WO2013032297A1 - Benzocarbazole compounds and electroluminescent devices involving them - Google Patents

Benzocarbazole compounds and electroluminescent devices involving them Download PDF

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WO2013032297A1
WO2013032297A1 PCT/KR2012/007022 KR2012007022W WO2013032297A1 WO 2013032297 A1 WO2013032297 A1 WO 2013032297A1 KR 2012007022 W KR2012007022 W KR 2012007022W WO 2013032297 A1 WO2013032297 A1 WO 2013032297A1
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group
substituted
alkyl
unsubstituted
aryl
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PCT/KR2012/007022
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French (fr)
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Hyo-Jung Lee
Hye-Mi Kim
Soo-Yong Lee
Kyoung-Jin Park
Su-Hyun Lee
Hee-Choon Ahn
Nam-Kyun Kim
Jong-seok KU
Hyuck-Joo Kwon
Kyung-Joo Lee
Bong-Ok Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority to JP2014528295A priority Critical patent/JP2014531420A/en
Priority to CN201280050907.8A priority patent/CN103889975A/en
Publication of WO2013032297A1 publication Critical patent/WO2013032297A1/en

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Definitions

  • the present invention relates to novel organic electroluminescence compounds and organic electroluminescence device comprising the same.
  • n electroluminescence (EL) device is a self-light-emitting device which has advantages over other types of display devices in that it provides a wider viewing angle, a greater contrast ratio, and has a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small molecules which are aromatic diamines, and aluminum complexes as a material for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • 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 materials, respectively.
  • phosphorescent materials are being researched in Japan, Europe and U.S.A. recently.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • Pioneer (Japan) et al. developed a high performance organic EL device employing a derivative of BAlq as a host material.
  • an organic EL device Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum.
  • the power efficiency of an organic EL device is given by [( ⁇ /voltage) ⁇ current efficiency], and the power efficiency is inversely proportional to voltage, and thus in order to lower the power consumption, the power efficiency should be raised.
  • an organic EL device comprising phosphorescent materials provides much higher current efficiency (cd/A) than one comprising fluorescent materials
  • an organic EL device using conventional phosphorescent materials such as BAlq or CBP has a higher driving voltage than that using fluorescent materials.
  • the EL device using the conventional phosphorescent materials has no advantage in terms of power efficiency (lm/W). Further, the operation lifetime of the organic EL device is short.
  • Korean Patent Application Laying-Open No. 2010-0023783 discloses a carbazole compound substituted with an amine group and a green fluorescent organic EL device using the carbazole compound as a hole transport material. Further, said document also discloses a benzocarbazole compound substituted with a carbazole group and a phosphorescent organic EL device using the benzocarbazole compound as a host material. However, the device showed green emission.
  • Japanese Patent Application Laying-Open No. 2000-286056 discloses a carbazole compound to which an aromatic ring is condensed, and an organic EL device comprising a polymer of the compound. However, the device showed green or orange emission.
  • Japanese Patent Application Laying-Open No. 1999-144866 discloses a dicarbazole compound and an organic EL devise comprising the same. However, it discloses only the use of the compound as a hole transmitting material.
  • the objective of the present invention is to provide an organic electroluminescence compound imparting high luminous efficiency and a long operation lifetime to a device, and having proper color coordination; and an organic electroluminescence device having high efficiency and a long lifetime, using said compound as a light-emitting material.
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 3- to 30-membered heteroarylene group;
  • Ar 1 to Ar 3 each independently represent CR 11 or N, proviso that Ar 1 to Ar 3 do not simultaneously represent CH;
  • X represents -O-, -S-, -CR 12 R 13 -, or -NR 14 -;
  • R 1 , R 2 , R 11 , Ar 1 and Ar 2 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, -NR 15 R 16 , -SiR 17 R 18 R 19 , -SR 20 , -OR 21 , a cyano group, or a nitro group;
  • R 12 to R 14 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
  • R 15 to R 21 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (C5-C30)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; where a is an integer of 2 or more, each of R1 is the same or different
  • b represents an integer of 1 to 3; where b is an integer of 2 or more, each of R2 is the same or different;
  • the organic electroluminescence compounds according to the present invention have high luminous efficiency and long operation lifetime. Therefore, they can produce an organic electroluminescence device having enhanced power consumption efficiency.
  • the present invention relates to an organic electroluminescence compound represented by the above formula 1, an organic electroluminescence material comprising the organic electroluminescence compound, and an organic electroluminescence device comprising the material.
  • (C1-C30)alkyl(ene) is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.;
  • (C2-C30) alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • “(C2-C30)alkynyl” is a linear or branched alkynyl having 2 to 30 carbon atoms, in which
  • 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.
  • Substituents of the substituted alkyl group, the substituted aryl(ene) group, the substituted heteroaryl(ene) group, the substituted cycloalkyl(ene) group, the substituted heterocycloalkyl group and the substituted aralkyl group in L 1 , R 1 , R 2 , R 11 to R 21 , Ar 1 , and Ar 2 groups of formula 1, each independently are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group substituted or unsubstituted with a halogen; a (C6-C30)aryl group; a 3- to 30-membered heteroaryl group substituted or unsubstituted with a (C1-C30)alkyl and/or a (C6-C30)aryl; a (C3-C30)cycloalkyl group; a 5- to 7-membered heterocycloalkyl group; a
  • the organic electroluminescence compound according to the present invention is represented by the following formulae 2 or 3:
  • X, R 1 , R 2 , a, b, L 1 , A 1 to A 3 , Ar 1 , and Ar 2 are as defined in formula 1 above.
  • organic electroluminescence compound according to the present invention is represented by the following formulae 4 to 9:
  • X, R 1 , R 2 , a, b, L 1 , A 1 to A 3 , Ar 1 , and Ar 2 are as defined in formula 1 above.
  • L 1 represents a single bond or a (C6-C30)arylene group
  • Ar 1 to Ar 3 each independently represent CR 11 or N, proviso that Ar 1 to Ar 3 do not simultaneously represent CH
  • X represents -NR 14 -
  • R 11 represents hydrogen, deuterium, a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group
  • R 14 represents a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group
  • R 1 , R 2 , Ar 1 and Ar 2 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group.
  • the arylene of L 1 , and the alkyl, aryl, and heteroaryl of R 1 , R 2 , R 11 , R 14 , Ar 1 and Ar 2 may be substituted with at least one selected from the group consisting of deuterium, a halogen, a (C1-C30)alky, a halo(C1-C30)alkyl, a (C6-C30)aryl, a 3- to 30-membered heteroaryl group, a 3- to 30-membered heteroaryl group substituted with a (C6-C30)aryl and/or a (C1-C30)alkyl, a (C3-C30)cycloalkyl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl group, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi
  • L1 represents a single bond, phenylene, naphthylene, biphenylene, terphenylene, anthrylene, indenylene, fluorenylene, phenanthrylene, triphenylenylene, pyrenylene, perylenylene, crysenylene, naphthacenylene, fluoranthenylene, phenylene-naphthylene, furylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, furazanylene, pyridylene, pyrazinylene, pyrimidinylene, pyridazinylene, benzofuranylene, benzothiophenylene, isobenzofur
  • R 1 , R 2 , R 11 , Ar 1 and Ar 2 each independently represent hydrogen, a halogen, a (C1-C30)alkyl, or a group selected from the following:
  • R 21 to R 28 each independently represent a halogen, a (C1-C30)alkyl, a (C6-C30)aryl, a 3- to 30-membered heteroaryl, or a (C3-C30)cycloalkyl.
  • the organic electroluminescence compounds of the present invention include the following compounds:
  • the present invention provides an organic electroluminescence material comprising the organic electroluminescence compound of formula 1, and an organic electroluminescence device comprising the material.
  • the above material can be comprised of the organic electroluminescence compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescence materials.
  • Said organic electroluminescence device comprises a first electrode, a second electrode, and at least one organic layer between said first and second electrodes.
  • Said organic layer comprises at least one compound of formula 1 according to the present invention.
  • said organic layer comprises a light-emitting layer in which the compound of formula 1 is comprised as a host material.
  • the layer comprises at least one phosphorescent dopant.
  • the phosphorescent dopant for an organic electroluminescence device of the present invention is not specifically limited, but the phosphorescent dopant, which is used for an organic electroluminescence device according to the present invention, may be selected from compounds represented by the following formula 10:
  • R 201 to R 203 each independently represent hydrogen, deuterium, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a (C6-C30)aryl group unsubstituted or substituted with (C1-C30)alkyl group(s), or a halogen;
  • R 204 to R 219 each independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino group, a substituted or unsubstituted mono- or di-(C6-C30)arylamino group, SF 5 , a substituted or unsubstituted tri(C1-C30)alkylsilyl group, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)aryl
  • R 220 to R 223 each independently represent hydrogen, deuterium, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), or a (C6-C30)aryl group unsubstituted or substituted with (C1-C30)alkyl group(s);
  • R 224 and R 225 each independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a halogen, or R 224 and R 225 are linked to an adjacent substituent(s) to form a mono- or polycyclic, (C5-C30)alicyclic or aromatic ring;
  • R 226 represents a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- or 30-membered heteroaryl group or a halogen;
  • R 227 to R 229 each independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group or a halogen;
  • R 231 to R 242 each independently represent hydrogen, deuterium, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a (C1-C30)alkoxy group, a halogen, a substituted or unsubstituted (C6-C30)aryl group, a cyano group, or a substituted or unsubstituted (C5-C30)cycloalkyl group, or each of R 231 to R 242 may be linked to an adjacent substituent via alkylene group or alkenylene group to form a spiro ring or a fused ring or may be linked to R 207 or R 208 via alkylene group or alkenylene group to form a saturated or unsaturated fused ring.
  • the dopants of formula 10 preferably include the following:
  • the organic electroluminescence device may further comprise, in addition to the compounds represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise 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 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 electroluminescence device 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 according to the present invention.
  • a surface layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s).
  • a chalcogenide(includes oxides) layer of silicon or aluminum is placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer.
  • Such a surface layer provides operation stability for the organic electroluminescence device.
  • said chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and said metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an 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; 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 electroluminescence device having two or more electroluminescent layers and emitting white light.
  • N-bromosuccinimide (16.3 g, 92 mmol) was slowly added to the reaction mixture and the reaction mixture was stirred for 24 hours. After completing the reaction, the organic layer was extracted EA and was dried with MgSO 4 to remove the remaining moisture. The obtained organic layer was separated through column to obtain compound 3-3 (23.5 g, 87 %).
  • reaction mixture was quenched by adding 1M HCl, and the organic layer was extracted with distilled water and EA, and was dried with MgSO 4 to remove the remaining moisture.
  • the obtained organic layer was recrystallized with MC and Hex to obtain compound 4-2 (16.5 g, 71 %).
  • An OLED device was produced using the compound according to 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. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(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 introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • compound A-1 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material
  • compound D-7 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and deposited in a doping amount of 4 wt% of the dopant, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate (Liq) was introduced into another cell.
  • Liq lithium quinolate
  • the two materials were evaporated at the same rate and were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30nm on the light-emitting layer. Then, 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 deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
  • the produced OLED device showed red emission having a luminance of 740 cd/m 2 and a current density of 5.3 mA/cm 2 at a driving voltage of 5.9 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 100 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound A-47 as a host material and compound D-7 as a dopant.
  • the produced OLED device showed red emission having a luminance of 1430 cd/m 2 and a current density of 12.31 mA/cm 2 at a driving voltage of 3.5 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 80 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound A-48 as a host material and compound D-11 as a dopant.
  • the produced OLED device showed red emission having a luminance of 835 cd/m 2 and a current density of 13.6 mA/cm 2 at a driving voltage of 3.0 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 30 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound A-49 as a host material and compound D-7 as a dopant.
  • the produced OLED device showed red emission having a luminance of 2100 cd/m 2 and a current density of 16.2 mA/cm 2 at a driving voltage of 6.1 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 70 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound B-1 as a host material and compound D-7 as a dopant.
  • the produced OLED device showed red emission having a luminance of 1010 cd/m 2 and a current density of 6.6 mA/cm 2 at a driving voltage of 3.8 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 50 hours.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound B-39 as a host material and compound D-11 as a dopant.
  • the produced OLED device showed red emission having a luminance of 420 cd/m 2 and a current density of 5.46 mA/cm 2 at a driving voltage of 2.9 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 20 hours.
  • Comparative Example 1 Production of an OLED device using conventional electroluminescent compounds
  • An OLED device was produced in the same manner as in Device Example 1, except that a light-emitting layer was deposited by using 4,4’-bis(carbazol-9-yl)biphenyl (CBP) as a host material and compound D-7 as a dopant, and between the light-emitting layer and the electron transport layer, a hole blocking layer having a thickness of 10 nm was deposited by using bis(2-methyl-8-quinolinato)(p-phenylphenolato)aluminum(III) (Balq).
  • CBP 4,4’-bis(carbazol-9-yl)biphenyl
  • the produced OLED device showed red emission having a luminance of 1000 cd/m 2 and a current density of 14.1 mA/cm 2 at a driving voltage of 7.8 V.
  • Comparative Example 2 Production of an OLED device using conventional electroluminescent compounds
  • An OLED device was produced in the same manner as in Device Example 1, except that a light-emitting layer was deposited by using 4,4’-bis(carbazol-9-yl)biphenyl (CBP) as a host material and compound D-11 as a dopant, and between the light-emitting layer and the electron transport layer, a hole blocking layer having a thickness of 10 nm was deposited by using bis(2-methyl-8-quinolinato)(p-phenylphenolato)aluminum(III) (Balq).
  • CBP 4,4’-bis(carbazol-9-yl)biphenyl
  • the produced OLED device showed red emission having a luminance of 1000 cd/m 2 and a current density of 20.4 mA/cm 2 at a driving voltage of 8.2 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least10 hours.
  • the organic electroluminescence compounds of the present invention have superior luminous characteristics than the conventional materials.
  • a device using the organic electroluminescence compounds according to the present invention as a host material not only has excellent luminous characteristics, but also increases power efficiency by reducing the driving voltage.

Abstract

The present invention relates to novel organic electroluminescence compounds and an organic electroluminescence device containing the same. The compounds according to the present invention have high luminous efficiency and long operation lifetime. Therefore, they can produce an organic electroluminescence device having enhanced power consumption efficiency.

Description

NOVEL ORGANIC ELECTROLUMINESCENCE COMPOUNDS AND ORGANIC ELECTROLUMINESCENCE DEVICE COMPRISING THE SAME
The present invention relates to novel organic electroluminescence compounds and organic electroluminescence device comprising the same.
n electroluminescence (EL) device is a self-light-emitting device which has advantages over other types of display devices in that it provides a wider viewing angle, a greater contrast ratio, and has a faster response time. An organic EL device was first developed by Eastman Kodak, by using small molecules which are aromatic diamines, and aluminum complexes as a material for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor to determine luminous efficiency in an organic EL device is a light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, developing phosphorescent materials is one of the best methods to theoretically enhance the luminous efficiency by four (4) times. 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 materials, respectively. Especially, many phosphorescent materials are being researched in Japan, Europe and U.S.A. recently.
Until now, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent substances. Further, an organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) for a hole blocking layer is known, and Pioneer (Japan) et al. developed a high performance organic EL device employing a derivative of BAlq as a host material.
Though these materials provide good light-emitting characteristics, they have the following disadvantages. Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. The power efficiency of an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to voltage, and thus in order to lower the power consumption, the power efficiency should be raised. Although an organic EL device comprising phosphorescent materials provides much higher current efficiency (cd/A) than one comprising fluorescent materials, an organic EL device using conventional phosphorescent materials such as BAlq or CBP has a higher driving voltage than that using fluorescent materials. Thus, the EL device using the conventional phosphorescent materials has no advantage in terms of power efficiency (lm/W). Further, the operation lifetime of the organic EL device is short.
Korean Patent Application Laying-Open No. 2010-0023783 discloses a carbazole compound substituted with an amine group and a green fluorescent organic EL device using the carbazole compound as a hole transport material. Further, said document also discloses a benzocarbazole compound substituted with a carbazole group and a phosphorescent organic EL device using the benzocarbazole compound as a host material. However, the device showed green emission.
Japanese Patent Application Laying-Open No. 2000-286056 discloses a carbazole compound to which an aromatic ring is condensed, and an organic EL device comprising a polymer of the compound. However, the device showed green or orange emission.
Japanese Patent Application Laying-Open No. 1999-144866 discloses a dicarbazole compound and an organic EL devise comprising the same. However, it discloses only the use of the compound as a hole transmitting material.
The objective of the present invention is to provide an organic electroluminescence compound imparting high luminous efficiency and a long operation lifetime to a device, and having proper color coordination; and an organic electroluminescence device having high efficiency and a long lifetime, using said compound as a light-emitting material.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2012007022-appb-I000001
wherein
Z represents
Figure PCTKR2012007022-appb-I000002
;
L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 3- to 30-membered heteroarylene group;
Ar1 to Ar3 each independently represent CR11 or N, proviso that Ar1 to Ar3 do not simultaneously represent CH;
X represents -O-, -S-, -CR12R13-, or -NR14-;
R1, R2, R11, Ar1 and Ar2 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, -NR15R16, -SiR17R18R19, -SR20, -OR21, a cyano group, or a nitro group;
R12 to R14 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
R15 to R21 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (C5-C30)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; where a is an integer of 2 or more, each of R1 is the same or different
b represents an integer of 1 to 3; where b is an integer of 2 or more, each of R2 is the same or different;
the heterocycloalkyl group and the heteroaryl(ene) group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
The organic electroluminescence compounds according to the present invention have high luminous efficiency and long operation lifetime. Therefore, they can produce an organic electroluminescence device having enhanced power consumption 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 relates to an organic electroluminescence compound represented by the above formula 1, an organic electroluminescence material comprising the organic electroluminescence compound, and an organic electroluminescence device comprising the material.
Herein, “(C1-C30)alkyl(ene)” is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C2-C30) alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.; “(C2-C30)alkynyl” is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.; “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “3- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably O, S and N, and 3 to 7 ring backbone atoms, and includes tetrahydrofurane, pyrrolidine, thiolan, tetrahydropyran, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “3- to 30-membered heteroaryl(ene)” is an aryl group having at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, and 3 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; has preferably 5 to 20, more preferably 5 to 15 ring backbone atoms; 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 including 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 including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Further, “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.
Substituents of the substituted alkyl group, the substituted aryl(ene) group, the substituted heteroaryl(ene) group, the substituted cycloalkyl(ene) group, the substituted heterocycloalkyl group and the substituted aralkyl group in L1, R1, R2, R11 to R21, Ar1, and Ar2 groups of formula 1, each independently are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group substituted or unsubstituted with a halogen; a (C6-C30)aryl group; a 3- to 30-membered heteroaryl group substituted or unsubstituted with a (C1-C30)alkyl and/or a (C6-C30)aryl; a (C3-C30)cycloalkyl group; a 5- to 7-membered heterocycloalkyl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a cyano group; an N-carbazolyl group; a di(C1-C30)alkylamino group; a di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; a (C1-C30)alkyl(C6-C30)aryl group; a carboxyl group; a nitro group; and a hydroxyl group.
The organic electroluminescence compound according to the present invention is represented by the following formulae 2 or 3:
Figure PCTKR2012007022-appb-I000003
Figure PCTKR2012007022-appb-I000004
wherein
X, R1, R2, a, b, L1, A1 to A3, Ar1, and Ar2 are as defined in formula 1 above.
More specifically, the organic electroluminescence compound according to the present invention is represented by the following formulae 4 to 9:
Figure PCTKR2012007022-appb-I000005
Figure PCTKR2012007022-appb-I000006
Figure PCTKR2012007022-appb-I000007
Figure PCTKR2012007022-appb-I000008
Figure PCTKR2012007022-appb-I000009
Figure PCTKR2012007022-appb-I000010
wherein
X, R1, R2, a, b, L1, A1 to A3, Ar1, and Ar2 are as defined in formula 1 above.
More specifically, L1 represents a single bond or a (C6-C30)arylene group; Ar1 to Ar3 each independently represent CR11 or N, proviso that Ar1 to Ar3 do not simultaneously represent CH; X represents -NR14-; R11 represents hydrogen, deuterium, a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group; R14 represents a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group; and R1, R2, Ar1 and Ar2 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group. The arylene of L1, and the alkyl, aryl, and heteroaryl of R1, R2, R11, R14, Ar1 and Ar2 may be substituted with at least one selected from the group consisting of deuterium, a halogen, a (C1-C30)alky, a halo(C1-C30)alkyl, a (C6-C30)aryl, a 3- to 30-membered heteroaryl group, a 3- to 30-membered heteroaryl group substituted with a (C6-C30)aryl and/or a (C1-C30)alkyl, a (C3-C30)cycloalkyl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl group, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl group, a (C6-C30)aryl(C1-C30)alkyl group, and a (C1-C30)alkyl(C6-C30)aryl.
More specifically, L1 represents a single bond, phenylene, naphthylene, biphenylene, terphenylene, anthrylene, indenylene, fluorenylene, phenanthrylene, triphenylenylene, pyrenylene, perylenylene, crysenylene, naphthacenylene, fluoranthenylene, phenylene-naphthylene, furylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, furazanylene, pyridylene, pyrazinylene, pyrimidinylene, pyridazinylene, benzofuranylene, benzothiophenylene, isobenzofuranylene, benzoimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoxazolylene, isoindolylene, indolylene, indazolylene, benzothiadiazolylene, quinolylene, isoquinolylene, cinolynylene, quinazolinylene, quinoxalynylene, carbazolylene, phenanthrydinylene, benzodioxolylene, dibenzofuranylene, and dibenzocyophenylene.
Further, R1, R2, R11, Ar1 and Ar2 each independently represent hydrogen, a halogen, a (C1-C30)alkyl, or a group selected from the following:
Figure PCTKR2012007022-appb-I000011
Figure PCTKR2012007022-appb-I000012
Figure PCTKR2012007022-appb-I000013
wherein R21 to R28 each independently represent a halogen, a (C1-C30)alkyl, a (C6-C30)aryl, a 3- to 30-membered heteroaryl, or a (C3-C30)cycloalkyl.
The organic electroluminescence compounds of the present invention include the following compounds:
Figure PCTKR2012007022-appb-I000014
Figure PCTKR2012007022-appb-I000015
Figure PCTKR2012007022-appb-I000016
Figure PCTKR2012007022-appb-I000017
Figure PCTKR2012007022-appb-I000018
Figure PCTKR2012007022-appb-I000019
Figure PCTKR2012007022-appb-I000020
Figure PCTKR2012007022-appb-I000021
Figure PCTKR2012007022-appb-I000022
Figure PCTKR2012007022-appb-I000023
Figure PCTKR2012007022-appb-I000024
Figure PCTKR2012007022-appb-I000025
Figure PCTKR2012007022-appb-I000026
Figure PCTKR2012007022-appb-I000027
Figure PCTKR2012007022-appb-I000028
Figure PCTKR2012007022-appb-I000029
Figure PCTKR2012007022-appb-I000030
Figure PCTKR2012007022-appb-I000031
Figure PCTKR2012007022-appb-I000032
Figure PCTKR2012007022-appb-I000033
Figure PCTKR2012007022-appb-I000034
Figure PCTKR2012007022-appb-I000035
Figure PCTKR2012007022-appb-I000036
Figure PCTKR2012007022-appb-I000037
Figure PCTKR2012007022-appb-I000038
Figure PCTKR2012007022-appb-I000039
Figure PCTKR2012007022-appb-I000040
Figure PCTKR2012007022-appb-I000041
Figure PCTKR2012007022-appb-I000042
Figure PCTKR2012007022-appb-I000043
Figure PCTKR2012007022-appb-I000044
Figure PCTKR2012007022-appb-I000045
Figure PCTKR2012007022-appb-I000046
The organic electroluminescence compounds according to the present invention can be prepared according to the following reaction scheme.
[Reaction Scheme 1]
Figure PCTKR2012007022-appb-I000047
wherein Z, X, R1, R2, a, b, L1, Ar1 to Ar3, Ar1 and Ar2 are as defined in formula 1 above, and Hal represents a halogen.
In addition, the present invention provides an organic electroluminescence material comprising the organic electroluminescence compound of formula 1, and an organic electroluminescence device comprising the material. The above material can be comprised of the organic electroluminescence compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescence materials. Said organic electroluminescence device comprises a first electrode, a second electrode, and at least one organic layer between said first and second electrodes. Said organic layer comprises at least one compound of formula 1 according to the present invention. Further, said organic layer comprises a light-emitting layer in which the compound of formula 1 is comprised as a host material.
When the organic electroluminescence compounds of formula 1 is used as a host in the light-emitting layer, the layer comprises at least one phosphorescent dopant. The phosphorescent dopant for an organic electroluminescence device of the present invention is not specifically limited, but the phosphorescent dopant, which is used for an organic electroluminescence device according to the present invention, may be selected from compounds represented by the following formula 10:
Figure PCTKR2012007022-appb-I000048
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 PCTKR2012007022-appb-I000049
Figure PCTKR2012007022-appb-I000050
Figure PCTKR2012007022-appb-I000051
Figure PCTKR2012007022-appb-I000052
R201 to R203 each independently represent hydrogen, deuterium, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a (C6-C30)aryl group unsubstituted or substituted with (C1-C30)alkyl group(s), or a halogen;
R204 to R219 each independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C2-C30)alkenyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted mono- or di-(C1-C30)alkylamino group, a substituted or unsubstituted mono- or di-(C6-C30)arylamino group, SF5, a substituted or unsubstituted tri(C1-C30)alkylsilyl group, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl group, a substituted or unsubstituted tri(C6-C30)arylsilyl group, a cyano group or a halogen;
R220 to R223 each independently represent hydrogen, deuterium, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), or a (C6-C30)aryl group unsubstituted or substituted with (C1-C30)alkyl group(s);
R224 and R225 each independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a halogen, or R224 and R225 are linked to an adjacent substituent(s) to form a mono- or polycyclic, (C5-C30)alicyclic or aromatic ring;
R226 represents a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- or 30-membered heteroaryl group or a halogen;
R227 to R229 each independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group or a halogen;
Q represents
Figure PCTKR2012007022-appb-I000053
; R231 to R242 each independently represent hydrogen, deuterium, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a (C1-C30)alkoxy group, a halogen, a substituted or unsubstituted (C6-C30)aryl group, a cyano group, or a substituted or unsubstituted (C5-C30)cycloalkyl group, or each of R231 to R242 may be linked to an adjacent substituent via alkylene group or alkenylene group to form a spiro ring or a fused ring or may be linked to R207 or R208 via alkylene group or alkenylene group to form a saturated or unsaturated fused ring.
The dopants of formula 10 preferably include the following:
Figure PCTKR2012007022-appb-I000054
Figure PCTKR2012007022-appb-I000055
Figure PCTKR2012007022-appb-I000056
Figure PCTKR2012007022-appb-I000057
Figure PCTKR2012007022-appb-I000058
Figure PCTKR2012007022-appb-I000059
Figure PCTKR2012007022-appb-I000060
The organic electroluminescence device according to the present invention may further comprise, in addition to the compounds represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescence device according to the present invention, the organic layer may further comprise 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 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 electroluminescence device 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 according to the present invention.
Preferably, in the organic electroluminescence device according to the present invention, at least one layer (hereinafter, "a surface layer”) selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s). Specifically, it is preferred that a chalcogenide(includes oxides) layer of silicon or aluminum is placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescence device. Preferably, said chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and said metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
Preferably, in the organic electroluminescence device according to the present invention, a mixed region of an electron transport compound and an 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. Further, 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 electroluminescence device having two or more electroluminescent layers and emitting white light.
Hereinafter, the organic electroluminescence compound, the preparation method of the compound, and the luminescent properties of the device comprising the compound of the present invention will be explained in detail with reference to the following examples:
Example 1: Preparation of compound A-47
Figure PCTKR2012007022-appb-I000061
Figure PCTKR2012007022-appb-I000062
Preparation of compound 1-1
After adding 1,4-dibromo-2-nitrobenzene (30.0 g, 106.8 mmol), 1-naphthalene boronic acid (220.0 g, 128.1 mmol), Na2CO3 (34.0 g, 320.4 mmol), and tetrakis(triphenylphosphine)palladium(O) [Pd(PPh3)4] (6.17 g, 5.3 mmol) to toluene (640 mL)/EtOH (160 mL), the reaction mixture was stirred for 3 hours at 90°C. After terminating stirring, the reaction was completed by adding purified water (160 mL), was cooled to the room temperature, and was extracted with distilled water and ethylene acetate (EA). The obtained organic layer was concentrated, and was separated through column [methylene chloride/hexane (MC/Hex)] to obtain compound 1-1 (30 g, 86 %).
Preparation of compound 1-2
After mixing compound 1-1 (47.5 g, 144.75 mmol), triethyl phosphite [P(OEt)3] (300 mL), and 1,2-dichlorobenzene (200 mL), the reaction mixture was stirred for one day at 150°C. After terminating the reaction, the reaction mixture was concentrated under reduced pressure and was extracted with EA, and the organic layer was concentrated. The obtained organic layer was separated through column (MC/Hex) to obtain compound 1-2 (16 g, 37 %).
Preparation of compound 1-3
After adding compound 1-2 (15.5 g, 52.3 mmol), iodobenzene (11.7 mL, 104.7 mmol), CuI (5.0 g, 26.2 mmol), ethylene diamine (EDA) (1.8 mL, 26.2 mmol), and Cs2CO3 (51.2 g, 157.0 mmol) to toluene (250 mL), the reaction mixture was stirred for one day. The reaction mixture was extracted with EA, was distillated under reduced pressure, and was separated through column (MC/Hex) to obtain compound 1-3 (7.9 g, 40 %).
Preparation of compound 1-4
After dissolving compound 1-3 (7.84 g, 21.1 mmol) in tetrahydrofuran (THF) (200 mL), and cooling the reaction mixture to -78°C, 2.5 M n-BuLi in hexane (10.1 mL, 25.3 mmol) was slowly added to the reaction mixture, and the reaction mixture was stirred for 1 hour. B(Oi-Pr)3 (6.3 mL, 27.4 mmol) was added to the reaction mixture at the same temperature, and the reaction mixture was stirred for one day. After terminating stirring, the reaction mixture was quenched by adding 2M HCl, was extracted with distilled water and EA, and the organic layer was concentrated. The obtained organic layer was recrystallized with MC and Hex to obtain compound 1-4 (5.54 g, 78 %).
Preparation of compound 1-5
Cyanuric chloride (36 g, 195 mmol) was added to a flask and was dissolved with THF (360 mL). The reaction mixture was cooled to 0°C and PhMgBr (160 mL) was slowly added thereto. After increasing to room temperature, the reaction mixture was stirred for 2 hours and distilled water was added to complete the reaction. The organic layer was extracted with EA, was dried with MgSO4 to remove the remaining moisture, and was recrystallized with MC/MeOH to obtain compound 1-5 (30 g, 57 %).
Preparation of compound A-47
After dissolving compound 1-4 (3.0 g, 11.2 mmol), compound 1-5 (4.5 g, 13.5 mmol), Pd(PPh3)4 (648 mg, 0.561 mmol) and Na2CO3 (3.6 g, 33.6 mmol) in toluene (80 mL)/EtOH (20 mL)/distilled water (20mL), the reaction mixture was stirred for one day under reflux. Purified water was added to the reaction mixture, and the reaction mixture was filtered under reduced pressure. The obtained solid was dissolved with MC, and was separated through column (MC/Hex) to obtain compound A-47 (3.5 g, 60 %).
MS/FAB found 524.61; calculated 524.20
Example 2: Preparation of compound A- 48
Figure PCTKR2012007022-appb-I000063
Figure PCTKR2012007022-appb-I000064
Preparation of compound 2-1
Compound 1-4 (7.3 g, 21.65 mmol), 1-bromo-4-iodobenzene (18.3 g, 64.95 mmol), Pd(PPh3)4 (1.25 g, 1.08 mmol) and Na2CO3 (6.9 g, 64.95 mmol) were added to a flask, were dissolved with THF (200 mL)/EtOH (32 mL), and the reaction mixture was stirred for 3 hours at 90°C. After terminating stirring, distilled water was slowly added to the reaction mixture to complete the reaction, the reaction mixture was cooled to room temperature, and was extracted with distilled water and EA. The obtained organic layer was concentrated and was separated through column to obtain compound 2-1 (6.7 g, 68 %).
Preparation of compound 2-2
Compound 2-1 (6.7 g, 14.94 mmol) was added to a flask, was dissolved with THF (100 mL), and the reaction mixture was cooled to -78°C. After 10 minutes, 2.5 M n-BuLi in hexane (7.1 mL, 17.93 mmol) was slowly added to the flask, and the reaction mixture was stirred for 1 hour. At the same temperature, B(Oi-Pr)3 (5.15 mL, 22.4 mmol) was slowly added to the reaction mixture and the reaction mixture was stirred for 24 hours. After completing stirring, the reaction mixture was quenched by adding 1M HCl, and was extracted with distilled water and EA. The obtained organic layer was concentrated and was recrystallized with MC and Hex to obtain compound 2-2 (4 g, 65 %).
Preparation of compound A-48
Compound 2-2 (2.39 g, 8.95 mmol), compound 1-5 (4.079 g, 9.84 mmol), Pd(PPh3)4 (0.516 g, 0.44 mmol) and K2CO3 (3.7 g, 26.7 mmol) were added to a flask, were dissolved with toluene (50 mL)/EtOH (13 mL), and the reaction mixture was refluxed for 24 hours at 120°C. After completing the reaction by adding distilled water, the reaction mixture was cooled to room temperature and was extracted with distilled water and EA. The obtained organic layer was concentrated and was recrystallized with EA and MeOH to obtain compound A-48 (1.8 g, 35 %).
MS/FAB found 600.71; calculated 600.23
Example 3: Preparation of compound A-1
Figure PCTKR2012007022-appb-I000065
Figure PCTKR2012007022-appb-I000066
Preparation of compound 3-1
After adding 1-bromo-2-nitrobenzene (100 g, 495 mmol), 1-naphthalene boronic acid (102 g, 593 mmol), Pd(PPh3)4 (23 g, 19.9 mmol) and K2CO3 (171 g, 1237 mmol) to a flask and dissolving the reaction mixture by adding toluene (1.2 L)/EtOH (600 mL), the reaction mixture was stirred for 3 hours at 90°C. After terminating stirring, the reaction was completed by slowly adding purified water, and the organic layer was extracted EA and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was separated through column to obtain compound 3-1 (106 g, 86 %).
Preparation of compound 3-2
After adding compound 3-1 (106 g, 425 mmol) to a flask and dissolving the compound by adding triethyl phosphite (500 mL), the reaction mixture was stirred for 24 hours at 150°C. After completing the reaction, the remaining solvent was removed by a distillation device and was separated through column to obtain compound 3-2 (55 g, 60 %).
Preparation of compound 3-3
After dissolving compound 3-2 (20 g, 92 mmol) in dimethylformamide (DMF) at 0°C, N-bromosuccinimide (NBS) (16.3 g, 92 mmol) was slowly added to the reaction mixture and the reaction mixture was stirred for 24 hours. After completing the reaction, the organic layer was extracted EA and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was separated through column to obtain compound 3-3 (23.5 g, 87 %).
Preparation of compound 3-4
After adding compound 3-3 (20 g, 6.5 mmol), iodobenzene (15 mL, 135 mmol), CuI (6.4 g, 33.6 mmol), ethylenediamine (2.3 mL, 33.6 mmol) and K2PO4 (43 g, 202.5 mmol) to a flask and dissolving the reaction mixture by adding toluene (300 mL), the reaction mixture was stirred for 24 hours at 120°C. After completing the reaction, the organic layer was extracted EA and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was separated through column to obtain compound 3-4 (19 g, 76 %).
Preparation of compound 3-5
Compound 3-4 (19 g, 51 mmol) was added to a flask, was dissolved with THF (300 mL), and the reaction mixture was cooled to -78°C. After 10 minutes, 2.5 M n-BuLi in hexane (24.4 mL, 61.2 mmol) was slowly added to the flask, and the reaction mixture was stirred for 1 hour. At the same temperature, triisopropyl borate (14.1 mL, 61.2 mmol) was slowly added to the reaction mixture and the reaction mixture was stirred for 24 hours. After completing stirring, the reaction mixture was quenched by adding 1M HCl, was extracted with distilled water and EA, and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was concentrated and was recrystallized with MC and Hex to obtain compound 3-5 (12 g, 70 %).
Preparation of compound A-1
Compound 3-5 (8.2 g, 24.3 mmol), compound 1-5 (5.43 g, 20.1 mmol), Pd(PPh3)4 (0.93 g, 0.81 mmol) and K2CO3 (8.4 g, 60.8 mmol) were added to a flask, were dissolved with toluene (70 mL)/EtOH (30 mL), and the reaction mixture was stirred for 24 hours at 120°C. After completing the reaction by adding distilled water, the organic layer was extracted with EA, and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was recrystallized with EA and MeOH to obtain compound A-1 (2.3 g, 23 %).
MS/FAB found 524.61; calculated 524.20
Example 4: Preparation of compound A-49
Figure PCTKR2012007022-appb-I000067
Figure PCTKR2012007022-appb-I000068
Preparation of compound 4-1
After adding compound 3-5 (22 g, 65 mmol), 1-bromo-4-iodobenzene (28 g, 98.95 mmol), Pd(PPh3)4 (3.7 g, 3.2 mmol) and Na2CO3 (20.7 g, 195 mmol) to a flask and dissolving the reaction mixture by adding toluene (330 mL)/EtOH (150 mL), the reaction mixture was stirred for 3 hours at 90°C. After terminating stirring, the reaction was completed by adding purified water, and the organic layer was extracted EA and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was separated through column to obtain compound 4-1 (25 g, 86 %).
Preparation of compound 4-2
After dissolving compound 4-1 (25 g, 55.7 mmol) in tetrahydrofuran (THF) (300 mL) in a flask, and cooling the reaction mixture to -78°C. After 10 minutes, 2.5 M n-BuLi in hexane (29 mL, 72.41 mmol) was slowly added to the reaction mixture, and the reaction mixture was stirred for 1 hour. At the same temperature, triisopropyl borate (19.2 mL, 83.5 mmol) was slowly added to the reaction mixture and the reaction mixture was stirred for 24 hours. After completing stirring, the reaction mixture was quenched by adding 1M HCl, and the organic layer was extracted with distilled water and EA, and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was recrystallized with MC and Hex to obtain compound 4-2 (16.5 g, 71 %).
Preparation of compound A- 49
Compound 4-2 (16.5 g, 40 mmol), compound 1-5 (8 g, 29.8 mmol), Pd(PPh3)4 (1.7 g, 1.5 mmol) and K2CO3 (12.4 g, 89.4 mmol) were added to a flask, were dissolved with toluene (150 mL)/EtOH (75 mL), and the reaction mixture was refluxed for 24 hours at 120°C. After completing the reaction by adding distilled water, the organic layer was extracted with EA, and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was recrystallized with EA and MeOH to obtain compound A-49 (6 g, 32 %).
MS/FAB found 600.71; calculated 600.23
Example 5: Preparation of compound B-1
Figure PCTKR2012007022-appb-I000069
Figure PCTKR2012007022-appb-I000070
Preparation of compound 5-1
After adding 2-bromonitrobenzene (29.3 g, 145 mmol), 1-naphthaleneboronic acid (30 g, 174 mmol), Pd(PPh3)4 (6.7 g, 5.8 mmol) and Na2CO3 (38 g, 362 mmol) to toluene (550 mL)/EtOH (180 mL)/distilled water (180 mL), the reaction mixture was stirred for 2 hours at 110°C. After cooling to room temperature, the reaction mixture was extracted with distilled water and EA, and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was concentrated and was separated through column (MC/Hex) to obtain compound 5-1 (30 g, 82 %).
Preparation of compound 5-2
Compound 5-1 (26.5 g, 106 mmol) and CCl4 (250 mL) were mixed, were cooled to -5°C, were added with FeCl3 (1.7 g, 10.6 mmol) and were dropwise added with Br2 (17 g, 176 mmol). After stirring overnight, the reaction mixture was quenched with aqueous Na2S2O3 solution, was washed with aqueous 2M NaOH solution, was extracted with distilled water and MC, and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was concentrated and was separated through column (MC/Hex) to obtain compound 5-2 (31 g, 90 %).
Preparation of compound 5-3
Compound 5-2 (31 g, 95 mmol), P(OEt)3 (150 mL), and 1,2-dichlorobenzene (150 mL) were mixed, and were stirred overnight at 140°C. After completing the reaction, the reaction mixture was concentrated under reduced pressure and was extracted with EA. The obtained organic layer was concentrated and was separated through column (MC/Hex) to obtain compound 5-3 (15 g, 52 %).
Preparation of compound 5-4
After adding compound 5-3 (7.5 g, 25.3 mmol), iodobenzene (7.5 mL, 51 mmol), CuI (5.4 g, 12.7 mmol), ethylenediamine (EDA) (0.88 mL, 12.7 mmol) and Cs2CO3 (23 g, 76 mmol) to toluene (125 mL), the reaction mixture was stirred for one day at 120°C. The reaction mixture was extracted with distilled water and EA, and was dried with MgSO4 to remove the remaining moisture. The obtained organic layer was concentrated and was separated through column (MC/Hex) to obtain compound 5-4 (7.9 g, 84 %).
Preparation of compound 5-5
After dissolving compound 5-4 (7.5 g, 79 mmol) THF (75 mL), the reaction mixture was cooled to -78°C, 2.5 M n-BuLi in hexane (10 mL, 103 mmol) was slowly added to the reaction mixture, and the reaction mixture was stirred for 1 hour. At the same temperature, B(Oi-Pr)3 (6.8 mL, 119 mmol) was added to the reaction mixture and the reaction mixture was stirred for one day. After completing stirring, the reaction mixture was quenched by adding 2M HCl, was extracted with distilled water and EA. The obtained organic layer was concentrated and was recrystallized with MC and Hex to obtain compound 5-5 (5 g, 75 %).
Preparation of compound 5-6
Cyanuric chloride (50 g, 91 mmol) was added to a flask and was dissolved with THF (1.3 L). The reaction mixture was cooled to 0°C and 3M solution of PhMgBr (225 mL) in diethyl ether was slowly added thereto. After increasing to room temperature, the reaction mixture was stirred for 3 hours and added with distilled water to complete the reaction. The organic layer was extracted with EA, was dried with MgSO4 to remove the remaining moisture, and was distilled under reduced pressure. The crude product 5-6 (37 g, 63 %) was obtained by filtering the mixture under silica by using MC as an elution solvent, which showed a high purity sufficient to be used in next steps.
Preparation of compound B-1
After dissolving compound 5-5 (6.5 g, 19.2 mmol), compound 5-6 (4.3 g, 16 mmol), Pd(PPh3)4 (0.9 g, 0.8 mmol) and K2CO3 (6.6 g, 48 mmol) to toluene (100 mL)/EtOH (24 mL)/distilled water (24 mL), the reaction mixture was stirred for one day at 100°C. After adding distilled water and filtering under reduced pressure, the obtained solid was dissolved with MC and was separated through column (MC/Hex) to obtain compound B-1 (5.4 g, 64 %).
MS/FAB found 524.61; calculated 524.20
Example 6: Preparation of compound B-39
Figure PCTKR2012007022-appb-I000071
Preparation of compound 6-1
After adding compound 5-5 (22 g, 65 mmol), 1-bromo-4-iodobenzene (28 g, 98.95 mmol), Pd(PPh3)4 (3.7 g, 3.2 mmol) and Na2CO3 (20.7 g, 195 mmol) to a flask, and dissolving the mixture by adding toluene (330 mL)/EtOH (150 mL), the reaction mixture was stirred for 3 hours at 90°C. After completing stirring, the reaction was completed by slowly adding distilled water thereto, was cooled to room temperature, and was extracted with distilled water and EA. The obtained organic layer was concentrated and separated through column to obtain compound 6-1 (25 g, 86 %).
Preparation of compound 6-2
Compound 6-1 (25 g, 55.7 mmol) was added to a flask, was dissolved with THF (300 mL), and the reaction mixture was cooled to -78°C. After 10 minutes, 2.5 M n-BuLi in hexane (29 mL, 72.4 mmol) was slowly added to the flask, and the reaction mixture was stirred for 1 hour. At the same temperature, B(Oi-Pr)3 (19.2 mL, 83.5 mmol) was slowly added to the reaction mixture and the reaction mixture was stirred for 24 hours. After completing stirring, the reaction mixture was quenched by adding 1M HCl, was extracted with distilled water and EA. The obtained organic layer was concentrated and was recrystallized with MC and Hex to obtain compound 6-2 (16.5 g, 71 %).
Preparation of compound B-39
After adding compound 6-2 (16.5 g, 40 mmol), compound 5-6 (8 g, 29.8 mmol), Pd(PPh3)4 (1.7 g, 1.5 mmol) and K2CO3 (12.4 g, 89.4 mmol) to a flask, and dissolving the mixture by adding toluene (150 mL)/EtOH (75 mL), the reaction mixture was stirred for 24 hours at 120°C. The reaction was completed by slowly adding distilled water, was cooled to room temperature, and was extracted with distilled water and EA. The obtained organic layer was concentrated and was recrystallized with EA and MeOH to obtain compound B-39 (6 g, 32 %).
MS/FAB found 600.71; calculated 600.23
Device Example 1: Production of an OLED device using the compound according to the present invention
An OLED device was produced using the compound according to 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. Then, the ITO substrate was 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. Then, N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound A-1 was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-7 was introduced into another cell as a dopant. The two materials were evaporated at different rates and deposited in a doping amount of 4 wt% of the dopant, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate (Liq) was introduced into another cell. The two materials were evaporated at the same rate and were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30nm on the light-emitting layer. Then, 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 deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed red emission having a luminance of 740 cd/m2 and a current density of 5.3 mA/cm2 at a driving voltage of 5.9 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 100 hours.
Device Example 2: Production of an OLED device using the compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound A-47 as a host material and compound D-7 as a dopant.
The produced OLED device showed red emission having a luminance of 1430 cd/m2 and a current density of 12.31 mA/cm2 at a driving voltage of 3.5 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 80 hours.
Device Example 3: Production of an OLED device using the compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound A-48 as a host material and compound D-11 as a dopant.
The produced OLED device showed red emission having a luminance of 835 cd/m2 and a current density of 13.6 mA/cm2 at a driving voltage of 3.0 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 30 hours.
Device Example 4: Production of an OLED device using the compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound A-49 as a host material and compound D-7 as a dopant.
The produced OLED device showed red emission having a luminance of 2100 cd/m2 and a current density of 16.2 mA/cm2 at a driving voltage of 6.1 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 70 hours.
Device Example 5: Production of an OLED device using the compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound B-1 as a host material and compound D-7 as a dopant.
The produced OLED device showed red emission having a luminance of 1010 cd/m2 and a current density of 6.6 mA/cm2 at a driving voltage of 3.8 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 50 hours.
Device Example 6: Production of an OLED device using the compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound B-39 as a host material and compound D-11 as a dopant.
The produced OLED device showed red emission having a luminance of 420 cd/m2 and a current density of 5.46 mA/cm2 at a driving voltage of 2.9 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least 20 hours.
Comparative Example 1: Production of an OLED device using conventional electroluminescent compounds
An OLED device was produced in the same manner as in Device Example 1, except that a light-emitting layer was deposited by using 4,4’-bis(carbazol-9-yl)biphenyl (CBP) as a host material and compound D-7 as a dopant, and between the light-emitting layer and the electron transport layer, a hole blocking layer having a thickness of 10 nm was deposited by using bis(2-methyl-8-quinolinato)(p-phenylphenolato)aluminum(III) (Balq).
The produced OLED device showed red emission having a luminance of 1000 cd/m2 and a current density of 14.1 mA/cm2 at a driving voltage of 7.8 V.
Comparative Example 2: Production of an OLED device using conventional electroluminescent compounds
An OLED device was produced in the same manner as in Device Example 1, except that a light-emitting layer was deposited by using 4,4’-bis(carbazol-9-yl)biphenyl (CBP) as a host material and compound D-11 as a dopant, and between the light-emitting layer and the electron transport layer, a hole blocking layer having a thickness of 10 nm was deposited by using bis(2-methyl-8-quinolinato)(p-phenylphenolato)aluminum(III) (Balq).
The produced OLED device showed red emission having a luminance of 1000 cd/m2 and a current density of 20.4 mA/cm2 at a driving voltage of 8.2 V. Further, the time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was at least10 hours.
The organic electroluminescence compounds of the present invention have superior luminous characteristics than the conventional materials. In addition, a device using the organic electroluminescence compounds according to the present invention as a host material not only has excellent luminous characteristics, but also increases power efficiency by reducing the driving voltage.

Claims (6)

  1. An organic electroluminescence compound represented by the following formula 1:
    Figure PCTKR2012007022-appb-I000072
    wherein
    Z represents
    Figure PCTKR2012007022-appb-I000073
    ;
    L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 3- to 30-membered heteroarylene group;
    Ar1 to Ar3 each independently represent CR11 or N, proviso that Ar1 to Ar3 simultaneously do not represent CH;
    X represents -O-, -S-, -CR12R13-, or -NR14-;
    R1, R2, R11, Ar1 and Ar2 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group, -NR15R16, -SiR17R18R19, -SR20, -OR21, a cyano group, or a nitro group;
    R12 to R14 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 3- to 30-membered heteroaryl group;
    R15 to R21 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (C5-C30)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; where a is an integer of 2 or more, each of R1 is the same or different
    b represents an integer of 1 to 3; where b is an integer of 2 or more, each of R2 is the same or different;
    the heterocycloalkyl group and the heteroaryl(ene) group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescence compound according to claim 1, which is selected from the group consisting of following formulae 2 and 3:
    Figure PCTKR2012007022-appb-I000074
    Figure PCTKR2012007022-appb-I000075
    wherein
    X, R1, R2, a, b, L1, A1 to A3, Ar1, and Ar2 are as defined in claim 1.
  3. The organic electroluminescence compound according to claim 1, wherein the substituents of the substituted alkyl group, the substituted aryl(ene) group, the substituted heteroaryl(ene) group, the substituted cycloalkyl(ene) group, the substituted heterocycloalkyl group and the substituted aralkyl group in L1, R1, R2, R11 to R21, Ar1, and Ar2 of formula 1 each independently are at least one selected from the group consisting of deuterium; a halogen; a (C1-C30)alkyl group substituted or unsubstituted with a halogen; a (C6-C30)aryl group; a 3- to 30-membered heteroaryl group substituted or unsubstituted with a (C1-C30)alkyl or a (C6-C30)aryl; a (C3-C30)cycloalkyl group; a 5- to 7-membered heterocycloalkyl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a cyano group; an N-carbazolyl group; a di(C1-C30)alkylamino group; a di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; a (C1-C30)alkyl(C6-C30)aryl group; a carboxyl group; a nitro group; and a hydroxyl group.
  4. The organic electroluminescence compound according to claim 1, wherein L1 represents a single bond or a (C6-C30)arylene group; Ar1 to Ar3 each independently represent CR11 or N, proviso that Ar1 to Ar3 do not simultaneously represent CH; X represents -NR14-; R11 represents hydrogen, deuterium, a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group; R14 represents a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group; and R1, R2, Ar1 and Ar2 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group; the arylene of L1, and the alkyl, aryl, and heteroaryl of R1, R2, R11, R14, Ar1 and Ar2 may be substituted with at least one selected from the group consisting of deuterium, a halogen, a (C1-C30)alky,; a halo(C1-C30)alkyl, a (C6-C30)aryl, a 3- to 30-membered heteroaryl group, a 3- to 30-membered heteroaryl group substituted with a (C6-C30)aryl and/or a (C1-C30)alkyl, a (C3-C30)cycloalkyl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl group, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl group, a (C6-C30)aryl(C1-C30)alkyl group, and a (C1-C30)alkyl(C6-C30)aryl.
  5. The organic electroluminescence compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2012007022-appb-I000076
    Figure PCTKR2012007022-appb-I000077
    Figure PCTKR2012007022-appb-I000078
    Figure PCTKR2012007022-appb-I000079
    Figure PCTKR2012007022-appb-I000080
    Figure PCTKR2012007022-appb-I000081
    Figure PCTKR2012007022-appb-I000082
    Figure PCTKR2012007022-appb-I000083
    Figure PCTKR2012007022-appb-I000084
    Figure PCTKR2012007022-appb-I000085
    Figure PCTKR2012007022-appb-I000086
    Figure PCTKR2012007022-appb-I000087
    Figure PCTKR2012007022-appb-I000088
    Figure PCTKR2012007022-appb-I000089
    Figure PCTKR2012007022-appb-I000090
    Figure PCTKR2012007022-appb-I000091
    Figure PCTKR2012007022-appb-I000092
    Figure PCTKR2012007022-appb-I000093
    Figure PCTKR2012007022-appb-I000094
    Figure PCTKR2012007022-appb-I000095
    Figure PCTKR2012007022-appb-I000096
    Figure PCTKR2012007022-appb-I000097
    Figure PCTKR2012007022-appb-I000098
    Figure PCTKR2012007022-appb-I000099
    Figure PCTKR2012007022-appb-I000100
    Figure PCTKR2012007022-appb-I000101
    Figure PCTKR2012007022-appb-I000102
    Figure PCTKR2012007022-appb-I000103
    Figure PCTKR2012007022-appb-I000104
    Figure PCTKR2012007022-appb-I000105
    Figure PCTKR2012007022-appb-I000106
    Figure PCTKR2012007022-appb-I000107
    and
    Figure PCTKR2012007022-appb-I000108
  6. An organic electroluminescence device comprising the compound according to claim 1.
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