescent material. At present, fluorescent materials are widely used for the electroluminescent material. But, phosphorescent materials are better when considering the electroluminescence mechanism.
  • CBP is the most widely known as a host material for a phosphorescent material.
  • High-efficiency OLEDs using a hole blocking layer comprising BCP, BAlq, etc. are reported.
  • High-performance OLEDs using BAlq derivatives as a host were reported.
  • OLEDs using phosphorescent materials provide much better current efficiency (cd/A) than those using fluorescent materials.
  • cd/A current efficiency
  • BAlq, CBP, etc. are used as a host of the phosphorescent material
  • power efficiency lm/W
  • the OLED devices do not have satisfactory operation life. Therefore, development of more stable, higher-performance host materials is required.
  • the object of the present invention is to provide organic electroluminescent compounds having a superior backbone to provide better luminous efficiency and device life with appropriate color coordinate as compared to conventional host or dopant material, while overcoming the problems described above.
  • organic electroluminescent compound represented by following Chemical Formula 1 and an organic electroluminescent device using the same. Since the organic electroluminescent compound according to the present invention 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.
  • a 1 through A 4 independently represent -C(R 3 )- or -N-;
  • R 1 through R 3 independently represent -L 1 -L 2 -L 3 -R 4 ;
  • L 1 through L 3 independently represent a chemical bond, (C6-C30)arylene with or without substituent(s), (C3-C30)heteroarylene with or without substituent(s), (C3-C30)cycloalkylene with or without substituent(s), (C2-C30)alkenylene with or without substituent(s), (C2-C30)alkynylene with or without substituent(s);
  • R 4 represents 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-
  • R 1 through R 3 include at least one or ;
  • R 11 through R 22 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);
  • Y represents S or O;
  • the A 1 through A 4 independently -C(R 3 )- or -N-, and the A 1 to A 4 may be the same or different;
  • R 1 to R 3 independently represent -L 1 -L 2 -L 3 -R 4 and the R 1 to R 3 may be the same or different.
  • 'alkyl' 'alkoxy' and other substituents containing 'alkyl' moiety include both linear and branched species.
  • 'cycloalkyl' includes both adamantyl with or without substituent(s) and (C7-C30)bicycloalkyl with or without substituent(s).
  • '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
  • 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 group 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.
  • monocyclic 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, benzoxazo
  • 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.
  • R 1 to R 4 , R 11 to R 22 , R 31 to R 33 , R 41 to R 48 are independently further substituted with more than one selected from the group consisting of deuterium, halogen, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl, (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
  • the present invention is selected from the following compounds but is not limited thereto:
  • R 1 , R 2 and R 51 to R 54 are the same as the definition of R 1 to R 3 in Chemical Formula 1.
  • the L 1 to L 3 are independently selected from the following structures but are not limited thereto:
  • the R 4 is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluore, cyano, methoxy, ethoxy, n-porpoxy, i-porpoxy, n-butoxy, i-butoxy, t-butoxy, n-pentoxy, i-pentoxy, n-hexyloxy, n-heptoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
  • the R 4 isselectedfromthefollowingstructuresbut is not limited thereto.
  • organic electroluminescent compound according to the present invention may be exemplified by the following compounds, but are not limited thereto:
  • an organic electroluminescent device including: 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 includes one or more organic electroluminescent compound(s) represented by Chemical Formula 1.
  • the organic layer may include one or more organic electroluminescent compounds of Chemical Formula 1 as an electroluminescent host and may include one or more dopant(s).
  • 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 a metal selected from a 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)alky
  • R 226 represents (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), (C5-C30)heteroaryl with or without substituent(s) or halogen;
  • R 227 through R 229 independently represent hydrogen, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen;
  • Q represents , or , wherein R 231 through R 242 independently represent hydrogen, (C1-C30)alkylwith 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), 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 compound represented by Chemical Formula 2 may be exemplified by the compounds having following structures, but is 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 compounds.
  • 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, 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 Nos. 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 chalcogenide (including oxide) layer of silicon or aluminum metal 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. An operation stability may be attained therefrom.
  • the chalcogenide may be, for example, SiO x (1 ⁇ x ⁇ 2), AlO x (1 ⁇ x ⁇ 1.5), SiON, SiAlON, etc.
  • the metal halide may be, for example, LiF, MgF 2 ,CaF 2 ,arareearthmetalfluoride,etc.
  • the metal oxide may be, for example, Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • an 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.
  • the compound 1-1 (30 g, 0.12 mol) was dissolved in hydrazine hydrate (70 mL) and the mixture was stirred for 2hours at 100°C. Upon completion of the reaction, the temperature was slowly raised to room temperature and then a solid was produced. Washing the solid with diethyl ether and filtering under reduced pressure gave a compound 1-2 (26g,92%).
  • a compound 1-2 (29 g, 0.13 mol) was dissolved in acetic acid (625 mL). A solution that NaNO 2 (10.1 g, 0.14 mol) was dissolved in water (70 mL) was slowly added dropwise thereto at 0°C and the mixture was stirred for 15 minutes. Upon completion of the reaction, a solid was produced. The solid was dissolved by adding ethylacetate (500 mL) to the mixture and stirring the mixture for 15 minutes. Na 2 CO 3 aqueous solution was added to the mixture until a pH level becomes 7. After washing with distilled water, extracting with ethylacetate, and drying an organic layer with MgSO 4 , a solvent is removed by the rotary evaporator. A compound 1-3 (25 g,80 %) was given through purification by column chromatography using ethylacetate as a developing solvent.
  • the compound 1-4 (21 g,68.06 mmol) was dissolved in EtOH (500 mL) and Pd/C 10 g was slowly added thereto. The reaction was performed for 6 hours while continuously introducing H 2 (gas). 1,2-bis(4-bromophenyl)ethane-1,2-dione (25 g, 68.06 mmol) was added thereto and the mixture was stirred under reflux for 24 hours at 100 °C. Upon completion of the reaction, EtOH was removed by the rotary evaporator. After washing with distilled water, extracting with ethylacetate, and drying an organic layer with MgSO 4 , a solvent is removed by the rotary evaporator. A compound 1-5 (28 g,82 %) was given through purification by column chromatography using ethylacetate as a developing solvent.
  • the compound 2-1 (18 g, 55.86 mmol) was dissolved in THF (200 mL) and n-buLi (24.58 mL, 61.45 mmol, 2.5 M in Hexane) was slowly added thereto at -78°C. 1 hours later, DMF (5.6 mL, 72.65 mmol) was added and the mixture was stirred for 12 hours at room temperature. Distilled water was added thereto and the product was extracted with EA. After drying with MgSO 4 and distilling under reduced pressure, a compound 2-2 ( 11 g, 40.54 mmol, 72.58 %) was given by column separation.
  • Organic electroluminescent Compounds 1 to 52 were prepared according to Preparation Examples 1 and 2.
  • Table 1 shows 1 H NMR and MS/FAB of the prepared organic electroluminescent compounds.
  • 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. A compound 1 was placed in a cell of a vacuum vapor deposition apparatus as a host, and a compound 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 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 according to the same method as Example 1 except that a compound 3 was used on the electro luminescent layer as a host material and (piq) 2 Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] was used as an electroluminescent dopant.
  • An OLED device was manufactured according to the same method as Example 1 except that a compound 26 was used on the electro luminescent layer as a host material and Ir(ppy) 3 [tris(2-phenylpyridine)iridium] was used as an electroluminescent dopant.
  • An OLED device was manufactured in the same manner as Example 1 except that 4,4'-bis(carbazol-9-yl)biphenyl (CBP) as a host material instead of the compounds of the present invention and Ir(ppy) 3 [tris(2-phenylpyridine)iridium] as a dopant were used in a cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)( p -phenyl-phenolato)aluminum(III)(BAlq) was used as the hole blocking layer.
  • CBP 4,4'-bis(carbazol-9-yl)biphenyl
  • Ir(ppy) 3 tris(2-phenylpyridine)iridium]
  • Bis(2-methyl-8-quinolinato)( p -phenyl-phenolato)aluminum(III)(BAlq) was used as the hole blocking layer.
  • An OLED device was manufactured in the same manner as Example 6 except that 4,4'-bis(carbazol-9-yl)biphenyl (CBP) as a host material instead of the compounds of the present invention and (piq) 2 Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] as a dopant were used in a cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)( p -phenyl-phenolato)aluminum(III)(BAlq) was used as the hole blocking layer.
  • CBP 4,4'-bis(carbazol-9-yl)biphenyl
  • Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] as a dopant were used in a cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)( p
  • 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 a host material has excellent electroluminescent properties and drops driving voltage, thereby increasing power efficiency and improving power consumption.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

Organic electroluminescent compounds of Chemical Formula 1 : wherein the variables A1, A2, A3, A4, R1 and R2 are as defined therein in the specification. These compounds exhibit high luminous efficiency and excellent life property of material and are used in organic electroluminescent devices. An OLED having a very good operation life and improved consumption power is manufactured using these compounds.

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.
The most important factor that determines luminous efficiency of an OLED is the electroluminescent material. At present, fluorescent materials are widely used for the electroluminescent material. But, phosphorescent materials are better when considering the electroluminescence mechanism.
At present, CBP is the most widely known as a host material for a phosphorescent material. High-efficiency OLEDs using a hole blocking layer comprising BCP, BAlq, etc. are reported. High-performance OLEDs using BAlq derivatives as a host were reported.
Although these materials provide good electroluminescence characteristics, they are disadvantageous in that degradation may occur during the high-temperature deposition process in vacuum because of low glass transition temperature and poor thermal stability. Since the power efficiency of an OLED is given by (π / voltage) × current efficiency, the power efficiency is inversely proportional to the voltage. High power efficiency is required to reduce the power consumption of an OLED.
Actually, OLEDs using phosphorescent materials provide much better current efficiency (cd/A) than those using fluorescent materials. However, when the existing materials such as BAlq, CBP, etc. are used as a host of the phosphorescent material, there is no significant advantage in power efficiency (lm/W) over the OLEDs using fluorescent materials because of high driving voltage. Further, the OLED devices do not have satisfactory operation life. Therefore, development of more stable, higher-performance host materials is required.
The object of the present invention is to provide organic electroluminescent compounds having a superior backbone to provide better luminous efficiency and device life with appropriate color coordinate as compared to conventional host or dopant material, while overcoming the problems described above.
Provided are a novel organic electroluminescent compound represented by following Chemical Formula 1 and an organic electroluminescent device using the same. Since the organic electroluminescent compound according to the present invention 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.
[Chemical Formula 1]
Figure PCTKR2010006796-appb-I000001
wherein
A1 through A4 independently represent -C(R3)- or -N-;
R1 through R3 independently represent -L1-L2-L3-R4; L1 through L3 independently represent a chemical bond, (C6-C30)arylene with or without substituent(s), (C3-C30)heteroarylene with or without substituent(s), (C3-C30)cycloalkylene with or without substituent(s), (C2-C30)alkenylene with or without substituent(s), (C2-C30)alkynylene with or without substituent(s); and R4 represents 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 aromaticring(s) with or withoutsubstituent(s), (C3-C30)cycloalkyl with or without substituent(s),(C3-C30)cycloalkyl fused with one or more aromaticring(s) with or without substituent(s), cyano, nitro, NR11R12, BR13R14, PR15R16, P(=O)R17R18, R19R20R21Si-, R22Y-, (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 PCTKR2010006796-appb-I000002
or
Figure PCTKR2010006796-appb-I000003
, 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; the rings A and B independently represent a mono- or polycyclic aromatic ring or a mono- or polycyclic heteroaromatic ring;
only, R1 through R3 include at least one
Figure PCTKR2010006796-appb-I000004
or
Figure PCTKR2010006796-appb-I000005
; R11 through R22 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); Y represents S or O; W represents -(CR41R42)m-, -(R41)C=C(R42)-, -N(R43)-, -S-, -O-, -Si(R44)(R45)-, -P(R46)-, -P(=O)(R47)-, -C(=O)-or-B(R48)-, and R31 through R33 and R41 through R48 are the same as defined in R1 through R3; and
the heterocycloalkyl, heteroaryl and heteroaromatic ring include more than one heteroatom(s) selected from B, N, O, S, P(=O), Si and P; and m is an integer ranging from 0 to 2.
The A1 through A4 independently -C(R3)- or -N-, and the A1 to A4 may be the same or different; and
R1 to R3 independently represent -L1-L2-L3-R4 and the R1 to R3 may be the same or different.
In the present invention, 'alkyl' 'alkoxy' and other substituents containing 'alkyl' moiety include both linear and branched species. In the present invention, 'cycloalkyl' includes both adamantyl with or without substituent(s) and (C7-C30)bicycloalkyl with or without substituent(s).
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 group includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt. Specific examples include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, 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 to be further substituted by an unsubstituted substituent. A substituent further substituted by the R1 to R4, R11 to R22, R31 to R33, R41 to R48 are independently further substituted with more than one selected from the group consisting of deuterium, halogen, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl, (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 or hydroxy, or is linked to an adjacent substituent to formaring; R61 to 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, the present invention is selected from the following compounds but is not limited thereto:
Figure PCTKR2010006796-appb-I000006
wherein
R1, R2 and R51 to R54 are the same as the definition of R1 to R3 in Chemical Formula 1.
The L1 to L3 are independently selected from the following structures but are not limited thereto:
Figure PCTKR2010006796-appb-I000007
The R4 is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluore, cyano, methoxy, ethoxy, n-porpoxy, i-porpoxy, n-butoxy, i-butoxy, t-butoxy, n-pentoxy, i-pentoxy, n-hexyloxy, n-heptoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, trifluoremethyl, perfluoreethyl, trifluoreethyl, perfluorepropyl, perfluorebutyl, phenyl, naphthyl, biphenyl, fluorenyl, phenanthryl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, crycenyl, naphthacenyl, perylenyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzoimidazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, triazinyl, phenazinyl, phenothiazinyl, phenooxazinyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, pyrazolyl, indolyl, carbazolyl, carborinyl, thiazolyl, oxazolyl, benzothiazolyl, benzooxazolyl, trimethylsilyl, triphenylsilyl and benzyl, but is not limited thereto.
More preferably, the R4isselectedfromthefollowingstructuresbut is not limited thereto.
Figure PCTKR2010006796-appb-I000008
More specifically, the organic electroluminescent compound according to the present invention may be exemplified by the following compounds, but are not limited thereto:
Figure PCTKR2010006796-appb-I000009
Figure PCTKR2010006796-appb-I000010
Figure PCTKR2010006796-appb-I000011
Figure PCTKR2010006796-appb-I000012
Figure PCTKR2010006796-appb-I000013
Figure PCTKR2010006796-appb-I000014
Figure PCTKR2010006796-appb-I000015
Figure PCTKR2010006796-appb-I000016
Figure PCTKR2010006796-appb-I000017
Figure PCTKR2010006796-appb-I000018
Figure PCTKR2010006796-appb-I000019
Figure PCTKR2010006796-appb-I000020
Figure PCTKR2010006796-appb-I000021
Figure PCTKR2010006796-appb-I000022
Provided is an organic electroluminescent device including: 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 includes one or more organic electroluminescent compound(s) represented by Chemical Formula 1. The organic layer may include one or more organic electroluminescent compounds of Chemical Formula 1 as an electroluminescent host and may include one or more dopant(s). 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 a metal selected from a 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 PCTKR2010006796-appb-I000023
Figure PCTKR2010006796-appb-I000024
Figure PCTKR2010006796-appb-I000025
Figure PCTKR2010006796-appb-I000026
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, (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, (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 alicylic 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, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen; and
Q represents
Figure PCTKR2010006796-appb-I000027
,
Figure PCTKR2010006796-appb-I000028
or
Figure PCTKR2010006796-appb-I000029
, wherein R231 through R242 independently represent hydrogen, (C1-C30)alkylwith 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), 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 compound represented by Chemical Formula 2 may be exemplified by the compounds having following structures, but is not limited thereto:
Figure PCTKR2010006796-appb-I000030
Figure PCTKR2010006796-appb-I000031
Figure PCTKR2010006796-appb-I000032
Figure PCTKR2010006796-appb-I000033
Figure PCTKR2010006796-appb-I000034
Figure PCTKR2010006796-appb-I000035
Figure PCTKR2010006796-appb-I000036
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 compounds. 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, 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 Nos. 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 chalcogenide (including oxide) layer of silicon or aluminum metal 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. An 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,arareearthmetalfluoride,etc. The metal oxide may be, for example, Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In an 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 1
Figure PCTKR2010006796-appb-I000037
Figure PCTKR2010006796-appb-I000038
Preparation of compound 1-1
Phenylhydrazine (40 g, 0.36 mol), (E)-ethyl 2-cyano-3-ethoxyacrylate (62 g, 0.36 mol), and EtOH (400 mL) were added and the mixture was stirred for 2 hours at 100 ℃. Upon completion of the reaction, a compound 1-1 (70g, 82%) was given through purification by column chromatography after removing EtOH by a rotary evaporator.
Preparation of compound 1-2
The compound 1-1 (30 g, 0.12 mol) was dissolved in hydrazine hydrate (70 mL) and the mixture was stirred for 2hours at 100℃. Upon completion of the reaction, the temperature was slowly raised to room temperature and then a solid was produced. Washing the solid with diethyl ether and filtering under reduced pressure gave a compound 1-2(26g,92%).
Preparation of compound 1-3
A compound 1-2 (29 g, 0.13 mol) was dissolved in acetic acid (625 mL). A solution that NaNO2 (10.1 g, 0.14 mol) was dissolved in water (70 mL) was slowly added dropwise thereto at 0℃ and the mixture was stirred for 15 minutes. Upon completion of the reaction, a solid was produced. The solid was dissolved by adding ethylacetate (500 mL) to the mixture and stirring the mixture for 15 minutes. Na2CO3 aqueous solution was added to the mixture until a pH level becomes 7. After washing with distilled water, extracting with ethylacetate, and drying an organic layer with MgSO4, a solvent is removed by the rotary evaporator. A compound 1-3 (25 g,80 %) was given through purification by column chromatography using ethylacetate as a developing solvent.
Preparation of compound 1-4
Under nitrogen atmosphere, the compound 1-3 (47 g,0.20 mol), benzylalcohol(85 mL, (0.82 mol) andxylene (700 mL) were stirred under reflux for 5hours at 140℃. Upon completion of the reaction, the product was washed with distilled water. After extracting with ethylacetate and drying an organic layer with MgSO4, a solvent is removed by the rotary evaporator. A compound 1-4 (25 g, 40 %) was given through purification by column chromatography using ethylacetate as a developing solvent.
Preparation of compound 1-6
The compound 1-4 (21 g,68.06 mmol) was dissolved in EtOH (500 mL) and Pd/C 10 g was slowly added thereto. The reaction was performed for 6 hours while continuously introducing H2(gas). 1,2-bis(4-bromophenyl)ethane-1,2-dione (25 g, 68.06 mmol) was added thereto and the mixture was stirred under reflux for 24 hours at 100 ℃. Upon completion of the reaction, EtOH was removed by the rotary evaporator. After washing with distilled water, extracting with ethylacetate, and drying an organic layer with MgSO4, a solvent is removed by the rotary evaporator. A compound 1-5 (28 g,82 %) was given through purification by column chromatography using ethylacetate as a developing solvent.
Preparation of compound 1
The compound 1-5 (3 g,5.92 mmol), carbazole (2.5 g,14.8 mmol), Pd(dba)3 (270 mg, 0.2 mmol), Dave-phos (230 mg, 0.5 mol) and Naot-Bu (1.7 g,17.7 mmol) were dissolved in toluene(100 mL). The mixture was stirred under reflux for 24 hours at 120 ℃. Upon completion of the reaction, EtOH was removed by the rotary evaporator. After washing with distilled water, extracting with ethylacetate, and drying an organic layer with MgSO4, a solvent is removed by the rotary evaporator. A compound 1 (3 g, 75 %) was given through purification by column chromatography using ethylacetate as a developing solvent.
[Preparation Example 2] Preparation of compound 37
Figure PCTKR2010006796-appb-I000039
Figure PCTKR2010006796-appb-I000040
Preparation of compound 2-1
After carbazole (20 g, 119.6 mmol), 1,4-dibromobenzene (56.4 g, 239.2 mmol), Cu (11.4 g, 178.4 mmol), K2CO3 (49 g, 358.8 mmol) and 18-crown-6 (6.3 g, 23.92 mmol) were dissolved in 1,2-dichlorobenzene (400 mL), the mixture was heated for 20hours at 200℃. After distilling under reduced pressure and extracting with EA, the product was washed with distilled water and dried with MgSO4. A compound 2-1 (18 g, 55.86 mmol, 46.94 %) was given by distillation under reduced pressure and column separation.
Preparation of compound 2-2
The compound 2-1(18 g, 55.86 mmol) was dissolved in THF (200 mL) and n-buLi (24.58 mL, 61.45 mmol, 2.5 M in Hexane) was slowly added thereto at -78℃. 1 hours later, DMF (5.6 mL, 72.65 mmol) was added and the mixture was stirred for 12 hours at room temperature. Distilled water was added thereto and the product was extracted with EA. After drying with MgSO4 and distilling under reduced pressure, a compound 2-2 (11 g, 40.54 mmol, 72.58 %) was given by column separation.
Preparation of compound 2-3
After the compound 2-2(11 g, 40.54 mmol), and 5-bromopyridine-2,3-diamine (7.6 g, 40.54 mmol) were dissolved in DMSO (200 mL),the mixture was heated at 200℃ for 12 hours. After cooling to room temperature, the product was washed with distilled water and extracted with EA. After drying with MgSO4 and distilling under reduced pressure, acompound 2-3 (5 g, 11.38 mmol, 28.07 %) was given by column separation.
Preparation of compound 2-4
The compound 2-3 (5 g,11.38 mmol), iodobenzene (2.53 mL, 22.76 mmol), Cu (1.08 g, 17.07 mmol), K2CO3 (4.7 g, 34.11 mmol) and 18-crown-6 (0.3 g, 1.13 mmol) were dissolved in 1,2-dichlorobenzene(100 mL), and the mixture was heated at 200℃ for 20 hours. After distillation under reduced pressure and extraction with EA, the product was washed with distilled water and dried with MgSO4. Distilling under reduced pressure followed by column separation gave a compound 2-4 (3 g, 5.82mmol, 51.14%).
Preparation of compound 37
The compound 2-4 (3 g,5.80 mmol), phenylboronicacid (1.06 g,8.73 mmol), Pd(PPh3)4 (0.20 g,0.17 mmol), 2M K2CO3 (6 mL), toluene (50 mL) and ethanol (20 mL) were mixed and the mixture was stirred under reflux for 6 hours. After cooling to room temperature, the product was washed with distilled water and extracted with EA. After drying with MgSO4 and distilling under reduced pressure, acompound 37 (2.5 g,4.87 mmol,84.08 %) was given by column separation.
Organic electroluminescent Compounds 1 to 52 were prepared according to Preparation Examples 1 and 2. Table 1 shows 1H NMR and MS/FAB of the prepared organic electroluminescent compounds.
[Table 1]
Figure PCTKR2010006796-appb-I000041
Figure PCTKR2010006796-appb-I000042
Figure PCTKR2010006796-appb-I000043
[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(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. After forming the hole injection layer and the hole transport layer, an electroluminescent layer was formed thereon as follows. A compound 1 was placed in a cell of a vacuum vapor deposition apparatus as a host, and a compound 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 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. 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, current of 4.1 mA/cm2 with voltage of 6.4 V flows and it was confirmed that green light of 1190 cd/m2 was emitted.
[Example 2]
An OLED device was manufactured according to the same method as Example 1 except that a compound 3 was used on the electro luminescent layer as a host material and (piq)2Ir(acac)[bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate] was used as an electroluminescent dopant.
As a result, current of 13.4 mA/cm2 with voltage of 7.0 V flows and it is confirmed that red light of 1000 cd/m2 was emitted.
[Example 3]
An OLED device was manufactured according to the same method as Example 1 except that a compound 26 was used on the electro luminescent layer as a host material and Ir(ppy)3[tris(2-phenylpyridine)iridium] was used as an electroluminescent dopant.
As a result, current of 4.1 mA/cm2 with voltage of 7.0 V flows and it is confirmed that green light of 1120 cd/m2 was emitted.
[Comparative Example 1]
An OLED device was manufactured in the same manner as Example 1 except that 4,4'-bis(carbazol-9-yl)biphenyl (CBP) as a host material instead of the compounds of the present invention and Ir(ppy)3[tris(2-phenylpyridine)iridium] as a dopant were used in a cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III)(BAlq) was used as the hole blocking layer.
As a result, current of 3.8 mA/cm2 with voltage of 7.5 V flows and it is confirmed that green light of 1000 cd/m2 was emitted.
[Comparative Example 2]
An OLED device was manufactured in the same manner as Example 6 except that 4,4'-bis(carbazol-9-yl)biphenyl (CBP) as a host material instead of the compounds of the present invention and (piq)2Ir(acac)[bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate] as a dopant were used in a cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III)(BAlq) was used as the hole blocking layer.
As a result, current of 15.3 mA/cm2 with voltage of 7.5 V flows and it is confirmed that 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 a 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 the following Chemical Formula 1:
    [Chemical Formula 1]
    Figure PCTKR2010006796-appb-I000044
    wherein
    A1 through A4 independently represent -C(R3)- or -N-;
    R1 through R3 independently represent -L1-L2-L3-R4; L1 through L3 independently represent a chemical bond, (C6-C30)arylene with or without substituent(s), (C3-C30)heteroarylene with or without substituent(s), (C3-C30)cycloalkylene with or without substituent(s), (C2-C30)alkenylene with or without substituent(s), (C2-C30)alkynylene with or without substituent(s); and R4 represents 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 aromaticring(s) with or withoutsubstituent(s), (C3-C30)cycloalkyl with or without substituent(s),(C3-C30)cycloalkyl fused with one or more aromaticring(s) with or without substituent(s), cyano, nitro, NR11R12, BR13R14, PR15R16, P(=O)R17R18, R19R20R21Si-, R22Y-, (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 PCTKR2010006796-appb-I000045
    or
    Figure PCTKR2010006796-appb-I000046
    , 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; the rings A and B independently represent a mono- or polycyclic aromatic ring or a mono- or polycyclic heteroaromatic ring;
    only, R1 through R3 include at least one
    Figure PCTKR2010006796-appb-I000047
    or
    Figure PCTKR2010006796-appb-I000048
    ; R11 through R22 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); Y represents S or O; W represents -(CR41R42)m-, -(R41)C=C(R42)-, -N(R43)-, -S-, -O-, -Si(R44)(R45)-, -P(R46)-, -P(=O)(R47)-, -C(=O)-or-B(R48)-, and R31 through R33 and R41 through R48 are the same as defined in R1 through R3; and
    the heterocycloalkyl, heteroaryl and heteroaromatic ring include more than one heteroatom(s) selected from B, N, O, S, P(=O), Si and P; and m is an integer ranging from 0 to 2.
  2. The organic electroluminescent compound of claim 1, which is selected from the following compounds.
    Figure PCTKR2010006796-appb-I000049
    [wherein
    R1, R2 and R51 to R54 are the same as the definition of R1 through R3 of claim 1.]
  3. The organic electroluminescent compound of claim 1, wherein substituents that are further substituted with R1 through R4, R11 through R22, R31 through R33, R41 through R48 are independently further substituted with more than one selected from the group consisting of deuterium, halogen, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl, (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 or hydroxy, or is linked to an adjacent substituent to formaring; R61 to 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 of claim 1, wherein L1 through L3 are selected from the following structures.
    Figure PCTKR2010006796-appb-I000050
  5. The organic electroluminescent compound of claim 1, wherein R4isselectedfromthefollowingstructures.
    Figure PCTKR2010006796-appb-I000051
  6. An organic electroluminescent device comprising the organic electroluminescent compound according 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):
    [Chemical Formula 2]
    M1L101L102L103
    wherein
    M1 is a metal selected from a 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 PCTKR2010006796-appb-I000052
    Figure PCTKR2010006796-appb-I000053
    Figure PCTKR2010006796-appb-I000054
    Figure PCTKR2010006796-appb-I000055
    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, (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, (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 alicylic 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, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen; and
    Q represents
    Figure PCTKR2010006796-appb-I000056
    ,
    Figure PCTKR2010006796-appb-I000057
    or
    Figure PCTKR2010006796-appb-I000058
    , wherein R231 through R242 independently represent hydrogen, (C1-C30)alkylwith 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), 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 organic electroluminescent device wherein the organic layer further comprises one or more organic compound layer(s) emitting blue, red or green light at the same time.
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