WO2011105700A1 - 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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WO2011105700A1
WO2011105700A1 PCT/KR2011/000404 KR2011000404W WO2011105700A1 WO 2011105700 A1 WO2011105700 A1 WO 2011105700A1 KR 2011000404 W KR2011000404 W KR 2011000404W WO 2011105700 A1 WO2011105700 A1 WO 2011105700A1
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organic electroluminescent
alkyl
aryl
arylsilyl
tri
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Sung Jin Eum
Hyuck Joo Kwon
Bong Ok Kim
Sung Min Kim
Seung Soo Yoon
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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    • H05B33/14—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Definitions

  • the electroluminescent material In an organic EL device, the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. Some requirements of the electroluminescent material include high fluorescence quantum yield in solid state, high electron and hole mobility, resistance to decomposition during vacuum deposition, ability to form uniform film and stability.
  • R 13 through R 19 independently represent hydrogen, (C1-C60)alkyl, (C3-C60)cycloalkyl, (C6-C60)aryl, (C2-60)heteroaryl containing one or more heteroatom(s) selected from N, O, S, Si and Se, (C1-60)alkoxy, (C1-C60)alkylthio, (C6-60)aryloxy, (C6-C60)arylthio, mono- or di(C1-60)alkylamino, mono- or di(C6-60)arylamino, (C6-30)aryl(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl, or R 13 and R 14 , R 16 and R 17 , and R 18 and R 19 are linked via (C3-C60)alkylene
  • a, b and c independently represent an integer from 1 to 4;
  • d represents an integer from 1 to 3;
  • the substituents comprising "(C3-C60)cycloalkyl” moiety may contain 3 to 60 carbon atoms, 3 to 20 carbon atoms, or 3 to 7 carbon atoms.
  • the substituents comprising "(C2-C60)alkenyl or alkynyl” moiety may contain 2 to 60 carbon atoms, 2 to 20 carbon atoms, or 2 to 10 carbon atoms.
  • the Y is a divalent group selected from following structures.
  • the electroluminescent layer means the layer where electroluminescence occurs, and it may be a single layer or a multi-layer that two or more layers are laminated.
  • a mixture of host-dopant is used according to the constitution of the present invention, noticeable improvement in luminous efficiency by the electroluminescent host may be confirmed.
  • R 91 through R 93 independently represent hydrogen, (C1-C60)alkyl or (C6-C60)aryl;
  • 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.
  • N , N '-bis( ⁇ -naphthyl)- N , N '-diphenyl-4,4'-diamine (NPB) was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • the organic electroluminescent compound according to the present invention exhibits good luminous efficiency in a blue color and excellent life property, it may be used to manufacture OLED devices having very superior operation life.

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Abstract

Provided are novel organic electroluminescent compounds, and organic electroluminescent devices comprising the same. Since the organic electroluminescent compounds exhibit high luminous efficiency in blue color, and excellent life property of the material, they may be used to manufacture OLEDs having very good operation life.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device using the same, more particularly, to novel organic electroluminescent compounds used as an electroluminescent material and an organic electroluminescent device using the same as dopant.
Among display devices, electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices. In 1987, Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [Appl. Phys. Lett. 51, 913, 1987].
In an organic EL device, the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. Some requirements of the electroluminescent material include high fluorescence quantum yield in solid state, high electron and hole mobility, resistance to decomposition during vacuum deposition, ability to form uniform film and stability.
Organic electroluminescent materials can be generally classified into high-molecular materials and low-molecular materials. The low-molecular materials include metal complexes and thoroughly organic electroluminescent materials which do not contain metal, in view of molecular structure. Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives and oxadiazole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained, so that realization of full-colored display devices is anticipated thereby.
In the meanwhile, for conventional blue materials, a number of materials have been developed and commercialized since the development of diphenylvinyl-biphenyl (DPVBi) (Compound a) by Idemitsu-Kosan. In addition to the blue material system from Idemitsu-Kosan, dinaphthylanthracene (DNA) (Compound b) of Kodac, tetra(t-butyl)perylene (Compound c) system or the like have been known. However, extensive research and development should be performed with respect to these materials.
The distryl compound system of Idemitsu-Kosan, which is known to have highest efficiency up to now, has 6 lm/W power efficiency and beneficial device lifetime of more than 30,000 hr. However, when it is applied to a full-colored display, the lifetime is merely several thousand hours, owing to decrease of color purity over operation time. In case of blue electroluminescence, it becomes advantageous from the aspect of the luminous efficiency, if the electroluminescent wavelength is shifted a little toward longer wavelength. However, it is not easy to apply the material to a display of high quality because of unsatisfactory color purity in blue. Furthermore, the research and development of such materials are urgent because of the problems in color purity, efficiency and thermal stability.
Figure PCTKR2011000404-appb-I000001
With intensive efforts to overcome the problems of conventional techniques as described above, the present inventors have invented novel electroluminescent compounds which realize organic electroluminescent devices having excellent luminous efficiency and noticeably improved life property.
The object of the present invention is to provide organic electroluminescent compounds having the backbone to provide better luminous efficiency and device life with appropriate color coordinate as compared to conventional dopant material, while overcoming the problems described above, and an organic electroluminescent device having high luminous efficiency and improved life property.
Provided are novel organic electroluminescent compounds, and organic electroluminescent devices comprising the same. Specifically, the organic electroluminescent compounds according to the invention are represented by Chemical Formula 1 or 2. Since the organic electroluminescent compounds exhibit high luminous efficiency and excellent life property of the material, they may be used to manufacture OLEDs having very good operation life.
[Chemical Formula 1]
Figure PCTKR2011000404-appb-I000002
[Chemical Formula 2]
Figure PCTKR2011000404-appb-I000003
wherein
R1 through R5 independently represent hydrogen, (C1-C60)alkyl, (C3-C60)cycloalkyl, (C6-C60)aryl, (C2-60)heteroaryl containing one or more heteroatom(s) selected from N, O, S, P, Si and Se, (C1-60)alkoxy, (C1-C60)alkylthio, (C6-60)aryloxy, (C6-C60)arylthio, (C6-30)aryl(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl;
X represents a chemical bond, -(CR6R7)m-, -N(R8)-, -Si(R9)(R10)-, -O-, -S-, -Se- or -(CR11)C=C(R12)-;
R6 through R12 independently represent hydrogen, (C1-C60)alkyl, (C3-C60)cycloalkyl, (C6-C60)aryl, (C2-60)heteroaryl containing one or more heteroatom(s) selected from N, O, S, Si and Se, (C1-60)alkoxy, (C1-C60)alkylthio, (C6-60)aryloxy, (C6-C60)arylthio, mono- or di(C1-60)alkylamino, mono- or di(C6-60)arylamino, (C6-30)aryl(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl, or R6 and R7, R9 and R10, and R11 and R12 are linked via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an aliphatic ring or a mono- or polycyclic aromatic ring;
Y represents (C6-C60)arylene, adamantylene, (C3-C60)heteroarylene containing one or more heteroatom(s) selected from N, O, S, P, Si and Se,
Figure PCTKR2011000404-appb-I000004
or
Figure PCTKR2011000404-appb-I000005
;
Y1 represents (C2-60)heteroarylene containing one or more heteroatom(s) selected from N, O, S, P, Si and Se;
Z1 and Z2 independently represent a chemical bond, -(CR13R14)n-, -N(R15)-, -Si(R16)(R17)-, -O-, -S-, -Se- or -(R18)C=C(R19)-, provided that Z1 and Z2 are not chemical bonds at the same time;
R13 through R19 independently represent hydrogen, (C1-C60)alkyl, (C3-C60)cycloalkyl, (C6-C60)aryl, (C2-60)heteroaryl containing one or more heteroatom(s) selected from N, O, S, Si and Se, (C1-60)alkoxy, (C1-C60)alkylthio, (C6-60)aryloxy, (C6-C60)arylthio, mono- or di(C1-60)alkylamino, mono- or di(C6-60)arylamino, (C6-30)aryl(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl, or R13 and R14, R16 and R17, and R18 and R19 are linked via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an aliphatic ring or a mono- or polycyclic aromatic ring;
a, b and c independently represent an integer from 1 to 4;
d represents an integer from 1 to 3; and
m and n independently represent an integer from 1 to 4.
In the present invention, "alkyl", "alkoxy" and other substituents including "alkyl" moiety include both linear and branched species. The term "aryl" described herein means an organic radical derived from aromatic hydrocarbon via elimination of one hydrogen atom. Each ring includes a monocyclic or fused ring system including from 4 to 7, preferably from 5 to 6 cyclic atoms. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl and fluoranthenyl, but they are not restricted thereto.
The term "heteroaryl" described herein means an aryl group including from 1 to 4 heteroatom(s) selected from N, O, S, P, Si and Se for the aromatic cyclic backbone atoms, and carbon atom(s) for remaining aromatic cyclic backbone atoms. The heteroaryl may be a 5- or 6-membered monocyclic heteroaryl or a polycyclic heteroaryl which is fused with one or more benzene ring(s), and may be partially saturated.
The heteroaryl groups may include divalent aryl groups of which the heteroatoms are oxidized or quarternized to form N-oxides, quaternary salts, or the like. Specific examples of the heteroaryl include monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl; polycyclic heteroaryl groups such as benzofuryl, benzothienyl, isobenzofuryl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl, phenanthridinyl and benzodioxolyl; and corresponding N-oxides (for example, pyridyl N-oxide, quinolyl N-oxide) and quaternary salts thereof; but they are not restricted thereto.
The substituents comprising "(C1-C60)alkyl" moiety described herein may contain 1 to 60 carbon atoms, 1 to 20 carbon atoms, or 1 to 10 carbon atoms. The substituents comprising "(C6-C60)aryl" moiety may contain 6 to 60 carbon atoms, 6 to 20 carbon atoms, or 6 to 12 carbon atoms. The substituents comprising "(C3-C60)heteroaryl" moiety may contain 3 to 60 carbon atoms, 4 to 20 carbon atoms, or 4 to 12 carbon atoms. The substituents comprising "(C3-C60)cycloalkyl" moiety may contain 3 to 60 carbon atoms, 3 to 20 carbon atoms, or 3 to 7 carbon atoms. The substituents comprising "(C2-C60)alkenyl or alkynyl" moiety may contain 2 to 60 carbon atoms, 2 to 20 carbon atoms, or 2 to 10 carbon atoms.
Y represents 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 2,6-naphthylene, 2,7-naphthylene, 1,2-anthracenylene, 1,3-anthracenylene, 1,4-anthracenylene, 1,5-anthracenylene, 1,6-anthracenylene, 1,7-anthracenylene, 1,8-anthracenylene, 1,9-anthracenylene, 1,10-anthracenylene, 2,3-anthracenylene, 2,6-anthracenylene, 2,7-anthracenylene, 2,9-anthracenylene, 2,10-anthracenylene, 9,10-anthracenylene, 4,2'-biphenylene, 4,3'-biphenylene, 4,4'-biphenylene, 1,2-triphenylenylene, 1,3-triphenylenylene, 1,4-triphenylenylene, 1,6-triphenylenylene, 1,7-triphenylenylene, 1,8-triphenylenylene, 1,10-triphenylenylene, 1,11-triphenylenylene, 1,12-triphenylenylene, 2,3-triphenylenylene, 2,6-triphenylenylene, 2,7-triphenylenylene, 2,11-triphenylenylene, 1,2-fluoranthenylene, 1,3-fluoranthenylene, 1,4-fluoranthenylene, 1,5-fluoranthenylene, 1,6-fluoranthenylene, 1,7-fluoranthenylene, 1,8-fluoranthenylene, 1,9-fluoranthenylene, 1,10-fluoranthenylene, 2,3-fluoranthenylene, 2,4-fluoranthenylene, 2,5-fluoranthenylene, 2,7-fluoranthenylene, 2,8-fluoranthenylene, 2,9-fluoranthenylene, 2,10-fluoranthenylene, 3,4-fluoranthenylene, 3,7-fluoranthenylene, 3,8-fluoranthenylene, 3,9-fluoranthenylene, 3,10-fluoranthenylene, 7,8-fluoranthenylene, 7,9-fluoranthenylene, 7,10-fluoranthenylene, 8,9-fluoranthenylene, 1,2-chrysenylene, 1,3-chrysenylene, 1,4-chrysenylene, 1,5-chrysenylene, 1,6-chrysenylene, 1,7-chrysenylene, 1,8-chrysenylene, 1,9-chrysenylene, 1,10-chrysenylene, 1,11-chrysenylene, 1,12-chrysenylene, 2,3-chrysenylene, 2,4-chrysenylene, 2,5-chrysenylene, 2,6-chrysenylene, 2,8-chrysenylene, 2,9-chrysenylene, 2,10-chrysenylene, 2,11-chrysenylene, 2,12-chrysenylene, 3,4-chrysenylene, 3,5-chrysenylene, 3,6-chrysenylene, 3,9-chrysenylene, 3,10-chrysenylene, 3,11-chrysenylene, 3,12-chrysenylene, 4,5-chrysenylene, 4,6-chrysenylene, 4,11-chrysenylene, 4,12-chrysenylene, 5,6-chrysenylene, 5,11-chrysenylene, 5,12-chrysenylene, 6,12-chrysenylene, 4,4''-p-terphenylene, 1,1'-binaphthylene, 9,9'-bianthracenylene, 1,2-phenanthrylene, 1,3-phenanthrylene, 1,4-phenanthrylene, 1,5-phenanthrylene, 1,6-phenanthrylene, 1,7-phenanthrylene, 1,8-phenanthrylene, 1,9-phenanthrylene, 1,10-phenanthrylene, 2,3-phenanthrylene, 2,4-phenanthrylene, 2,5-phenanthrylene, 2,6-phenanthrylene, 2,7-phenanthrylene, 2,9-phenanthrylene, 2,10-phenanthrylene, 3,4-phenanthrylene, 3,5-phenanthrylene, 3,6-phenanthrylene, 3,9-phenanthrylene, 3,10-phenanthrylene, 4,5-phenanthrylene, 4,9-phenanthrylene, 4,10-phenanthrylene, 9,10-phenanthrylene, 1,2-pyrenylene, 1,3-pyrenylene, 1,4-pyrenylene, 1,5-pyrenylene, 1,6-pyrenylene, 1,7-pyrenylene, 1,8-pyrenylene, 1,9-pyrenylene, 1,10-pyrenylene, 2,4-pyrenylene, 2,5-pyrenylene, 2,7-pyrenylene, 4,5-pyrenylene, 4,9-pyrenylene, 4,10-pyrenylene, 1,2-perylenylene, 1,3-perylenylene, 1,4-perylenylene, 1,5-perylenylene, 1,6-perylenylene, 1,7-perylenylene, 1,8-perylenylene, 1,9-perylenylene, 1,10-perylenylene, 1,11-perylenylene, 1,12-perylenylene, 2,3-perylenylene, 2,4-perylenylene, 2,5-perylenylene, 2,8-perylenylene, 2,9-perylenylene, 2,10-perylenylene, 2,11-perylenylene, 3,4-perylenylene, 3,9-perylenylene, 3,10-perylenylene, 2,2-adamantylene, 2,4-pyridinylene, 3,4-pyridinylene, 3,5-pyridinylene, 2,6-pyridinylene, 2,5-pyridinylene, 2,3-pyridinylene, 2,3-pyrazinylene, 2,5-pyrazinylene, 2,6-pyrazinylene, 2,4-triazinylene, 2,3-furylene, 2,4-furylene, 2,5-furylene, 3,4-furylene, 2,3-thiophenylene, 2,4-thiophenylene, 2,5-thiophenylene, 3,4-thiophenylene, 2,3-selenophenylene, 2,4-selenophenylene, 2,5-selenophenylene, 3,4-selenophenylene, 2,5-(1,3,4-oxadiazol)ylene, 2,5-(1,3,4-thiadiazol)ylene, 2,5-(1,3,4-selenadiazol)ylene, 2,3-quinolinylene, 2,4-quinolinylene, 2,5-quinolinylene, 2,6-quinolinylene, 2,7-quinolinylene, 2,8-quinolinylene, 3,4-quinolinylene, 3,5-quinolinylene, 3,6-quinolinylene, 3,7-quinolinylene, 3,8-quinolinylene, 4,5-quinolinylene, 4,6-quinolinylene, 4,7-quinolinylene, 4,8-quinolinylene, 5,6-quinolinylene, 5,7-quinolinylene, 5,8-quinolinylene, 6,7-quinolinylene, 6,8-quinolinylene, 7,8-quinolinylene, 2,3-quinoxalinylene, 2,5-quinoxalinylene, 2,6-quinoxalinylene, 2,7-quinoxalinylene, 2,8-quinoxalinylene, 5,6-quinoxalinylene, 5,7-quinoxalinylene, 5,8-quinoxalinylene, 6,7-quinoxalinylene, 2,3-(thieno[3,4-b]pyrazin)ylene, 2,5-(thieno[3,4-b]pyrazin)ylene, 2,7-(thieno[3,4-b]pyrazin)ylene, 5,7-(thieno[3,4-b]pyrazin)ylene, 2,3-(selenopheno[3,4-b]pyrazin)ylene, 2,5-(selenopheno[3,4-b]pyrazin)ylene, 2,7-(selenopheno[3,4-b]pyrazin)ylene, 5,7-(selenopheno[3,4-b]pyrazin)ylene, 2,7-(benzo[d]thiazol)ylene, 2,6-(benzo[d]thiazol)ylene, 2,5-(benzo[d]thiazol)ylene, 2,4-(benzo[d]thiazol)ylene, 4,7-(benzo[d]thiazol)ylene, 5,7-(benzo[d]thiazol)ylene, 6,7-(benzo[d]thiazol)ylene, 5,6-(benzo[d]thiazol)ylene, 4,6-(benzo[d]thiazol)ylene, 4,5-(benzo[d]thiazol)ylene, 2,3-(1,10-phenanthrolin)ylene, 2,4-(1,10-phenanthrolin)ylene, 2,5-(1,10-phenanthrolin)ylene, 2,6-(1,10-phenanthrolin)ylene, 2,7-(1,10-phenanthrolin)ylene, 2,8-(1,10-phenanthrolin)ylene, 2,9-(1,10-phenanthrolin)ylene, 3,4-(1,10-phenanthrolin)ylene, 3,5-(1,10-phenanthrolin)ylene, 3,6-(1,10-phenanthrolin)ylene, 3,7-(1,10-phenanthrolin)ylene, 3,8-(1,10-phenanthrolin)ylene, 4,5-(1,10-phenanthrolin)ylene, 4,6-(1,10-phenanthrolin)ylene, 4,7-(1,10-phenanthrolin)ylene, 5,6-(1,10-phenanthrolin)ylene, 9,9-dimethyl-1,2-fluorenylene, 9,9-dimethyl-1,3-fluorenylene, 9,9-dimethyl-1,4-fluorenylene, 9,9-dimethyl-1,5-fluorenylene, 9,9-dimethyl-1,6-fluorenylene, 9,9-dimethyl-1,7-fluorenylene, 9,9-dimethyl-1,8-fluorenylene, 9,9-dimethyl-2,3-fluorenylene, 9,9-dimethyl-2,4-fluorenylene, 9,9-dimethyl-2,5-fluorenylene, 9,9-dimethyl-2,6-fluorenylene, 9,9-dimethyl-2,7-fluorenylene, 9,9-dimethyl-3,4-fluorenylene, 9,9-dimethyl-3,5-fluorenylene, 9,9-dimethyl-3,6-fluorenylene, 9,9-dimethyl-4,5-fluorenylene, 9,9-diethyl-1,2-fluorenylene, 9,9-diethyl-1,3-fluorenylene, 9,9-diethyl-1,4-fluorenylene, 9,9-diethyl-1,5-fluorenylene, 9,9-diethyl-1,6-fluorenylene, 9,9-diethyl-1,7-fluorenylene, 9,9-diethyl-1,8-fluorenylene, 9,9-diethyl-2,3-fluorenylene, 9,9-diethyl-2,4-fluorenylene, 9,9-diethyl-2,5-fluorenylene, 9,9-diethyl-2,6-fluorenylene, 9,9-diethyl-2,7-fluorenylene, 9,9-diethyl-3,4-fluorenylene, 9,9-diethyl-3,5-fluorenylene, 9,9-diethyl-3,6-fluorenylene, 9,9-diethyl-4,5-fluorenylene, 9,9-diphenyl-1,2-fluorenylene, 9,9-diphenyl-1,3-fluorenylene, 9,9-diphenyl-1,4-fluorenylene, 9,9-diphenyl-1,5-fluorenylene, 9,9-diphenyl-1,6-fluorenylene, 9,9-diphenyl-1,7-fluorenylene, 9,9-diphenyl-1,8-fluorenylene, 9,9-diphenyl-2,3-fluorenylene, 9,9-diphenyl-2,4-fluorenylene, 9,9-diphenyl-2,5-fluorenylene, 9,9-diphenyl-2,6-fluorenylene, 9,9-diphenyl-2,7-fluorenylene, 9,9-diphenyl-3,4-fluorenylene, 9,9-diphenyl-3,5-fluorenylene, 9,9-diphenyl-3,6-fluorenylene, 9,9-diphenyl-4,5-fluorenylene, 9,9-dicyclohexyl-1,2-fluorenylene, 9,9-dicyclohexyl-1,3-fluorenylene, 9,9-dicyclohexyl-1,4-fluorenylene, 9,9-dicyclohexyl-1,5-fluorenylene, 9,9-dicyclohexyl-1,6-fluorenylene, 9,9-dicyclohexyl-1,7-fluorenylene, 9,9-dicyclohexyl-1,8-fluorenylene, 9,9-dicyclohexyl-2,3-fluorenylene, 9,9-dicyclohexyl-2,4-fluorenylene, 9,9-dicyclohexyl-2,5-fluorenylene, 9,9-dicyclohexyl-2,6-fluorenylene, 9,9-dicyclohexyl-2,7-fluorenylene, 9,9-dicyclohexyl-3,4-fluorenylene, 9,9-dicyclohexyl-3,5-fluorenylene, 9,9-dicyclohexyl-3,6-fluorenylene, 9,9-dicyclohexyl-4,5-fluorenylene or a bivalent group selected from the following structures but is not limited thereto:
Figure PCTKR2011000404-appb-I000006
Figure PCTKR2011000404-appb-I000007
Figure PCTKR2011000404-appb-I000008
Figure PCTKR2011000404-appb-I000009
Figure PCTKR2011000404-appb-I000010
Figure PCTKR2011000404-appb-I000011
Figure PCTKR2011000404-appb-I000012
More specifically, the Y is a divalent group selected from following structures.
Figure PCTKR2011000404-appb-I000013
Figure PCTKR2011000404-appb-I000014
Figure PCTKR2011000404-appb-I000015
Figure PCTKR2011000404-appb-I000016
Figure PCTKR2011000404-appb-I000017
Figure PCTKR2011000404-appb-I000018
Figure PCTKR2011000404-appb-I000019
Figure PCTKR2011000404-appb-I000020
Figure PCTKR2011000404-appb-I000021
Figure PCTKR2011000404-appb-I000022
Figure PCTKR2011000404-appb-I000023
Figure PCTKR2011000404-appb-I000024
The
Figure PCTKR2011000404-appb-I000025
or
Figure PCTKR2011000404-appb-I000026
is selected from following structures but are not limited thereto:
Figure PCTKR2011000404-appb-I000027
Figure PCTKR2011000404-appb-I000028
Figure PCTKR2011000404-appb-I000029
More specifically, the
Figure PCTKR2011000404-appb-I000030
or
Figure PCTKR2011000404-appb-I000031
is selected from following structures.
Figure PCTKR2011000404-appb-I000032
Figure PCTKR2011000404-appb-I000033
Figure PCTKR2011000404-appb-I000034
The organic electroluminescent compound according to the present invention may be prepared as shown in following Schemes 1 to 4.
[Scheme 1]
Figure PCTKR2011000404-appb-I000035
[Scheme 2]
Figure PCTKR2011000404-appb-I000036
[Scheme 3]
Figure PCTKR2011000404-appb-I000037
[Scheme 4]
Figure PCTKR2011000404-appb-I000038
Wherein
R1 through R5, X, Y, a, b, c and d are the same as defined in Chemical Formulas 1 and 2.
Provided is an organic electroluminescent device, which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic electroluminescent compound(s) represented by Chemical Formula 1 or 2.
The organic layer comprises an electroluminescent layer, which includes one or more hosts with one or more organic electroluminescent compounds of Chemical Formula 1 or 2 as a dopant.
The host used in the organic electroluminescent device of the present invention is not particularly limited, but may be selected from the compounds represented by Chemical Formula 3 or 4.
[Chemical Formula 3]
(Ar1)e-L1-(Ar2)f
[Chemical Formula 4]
(Ar3)g-L2-(Ar4)h
wherein
L1 represents (C6-C60)arylene or (C4-C60)heteroarylene;
L2 represents anthracenylene;
Ar1 through Ar4 are independently selected from hydrogen, deuterium, (C1-C60)alkyl, (C1-C60)alkoxy, halogen, (C4-C60)heteroaryl, (C5-C60)cycloalkyl and (C6-C60)aryl, and the cycloalkyl, aryl or heteroaryl of Ar1 through Ar4 may be further substituted by one or more substituent(s) selected from the group consisting of (C6-C60)aryl or (C4-C60)heteroaryl with or without one or more substituent(s) selected from (C1-C60)alkyl substituted or unsubstituted by halogen, (C1-C60)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl; (C1-C60)alkyl substituted or unsubstituted by halogen, (C1-C60)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl; and
e, f, g and h independently represent an integer from 0 to 4.
The host of the Chemical Formulas 3 and 4 may be exemplified as Compounds of Chemical Formulas 5 to 7.
[Chemical Formula 5]
Figure PCTKR2011000404-appb-I000039
[Chemical Formula 6]
Figure PCTKR2011000404-appb-I000040
[Chemical Formula 7]
Figure PCTKR2011000404-appb-I000041
wherein
R21 and R22 independently represent hydrogen, deuterium, (C1-C60)alkyl, halogen, (C6-C60)aryl, (C4-C60)heteroaryl, 5- or 6-membered heterocycloalkyl containing one or more heteroatom(s) selected from N, O and S, or (C3-C60)cycloalkyl, and the aryl or heteroaryl of R21 and R22 may be further substituted by one or more substituent(s) selected from the group consisting of (C1-C60)alkyl, halo(C1-C60)alkyl, (C1-C60)alkoxy, (C3-C60)cycloalkyl, (C6-C60)aryl, (C4-C60)heteroaryl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl;
R23 through R26 independently represent hydrogen, deuterium, (C1-C60)alkyl, (C1-C60)alkoxy, halogen, (C4-C60)heteroaryl, (C5-C60)cycloalkyl or (C6-C60)aryl, and the heteroaryl, cycloalkyl or aryl of R103 through R106 may be further substituted by one or more substituent(s) selected from the group consisting of (C1-C60)alkyl substituted or unsubstituted by halogen, (C1-C60)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl;
L11 and L13 independently represent a chemical bond or (C6-C60)arylene with or without one or more substituent(s) selected from (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl, (C4-C60)heteroaryl and halogen;
Ar11 and Ar12 independently represent aryl selected from the following structures or (C4-C60)heteroaryl;
Figure PCTKR2011000404-appb-I000042
wherein
the aryl or heteroaryl of Ar11 and Ar12 may be further substituted by one or more substituent(s) selected from (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl and (C4-C60)heteroaryl;
L12 represents (C6-C60)arylene, (C4-C60)heteroarylene or
Figure PCTKR2011000404-appb-I000043
, and the arylene or heteroarylene of L12 may be further substituted by one or more substituent(s) selected from (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl, (C4-C60)heteroaryl and halogen;
R31 through R34 independently represent hydrogen, deuterium, (C1-C60)alkyl or (C6-C60)aryl, or they may be linked with an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an aliphatic ring or a mono- or polycyclic aromatic ring; and
R35 through R38 independently represent hydrogen, deuterium, (C1-C60)alkyl, (C1-C60)alkoxy, (C6-C60)aryl, (C4-C60)heteroaryl or halogen, or they may be linked with an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an aliphatic ring or a mono- or polycyclic aromatic ring.
The electroluminescent layer means the layer where electroluminescence occurs, and it may be a single layer or a multi-layer that two or more layers are laminated. When a mixture of host-dopant is used according to the constitution of the present invention, noticeable improvement in luminous efficiency by the electroluminescent host may be confirmed.
The doping concentration may be 0.5 to 10 wt%. When compared with existing other host materials, the electroluminescent host according to the present invention provides excellent conductivity for holes and electrons, as well as very superior stability and remarkably improved luminescence efficiency and operation life.
Accordingly, when the compound represented by Chemical Formulas 3 to 7 is selected as an electroluminescent host, it may considerably compensate for the electrical disadvantage of the organic electroluminescent compound represented by Chemical Formula 1 or 2 according to the present invention.
The organic electroluminescent device may comprise organic electroluminescent compound of Chemical Formula 1 or 2 and may comprise one or more compounds selected from the group consisting of arylamine or styrylamine compounds. Examples of arylamine or styrylamine compounds include the compounds of following Chemical Formula 8 but are not limited thereto.
[Chemical Formula 8]
Figure PCTKR2011000404-appb-I000044
Wherein
Ar31 and Ar32 independently represent C1-C60)alkyl, (C6-C60)aryl, (C4-C60)heteroaryl, (C6-C60)arylamino, (C1-C60)alkylamino, 5- to 6-membered heterocycloalkyl containing one or more selected from N, O and S or (C3-C60)cycloalkyl, and Ar31 and Ar32 are linked to an adjacent substituent via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an aliphatic ring or a mono- or polycyclic aromatic ring;
when k is 1, Ar33 represents (C6-C60)aryl or (C4-C60)heteroaryl or substituents having following structures;
Figure PCTKR2011000404-appb-I000045
when k is 2, Ar33 represents (C6-C60)arylene, (C4-C60)heteroarylene or substituents having following structures;
Figure PCTKR2011000404-appb-I000046
Ar34 and Ar35 independently represent (C6-C60)arylene or (C4-C60)heteroarylene;
R91 through R93 independently represent hydrogen, (C1-C60)alkyl or (C6-C60)aryl;
p represents an integer of 1 to 4, and q represents an integer of 0 or 1,
alkyl, aryl, heteroaryl, arylamino, alkylamino, cycloalkyl or heterocycloalkyl of the Ar31 and Ar32, or aryl, heteroaryl, arylene or heteroarylene of the Ar33, or arylene and heteroarylene of the Ar34 and Ar35, or alkyl or aryl of R191 through R193 may be further substituted by one or more substituent(s) selected from the group consisting of halogen, (C1-C60)alkyl, (C6-C60)aryl, (C4-C60)heteroaryl, 5- to 6-membered heterocycloalkyl containing one or more selected from N, O and S, (C3-C60)cycloalkyl, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl, tri(C6-C60)arylsilyl, adamantyl, (C7-C60)bicycloalkyl, (C2-C60)alkenyl, (C2-C60)alkynyl, cyano, (C1-C60)alkylamino, (C6-C60)arylamino, (C6-C60)ar(C1-C60)alkyl, (C6-C60)aryloxy, (C1-C60)alkyloxy, (C6-C60)arylthio, (C1-C60)alkylthio, (C1-C60)alkoxycarbonyl, (C1-C60)alkylcarbonyl, (C6-C60)arylcarbonyl, carboxyl, nitro, and hydroxyl.
More specifically, the arylamine Compound or styrylarylamine Compound may be exemplified as following Compounds, but is not limited to the following Compounds.
Figure PCTKR2011000404-appb-I000047
Figure PCTKR2011000404-appb-I000048
Figure PCTKR2011000404-appb-I000049
Figure PCTKR2011000404-appb-I000050
Figure PCTKR2011000404-appb-I000051
Figure PCTKR2011000404-appb-I000052
Figure PCTKR2011000404-appb-I000053
In the organic electroluminescent device, the organic layer may further comprise one or more metal(s) selected from the group consisting of Group 1, Group 2, 4th period and 5th transition metals, lanthanide metals and d-transition metals besides the organic electroluminescent compound of Chemical Formula 1 or 2. The organic layer may comprise an electroluminescent layer and a charge generating layer.
The present invention realizes an organic electroluminescent device having a pixel structure of independent light-emitting mode, which comprises an organic electroluminescent device containing the organic electroluminescent compound of Chemical Formula 1 or 2 as a sub-pixel and one or more sub-pixel(s) comprising one or more metal compound(s) selected from the group consisting of Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag, patterned in parallel at the same time.
Also, the organic layer may form a white light-emitting electroluminescent device wherein the organic layer further comprises one or more organic electroluminescent layer(s) emitting blue, red or green light at the same time.
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.
Since the organic electroluminescent compound according to the present invention exhibits good luminous efficiency in a blue color and excellent life property, it may be used to manufacture OLED devices having very superior operation life.
The present invention is further described with respect to organic electroluminescent compounds according to the present invention, processes for preparing the same, and luminescence properties of devices employing the same. However, the following examples are provided for illustrative purposes only and they are not intended to limit the scope of the present invention.
[Preparation Example 1] Preparation of Compound 91
Figure PCTKR2011000404-appb-I000054
Preparation of Compound A
4-bromobiphenyl (30g, 0.12mol) was added to a one-neck flask and an argon atmosphere was established in a vacuum. Tetrahydrofuran (THF) (500ml) was added and the mixture was stirred at -78℃ for 10 minutes. After adding n-BuLi(2.5M in hexane) (77ml, 0.19mol), the mixture was stirred for 1 hour and 30 minutes at -78℃. Then, trimethyl borate (21.9ml, 0.19mol) was added at -78℃. After stirring the mixture for 30 minutes at -78℃, the mixture was stirred at room temperature for 4 hours. After the reaction was completed, extraction was performed using distilled water and ethyl acetate (EA). The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound A (21g, 84%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound B
1-bromo-4-iodobenzene (29g, 0.10mol), Compound A (21g, 0.10mol) and tetrakis(triphenylphosphine)Palladium (5.9g, 5.1mmol) were added to a two-neck(two-neck) flask. After stirring the mixture while adding toluene, 2M K2CO3 (265ml, 0.5mol) and ethanol (265ml) were added. After refluxing at 100℃ for 5 hours, the mixture was cooled to room temperature when the reaction was completed. Then, after extracting with distilled water and EA, the organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound B (23g, 74%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound C
Compound B (2g, 0.074mol) was added to the one-neck flask and a nitrogen atmosphere was established. After adding THF, the mixture was stirred at -78℃ for 10 minutes. After adding n-butyllithium(2.5M in hexane) (44.6ml, 0.11mol) dropwise, the mixture was stirred for 1 hour at -78℃. Then, after adding DMF (8.1ml, 0.11mmol) and stirring for 10 minutes, the mixture was stirred at room temperature for 4 hours. After the reaction was completed, HCl (2.5 mL) was added and extraction was performed at room temperature using distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound C (19g, 89%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound D
9H-fluorene (60g, 0.36mol) was added to the one-neck flask and an argon atmosphere was established in a vacuum. Propylene carbonate (500ml) was added and stirred at 60℃ until 9H-fluorene was dissolved. NBS (64g, 0.36mol) was added and the mixture was stirred at 60℃ for 1 hour. Upon completion of the reaction, a solid produced by filtration with distilled water was dissolved with EA and the mixture was extracted with distilled water. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound D (64g, 73%) was obtained by recrystallization using ethanol.
Preparation of Compound E
Compound D (40g, 0.16mol), iodine (16.9g, 0.066mol), iodic acid (6.89g, 0.039mol) were added to the two-neck flask. distilled water (30ml), acetic acid (600mL), and sulfuric acid (14.4mL) were added and the mixture was stirred at 85℃ for 4 hours. Upon completion of the reaction, the mixture was completely cooled to room temperature and washed with acetic acid and distilled water. Pure Compound E (49g, 82%) was obtained by filtration.
Preparation of Compound F
Compound E (49g, 0.13mol), KOH (33g, 0.60mol), and KI (2.2g, 0.013mol) were added to the one-neck flask, an argon atmosphere was established in a vacuum. DMSO(anhydrous) (500ml) was added and the mixture was stirred at 0℃ for 10 minutes. After adding bromoethane (23mL, 0.30mol) dropwise, the mixture was stirred at -10℃ for 30 minutes and then stirred at room temperature for 9 hours. Upon completion of the reaction, a solid produced by adding excess distilled water was filtered and the filtered solid was extracted with methylene chloride (MC). The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound F (37g, 66%) was separated by column chromatography using hexane as an eluent.
Preparation of Compound G
After Compound F (30g, 0.07mol), carbazole (15.2g, 0.09mol), cupper (2.5g, 0.03mol), 18-crown-6 (1.4g, 0.005mol), and K2CO3 (38.8g, 0.28mol) were added to the two-neck flask, an argon atmosphere was established in a vacuum. 1,2-dichlorobenzene (250ml) was added and the mixture was stirred under reflux at 180℃ for 6 hours. Upon completion of the reaction, cupper was removed by using celite filter and the reaction mixture was dissolved with MC. After removing a solvent, Pure Compound G (23g, 76%) was separated by column chromatography using dichloromethane and hexane as an eluent.
Preparation of Compound H
Compound G (20g, 0.042mol) was added to the one-neck flask and a nitrogen atmosphere was established. After adding THF, the mixture was stirred at -78℃ for 10 minutes. After adding n-butyllithium(2.5M in hexane) (40ml, 0.063mol) dropwise, the mixture was stirred at -78℃ for 1 hour. DMF (4.8ml, 0.063mmol) was added and the mixture was stirred for 10 minutes and then stirred at room temperature for 4 hours. Upon completion of the reaction, HCl (2.5mL) wad added and cooled to room temperature. The reaction mixture was extracted with distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound H (13g, 72%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound I
Compound H (13g, 0.031mol) and triethylphosphite (10mL, 0.062mol) were added to the one-neck flask. After iodine (7.9g, 0.031mol) was added at 0℃, the mixture was stirred for 30 minutes and then stirred at room temperature for 12 hours. After the reaction was completed, phosphite was removed using a vacuum sublimator and extraction was performed using distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound I (16g, 87%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound 91
After Compound I (16g, 0.029mol) and Compound C (7.6g, 0.029mol) were added to the one-neck flask, an argon atmosphere was established in a vacuum. After adding THF (600mL), the mixture was stirred at 0℃ for 10 minutes and potassium tert-butoxide (35.7mL, 0.035mol) was slowly added thereto. After stirring the mixture at 0℃ for 10 minutes, the mixture was further stirred at room temperature for 3 hours and extracted with distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound Compound 91 (17g, 89%) was separated by column chromatography using hexane and EA as an eluent.
1H NMR(CDCl3, 200 MHz): δ = 0.9(6H, m), 1.91(4H, m), 6.95(2H, m), 7.17(1H, m), 7.25~7.34(9H, m), 7.41(1H, m), 7.5~7.56(8H, m), 7.63~7.64(3H, m), 7.87(2H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m).
MS/FAB: 641.84(found), 641.34(calculated)
[Preparation Example 2] Preparation of Compound 92
Figure PCTKR2011000404-appb-I000055
Preparation of Compound A
4-bromobiphenyl (30g, 0.12mol) was added to the one-neck flask and an argon atmosphere was established in a vacuum. After adding THF (500 mL) and stirring at 78℃ for 10 minutes, n-BuLi(2.5M in hexane) (77ml, 0.19mol) was added dropwise. The mixture was stirred at -78℃ for 1 hour and 30 minutes and trimethyl borate (21.9ml, 0.19mol) was added at -78℃. The mixture was stirred at -78℃ for 30 minutes and then stirred at room temperature for 4 hours. Upon completion of the reaction, the mixture was extracted with distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound A (21g, 84%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound B
1-bromo-4-iodobenzene (29g, 0.10mol), Compound A (21g, 0.10mol) and tetrakis(triphenylphosphine)Palladium (5.9g, 5.1mmol) were added to the two-neck flask. The mixture was stirred while adding toluene. After adding 2M K2CO3 (265ml, 0.5mol) and ethanol (265ml), the mixture was stirred under reflux at 100℃ for 5 hours. Upon completion of the reaction, the mixture was cooled to room temperature and extracted with distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound B (23g, 74%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound C
Compound B (2g, 0.074mol) was added to the one-neck flask and a nitrogen atmosphere was established. After adding THF, the mixture was stirred at constant temperature of -78℃ for 10 minutes. After adding n-butyllithium(2.5M in hexane) (44.6ml, 0.11mol) dropwise, the mixture was stirred at -78℃ for 1 hour. After adding DMF (8.1ml, 0.11mmol) thereto, the mixture was stirred for 10 minutes and then stirred at room temperature for 4 hours. After the reaction was completed, HCl (2.5mL) was added. The mixture was cooled to room temperature and extracted with distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound C (19g, 89%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound J
Compound C (20g, 0.077mol) was added to the one-neck flask and a nitrogen atmosphere was established. After adding ethanol (300ml), the mixture was stirred at constant temperature of 0℃ for 10 minutes. After adding sodium borohydride (3.2g, 0.085mol), the mixture was stirred at room temperature for 6 hours. After the reaction was completed, HCl (5mL) was added and the mixture was extracted with distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound J (17.4g, 86%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound K
Compound J (15g, 0.057mol) and triethylphosphite (19.4mL, 0.12mol) were added to the one-neck flask. After adding iodine (14.5g, 0.057mol) at 0℃, the mixture was stirred for 30 minutes and then stirred at room temperature for 12 hours. After the reaction was completed, phosphite was removed using a vacuum sublimator and extraction was performed using distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound K (16g, 72%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound L
1-amino-4-bromonaphthalene (60g, 0.27mol) was added to the one-neck flask and an argon atmosphere was established in a vacuum. After adding acetonitrile (500ml), the mixture was stirred at 0℃ until 1-amino-4-bromonaphthalene is dissolved. t-Butylnitrite (42g, 48ml, 0.41mol), and copper bromide (73g, 0.32mol) was stirred at room temperature for 3 hours. Upon completion of the reaction, 1N HCl aqueous solution (600ml) was added and stirred. After filtering a produced solid, the obtained solid was washed with distilled water and ether. Pure Compound L (76g, 85%) was obtained by column.
Preparation of Compound M
Compound L (40g, 0.12mol), carbazole (24.1g, 0.14mol), cupper (3.3g, 0.05mol), 18-crown-6 (2.3g, 0.009mol), and K2CO3 (66.3g, 0.48mol) were added to the two-neck flask and an argon atmosphere was established in a vacuum. 1,2-dichlorobenzene (250ml) was added and the mixture was stirred under reflux at 180℃ for 6 hours. Upon completion of the reaction, cupper was removed by using Celite filter and the reaction mixture was dissolved with MC. After removing a solvent, Pure Compound M (36g, (81%) was separated by column chromatography using dichloromethane and hexane as an eluent.
Preparation of Compound N
Compound M (20g, 0.054mol) was added to the one-neck flask and a nitrogen atmosphere was established. After adding THF, the mixture was stirred at -78℃ for 10 minutes. After adding n-butyllithium(2.5M in hexane) (32ml, 0.081mol) dropwise, the mixture was stirred at -78℃ for 1 hour. After adding DMF (6.3ml, 0.081mmol), the mixture was stirred for 10 minutes and then stirred at room temperature for 4 hours. Upon completion of the reaction, HCl (3mL) was added. The mixture was cooled to room temperature and extracted with distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound N (12.4g, 71%) was separated by column chromatography using hexane and EA as an eluent.
Preparation of Compound 92
Compound K (10g, 0.026mol) and Compound N (8.4g, 0.026mol) were added to the one-neck flask and an argon atmosphere was established in a vacuum. After adding THF (600 mL) and stirring at 0℃ for 10 minutes, potassium tert-butoxide (1.0M in THF) (31 mL, 0.031mol) was slowly added. After stirring the mixture at 0℃ for 10 minutes, the mixture was further stirred at room temperature for 3 hours and extracted with distilled water and EA. The organic layer was dried with MgSO4 and the solvent was removed using a rotary evaporator. Pure Compound 92 (12g, 84%) was separated by column chromatography using hexane and EA as an eluent.
1H NMR(CDCl3, 200 MHz): δ = 6.95(2H, m), 7.25~7.33(7H, m), 7.41(1H, m), 7.5~7.55(13H, m), 7.9~7.94(3H, m), 8.08~8.12(2H, m), 8.55(1H, m).
MS/FAB: 547.69(found), 547.23(calculated).
Compounds 1 to 90 were prepared according to the procedure of Preparation Examples 1 and 2. 1H NMR and MS/FAB data of thus prepared organic electroluminescent compounds are given in Table 1. In Table 1 below, "L" represents
Figure PCTKR2011000404-appb-I000056
or
Figure PCTKR2011000404-appb-I000057
.
Table 1
Compd. L Y 1H NMR(CDCl3, 200 MHz) MS/FAB
found calculated
1 TL1 TAR1 δ = 6.95(2H, m), 7.25~7.33(7H, m), 7.41(1H, m), 7.5~7.56(9H, m), 7.62~7.64(5H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 497.6 497.2
2 TL1 TAR6 δ = 6.95(2H, m), 7.25~7.33(7H, m), 7.41(1H, m), 7.5~7.56(9H, m), 7.63~7.68(7H, m), 7.79(2H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 573.7 573.2
3 TL1 TAR11 δ = 6.95(2H, m), 7.25~7.41(12H, m), 7.5~7.56(11H, m), 7.63~7.66(4H, m), 7.91~7.96(9H, m), 8.08~8.12(2H, m), 8.55(3H, m) 850.1 849.3
4 TL1 TAR16 δ = 6.95(2H, m), 7.25~7.41(13H, m), 7.5~7.56(8H, m), 7.63~7.64(3H, m), 7.9~7.94(5H, m), 8.12(1H, m), 8.55(1H, m) 671.8 671.3
5 TL1 TAR20 δ = 6.95(2H, m), 7.25~7.33(7H, m), 7.41(1H, m), 7.5~7.56(7H, m), 7.63~7.64(3H, m), 7.7~7.71(4H, m), 7.8(1H, m), 7.9~8(3H, m), 8.1~8.12(2H, m), 8.55(1H, m) 621.8 621.2
6 TL1 THA1 δ = 6.95(2H, m), 7.25~7.33(7H, m), 7.41~7.52(8H, m), 7.59~7.63(3H, m), 7.77(1H, m), 7.9~7.94(2H, m), 8.12(1H, m), 8.36(1H, m), 8.55(1H, m) 498.6 498.2
7 TL1 THA10 δ = 6.95~6.99(2H, m), 7.25~7.35(9H, m), 7.41~7.52(8H, m), 7.59~7.63(3H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 503.7 503.2
8 TL1 THA7 δ = 6.95(2H, m), 7.25~7.33(8H, m), 7.41(1H, m), 7.5~7.56(7H, m), 7.63~7.64(3H, m), 7.83(1H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m), 8.7(2H, m) 549.7 549.2
9 TL1 TY2 δ = 6.95(2H, m), 7.25~7.33(7H, m), 7.41(1H, m), 7.5~7.56(9H, m), 7.63~7.79(11H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 655.8 655.2
10 TL1 THA26 δ = 6.54(1H, m), 6.82(1H, m), 6.95~6.99(2H, m), 7.07(4H, m), 7.25~7.33(7H, m), 7.41~7.52(8H, m), 7.59~7.63(3H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 619.7 619.2
11 TL1 TY7 δ = 6.95(2H, m), 7.25(7H, s), 7.25~7.33(2H, m), 7.41(1H, m), 7.5~7.56(9H, m), 7.63~7.68(5H, m), 7.79(4H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 711.9 711.2
12 TL1 THA21 δ = 6.95~6.99(2H, m), 7.25(5H, m), 7.26(2H, s), 7.29~7.33(2H, m), 7.41~7.52(8H, m), 7.59~7.63(3H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 579.6 579.2
13 TL1 TF5 δ = 1.48(6H, m), 2.02(4H, m), 6.95(2H, m), 7.17(1H, m), 7.25~7.34(9H, m), 7.41(1H, m), 7.5~7.56(8H, m), 7.63~7.64(3H, m), 7.87(2H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 653.9 653.3
14 TL1 TF17 δ = 2.26(6H, s), 5(1H, s), 6.95(2H, m), 7.17(1H, m), 7.25~7.34(9H, m), 7.41(1H, m), 7.5~7.56(8H, m), 7.63~7.64(3H, m), 7.87(2H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 628.8 628.3
15 TL1 TF10 δ = 3.2(3H, s), 3.81(2H, s), 6.41(1H, m), 6.49(1H, m), 6.56(1H, m), 6.95~7.03(5H, m), 7.25~7.33(7H, m), 7.41(1H, m), 7.5~7.56(7H, m), 7.63~7.64(3H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 614.8 614.3
16 TL1 TF15 δ = 3.2(3H, s), 6.61(1H, m), 6.86(1H, m), 6.94~6.99(4H, m), 7.25~7.34(13H, m), 7.41(1H, m), 7.5~7.52(5H, m), 7.63(1H, m), 7.94(1H, m), 8.12(1H, m), 8.55(1H, m) 600.7 600.3
17 TL2 TAR4 δ = 3.81(2H, s), 6.51(2H, m), 6.69(2H, m), 6.95~7.01(6H, m), 7.25(4H, m), 7.38~7.41(5H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.88~7.9(4H, m) 611.8 611.3
18 TL2 TAR9 δ = 3.81(2H, s), 6.51(2H, m), 6.69(2H, m), 6.95~7.01(6H, m), 7.25(4H, m), 7.38~7.41(9H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.88~7.91(8H, m) 788.0 787.3
19 TL4 TAR14 δ = 6.59(2H, m), 6.77(2H, m), 6.89(2H, m), 6.91(1H, s), 6.92~6.95(4H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.82~7.88(4H, m), 8.12(2H, m), 8.93(2H, m), 9.09(1H, s) 663.8 663.3
20 TL4 TAR18 δ = 6.59(2H, m), 6.77(2H, m), 6.89~6.95(7H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.82~7.88(2H, m), 7.98(1H, m), 8.12(2H, m), 8.93(1H, m), 9.09(1H, m) 613.7 613.2
21 TL5 THA29 δ = 6.95~6.97(4H, m), 7.12~7.25(11H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m), 7.72(1H, m), 7.83(1H, m), 8.25(1H, m), 8.5(1H, m), 8.97(1H, m) 631.8 631.2
22 TL5 THA4 δ = 6.95~6.99(4H, m), 7.16~7.25(10H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m), 8.25(1H, s) 532.7 532.2
23 TL6 THA13 δ = 2.88(4H, m), 6.58(2H, m), 6.76(2H, m), 6.95~7.04(6H, m), 7.25(4H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m) 533.7 533.2
24 TL6 THA18 δ = 2.88(4H, m), 6.58(2H, m), 6.73~6.76(3H, m), 6.95(2H, m), 7.02~7.04(4H, m), 7.11(1H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m), 9.23(1H, s) 582.8 582.2
25 TL6 THA25 δ = 2.88(4H, m), 6.3(1H, m), 6.58(2H, m), 6.76(2H, m), 6.95~7.04(6H, m), 7.25~7.28(5H, m), 7.35(1H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m), 7.73(3H, m) 696.0 695.2
26 TL7 TY4 δ = 6.63(2H, m), 6.69(2H, m), 6.81(2H, m), 6.95~7.05(6H, m), 7.25(6H, m), 7.41(1H, m), 7.51~7.56(10H, m), 7.64(2H, m), 7.79(2H, m) 667.8 667.3
27 TL7 TF1 δ = 6.58~6.63(3H, m), 6.75~6.81(3H, m), 6.95~7.05(6H, m), 7.11(4H, m), 7.25~7.26(8H, m), 7.33(4H, m), 7.41(1H, m), 7.51~7.56(7H, m), 7.62~7.64(3H, m), 7.71(1H, m), 7.87(1H, m) 764.0 763.3
28 TL7 TF6 δ = 1.51(4H, m), 2.09(4H, m), 6.58~6.63(3H, m), 6.75~6.81(3H, m), 6.95~7.05(6H, m), 7.25(6H, m), 7.41(1H, m), 7.51~7.56(7H, m), 7.62~7.64(3H, m), 7.71(1H, m), 7.87(1H, m) 665.9 665.3
29 TL7 TF18 δ = 5(1H, s), 6.58~6.63(3H, m), 6.75~6.81(5H, m), 6.95~7.05(6H, m), 7.23~7.25(10H, m), 7.33(4H, m), 7.41(1H, m), 7.51~7.56(7H, m), 7.62~7.64(3H, m), 7.71(1H, m), 7.87(1H, m) 779.0 778.3
30 TL7 TF11 δ = 3.2(3H, s), 5.7(1H, m), 5.91(1H, m), 6.49(1H, m), 6.63~6.67(3H, m), 6.81(2H, m), 6.92~7.05(7H, m), 7.13(1H, m), 7.25(6H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m) 642.8 642.3
31 TL8 THA27 δ = 6.59(1H, s), 6.69(2H, m), 6.81~6.87(4H, m), 7.14(5H, s), 7.16(2H, m), 7.25(4H, m), 7.41~7.59(13H, m), 7.85(2H, m) 884.7 887.0
32 TL8 TY5 δ = 6.69(4H, m), 6.87(2H, m), 6.95(2H, m), 7.16(2H, m), 7.25(4H, m), 7.41~7.56(13H, m), 7.64(2H, m), 7.76~7.85(6H, m) 733.9 733.3
33 TL8 TF2 δ = 6.58(1H, m), 6.69~6.75(3H, m), 6.87(2H, m), 6.95(2H, m), 7.16~7.25(10H, m), 7.35(2H, m), 7.41~7.56(12H, m), 7.62~7.64(3H, m), 7.71~7.75(3H, m), 7.85~7.87(3H, m) 812.0 811.3
34 TL8 TF7 δ = 3.49(4H, s), 6.58(1H, m), 6.69~6.75(3H, m), 6.87(2H, m), 6.95(2H, m), 7.16~7.25(10H, m), 7.41~7.56(12H, m), 7.62~7.64(3H, m), 7.71(1H, m), 7.85~7.87(3H, m) 764.0 763.3
35 TL8 TF13 δ = 3.2(3H, m), 5.88(1H, m), 6.47(1H, m), 6.69(2H, m), 6.87~6.97(5H, m), 7.16~7.25(11H, m), 7.41~7.54(9H, m), 7.85(2H, m) 682.9 682.2
36 TL8 TF16 δ = 3.2(3H, m), 5.8(1H, m), 6.01(1H, m), 6.57(1H, m), 6.69(2H, m), 6.87~6.92(3H, m), 7.16(2H, m), 7.25(8H, m), 7.32(1H, m), 7.41~7.54(11H, m), 7.63(1H, m), 7.85(4H, m) 726.9 726.3
37 TL9 TAR7 δ = 3.82(3H, s), 6.95(2H, m), 7.25(12H, m), 7.41~7.42(3H, m), 7.51~7.64(14H, m), 7.79(1H, m), 8.17~8.18(2H, m) 663.85 663.29
38 TL9 TAR17 δ = 3.82(3H, s), 6.95(2H, m), 7.25(4H, m), 7.41~7.42(3H, m), 7.51~7.64(10H, m), 7.71(2H, m), 7.79(1H, m), 7.98~8.04(2H, m), 8.12~8.18(4H, m), 9.09(1H, m), 9.15(1H, m) 611.77 611.26
39 TL9 THA2 δ = 3.82(3H, s), 7.2~7.25(5H, m), 7.41(1H, m), 7.42~7.51(14H, m), 7.79~7.83(2H, m), 8.17~8.18(2H, m), 8.85(1H, m) 512.64 512.23
40 TL9 THA15 δ = 3.82(3H, s), 6.95~6.99(2H, m), 7.25(4H, m), 7.41~7.44(5H, m), 7.51~7.52(4H, m), 7.59~7.62(4H, m), 7.79(1H, m), 8.17~8.18(2H, m), 8.63(2H, m) 569.72 569.19
41 TL9 THA25 δ = 3.82(3H, s), 6.95~6.99(2H, m), 7.25(4H, m), 7.35(1H, m), 7.41~7.44(5H, m), 7.51~7.52(4H, m), 7.59~7.62(4H, m), 7.73~7.79(6H, m), 8.17~8.18(2H, m) 681.93 681.16
42 TL9 TF1 δ = 3.82(3H, s), 6.95(2H, m), 7.11(4H, m), 7.25~7.26(6H, m), 7.33(4H, m), 7.41~7.42(3H, m), 7.51~7.56(12H, m), 7.71~7.79(3H, m), 7.87~7.93(2H, m), 8.17~8.18(2H, m) 751.95 751.32
43 TL9 TF18 δ = 3.82(3H, s), 5(1H, s), 6.77(2H, m), 6.95(2H, m), 7.23~7.25(8H, m), 7.33(4H, m), 7.41~7.42(3H, m), 7.51~7.56(12H, m), 7.71~7.79(3H, m), 7.87~7.93(2H, m), 8.17~8.18(2H, m) 766.97 766.33
44 TL9 TF16 δ = 3.2(3H, s), 3.82(3H, s), 6.57~6.59(2H, m), 6.88~6.95(4H, m), 7.25(4H, m), 7.41(1H, m), 7.42(2H, m), 7.47(2H, m), 7.51~7.57(12H, m), 7.79~7.85(3H, m), 8.17~8.18(2H, m) 690.87 690.30
45 TL10 TAR10 δ = 1.72(6H, s), 3.2(3H, s), 6.52(1H, m), 6.69(2H, m), 6.78(1H, m), 6.95(2H, m), 7.05~7.14(3H, m), 7.25(8H, m), 7.39~7.41(5H, m), 7.51~7.56(8H, m), 7.64(4H, m), 7.91(4H, m) 806.04 805.37
46 TL10 TAR19 δ = 1.72(6H, s), 3.2(3H, s), 6.52(1H, m), 6.69(2H, m), 6.78(1H, m), 6.95(2H, m), 7.05~7.14(3H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.71(2H, m), 7.82~7.88(3H, m), 8.04(1H, m), 8.12(1H, m), 8.18(1H, m) 677.87 677.31
47 TL10 THA9 δ = 1.72(6H, s), 3.2(3H, s), 6.52(1H, m), 6.69(1H, m), 6.78~6.82(2H, m), 6.95~7.14(7H, m), 7.25(4H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m) 543.70 543.26
48 TL10 TY1 δ = 1.72(6H, s), 3.2(3H, s), 6.52(1H, m), 6.69(2H, m), 6.78(1H, m), 6.95(2H, m), 7.05~7.14(5H, m), 7.25(6H, m), 7.41(1H, m), 7.51~7.56(8H, m), 7.64(2H, m), 7.85(2H, m), 7.95(2H, m) 695.89 695.32
49 TL10 THA28 δ = 0.14(6H, s), 1.72(6H, s), 3.2(3H, s), 6.52(1H, m), 6.69(1H, m), 6.78(1H, m), 6.95~7.03(3H, m), 7.04(2H, s), 7.05~7.14(4H, m), 7.25(4H, m), 7.35(2H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m), 7.89(1H, m) 750.10 749.26
50 TL10 TF4 δ = 1.72(6H, s), 3.2(3H, s), 6.52(1H, m), 6.69(2H, m), 6.78~6.81(3H, m), 6.95(2H, m), 7.05~7.14(3H, m), 7.25(4H, m), 7.41(1H, m), 7.48~7.56(9H, m), 7.63~7.64(3H, m), 7.71~7.77(2H, m), 7.87~7.93(2H, m), 8.51(2H, m) 793.99 793.35
51 TL10 TF9 δ = 0.66(6H, s), 1.72(6H, s), 3.2(3H, s), 6.52(1H, m), 6.69(2H, m), 6.78(1H, m), 6.95(2H, m), 7.05~7.14(3H, m), 7.25(4H, m), 7.35(1H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64~7.66(3H, m), 7.76(1H, m), 7.82(1H, m), 7.89(1H, m), 7.95(1H, m) 685.97 685.32
52 TL12 TAR3 δ = 3.2(3H, s), 6.56(1H, m), 6.73(1H, m), 6.82(1H, m), 6.92~6.98(5H, m), 7.07(1H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.64(10H, m), 7.73(1H, m), 7.8(1H, m), 7.92~7.95(2H, m) 577.71 577.24
53 TL12 TAR13 δ = 3.2(3H, s), 6.56(1H, m), 6.73(1H, m), 6.82(1H, m), 6.92~6.98(5H, m), 7.07(1H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.82~7.88(2H, m), 7.98~8.04(2H, m), 8.12(2H, m), 8.18(1H, m), 8.93(1H, m), 9.09(1H, m), 9.15(1H, m) 677.83 677.27
54 TL12 THA6 δ = 3.2(3H, s), 6.56(1H, m), 6.73(1H, m), 6.82(1H, m), 6.92~6.98(5H, m), 7.07(1H, m), 7.25(4H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m), 8.03(1H, m), 8.12(1H, m), 8.27(1H, m), 8.5(1H, m), 8.97(1H, m) 578.70 578.24
55 TL12 THA12 δ = 3.2(3H, s), 6.56(1H, m), 6.73(1H, m), 6.82(1H, m), 6.92~6.99(5H, m), 7.25(4H, m), 7.41~7.44(4H, m), 7.51~7.52(4H, m), 7.59(2H, m) 519.59 519.19
56 TL12 THA22 δ = 3.2(3H, s), 6.56(1H, m), 6.73(1H, m), 6.82(1H, m), 6.92~6.99(5H, m), 7.07(1H, m), 7.25(4H, m), 7.35(1H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m), 7.73(3H, m) 615.81 615.17
57 TL12 TY5 δ = 3.2(3H, s), 6.56(1H, m), 6.73(1H, m), 6.82(1H, m), 6.92~6.98(5H, m), 7.07(1H, m), 7.25(6H, m), 7.41(1H, m), 7.51~7.56(8H, m), 7.64(2H, m), 7.79~7.85(4H, m) 687.85 687.23
58 TL12 TF7 δ = 3.2(3H, s), 3.49(4H, s), 6.56(1H, m), 6.73(1H, m), 6.82(1H, m), 6.92~6.98(5H, m), 7.07(1H, m), 7.2~7.25(8H, m), 7.41(1H, m), 7.51~7.56(7H, m), 7.63~7.64(3H, m), 7.71~7.77(2H, m), 7.87~7.93(2H, m) 717.89 717.30
59 TL12 TF12 δ = 3.2(6H, s), 6.53~6.56(2H, m), 6.73(1H, m), 6.82~6.98(8H, m), 7.07~7.11(2H, m), 7.22~7.28(6H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m) 709.73 710.18
60 TL13 TAR6 δ = 3.2(3H, s), 6.9~6.97(5H, m), 7.16~7.25(12H, m), 7.41(1H, m), 7.51~7.56(8H, m), 7.64(4H, m) 619.82 619.23
61 TL13 TAR16 δ = 3.2(3H, s), 6.9~6.97(5H, m), 7.16~7.25(8H, m), 7.39~7.41(5H, m), 7.51~7.64(10H, m), 7.91~7.97(4H, m) 717.92 717.25
62 TL13 THA1 δ = 3.2(3H, s), 6.95~6.97(3H, m), 7.16~7.25(8H, m), 7.41~7.52(10H, m), 7.59(2H, m), 7.97(1H, m), 8.33(1H, m) 544.71 544.20
63 TL13 THA7 δ = 3.2(3H, s), 6.9~6.97(5H, m), 7.16~7.25(8H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.9(2H, m), 8.74(2H, m) 595.75 595.21
64 TL13 THA26 δ = 3.2(3H, s), 6.82(1H, m), 6.9~6.99(5H, m), 7.07(5H, m), 7.16~7.25(8H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m) 665.80 665.20
65 TL13 THA21 δ = 3.2(3H, s), 6.9~6.99(5H, m), 7.16~7.25(8H, m), 7.26(2H, s), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m) 625.74 625.18
66 TL13 TF17 δ = 2.26(6H, s), 3.2(3H, s), 5(1H, s), 6.9~6.97(5H, m), 7.16~7.25(8H, m), 7.41(1H, m), 7.51~7.56(7H, m), 7.63~7.64(3H, m), 7.71~7.77(2H, m), 7.87~7.93(2H, m) 674.89 674.28
67 TL13 TF15 δ = 3.2(6H, s), 6.53(1H, m), 6.82~6.99(10H, m), 7.16~7.34(10H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m) 672.88 672.26
68 TL14 TAR9 δ = 2.88(4H, m), 3.2(3H, s), 6.55(1H, m), 6.72(2H, m), 6.81(1H, m), 6.95(2H, m), 7.05~7.13(3H, m), 7.25(4H, m), 7.39~7.41(9H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.91(8H, m) 816.04 815.36
69 TL14 TAR18 δ = 2.88(4H, m), 3.2(3H, s), 6.55(1H, m), 6.72(2H, m), 6.81(1H, m), 6.95(2H, m), 7.05~7.13(3H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.82~7.98(4H, m), 8.12(2H, m), 8.93(1H, m), 9.09(1H, m) 639.82 639.29
70 TL14 THA4 δ = 2.88(4H, m), 3.2(3H, s), 6.55(1H, m), 6.72(1H, m), 6.81(1H, m), 6.95~7.13(5H, m), 7.25(4H, m), 7.41~7.44(3H, m), 7.51~7.52(4H, m), 7.59(2H, m), 7.91(1H, m), 8.7(1H, s) 542.67 542.25
71 TL14 THA18 δ = 2.88(4H, m), 3.2(3H, s), 6.55(1H, m), 6.72(2H, m), 6.81(1H, m), 6.95(2H, m), 7.05~7.13(3H, m), 7.25(4H, m), 7.41~7.42(2H, m), 7.51~7.56(6H, m), 7.64(2H, m), 7.77(1H, m), 9.23(1H, s) 596.78 596.23
72 TL14 THA19 δ = 2.88(4H, m), 3.2(3H, s), 6.55(1H, m), 6.72(1H, m), 6.81(1H, m), 6.95~7.13(6H, m), 7.25(5H, s), 7.25(0H, m), 7.41~7.44(3H, m), 7.47(1H, s), 7.51~7.52(4H, m), 7.59(2H, m) 601.82 601.19
73 TL14 TF3 δ = 1.4(8H, m), 1.48(12H, m), 2.19(2H, m), 2.88(4H, m), 3.2(3H, s), 6.55(1H, m), 6.72(2H, m), 6.81(1H, m), 6.95(2H, m), 7.05~7.13(3H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.56(7H, m), 7.63~7.64(3H, m), 7.71~7.77(2H, m), 7.87~7.93(2H, m) 792.10 791.45
74 TL14 TF19 δ = 0.21(9H, s), 2.88(4H, m), 3.2(3H, s), 3.9(1H, s), 6.55(1H, m), 6.72(2H, m), 6.81(1H, m), 6.95(2H, m), 7.05~7.13(3H, m), 7.25(4H, m), 7.41(1H, m), 7.51~7.56(7H, m), 7.63~7.64(3H, m), 7.71~7.77(2H, m), 7.87~7.93(2H, m) 700.00 699.33
75 TL15 TAR2 δ = 3.2(3H, s), 6.6(1H, m), 6.77(1H, m), 6.86(1H, m), 6.95~6.99(5H, m), 7.08(1H, m), 7.25~7.34(6H, m), 7.41(1H, m), 7.51~7.56(8H, m), 7.64(2H, m), 7.93~7.96(3H, m), 8.55(1H, m) 587.75 587.26
76 TL15 TAR12 δ = 3.2(3H, s), 6.6(1H, m), 6.77(1H, m), 6.86(1H, m), 6.95~6.99(5H, m), 7.08(1H, m), 7.19~7.34(7H, m), 7.41(1H, m), 7.48~7.64(11H, m), 7.74~7.79(2H, m), 7.9(2H, m) 661.83 661.28
77 TL15 THA5 δ = 3.2(3H, s), 6.6(1H, m), 6.77(1H, m), 6.86(1H, m), 6.95~6.99(5H, m), 7.08(1H, m), 7.25~7.34(6H, m), 7.41(1H, m), 7.51~7.66(10H, m), 8.21(1H, m), 8.38(1H, m), 8.83(1H, m) 588.74 588.26
78 TL15 THA11 δ = 3.2(3H, s), 6.41(1H, m), 6.6(1H, m), 6.7(1H, m), 6.77~6.85(3H, m), 6.99(2H, m), 7.08(1H, m), 7.14(1H, s), 7.23~7.28(6H, m), 7.41~7.44(3H, m), 7.48(1H, s), 7.51~7.52(4H, m), 7.59(2H, m) 590.61 591.15
79 TL15 TY3 δ = 3.2(3H, s), 6.6(1H, m), 6.77(1H, m), 6.86(1H, m), 6.95~6.99(5H, m), 7.08(1H, m), 7.25~7.45(13H, m), 7.48(2H, s), 7.51~7.64(10H, m) 742.81 743.21
80 TL15 TY4 δ = 3.2(3H, s), 6.6(1H, m), 6.77(1H, m), 6.86(1H, m), 6.95~6.99(5H, m), 7.08(1H, m), 7.25~7.34(8H, m), 7.41(1H, m), 7.51~7.56(8H, m), 7.64(2H, m), 7.79~7.85(4H, m) 681.82 681.28
81 TL15 TF6 δ = 1.51(4H, m), 2.09(4H, m), 3.2(3H, s), 6.6(1H, m), 6.77(1H, m), 6.86(1H, m), 6.95~6.99(5H, m), 7.08(1H, m), 7.25~7.34(6H, m), 7.41(1H, m), 7.51~7.56(7H, m), 7.63~7.64(3H, m), 7.71~7.77(2H, m), 7.87~7.93(2H, m) 679.89 679.32
82 TL15 TF11 δ = 3.2(6H, s), 6.49(1H, m), 6.6(1H, m), 6.77~6.92(10H, m), 7.07~7.13(3H, m), 7.25~7.34(6H, m), 7.41(1H, m), 7.51~7.56(6H, m), 7.64(2H, m) 656.81 656.28
83 TL16 TAR5 δ = 3.2(3H, s), 6.57(1H, m), 6.66(1H, m), 6.83(1H, m), 6.92~6.95(3H, m), 7.19~7.25(5H, m), 7.41(1H, m), 7.47(2H, m), 7.51~7.56(12H, m), 7.85(2H, m), 7.91~7.97(2H, m), 8.07(1H, m), 8.13(1H, m), 8.31(2H, m) 687.87 687.29
84 TL16 TAR15 δ = 3.2(3H, s), 6.57(1H, m), 6.66(1H, m), 6.83(1H, m), 6.92~6.95(3H, m), 7.19~7.25(5H, m), 7.41~7.52(13H, m), 7.71(2H, m), 7.85~7.88(3H, m), 8.04(1H, m), 8.1(1H, m), 8.28(1H, m), 8.34(1H, m), 8.93(2H, m), 8.99(1H, m) 737.93 737.31
85 TL16 THA8 δ = 3.2(3H, s), 6.57(1H, m), 6.66(1H, m), 6.83(1H, m), 6.92(1H, m), 7.19~7.25(6H, m), 7.37(1H, m), 7.41(1H, m), 7.44(2H, m), 7.47~7.56(12H, m), 7.85~7.9(3H, m), 8.24(1H, m), 8.38(1H, m), 8.83(1H, m) 689.84 689.28
86 TL16 THA14 δ = 3.2(3H, s), 5.67(1H, m), 6.66(1H, m), 6.79~6.83(2H, m), 7.06(1H, m), 7.19~7.25(6H, m), 7.41~7.51(13H, m), 7.85(2H, m) 642.65 643.15
87 TL16 THA24 δ = 3.2(3H, s), 6.47(1H, m), 6.66(1H, m), 6.76~6.85(4H, m), 7.14(3H, s), 7.19~7.25(5H, m), 7.41~7.47(5H, m), 7.48(1H, s), 7.51~7.59(8H, m), 7.85(2H, m) 769.69 771.09
88 TL16 THA20 δ = 3.2(3H, s), 6.66(1H, m), 6.83(1H, m), 6.92~6.99(3H, m), 7.17~7.25(6H, m), 7.26(2H, s), 7.41~7.51(13H, m), 7.85(2H, m) 669.77 669.24
89 TL16 TF8-1 δ = 3.2(3H, s), 3.82(3H, s), 6.57(1H, m), 6.66(1H, m), 6.83(1H, m), 6.92~6.95(3H, m), 7.17~7.25(6H, m), 7.33(1H, m), 7.41(1H, m), 7.47~7.56(13H, m), 7.79~7.85(3H, m), 8.05(1H, m), 8.18(1H, m) 690.87 690.30
90 TL16 TF14 δ = 2.88(4H, m), 3.2(6H, s), 6.48(1H, m), 6.57(1H, m), 6.66~6.72(2H, m), 6.81~6.83(2H, m), 6.92~6.95(3H, m), 7.07~7.13(3H, m), 7.19~7.25(5H, m), 7.41~7.52(13H, m), 7.85(2H, m) 718.92 718.33
[Examples 1-11] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured using the electroluminescent material according to the present invention. First, a transparent electrode ITO thin film (15Ω/□) obtained from a glass for OLED (produced by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use. Then, an ITO substrate was equipped in a substrate folder of a vacuum vapor deposition apparatus, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum vapor deposition apparatus, which was then ventilated up to 10-6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate 2-TNATA, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
Then, N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
After forming the hole injection layer and the hole transport layer, an electroluminescent layer was formed thereon as follows. DNA (Examples 1 to 4), H-36(Examples 8 to 11) or H-38(Examples 5 to 7) was placed in a cell of the vacuum vapor deposition apparatus as host, and the organic electroluminescent compound according to the present invention was placed in another cell as a dopant. The two materials were vapor-deposited at a rate of 100:1 to form an electroluminescent layer having a thickness of 30 nm on the hole transport layer.
Figure PCTKR2011000404-appb-I000058
Then, tris(8-hydroxyquinoline)-aluminum(III) (Alq) was vapor-deposited with a thickness of 20 nm as an electron transport layer on the electroluminescent layer. Then, after vapor-depositing lithium quinolate (Liq) with a thickness of 1 to 2 nm as an electron injection layer, an Al cathode having a thickness of 150 nm was formed using another vacuum vapor deposition apparatus to manufacture an OLED.
Each compound used in the OLED had been purified by vacuum sublimation at 10-6torr.
[Comparative Example 1] Manufacture of OLED device using existing electroluminescent material
After forming a hole injection layer and a hole transport layer in the same manner as Example 1, blue-emitting DNA was placed in another cell of the vacuum vapor deposition apparatus as host, and Compound A was placed in still another cell. The two materials were vapor-deposited at a rate of 100:1 to form an electroluminescent layer having a thickness of 30 nm on the hole transport layer.
Figure PCTKR2011000404-appb-I000059
Then, after forming an electron transport layer and an electron injection layer in the same manner as Example 1, an Al cathode was vapor-deposited with a thickness of 150 nm using another vacuum vapor deposition apparatus to manufacture an OLED.
Luminescence efficiency of the OLED devices manufactured in Examples 1 to 11 and Comparative Example 1 was measured at 1,000 cd/m2. The result is given in Table 2.
Table 2
No. EL material 1 EL material 2 Luminescence efficiency (cd/A) Color
L Y
Example 1 DNA TL1 THA1 2.2 Deep blue
2 DNA TL1 TF8 1.9 Deep blue
3 DNA TL1 TAR6 2.5 Deep blue
4 DNA TL8 TF6 4.0 Deep blue
5 H-38 TL1 THA10 5.0 blue
6 H-38 TL5 THA9 4.5 blue
7 H-38 TL8 TF8-1 3.5 blue
8 H-36 TL1 THA2 2.6 Deep blue
9 H-36 TL1 TF1 3.1 Deep blue
10 H-36 TL5 THA10 4.7 blue
11 H-36 TL8 TF11 5.1 blue
Comp. Ex. 1 DNA Compound A 9 jade green
As seen from Table 2, the organic electroluminescent compounds of the present invention provide pure blue color as compared to the existing electroluminescent compound. That, when a blue color having the level of about CIE y = 0.1 is required for realizing the color close to the NTSC standard in the organic electroluminescent display, the organic electroluminescent compounds of the present invention may be useful. As described, the organic electroluminescent compound of the present invention is used as a blue-emitting material having the high purity.
Since the organic electroluminescent compound according to the present invention exhibits good luminous efficiency in a blue color and excellent life property, it may be used to manufacture OLED devices having very superior operation life.

Claims (9)

  1. An organic electroluminescent compound represented by Chemical Formula 1 or 2:
    [Chemical Formula 1]
    Figure PCTKR2011000404-appb-I000060
    [Chemical Formula 2]
    Figure PCTKR2011000404-appb-I000061
    wherein
    R1 through R5 independently represent hydrogen, (C1-C60)alkyl, (C3-C60)cycloalkyl, (C6-C60)aryl, (C2-60)heteroaryl containing one or more heteroatom(s) selected from N, O, S, P, Si and Se, (C1-60)alkoxy, (C1-C60)alkylthio, (C6-60)aryloxy, (C6-C60)arylthio, (C6-30)aryl(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl;
    X represents a chemical bond, -(CR6R7)m-, -N(R8)-, -Si(R9)(R10)-, -O-, -S-, -Se- or -(CR11)C=C(R12)-;
    R6 through R12 independently represent hydrogen, (C1-C60)alkyl, (C3-C60)cycloalkyl, (C6-C60)aryl, (C2-60)heteroaryl containing one or more heteroatom(s) selected from N, O, S, Si and Se, (C1-60)alkoxy, (C1-C60)alkylthio, (C6-60)aryloxy, (C6-C60)arylthio, mono- or di(C1-60)alkylamino, mono- or di(C6-60)arylamino, (C6-30)aryl(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl, or R6 and R7, R9 and R10, and R11 and R12 are linked via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an aliphatic ring or a mono- or polycyclic aromatic ring;
    Y represents (C6-C60)arylene, adamantylene, (C3-C60)heteroarylene containing one or more heteroatom(s) selected from N, O, S, P, Si and Se,
    Figure PCTKR2011000404-appb-I000062
    or
    Figure PCTKR2011000404-appb-I000063
    ;
    Y1 represents (C2-60)heteroarylene containing one or more heteroatom(s) selected from N, O, S, P, Si and Se;
    Z1 and Z2 independently represent a chemical bond, -(CR13R14)n-, -N(R15)-, -Si(R16)(R17)-, -O-, -S-, -Se- or -(R18)C=C(R19)-, provided that Z1 and Z2 are not chemical bonds at the same time;
    R13 through R19 independently represent hydrogen, (C1-C60)alkyl, (C3-C60)cycloalkyl, (C6-C60)aryl, (C2-60)heteroaryl containing one or more heteroatom(s) selected from N, O, S, Si and Se, (C1-60)alkoxy, (C1-C60)alkylthio, (C6-60)aryloxy, (C6-C60)arylthio, mono- or di(C1-60)alkylamino, mono- or di(C6-60)arylamino, (C6-30)aryl(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl, or R13 and R14, R16 and R17, and R18 and R19 are linked via (C3-C60)alkylene or (C3-C60)alkenylene with or without a fused ring to form an aliphatic ring or a mono- or polycyclic aromatic ring;
    a, b and c independently represent an integer from 1 to 4;
    d represents an integer from 1 to 3; and
    m and n independently represent an integer from 1 to 4.
  2. The organic electroluminescent compound according to claim 1, the
    Figure PCTKR2011000404-appb-I000064
    or
    Figure PCTKR2011000404-appb-I000065
    is selected from following structures:
    Figure PCTKR2011000404-appb-I000066
    Figure PCTKR2011000404-appb-I000067
    Figure PCTKR2011000404-appb-I000068
  3. An organic electroluminescent device comprising the organic electroluminescent compound according to any one of claims 1 to 2.
  4. The organic electroluminescent device according to claim 3, which comprises a first electrode; a second electrode; and at least one organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more of the organic electroluminescent compound(s) and one or more of host(s) selected from the compounds represented by Chemical Formula 3 or Chemical Formula 4:
    [Chemical Formula 3]
    (Ar1)e-L1-(Ar2)f
    [Chemical Formula 4]
    (Ar3)g-L2-(Ar4)h
    wherein
    L1 represents (C6-C60)arylene or (C4-C60)heteroarylene;
    L2 represents anthracenylene;
    Ar1 through Ar4 are independently selected from hydrogen, deuterium, (C1-C60)alkyl, (C1-C60)alkoxy, halogen, (C4-C60)heteroaryl, (C5-C60)cycloalkyl and (C6-C60)aryl, and the cycloalkyl, aryl or heteroaryl of Ar1 through Ar4 may be further substituted by one or more substituent(s) selected from the group consisting of (C6-C60)aryl or (C4-C60)heteroaryl with or without one or more substituent(s) selected from (C1-C60)alkyl substituted or unsubstituted by halogen, (C1-C60)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl; (C1-C60)alkyl substituted or unsubstituted by halogen, (C1-C60)alkoxy, (C3-C60)cycloalkyl, halogen, cyano, tri(C1-C60)alkylsilyl, di(C1-C60)alkyl(C6-C60)arylsilyl and tri(C6-C60)arylsilyl; and
    e, f, g and h independently represent an integer from 0 to 4.
  5. The organic electroluminescent device according to claim 4, wherein the organic layer comprises one or more compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds.
  6. The organic electroluminescent device according to claim 4, wherein the organic layer further comprises one or more metal(s) selected from the group consisting of Group 1, Group 2, 4th period and 5th transition metals, lanthanide metals and d-transition metals.
  7. The organic electroluminescent device according to claim 4, which is a white light-emitting electroluminescent device wherein the organic layer further comprises one or more organic electroluminescent layer(s) emitting blue, red or green light.
  8. The organic electroluminescent device according to claim 4, wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
  9. The organic electroluminescent device according to claim 4, wherein a mixed region of a reductive dopant and an organic substance, or a mixed region of an oxidative dopant and an organic substance is placed on the inner surface of one or both of the pair of electrodes.
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