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WO2012015265A1 - 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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WO2012015265A1
WO2012015265A1 PCT/KR2011/005584 KR2011005584W WO2012015265A1 WO 2012015265 A1 WO2012015265 A1 WO 2012015265A1 KR 2011005584 W KR2011005584 W KR 2011005584W WO 2012015265 A1 WO2012015265 A1 WO 2012015265A1
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substituted
unsubstituted
mmol
compound
organic electroluminescent
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PCT/KR2011/005584
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French (fr)
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Soo Young Lee
Young Jun Cho
Bong Ok Kim
Sung Min Kim
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Rohm And Haas Electronic Materials Korea Ltd
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Priority to CN2011800470321A priority Critical patent/CN103298800A/en
Priority to JP2013521715A priority patent/JP2013539205A/en
Publication of WO2012015265A1 publication Critical patent/WO2012015265A1/en

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Definitions

  • the present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device including the same, and more particularly to novel organic electroluminescent compounds, suitable for use as a hole transport material or a hole injection material, and to an organic electroluminescent device using the same.
  • LCDs Liquid crystal displays
  • organic electroluminescent devices are recently receiving attention as a next-generation flat panel display, and thorough research into them is ongoing.
  • electroluminescent (EL) devices are advantageous as self-emissive display devices in that they provide a wide view angle, superior contrast and a fast response rate.
  • EL electroluminescent
  • Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex to form an electroluminescent layer [Appl. Phys. Lett. 51, 913, 1987].
  • the light emission mechanism of the organic EL device is that charges are injected into an organic layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode) thus forming electron-hole pairs which then decay to emit light.
  • Such a device may be formed on a flexible transparent substrate such as plastic, and as well, may operate at a lower voltage (10 V or less) than a plasma display panel or an inorganic EL display, and may exhibit comparatively low power consumption and superior color.
  • the organic materials of the organic EL device are largely classified into a light-emitting material and a charge generating material.
  • the light-emitting material is directly related with emission color and luminous efficiency, and some requirements thereof include high fluorescent quantum yield in a solid phase, high mobility of electrons and holes, slow decomposition upon vacuum deposition, and forming a uniform stable thin film.
  • a hole injection and transport material includes copper phthalocyanine (CuPc), NPB, TPD, MTDATA (4,4’,4”-tris(3-methylphenylphenylamino)triphenylamine), etc.
  • CuPc copper phthalocyanine
  • NPB NPB
  • TPD TPD
  • MTDATA 4,4’,4”-tris(3-methylphenylphenylamino)triphenylamine
  • a device including such a material in the hold injection and transport layer is problematic because efficiency and lifetime are decreased. The reason for this is that when the organic EL device operates at high current, thermal stress occurs between the anode and the hole injection layer, and the lifetime of the device may be drastically shortened by such thermal stress. Also, the organic material used for the hole injection layer has very high hole mobility, thus breaking the hole-electron charge balance, thereby reducing quantum yield (cd/A).
  • the use of a compound having good thin film stability and a compound having high non-crystallinity is reported to exhibit high thin film stability.
  • the glass transition temperature (Tg) is used as an indicator of the non-crystallinity.
  • the conventional MTDATA has a Tg of 76°C, and is thus not regarded as having non-crystallinity. Such materials are unsatisfactory in terms of the durability of organic EL devices and also luminous efficiency based on hole injection and transport properties.
  • an object of the present invention is to provide an organic EL compound the backbone of which is superior in luminous efficiency and device lifetime to conventional hole injection or hole transport materials, and an organic EL device using such a novel organic EL compound as a hole injection layer or a hole transport layer.
  • an organic EL compound represented by Chemical Formula 1 below is provided in the hole injection layer or the hole transport layer of the organic EL device, thus reducing the operating voltage of the device and increasing the luminous efficiency thereof.
  • the present invention provides an organic EL compound represented by Chemical Formula 1 below.
  • X represents -O-, -S-, -C(R 11 R 12 )- or -Si(R 13 R 14 )-, wherein R 11 to R 14 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or substituted or unsubstituted (C3-C30)cycloalkyl, or are linked to adjacent substituents to form a ring;
  • R 1 to R 4 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl fused with one or more cycloalkyls, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic rings, substituted or unsubstituted (
  • R 5 and R 6 represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, or substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or are linked to adjacent substituents to form a ring;
  • L 1 and L 2 independently represent a chemical bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (C3-C30)heteroarylene, in which the case where both L 1 and L 2 are a chemical bond is excluded;
  • Ar represents substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl except for carbazole, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl fused with one or more cycloalkyls, substituted or unsubstituted(C3-C30)heteroaryl fused with one or more substituted or unsubstituted aromatic rings, or 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubsittuted aromatic rings, or is linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;
  • a to d independently represent an integer of 0 to 4, in which when a to d are an integer of 2 or more, R 1 , R 2 , R 3 and R 4 are the same as or different from each other, and are linked to adjacent substituents to form a ring; and
  • a substituent which is further substituted with R 1 to R 4 , R 5 and R 6 , R 11 to R 14 , L 1 , L 2 and Ar, independently represents one or more selected from among deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, (C6-C30)aryl, (C6-C30)aryl-substituted or unsubstituted (C3-C30)heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, (C3-C30)cycloalkyl, (C6-C30)cycloalkyl fused with one or more aromatic rings, R 21 R 22 R 23 Si-, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, NR 24 R 25 , BR 26 R 27 , PR 28
  • alkyl and other substituents containing “alkyl” moiety include both linear and branched species.
  • cycloalkyl includes a monocyclic hydrocarbon and a polycyclic hydrocarbon such as substituted or unsubstituted adamantyl or substituted or unsubstituted (C7-C30)bicycloalkyl.
  • 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, and also includes a plurality of aryls which are linked via single bonds.
  • 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.
  • the heteroaryl group includes a divalent aryl group wherein the heteroatoms in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt.
  • monocyclic heteroaryl such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuryl, benzothienyl, isobenzofuryl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl,
  • the alkyl moiety of “(C1-C30)alkyl or (C6-C30)ar(C1-C30)alkyl” includes (C1-C20)alkyl, more specifically (C1-C10)alkyl.
  • the aryl moiety of “(C6-C30)aryl and (C6-C30)ar(C1-C30)alkyl” includes (C6-C20)aryl, more specifically (C6-C12)aryl.
  • (C3-C30)heteroaryl includes (C3-C20)heteroaryl, more specifically (C3-C12)heteroaryl
  • (C3-C30)cycloalkyl includes (C3-C20)cycloalkyl, more specifically (C3-C7)cycloalkyl
  • (C3-C30)alkylene or alkenylene includes (C3-C20)alkylene or alkenylene, more specifically (C3-C10)alkylene or alkenylene.
  • substituted means that an unsubstituted substituent is further substituted.
  • organic EL compound according to the present invention is selected from among compounds represented by Chemical Formulas 2 to 5 below.
  • Ar is selected from among the following structures, but is not limited thereto.
  • organic EL compound according to the present invention is exemplified by the following compounds, but the present invention is not limited thereto.
  • organic EL compound according to the present invention may be prepared as shown in, for example, Scheme 1 below, but is not limited thereto.
  • the present invention provides an organic EL device, in which the organic EL compound according to the present invention is used as a hole injection material or a hole transport material.
  • the organic EL device comprises a first electrode; a second electrode; and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic EL compounds of Chemical Formula 1.
  • the organic EL device includes the organic EL compound of Chemical Formula 1, and may further include one or more compounds selected from among an arylamine based compound and a styrylamine based compound, and specific examples of the arylamine based compound or styrylamine based compound are illustrated in paragraph numbers ⁇ 212> to ⁇ 224> of Korean Patent Application No. 10-2008-0060393, but is not limited thereto.
  • the organic layer may further comprise one or more metals selected from among organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements of the Periodic Table or complex compounds, in addition to the organic EL compound of Chemical Formula 1.
  • the organic layer may comprise an electroluminescent layer and a charge generating layer.
  • An organic EL device having a pixel structure of independent light-emitting mode may be embodied, wherein the organic EL device including the organic EL compound represented by Chemical Formula 1 according to the present invention is taken as a subpixel and one or more subpixels including one or more metal compounds selected from among Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag which are patterned in parallel at the same time.
  • the organic layer may include, in addition to the organic EL compound, one or more organic electroluminescent layers emitting red, green or blue light in order to embody a white-light emitting organic EL device.
  • the compound emitting red, green or blue light may be exemplified by the compounds described in Korean Patent Application Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but is not limited thereto.
  • a layer selected from among a chalcogenide layer, a metal halide layer and a metal oxide layer may be disposed on the inner surface of at least one of the pair of electrodes. More specifically, a chalcogenide (including oxide) layer of silicon or aluminum may be disposed on the surface of the anode of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be disposed on the surface of the cathode of the electroluminescent medium layer, thereby attaining operating stability.
  • the chalcogenide may include, for example, SiOx (1 ⁇ x ⁇ 2), AlOx (1 ⁇ x ⁇ 1.5), SiON, SiAlON, etc.
  • the metal halide may include, for example, LiF, MgF2, CaF2, a rare-earth metal fluoride, etc.
  • the metal oxide may include, for example, Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
  • 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 be disposed on the surface of at least one of the pair of electrodes thus manufactured.
  • the electron transport compound is reduced to an anion, it becomes easy to inject and transport electrons from the mixed region to the electroluminescent medium.
  • the hole transport compound is oxidized to a cation, it becomes easy to inject and transport holes from the mixed region to the electroluminescent medium.
  • Preferable oxidative dopants include a variety of 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-light emitting organic EL device having two or more electroluminescent layers may be manufactured by adopting a reductive dopant layer as a charge generating layer.
  • an organic EL compound can be used as a hole transport material or a hole injection material, so that the resultant organic EL device can exhibit good luminous efficiency and can have excellent material lifetime properties, and can be used to manufacture OLED devices having very superior operating lifetime.
  • reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO 4 , evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 6.7 g (19.8 mmol) of Compound 1-3.
  • reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO 4 , evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and then recrystallized, thus obtaining 7.3 g (10.9 mmol, 45%) of Compound 28.
  • reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO 4 , evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and then recrystallized, thus obtaining 7.0 g (9.9 mmol, 50%) of Compound 30.
  • An OLED device was manufactured using the light-emitting material according to the present invention.
  • a transparent electrode ITO thin film (15 ⁇ / ⁇ ) obtained from OLED glass (produced by Samsung-Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water in that order, and then stored in isopropanol before use.
  • an ITO substrate was equipped in a substrate folder of a vacuum deposition apparatus, and 4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum deposition apparatus, which was then evacuated up to 10-6 torr of vacuum in the chamber.
  • a 4,4’-N,N’-dicarbazole-biphenyl (CBP) host was placed in one cell of the vacuum deposition apparatus and a bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate ((piq) 2 Ir(acac)) dopant was placed in another cell.
  • CBP 4,4’-N,N’-dicarbazole-biphenyl
  • deposited on the electroluminescent layer was a hole blocking layer comprising bis(2-methyl-8-quinolinato)(p-phenylphenonate)aluminum (III) (BAlq) 10 nm thick, after which an electron transport layer comprising tris(8-hydroxyquinoline)-aluminum(III) (Alq) 20 nm thick was deposited.
  • a hole blocking layer comprising bis(2-methyl-8-quinolinato)(p-phenylphenonate)aluminum (III) (BAlq) 10 nm thick
  • an electron transport layer comprising tris(8-hydroxyquinoline)-aluminum(III) (Alq) 20 nm thick was deposited.
  • Liq lithium quinolate
  • Al cathode was deposited to a thickness of 150 nm using another vacuum deposition apparatus, thereby manufacturing an OLED device.
  • Each compound used in the OLED device as the light-emitting material was purified by vacuum sublimation at 10 -6 torr.
  • An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 3 according to the present invention was used as a hole transport material.
  • An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 35 according to the present invention was used as a hole transport material.
  • An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 49 according to the present invention was used as a hole transport material, and an organic iridium complex tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) was used as a dopant in the electroluminescent layer.
  • An OLED device was manufactured in the same manner as in Example 4, with the exception that Compound 58 according to the present invention was used as a hole transport material.
  • An OLED device was manufactured in the same manner as in Example 4, with the exception that Compound 4 according to the present invention was used as a hole transport material.
  • An OLED device was manufactured in the same manner as in Example 4, with the exception that Compound 61 according to the present invention was used as a hole transport material.
  • An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 42 according to the present invention was used as a hole injection material, instead of 2-TNATA (4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine).
  • An OLED device was manufactured in the same manner as in Example 4, with the exception that Compound 45 according to the present invention was used as a hole injection material, instead of 2-TNATA (4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine).
  • An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 46 according to the present invention was used as a hole injection material, instead of 2-TNATA (4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine).
  • An OLED device was manufactured in the same manner as in Example 1, with the exception that N,N’-bis( ⁇ -naphthyl)-N,N’-diphenyl-4,4’-diamine (NPB) was used as a hole transport material in one cell of the vacuum deposition apparatus, instead of the compound according to the present invention.
  • NPB N,N’-bis( ⁇ -naphthyl)-N,N’-diphenyl-4,4’-diamine
  • An OLED device was manufactured in the same manner as in Example 4, with the exception that N,N’-bis( ⁇ -naphthyl)-N,N’-diphenyl-4,4’-diamine (NPB) was used as a hole transport material in one cell of the vacuum deposition apparatus, instead of the compound according to the present invention.
  • NPB N,N’-bis( ⁇ -naphthyl)-N,N’-diphenyl-4,4’-diamine
  • the organic EL compounds according to the present invention have superior luminous properties compared to conventional materials. Also, an organic EL device using the organic EL compound according to the present invention as a hole transport material or a hole injection material can increase the LUMO (Lowest Unoccupied Molecular Orbital) and the triplet, thus enhancing hole blocking effects, resulting in good phosphorescence efficiency and superior material lifetime properties. Furthermore, operating voltage can be decreased, and power efficiency can be increased, thereby manufacturing excellent OLED devices.
  • LUMO Large Unoccupied Molecular Orbital

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Abstract

Provided are novel organic electroluminescent compounds and an organic electroluminescent device using the same. Because the organic electroluminescent device using the organic electroluminescent compound as a hole transport material or a hole injection material exhibits good luminous efficiency and excellent lifetime properties, it is used to manufacture OLED devices having superior operating lifetime 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 including the same, and more particularly to novel organic electroluminescent compounds, suitable for use as a hole transport material or a hole injection material, and to an organic electroluminescent device using the same.
Liquid crystal displays (LCDs), currently widely available, are a non-emissive display device which has low power consumption and is lightweight but has a complicated operating system and unsatisfactory properties including response time and contrast. Thus, organic electroluminescent devices are recently receiving attention as a next-generation flat panel display, and thorough research into them is ongoing.
Among display devices, electroluminescent (EL) devices are advantageous as self-emissive display devices in that they provide a wide view angle, superior contrast and a fast response rate. In 1987, Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex to form an electroluminescent layer [Appl. Phys. Lett. 51, 913, 1987].
The light emission mechanism of the organic EL device is that charges are injected into an organic layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode) thus forming electron-hole pairs which then decay to emit light. Such a device may be formed on a flexible transparent substrate such as plastic, and as well, may operate at a lower voltage (10 V or less) than a plasma display panel or an inorganic EL display, and may exhibit comparatively low power consumption and superior color.
The organic materials of the organic EL device are largely classified into a light-emitting material and a charge generating material. The light-emitting material is directly related with emission color and luminous efficiency, and some requirements thereof include high fluorescent quantum yield in a solid phase, high mobility of electrons and holes, slow decomposition upon vacuum deposition, and forming a uniform stable thin film.
Meanwhile, a hole injection and transport material includes copper phthalocyanine (CuPc), NPB, TPD, MTDATA (4,4’,4”-tris(3-methylphenylphenylamino)triphenylamine), etc. A device including such a material in the hold injection and transport layer is problematic because efficiency and lifetime are decreased. The reason for this is that when the organic EL device operates at high current, thermal stress occurs between the anode and the hole injection layer, and the lifetime of the device may be drastically shortened by such thermal stress. Also, the organic material used for the hole injection layer has very high hole mobility, thus breaking the hole-electron charge balance, thereby reducing quantum yield (cd/A).
In order to increase durability of the organic EL device, the use of a compound having good thin film stability and a compound having high non-crystallinity is reported to exhibit high thin film stability. As such, the glass transition temperature (Tg) is used as an indicator of the non-crystallinity. The conventional MTDATA has a Tg of 76℃, and is thus not regarded as having non-crystallinity. Such materials are unsatisfactory in terms of the durability of organic EL devices and also luminous efficiency based on hole injection and transport properties.
Therefore, the present invention has been made keeping in mind the problems encountered in the related art and an object of the present invention is to provide an organic EL compound the backbone of which is superior in luminous efficiency and device lifetime to conventional hole injection or hole transport materials, and an organic EL device using such a novel organic EL compound as a hole injection layer or a hole transport layer.
Provided are an organic EL compound represented by Chemical Formula 1 below, and an organic EL device including the same. The organic EL compound according to the present invention is contained in the hole injection layer or the hole transport layer of the organic EL device, thus reducing the operating voltage of the device and increasing the luminous efficiency thereof.
In one aspect, the present invention provides an organic EL compound represented by Chemical Formula 1 below.
[Chemical Formula 1]
Figure PCTKR2011005584-appb-I000001
In Chemical Formula 1, X represents -O-, -S-, -C(R11R12)- or -Si(R13R14)-, wherein R11 to R14 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or substituted or unsubstituted (C3-C30)cycloalkyl, or are linked to adjacent substituents to form a ring;
R1 to R4 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl fused with one or more cycloalkyls, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic rings, substituted or unsubstituted (C1-C30)silyl, cyano, nitro or hydroxyl, in which when R1 to R4 are plurally present, they may be linked to each other to form a cyclic structure;
R5 and R6 represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, or substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or are linked to adjacent substituents to form a ring;
L1 and L2 independently represent a chemical bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (C3-C30)heteroarylene, in which the case where both L1 and L2 are a chemical bond is excluded;
Ar represents substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl except for carbazole, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl fused with one or more cycloalkyls, substituted or unsubstituted(C3-C30)heteroaryl fused with one or more substituted or unsubstituted aromatic rings, or 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubsittuted aromatic rings, or is linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;
a to d independently represent an integer of 0 to 4, in which when a to d are an integer of 2 or more, R1, R2, R3 and R4 are the same as or different from each other, and are linked to adjacent substituents to form a ring; and
the heterocycloalkyl and heteroaryl include one or more hetero atoms selected from among B, N, O, S, P(=O), Si and P.
A substituent, which is further substituted with R1 to R4, R5 and R6, R11 to R14, L1, L2 and Ar, independently represents one or more selected from among deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, (C6-C30)aryl, (C6-C30)aryl-substituted or unsubstituted (C3-C30)heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, (C3-C30)cycloalkyl, (C6-C30)cycloalkyl fused with one or more aromatic rings, R21R22R23Si-, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, NR24R25, BR26R27, PR28R29, P(=O)R30R31, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, R32S-, R33O-, R34C(=O)-, R35C(=O)O-, carboxyl, nitro and hydroxyl, in which R21 to R33 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, or substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or are linked to an adjacent substituent via substituted or unsubstituted (C3-C30)alkylene or substituted or unsubstituted (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, carbon atoms of the formed alicyclic ring and monocyclic or polycyclic aromatic ring may be substituted with one or more hetero atoms selected from among nitrogen, oxygen and sulfur, and R34 and R35 represent (C1-C30)alkyl, (C1-C30)alkoxy, (C6-C30)aryl or (C6-C30)aryloxy.
In the present invention, “alkyl” and other substituents containing “alkyl” moiety include both linear and branched species. In the present invention, “cycloalkyl” includes a monocyclic hydrocarbon and a polycyclic hydrocarbon such as substituted or unsubstituted adamantyl or substituted or unsubstituted (C7-C30)bicycloalkyl. 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, and also includes a plurality of aryls which are linked via single bonds. Specific examples thereof include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. 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 heteroatoms selected from among B, N, O, S, P, P(=O), Si and Se as aromatic ring backbone atoms, the remaining aromatic ring backbone atom being carbon, and is exemplified by 5- or 6-membered monocyclic heteroaryl and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. The heteroaryl group includes a divalent aryl group wherein the heteroatoms in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt. Specific examples thereof include, but are not limited to, monocyclic heteroaryl such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuryl, benzothienyl, isobenzofuryl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, naphthylidinyl, dibenzofuryl, dibenzothiophenyl, etc., an N-oxide thereof (e.g., pyridyl N-oxide, quinolyl N-oxide, etc.), a quaternary salt thereof, etc.
In the present invention, the alkyl moiety of “(C1-C30)alkyl or (C6-C30)ar(C1-C30)alkyl” includes (C1-C20)alkyl, more specifically (C1-C10)alkyl. The aryl moiety of “(C6-C30)aryl and (C6-C30)ar(C1-C30)alkyl” includes (C6-C20)aryl, more specifically (C6-C12)aryl. Also, “(C3-C30)heteroaryl” includes (C3-C20)heteroaryl, more specifically (C3-C12)heteroaryl, and “(C3-C30)cycloalkyl” includes (C3-C20)cycloalkyl, more specifically (C3-C7)cycloalkyl. Also, “(C3-C30)alkylene or alkenylene” includes (C3-C20)alkylene or alkenylene, more specifically (C3-C10)alkylene or alkenylene.
In the expression “substituted or unsubstituted” used herein, “substituted” means that an unsubstituted substituent is further substituted.
Furthermore, the organic EL compound according to the present invention is selected from among compounds represented by Chemical Formulas 2 to 5 below.
[Chemical Formula 2]
Figure PCTKR2011005584-appb-I000002
[Chemical Formula 3]
Figure PCTKR2011005584-appb-I000003
[Chemical Formula 4]
Figure PCTKR2011005584-appb-I000004
[Chemical Formula 5]
Figure PCTKR2011005584-appb-I000005
In Chemical Formulas 2 to 5, X, R1 to R4, R5 and R6, L1, L2, Ar, and a to d are defined as in Chemical Formula 1.
Specifically, Ar is selected from among the following structures, but is not limited thereto.
Figure PCTKR2011005584-appb-I000006
Figure PCTKR2011005584-appb-I000007
Figure PCTKR2011005584-appb-I000008
Figure PCTKR2011005584-appb-I000009
Figure PCTKR2011005584-appb-I000010
Figure PCTKR2011005584-appb-I000011
Figure PCTKR2011005584-appb-I000012
Figure PCTKR2011005584-appb-I000013
More specifically, the organic EL compound according to the present invention is exemplified by the following compounds, but the present invention is not limited thereto.
Figure PCTKR2011005584-appb-I000014
Figure PCTKR2011005584-appb-I000015
Figure PCTKR2011005584-appb-I000016
Figure PCTKR2011005584-appb-I000017
Figure PCTKR2011005584-appb-I000018
Figure PCTKR2011005584-appb-I000019
Figure PCTKR2011005584-appb-I000020
Figure PCTKR2011005584-appb-I000021
Figure PCTKR2011005584-appb-I000022
Figure PCTKR2011005584-appb-I000023
Figure PCTKR2011005584-appb-I000024
Figure PCTKR2011005584-appb-I000025
Figure PCTKR2011005584-appb-I000026
Figure PCTKR2011005584-appb-I000027
Figure PCTKR2011005584-appb-I000028
Figure PCTKR2011005584-appb-I000029
Figure PCTKR2011005584-appb-I000030
Figure PCTKR2011005584-appb-I000031
Figure PCTKR2011005584-appb-I000032
Figure PCTKR2011005584-appb-I000033
Figure PCTKR2011005584-appb-I000034
Figure PCTKR2011005584-appb-I000035
Figure PCTKR2011005584-appb-I000036
The organic EL compound according to the present invention may be prepared as shown in, for example, Scheme 1 below, but is not limited thereto.
[Scheme 1]
Figure PCTKR2011005584-appb-I000037
In Scheme 1, X, R1 to R4, R5 and R6, L1, L2, Ar, and a to d are defined as in Chemical Formula 1.
In addition, the present invention provides an organic EL device, in which the organic EL compound according to the present invention is used as a hole injection material or a hole transport material.
The organic EL device according to the present invention comprises a first electrode; a second electrode; and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic EL compounds of Chemical Formula 1.
The organic EL device according to the present invention includes the organic EL compound of Chemical Formula 1, and may further include one or more compounds selected from among an arylamine based compound and a styrylamine based compound, and specific examples of the arylamine based compound or styrylamine based compound are illustrated in paragraph numbers <212> to <224> of Korean Patent Application No. 10-2008-0060393, but is not limited thereto.
In the organic EL device according to the present invention, the organic layer may further comprise one or more metals selected from among organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements of the Periodic Table or complex compounds, in addition to the organic EL compound of Chemical Formula 1. The organic layer may comprise an electroluminescent layer and a charge generating layer.
An organic EL device having a pixel structure of independent light-emitting mode may be embodied, wherein the organic EL device including the organic EL compound represented by Chemical Formula 1 according to the present invention is taken as a subpixel and one or more subpixels including one or more metal compounds selected from among Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag which are patterned in parallel at the same time.
Further, the organic layer may include, in addition to the organic EL compound, one or more organic electroluminescent layers emitting red, green or blue light in order to embody a white-light emitting organic EL device. The compound emitting red, green or blue light may be exemplified by the compounds described in Korean Patent Application Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but is not limited thereto.
In the organic EL device according to the present invention, a layer (hereinafter referred to as “surface layer”) selected from among a chalcogenide layer, a metal halide layer and a metal oxide layer may be disposed on the inner surface of at least one of the pair of electrodes. More specifically, a chalcogenide (including oxide) layer of silicon or aluminum may be disposed on the surface of the anode of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be disposed on the surface of the cathode of the electroluminescent medium layer, thereby attaining operating stability. The chalcogenide may include, for example, SiOx (1 ≤ x ≤ 2), AlOx (1 ≤ x ≤ 1.5), SiON, SiAlON, etc. The metal halide may include, for example, LiF, MgF2, CaF2, a rare-earth metal fluoride, etc. The metal oxide may include, for example, Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In an organic EL device according to the present invention, it is also preferred that 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 be disposed on the surface of at least one of the pair of electrodes thus manufactured. In that case, because the electron transport compound is reduced to an anion, it becomes easy to inject and transport electrons from the mixed region to the electroluminescent medium. In addition, because the hole transport compound is oxidized to a cation, it becomes easy to inject and transport holes from the mixed region to the electroluminescent medium. Preferable oxidative dopants include a variety of 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-light emitting organic EL device having two or more electroluminescent layers may be manufactured by adopting a reductive dopant layer as a charge generating layer.
According to the present invention, an organic EL compound can be used as a hole transport material or a hole injection material, so that the resultant organic EL device can exhibit good luminous efficiency and can have excellent material lifetime properties, and can be used to manufacture OLED devices having very superior operating lifetime.
The present invention is further described with respect to organic EL compounds according to the present invention, processes for preparing the same, and electroluminescent properties of devices using 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.
[Preparative Example 1] Preparation of Compound 3
Figure PCTKR2011005584-appb-I000038
Preparation of Compound 1-1
30 g (128.7 mmol) of 4-bromobiphenyl, 27 mL (772 mmol) of ammonia water, 2.45 g (12.87 mmol) of CuI, 12.9 mL (128.7 mmol) of acetylacetone, 83.9 g (257.4 mmol) of Cs2CO3, and 1000 mL of DMF were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 15.2 g (88.64 mmol) of Compound 1-1.
Preparation of Compound 1-2
15 g (88.64 mmol) of Compound 1-1, 24.1 g (88.64 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 1000 mL of toluene were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 11.2 g (30.98 mmol) of Compound 1-2.
Preparation of Compound 1-3
10 g (44 mmol) of 4-dibenzothiophene boronic acid, 31 g (132 mmol) of 1,4-dibromobenzenee, 2.5 g (2.2 mmol) of Pd(PPh3)4, 132 mL (132 mmol) of 1M Na2CO3, 500 mL of toluene, and 200 mL of ethanol were stirred under reflux at 120℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 6.7 g (19.8 mmol) of Compound 1-3.
Preparation of Compound 3
7.9 g (23.28 mmol) of Compound 1-3, 7 g (19.4 mmol) of Compound 1-2, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 8.0 g (12.9 mmol, 66%) of Compound 3.
1H NMR(CDCl3, 200 MHz) δ = 1.72(6H, s), 6.58(1H, m), 6.69~6.75(5H, m), 7.28(1H, m), 7.38~7.41(2H, m), 7.5~7.62(13H, m), 7.87(1H, m), 7.98(1H, m), 8.2(1H, m), 8.41~8.45(2H, m); MS/FAB found 620, calculated 619.82
[Preparative example 2] Preparation of Compound 9
Figure PCTKR2011005584-appb-I000039
Preparation of Compound 2-1
20.0 g (138.8 mmol) of 2-naphthol, 28.8 g (277.4 mmol) of NaHSO3, 160 mL of distilled water, and 31.2 mL (166.4 mmol) of 4-bromophenylhydrazine were heated to 120℃. After 12 hours, the reaction mixture was added with distilled water, and the produced solid was vacuum filtered. The solid thus obtained was added to an aqueous hydrochloric acid solution and heated to 100℃. After 1 hour, the resultant product was extracted with dichloromethane, washed with distilled water and aqueous NaOH, and purified by column separation, thus obtaining 9.2 g (31.0 mmol) of Compound 2-1.
Preparation of Compound 2-2
9.2 g (31.0 mmol) of Compound 2-1, 2.0 g (31.0 mmol) of Cu, 0.4 g (1.6 mmol) of 18-crown-6, 12.8 g (93.2 mmol) of K2CO3, and 100 mL of 1,2-dichlorobenzen were mixed and stirred under reflux to 180℃ for 12 hours. The reaction mixture was cooled to room temperature, vacuum distilled, extracted with dichloromethane and then washed with distilled water, followed by performing drying with MgSO4, vacuum distillation, and column separation, thus obtaining 7.6 g (20.4 mmol) of Compound 2-2.
Preparation of Compound 2-3
35.2g (128.7 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene, 27 mL (772 mmol) of ammonia water, 2.45 g (12.87 mmol) of CuI, 12.9 mL (128.7 mmol) of acetylacetone, 83.9 g (257.4 mmol) of Cs2CO3, and 1000 mL of DMF were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 11.3 g (54 mmol) of Compound 2-3.
Preparation of Compound 2-4
18.5 g (88.64 mmol) of Compound 2-3, 33 g (88.64 mmol) of Compound 2-2, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 1000 mL of toluene were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 14.2 g (28.4 mmol) of Compound 2-4.
Preparation of Compound 9
7.9 g (23.28 mmol) of Compound 1-3, 9.7 g (19.4 mmol) of Compound 2-4, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 7.3 g (9.62 mmol, 50%) of Compound 9.
1H NMR(CDCl3, 200 MHz)δ = 1.72(6H, s), 5.93(1H, m), 6.58(1H, m), 6.69~6.75(3H, m), 7.28(1H, m), 7.38(1H, m), 7.45(1H, m), 7.5(3H, m), 7.52(1H, m), 7.54~7.62(13H, m), 7.87(1H, m), 7.98(1H, m), 8.16~8.2(2H, m), 8.41~8.45(2H, m), 8.54(1H, m); MS/FAB found 759, calculated 758.97
[Preparative Example 3] Preparation of Compound 28
Figure PCTKR2011005584-appb-I000040
Preparation of Compound 3-1
5.4 g (44 mmol) of phenylboronic acid, 18.9 g (66 mmol) of 1,4-dibromonaphthalene, 2.0 g (1.76 mmol) of Pd(PPh3)4, 14.0 g (132 mmol) of Na2CO3, 200 mL of toluene, and 100 mL of ethanol were stirred under reflux at 120℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 9.1 g (32.14 mmol) of Compound 3-1.
Preparation of Compound 3-2
18.6 g (88.64 mmol) of Compound 2-3, 25 g (88.64 mmol) of Compound 3-1, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 1000 mL of toluene were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 14.2 g (34.5 mmol) of Compound 3-2.
Preparation of Compound 28
7.9 g (23.28 mmol) of Compound 1-3, 8.0 g (19.4 mmol) of Compound 3-2, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and then recrystallized, thus obtaining 7.3 g (10.9 mmol, 45%) of Compound 28.
1H NMR(CDCl3, 200 MHz)δ = 1.72(6H, s), 6.58(1H, m), 6.69~6.75(3H, m), 7.04(1H, m), 7.28(1H, m), 7.38~7.41(2H, m), 7.5~7.53(11H, m), 7.78~7.79(3H, m), 7.87(1H, m), 7.98(1H, m), 8.07(1H, m), 8.2(1H, m), 8.41~8.49(3H, m); MS/FAB found 670, calculated 669.87
[Preparative Example 4] Preparation of Compound 30
Figure PCTKR2011005584-appb-I000041
Preparation of Compound 4-1
8.2 g (23.28 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 3.2 g (19.4 mmol) of carbazole, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 200 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and then recrystallized, thus obtaining 5.8 g (13.2 mmol) of Compound 4-1.
Preparation of Compound 4-2
8.3 g (88.64 mmol) of aniline, 38.9 g (88.64 mmol) of Compound 4-1, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 800 mL of toluene were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 17.2 g (38.2 mmol) of Compound 4-2.
Preparation of Compound 30
7.9 g (23.28 mmol) of Compound 1-3, 8.7 g (19.4 mmol) of Compound 4-2, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and then recrystallized, thus obtaining 7.0 g (9.9 mmol, 50%) of Compound 30.
1H NMR(CDCl3, 200 MHz) δ = 1.72(6H, s), 6.37(1H, m), 6.54(1H, m), 6.63(2H, m), 6.69(2H, m), 6.81(1H, m), 7.17~7.34(7H, m), 7.5~7.63(8H, m), 7.87(1H, m), 7.94~7.98(2H, m), 8.12(1H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.55(1H, m); MS/FAB found 709, calculated 708.91
[Preparative Example 5] Preparation of Compound 32
Figure PCTKR2011005584-appb-I000042
Preparation of Compound 5-1
8.3 g (88.64 mmol) of aniline, 24.1 g (88.64 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 800 mL of toluene were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 14.2 g (49.8 mmol) of Compound 5-1.
Preparation of Compound 5-2
10 g (44 mmol) of 4-dibenzothiophene boronic acid, 41.2g (132 mmol) of 1,4-dibromobiphenyl, 2.5 g (2.2 mmol) of Pd(PPh3)4, 132 mL (132 mmol) of 1M Na2CO3, 500 mL of toluene, and 200 mL of ethanol were stirred under reflux at 120℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 15.3 g (36.8 mmol) of Compound 5-2.
Preparation of Compound 32
9.7 g (23.28 mmol) of Compound 5-2, 5.54 g (19.4 mmol) of Compound 5-1, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 5.8 g (9.4 mmol, 48%) of Compound 32.
1H NMR(CDCl3, 200 MHz)δ = 1.72(6H, s), 6.58~6.63(3H, m), 6.69~6.81(4H, m), 7.2~7.28(7H, m), 7.38(1H, m), 7.5~7.62(7H, m), 7.87(1H, m), 7.98(1H, m), 8.2(1H, m), 8.41~8.45(2H, m); MS/FAB found 620, calculated 619.82
[Preparative Example 6] Preparation of Compound 37
Figure PCTKR2011005584-appb-I000043
Preparation of Compound 6-1
150 g (426 mmol) of 2,7-dibromo-9,9-dimethylfluorene was dissolved in 2.1 L of tetrahydrofuran, and cooled to -78℃, after which 170 mL (2.5M in hexane, 426 mmol) of n-BuLi was slowly added in droplets thereto and stirred for 1 hour.
53 mL (469 mmol) of trimethylborate was added thereto, and stirred for 12 hours. After the reaction completed, the reaction was terminated with 2M HCl, and the reaction product was extracted with EA/H2O, dewatered with MgSO4, vacuum distilled, and column separated, thus obtaining 70 g (220.8 mmol) of Compound 6-1.
Preparation of Compound 6-2
70 g (220 mmol) of Compound 6-1, 50 g (200 mmol) of 2-iodonitrobenzene, 7 g (6 mmol) of Pd(PPh3)4, 64 g (600 mmol) of Na2CO3, 1 L of toluene, 0.5 L of ethanol, and 0.3 L of water were stirred at 90℃ for 7.5 hours. After the reaction completed, the reaction product was extracted with EA/H2O, dewatered with MgSO4, and vacuum distilled thus obtaining Compound 6-2, which was then immediately subjected to a subsequent procedure without additional purification.
Preparation of Compound 6-3
90 g of Compound 6-2 and 750 mL of P(OEt)3 were dissolved in 750 mL of 1,2-dichlorobenzene, and stirred at 150℃ for 9 hours, after which the stirred solution was washed with distilled water and treated to remove the solvent, and the resulting red liquid was then column separated, thus obtaining 26 g (79.69 mmol) of Compound 6-3.
Preparation of Compound 6-4
2.6 g (23.28 mmol) of chlorobenzene, 7.0 g (19.4 mmol) of Compound 6-3, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, 200 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 6.8 g (15.5 mmol) of Compound 6-4.
Preparation of Compound 6-5
18.6 g (88.64 mmol) of Compound 2-3, 38.9 g (88.64 mmol) of Compound 6-4, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 800 mL of toluene were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 15.6 g (27.5 mmol) of Compound 6-5.
Preparation of Compound 37
7.9 g (23.28 mmol) of Compound 1-3, 11 g (19.4 mmol) of Compound 6-5, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 6.9 g (8.4 mmol, 43%) of Compound 37.
1H NMR(CDCl3, 200 MHz)δ = 1.72(12H, s), 6.58~6.81(6H, m), 7.28~7.29(2H, m), 7.38(1H, m), 7.45~7.52(6H, m), 7.54(3H, s), 7.54~7.63(6H, m), 7.84~7.87(2H, m), 7.98(1H, m), 8.12(1H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.85(1H, s), (H, ); MS/FAB found 825, calculated 825.07
[Preparative Example 7] Preparation of Compound 43
Figure PCTKR2011005584-appb-I000044
Preparation of Compound 7-1
41.7 g (128.7 mmol) of 4-bromo-N,N-diphenylaniline, 27 mL (772 mmol) of ammonia water, 2.45 g (12.87 mmol) of CuI, 12.9 mL (128.7 mmol) of acetylacetone, 83.9 g (257.4 mmol) of Cs2CO3, and 1000 mL of DMF were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 12.2 g (46.9 mmol) of Compound 7-1.
Preparation of Compound 7-2
23.1 g (88.64 mmol) of Compound 7-1, 24.1 g (88.64 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 1000 mL of toluene were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 18.4 g (40.65 mmol) of Compound 7-2.
Preparation of Compound 43
7.9 g (23.28 mmol) of Compound 1-3, 8.8 g (19.4 mmol) of Compound 7-2, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 5.7 g (8.0 mmol, 41%) of Compound 43.
1H NMR(CDCl3, 200 MHz)δ = 1.72(6H, s), 6.38(4H, m), 6.58~6.63(5H, m), 6.69~6.81(5H, m), 7.2(4H, m), 7.28(1H, m), 7.38(1H, m), 7.5~7.62(7H, m), 7.87(1H, m), 7.98(1H, m), 8.2(1H, m), 8.41~8.45(2H, m); MS/FAB found 711, calculated 710.93
[Preparative Example 8] Preparation of Compound 69
Figure PCTKR2011005584-appb-I000045
Preparation of Compound 8-1
10 g (44 mmol) of 2-dibenzothiophene boronic acid, 31 g (132 mmol) of 1,4-dibromobenzene, 2.5 g (2.2 mmol) of Pd(PPh3)4, 132 mL (132 mmol) of 1M Na2CO3, 500 mL of toluene, and 200 mL of ethanol were stirred under reflux at 120℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 12.9 g (38.0 mmol) of Compound 8-1.
Preparation of Compound 69
7.9 g (23.28 mmol) of Compound 8-1, 7 g (19.4 mmol) of Compound 1-2, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 7.1 g (11.5 mmol, 59%) of Compound 69.
1H NMR(CDCl3, 200 MHz)δ = 1.72(6H, s), 5.93(1H, m), 6.38(4H, m), 6.58~6.63(3H, m), 6.69~6.81(4H, m), 7.2(2H, m), 7.28~7.29(2H, m), 7.38(1H, m), 7.45~7.54(15H, m), 7.69(1H, m), 7.87(1H, m), 7.98(1H, m), 8.12(1H, m), 8.2(1H, m), 8.41~8.45(2H, m); MS/FAB found 620, calculated 619.82
[Preparative Example 9] Preparation of Compound 76
Figure PCTKR2011005584-appb-I000046
Preparation of Compound 9-1
10.5 g (44 mmol) of 9,9-dimethyl-9H-fluoren-2-ylboronic acid, 31 g (132 mmol) of 1,4-dibromobenzene, 2.5 g (2.2 mmol) of Pd(PPh3)4, 132 mL (132 mmol) of 1M Na2CO3, 500 mL of toluene, and 200 mL of ethanol were stirred under reflux at 120℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 11.5 g (32.9 mmol) of Compound 9-2.
Preparation of Compound 76
8.1 g (23.28 mmol) of Compound 9-1, 8.7 g (19.4 mmol) of Compound 1-2, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 6.5 g (9.0 mmol, 47%) of Compound 76.
1H NMR(CDCl3, 200 MHz)δ = 1.72(12H, s), 6.58(1H, m), 6.69~6.75(5H, m), 7.28(2H, m), 7.38~7.41(3H, m), 7.51~7.55(10H, m), 7.62~7.63(2H, m), 7.77(1H, m), 7.87~7.93(3H, m); MS/FAB found 630, calculated 629.83
[Preparative Example 10] Preparation of Compound 78
Figure PCTKR2011005584-appb-I000047
Preparation of Compound 10-1
40 g (152.6 mmol) of methyl 2-bromobenzoate, 31.5 g (183.2 mmol) of naphthalen-1-ylboronic acid, and 8.8 g (7.62 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] was placed in a two-neck flask. While 1 L of toluene was added thereto, stirring was performed, and 228 mL (458 mmol) of 2M potassium carbonate and 228 mL of ethanol were added thereto. Refluxing at 100℃ for 5 hours was carried out. After termination of the reaction, the reaction product was cooled to room temperature, and extracted with distilled water and ethylacetate. The resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and subjected to column chromatography using hexane and ethylacetate as a developing solvent, thus obtaining 35 g (87%) of Compound 10-1.
Preparation of Compound 10-2
24 g (91.49 mmol) of Compound 10-1 was placed in a one-neck flask, and the flask was made vacuous and filled with argon. 1 L of tetrahydrofuran was added thereto, stirring was performed at -75℃ for 10 minutes. Subsequently, 257 mL (0.41 mol) of MeLi (1.6 M in hexane) was added thereto, stirred at -75℃ for 10 minutes, and stirred at room temperature for 3 hours. After termination of the reaction, the reaction product was extracted with distilled water and ethylacetate. The resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and subjected to column chromatography using hexane and ethylacetate as a developing solvent, thus obtaining 20 g (83%) of Compound 10-2.
Preparation of Compound 10-3
20 g (76.23 mmol) of Compound 10-2 was placed in a one-neck flask, and 300 mL of AcOH was added thereto and stirred at 0℃ for 10 minutes. The reaction mixture was added with 400 mL of H3PO4 and stirred at room temperature for 1 hour. After termination of the reaction, the reaction product was neutralized with NaOH, and extracted with distilled water and ethylacetate. The resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and subjected to column chromatography using hexane and ethylacetate as a developing solvent, thus obtaining 13.5 g (72%) of Compound 10-3.
Preparation of Compound 10-4
13.5 g (55.25 mmol) of Compound 10-3 was placed in a one-neck flask, and the flask was made vacuous and filled with argon. 500 mL of tetrahydrofuran was added thereto, stirring was performed at 0℃ for 10 minutes. Subsequently, the reaction mixture was added with 19.6 g (0.11 mol) of NBS and stirred at room temperature for one day. After termination of the reaction, the reaction product was extracted with distilled water and ethylacetate. The resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and subjected to column chromatography using hexane and ethylacetate as a developing solvent, thus obtaining 13 g (73%) of Compound 10-4.
Preparation of Compound 10-5
8.3 g (88.64 mmol) of aniline, 28.6 g (88.64 mmol) of Compound 10-4, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 800 mL of toluene were stirred under heat at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and purified using column chromatography, thus obtaining 10.1 g (30.1 mmol) of Compound 10-5.
Preparation of Compound 78
7.9 g (23.28 mmol) of Compound 1-3, 6.5 g (19.4 mmol) of Compound 10-5, 0.13 g (0.58 mmol) of Pd(OAc)2, 0.94 mL (2.32 mmol) of P(t-Bu)3, 6.7 g (69.84 mmol) of NaOt-Bu, and 500 mL of toluene were stirred under reflux at 100℃ for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, purified using column chromatography, and recrystallized, thus obtaining 6.0 g (10.1 mmol, 52%) of Compound 78.
1H NMR(CDCl3, 200 MHz)δ = 1.78(6H, s), 6.63~6.69(5H, m), 6.81(2H, m), 7.14(1H, m), 7.2(2H, m), 7.5~7.58(7H, m), 7.84(1H, m), 7.98(2H, m), 8.09(1H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.52(1H, m); MS/FAB found 594, calculated 593.78
[Example 1] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured using the light-emitting material according to the present invention. First, a transparent electrode ITO thin film (15 Ω/□) obtained from OLED glass (produced by Samsung-Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water in that order, and then stored in isopropanol before use. Then, an ITO substrate was equipped in a substrate folder of a vacuum deposition apparatus, and 4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum deposition apparatus, which was then evacuated up to 10-6 torr of vacuum in the chamber. Then, current was applied to the cell to evaporate 2-TNATA, thereby depositing a hole injection layer having a thickness of 60 nm on the ITO substrate. Subsequently, Compound 13 according to the present invention was placed in another cell of the vacuum deposition apparatus, and current was applied to the cell to evaporate the Compound 13, thereby depositing 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 deposited on the formed layers. Specifically, a 4,4’-N,N’-dicarbazole-biphenyl (CBP) host was placed in one cell of the vacuum deposition apparatus and a bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate ((piq)2Ir(acac)) dopant was placed in another cell. Then, two materials were evaporated at different rates so as to be doped in an amount of 4 ~ 10 wt%, thus depositing the electroluminescent layer 30 nm thick on the hole transport layer. Subsequently, deposited on the electroluminescent layer was a hole blocking layer comprising bis(2-methyl-8-quinolinato)(p-phenylphenonate)aluminum (III) (BAlq) 10 nm thick, after which an electron transport layer comprising tris(8-hydroxyquinoline)-aluminum(III) (Alq) 20 nm thick was deposited. Subsequently, as an electron injection layer lithium quinolate (Liq) was deposited to a thickness of 1 ~ 2 nm, and an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition apparatus, thereby manufacturing an OLED device.
Each compound used in the OLED device as the light-emitting material was purified by vacuum sublimation at 10-6 torr.
Consequently, a current of 15.3 mA/㎠ flowed at a voltage of 7.0 V, and a red luminescence of 1120 cd/㎠ was obtained.
[Example 2] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 3 according to the present invention was used as a hole transport material.
Consequently, a current of 15.1 mA/㎠ flowed at a voltage of 7.2 V, and a red luminescence of 1075 cd/㎠ was obtained.
[Example 3] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 35 according to the present invention was used as a hole transport material.
Consequently, a current of 16.3 mA/㎠ flowed at a voltage of 7.3 V, and a red luminescence of 1115 cd/㎠ was obtained.
[Example 4] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 49 according to the present invention was used as a hole transport material, and an organic iridium complex tris(2-phenylpyridine)iridium (Ir(ppy)3) was used as a dopant in the electroluminescent layer.
Consequently, a current of 4.0 mA/㎠ flowed at a voltage of 6.8 V, and a green luminescence of 1160 cd/㎠ was obtained.
[Example 5] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 4, with the exception that Compound 58 according to the present invention was used as a hole transport material.
Consequently, a current of 4.2 mA/㎠ flowed at a voltage of 7.1 V, and a green luminescence of 1230 cd/㎠ was obtained.
[Example 6] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 4, with the exception that Compound 4 according to the present invention was used as a hole transport material.
Consequently, a current of 5.0 mA/㎠ flowed at a voltage of 7.2 V, and a green luminescence of 1570 cd/㎠ was obtained.
[Example 7] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 4, with the exception that Compound 61 according to the present invention was used as a hole transport material.
Consequently, a current of 3.9 mA/㎠ flowed at a voltage of 7.0 V, and a green luminescence of 1300 cd/㎠ was obtained.
[Example 8] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 42 according to the present invention was used as a hole injection material, instead of 2-TNATA (4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine).
Consequently, a current of 13.5 mA/㎠ flowed at a voltage of 6.8 V, and a red luminescence of 1040 cd/㎠ was obtained.
[Example 9] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 4, with the exception that Compound 45 according to the present invention was used as a hole injection material, instead of 2-TNATA (4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine).
Consequently, a current of 4.0 mA/㎠ flowed at a voltage of 6.6 V, and a green luminescence of 1235 cd/㎠ was obtained.
[Example 10] Manufacture of OLED device using the organic EL compound according to the present invention
An OLED device was manufactured in the same manner as in Example 1, with the exception that Compound 46 according to the present invention was used as a hole injection material, instead of 2-TNATA (4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine).
Consequently, a current of 13.7 mA/㎠ flowed at a voltage of 7.2 V, and a red luminescence of 1005 cd/㎠ was obtained.
[Comparative Example 1] Luminous Properties of OLED using conventional light-emitting material
An OLED device was manufactured in the same manner as in Example 1, with the exception that N,N’-bis(α-naphthyl)-N,N’-diphenyl-4,4’-diamine (NPB) was used as a hole transport material in one cell of the vacuum deposition apparatus, instead of the compound according to the present invention.
Consequently, a current of 15.3 mA/㎠ flowed at a voltage of 7.5 V, and a red luminescence of 1000 cd/㎠ was obtained.
[Comparative Example 2] Luminous Properties of OLED using conventional light-emitting material
An OLED device was manufactured in the same manner as in Example 4, with the exception that N,N’-bis(α-naphthyl)-N,N’-diphenyl-4,4’-diamine (NPB) was used as a hole transport material in one cell of the vacuum deposition apparatus, instead of the compound according to the present invention.
Consequently, a current of 3.8 mA/㎠ flowed at a voltage of 7.5 V, and a green luminescence of 1000 cd/㎠ was obtained.
The organic EL compounds according to the present invention have superior luminous properties compared to conventional materials. Also, an organic EL device using the organic EL compound according to the present invention as a hole transport material or a hole injection material can increase the LUMO (Lowest Unoccupied Molecular Orbital) and the triplet, thus enhancing hole blocking effects, resulting in good phosphorescence efficiency and superior material lifetime properties. Furthermore, operating voltage can be decreased, and power efficiency can be increased, thereby manufacturing excellent OLED devices.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions, and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (10)

  1. An organic electroluminescent compound represented by Chemical Formula 1 below:
    [Chemical Formula 1]
    Figure PCTKR2011005584-appb-I000048
    wherein X represents -O-, -S-, -C(R11R12)- or -Si(R13R14)-, wherein R11 to R14 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or substituted or unsubstituted (C3-C30)cycloalkyl, or are linked to adjacent substituents to form a ring;
    R1 to R4 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl fused with one or more cycloalkyls, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic rings, substituted or unsubstituted (C1-C30)silyl, cyano, nitro or hydroxyl, in which when R1 to R4 are plurally present, they may be linked to each other to form a cyclic structure;
    R5 and R6 represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, or substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or are linked to adjacent substituents to form a ring;
    L1 and L2 independently represent a chemical bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (C3-C30)heteroarylene, in which the case where both L1 and L2 are a chemical bond is excluded;
    Ar represents substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl except for carbazole, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl fused with one or more cycloalkyls, substituted or unsubstituted(C3-C30)heteroaryl fused with one or more substituted or unsubstituted aromatic rings, or 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubsittuted aromatic rings, or is linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;
    a to d independently represent an integer of 0 to 4, in which when a to d are an integer of 2 or more, R1, R2, R3 and R4 are the same as or different from each other, and are linked to adjacent substituents to form a ring; and
    the heterocycloalkyl and heteroaryl include one or more hetero atoms selected from among B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound of claim 1, wherein a substituent, which is further substituted with R1 to R4, R5 and R6, R11 to R14, L1, L2 and Ar, independently represents one or more selected from among deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, (C6-C30)aryl, (C6-C30)aryl-substituted or unsubstituted (C3-C30)heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, (C3-C30)cycloalkyl, (C6-C30)cycloalkyl fused with one or more aromatic rings, R21R22R23Si-, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, NR24R25, BR26R27, PR28R29, P(=O)R30R31, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, R32S-, R33O-, R34C(=O)-, R35C(=O)O-, carboxyl, nitro and hydroxyl, in which R21 to R33 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C3-C30)heteroaryl, or substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or are linked to an adjacent substituent via substituted or unsubstituted (C3-C30)alkylene or substituted or unsubstituted (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, carbon atoms of the formed alicyclic ring and monocyclic or polycyclic aromatic ring may be substituted with one or more hetero atoms selected from among nitrogen, oxygen and sulfur, and R34 and R35 represent (C1-C30)alkyl, (C1-C30)alkoxy, (C6-C30)aryl or (C6-C30)aryloxy.
  3. The organic electroluminescent compound of claim 1, wherein the organic electroluminescent compound of Chemical Formula 1 comprises compounds represented by Chemical Formulas 2 to 5 below.
    [Chemical Formula 2]
    Figure PCTKR2011005584-appb-I000049
    [Chemical Formula 3]
    Figure PCTKR2011005584-appb-I000050
    *[Chemical Formula 4]
    Figure PCTKR2011005584-appb-I000051
    [Chemical Formula 5]
    Figure PCTKR2011005584-appb-I000052
    in Chemical Formulas 2 to 5, X, R1 to R4, R5 and R6, L1, L2, Ar, and a to d are defined as in Chemical Formula 1.
  4. The organic electroluminescent compound of claim 1, which is selected from the group consisting of following compounds.
    Figure PCTKR2011005584-appb-I000053
    Figure PCTKR2011005584-appb-I000054
    Figure PCTKR2011005584-appb-I000055
    Figure PCTKR2011005584-appb-I000056
    Figure PCTKR2011005584-appb-I000057
    Figure PCTKR2011005584-appb-I000058
    Figure PCTKR2011005584-appb-I000059
    Figure PCTKR2011005584-appb-I000060
    Figure PCTKR2011005584-appb-I000061
    Figure PCTKR2011005584-appb-I000062
    Figure PCTKR2011005584-appb-I000063
    Figure PCTKR2011005584-appb-I000064
    Figure PCTKR2011005584-appb-I000065
    Figure PCTKR2011005584-appb-I000066
    Figure PCTKR2011005584-appb-I000067
    Figure PCTKR2011005584-appb-I000068
    Figure PCTKR2011005584-appb-I000069
    Figure PCTKR2011005584-appb-I000070
    Figure PCTKR2011005584-appb-I000071
    Figure PCTKR2011005584-appb-I000072
    Figure PCTKR2011005584-appb-I000073
    Figure PCTKR2011005584-appb-I000074
    Figure PCTKR2011005584-appb-I000075
  5. An organic electroluminescent device, comprising the organic electroluminescent compound of any one of claims 1 to 4.
  6. The organic electroluminescent device of claim 5, wherein the organic electroluminescent compound is used as a hole injection material or a hole transport material.
  7. The organic electroluminescent device of claim 6, which comprises a first electrode; a second electrode; and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic electroluminescent compounds of Chemical Formula 1.
  8. The organic electroluminescent device of claim 7, wherein the organic layer further comprises one or more metals 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 of the Periodic Table or complex compounds.
  9. The organic electroluminescent device of claim 7, wherein the organic layer comprises both an electroluminescent layer and a charge generating layer.
  10. The organic electroluminescent device of claim 7, wherein the organic layer further comprises one or more organic electroluminescent layers emitting red, green or blue light to emit white light.
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