WO2014104720A1 - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Organic electroluminescent compounds and organic electroluminescent device comprising the same Download PDF

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WO2014104720A1
WO2014104720A1 PCT/KR2013/012123 KR2013012123W WO2014104720A1 WO 2014104720 A1 WO2014104720 A1 WO 2014104720A1 KR 2013012123 W KR2013012123 W KR 2013012123W WO 2014104720 A1 WO2014104720 A1 WO 2014104720A1
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substituted
unsubstituted
alkyl
aryl
membered
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Inventor
Hee-Ryong Kang
Hyun-Ju Kang
Hee-Sook Kim
Nam-Kyun Kim
Kyung-Joo Lee
Hyuck-Joo Kwon
Bong-Ok Kim
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Priority to CN201380065763.8A priority Critical patent/CN104870434A/en
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Definitions

  • the present invention relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
  • fluorescent materials have been widely used as light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials are widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red-, green- and blue-emitting materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • Korean Patent Application Laying-Open No. 2005-0100694 discloses compounds for an organic EL device, in which a benzocarbazole backbone is substituted with an aryl group; and Korean Patent Application Laying-Open No. 2010-0015581 discloses compounds for an organic EL device, in which a dibenzocarbazole backbone is substituted with a nitrogen-containing heteroaryl group.
  • the above references fail to specifically disclose organic electroluminescent compounds, in which a cycloalkyl group, an aryl group, or a heteroaryl group is bonded to one of the carbon atoms of a benzocarbazole backbone and a nitrogen-containing heteroaryl group is bonded to a nitrogen atom of the benzocarbazole backbone.
  • Korean Patent Application Laying-Open No. 2010-0108924 discloses compounds in which an aryl group is bonded to a carbon atom of a benzocarbazole and a nitrogen-containing heteroaryl group is bonded to a nitrogen atom of the benzocarbazole.
  • the above reference fails to specifically disclose organic electroluminescent compounds, in which a substituent such as a cycloalkyl group, an aryl group, a hexahydrocarbazole group, or a heteroaryl group is bonded to the 2 position of a benzocarbazole.
  • the device using the compound of the above reference needs to be improved in terms of driving voltage, lifespan, and power efficiency.
  • the objective of the present invention is to provide an organic electroluminescent compound, which can provide an organic electroluminescent device having a low driving voltage, a long lifespan, and high power efficiency.
  • L 1 represents a single bond, a substituted or unsubstituted (3- to 30-membered) heteroarylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (C6-C30)cycloalkylene;
  • X 1 and X 2 each independently, represent -CH- or -N-;
  • Ar 1 and Ar 2 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
  • Ar 3 represents a substituted or unsubstituted (C6-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted hexahydrocarbazole, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
  • R 1 and R 2 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR 3 R 4 , -SiR 5 R 6 R 7 , -SR 8 , -OR 9 , a cyano, a nitro or a hydroxyl;
  • R 3 to R 9 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
  • the organic electroluminescent compound can provide an organic electroluminescent device having a low driving voltage, a long lifespan, and high power efficiency.
  • the present invention provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
  • alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • Alkenyl includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • Alkynyl includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • aryl(ene) indicates a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
  • the substituents for the substituted groups of L 1 , Ar 1 to Ar 3 , and R 1 to R 9 of formula 1, each independently, are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen; a (C1-C30)alkoxy; a (C6-C30)aryl; a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl; a (C3-C30)cycloalkyl; a (5- to 7-membered)heterocycloalkyl; a tri(C1-C30)alkylsilyl
  • L 1 represents a single bond, a substituted or unsubstituted (3- to 30-membered)heteroarylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (C6-C30)cycloalkylene; preferably, a single bond, or a substituted or unsubstituted (C6-C20)arylene; and more preferably, a single bond, or a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl.
  • X 1 and X 2 each independently, represent -CH- or -N-.
  • Ar 1 and Ar 2 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, each independently, hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and, more preferably, each independently, hydrogen; a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, a (C1-C6)alkoxy, a (5- to 15-member
  • Ar 3 represents a substituted or unsubstituted (C6-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted a hexahydrocarbazole, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; and preferably, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted hexahydrocarbazole, or a substituted or unsubstituted (5- to 20-membered)heteroaryl.
  • Ar 3 represents a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with a (5- to 15-membered)heteroaryl or a di(C6-C10)arylamino; a hexahydrocarbazole unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl; or a (5- to 19-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl.
  • R 1 and R 2 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR 3 R 4 , -SiR 5 R 6 R 7 , -SR 8 , -OR 9 , a cyano, a nitro or a hydroxyl; and preferably, each independently, hydrogen, a substituted or unsubstituted (C1-C20)alkyl,
  • R 1 and R 2 each independently, represent hydrogen; a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with a (C1-C6)alkyl; or a (5- to 19-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl.
  • R 3 to R 9 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or may be linked with an adjacent substituent(s) to form a substituted or unsubstituted, (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur.
  • L 1 represents a single bond, or a substituted or unsubstituted (C6-C20)arylene;
  • X 1 and X 2 each independently, represent -CH- or -N-;
  • Ar 1 and Ar 2 each independently, represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl;
  • Ar 3 represents a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted hexahydrocarbazole, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and
  • R 1 and R 2 each independently, represent hydrogen, a substituted or unsubstituted (C1-C20)al
  • L 1 represents a single bond, or a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl
  • X 1 and X 2 each independently, represent -CH- or -N-
  • Ar 1 and Ar 2 each independently, represent hydrogen; a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, a (C1-C6)alkoxy, a (5- to 15-membered)heteroaryl, a tri(C6-C10)arylsilyl, a (C1-C6)alkyldi(C6-C10)arylsilyl, a di(C6-C10)arylamino or a (C1-C6)alkyl(C6-C15)aryl; or a (5
  • L 1 represents a single bond, a (3- to 30-membered)heteroarylene or a (C6-C30)arylene
  • X 1 and X 2 each independently, represent -CH- or -N-
  • Ar 1 and Ar 2 each independently, represent hydrogen, a (C1-C30)alkyl, a (C6-C30)aryl or a (3- to 30-membered)heteroaryl
  • Ar 3 represents a (C6-C30)cycloalkyl, a (C6-C30)aryl or a (3- to 30-membered)heteroaryl
  • R 1 and R 2 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl, a (C6-C30)aryl, a (3- to 30-membered)heteroaryl, -NR 3 R 4 or -SiR 5 R 6 R 7 ; R 3 to R 7 , each independently,
  • organic electroluminescent compounds of formula 1 of the present invention include the following, but are not limited thereto:
  • organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1.
  • L 1 , X 1 , X 2 , Ar 1 to Ar 3 , R 1 , R 2 , a, and b are as defined in formula 1 above, and Hal represents a halogen.
  • the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material may consist of the organic electroluminescent compound of formula 1. Otherwise, the material may further comprise a conventional compound(s) which has been comprised of an organic electroluminescent material, in addition to the compound of formula 1.
  • the organic electroluminescent device may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise at least one organic electroluminescent compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic layer may comprise a light-emitting layer in which the organic electroluminescent compound of formula 1 may be comprised as a host material, and if needed, another compound(s) other than the compound of formula 1 may be further comprised.
  • a phosphorescent dopant which is used for an organic electroluminescent device together with the host material according to the present invention, may be selected from the compounds represented by the following formula 2:
  • M 1 is selected from the group consisting of Ir, Pt, Pd and Os;
  • L 101 , L 102 and L 103 are each independently selected from the following structures:
  • R 201 to R 203 each independently, represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl, or a halogen;
  • R 204 to R 219 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, SF 5 , a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a
  • R 220 to R 223 each independently, represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen, or a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl;
  • R 224 and R 225 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a halogen, or R 224 and R 225 may be linked with an adjacent substituent(s) to form a (C5-C30), mono- or polycyclic, alicyclic or aromatic ring;
  • R 226 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- or 30-membered) heteroaryl or a halogen;
  • R 227 to R 229 each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl or a halogen;
  • R 231 to R 242 each independently represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a (C1-C30)alkoxy, a halogen, a substituted or unsubstituted (C6-C30)aryl, a cyano, or a substituted or unsubstituted (C5-C30)cycloalkyl, or may be linked with an adjacent substituent(s) via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked with R 207 or R 208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
  • the dopants of formula 2 are preferred as the dopants of formula 2, but the dopants of formula 2 are not limited thereto:
  • the present invention provides a composition for preparing an organic electroluminescent device.
  • the composition may comprise the compound of the present invention as a host material.
  • the organic electroluminescent device of the present invention comprises a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer comprises a light-emitting layer in which the composition of the present invention may be comprised.
  • the organic electroluminescent device of the present invention comprises the organic electroluminescent compound of formula 1 of the present invention, and may further comprise at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising said metal.
  • the organic layer may comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device of the present invention may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound, besides the compound of the present invention.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer.
  • a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • Compound 2-2 (14.2 g, 41%) was prepared in the same manner as in the preparation of compound 1-2 of Example 1 by using compound 2-1 (22 g, 128.16 mmol) and 2,5-dibromonitrobenzene (30 g, 106.80 mmol).
  • Compound 2-3 (12 g, 92%) was prepared in the same manner as in the preparation of compound 1-2 of Example 1 by using compound 2-2 (14.2 g, 43.27 mmol) and phenylboronic acid (5.3 g, 43.27 mmol).
  • Compound C-29 (6.5 g, 81%) was prepared in the same manner as in the preparation of compound C-27 of Example 1 by using compound 2-5 (3.6 g, 13.4 mmol) and compound 1-4 (4.8 g, 13.4 mmol).
  • Compound C-54 (6.0 g, 60%) was prepared in the same manner as in the preparation of compound C-27 of Example 1 by using compound 4-1 (6.4 g, 17.30 mmol) and compound 2-5 (5.1 g, 19.10 mmol).
  • Compound 5-3 (7.6 g, 92%) was prepared in the same manner as in the preparation of compound 1-2 of Example 1 by using compound 5-2 (7.0 g, 18.80 mmol) and [1,1'-biphenyl]-4-yl boronic acid (4.1 g, 20.70 mmol).
  • OLED device was produced using the compound of the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • 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 introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound C-28 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-11 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates, so that the dopant was deposited in a doping amount of 4 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • 2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell.
  • the two materials were evaporated at the same rate, so that they were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the material used for producing the OLED device were those purified by vacuum sublimation at 10 -6 torr.
  • the produced OLED device showed red emission having a luminance of 1,030 cd/m 2 and a current density of 8.7 mA/cm 2 at a driving voltage of 4.1 V.
  • the time taken to be reduced to 90% of the luminance at 5,000 nit was 60 hours or more.
  • OLED device was produced in the same manner as in Device Example 1, except for using compound C-29 as a host material and compound D-7 as a dopant to form a light-emitting layer.
  • the produced OLED device showed red emission having a luminance of 980 cd/m 2 and a current density of 5.5 mA/cm 2 at a driving voltage of 3.8 V.
  • the time taken to be reduced to 90% of the luminance at 5,000 nit was 90 hours or more.
  • OLED device was produced in the same manner as in Device Example 1, except for using compound C-54 as a host material and compound D-11 as a dopant to form a light-emitting layer.
  • the produced OLED device showed red emission having a luminance of 1,020 cd/m 2 and a current density of 11.0 mA/cm 2 at a driving voltage of 3.7 V.
  • the time taken to be reduced to 90% of the luminance at 5,000 nit was 60 hours or more.
  • OLED device was produced in the same manner as in Device Example 1, except for using compound C-83 as a host material and compound D-11 as a dopant to form a light-emitting layer.
  • the produced OLED device showed red emission having a luminance of 950 cd/m 2 and a current density of 10.7 mA/cm 2 at a driving voltage of 3.8 V.
  • the time taken to be reduced to 90% of the luminance at 5,000 nit was 75 hours or more.
  • OLED device was produced in the same manner as in Device Example 1, except for using compound C-56 as a host material and compound D-7 as a dopant to form a light-emitting layer.
  • the produced OLED device showed red emission having a luminance of 980 cd/m 2 and a current density of 7.2 mA/cm 2 at a driving voltage of 3.5 V.
  • the time taken to be reduced to 90% of the luminance at 5,000 nit was 90 hours or more.
  • OLED device was produced in the same manner as in Device Example 1, except for using compound C-27 as a host material and compound D-7 as a dopant to form a light-emitting layer.
  • the produced OLED device showed red emission having a luminance of 1,050 cd/m 2 and a current density of 6.6 mA/cm 2 at a driving voltage of 3.7 V.
  • the time taken to be reduced to 90% of the luminance at 5,000 nit was 90 hours or more.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound A-1 shown below as a host material and compound D-11 as a dopant to form a light-emitting layer.
  • the produced OLED device showed red emission having a luminance of 1,000 cd/m 2 and a current density of 10.6 mA/cm 2 at a driving voltage of 4.7 V.
  • the time taken to be reduced to 90% of the luminance at 5,000 nit was 20 hours or more.
  • the organic electroluminescent compound of the present invention can produce an organic electroluminescent device having an excellent lifespan and a lowered driving voltage so that power efficiency is improved. Furthermore, by using the compound of the present invention, it is possible to omit a hole blocking layer which has been necessary for an organic electroluminescent device using a conventional compound.

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Abstract

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. By using the organic electroluminescent compound according to the present invention, an organic electroluminescent device can have a low driving voltage, a long lifespan, and high power efficiency.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in the organic EL device is light-emitting materials. Until now, fluorescent materials have been widely used as light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials are widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red-, green- and blue-emitting materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Recently, Pioneer (Japan) et al., developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc., as host materials, which were known as hole blocking materials.
Although these materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of the organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still required in order to be improved.
Korean Patent Application Laying-Open No. 2005-0100694 discloses compounds for an organic EL device, in which a benzocarbazole backbone is substituted with an aryl group; and Korean Patent Application Laying-Open No. 2010-0015581 discloses compounds for an organic EL device, in which a dibenzocarbazole backbone is substituted with a nitrogen-containing heteroaryl group. However, the above references fail to specifically disclose organic electroluminescent compounds, in which a cycloalkyl group, an aryl group, or a heteroaryl group is bonded to one of the carbon atoms of a benzocarbazole backbone and a nitrogen-containing heteroaryl group is bonded to a nitrogen atom of the benzocarbazole backbone.
Korean Patent Application Laying-Open No. 2010-0108924 discloses compounds in which an aryl group is bonded to a carbon atom of a benzocarbazole and a nitrogen-containing heteroaryl group is bonded to a nitrogen atom of the benzocarbazole. However, the above reference fails to specifically disclose organic electroluminescent compounds, in which a substituent such as a cycloalkyl group, an aryl group, a hexahydrocarbazole group, or a heteroaryl group is bonded to the 2 position of a benzocarbazole. Furthermore, the device using the compound of the above reference needs to be improved in terms of driving voltage, lifespan, and power efficiency.
The objective of the present invention is to provide an organic electroluminescent compound, which can provide an organic electroluminescent device having a low driving voltage, a long lifespan, and high power efficiency.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2013012123-appb-I000001
wherein
L1 represents a single bond, a substituted or unsubstituted (3- to 30-membered) heteroarylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (C6-C30)cycloalkylene;
X1 and X2, each independently, represent -CH- or -N-;
Ar1 and Ar2, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
Ar3 represents a substituted or unsubstituted (C6-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted hexahydrocarbazole, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
R1 and R2, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR3R4, -SiR5R6R7, -SR8, -OR9, a cyano, a nitro or a hydroxyl;
R3 to R9, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
a represents an integer of 1 to 6; b represents an integer of 1 to 3; where a or b represents an integer of 2 or more, each of R1 or R2 may be the same or different; and
the heteroarylene, the heterocycloalkyl and the heteroaryl, each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P.
The organic electroluminescent compound, according to the present invention, can provide an organic electroluminescent device having a low driving voltage, a long lifespan, and high power efficiency.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.
The compound of formula 1 of the present invention is described in detail.
Herein, “alkyl” includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “Alkenyl” includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “Alkynyl” includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “(5- to 7-membered) heterocycloalkyl” indicates a cycloalkyl having 5 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, P(=O), Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. Furthermore, “aryl(ene)” indicates a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “(3- to 30-membered) heteroaryl(ene)” indicates an aryl group having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4, hetero atom selected from the group consisting of B, N, O, S, P(=O), Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, etc. Furthermore, “halogen” includes F, Cl, Br, and I.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. The substituents for the substituted groups of L1, Ar1 to Ar3, and R1 to R9 of formula 1, each independently, are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen; a (C1-C30)alkoxy; a (C6-C30)aryl; a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl; a (C3-C30)cycloalkyl; a (5- to 7-membered)heterocycloalkyl; a tri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; a di(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a cyano; a di(C1-C30)alkylamino; a di(C6-C30)arylamino; a (C1-C30)alkyl(C6-C30)arylamino; a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a (C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; a (C1-C30)alkyl(C6-C30)aryl; a carboxyl; a nitro; and a hydroxyl; and preferably, at least one selected from the group consisting of deuterium; a halogen; a (C1-C6)alkyl; a (C1-C6)alkoxy; a (C6-C15)aryl; a (5- to 15-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl; a tri(C6-C10)arylsilyl; a (C1-C6)alkyldi(C6-C10)arylsilyl; a di(C6-C10)arylamino; and a (C1-C6)alkyl(C6-C15)aryl.
In formula 1, L1 represents a single bond, a substituted or unsubstituted (3- to 30-membered)heteroarylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (C6-C30)cycloalkylene; preferably, a single bond, or a substituted or unsubstituted (C6-C20)arylene; and more preferably, a single bond, or a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl.
X1 and X2, each independently, represent -CH- or -N-.
Ar1 and Ar2, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, each independently, hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and, more preferably, each independently, hydrogen; a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, a (C1-C6)alkoxy, a (5- to 15-membered)heteroaryl, a tri(C6-C10)arylsilyl, a (C1-C6)alkyldi(C6-C10)arylsilyl, a di(C6-C10)arylamino, or a (C1-C6)alkyl(C6-C15)aryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl.
Ar3 represents a substituted or unsubstituted (C6-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted a hexahydrocarbazole, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; and preferably, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted hexahydrocarbazole, or a substituted or unsubstituted (5- to 20-membered)heteroaryl. More preferably, Ar3 represents a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with a (5- to 15-membered)heteroaryl or a di(C6-C10)arylamino; a hexahydrocarbazole unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl; or a (5- to 19-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl.
R1 and R2, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR3R4, -SiR5R6R7, -SR8, -OR9, a cyano, a nitro or a hydroxyl; and preferably, each independently, hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl. More preferably, R1 and R2, each independently, represent hydrogen; a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with a (C1-C6)alkyl; or a (5- to 19-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl.
R3 to R9, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or may be linked with an adjacent substituent(s) to form a substituted or unsubstituted, (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur.
According to one embodiment of the present invention, in formula 1 above, L1 represents a single bond, or a substituted or unsubstituted (C6-C20)arylene; X1 and X2, each independently, represent -CH- or -N-; Ar1 and Ar2, each independently, represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; Ar3 represents a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted hexahydrocarbazole, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and R1 and R2, each independently, represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl.
According to another embodiment of the present invention, in formula 1 above, L1 represents a single bond, or a (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl; X1 and X2, each independently, represent -CH- or -N-; Ar1 and Ar2, each independently, represent hydrogen; a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, a (C1-C6)alkoxy, a (5- to 15-membered)heteroaryl, a tri(C6-C10)arylsilyl, a (C1-C6)alkyldi(C6-C10)arylsilyl, a di(C6-C10)arylamino or a (C1-C6)alkyl(C6-C15)aryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl; Ar3 represents a (C6-C19)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (5- to 15-membered)heteroaryl or a di(C6-C10)arylamino; a hexahydrocarbazole unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl; or a (5- to 19-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl; and R1 and R2, each independently, represent hydrogen, a (C1-C6)alkyl, a (C6-C19)aryl unsubstituted or substituted with a (C1-C6)alkyl, or a (5- to 19-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl.
Specifically, L1 represents a single bond, a (3- to 30-membered)heteroarylene or a (C6-C30)arylene; X1 and X2, each independently, represent -CH- or -N-; Ar1 and Ar2, each independently, represent hydrogen, a (C1-C30)alkyl, a (C6-C30)aryl or a (3- to 30-membered)heteroaryl; Ar3 represents a (C6-C30)cycloalkyl, a (C6-C30)aryl or a (3- to 30-membered)heteroaryl; R1 and R2, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl, a (C6-C30)aryl, a (3- to 30-membered)heteroaryl, -NR3R4 or -SiR5R6R7; R3 to R7, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl, a (C6-C30)aryl or a (3- to 30-membered)heteroaryl; the arylene and the heteroarylene of L1 and the alkyl, the cycloalkyl, the aryl and the heteroaryl of Ar1, Ar2, and R1 to R9 may be further substituted with at least one selected from the group consisting of deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a (C6-C30)aryl, a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, a di(C1-C30)alkylamino, a di(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, and a (C1-C30)alkyl(C6-C30)aryl.
More specifically, L1 represents a single bond, phenylene, biphenylene, terphenylene, indenylene, fluorenylene, triphenylenylene, pyrenylene, perylenylene, chrysenylene, naphthacenylene, fluoranthenylene, thiophenylene, pyrrolylene, pyrazolylene, thiazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, furazanylene, pyridylene, benzofuranylene, benzothiophenylene, indolylene, benzoimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoxazolylene, benzothiadiazolylene, dibenzofuranylene or dibenzothiophenylene; Ar1 and Ar2, each independently, represent hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, biphenyl, fluorenyl, fluoranthenyl, terphenylyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzoimidazolyl, quinolyl, triazinyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, pyrazolyl, indolyl, carbazolyl, thiazolyl, oxazolyl, benzothiazolyl, benzoxazolyl, phenanthrolinyl, or quinoxalinyl; R1 and R2, each independently, represent hydrogen, deuterium, chloro, fluoro, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, naphthyl, anthryl, biphenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzoimidazolyl, indenyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, triazinyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, pyrazolyl, indolyl, carbazolyl, thiazolyl, oxazolyl, benzothiazolyl, benzoxazolyl, phenanthrolinyl, dimethylamino, diethylamino, methylphenylamino, diphenylamino, trimethylsilyl, triethylsilyl, tripropylsilyl, tri(t-butyl)silyl, t-butyldimethylsilyl, dimethylphenylsilyl or triphenylsilyl; the groups of L1, Ar1, Ar2, R1 and R2 may be further substituted with at least one selected from the group consisting of deuterium, chloro, fluoro, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, naphthyl, biphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzoimidazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, triazinyl, benzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzothiophenyl, pyrazolyl, indolyl, carbazolyl, thiazolyl, oxazolyl, benzothiazolyl, benzoxazolyl, phenanthrolinyl, dimethylamino, diethylamino, methylphenylamino, diphenylamino, trimethylsilyl, triethylsilyl, tripropylsilyl, tri(t-butyl)silyl, t-butyldimethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, N-carbazolyl, and N-phenylcarbazolyl.
Even more specifically, organic electroluminescent compounds of formula 1 of the present invention include the following, but are not limited thereto:
Figure PCTKR2013012123-appb-I000002
Figure PCTKR2013012123-appb-I000003
Figure PCTKR2013012123-appb-I000004
Figure PCTKR2013012123-appb-I000005
Figure PCTKR2013012123-appb-I000006
Figure PCTKR2013012123-appb-I000007
Figure PCTKR2013012123-appb-I000008
Figure PCTKR2013012123-appb-I000009
Figure PCTKR2013012123-appb-I000010
Figure PCTKR2013012123-appb-I000011
Figure PCTKR2013012123-appb-I000012
Figure PCTKR2013012123-appb-I000013
Figure PCTKR2013012123-appb-I000014
Figure PCTKR2013012123-appb-I000015
Figure PCTKR2013012123-appb-I000016
Figure PCTKR2013012123-appb-I000017
Figure PCTKR2013012123-appb-I000018
Figure PCTKR2013012123-appb-I000019
Figure PCTKR2013012123-appb-I000020
Figure PCTKR2013012123-appb-I000021
Figure PCTKR2013012123-appb-I000022
Figure PCTKR2013012123-appb-I000023
Figure PCTKR2013012123-appb-I000024
Figure PCTKR2013012123-appb-I000025
Figure PCTKR2013012123-appb-I000026
Figure PCTKR2013012123-appb-I000027
Figure PCTKR2013012123-appb-I000028
The organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1.
[Reaction Scheme 1]
Figure PCTKR2013012123-appb-I000029
In reaction scheme 1, L1, X1, X2, Ar1 to Ar3, R1, R2, a, and b are as defined in formula 1 above, and Hal represents a halogen.
The present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
The material may consist of the organic electroluminescent compound of formula 1. Otherwise, the material may further comprise a conventional compound(s) which has been comprised of an organic electroluminescent material, in addition to the compound of formula 1.
The organic electroluminescent device may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
Furthermore, the organic layer may comprise a light-emitting layer in which the organic electroluminescent compound of formula 1 may be comprised as a host material, and if needed, another compound(s) other than the compound of formula 1 may be further comprised.
In addition, a phosphorescent dopant, which is used for an organic electroluminescent device together with the host material according to the present invention, may be selected from the compounds represented by the following formula 2:
Figure PCTKR2013012123-appb-I000030
wherein
M1 is selected from the group consisting of Ir, Pt, Pd and Os;
L101, L102 and L103 are each independently selected from the following structures:
Figure PCTKR2013012123-appb-I000031
Figure PCTKR2013012123-appb-I000032
Figure PCTKR2013012123-appb-I000033
Figure PCTKR2013012123-appb-I000034
R201 to R203, each independently, represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl, or a halogen;
R204 to R219, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, SF5, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a cyano or a halogen;
R220 to R223, each independently, represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen, or a (C6-C30)aryl unsubstituted or substituted with a (C1-C30)alkyl;
R224 and R225, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a halogen, or R224 and R225 may be linked with an adjacent substituent(s) to form a (C5-C30), mono- or polycyclic, alicyclic or aromatic ring;
R226 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- or 30-membered) heteroaryl or a halogen;
R227 to R229, each independently, represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl or a halogen;
Q represents
Figure PCTKR2013012123-appb-I000035
or
Figure PCTKR2013012123-appb-I000036
R231 to R242 each independently represent hydrogen, deuterium, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a (C1-C30)alkoxy, a halogen, a substituted or unsubstituted (C6-C30)aryl, a cyano, or a substituted or unsubstituted (C5-C30)cycloalkyl, or may be linked with an adjacent substituent(s) via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked with R207 or R208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
Specifically, the following compounds are preferred as the dopants of formula 2, but the dopants of formula 2 are not limited thereto:
Figure PCTKR2013012123-appb-I000037
Figure PCTKR2013012123-appb-I000038
Figure PCTKR2013012123-appb-I000039
Figure PCTKR2013012123-appb-I000040
Figure PCTKR2013012123-appb-I000041
Figure PCTKR2013012123-appb-I000042
Figure PCTKR2013012123-appb-I000043
Figure PCTKR2013012123-appb-I000044
Figure PCTKR2013012123-appb-I000045
Figure PCTKR2013012123-appb-I000046
Figure PCTKR2013012123-appb-I000047
Figure PCTKR2013012123-appb-I000048
Figure PCTKR2013012123-appb-I000049
Figure PCTKR2013012123-appb-I000050
Figure PCTKR2013012123-appb-I000051
Figure PCTKR2013012123-appb-I000052
Figure PCTKR2013012123-appb-I000053
Figure PCTKR2013012123-appb-I000054
Figure PCTKR2013012123-appb-I000055
Figure PCTKR2013012123-appb-I000056
Figure PCTKR2013012123-appb-I000057
Furthermore, the present invention provides a composition for preparing an organic electroluminescent device. The composition may comprise the compound of the present invention as a host material.
The organic electroluminescent device of the present invention comprises a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer comprises a light-emitting layer in which the composition of the present invention may be comprised.
The organic electroluminescent device of the present invention comprises the organic electroluminescent compound of formula 1 of the present invention, and may further comprise at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present invention, the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising said metal. The organic layer may comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device of the present invention may emit white light by further comprising at least one light-emitting layer, which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound, besides the compound of the present invention.
In the organic electroluminescent device of the present invention, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device of the present invention, 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 may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds, and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the organic electroluminescent compound, the preparation method of the compound, and the luminescent characteristics of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound C-27
Figure PCTKR2013012123-appb-I000058
Preparation of compound 1-2
Compound 1-1 (18.5 g, 66 mmol), 2,5-dibromonitrobenzene (18 g, 72.6 mmol), Na2CO3 (16.8 g, 158.4 mmol), and Pd(PPh3)4 (3.8 g, 3.3 mmol) were added to a mixture of toluene (320 mL), ethanol (80 mL), and purified water (80 mL). The mixture was stirred at 90-100 ℃ for 3 hours. After completing the reaction, the mixture was stood to remove an aqueous layer. The organic layer was concentrated, was subjected to trituration with methylene chloride (MC), and was filtered to obtain compound 1-2 (19 g, 71.2%).
Preparation of compound 1-3
Compound 1-2 (10 g, 24.7 mmol), phenylboronic acid (3.6 g, 29.7 mmol), Na2CO3 (7.8 g, 74.1 mmol) and Pd(PPh3)4 (1.4 g, 1.2 mmol) were added to a mixture of toluene (150 mL), ethanol (37 mL), and purified water (37 mL). The mixture was stirred at 90-100 ℃ for 3 hours. After completing the reaction, the mixture was cooled to room temperature, and then was stood to remove an aqueous layer. The organic layer was concentrated, was subjected to trituration with MC, and was filtered to obtain compound 1-3 (9 g, 90.9%).
Preparation of compound 1-4
Compound 1-3 (9 g, 22.4 mmol) was dissolved in P(OEt)3 (100 mL). The mixture was stirred at 160 ℃ for a day, and then was distilled under vacuum to remove P(OEt)3. Thereafter, the mixture was extracted with MC and distilled water, was subjected to trituration with MC, and then was filtered to obtain compound 1-4 (4.9 g, 60%).
Preparation of compound C-27
After suspending compound 1-4 (4.0 g, 10.83 mmol) and compound 1-5 (3.1 g, 11.91 mmol) in dimethylformamide (DMF) (80 mL), 60% NaH (702 mg, 16.1 mmol) was added to the mixture at room temperature. Thereafter, the mixture was stirred for 12 hours, and then purified water (1L) was added thereto. After a filteration under reduced pressure, the obtained solids was subjected to trituration with methanol/ethylacetate (EA), was dissolved in MC, was filtered through silica, and then was subjected to trituration with MC/n-hexane to obtain compound C-27 (4.5 g, 69%).
MW : 600.71, UV : 382 nm, PL : 493 nm, melting point : 324 ℃
Example 2: Preparation of compound C-28
Figure PCTKR2013012123-appb-I000059
Preparation of compound 2-2
Compound 2-2 (14.2 g, 41%) was prepared in the same manner as in the preparation of compound 1-2 of Example 1 by using compound 2-1 (22 g, 128.16 mmol) and 2,5-dibromonitrobenzene (30 g, 106.80 mmol).
Preparation of compound 2-3
Compound 2-3 (12 g, 92%) was prepared in the same manner as in the preparation of compound 1-2 of Example 1 by using compound 2-2 (14.2 g, 43.27 mmol) and phenylboronic acid (5.3 g, 43.27 mmol).
Preparation of compound 2-4
After dissolving compound 2-3 (12 g, 36.88 mmol) in triethylphosphate (120 mL), compound 2-4 (6.4 g, 62%) was prepared in the same manner as in the preparation of compound 1-3 of Example 1.
Preparation of compound C-28
Compound C-28 (6.4 g, 58%) was prepared in the same manner as in the preparation of compound C-27 of Example 1 by using compound 2-4 (6.4 g, 21.81 mmol) and compound 2-5 (5.8 g, 23.99 mmol).
MW : 524.61, UV : 334 nm, PL : 495 nm, melting point: 273 ℃
Example 3: Preparation of compound C-29
Figure PCTKR2013012123-appb-I000060
Compound C-29 (6.5 g, 81%) was prepared in the same manner as in the preparation of compound C-27 of Example 1 by using compound 2-5 (3.6 g, 13.4 mmol) and compound 1-4 (4.8 g, 13.4 mmol).
MW : 600.71, UV : 334 nm, PL : 385 nm, melting point: 349 ℃
Example 4: Preparation of compound C-54
Figure PCTKR2013012123-appb-I000061
Compound C-54 (6.0 g, 60%) was prepared in the same manner as in the preparation of compound C-27 of Example 1 by using compound 4-1 (6.4 g, 17.30 mmol) and compound 2-5 (5.1 g, 19.10 mmol).
MW : 676.81, UV : 344 nm, PL : 495 nm, melting point: 336 ℃
Example 5: Preparation of compound C-56
Figure PCTKR2013012123-appb-I000062
Figure PCTKR2013012123-appb-I000063
Preparation of compound 5-2
After dissolving compound 5-1 (35 g, 86.60 mmol) in triethylphosphate (350 mL), compound 5-2 (7.0 g, 22%) was prepared in the same manner as in the preparation of compound 1-4 of Example 1.
Preparation of compound 5-3
Compound 5-3 (7.6 g, 92%) was prepared in the same manner as in the preparation of compound 1-2 of Example 1 by using compound 5-2 (7.0 g, 18.80 mmol) and [1,1'-biphenyl]-4-yl boronic acid (4.1 g, 20.70 mmol).
Preparation of compound C-56
Compound C-56 (4 g, 70%) was prepared in the same manner as in the preparation of compound C-27 of Example 1 by using compound 5-3 (3.8 g, 8.53 mmol) and compound 2-5 (2.5 g, 9.38 mmol).
MW : 599.72, UV : 324 nm, PL : 485 nm, melting point: 264 ℃
Example 6: Preparation of compound C-83
Figure PCTKR2013012123-appb-I000064
Preparation of compound 6-1
After dissolving compound 2-4 (3.7 g, 13 mmol) and cyanuric acid (12 g, 63 mmol) in tetrahydrofuran (THF) (300 mL), compound 6-1 (4.3 g, 77%) was prepared in the same manner as in the preparation of compound C-27 of Example 1.
Preparation of compound C-83
Compound C-83 (37 g, 62%) was prepared in the same manner of in the preparation of compound 1-2 of Example 1 by using compound 6-1 (4 g, 9 mmol) and 3-biphenyl boronic acid (7.2 g, 36 mmol).
MW : 599.72, UV : 324 nm, PL : 485 nm, melting point: 264 ℃
[Device Example 1] Production of an OLED device using the organic
electroluminescent compound of the present invention
OLED device was produced using the compound of the present invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound C-28 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-11 was introduced into another cell as a dopant. The two materials were evaporated at different rates, so that the dopant was deposited in a doping amount of 4 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. 2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate, so that they were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. After depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the material used for producing the OLED device were those purified by vacuum sublimation at 10-6 torr.
The produced OLED device showed red emission having a luminance of 1,030 cd/m2 and a current density of 8.7 mA/cm2 at a driving voltage of 4.1 V. The time taken to be reduced to 90% of the luminance at 5,000 nit was 60 hours or more.
[Device Example 2] Production of an OLED device using the organic
electroluminescent compound of the present invention
OLED device was produced in the same manner as in Device Example 1, except for using compound C-29 as a host material and compound D-7 as a dopant to form a light-emitting layer.
The produced OLED device showed red emission having a luminance of 980 cd/m2 and a current density of 5.5 mA/cm2 at a driving voltage of 3.8 V. The time taken to be reduced to 90% of the luminance at 5,000 nit was 90 hours or more.
[Device Example 3] Production of an OLED device using the organic
electroluminescent compound of the present invention
OLED device was produced in the same manner as in Device Example 1, except for using compound C-54 as a host material and compound D-11 as a dopant to form a light-emitting layer.
The produced OLED device showed red emission having a luminance of 1,020 cd/m2 and a current density of 11.0 mA/cm2 at a driving voltage of 3.7 V. The time taken to be reduced to 90% of the luminance at 5,000 nit was 60 hours or more.
[Device Example 4] Production of an OLED device using the organic
electroluminescent compound of the present invention
OLED device was produced in the same manner as in Device Example 1, except for using compound C-83 as a host material and compound D-11 as a dopant to form a light-emitting layer.
The produced OLED device showed red emission having a luminance of 950 cd/m2 and a current density of 10.7 mA/cm2 at a driving voltage of 3.8 V. The time taken to be reduced to 90% of the luminance at 5,000 nit was 75 hours or more.
[Device Example 5] Production of an OLED device using the organic
electroluminescent compound of the present invention
OLED device was produced in the same manner as in Device Example 1, except for using compound C-56 as a host material and compound D-7 as a dopant to form a light-emitting layer.
The produced OLED device showed red emission having a luminance of 980 cd/m2 and a current density of 7.2 mA/cm2 at a driving voltage of 3.5 V. The time taken to be reduced to 90% of the luminance at 5,000 nit was 90 hours or more.
[Device Example 6] Production of an OLED device using the organic
electroluminescent compound of the present invention
OLED device was produced in the same manner as in Device Example 1, except for using compound C-27 as a host material and compound D-7 as a dopant to form a light-emitting layer.
The produced OLED device showed red emission having a luminance of 1,050 cd/m2 and a current density of 6.6 mA/cm2 at a driving voltage of 3.7 V. The time taken to be reduced to 90% of the luminance at 5,000 nit was 90 hours or more.
[Comparative Device Example 1] Production of an OLED device by using
conventional organic electroluminescent compounds
An OLED device was produced in the same manner as in Device Example 1, except for using compound A-1 shown below as a host material and compound D-11 as a dopant to form a light-emitting layer.
The produced OLED device showed red emission having a luminance of 1,000 cd/m2 and a current density of 10.6 mA/cm2 at a driving voltage of 4.7 V. The time taken to be reduced to 90% of the luminance at 5,000 nit was 20 hours or more.
Figure PCTKR2013012123-appb-I000065
The organic electroluminescent compound of the present invention can produce an organic electroluminescent device having an excellent lifespan and a lowered driving voltage so that power efficiency is improved. Furthermore, by using the compound of the present invention, it is possible to omit a hole blocking layer which has been necessary for an organic electroluminescent device using a conventional compound.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2013012123-appb-I000066
    wherein
    L1 represents a single bond, a substituted or unsubstituted (3- to 30-membered) heteroarylene, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (C6-C30)cycloalkylene;
    X1 and X2, each independently, represent -CH- or -N-;
    Ar1 and Ar2, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    Ar3 represents a substituted or unsubstituted (C6-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted hexahydrocarbazole, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    R1 and R2, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR3R4, -SiR5R6R7, -SR8, -OR9, a cyano, a nitro or a hydroxyl;
    R3 to R9, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (5- to 7-membered)heterocycloalkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    a represents an integer of 1 to 6; b represents an integer of 1 to 3; where a or b represents an integer of 2 or more, each of R1 or R2 may be the same or different; and
    the heteroarylene, the heterocycloalkyl and the heteroaryl, each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P.
  2. The organic electroluminescent compound according to claim 1, wherein the substituents for the substituted groups of L1, Ar1 to Ar3, and R1 to R9, each independently, are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen; a (C1-C30)alkoxy; a (C6-C30)aryl; a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl; a (C3-C30)cycloalkyl; a (5- to 7-membered) heterocycloalkyl; a tri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; a di(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a cyano; a di(C1-C30)alkylamino; a di(C6-C30)arylamino; a (C1-C30)alkyl(C6-C30)arylamino; a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a (C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; a (C1-C30)alkyl(C6-C30)aryl; a carboxyl; a nitro; and a hydroxyl.
  3. The organic electroluminescent compound according to claim 1, wherein
    L1 represents a single bond, or a substituted or unsubstituted (C6-C20)arylene;
    X1 and X2, each independently, represent -CH- or -N-;
    Ar1 and Ar2, each independently, represent hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl;
    Ar3 represents a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted hexahydrocarbazole, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and
    R1 and R2, each independently, represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl.
  4. The organic electroluminescent compound according to claim 1, wherein
    L1 represents a single bond, or an (C6-C15)arylene unsubstituted or substituted with a (C1-C6)alkyl;
    X1 and X2, each independently, represent -CH- or -N-;
    Ar1 and Ar2, each independently, represent hydrogen; a (C1-C6)alkyl; a (C6-C19)aryl unsubstituted or substituted with deuterium, a halogen, a (C1-C6)alkyl, a (C1-C6)alkoxy, a (5- to 15-membered)heteroaryl, a tri(C6-C10)arylsilyl, a (C1-C6)alkyldi(C6-C10)arylsilyl, a di(C6-C10)arylamino, or a (C1-C6)alkyl(C6-C15)aryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl;
    Ar3 represents a (C6-C19)aryl unsubstituted or substituted with a (C1-C6)alkyl, a (5- to 15-membered)heteroaryl, or a di(C6-C10)arylamino; a hexahydrocarbazole unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C10)aryl; or a (5- to 19-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl; and
    R1 and R2, each independently, represent hydrogen, a (C1-C6)alkyl, a (C6-C19)aryl unsubstituted or substituted with a (C1-C6)alkyl, or a (5- to 19-membered)heteroaryl unsubstituted or substituted with a (C6-C10)aryl.
  5. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is selected from the group consisting of:
    Figure PCTKR2013012123-appb-I000067
    Figure PCTKR2013012123-appb-I000068
    Figure PCTKR2013012123-appb-I000069
    Figure PCTKR2013012123-appb-I000070
    Figure PCTKR2013012123-appb-I000071
    Figure PCTKR2013012123-appb-I000072
    Figure PCTKR2013012123-appb-I000073
    Figure PCTKR2013012123-appb-I000074
    Figure PCTKR2013012123-appb-I000075
    Figure PCTKR2013012123-appb-I000076
    Figure PCTKR2013012123-appb-I000077
    Figure PCTKR2013012123-appb-I000078
    Figure PCTKR2013012123-appb-I000079
    Figure PCTKR2013012123-appb-I000080
    Figure PCTKR2013012123-appb-I000081
    Figure PCTKR2013012123-appb-I000082
    Figure PCTKR2013012123-appb-I000083
    Figure PCTKR2013012123-appb-I000084
    Figure PCTKR2013012123-appb-I000085
    Figure PCTKR2013012123-appb-I000086
    Figure PCTKR2013012123-appb-I000087
    Figure PCTKR2013012123-appb-I000088
    Figure PCTKR2013012123-appb-I000089
    Figure PCTKR2013012123-appb-I000090
    Figure PCTKR2013012123-appb-I000091
    Figure PCTKR2013012123-appb-I000092
    Figure PCTKR2013012123-appb-I000093
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2013/012123 2012-12-24 2013-12-24 Organic electroluminescent compounds and organic electroluminescent device comprising the same Ceased WO2014104720A1 (en)

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