WO2012165832A1 - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents

Novel compounds for organic electronic material and organic electroluminescent device using the same Download PDF

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WO2012165832A1
WO2012165832A1 PCT/KR2012/004214 KR2012004214W WO2012165832A1 WO 2012165832 A1 WO2012165832 A1 WO 2012165832A1 KR 2012004214 W KR2012004214 W KR 2012004214W WO 2012165832 A1 WO2012165832 A1 WO 2012165832A1
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Hee-Sook Kim
Nam-Kyun 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 JP2014513430A priority patent/JP2014522400A/en
Publication of WO2012165832A1 publication Critical patent/WO2012165832A1/en
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Definitions

  • the present invention relates to novel compounds for organic electronic material and an organic electroluminescent device using the same.
  • An electroluminescent (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 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)pic
  • 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.
  • WO 2006/049013 discloses compounds for organic electroluminescent materials having a condensed bicyclic group as a backbone structure. However, it does not disclose a compound having a nitrogen-containing condensed bicyclic group substituted with a carbazole group which is fused with an aromatic ring-fused heterocycloalkyl or cycloalkyl group.
  • the objective of the present invention is to provide a compound for organic electronic material which has an excellent structure imparting high luminous efficiency and a long operation lifetime to a device, and having proper color coordination; and an organic electroluminescent device having high efficiency and a long lifetime, using said compounds.
  • L 1 and L 2 each independently represent a single bond, a substituted or
  • X 1 represents CH or N
  • Y 1 to Y 3 each independently represent -O-, -S-, -CR 6 R 7 - or -NR 8 -,
  • R 1 to R 5 each independently represent hydrogen, deuterium, a halogen, a
  • R 6 to R 8 and R 11 to R 17 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, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a 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, b, c and e each independently represent an integer of 1 to 4;
  • a, b, c or e is an integer of 2 or more, each of R 1 , each of R 2 , each of R 3 or each of R 5 is the same or different;
  • d represents an integer of 1 to 3; where d is an integer of 2 or more,
  • each of R 4 is the same or different.
  • the compounds for organic electronic materials according to the present invention can manufacture an organic electroluminescent device which has high luminous efficiency and a long operation lifetime.
  • the compounds for organic electronic materials according to the present invention have high efficiency in transporting electrons, crystallization could be prevented when manufacturing a device. Further, the compounds have good layer formability and improve the current characteristic of the device. Therefore, they can produce an organic electroluminescent device having lowered driving voltages and enhanced power efficiency.
  • the present invention relates to a compound for organic electronic materials represented by the above formula 1 and an organic electroluminescent device comprising the compound.
  • (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., but are not limited thereto;
  • “(C2-C30) alkenyl(ene)” is meant to be a linear or branched alkenyl(ene) 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., but are not limited thereto; “(C2-C30)alkynyl” is meant to be
  • 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.
  • L 1 and L 2 each independently are preferably a single bond, a (C6-C12)arylene group substituted or unsubstituted with a (C1-C6)alkyl or an unsubstituted (C1-C6)cycloalkylene, more preferably a single bond, phenylene, biphenylene, dimethylphenylene or cyclohexylene.
  • Y 1 to Y 3 each independently represent -O-, -S-,
  • R 6 and R 8 each independently are preferably 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 spiro ring or a fused spiro ring, more preferably deuterium, a halogen, a (C1-C6)alkyl group, a (C6-C20)aryl group substituted or unsubstituted with a (C6-C12)aryl, or a 5- to 21-membered heteroaryl group substituted or unsubstituted with a (C6-C12)aryl; or are linked to an adjacent substituent(s) to form a spir
  • R 1 to R 5 each independently are preferably 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, N-carbazolyl, -NR 11 R 12 or -SiR 13 R 14 R 15 ; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a 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, wherein R 11 to R 15 each independently are preferably a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubsti
  • R 1 to R 5 each independently are more preferably an unsubstituted (C6-C20)aryl group, an unsubstituted 5- to 21-membered heteroaryl group, -NR 11 R 12 or -SiR 13 R 14 R 15 ; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring, even more preferably phenyl, carbazolyl, diphenylamino or methyldiphenylsilyl; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring.
  • the representative compounds of the present invention include the following compounds, but are not limited thereto:
  • the compounds for organic electronic materials according to the present invention can be prepared according to the following reaction scheme.
  • R 1 to R 5 , Y 1 to Y 3 , X 1 , L 1 , L 2 , a, b, c, d and e are as defined in formula 1 above, and X represents a halogen.
  • the present invention provides an organic electroluminescent device comprising the compound of formula 1.
  • Said organic electroluminescent 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.
  • 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 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 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 may be linked to each other via a (C3-C12)alkylene group or (C3-C12)alkenylene group with or without a fused ring, to form a mono- or polycyclic, 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 (C2-C30)alkylene group or (C2-C30)alkenylene group to form a spiro ring or a fused ring or may be linked to R 207 or R 208 via a (C2-C30)alkylene group or (C2-C30)alkenylene group to form a saturated or unsaturated fused ring.
  • the dopants of formula 2 include the following, but are not limited thereto:
  • the organic electroluminescent 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.
  • 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 electroluminescent 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, 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 electroluminescent 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 electroluminescent device having two or more electroluminescent layers and emitting white light.
  • Example 1 Production of an OLED device using the compound according to the present invention
  • 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.
  • N 1 N 1 ’-([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 60nm 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 C-16 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 were deposited in a doping amount of 4 wt% to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • the produced OLED device showed red emission having a luminance of 1,030 cd/m 2 and a current density of 10.0 mA/cm 2 at a driving voltage of 4.1 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 30 hours.
  • 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 Example 1, except for using compound C-48 as a host material, and compound D-11 as a dopant.
  • the produced OLED device showed red emission having a luminance of 1,030 cd/m 2 and a current density of 12.7 mA/cm 2 at a driving voltage of 4.2 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 100 hours.
  • 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 Example 1, except for using compound C-51 as a host material, and compound D-11 as a dopant.
  • the produced OLED device showed red emission having a luminance of 1,010 cd/m 2 and a current density of 13.7 mA/cm 2 at a driving voltage of 4.5 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 100 hours.
  • 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 Example 1, except for using compound C-94 as a host material, and compound D-11 as a dopant.
  • the produced OLED device showed red emission having a luminance of 1,060 cd/m 2 and a current density of 12.2 mA/cm 2 at a driving voltage of 4.2 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 40 hours.
  • 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 Example 1, except for using compound C-96 as a host material, and compound D-7 as a dopant.
  • the produced OLED device showed red emission having a luminance of 1,010 cd/m 2 and a current density of 9.8 mA/cm 2 at a driving voltage of 3.9 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 20 hours.
  • Comparative Example 1 Production of an OLED device using conventional electroluminescent compounds
  • An OLED device was produced in the same manner as that of Example 1, except that a light-emitting layer having a thickness of 30 nm was deposited on the hole transport layer by using 4,4’-N,N’-dicarbazol-biphenyl (CBP) as a host material and compound D-11 as a dopant and that a hole blocking layer having a thickness of 10 nm was deposited by using aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • the produced OLED device showed red emission having a luminance of 1,000 cd/m 2 and a current density of 20.0 mA/cm 2 at a driving voltage of 8.2V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was 10 hours.
  • the compounds for organic electronic material according to the present invention have high efficiency in transporting electrons, crystallization could be prevented when manufacturing a device. Further, the compounds have good layer formability and improve the current characteristic of the device. Therefore, they can produce an organic electroluminescent device having lowered driving voltages and enhanced power efficiency. In addition, while the OLED device using conventional compounds for organic electronic material needed hole blocking layer, the hole blocking layer is not necessary in the OLED device using the compounds according to the present invention.

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Abstract

The present invention relates to a novel compound and an organic electroluminescent device containing the same. Since the compounds for organic electronic materials according to the present invention have high efficiency in transporting electrons, crystallization could be prevented when manufacturing a device. Further, the compounds have good layer formability and improve the current characteristic of the device. Therefore, they can produce an organic electroluminescent device having lowered driving voltages and enhanced power efficiency.

Description

NOVEL COMPOUNDS FOR ORGANIC ELECTRONIC MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel compounds for organic electronic material and an organic electroluminescent device using the same.
An electroluminescent (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, phosphorescent materials theoretically show four (4) times higher luminous efficiency than fluorescent materials. Thus, recently, phosphorescent materials have been investigated. 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, a lot of phosphorescent materials are being researched in Japan, Europe and U.S.A recently.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent substances. Further, an organic EL device having high efficiency 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 phosphorous host 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 an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage, and thus the power efficiency should be high in order to reduce power consumption. Although an organic EL device comprising phosphorescent materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, when the conventional materials such as BAlq or CBP are used as phosphorescent host materials, a significantly high driving voltage is necessary compared to an organic EL device using a fluorescent material. Thus, there is no merit in terms of power efficiency (lm/W). (3) Further, the operation lifetime of an organic EL device is short and luminous efficiency is still required to be improved.
International Patent Publication No. WO 2006/049013 discloses compounds for organic electroluminescent materials having a condensed bicyclic group as a backbone structure. However, it does not disclose a compound having a nitrogen-containing condensed bicyclic group substituted with a carbazole group which is fused with an aromatic ring-fused heterocycloalkyl or cycloalkyl group.
The objective of the present invention is to provide a compound for organic electronic material which has an excellent structure imparting high luminous efficiency and a long operation lifetime to a device, and having proper color coordination; and an organic electroluminescent device having high efficiency and a long lifetime, using said compounds.
The present inventors found that the above objective can be achieved by
a compound represented by the following formula 1:
Figure PCTKR2012004214-appb-I000001
wherein
L1 and L2 each independently represent a single bond, a substituted or
unsubstituted 3- to 30-membered heteroarylene group, a substituted or
unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (C6-C30)cycloalkylene group;
X1 represents CH or N;
Y1 to Y3 each independently represent -O-, -S-, -CR6R7- or -NR8-,
provided that Y2 and Y3 do not simultaneously exist;
R1 to R5 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, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl group, -NR11R12, -SiR13R14R15, -SR16, -OR17, a cyano group, a nitro group, or a hydroxyl group; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a 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;
R6 to R8 and R11 to R17 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, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a 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, b, c and e each independently represent an integer of 1 to 4; where
a, b, c or e is an integer of 2 or more, each of R1, each of R2, each of R3 or each of R5 is the same or different;
d represents an integer of 1 to 3; where d is an integer of 2 or more,
each of R4 is the same or different; and
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 compounds for organic electronic materials according to the present invention can manufacture an organic electroluminescent device which has high luminous efficiency and a long operation lifetime.
In addition, since the compounds for organic electronic materials according to the present invention have high efficiency in transporting electrons, crystallization could be prevented when manufacturing a device. Further, the compounds have good layer formability and improve the current characteristic of the device. Therefore, they can produce an organic electroluminescent device having lowered driving voltages and enhanced 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 relates to a compound for organic electronic materials represented by the above formula 1 and an organic electroluminescent device comprising the compound.
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., but are not limited thereto; “(C2-C30) alkenyl(ene)” is meant to be a linear or branched alkenyl(ene) 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., but are not limited thereto; “(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., but are not limited thereto; “(C1-C30)alkoxy” is a linear or branched alkoxy 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 methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy, etc., but are not limited thereto; “(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., but are not limited thereto; “(C6-C30)cycloalkylene” is one formed by removing a hydrogen from cycloalkyl having 6 to 30, preferably 6 to 20, more preferably 6 or 7 carbon atoms; “5- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably N, O and S, and 5 to 7 ring backbone atoms, and includes tetrahydrofurane, pyrrolidine, thiolan, tetrahydropyran, etc., but are not limited thereto; “(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 12, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., but are not limited thereto; “3- to 30-membered heteroaryl(ene)” is an aryl 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 21, more preferably 5 to 12 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., but are not limited thereto. 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(ene) group, the substituted alkenyl group, the substituted alkynyl group, the substituted cycloalkylene group, the substituted cycloalkyl group, the substituted heterocycloalkyl group, the substituted aryl(ene) group, the substituted heteroaryl(ene) group and the substituted aromatic ring in L1, L2, R1 to R5, R6 to R8, and R11 to R17 groups each independently are preferably 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 (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, a 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, more preferably 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 (C1-C30)alkyl(C6-C30)aryl group, a 3- to 30-membered heteroaryl group substituted or unsubstituted with a (C6-C30)aryl, a (C3-C30)cycloalkyl group and a (C6-C30)aryl(C1-C30)alkyl group, even more preferably are at least one selected from the group consisting of deuterium, fluorine, methyl, phenyl and naphthyl.
In the above formula 1, L1 and L2 each independently are preferably a single bond, a (C6-C12)arylene group substituted or unsubstituted with a (C1-C6)alkyl or an unsubstituted (C1-C6)cycloalkylene, more preferably a single bond, phenylene, biphenylene, dimethylphenylene or cyclohexylene.
In the above formula 1, Y1 to Y3 each independently represent -O-, -S-,
-CR6R7- or -NR8-, wherein R6 and R8 each independently are preferably 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 spiro ring or a fused spiro ring, more preferably deuterium, a halogen, a (C1-C6)alkyl group, a (C6-C20)aryl group substituted or unsubstituted with a (C6-C12)aryl, or a 5- to 21-membered heteroaryl group substituted or unsubstituted with a (C6-C12)aryl; or are linked to an adjacent substituent(s) to form a spiro ring or a fused spiro ring, or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring, even more preferably methyl; phenyl; biphenyl; terphenyl; naphthyl; phenyl substituted with deuterium; phenyl substituted with fluorine; fluorenyl substituted with methyl; naphthylphenyl; or carbazolyl substituted with phenyl; or are linked to an adjacent substituent(s) to form a spiro ring or a fused spiro ring; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring.
In the above formula 1, R1 to R5 each independently are preferably 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, N-carbazolyl, -NR11R12 or -SiR13R14R15; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a 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, wherein R11 to R15 each independently are preferably 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, more preferably an unsubstituted (C1-C6)alkyl group, an unsubstituted (C6-C12)aryl group, or an unsubstituted 5- to 21-membered heteroaryl group, even more preferably methyl, phenyl or carbazolyl.
In the above formula 1, R1 to R5 each independently are more preferably an unsubstituted (C6-C20)aryl group, an unsubstituted 5- to 21-membered heteroaryl group, -NR11R12 or -SiR13R14R15; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring, even more preferably phenyl, carbazolyl, diphenylamino or methyldiphenylsilyl; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring.
In the above formula 1,
Figure PCTKR2012004214-appb-I000002
is selected from the following structures, but are not limited thereto:
Figure PCTKR2012004214-appb-I000003
Figure PCTKR2012004214-appb-I000004
The representative compounds of the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2012004214-appb-I000005
Figure PCTKR2012004214-appb-I000006
Figure PCTKR2012004214-appb-I000007
Figure PCTKR2012004214-appb-I000008
Figure PCTKR2012004214-appb-I000009
Figure PCTKR2012004214-appb-I000010
Figure PCTKR2012004214-appb-I000011
Figure PCTKR2012004214-appb-I000012
Figure PCTKR2012004214-appb-I000013
Figure PCTKR2012004214-appb-I000014
Figure PCTKR2012004214-appb-I000015
Figure PCTKR2012004214-appb-I000016
Figure PCTKR2012004214-appb-I000017
Figure PCTKR2012004214-appb-I000018
Figure PCTKR2012004214-appb-I000019
Figure PCTKR2012004214-appb-I000020
Figure PCTKR2012004214-appb-I000021
Figure PCTKR2012004214-appb-I000022
Figure PCTKR2012004214-appb-I000023
Figure PCTKR2012004214-appb-I000024
Figure PCTKR2012004214-appb-I000025
Figure PCTKR2012004214-appb-I000026
The compounds for organic electronic materials according to the present invention can be prepared according to the following reaction scheme.
[Reaction Scheme 1]
Figure PCTKR2012004214-appb-I000027
[Reaction Scheme 2]
Figure PCTKR2012004214-appb-I000028
wherein R1 to R5, Y1 to Y3, X1, L1, L2, a, b, c, d and e are as defined in formula 1 above, and X represents a halogen.
In addition, the present invention provides an organic electroluminescent device comprising the compound of formula 1. Said organic electroluminescent 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.
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 compounds represented by the following formula 2:
Figure PCTKR2012004214-appb-I000029
--------------------- (2)
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 PCTKR2012004214-appb-I000030
Figure PCTKR2012004214-appb-I000031
Figure PCTKR2012004214-appb-I000032
Figure PCTKR2012004214-appb-I000033
;
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 may be linked to each other via a (C3-C12)alkylene group or (C3-C12)alkenylene group with or without a fused ring, to form a mono- or polycyclic, 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 PCTKR2012004214-appb-I000034
; 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 (C2-C30)alkylene group or (C2-C30)alkenylene group to form a spiro ring or a fused ring or may be linked to R207 or R208 via a (C2-C30)alkylene group or (C2-C30)alkenylene group to form a saturated or unsaturated fused ring.
The dopants of formula 2 include the following, but are not limited thereto:
Figure PCTKR2012004214-appb-I000035
Figure PCTKR2012004214-appb-I000036
Figure PCTKR2012004214-appb-I000037
Figure PCTKR2012004214-appb-I000038
Figure PCTKR2012004214-appb-I000039
Figure PCTKR2012004214-appb-I000040
The organic electroluminescent 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 electroluminescent 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 electroluminescent 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 electroluminescent 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 electroluminescent 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 electroluminescent 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 electroluminescent device having two or more electroluminescent layers and emitting white light.
Hereinafter, the compound for organic electronic materials, 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:
Preparation Example 1: Preparation of compound C-16
Figure PCTKR2012004214-appb-I000041
Preparation of compound 1-1
After dissolving 2,4-dichloroquinazoline (30 g, 151 mmol), 9-phenyl-9H-carbazol-3-yl boronic acid (15.6 g, 75.3 mmol), Pd(PPh3)4 (2.6 g, 2.3 mmol) and Na2CO3 (16 g, 150 mmol) in a mixture of toluene (300 mL) and distilled water (75 mL), the reaction mixture was stirred for 2 hours at 90°C. The resulting organic layer was distillated under reduced pressure, and then was triturated with MeOH. The obtained solid was dissolved in methylene chloride (MC), was filtered through silica, and then was triturated with MC and hexane to produce compound 1-1 (9.3 g, 51.4 %).
Preparation of compound 1-2
After dissolving dibenzo[b,d]furan-4-yl boronic acid (30 g, 142 mmol), 1-bromo-2-nitrobenzene (23.8 g, 118 mmol), K2CO3 (39.1 g, 283 mmol) and Pd(PPh3)4 (6.8 g, 5.8 mmol) in a mixture of toluene (600 mL), EtOH (150 mL) and purified water (150 mL), the reaction mixture was stirred under reflux for 24 hours. After terminating the reaction, the reaction mixture was cooled to room temperature, and an aqueous layer was removed from the mixture by a gravity separation. The obtained organic layer was concentrated, was triturated with MC, and was filtered to obtain compound 1-2 (34 g, 99.7 %).
Preparation of compound 1-3
After dissolving compound 1-2 (34 g, 117.5 mmol) in a mixture of P(OEt)3 (300 mL) and 1,2-dichlorobenzene (300 mL), the reaction mixture was stirred for 24 hours at 150°C. After terminating the reaction, the reaction mixture was concentrated under reduced pressure, was extracted with ethyl acetate (EA), and the organic layer was concentrated and purified through silica column to obtain compound 1-3 (11 g, 37 %).
Preparation of compound C-16
After suspending compound 1-1 (6.3 g, 15.5 mmol) and compound 1-3 (4.0 g, 15.5 mmol) in dimethyl formamide (DMF) 80mL, 60% NaH (930 mg, 23.2 mmol) was added to the mixture at room temperature. The obtained reaction mixture was stirred for 12 hours. After adding purified water (1L), the mixture was filtered under reduced pressure. The obtained solid was triturated with MeOH/EA, was triturated with DMF, and was triturated with EA/tetrahydrofurane (THF). It was dissolved in MC, was filtered through silica, and then was triturated with MeOH/EA to obtain compound C-16 (6 g, 62 %).
MS/FAB found 627; calculated 626.70
Preparation Example 2: Preparation of compound C-32
Figure PCTKR2012004214-appb-I000042
Preparation of compound 2-1
After dissolving 2,4-dichloroquinazoline (50 g, 251 mmol) and dibenzo[b,d]furan-4-yl boronic acid (53.2 g, 251 mmol) in a mixture of toluene (1 L) and water (200 mL), tetrakistriphenylphosphine palladium (14.5 g, 12.5 mmol) and sodium carbonate (80 g, 755 mmol) were added to the reaction mixture. The reaction mixture was stirred for 20 hours at 80°C, and cooled to room temperature. After terminating the reaction with ammonium chloride aqueous solution 200 mL, the reaction mixture was extracted with ethyl acetate 1 L, and further an aqueous layer was extracted with dichloromethane 1 L. The obtained organic layer was dried with anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was filtered through silica gel, and the solvent was removed under reduced pressure. The obtained solid was washed with ethyl acetate 100 mL to produce compound 2-1 (50 g, 74 %).
Preparation of compound 2-2
After dissolving dibenzo[b,d]thiophen-2-yl boronic acid (40 g, 136.8 mmol), iodonitrobenzene (37.4 g, 150.5 mmol) and Pd(PPh3)4 (6.32 g, 5.47 mmol) in a mixture of 2M Na2CO3 (170 mL) and toluene (700 mL), the reaction mixture was stirred for 4 hours at 100°C. The reaction mixture was cooled to room temperature, distilled water was inserted, and was extracted with ethyl acetate. It was dried with MgSO4, was distillated under reduced pressure, and was filtered through column to obtain compound 2-2 (28 g, 72.86 mmol, 52.94 %).
Preparation of compound 2-3
After mixing compound 2-2 (28 g, 72.86 mmol) with triethylphosphite 300 mL, the reaction mixture was stirred for 12 hours at 150°C. The reaction mixture was cooled to room temperature, was distillated under reduced pressure, was extracted with ethyl acetate, and was washed with distilled water. It was dried with MgSO4, was distillated under reduced pressure, and was filtered through column to obtain compound 2-3 (11 g, 31.22 mmol, 43.05 %).
Preparation of compound C-32
After suspending compound 2-1 (5.1 g, 15.5 mmol) and compound 2-3 (4.2 g, 15.5 mmol) in DMF 80mL, 60% NaH (930 mg, 23.2 mmol) was added to the mixture at room temperature. The obtained reaction mixture was stirred for 12 hours. After adding purified water (1L), the mixture was filtered under reduced pressure. The obtained solid was triturated with MeOH/EA, was triturated with DMF, and was triturated with EA/THF. It was dissolved in MC, was filtered through silica, and then was triturated with MeOH/EA to obtain compound C-32 (5.4 g, 62 %).
MS/FAB found 568; calculated 567.66
Preparation Example 3: Preparation of compound C-51
Figure PCTKR2012004214-appb-I000043
Preparation of compound C-51
After suspending compound 2-1 (5.1 g, 15.5 mmol) and compound 1-3 (4.0 g, 15.5 mmol) in DMF 80mL, 60% NaH (930 mg, 23.2 mmol) was added to the mixture at room temperature, and was stirred for 12 hours. After adding purified water (1L), the mixture was filtered under reduced pressure. The obtained solid was triturated with MeOH/EA, was triturated with DMF, and was triturated with EA/THF. It was dissolved in MC, was filtered through silica, and then was triturated with MeOH/EA to obtain compound C-51 (5.9 g, 69 %).
MS/FAB found 552; calculated 551.59
Preparation Example 4: Preparation of compound C-94
Figure PCTKR2012004214-appb-I000044
Preparation of compound 4-1
After dissolving compound 1-3 (27.3 g, 106.1 mmol), 1-bromo-4-iodobenzene (45 g, 159.2 mmol), CuI (10 g, 53 mmol), K3PO4 (67.5 g, 318.3 mmol) and ethylenediamine (EDA) (7.2 mL, 106.1 mmol) in toluene (300 mL), the reaction mixture was stirred under reflux for 24 hours. It was extracted with EA, the resulting organic layer was distillated under reduced pressure, and then was filtered through column with MC and hexane to obtain compound 4-1 (32 g, 73.2 %).
Preparation of compound C-4-2
After dissolving compound 4-1 (30.9 g, 74.9 mmol) in THF (250 mL), and adding 2.5 M n-BuLi in hexane (44.9 mL, 112.4 mmol) to the reaction mixture in -78°C, the reaction mixture was stirred for 1 hour. The reaction mixture was stirred for 2 hours with adding B(Oi-Pr)3 (29.3 mL, 127.3 mmol) slowly to the reaction mixture. After quenching the reaction mixture with adding 2 M HCl, the reaction mixture was extracted with distilled water and EA. The resulting organic layer was distillated under reduced pressure, and then was recrystallized with MC and hexane to obtain compound 4-2 (22.3 g, 80%).
Preparation of compound C-94
After dissolving compound 2-1 (3.9 g, 11.9 mmol), compound 4-2 (4.0 g, 11.9 mmol), Pd(PPh3)4 (687 mg, 0.59 mmol) and Na2CO3 (3.8 g, 35.7 mmol) in a mixture of toluene (55 mL), EtOH (14 mL) and distilled water (14 mL), the reaction mixture was stirred for 2 hours at 90°C. It was extracted with distilled water and EA, the resulting organic layer was distillated under reduced pressure, and then was filtered through column with MC and hexane to obtain compound C-94 (4.5 g, 60.3 %).
MS/FAB found 628; calculated 627.69
Preparation Example 5: Preparation of compound C-96
Figure PCTKR2012004214-appb-I000045
Preparation of compound C-96
After dissolving compound 1-1 (4.8 g, 11.9 mmol), compound 4-2 (4.0 g, 11.9 mmol), Pd(PPh3)4 (687 mg, 0.59 mmol) and Na2CO3 (3.8 g, 35.7 mmol) in a mixture of toluene (55 mL), EtOH (14 mL) and distilled water (14 mL), the reaction mixture was stirred for 2 hours at 90°C. It was extracted with distilled water and EA, the resulting organic layer was distillated under reduced pressure, and then was filtered through column with MC and hexane to obtain compound C-96 (1.85 g, 22.1 %).
MS/FAB found 703; calculated 702.80
Example 1: Production of an OLED device using the compound according to the present invention
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. N1N1’-([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 60nm 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 C-16 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 were deposited in a doping amount of 4 wt% to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then,2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at same rates and were 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 150nm was 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 10.0 mA/cm2 at a driving voltage of 4.1 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 30 hours.
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 Example 1, except for using compound C-48 as a host material, and compound D-11 as a dopant.
The produced OLED device showed red emission having a luminance of 1,030 cd/m2 and a current density of 12.7 mA/cm2 at a driving voltage of 4.2 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 100 hours.
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 Example 1, except for using compound C-51 as a host material, and compound D-11 as a dopant.
The produced OLED device showed red emission having a luminance of 1,010 cd/m2 and a current density of 13.7 mA/cm2 at a driving voltage of 4.5 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 100 hours.
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 Example 1, except for using compound C-94 as a host material, and compound D-11 as a dopant.
The produced OLED device showed red emission having a luminance of 1,060 cd/m2 and a current density of 12.2 mA/cm2 at a driving voltage of 4.2 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 40 hours.
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 Example 1, except for using compound C-96 as a host material, and compound D-7 as a dopant.
The produced OLED device showed red emission having a luminance of 1,010 cd/m2 and a current density of 9.8 mA/cm2 at a driving voltage of 3.9 V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000 nit was 20 hours.
Comparative Example 1: Production of an OLED device using conventional electroluminescent compounds
An OLED device was produced in the same manner as that of Example 1, except that a light-emitting layer having a thickness of 30 nm was deposited on the hole transport layer by using 4,4’-N,N’-dicarbazol-biphenyl (CBP) as a host material and compound D-11 as a dopant and that a hole blocking layer having a thickness of 10 nm was deposited by using aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate.
The produced OLED device showed red emission having a luminance of 1,000 cd/m2 and a current density of 20.0 mA/cm2 at a driving voltage of 8.2V. Further, the minimum time taken to be reduced to 90 % of the luminance at a luminance of 5,000nit was 10 hours.
Since the compounds for organic electronic material according to the present invention have high efficiency in transporting electrons, crystallization could be prevented when manufacturing a device. Further, the compounds have good layer formability and improve the current characteristic of the device. Therefore, they can produce an organic electroluminescent device having lowered driving voltages and enhanced power efficiency. In addition, while the OLED device using conventional compounds for organic electronic material needed hole blocking layer, the hole blocking layer is not necessary in the OLED device using the compounds according to the present invention.

Claims (6)

  1. A compound represented by the following formula 1:
    Figure PCTKR2012004214-appb-I000046
    wherein
    L1 and L2 each independently represent a single bond, a substituted or unsubstituted 3- to 30-membered heteroarylene group, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted (C6-C30)cycloalkylene group;
    X1 represents CH or N;
    Y1 to Y3 each independently represent -O-, -S-, -CR6R7- or -NR8-, provided that Y2 and Y3 do not simultaneously exist;
    R1 to R5 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, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl group, -NR11R12, -SiR13R14R15, -SR16, -OR17, a cyano group, a nitro group, or a hydroxyl group; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a 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;
    R6 to R8 and R11 to R17 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, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a 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, b, c and e each independently represent an integer of 1 to 4; where a, b, c or e is an integer of 2 or more, each of R1, each of R2, each of R3 or each of R5 is the same or different;
    d represents an integer of 1 to 3; where d is an integer of 2 or more, each of R4 is the same or different; and
    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 compound according to claim 1, wherein substituents of the substituted alkyl(ene) group, the substituted alkenyl group, the substituted alkynyl group, the substituted cycloalkylene group, the substituted cycloalkyl group, the substituted heterocycloalkyl group, the substituted aryl(ene) group, the substituted heteroaryl(ene) group and the substituted aromatic ring in said L1 and L2, R1 to R5, R6 to R8 and R11 to R17 groups 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 (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, a 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.
  3. The compound according to claim 1, wherein L1 and L2 each independently represent a single bond, a 3- to 30-membered heteroarylene group, a (C6-C30)arylene group, or a (C6-C30)cycloalkylene group;
    X1 is CH or N;
    Y1 to Y3 each independently represent -O-, -S-, -CR6R7- or -NR8-, provided that Y2 and Y3 do not simultaneously exist;
    R1 to R5 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, a N-carbazolyl group, -NR11R12, or -SiR13R14R15; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a 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;
    R6 to R8 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) via a substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring;
    R11 to R15 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; and
    the arylene group, the heteroarylene group and the cycloalkylene group in L1 and L2, the alkyl group, the aryl group and the heteroaryl group in R1 to R5 and R11 to R15 can be substituted with 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 (C1-C30)alkyl (C6-C30)aryl group, a 3- to 30-membered heteroaryl group substituted or unsubstituted with a (C6-C30)aryl, a (C3-C30)cycloalkyl group and a (C6-C30)aryl(C1-C30)alkyl group.
  4. The compound according to claim 1, wherein
    the moiety:
    Figure PCTKR2012004214-appb-I000047
    in formula 1 is selected from the following structures:
    Figure PCTKR2012004214-appb-I000048
    Figure PCTKR2012004214-appb-I000049
    Figure PCTKR2012004214-appb-I000050
    Figure PCTKR2012004214-appb-I000051
  5. The compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2012004214-appb-I000052
    Figure PCTKR2012004214-appb-I000053
    Figure PCTKR2012004214-appb-I000054
    Figure PCTKR2012004214-appb-I000055
    Figure PCTKR2012004214-appb-I000056
    Figure PCTKR2012004214-appb-I000057
    Figure PCTKR2012004214-appb-I000058
    Figure PCTKR2012004214-appb-I000059
    Figure PCTKR2012004214-appb-I000060
    Figure PCTKR2012004214-appb-I000061
    Figure PCTKR2012004214-appb-I000062
    Figure PCTKR2012004214-appb-I000063
    Figure PCTKR2012004214-appb-I000064
    Figure PCTKR2012004214-appb-I000065
    Figure PCTKR2012004214-appb-I000066
    Figure PCTKR2012004214-appb-I000067
    Figure PCTKR2012004214-appb-I000068
    Figure PCTKR2012004214-appb-I000069
    Figure PCTKR2012004214-appb-I000070
    Figure PCTKR2012004214-appb-I000071
    Figure PCTKR2012004214-appb-I000072
    Figure PCTKR2012004214-appb-I000073
  6. An organic electroluminescent device comprising the compound according to claim 1.
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