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WO2012026780A1 - 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
WO2012026780A1
WO2012026780A1 PCT/KR2011/006314 KR2011006314W WO2012026780A1 WO 2012026780 A1 WO2012026780 A1 WO 2012026780A1 KR 2011006314 W KR2011006314 W KR 2011006314W WO 2012026780 A1 WO2012026780 A1 WO 2012026780A1
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Prior art keywords
substituted
unsubstituted
compound
organic electroluminescent
mixture
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PCT/KR2011/006314
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French (fr)
Inventor
Hyo Nim Shin
Soo Yong Lee
Hee Choon Ahn
Young Gil Kim
Mi Ran Seo
Young Jun Cho
Hyuck Joo Kwon
Kyung Joo Lee
Bong Ok Kim
Original Assignee
Rohm And Haas Electronic Materials Korea Ltd.
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Priority claimed from KR1020110083247A external-priority patent/KR20120042633A/en
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to CN2011800519605A priority Critical patent/CN103189469A/en
Priority to JP2013525835A priority patent/JP2013537556A/en
Publication of WO2012026780A1 publication Critical patent/WO2012026780A1/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 or 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 being carried out.
  • electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices.
  • Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [ Appl. Phys. Lett. 51, 913, 1987].
  • the light emission mechanism of the organic electroluminescent 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 a plastic, and may also operate at a voltage that is 10 V or less than that of a plasma display panel or an inorganic electroluminescent display, and may exhibit comparatively low power consumption and superior color.
  • An organic material for the organic EL device may be largely divided into an electroluminescent material and a charge transport material.
  • the electroluminescent material is directly related to electroluminescent color and luminous efficiency, and requires several characteristics such as a high fluorescence quantum yield in a solid state, high mobility of electrons and holes, low degradability at the time of vacuum deposition, uniform thin-film formability and stability.
  • 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 using these materials in the hole injection or transport layer is problematic in efficiency and operation life. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. The thermal stress significantly reduces the operation life of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
  • Glass transition temperature (T g ) may be a measure of the amorphousness.
  • MTDATA has a glass transition temperature of 76°C and cannot be said to have high amorphousness. These materials are not satisfactory in the operation life of the organic EL device, as well as in the luminous efficiency, which is determined by the hole injection and transport properties.
  • an object of the present invention is to provide an organic electroluminescent compound the backbone of which is superior in luminous efficiency and device lifetime compared to conventional hole injection or hole transport materials, and an organic electroluminescent device using such a novel organic electroluminescent compound as a hole injection layer or a hole transport layer.
  • an organic electroluminescent compound represented by Chemical Formula 1 below and an organic electroluminescent device including the same.
  • the organic electroluminescent compound according to the present invention is contained in the hole injection layer or the hole transport layer of the organic electroluminescent device, thus reducing the operating voltage of the device and increasing the luminous efficiency thereof.
  • the present invention provides an organic electroluminescent compound represented by Chemical Formula 1 below.
  • ring A and ring C independently represent ;
  • ring B represents ;
  • X 1 and X 2 independently represent CR 3 or N;
  • Y 1 and Y 2 independently represent a chemical bond, -O-, -S-, -C(R 11 R 12 )-, -Si(R 13 R 14 )- or -N(R 15 )-, except for a case where both Y 1 and Y 2 are a chemical bond;
  • R 1 through R 3 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-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 (C1-C30)alkylsilyl, cyano, nitro or hydroxyl, and when there are two or more of either R 1 or R 2 , they are linked to each other to form a cyclic structure;
  • L represents substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (C2-C30)heteroarylene, and when there are two or more of L, they are linked to each other to form a cyclic structure;
  • Ar 1 and Ar 2 independently represent substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl or ;
  • Y 3 and Y 4 independently represent a chemical bond, -O-, -S-, -C(R 16 R 17 )-, -Si(R 18 R 19 )- or -N(R 20 )-, except for a case where both Y 3 and Y 4 are a chemical bond;
  • R 11 through R 20 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C2-C30)heteroaryl, or each of them may be 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;
  • n and n independently represent an integer of 0 to 4, and when m and n are an integer of 2 or greater, each of R 1 and L may be identical to or different from each other;
  • each of R 2 may be identical to or different from each other;
  • alkyl and other substituents containing the “alkyl” moiety include both linear and branched species, and “cycloalkyl” includes monocyclic hydrocarbon as well as polycyclic hydrocarbon such as substituted or unsubstituted adamantyl or substituted or unsubstituted (C7-C30)bicycloalkyl.
  • aryl means an organic radical derived from aromatic hydrocarbon by the removal of one hydrogen atom, and includes a 4- to 7-membered, particularly 5- or 6-membered, single ring or a fused ring, and even further includes a structure where a plurality of aryls are linked by single bonds.
  • the naphthyl includes 1-naphthyl and 2-naphthyl
  • the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl
  • the phenanthryl includes 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl
  • the naphthacenyl includes 1-naphthacenyl, 2-naphthacenyl and 9-naphthacenyl.
  • the pyrenyl includes 1-pyrenyl, 2-pyrenyl and 4-pyrenyl
  • the biphenyl includes 2-biphenyl, 3-biphenyl and 4-biphenyl
  • the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl
  • the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
  • the heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, N- oxide or quaternary salt.
  • Specific examples thereof include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, or the like, polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl
  • the pyrrolyl includes 1-pyrrolyl, 2-pyrrolyl and 3-pyrrolyl; the pyridyl includes 2-pyridyl, 3-pyridyl and 4-pyridyl; the indolyl includes 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl and 7-indolyl; the isoindolyl includes 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl and 7-isoindolyl; the furyl includes 2-furyl and 3-furyl; the benzofuranyl includes 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl and 7-benzofuranyl; the isobenzofur
  • (C1-C30)alkyl includes (C1-C20)alkyl or (C1-C10)alkyl
  • (C6-C30)aryl includes (C6-C20)aryl or (C6-C12)aryl.
  • (C2-C30)heteroaryl includes (C2-C20)heteroaryl or (C2-C12)heteroaryl
  • (C3-C30)cycloalkyl includes (C3-C20)cycloalkyl or (C3-C7)cycloalkyl.
  • (C2-C30)alkenyl or alkynyl includes (C2-C20)alkenyl or alkynyl, or (C2-C10)alkenyl or alkynyl.
  • substituted or unsubstituted or with or without substituent(s) used herein, “substituted (with substituent(s))” means that the unsubstituted substituent is further substituted with substituent(s).
  • each substituent of the R 1 , R 2 , R 3 , L, Ar 1 , Ar 2 and R 11 through R 20 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, (C6-C30)aryl, (C6-C30)aryl-substituted or unsubstituted (C2-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, (C2-C30)alkenyl, (C2-C30)alkynyl, , cyano, carbazolyl, (C6-C30)ar(C1-C30)alkyl,
  • ring A is fused to an indoline ring and represents a 6-membered aromatic ring or a 6-membered nitrogen-containing heteroaromatic ring
  • ring B is fused to the ring A and represents a 5- or 6-membered ring
  • ring C is fused to the ring B and represents a 6-membered aromatic ring or a 6-membered nitrogen-containing heteroaromatic ring.
  • Chemical Formula 1 is selected from the following structures, but is not limited thereto.
  • R 2 , R 11 through R 15 and p are the same as defined as in Chemical Formula 1.
  • the L represents (C6-C30)arylene
  • Ar 1 and Ar 2 independently represent (C6-C30)aryl, (C2-C30)heteroaryl, or ;
  • Y 3 and Y 4 independently represent -O-, -S-, -C(R 16 R 17 )- or -N(R 20 )-;
  • R 16 , R 17 and R 20 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C2-C30)heteroaryl, or R 16 and R 17 may be linked to 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 ora monocyclic or polycyclic aromatic ring;
  • R 1 represents hydrogen, (C6-C30)aryl or (C2-C30)heteroaryl, or may be linked to an adjacent substitu
  • organic electroluminescent compound according to the present invention may be exemplified by the following compounds, which are not intended to limit the present invention.
  • organic electroluminescent 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 electroluminescent device, in which the organic electroluminescent compound according to the present invention is used as a hole injection material or a hole transport material.
  • organic electroluminescent compound represented by Chemical Formula 1 according to the present invention When used to the hole injection layer or the hole transport layer, it may be used to manufacture OLED devices consuming less power due to improved power efficiency.
  • the organic electroluminescent 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 electroluminescent compounds of Chemical Formula 1.
  • the organic layer may include one or more electroluminescent layer, besides the layer that one or more organic electroluminescent compound(s) of Chemical Formula 1 is included.
  • the electroluminescent layer may further include one or more dopant(s) or host(s).
  • the dopant or host applied to the organic electroluminescent device of the present invention is not specifically limited but may be selected from following Chemical Formulas 2 to 6.
  • M 1 represents Ir, Pt, Pd or Os
  • ligands L 101 , L 102 and L 103 are independently selected from following structures:
  • R 201 through R 203 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkyl-substituted or unsubstituted (C6-C30)aryl or halogen;
  • R 204 through R 219 independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted mono or di-(C1-C30)alkylamino, substituted or unsubstituted mono or di-(C6-C30)arylamino, SF 5 , substituted or unsubstituted tri(C1-C30)alkylsilyl, substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C30)arylsilyl, cyan
  • R 220 through R 223 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, or (C1-C30)alkyl-substituted or unsubstituted (C6-C30)aryl;
  • R 224 and R 225 independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, halogen-substituted or unsubstituted (C6-C30)aryl, or halogen, or R 224 and R 225 may be linked to an adjacent substituent via substituted or unsubstituted (C3-C12)alkylene or substituted or unsubstituted (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
  • R 226 represents substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, or halogen;
  • R 227 through R 229 independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or halogen;
  • Q represents , or , wherein R 231 through R 242 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkoxy, halogen, substituted or unsubstituted (C6-C30)aryl, cyano, substituted or unsubstituted (C3-C30)cycloalkyl, or they may be linked to an adjacent substituent via alkylene or alkenylene to form a spiro ring or a fused ring, or linked to R 207 or R 208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
  • Z represents -O-, -S-, -C(R 41 R 42 )-, -Si(R 43 R 44 )- or -N(R 45 )-;
  • ring D and ring F independently represent ;
  • ring E represents ;
  • Y 21 and Y 22 independently represent CH or N;
  • Y 23 and Y 24 independently represent a chemical bond, -O-, -S-, -C(R 41 R 42 )-, -Si(R 43 R 44 )- or -N(R 45 )-, except for a case where both Y 23 and Y 24 are a chemical bond;
  • R 31 and R 32 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-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 (C1-C30)alkylsilyl, substituted or unsubstituted (C6-C30)arylsilyl, substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylsilyl, cyano, nitro or hydroxyl, or they may be linked to an adjacent substituent via substituted or unsub
  • R 41 through R 45 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or substituted or unsubstituted (C3-C30)cycloalkyl with or without substituent(s), or each of them may be linked to an adjacent substituent to form a ring;
  • each of R 31 and R 32 may be identical to or different from each other, or each of them may be linked to an adjacent substituent to form a ring;
  • Cz is selected from following structures,
  • ring G represents (C6-C30)aliphatic ring, (C6-C30)aromatic ring or (C2-C30)heteroaromatic ring;
  • R 51 and R 53 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted(C6-C30)aryl fused with one or more substituted or unsubstituted (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C3-C30)cycloal
  • Y represents O or S
  • R 61 through R 72 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted(C6-C30)aryl fused with one or more substituted or unsubstituted (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C3-C30)cyclo
  • L 2 represents a chemical bond, substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (C2-C30)heteroaryl;
  • M represents substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (C2-C30)heteroaryl;
  • a, b, c and d independently represent an integer of 0 to 4.
  • a 1 through A 19 independently represent CR 81 or N;
  • Ar 11 represents substituted or unsubstituted (C6-C40)arylene or substituted or unsubstituted (C2-C40)heteroarylene, except for the case that e is 0 and A 15 through A 19 are CR 81 at the same time;
  • R 81 through R 89 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted(C6-C30)aryl fused with one or more substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), cyano, trifluoromethyl, -NR 91 R
  • R 91 through R 98 independently represent substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C2-C30)heteroaryl;
  • R 99 through R 101 independently represent substituted or unsubstituted (C1-C30)alkyl or substituted or unsubstituted (C6-C30)aryl;
  • Y 21 represents S or O
  • R 102 represent substituted or unsubstituted (C1-C30)alkyl or substituted or unsubstituted (C6-C30)aryl;
  • R 103 represent substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (C6-C30)aryloxy;
  • R 104 represent substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C6-C30)aryloxy;
  • e represents an integer of 0 to 2;
  • the term 'substituted' means that the unsubstituted substituent is further substituted with substituent(s).
  • the substituent means one or more substituent(s) selected from the same group as that represented by Chemical Formula 1.
  • the organic electroluminescent device includes the organic electroluminescent compound of Chemical Formula 1, and may further include one or more compounds selected from the group consisting of arylamine compounds and styrylamine compounds, and specific examples of the arylamine compounds or styrylamine compounds 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 metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s), in addition to the organic electroluminescent compound of Chemical Formula 1.
  • the organic layer may comprise an electroluminescent layer and a charge generating layer.
  • An organic electroluminescent device having a pixel structure of independent light-emitting mode may be embodied, wherein the organic electroluminescent device including the organic electroluminescent 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 the group consisting of 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 electroluminescent compound of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device.
  • the compounds emitting blue, green or red light may be exemplified by the compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
  • a layer (hereinafter referred to as "surface layer" selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom.
  • the 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 , a rare earth metal fluoride, etc.
  • the metal oxide may be, for example, Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • the organic electroluminescent device it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant.
  • a mixed region of an electron transport compound and a reductive dopant or a mixed region of a hole transport compound and an oxidative dopant.
  • the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated.
  • the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated.
  • Preferable oxidative dopants include various Lewis acids and acceptor compounds.
  • Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. Further, a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.
  • an organic electroluminescent compound can be used as a hole transport material or a hole injection material, so that the resultant organic electroluminescent 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 lifetimes and that have improved power consumption thanks to increased power efficiency.
  • 2-iodobenzene 30g(120.4mmol), 4-bromophenyl boronic acid 26g(132.5mmol), Pd(PPh 3 ) 4 6.9g(6.02mmol), and 2M Na 2 CO 3 150mL were added in toluene 500mL and the mixture was heated at 100°C. 4 hours later, the mixture was cooled at room temperature and extracted with ethyl acetate. After washing with distilled water, removing moisture with MgSO 4 , and performing distillation under reduced pressure, Compound 1-1 28g(100.68mmol, 83,33%) was obtained via column separation.
  • Dibenzo[b,d]thiophen-4-ylboronic acid 10g(43.84mmol), bromonitrobenzene 8.85g(43.84mmol), 2M Na 2 CO 3 solution 70mL, toluene 200mL, and ethanol 70mL were mixed and stirred under reflux. 5 hours later, the mixture was cooled at room temperature and the mixture was extracted with ethyl acetate. The resultant material was washed with distilled water. After removing moisture with MgSO 4 , and performing distillation under reduced pressure, Compound 4-1 10g(32.74mmol, 74.68%) was obtained via column separation.
  • Compound 7-2 28g(72.86mmol) was mixed with triethylphosphite 300mL and stirred for 12 hours at 150°C. After cooling the mixture at room temperature and performing distillation under reduced pressure, the mixture was extracted with ethyl acetate and the resultant material was washed with the resultant material. After removing moisture with MgSO 4 , and performing distillation under reduced pressure, Compound 7-3 11g(31.22mmol, 43.05%) was obtained via column separation.
  • Compound 8-1 50g(152.36mmol), and triethylphosphite 500mL were mixed and stirred for 7 hours at 150°C. After cooling the mixture at room temperature and performing distillation under reduced pressure, the mixture was extracted with ethyl acetate. The resultant material was washed with distilled water. After removing moisture with MgSO 4 , and performing distillation under reduced pressure, Compound 8-2 30g(101.29mmol, 66.64%) was obtained via column separation.
  • Compound 8-2 30g(101.29mmol), N-(4-(9H-carbazole-9-yl)phenyl)-4-bromo-N-(4-tert-butyl-phenyl)aniline 41.3g(202.59mmol), CuI 9.6g(50.64mmol), Cs 2 CO 3 82.5g(253.2mmol), and toluene 600mL were mixed and heated at 50°C. Ethylenediamine 6.8mL(101.29mmol) was added and stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO 4 , and performing distillation under reduced pressure, Compound 8-3 32g(85.96mmol, 84.86%) was obtained via column separation.
  • 1-naphthalene boronic acid 10.2g(59.4mmol), 1-bromo-2-nitrobenzene 10.0g(49.5mmol), Pd(PPh 3 ) 4 1.7g(1.4mmol), 2M K 2 CO 3 aqueous solution 70mL, toluene 200mL and ethanol 100mL were mixed and stirred under reflux for 12 hours. The mixture was washed with distilled water and extracted with ethyl acetate. After removing moisture with anhydrous MgSO 4 , and performing distillation under reduced pressure, Compound 9-1 9.0g(73.7%) was obtained via column separation on the obtained residue.
  • Compound 9-2 9.6g(29.3mmol), and Fe[C 2 O 4 ] 2H 2 O(iron oxalate dihydrate) 72.2g(175.5mmol) were mixed and heated at 205°C for 30 minutes. After cooling the mixture at room temperature, the mixture was extracted with ethyl acetate and the resultant material was washed with distilled water. Compound 9-3 5.2g(60.5%) was obtained via recrystallization using toluene.
  • An OLED device was manufactured by using the electroluminescent material of the present invention.
  • a transparent electrode ITO thin film (15 ⁇ / ⁇ ) obtained from a glass for OLED (manufactured by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use.
  • the ITO substrate was equipped in a substrate holder of a vacuum deposition apparatus, and 2-TNATA (4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine) was placed in a cell of the vacuum 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, Compound 1 was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate Compound 1 , thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • 2-TNATA 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine
  • an electroluminescent layer was formed thereon as follows.
  • CBP 4,4'-N,N'-dicarbazole-biphenyl
  • Ir(acac) bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] as a dopant was placed in another cell, within a vacuum vapor deposition apparatus.
  • 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 wt%.
  • BAlq bis(2-methyl-8-quinolinato)( p -phenylphenolato)aluminum(III)
  • BAlq bis(2-methyl-8-quinolinato)( p -phenylphenolato)aluminum(III)
  • Alq3 tris(8-hydroxyquinoline)-aluminum(III)
  • Liq lithium quinolate
  • 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 under 10 -6 torr.
  • An OLED device was manufactured by the same method as Example 1 except that Compound 19 was used as a hole transport material.
  • An OLED device was manufactured by the same method as Example 1 except that Compound 31 was used as a hole transport material.
  • An OLED device was manufactured by the same method as Example 1 except that Compound 69 was used as a hole transport material.
  • An OLED device was manufactured by the same method as Example 1 except that Compound 1 was used as a hole transport material and an organic iridium complex Ir(ppy) 3 [tris(2-phenylpyridine)iridium] as an electroluminescent dopant was doped on the electroluminescent layer at 15 wt%.
  • An OLED device was manufactured by the same method as Example 5 except that Compound 20 was used as a hole transport material.
  • An OLED device was manufactured by the same method as Example 5 except that Compound 31 was used as a hole transport material.
  • An OLED device was manufactured by the same method as Example 5 except that Compound 42 was used as a hole transport material.
  • An OLED device was manufactured by the same method as Example 5 except that Compound 43 was used as a hole transport material.
  • An OLED device was manufactured by the same method as Example 5 except that Compound 14 instead of 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was used as a hole transport material.
  • N 1 ,N 1' -([1,1'-biphenyl]-4,4'-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine) was placed as a hole injection material and then ventilated up to 10 -6 torr of vacuum in the chamber.
  • an electroluminescent layer was formed thereon as follows. After respectively adding H-31 as a host in a cell of a vacuum vapor deposition apparatus and D-58 as a dopant in another cell, the two cells were evaporated at different rates and doped at 15 wt% such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer.
  • Each compound used in the OLED was purified by vacuum sublimation at 10 -6 torr.
  • An OLED device was manufactured by the same method as Example 11 except that Compound 132 as a hole transport material, H-1 as a host and D-71 as a dopant were used.
  • An OLED device was manufactured by the same method as Example 11 except that Compound 138 as a hole transport material, H-34 as a host and D-31 as a dopant were used.
  • An OLED device was manufactured by the same method as Example 11 except that Compound 149 as a hole transport material, H-39 as a host and D-31 as a dopant were used.
  • An OLED device was manufactured by the same method as Example 11 except that Compound 109 as a hole transport material was used and H-45 as a host and D-6 as a dopant were doped at 4 wt%.
  • An OLED device was manufactured by the same method as Example 15 except that Compound 141 as a hole transport material, H-49 as a host and D-6 as a dopant were used.
  • An OLED device was manufactured by the same method as Example 15 except that Compound 142 as a hole transport material, H-52 as a host and D-6 as a dopant were used.
  • An OLED device was manufactured by the same method as Example 15 except that Compound 149 as a hole transport material, H-53 as a host and D-9 as a dopant were used.
  • An OLED device was manufactured by the same method as Example 1 except that N,N'-bis( ⁇ -naphthyl)-N,N'-diphenyl-4,4'-diamine [NPB] instead of the compound of the present invention as a hole transport material at one cell of the vacuum vapor deposition apparatus was used.
  • NPB N,N'-bis( ⁇ -naphthyl)-N,N'-diphenyl-4,4'-diamine
  • An OLED device was manufactured by the same method as Example 5 except that N,N'-bis( ⁇ -naphthyl)-N,N'-diphenyl-4,4'-diamine [NPB] instead of the compound of the present invention as a hole transport material at one cell of the vacuum vapor deposition apparatus was used.
  • NPB N,N'-bis( ⁇ -naphthyl)-N,N'-diphenyl-4,4'-diamine
  • An OLED device was manufactured by the same method as Example 11 except that NPB as a hole transport material, H-1 as a host and D-30 as a dopant were used.
  • An OLED device was manufactured by the same method as Example 15 except that NPB as a hole transport material, H-46 as a host and D-9 as a dopant were used.
  • organic electroluminescent compounds developed in the present invention showed superior electroluminescent properties compared to the conventional material.
  • the organic electroluminescent compounds of the present invention are very effective at blocking to prevent triplet excitons from migrating out of the luminescent layer by increasing triplet. Accordingly, there is a benefit that a very excellent OLED device is manufactured due to superior electroluminescent efficiency in phosphorescence.
  • an organic electroluminescent compound can be used as a hole transport material or a hole injection material, so that the resultant organic electroluminescent 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 lifetimes and that have improved power consumption thanks to increased power efficiency.

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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 lifetimes and that consume 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 or hole injection material, and to an organic electroluminescent device using the same.
Liquid crystal displays (LCDs) are currently widespread and are non-emissive display devices which have low power consumption and are lightweight but have 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 being carried out.
Among display devices, electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices. In 1987, Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [Appl. Phys. Lett. 51, 913, 1987].
The light emission mechanism of the organic electroluminescent 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 a plastic, and may also operate at a voltage that is 10 V or less than that of a plasma display panel or an inorganic electroluminescent display, and may exhibit comparatively low power consumption and superior color.
An organic material for the organic EL device may be largely divided into an electroluminescent material and a charge transport material. The electroluminescent material is directly related to electroluminescent color and luminous efficiency, and requires several characteristics such as a high fluorescence quantum yield in a solid state, high mobility of electrons and holes, low degradability at the time of vacuum deposition, uniform thin-film formability and stability.
Meanwhile, a hole injection and transport material includes copper phthalocyanine (CuPc), NPB, TPD, MTDATA (4,4',4''-tris(3-methylphenylphenylamino)triphenylamine), etc. A device using these materials in the hole injection or transport layer is problematic in efficiency and operation life. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. The thermal stress significantly reduces the operation life of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease.
It is known that an amorphous compound providing good stability of thin film improves the operation life of the organic EL device. Glass transition temperature (Tg) may be a measure of the amorphousness. MTDATA has a glass transition temperature of 76℃ and cannot be said to have high amorphousness. These materials are not satisfactory in the operation life of the organic EL device, as well as in the luminous efficiency, which is determined by the hole injection and transport properties.
Therefore, the present invention has been made keeping in mind the problems occurring in the related art and an object of the present invention is to provide an organic electroluminescent compound the backbone of which is superior in luminous efficiency and device lifetime compared to conventional hole injection or hole transport materials, and an organic electroluminescent device using such a novel organic electroluminescent compound as a hole injection layer or a hole transport layer.
Provided are an organic electroluminescent compound represented by Chemical Formula 1 below, and an organic electroluminescent device including the same. The organic electroluminescent compound according to the present invention is contained in the hole injection layer or the hole transport layer of the organic electroluminescent device, thus reducing the operating voltage of the device and increasing the luminous efficiency thereof.
In one aspect, the present invention provides an organic electroluminescent compound represented by Chemical Formula 1 below.
[Chemical Formula 1]
Figure PCTKR2011006314-appb-I000001
wherein, ring A and ring C independently represent
Figure PCTKR2011006314-appb-I000002
;
ring B represents
Figure PCTKR2011006314-appb-I000003
;
X1 and X2 independently represent CR3 or N;
Y1 and Y2 independently represent a chemical bond, -O-, -S-, -C(R11R12)-, -Si(R13R14)- or -N(R15)-, except for a case where both Y1 and Y2 are a chemical bond;
R1 through R3 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-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 (C1-C30)alkylsilyl, cyano, nitro or hydroxyl, and when there are two or more of either R1 or R2, they are linked to each other to form a cyclic structure;
L represents substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (C2-C30)heteroarylene, and when there are two or more of L, they are linked to each other to form a cyclic structure;
Ar1 and Ar2 independently represent substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl or
Figure PCTKR2011006314-appb-I000004
;
Y3 and Y4 independently represent a chemical bond, -O-, -S-, -C(R16R17)-, -Si(R18R19)- or -N(R20)-, except for a case where both Y3 and Y4 are a chemical bond;
R11 through R20 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C2-C30)heteroaryl, or each of them may be 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;
m and n independently represent an integer of 0 to 4, and when m and n are an integer of 2 or greater, each of R1 and L may be identical to or different from each other;
p represents an integer of 0 to 2, and when p is 2, each of R2 may be identical to or different from each other; and
the heterocycloalkyl, heteroaryl and heteroarylene include one or more heteroatom(s) selected from the group consisting of B, N, O, S, P(=O), Si and P.
As described herein, "alkyl" and other substituents containing the "alkyl" moiety include both linear and branched species, and "cycloalkyl" includes monocyclic hydrocarbon as well as polycyclic hydrocarbon such as substituted or unsubstituted adamantyl or substituted or unsubstituted (C7-C30)bicycloalkyl. As described herein, the term "aryl" means an organic radical derived from aromatic hydrocarbon by the removal of one hydrogen atom, and includes a 4- to 7-membered, particularly 5- or 6-membered, single ring or a fused ring, and even further includes a structure where a plurality of aryls are linked by single bonds. Specific examples thereof include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, or the like, but are not limited thereto. The naphthyl includes 1-naphthyl and 2-naphthyl, and the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, the phenanthryl includes 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, and the naphthacenyl includes 1-naphthacenyl, 2-naphthacenyl and 9-naphthacenyl. The pyrenyl includes 1-pyrenyl, 2-pyrenyl and 4-pyrenyl, and the biphenyl includes 2-biphenyl, 3-biphenyl and 4-biphenyl, the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl, and the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
The "heteroaryl" described herein means an aryl group containing 1 to 4 heteroatom(s) selected from the group consisting of B, N, O, S, P, P(=O), Si and Se as aromatic ring backbone atom(s) and the remaining aromatic ring backbone atom is carbon. It may be 5- or 6-membered monocyclic heteroaryl or polycyclic heteroaryl condensed with one or more benzene ring(s), and may be partially saturated. In the present invention, "heteroaryl" includes a structure where one or more heteroaryls are linked by single bonds. The heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, N- oxide or quaternary salt. Specific examples thereof include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, or the like, polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl or the like, N-oxide thereof (e.g., pyridyl N-oxide, quinolyl N-oxide), quaternary salt thereof, and the like, but are not limited thereto. The pyrrolyl includes 1-pyrrolyl, 2-pyrrolyl and 3-pyrrolyl; the pyridyl includes 2-pyridyl, 3-pyridyl and 4-pyridyl; the indolyl includes 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl and 7-indolyl; the isoindolyl includes 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl and 7-isoindolyl; the furyl includes 2-furyl and 3-furyl; the benzofuranyl includes 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl and 7-benzofuranyl; the isobenzofuranyl includes 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl and 7-isobenzofuranyl; the quinolyl includes 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl and 8-quinolyl; the isoquinolyl includes 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl and 8-isoquinolyl; the quinoxalinyl includes 2-quinoxalinyl, 5-quinoxalinyl and 6-quinoxalinyl; the carbazolyl includes 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl and 9-carbazolyl; the phenanthridinyl includes 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl and 10-phenanthridinyl; the acridinyl includes 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl and 9-acridinyl; the phenanthrolinyl includes 1,7-phenanthrolin-2-yl, 1,7-phenanthrolin-3-yl, 1,7-phenanthrolin-4-yl, 1,7-phenanthrolin-5-yl, 1,7-phenanthrolin-6-yl, 1,7-phenanthrolin-8-yl, 1,7-phenanthrolin-9-yl, 1,7-phenanthrolin-10-yl, 1,8-phenanthrolin-2-yl, 1,8-phenanthrolin-3-yl, 1,8-phenanthrolin-4-yl, 1,8-phenanthrolin-5-yl, 1,8-phenanthrolin-6-yl, 1,8-phenanthrolin-7-yl, 1,8-phenanthrolin-9-yl, 1,8-phenanthrolin-10-yl, 1,9-phenanthrolin-2-yl, 1,9-phenanthrolin-3-yl, 1,9-phenanthrolin-4-yl, 1,9-phenanthrolin-5-yl, 1,9-phenanthrolin-6-yl, 1,9-phenanthrolin-7-yl, 1,9-phenanthrolin-8-yl, 1,9-phenanthrolin-10-yl, 1,10-phenanthrolin-2-yl,1,10-phenanthrolin-3-yl, 1,10-phenanthrolin-4-yl, 1,10-phenanthrolin-5-yl, 2,9-phenanthrolin-1-yl, 2,9-phenanthrolin-3-yl, 2,9-phenanthrolin-4-yl, 2,9-phenanthrolin-5-yl, 2,9-phenanthrolin-6-yl, 2,9-phenanthrolin-7-yl, 2,9-phenanthrolin-8-yl, 2,9-phenanthrolin-10-yl, 2,8-phenanthrolin-1-yl, 2,8-phenanthrolin-3-yl, 2,8-phenanthrolin-4-yl, 2,8-phenanthrolin-5-yl, 2,8-phenanthrolin-6-yl, 2,8-phenanthrolin-7-yl, 2,8-phenanthrolin-9-yl, 2,8-phenanthrolin-10-yl, 2,7-phenanthrolin-1-yl, 2,7-phenanthrolin-3-yl, 2,7-phenanthrolin-4-yl, 2,7-phenanthrolin-5-yl, 2,7-phenanthrolin-6-yl, 2,7-phenanthrolin-8-yl, 2,7-phenanthrolin-9-yl and 2,7-phenanthrolin-10-yl; the phenazinyl includes 1-phenazinyl and 2-phenazinyl; the phenothiazinyl includes 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl and 10-phenothiazinyl; the phenoxazinyl includes 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl and 10-phenoxazinyl; the oxazolyl includes 2-oxazolyl, 4-oxazolyl and 5-oxazolyl; the oxadiazolyl includes 2-oxadiazolyl and 5-oxadiazolyl; the furazanyl includes 3-furazanyl; the dibenzofuranyl includes 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl and 4-dibenzofuranyl; and the dibenzothiophenyl includes 1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl and 4-dibenzothiophenyl.
As described herein, the term "(C1-C30)alkyl" includes (C1-C20)alkyl or (C1-C10)alkyl, and the term "(C6-C30)aryl" includes (C6-C20)aryl or (C6-C12)aryl. The term "(C2-C30)heteroaryl" includes (C2-C20)heteroaryl or (C2-C12)heteroaryl, and the term "(C3-C30)cycloalkyl" includes (C3-C20)cycloalkyl or (C3-C7)cycloalkyl. The term, "(C2-C30)alkenyl or alkynyl" includes (C2-C20)alkenyl or alkynyl, or (C2-C10)alkenyl or alkynyl.
In the expression "substituted or unsubstituted (or with or without substituent(s))" used herein, "substituted (with substituent(s))" means that the unsubstituted substituent is further substituted with substituent(s). The each substituent of the R1, R2, R3, L, Ar1, Ar2 and R11 through R20 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, (C6-C30)aryl, (C6-C30)aryl-substituted or unsubstituted (C2-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, (C2-C30)alkenyl, (C2-C30)alkynyl,
Figure PCTKR2011006314-appb-I000005
, cyano, carbazolyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, -OR21, -SR22, -NR23R24, -PR25R26, -SiR27R28R29, nitro and hydroxyl, and Y11 and Y12 independently represent a chemical bond, -C(R31R32)-, -O-, -S- or -N(R33)-, except for a case where both Y11 and Y12 are a chemical bond; and R21 through R29 and R31 through R33 independently represent (C1-C30)alkyl, (C6-C30)aryl, (C2-C30)heteroaryl, or (C3-C30)cycloalkyl.
In the Chemical Formula 1, ring A
Figure PCTKR2011006314-appb-I000006
is fused to an indoline ring and represents a 6-membered aromatic ring or a 6-membered nitrogen-containing heteroaromatic ring, ring B
Figure PCTKR2011006314-appb-I000007
is fused to the ring A and represents a 5- or 6-membered ring, ring C
Figure PCTKR2011006314-appb-I000008
is fused to the ring B and represents a 6-membered aromatic ring or a 6-membered nitrogen-containing heteroaromatic ring.
Furthermore,
Figure PCTKR2011006314-appb-I000009
of Chemical Formula 1 is selected from the following structures, but is not limited thereto.
Figure PCTKR2011006314-appb-I000010
Figure PCTKR2011006314-appb-I000011
Figure PCTKR2011006314-appb-I000012
Figure PCTKR2011006314-appb-I000013
Figure PCTKR2011006314-appb-I000014
Figure PCTKR2011006314-appb-I000015
wherein, R2, R11 through R15 and p are the same as defined as in Chemical Formula 1.
To be specific, the L represents (C6-C30)arylene; Ar1 and Ar2 independently represent (C6-C30)aryl, (C2-C30)heteroaryl,
Figure PCTKR2011006314-appb-I000016
or
Figure PCTKR2011006314-appb-I000017
; Y3 and Y4 independently represent -O-, -S-, -C(R16R17)- or -N(R20)-; R16, R17 and R20 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C2-C30)heteroaryl, or R16 and R17 may be linked to 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 ora monocyclic or polycyclic aromatic ring; R1 represents hydrogen, (C6-C30)aryl or (C2-C30)heteroaryl, or may be linked to an adjacent substituent via
Figure PCTKR2011006314-appb-I000018
,
Figure PCTKR2011006314-appb-I000019
or
Figure PCTKR2011006314-appb-I000020
; each of arylene of the L, aryl, heteroaryl of Ar1 and Ar2, alkyl, aryl or heteroaryl of R16, R17 and R20, aryl or heteroaryl of R1 may be further substituted with one or more selected from the group consisting of deuterium, halogen, halogen-substituted or unsubstituted (C6-C30)aryl, (C1-C30)alkyl, (C6-C30)aryl-substituted or unsubstituted (C2-C30)heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s),
Figure PCTKR2011006314-appb-I000021
, carbazolyl, and -NR23R24, and the Y11 and Y12 independently represent -C(R31R32)-, -O-, -S- or -N(R30)-; R23, R24, R31, R32 and R33 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C2-C30)heteroaryl.
The organic electroluminescent compound according to the present invention may be exemplified by the following compounds, which are not intended to limit the present invention.
Figure PCTKR2011006314-appb-I000022
Figure PCTKR2011006314-appb-I000023
Figure PCTKR2011006314-appb-I000024
Figure PCTKR2011006314-appb-I000025
Figure PCTKR2011006314-appb-I000026
Figure PCTKR2011006314-appb-I000027
Figure PCTKR2011006314-appb-I000028
Figure PCTKR2011006314-appb-I000029
Figure PCTKR2011006314-appb-I000030
Figure PCTKR2011006314-appb-I000031
Figure PCTKR2011006314-appb-I000032
Figure PCTKR2011006314-appb-I000033
Figure PCTKR2011006314-appb-I000034
Figure PCTKR2011006314-appb-I000035
Figure PCTKR2011006314-appb-I000036
Figure PCTKR2011006314-appb-I000037
Figure PCTKR2011006314-appb-I000038
Figure PCTKR2011006314-appb-I000039
Figure PCTKR2011006314-appb-I000040
Figure PCTKR2011006314-appb-I000041
Figure PCTKR2011006314-appb-I000042
Figure PCTKR2011006314-appb-I000043
Figure PCTKR2011006314-appb-I000044
Figure PCTKR2011006314-appb-I000045
Figure PCTKR2011006314-appb-I000046
Figure PCTKR2011006314-appb-I000047
Figure PCTKR2011006314-appb-I000048
Figure PCTKR2011006314-appb-I000049
Figure PCTKR2011006314-appb-I000050
Figure PCTKR2011006314-appb-I000051
Figure PCTKR2011006314-appb-I000052
Figure PCTKR2011006314-appb-I000053
Figure PCTKR2011006314-appb-I000054
Figure PCTKR2011006314-appb-I000055
Figure PCTKR2011006314-appb-I000056
Figure PCTKR2011006314-appb-I000057
The organic electroluminescent 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 PCTKR2011006314-appb-I000058
wherein, A, B, C, R1, L, Ar1, Ar2, m and n are the same as defined in Chemical Formula 1.
In addition, the present invention provides an organic electroluminescent device, in which the organic electroluminescent compound according to the present invention is used as a hole injection material or a hole transport material.
When the organic electroluminescent compound represented by Chemical Formula 1 according to the present invention is used to the hole injection layer or the hole transport layer, it may be used to manufacture OLED devices consuming less power due to improved power efficiency.
The organic electroluminescent 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 electroluminescent compounds of Chemical Formula 1.
In addition, the organic layer may include one or more electroluminescent layer, besides the layer that one or more organic electroluminescent compound(s) of Chemical Formula 1 is included. The electroluminescent layer may further include one or more dopant(s) or host(s). The dopant or host applied to the organic electroluminescent device of the present invention is not specifically limited but may be selected from following Chemical Formulas 2 to 6.
[Chemical Formula 2]
M1L101L102L103
wherein
M1 represents Ir, Pt, Pd or Os;
ligands L101, L102 and L103 are independently selected from following structures:
Figure PCTKR2011006314-appb-I000059
Figure PCTKR2011006314-appb-I000060
Figure PCTKR2011006314-appb-I000061
Figure PCTKR2011006314-appb-I000062
R201 through R203 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkyl-substituted or unsubstituted (C6-C30)aryl or halogen;
R204 through R219 independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted mono or di-(C1-C30)alkylamino, substituted or unsubstituted mono or di-(C6-C30)arylamino, SF5, substituted or unsubstituted tri(C1-C30)alkylsilyl, substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C30)arylsilyl, cyano or halogen;
R220 through R223 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, or (C1-C30)alkyl-substituted or unsubstituted (C6-C30)aryl;
R224 and R225 independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, halogen-substituted or unsubstituted (C6-C30)aryl, or halogen, or R224 and R225 may be linked to an adjacent substituent via substituted or unsubstituted (C3-C12)alkylene or substituted or unsubstituted (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
R226 represents substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, or halogen;
R227 through R229 independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or halogen; and
Q represents
Figure PCTKR2011006314-appb-I000063
,
Figure PCTKR2011006314-appb-I000064
or
Figure PCTKR2011006314-appb-I000065
, wherein R231 through R242 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkoxy, halogen, substituted or unsubstituted (C6-C30)aryl, cyano, substituted or unsubstituted (C3-C30)cycloalkyl, or they may be linked to an adjacent substituent via alkylene or alkenylene to form a spiro ring or a fused ring, or linked to R207 or R208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
[Chemical Formula 3]
Figure PCTKR2011006314-appb-I000066
wherein
Z represents -O-, -S-, -C(R41R42)-, -Si(R43R44)- or -N(R45)-;
ring D and ring F independently represent
Figure PCTKR2011006314-appb-I000067
;
ring E represents
Figure PCTKR2011006314-appb-I000068
;
Y21 and Y22 independently represent CH or N;
Y23 and Y24 independently represent a chemical bond, -O-, -S-, -C(R41R42)-, -Si(R43R44)- or -N(R45)-, except for a case where both Y23 and Y24 are a chemical bond;
R31 and R32 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-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 (C1-C30)alkylsilyl, substituted or unsubstituted (C6-C30)arylsilyl, substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylsilyl, cyano, nitro or hydroxyl, or they may be 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 mono- or polycyclic aromatic ring;
R41 through R45 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or substituted or unsubstituted (C3-C30)cycloalkyl with or without substituent(s), or each of them may be linked to an adjacent substituent to form a ring;
r and q independently represent an integer of 0 to 4, and when r and q are an integer of 2 or greater, each of R31 and R32 may be identical to or different from each other, or each of them may be linked to an adjacent substituent to form a ring;
the heterocycloalkyl and heteroaryl include one or more heteroatom(s) selected from the group consisting of B, N, O, S, P(=O), Si and P.
[Chemical Formula 4]
(Cz-L2)a-M
[Chemical Formula 5]
(Cz)b-L2-M
wherein
Cz is selected from following structures,
Figure PCTKR2011006314-appb-I000069
ring G represents (C6-C30)aliphatic ring, (C6-C30)aromatic ring or (C2-C30)heteroaromatic ring;
R51 and R53 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted(C6-C30)aryl fused with one or more substituted or unsubstituted (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, cyano, nitro, hydroxyl, -BR61R62, -PR63R64, -P(=O)R65R66, R67R68R69Si-, -NR70R71 or -YR72, or they may be 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 mono- or polycyclic aromatic ring, and a carbon atom of the formed alicyclic ring and mono- or polycyclic aromatic ring is substituted with one or more hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur; each of R52 and R53 may be identical or different from each other;
Y represents O or S;
R61 through R72 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted(C6-C30)aryl fused with one or more substituted or unsubstituted (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, cyano, nitro or hydroxyl;
L2 represents a chemical bond, substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (C2-C30)heteroaryl;
M represents substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (C2-C30)heteroaryl;
a, b, c and d independently represent an integer of 0 to 4.
[Chemical Formula 6]
Figure PCTKR2011006314-appb-I000070
wherein
A1 through A19 independently represent CR81 or N;
X represent -C(R82R83)-, -N(R84)-, -S-, -O-, -Si(R85)(R86)-, -P(R87)-, -P(=O)(R88)- or -B(R89)-;
Ar11 represents substituted or unsubstituted (C6-C40)arylene or substituted or unsubstituted (C2-C40)heteroarylene, except for the case that e is 0 and A15 through A19 are CR81 at the same time;
R81 through R89 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted(C6-C30)aryl fused with one or more substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C2-C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), substituted or unsubstituted (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic ring(s), cyano, trifluoromethyl, -NR91R92, -BR93R94, -PR95R96, -P(=O)R97R98, R99R100R101Si-, R102Y21-, R103C(=O)-, R104C(=O)O-, substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted or unsubstituted (C2-C30)alkynyl, carboxyl, nitro or hydroxyl, or they may be 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 mono- or polycyclic aromatic ring;
R91 through R98 independently represent substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C2-C30)heteroaryl;
R99 through R101 independently represent substituted or unsubstituted (C1-C30)alkyl or substituted or unsubstituted (C6-C30)aryl;
Y21 represents S or O;
R102 represent substituted or unsubstituted (C1-C30)alkyl or substituted or unsubstituted (C6-C30)aryl;
R103 represent substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (C6-C30)aryloxy;
R104 represent substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C6-C30)aryloxy;
e represents an integer of 0 to 2;
the heterocycloalkyl, heteroaryl and heteroarylene include one or more heteroatom(s) selected from the group consisting of B, N, O, S, P(=O), Si and P.
In the term 'substituted or unsubstituted' described in Chemical Formulas 2 to 6, the term 'substituted' means that the unsubstituted substituent is further substituted with substituent(s). The substituent means one or more substituent(s) selected from the same group as that represented by Chemical Formula 1.
To be specific, following compounds may be used in Chemical Formulas 2 to 6.
Figure PCTKR2011006314-appb-I000071
Figure PCTKR2011006314-appb-I000072
Figure PCTKR2011006314-appb-I000073
Figure PCTKR2011006314-appb-I000074
Figure PCTKR2011006314-appb-I000075
Figure PCTKR2011006314-appb-I000076
Figure PCTKR2011006314-appb-I000077
Figure PCTKR2011006314-appb-I000078
Figure PCTKR2011006314-appb-I000079
Figure PCTKR2011006314-appb-I000080
Figure PCTKR2011006314-appb-I000081
Figure PCTKR2011006314-appb-I000082
Figure PCTKR2011006314-appb-I000083
Figure PCTKR2011006314-appb-I000084
Figure PCTKR2011006314-appb-I000085
Figure PCTKR2011006314-appb-I000086
Figure PCTKR2011006314-appb-I000087
Figure PCTKR2011006314-appb-I000088
Figure PCTKR2011006314-appb-I000089
Figure PCTKR2011006314-appb-I000090
Figure PCTKR2011006314-appb-I000091
Figure PCTKR2011006314-appb-I000092
Figure PCTKR2011006314-appb-I000093
Figure PCTKR2011006314-appb-I000094
Figure PCTKR2011006314-appb-I000095
Figure PCTKR2011006314-appb-I000096
Figure PCTKR2011006314-appb-I000097
Figure PCTKR2011006314-appb-I000098
Figure PCTKR2011006314-appb-I000099
Figure PCTKR2011006314-appb-I000100
Figure PCTKR2011006314-appb-I000101
Figure PCTKR2011006314-appb-I000102
The organic electroluminescent device according to the present invention includes the organic electroluminescent compound of Chemical Formula 1, and may further include one or more compounds selected from the group consisting of arylamine compounds and styrylamine compounds, and specific examples of the arylamine compounds or styrylamine compounds are illustrated in paragraph numbers <212> to <224> of Korean Patent Application No. 10-2008-0060393, but is not limited thereto.
In the organic electroluminescent device according to the present invention, the organic layer may further comprise one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s), in addition to the organic electroluminescent compound of Chemical Formula 1. The organic layer may comprise an electroluminescent layer and a charge generating layer.
An organic electroluminescent device having a pixel structure of independent light-emitting mode may be embodied, wherein the organic electroluminescent device including the organic electroluminescent 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 the group consisting of 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 electroluminescent compound of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device. The compounds emitting blue, green or red light may be exemplified by the compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
In the organic electroluminescent device of the present invention, a layer (hereinafter referred to as "surface layer" selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom. The chalcogenide may be, for example, SiOx (1 ≤ x ≤ 2), AlOx (1 ≤ x ≤ 1.5), SiON, SiAlON, etc. The metal halide may be, for example, LiF, MgF2, CaF2, a rare earth metal fluoride, etc. The metal oxide may be, for example, Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant. In that case, since the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated. In addition, since the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated. Preferable oxidative dopants include various Lewis acids and acceptor compounds. Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. Further, a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.
According to the present invention, an organic electroluminescent compound can be used as a hole transport material or a hole injection material, so that the resultant organic electroluminescent 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 lifetimes and that have improved power consumption thanks to increased power efficiency.
Hereinafter, the present invention is further described by taking representative compounds of the present invention as examples with respect to the organic electroluminescent compounds according to the invention, a preparing method thereof, and electroluminescent properties of the devices. But, those examples are provided only for illustration of the embodiments, not being intended to limit the scope of the invention.
[Preparation Example 1] Preparation of Compound 1
Figure PCTKR2011006314-appb-I000103
Preparation of Compound 1-1
2-iodobenzene 30g(120.4mmol), 4-bromophenyl boronic acid 26g(132.5mmol), Pd(PPh3)4 6.9g(6.02mmol), and 2M Na2CO3 150mL were added in toluene 500mL and the mixture was heated at 100℃. 4 hours later, the mixture was cooled at room temperature and extracted with ethyl acetate. After washing with distilled water, removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 1-1 28g(100.68mmol, 83,33%) was obtained via column separation.
Preparation of Compound 1-2
Compound 1-1 28g(100.68mmol) was added to triethylphosphite 300mL and stirred for 6 hours at 150℃. After cooling at room temperature, the mixture was distilled under reduced pressure, and extracted with ethyl acetate. The resultant material was washed with distilled water. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 1-2 11g(44.69mmol, 44.38%) was obtained via column separation.
Preparation of Compound 1-3
Compound 1-2 30g(101.29mmol), iodobenzene 41.3g(202.59mmol), CuI 9.6g(50.64mmol), Cs2CO3 82.5g(253.2mmol) and toluene 600mL were mixed and heated at 50℃. Ethylenediamine 6.8mL(101.29mmol) was added to the mixture and the mixture was stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added. The resultant mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 1-3 32g(85.96mmol, 84.86%) was obtained via column separation.
Preparation of Compound 1-4
Compound 1-3 32g(85.96mmol) was dissolved in THF 300mL and n-butyllithium 37.8mL(94.55mmol, 2.5M in hexane) was slowly added to the mixture at -78℃. 1 hour later, trimethylborate 12.4mL(111.7mmol) was added to the mixture. After stirring the mixture at room temperature for 12 hours, distilled water was added to the stirred mixture and the mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 1-4 20g(59.31mmol, 69.00%) was obtained via column separation.
Preparation of Compound 1-5
Compound 1-4 20g(59.31mmol), 1-bromo-2-nitrobenzene 14.3g(71.17mmol), Pd(PPh3)4 2.7g(2.37mmol), 2M Na2CO3 75mL, toluene 300mL, and ethanol 70mL were mixed and stirred under reflux. 5 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 1-5 20g(48.25mmol, 81.36%) was obtained via column separation.
Preparation of Compound 1-6
After triethylphosphite 200mL was added to Compound 1-5 20g(48.25mmol), the mixture was stirred for 6 hours at 150℃, and cooled at room temperature. After performing distillation under reduced pressure, the mixture was extracted with ethyl acetate and the resultant material was washed with distilled water. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 1-6 7g(18.30mmol, 37.93%) was obtained via column separation.
Preparation of Compound 1
Compound 1-6 7g(18.30mmol), 4-bromo-N,N-diphenylaniline 11.9g(36.60mmol), CuI 1.7g(9.15mmol), K3PO4 11.6g(54.90mmol), and toluene 100mL were mixed and heated at 50℃. After adding ethylenediamine 1.2mL(18.30mmol) to the mixture, the mixture was stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 1 8g(17.44mmol, 95.33%) was obtained via column separation.
MS/FAB found 576, calculated 575.70
[Preparation Example 2] Preparation of Compound 15
Figure PCTKR2011006314-appb-I000104
Preparation of Compound 2-1
After 1-bromo-2-nitrobenzene 15g (0.074mol) was added to 1L 2-neck RBF, d 9,9-dimethyl-9H-fluorene-2-yl boronic acid 23g(0.096mol), Pd(PPh3)4 4.2g(0.003mol), Na2CO3(2M) 111mL, and ethanol 111mL were mixed. After adding toluene 200mL to the mixture, the mixture was heated for 3 hours at 120℃ and was stirred. Upon completion of the reaction, the resultant material was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 2-1 22g (95%) was obtained by purification via column chromatography.
Preparation of Compound 2-2
After Compound 2-1 24g (0.076mol) was added to 1L 2-neck RBF, triethylphosphite 200mL, and 1,2-dichlorobenzene 200mL were added to the mixture, heated for 12 hours at 140℃ and stirred. Upon completion of the reaction, the solvent was distilled. The resultant material was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 2-2 7g (33%) was obtained by purification via column chromatography.
Preparation of Compound 15
Compound 2-2 7g(18.30mmol), N-(4-bromophenyl)-N-phenylnaphthalene-2-amine(N-(4-bromophenyl)-N-phenylnaphthalen-2-amine) 13.7g(36.60mmol), CuI 1.7g(9.15mmol), K3PO4 11.6g(54.90mmol), and toluene 100mL were mixed and heated at 50℃. Ethylenediamine 1.2mL(18.30mmol) was added to the mixture and the mixture was stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 15 8g(17.44mmol, 95.33%) was obtained via column separation.
MS/FAB found 577, calculated 576.73
[Preparation Example 3] Preparation of Compound 22
Figure PCTKR2011006314-appb-I000105
Preparation of Compound 3-1
2-bromo-9H-carbazole 7g(18.30mmol), N-(4-(9H-carbazole-9-yl)phenyl)-4-bromo-N-phenylaniline 13.7g(36.60mmol), CuI 1.7g(9.15mmol), K3PO4 11.6g(54.90mmol), and toluene 100mL were mixed and heated at 50℃. After adding ethylenediamine 1.2mL(18.30mmol, the mixture was stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 3-1 8g(17.44mmol, 95.33%) was obtained via column separation.
Preparation of Compound 3-2
Compound 3-1 12g(37.42mmol), 2-(methylthio)phenyl boronic acid 7.5g(44.69mmol), Pd(PPh3)4 2.15g(1.6mmol), 2M Na2CO3 aqueous solution 45mL, and THF 200mL were mixed and stirred under reflux. 5 hours later, the mixture was cooled at room temperature and extracted with ethyl acetate. The resultant material was washed with distilled water. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 3-2 10g(27.36mmol, 73.47%) was obtained via column separation.
Preparation of Compound 3-3
Compound 3-2 10g(27.36mmol) was added to acetic acid 100mL and H2O2 2.65mL(30.09mmol, 35%) was slowly added to the mixture. The mixture was stirred for 12 hours at room temperature and acetic acid was distilled under reduced pressure. The resultant material was extracted with dichloromethane and neutralized with NaHCO3 solution. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 3-3 10g(26.21mmol, 95.79%) was obtained.
Preparation of Compound 22
Compound 3-3 10g (26.21mmol) was mixed with trifluoromethanesulfonic acid 70mL and stirred for 5 hours at 100℃. The stirred mixture was cooled at room temperature and added to mixture 100mL(pyridine : distilled water = 1:5). After the mixture was stirred under reflux and cooled at room temperature, a produced solid was filtered under reduced pressure. Compound 22 6g(17.16mmol, 65.47%) was obtained via column separation.
MS/FAB found 682, calculated 681.84
[Preparation Example 4] Preparation of Compound 32
Figure PCTKR2011006314-appb-I000106
Preparation of Compound 4-1
Dibenzo[b,d]thiophen-4-ylboronic acid 10g(43.84mmol), bromonitrobenzene 8.85g(43.84mmol), 2M Na2CO3 solution 70mL, toluene 200mL, and ethanol 70mL were mixed and stirred under reflux. 5 hours later, the mixture was cooled at room temperature and the mixture was extracted with ethyl acetate. The resultant material was washed with distilled water. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 4-1 10g(32.74mmol, 74.68%) was obtained via column separation.
Preparation of Compound 4-2
Compound 4-1 10g(32.74mmol) was mixed with triethylphosphite 100mL and stirred for 7 hours at 150℃. After cooling the mixture at room temperature and performing distillation under reduced pressure, Compound 4-2 7g(25.60mmol, 78.19%) was obtained via recrystallization using ethyl acetate.
Preparation of Compound 32
Compound 4-2 7g(25.60mmol), N-(4-bromophenyl)-N,9-diphenyl-9H-carbazole-3-amine 10.44g(51.21mmol), CuI 2.5g(12.80mmol), K3PO4 16.30g(76.82mmol), and toluene 200mL were mixed and heated at 50℃. Ethylenediamine 1.72mL(25.60mmol) was added to the mixture. The mixture was stirred under reflux for 12 hours, cooled at room temperature and extracted with ethyl acetate. The resultant material was washed with NaHCO3 solution. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 32 8g(22.89mmol, 89.41%) was obtained via column separation.
MS/FAB found 682, calculated 681.84
[Preparation Example 5] Preparation of Compound 41
Figure PCTKR2011006314-appb-I000107
Preparation of Compound 5-1
After 2-(phenylamino)benzoic acid 50g(0.23mol) was dissolved in MeOH 1L, the mixture was added to an ice bath and stirred for 10 minutes at 0℃. After slowly adding SOCl2 60mL(0.58mol) at 0℃, the mixture was stirred under reflux for 12 hours at 90℃. Upon completion of the reaction, the resultant mixture was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 5-1 47g(92%) was obtained by purification via column chromatography using ethyl acetate as a developing solvent.
Preparation of Compound 5-2
After Compound 5-1 90g(0.3mol) was added to THF 1.5L, and MeMgBr(3.0M) 462mL(1.38mol) was slowly added to the mixture, the mixture was stirred for 12 hours at room temperature. Upon completion of the reaction, the resultant mixture was neutralized with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 5-2 80g(90%) was obtained by purification via column chromatography using ethyl acetate as a developing solvent.
Preparation of Compound 5-3
After Compound 5-2 80g(0.35mol) was added to H3PO4 1.7L, the mixture was stirred for 12 hours at room temperature. Upon completion of the reaction, the resultant mixture was neutralized with distilled water. a produced solid was filtered while being washed with water. The solid was dissolved with dichloromethane to be extracted and neutralized with neutralized with NaOH. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 5-3 64g(87%) was obtained via recrystallization using hexane.
Preparation of Compound 5-4
Compound 5-3 64g(0.30mol), bromobenzene 52.8g(0.33mol), Pd(OAc)2 1.37g(6.11mmol), P(t-Bu)3 50% 7.3mL(15.28mmol) and NaOt-Bu 58g(0.61mol) were dissolved in toluene 1.2L, and the mixture was stirred for 12 hours at 120℃. Upon completion of the reaction, the resultant mixture was neutralized with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 5-4 71g(81%) was obtained by purification via column chromatography using ethyl acetate as a developing solvent.
Preparation of Compound 5-5
Compound 5-4 20g(0.07mol) was dissolved in DMF 800mL and was stirred for 10 minutes at 0℃. After slowly adding solution that NBS 12.5g(0.07mol) was dissolved in DMF 350mL, the mixture was stirred for 6 hours at 0℃. Upon completion of the reaction, the resultant mixture was neutralized with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 5-5 21g(84%) was obtained by purification via column chromatography using ethyl acetate as a developing solvent.
Preparation of Compound 5-6
Compound 5-5 20g(0.054mol), 2-chloroaniline 8.4g(0.065mol), Pd(OAc)2 370mg(1.64mmol), P(t-Bu)3 50% 3.6mL(5.49mmol) and Cs2CO3 35.7g(0.109mol) were dissolved in toluene 300mL, and stirred for 4 hours at 120℃. Upon completion of the reaction, the resultant mixture was neutralized with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 5-6 13.6g(60%) was obtained by purification via column chromatography using ethyl acetate as a developing solvent.
Preparation of Compound 5-7
Compound 5-6 12.6g(0.03mol), Pd(OAc)2 1.37mg(6.13mmol), di-tert-butyl(methyl)phosphonium tetrafluoroborate 3g(12.26mmol) and Cs2CO3 50g(0.15mol) were dissolved in DMA 240mL, and stirred for 4 hours at 190℃. Upon completion of the reaction, the resultant mixture was neutralized with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 5-7 7g(70%) was obtained by purification via column chromatography using ethyl acetate as a developing solvent.
Preparation of Compound 41
Compound 5-7 7g(25.60mmol), N-(biphenyl-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 10.44g(51.21mmol), CuI 2.5g(12.80mmol), K3PO4 16.30g(76.82mmol), and toluene 200mL were mixed and heated at 50℃. Ethylenediamine 1.72mL(25.60mmol) was added to the mixture. After stirring the mixture under reflux for 12 hours, the mixture was cooled at room temperature and extracted with ethyl acetate. The resultant material was washed with NaHCO3 solution. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 41 8g(22.89mmol, 89.41%) was obtained via column separation.
MS/FAB found 811, calculated 810.04
[Preparation Example 6] Preparation of Compound 51
Figure PCTKR2011006314-appb-I000108
Preparation of Compound 6-1
Compound 2-2 8.1g(0.028mol) was added to 1L 2-neck RBF and DMF 300mL was added to the mixture. The mixture was stirred under reflux for 10 minutes at 0℃. After dissolving NBS 5.08g(0.028mol) in DMF 300mL and slowly adding the mixture to a reactant, the mixture was stirred under reflux for 6 hours at 0℃. Upon completion of the reaction, the resultant mixture was neutralized with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 6-1 9g(87%) was obtained by purification via column chromatography using ethyl acetate as a developing solvent.
Preparation of Compound 6-2
Compound 6-1 7g(18.30mmol), N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 13.7g (36.60mmol), CuI 1.7g(9.15mmol), K3PO4 11.6g(54.90mmol), and toluene 100mL were mixed and heated at 50℃. Ethylenediamine 1.2mL(18.30mmol) was added to the mixture and stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 6-2 8g(17.44mmol, 95.33%) was obtained via column separation.
Preparation of Compound 51
Compound 6-2 7g(18.30mmol), 9H-carbazole 13.7g(36.60mmol), CuI 1.7g(9.15mmol), K3PO4 11.6g(54.90mmol), and toluene 100mL were mixed and heated at 50℃. Ethylenediamine 1.2mL(18.30mmol) was added to the mixture and stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 51 8g(17.44mmol, 95.33%) was obtained via column separation.
MS/FAB found 742, calculated 741.92
[Preparation Example 7] Preparation of Compound 53
Figure PCTKR2011006314-appb-I000109
Preparation of Compound 7-1
2-bromodibenzo[b,d]thiophene 74g(216.3mmol) was dissolved in THF 1.5L and n-butyllithium 86.5mL(216.3mmol, 2.5M in hexane) was slowly added at -78℃. 1 hour later, trimethylborate 28.9mL(259.6mmol) was added to the mixture and stirred at room temperature for 12 hours. Distilled water was added to the mixture and the mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 7-1 40g(136.8mmol, 62.96%) was obtained via recrystallization using ethyl acetate and hexane.
Preparation of Compound 7-2
Compound 7-1 40g(136.8mmol), iodonitrobenzene 37.4g(150.5mmol), Pd(PPh3)4 6.32g(5.47mmol), 2M Na2CO3 170mL, and toluene 700mL were mixed and stirred for 4 hours at 100℃. After cooling the mixture at room temperature, distilled water was added to the mixture and the mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 7-2 28g(72.86mmol, 52.94%) was obtained via column separation.
Preparation of Compound 7-3
Compound 7-2 28g(72.86mmol) was mixed with triethylphosphite 300mL and stirred for 12 hours at 150℃. After cooling the mixture at room temperature and performing distillation under reduced pressure, the mixture was extracted with ethyl acetate and the resultant material was washed with the resultant material. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 7-3 11g(31.22mmol, 43.05%) was obtained via column separation.
Preparation of Compound 53
Compound 7-3 7g(18.30mmol), 4-bromo-N-(4-(dibenzo[b,d]thiophen-4-yl)phenyl)-N-phenylaniline 13.7g 36.60mmol), CuI 1.7g(9.15mmol), K3PO4 11.6g(54.90mmol), and toluene 100mL were mixed and heated at 50℃. Ethylenediamine 1.2ml(18.30mmol) was added and stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 53 8g(17.44mmol, 95.33%) was obtained via column separation.
MS/FAB found 699, calculated 698.90
[Preparation Example 8] Preparation of Compound 54
Figure PCTKR2011006314-appb-I000110
Preparation of Compound 8-1
2,5-dibromonitrobenzene 50g(177.99mol), 1-naphthalene boronic acid 36.7g(213.59mmol), Pd(PPh3)4 10.28g(8.89mmol), 2M Na2CO3 (533.97mmol), toluene 700mL, and ethanol 200mL were mixed and stirred for 5 hours at 100℃. After cooling the mixture at room temperature and adding distilled water to the mixture, the mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 8-1 50g(152.36mmol, 85.60%) was obtained via column separation.
Preparation of Compound 8-2
Compound 8-1 50g(152.36mmol), and triethylphosphite 500mL were mixed and stirred for 7 hours at 150℃. After cooling the mixture at room temperature and performing distillation under reduced pressure, the mixture was extracted with ethyl acetate. The resultant material was washed with distilled water. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 8-2 30g(101.29mmol, 66.64%) was obtained via column separation.
Preparation of Compound 8-3
Compound 8-2 30g(101.29mmol), N-(4-(9H-carbazole-9-yl)phenyl)-4-bromo-N-(4-tert-butyl-phenyl)aniline 41.3g(202.59mmol), CuI 9.6g(50.64mmol), Cs2CO3 82.5g(253.2mmol), and toluene 600mL were mixed and heated at 50℃. Ethylenediamine 6.8mL(101.29mmol) was added and stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 8-3 32g(85.96mmol, 84.86%) was obtained via column separation.
Preparation of Compound 8-4
Compound 8-3 32g(85.96mmol) was dissolved in THF 300mL and n-butyllithium 37.8mL(94.55mmol, 2.5M in hexane) was slowly added at -78℃. 1 hour later, trimethylborate 12.4mL(111.7mmol) was added to the mixture. After stirring the mixture at room temperature for 12 hours, distilled water was added to the mixture and the mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 8-4 20g(59.31mmol, 69.00%) was obtained via column separation.
Preparation of Compound 8-5
Compound 8-4 20g(59.31mmol), 1-bromo-2-nitrobenzene 14.3g(71.17mmol), Pd(PPh3)4 2.7g(2.37mmol), 2M Na2CO3 75ml, toluene 300mL, and ethanol 70mL were mixed and stirred under reflux. 5 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 8-5 20g(48.25mmol, 81.36%) was obtained via column separation.
Preparation of Compound 8-6
Compound 8-5 20g(48.25mmol) was mixed with triethylphosphite 200mL and stirred at 150℃ for 6 hours. After cooling the mixture at room temperature and performing distillation under reduced pressure, the mixture was extracted with ethyl acetate. The resultant material was washed with distilled water. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 8-6 7g(18.30mmol, 37.93%) was obtained via column separation.
Preparation of Compound 54
Compound 8-6 30g(101.29mmol), iodobenzene 41.3g(202.59mmol), CuI 9.6g(50.64mmol), Cs2CO3 82.5g(253.2mmol), and toluene 600mL were mixed and heated at 50℃. Ethylenediamine 6.8mL(101.29mmol) was added to the mixture and stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 54 32g(85.96mmol, 84.86%) was obtained via column separation.
MS/FAB found 848, calculated 847.06
[Preparation Example 9] Preparation of Compound 58
Figure PCTKR2011006314-appb-I000111
Preparation of Compound 9-1
1-naphthalene boronic acid 10.2g(59.4mmol), 1-bromo-2-nitrobenzene 10.0g(49.5mmol), Pd(PPh3)4 1.7g(1.4mmol), 2M K2CO3 aqueous solution 70mL, toluene 200mL and ethanol 100mL were mixed and stirred under reflux for 12 hours. The mixture was washed with distilled water and extracted with ethyl acetate. After removing moisture with anhydrous MgSO4, and performing distillation under reduced pressure, Compound 9-1 9.0g(73.7%) was obtained via column separation on the obtained residue.
Preparation of Compound 9-2
Compound 9-1 9.0g(36.1mmol) and n-bromosuccinimide 7.6g(43.3mmol) were dissolved in dichloromethane 300mL and stirred at room temperature for 12 hours. After the solid obtained via distillation under reduced pressure was washed with distilled water, methanol and hexane, Compound 9-2 9.6g(81.3%) was obtained.
Preparation of Compound 9-3
Compound 9-2 9.6g(29.3mmol), and Fe[C2O4] 2H2O(iron oxalate dihydrate) 72.2g(175.5mmol) were mixed and heated at 205℃ for 30 minutes. After cooling the mixture at room temperature, the mixture was extracted with ethyl acetate and the resultant material was washed with distilled water. Compound 9-3 5.2g(60.5%) was obtained via recrystallization using toluene.
Preparation of Compound 9-4
Compound 9-3 30g(101.29mmol), 4-bromo-N-phenyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)aniline) 41.3g(202.59mmol), CuI 9.6g(50.64mmol), Cs2CO3 82.5g(253.2mmol), and toluene 600mL were mixed and heated at 50℃. Ethylenediamine 6.8mL(101.29mmol) was added to the mixture and stirred under reflux. 14 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, was obtained via column separation Compound 9-4 32g(85.96mmol, 84.86%).
Preparation of Compound 9-5
Compound 9-4 23.1g(62.07mmol) was dissolved in THF 500mL and n-butyllithium 29.79mL(74.48mmol, 2.5M in Hexane) was slowly added to the mixture at -78℃. 1 hour later, trimethylborate 10.38mL(93.10mmol) was added to the mixture. After stirring the mixture at room temperature for 12 hours, distilled water was added to the mixture and the mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 9-5 14g(67%) was obtained via recrystallization using ethyl acetate and hexane.
Preparation of Compound 9-6
Compound 9-5 14g(41.79mmol), methyl-2-bromobenzoate 13.51g(45.97mmol), Pd(PPh3)4 1.9g(1.67mmol), 2M Na2CO3 60mL, and toluene 200mL were mixed and stirred under reflux. 12 hours later, the mixture was cooled at room temperature and distilled water was added to the mixture. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 9-6 8.8g(42%) was obtained via column separation.
Preparation of Compound 9-7
Compound 9-6 8.8g(17.53mmol) was dissolved in THF 200mL and methylmagnesium bromide 14.60mL(43.82mmol, 3.0M in diethyl ether) was added to the mixture. The mixture was heated at 60℃. 6 hours later, the mixture was cooled at room temperature and distilled water was added. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 9-7 6.6g(74%) was obtained via column separation.
Preparation of Compound 58
Compound 9-7 6.6g(13.14mmol), acetic acid 50mL, and phosphoric acid 50mL were mixed and stirred for 5 hours at 50℃. The mixture was cooled at room temperature and neutralized with NaOH solution. The mixture was extracted with ethyl acetate. After removing moisture with MgSO4, and performing distillation under reduced pressure, Compound 58 5.1g(80%) was obtained via column separation.
MS/FAB found 819, calculated 818.01
[Preparation Example 10] Preparation of Compound 122
Figure PCTKR2011006314-appb-I000112
Preparation of Compound 10-1
2-bromo-9,9-dimethyl-9H-fluorene 60g(0.219mol), 2-chloroaniline 56g(0.439mol), Pd(OAc)2 1.5g(0.006mol), P(t-Bu)3 14mL(0.021mol) and CsCO3 143g(0.439mol) were mixed and toluene 600mL was added to the mixture. The mixture was stirred for 12 hours at 120℃. Upon completion of the reaction, the resultant material was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 10-1 65g(92%) was obtained via column purification.
Preparation of Compound 10-2
After DMA 1000mL was added to the mixture of Compound 10-1 65g(0.20mol), Pd(OAc)2 2.3g(0.01mol), di-tert-butyl(methyl)phosphonium tetrafluoroborate 5.9g(0.02mol) and Na2CO3 64g(0.60mol), the mixture was stirred for 16 hours at 190℃. Upon completion of the reaction, the resultant material was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 10-2 31g(54%) was obtained via column purification.
Preparation of Compound 10-3
After toluene 130mL was added to the mixture of Compound 10-2 17g(0.061mol), CuI 2.3g(0.012mol), ethylenediamine 3.3mL(0.049mol) and K3PO3 16g(0.074mol), the mixture was stirred for 12 hours 120℃. Upon completion of the reaction, the resultant material was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 10-3 7.8g(72%) was obtained via column purification.
Preparation of Compound 122
The mixture of Compound 10-3 4g(0.009mol), 4-(diphenylamino)phenyl boronic acid 3.1g(0.010mol), Pd(PPh3)4 527mg(0.4mmol), K2CO3(2M) 14mL, EtOH 14mL and toluene 28mL was stirred for 8 hours at 120℃. Upon completion of the reaction, the resultant material was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 122 2.6g(47%) was obtained via column purification.
MS/FAB found 603. calculated 602.76
[Preparation Example 11] Preparation of Compound 132
Figure PCTKR2011006314-appb-I000113
Preparation of Compound 11-1
The mixture of Compound 4-2 10g(36.6mmol), iodo-4-bromobenzene 20g(73.2mmol), CuI 3.5g(18.3mmol), ethylenediamine 4.5mL(73.2mmol), K3PO4 19.4g(91.5mmol) and toluene 200mL was stirred at 120℃ overnight. Upon completion of the reaction, the resultant material was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 11-1 7.7g(49%) was obtained via column purification.
Preparation of Compound 132
The mixture of Compound 11-1 7g(16.3mmol), 4-(diphenylamino)phenyl boronic acid 5.6g(19.6mmol), Pd(PPh3)4 0.95g(0.82mmol), K2CO3 6g(40.8mmol), toluene 60mL, EtOH 20mL and H2O 20mL was stirred at 100℃ overnight. Upon completion of the reaction, the resultant material was washed with distilled water and extracted with ethyl acetate. After removing moisture of an organic layer with MgSO4 and removing a solvent by a rotary evaporator, Compound 132 5.4g(56%) was obtained via column purification.
MS/FAB found 593, calculated 592.75
Following compounds were prepared according to Preparation Examples 1 to 11.
Figure PCTKR2011006314-appb-I000114
Figure PCTKR2011006314-appb-I000115
Figure PCTKR2011006314-appb-I000116
[Example 1] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by using the electroluminescent material of the present invention. First, a transparent electrode ITO thin film (15 Ω/□) obtained from a glass for OLED (manufactured by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use. Then, the ITO substrate was equipped in a substrate holder of a vacuum deposition apparatus, and 2-TNATA (4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine) was placed in a cell of the vacuum 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, Compound 1 was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate Compound 1, 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. CBP [4,4'-N,N'-dicarbazole-biphenyl] as a host was placed in a cell, and (piq)2Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] as a dopant was placed in another cell, within a vacuum vapor deposition apparatus. 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 wt%.
Subsequently, BAlq (bis(2-methyl-8-quinolinato)(p-phenylphenolato)aluminum(III)) was vapor-deposited with a thickness of 10 nm as a hole blocking layer on the electroluminescent layer. Alq3 (tris(8-hydroxyquinoline)-aluminum(III)) was vapor-deposited with a thickness of 20 nm as an electron transport layer on the electroluminescent layer. Then, after vapor-depositing Liq (lithium quinolate) with a thickness of 1 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 under 10-6torr.
As a result, it was confirmed that current of 13.8 mA/cm2 flows at voltage of 6.9 V and a red light of 1020 cd/m2 was emitted.
[Example 2] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 1 except that Compound 19 was used as a hole transport material.
As a result, it was confirmed that current of 14.3 mA/cm2 flows at voltage of 6.7 V and a red light of 1060 cd/m2 was emitted.
[Example 3] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 1 except that Compound 31 was used as a hole transport material.
As a result, it was confirmed that current of 13.9 mA/cm2 flows at voltage of 6.7 V and a red light of 1044 cd/m2 was emitted.
[Example 4] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 1 except that Compound 69 was used as a hole transport material.
As a result, it was confirmed that current of 14.2 mA/cm2 flows at voltage of 6.8 V and a red light of 1015 cd/m2 was emitted.
[Example 5] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 1 except that Compound 1 was used as a hole transport material and an organic iridium complex Ir(ppy)3[tris(2-phenylpyridine)iridium] as an electroluminescent dopant was doped on the electroluminescent layer at 15 wt%.
As a result, it was confirmed that current of 3.8 mA/cm2 flows at voltage of 6.6 V and a green light of 1065 cd/m2 was emitted.
[Example 6] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 5 except that Compound 20 was used as a hole transport material.
As a result, it was confirmed that current of 3.9 mA/cm2 flows at voltage of 6.6 V and a green light of 1070 cd/m2 was emitted.
[Example 7] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 5 except that Compound 31 was used as a hole transport material.
As a result, it was confirmed that current of 3.7 mA/cm2 flows at voltage of 6.7 V and a green light of 1085 cd/m2 was emitted.
[Example 8] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 5 except that Compound 42 was used as a hole transport material.
As a result, it was confirmed that current of 3.5 mA/cm2 flows at voltage of 6.6 V and a green light of 1055 cd/m2 was emitted.
[Example 9] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 5 except that Compound 43 was used as a hole transport material.
As a result, it was confirmed that current of 3.6 mA/cm2 flows at voltage of 6.6 V and a green light of 1080 cd/m2 was emitted.
[Example 10] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 5 except that Compound 14 instead of 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was used as a hole transport material.
As a result, it was confirmed that current of 3.7 mA/cm2 flows at voltage of 6.6 V and a green light of 1050 cd/m2 was emitted.
[Example 11] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
N1,N1'-([1,1'-biphenyl]-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was placed as a hole injection material and then ventilated up to 10-6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate N1,N1'-([1,1'-biphenyl]-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzene-1,4-diamine), thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, Compound 122 was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate Compound 122, 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. After respectively adding H-31 as a host in a cell of a vacuum vapor deposition apparatus and D-58 as a dopant in another cell, the two cells were evaporated at different rates and doped at 15 wt% such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer. Subsequently, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was added in a cell of the hole transport layer and Lithium quinolate (Liq) was added in another cell. The two cells were evaporated at the same rate and doped at 50wt% to deposit a hole transport layer with a thickness of 30nm. Then, after vapor-depositing lithium quinolate (Liq) with a thickness of 1 nm as an electron injection layer, an Al cathode having a thickness of 150 nm was formed using another vacuum vapor deposition apparatus to manufacture an OLED.
Each compound used in the OLED was purified by vacuum sublimation at 10-6torr.
As a result, it was confirmed that current of 11.5 mA/cm2 flows at voltage of 5.4 V and a green light of 6200 cd/m2 was emitted.
[Example 12] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 11 except that Compound 132 as a hole transport material, H-1 as a host and D-71 as a dopant were used.
As a result, it was confirmed that current of 6.32 mA/cm2 flows at voltage of 4.0 V and a green light of 3300 cd/m2 was emitted.
[Example 13] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 11 except that Compound 138 as a hole transport material, H-34 as a host and D-31 as a dopant were used.
As a result, it was confirmed that current of 2.8 mA/cm2 flows at voltage of 3.6 V and a green light of 1500 cd/m2 was emitted.
[Example 14] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 11 except that Compound 149 as a hole transport material, H-39 as a host and D-31 as a dopant were used.
As a result, it was confirmed that current of 1.59 mA/cm2 flows at voltage of 3.1 V and a green light of 500 cd/m2 was emitted.
[Example 15] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 11 except that Compound 109 as a hole transport material was used and H-45 as a host and D-6 as a dopant were doped at 4 wt%.
As a result, it was confirmed that current of 7.5 mA/cm2 flows at voltage of 4.0 V and a red light of 1065 cd/m2 was emitted.
[Example 16] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 15 except that Compound 141 as a hole transport material, H-49 as a host and D-6 as a dopant were used.
As a result, it was confirmed that current of 17.0 mA/cm2 flows at voltage of 5.2 V and a red light of 2210 cd/m2 was emitted.
[Example 17] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 15 except that Compound 142 as a hole transport material, H-52 as a host and D-6 as a dopant were used.
As a result, it was confirmed that current of 32.1 mA/cm2 flows at voltage of 5.6 V and a red light of 3700 cd/m2 was emitted.
[Example 18] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured by the same method as Example 15 except that Compound 149 as a hole transport material, H-53 as a host and D-9 as a dopant were used.
As a result, it was confirmed that current of 12.9 mA/cm2 flows at voltage of 6.0 V and a red light of 1710 cd/m2 was emitted.
[Comparative Example 1] Manufacture of OLED device using an electroluminescent material of the prior art
An OLED device was manufactured by the same method as Example 1 except that N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine [NPB] instead of the compound of the present invention as a hole transport material at one cell of the vacuum vapor deposition apparatus was used.
As a result, it was confirmed that current of 20.0 mA/cm2 flows at voltage of 8.2 V and a red light of 1000 cd/m2 was emitted.
[Comparative Example 2] Manufacture of OLED device using an electroluminescent material of the prior art
An OLED device was manufactured by the same method as Example 5 except that N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine [NPB] instead of the compound of the present invention as a hole transport material at one cell of the vacuum vapor deposition apparatus was used.
As a result, it was confirmed that current of 5.0 mA/cm2 flows at voltage of 6.0 V and a green light of 1183 cd/m2 was emitted.
[Comparative Example 3] Manufacture of OLED device using an electroluminescent material of the prior art.
An OLED device was manufactured by the same method as Example 11 except that NPB as a hole transport material, H-1 as a host and D-30 as a dopant were used.
As a result, it was confirmed that current of 4.62 mA/cm2 flows at voltage of 3.0 V and a green light of 1000 cd/m2 was emitted.
[Comparative Example 4] Manufacture of OLED device using an electroluminescent material of the prior art.
An OLED device was manufactured by the same method as Example 15 except that NPB as a hole transport material, H-46 as a host and D-9 as a dopant were used.
As a result, it was confirmed that current of 13.2 mA/cm2 flows at voltage of 4.6 V and a red light of 1000 cd/m2 was emitted.
It was confirmed that the organic electroluminescent compounds developed in the present invention showed superior electroluminescent properties compared to the conventional material. The organic electroluminescent compounds of the present invention are very effective at blocking to prevent triplet excitons from migrating out of the luminescent layer by increasing triplet. Accordingly, there is a benefit that a very excellent OLED device is manufactured due to superior electroluminescent efficiency in phosphorescence.
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.
According to the present invention, an organic electroluminescent compound can be used as a hole transport material or a hole injection material, so that the resultant organic electroluminescent 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 lifetimes and that have improved power consumption thanks to increased power efficiency.

Claims (10)

  1. An organic electroluminescent compound represented by Chemical Formula 1 below.
    [Chemical Formula 1]
    Figure PCTKR2011006314-appb-I000117
    wherein, ring A and ring C independently represent
    Figure PCTKR2011006314-appb-I000118
    ;
    ring B represents
    Figure PCTKR2011006314-appb-I000119
    ;
    X1 and X2 independently represent CR3 or N;
    Y1 and Y2 independently represent a chemical bond, -O-, -S-, -C(R11R12)-, -Si(R13R14)- or -N(R15)-, except for a case where both Y1 and Y2 are a chemical bond;
    R1 through R3 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-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 (C1-C30)alkylsilyl, cyano, nitro or hydroxyl, and when there are two or more of either R1 or R2, they are linked to each other to form a cyclic structure;
    L represents substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (C2-C30)heteroarylene, and when there are two or more of L, they are linked to each other to form a cyclic structure;
    Ar1 and Ar2 independently represent substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl or
    Figure PCTKR2011006314-appb-I000120
    ;
    Y3 and Y4 independently represent a chemical bond, -O-, -S-, -C(R16R17)-, -Si(R18R19)- or -N(R20)-, except for a case where both Y3 and Y4 are a chemical bond;
    R11 through R20 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C2-C30)heteroaryl, or each of them may be 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;
    m and n independently represent an integer of 0 to 4, and when m and n are an integer of 2 or greater, each of R1 and L may be identical to or different from each other;
    p represents an integer of 0 to 2, and when p is 2, each of R2 may be identical to or different from each other; and
    the heterocycloalkyl, heteroaryl and heteroarylene include one or more heteroatom(s) selected from the group consisting of B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound of claim 1, wherein each substituent of the R1, R2, R3, L, Ar1, Ar2 and R11 through R20 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, (C6-C30)aryl, (C6-C30)aryl-substituted or unsubstituted (C2-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, (C2-C30)alkenyl, (C2-C30)alkynyl,
    Figure PCTKR2011006314-appb-I000121
    , cyano, carbazolyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, -OR21, -SR22, -NR23R24, -PR25R26, -SiR27R28R29, nitro and hydroxyl, and Y11 and Y12 independently represent a chemical bond, -C(R31R32)-, -O-, -S- or -N(R33)-, except for a case where both Y11 and Y12 are a chemical bond; and R21 through R29 and R31 through R33 independently represent (C1-C30)alkyl, (C6-C30)aryl, (C2-C30)heteroaryl, or (C3-C30)cycloalkyl.
  3. The organic electroluminescent compound of claim 1, wherein
    Figure PCTKR2011006314-appb-I000122
    of Chemical Formula 1 is selected from following structures.
    Figure PCTKR2011006314-appb-I000123
    Figure PCTKR2011006314-appb-I000124
    Figure PCTKR2011006314-appb-I000125
    Figure PCTKR2011006314-appb-I000126
    Figure PCTKR2011006314-appb-I000127
    Figure PCTKR2011006314-appb-I000128
    wherein, R2, R11 through R15 and p are the same as defined in Claim 1.
  4. The organic electroluminescent compound of claim 1, which is selected from following compounds.
    Figure PCTKR2011006314-appb-I000129
    Figure PCTKR2011006314-appb-I000130
    Figure PCTKR2011006314-appb-I000131
    Figure PCTKR2011006314-appb-I000132
    Figure PCTKR2011006314-appb-I000133
    Figure PCTKR2011006314-appb-I000134
    Figure PCTKR2011006314-appb-I000135
    Figure PCTKR2011006314-appb-I000136
    Figure PCTKR2011006314-appb-I000137
    Figure PCTKR2011006314-appb-I000138
    Figure PCTKR2011006314-appb-I000139
    Figure PCTKR2011006314-appb-I000140
    Figure PCTKR2011006314-appb-I000141
    Figure PCTKR2011006314-appb-I000142
    Figure PCTKR2011006314-appb-I000143
    Figure PCTKR2011006314-appb-I000144
    Figure PCTKR2011006314-appb-I000145
    Figure PCTKR2011006314-appb-I000146
    Figure PCTKR2011006314-appb-I000147
    Figure PCTKR2011006314-appb-I000148
    Figure PCTKR2011006314-appb-I000149
    Figure PCTKR2011006314-appb-I000150
    Figure PCTKR2011006314-appb-I000151
    Figure PCTKR2011006314-appb-I000152
    Figure PCTKR2011006314-appb-I000153
    Figure PCTKR2011006314-appb-I000154
    Figure PCTKR2011006314-appb-I000155
    Figure PCTKR2011006314-appb-I000156
    Figure PCTKR2011006314-appb-I000157
    Figure PCTKR2011006314-appb-I000158
    Figure PCTKR2011006314-appb-I000159
    Figure PCTKR2011006314-appb-I000160
    Figure PCTKR2011006314-appb-I000161
    Figure PCTKR2011006314-appb-I000162
    Figure PCTKR2011006314-appb-I000163
    Figure PCTKR2011006314-appb-I000164
  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 represented by Chemical Formula 1.
  8. The organic electroluminescent device of claim 7, wherein the organic layer further comprises one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s).
  9. The organic electroluminescent device 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 and blue light to emit white light.
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