WO2013032284A1 - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent device using the same Download PDF

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WO2013032284A1
WO2013032284A1 PCT/KR2012/007008 KR2012007008W WO2013032284A1 WO 2013032284 A1 WO2013032284 A1 WO 2013032284A1 KR 2012007008 W KR2012007008 W KR 2012007008W WO 2013032284 A1 WO2013032284 A1 WO 2013032284A1
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substituted
unsubstituted
alkyl
aryl
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Inventor
Hee-Choon Ahn
Young-Jun Cho
Nam-Kyun Kim
Hyo-Nim Shin
Hyuck-Joo Kwon
Kyung-Joo Lee
Bong-Ok Kim
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Priority to CN201280049555.4A priority Critical patent/CN103857680A/en
Priority to JP2014528289A priority patent/JP2014531747A/en
Publication of WO2013032284A1 publication Critical patent/WO2013032284A1/en
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Definitions

  • the present invention relates to novel organic electroluminescent compounds 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 together 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 an organic electroluminescent compound 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 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 (C3-C30)cycloalkylene group;
  • X 1 represents CH or N
  • Y 1 and Y 2 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 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, -NR 11 R 12 , -SiR 13 R 14 R 15 , -SR 16 , -OR 17 , a cyano group, a nitro group, or a hydroxyl group; or R 4 and R 5 each independently are linked to an adjacent substituent(s) via a substituted or unsubstituted (
  • 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 a substituted or unsubstituted (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 heteroatom 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 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; and
  • he organic electroluminescent compounds according to the present invention can manufacture an organic electroluminescent device which has high luminous efficiency and a long operation lifetime.
  • the organic electroluminescent compounds 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 characteristics 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 represented by the above formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent 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., 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.
  • (C3-C30)cycloalkylene is one formed by removing a hydrogen from cycloalkyl having 3 to 30, preferably 3 to 20, more preferably 3 to 7 carbon atoms.
  • halogen includes F, Cl, Br and I.
  • (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.
  • the naphthyl includes 1-naphthyl, 2-naphthyl, etc.; the anthracenyl includes 1-anthracenyl, 2- anthracenyl, 9-anthracenyl, etc.; the phenanthrenyl includes 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, etc.; the naphthacenyl includes 1-naphthacenyl, 2-naphthacenyl, 9-naphthacenyl, etc.; the pyrenyl includes 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, etc.; the biphenyl includes 2-biphenyl, 3-biphenyl, 4- biphenyl, etc.; the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-
  • the heteroaryl(ene) includes a divalent aryl group, which forms an N-oxide, a quaternary salt, etc., by oxidation or quaternarization of a heteroatom existing in a ring.
  • the heteroaryl(ene) 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., a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenz
  • the pyrrolyl includes 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, etc.; the pyridyl includes 2-pyridyl, 3-pyridyl, 4-pyridyl, etc.; the indolyl includes 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, etc.; the isoindolyl includes 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, etc.; the furyl includes 2-furyl, 3-furyl, etc.; the benzofuranyl includes 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl
  • 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 represent a single bond, a 3- to 30-membered heteroarylene group, a (C6-C30)arylene group, or a (C6-C30)cycloalkylene group;
  • X 1 is CH or N;
  • Y 1 and Y 2 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 (C1-C30)alkyl group, a (C6-C30)aryl group, a 3- to 30-membered heteroaryl group, a N-carbazolyl group, -NR 11 R 12 , or -SiR 13 R 14 R 15 ; or
  • R 4 and R 5 each independently are linked to an adjacent substituent(s) via a (C3-C30)alkylene or a (C3-C30)alkenylene group to form a mono- or poly
  • L 1 and L 2 each independently are preferably selected from the group consisting of a single bond, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, phenylene, methylphenylene, naphthylene, biphenylene, terphenylene, anthracenylene, indenylene, fluorenylene, phenanthrenylene, triphenylenylene, pyrenylene, phenylenylene, crycenylene, naphthacenylene, fluoranthenyl, furylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, tri
  • Y 1 and Y 2 each independently selected from the following structures:
  • R 1 to R 5 each independently are preferably a (C6-C20)aryl group, an 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 a substituted or unsubstituted (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring, more preferably phenyl, carbazolyl, diphenylamino or methyldiphenylsilyl; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or a substituted or unsubstituted (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring.
  • the R 11 to R 15 each independently are preferably are
  • R 6 to R 8 each independently are preferably hydrogen, a (C1-C6)alkyl group, a substituted or unsubstituted (C6-C20)aryl group, or a substituted or unsubstituted 5- to 21-membered heteroaryl group, more preferably hydrogen; methyl; phenyl; biphenyl; naphthyl; phenyl substituted with deuterium; phenyl substituted with fluorine; fluorenyl substituted with methyl; or naphthylphenyl.
  • the representative organic electroluminescent compounds of the present invention include the following compounds, but are not limited thereto:
  • organic electroluminescent compounds according to the present invention can be prepared according to the following reaction scheme.
  • L 1 , L 2 , X 1 , Y 1 , Y 2 , R 1 to R 5 , a, b, c, d and e are as defined in formula 1 above, and Hal represents a halogen.
  • the present invention provides an organic electroluminescent material comprising the compound of formula 1 and an organic electroluminescent device comprising the material.
  • the above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • 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 organic electroluminescent compound of formula 1 according to the present invention.
  • said organic layer comprises a light-emitting layer in which the organic electroluminescent 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 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 3- 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 organic electroluminescent 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 organic electroluminescent 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 SiOX(1 ⁇ X ⁇ 2), AlOX(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.
  • reaction mixture was extracted with ethyl acetate (EA) 1 L and an aqueous layer was further extracted with dichloromethane (1 L).
  • EA ethyl acetate
  • 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 EA (100 mL) to obtain compound 1-1 (50 g, 74%).
  • 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 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.
  • ITO indium tin oxide
  • N 1 N 1 ’-([1,1’-biphenyl]-4,4’-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was 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-18 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% of dopant with respect to the total amount of the host material and the dopant 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 the same rates and were deposited in a doping amount of 50 wt% for each material to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 1 to 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.
  • the produced OLED device showed red emission having a luminance of 3,400 cd/m 2 and a current density of 44.7 mA/cm 2 at a driving voltage of 5.6 V.
  • Comparative Example 1 Production of an OLED device using conventional
  • An OLED device was produced in the same manner as that of Device Example 1, except that a light-emitting layer 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 between the light-emitting layer and a electron transport layer 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 8.2 V.

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Abstract

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

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device 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.
Figure PCTKR2012007008-appb-I000001
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.
Figure PCTKR2012007008-appb-I000002
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 together 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 an organic electroluminescent compound 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 an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2012007008-appb-I000003
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 (C3-C30)cycloalkylene group;
X1 represents CH or N;
Y1 and Y2 each independently represent -O-, -S-, -CR6R7- or -NR8-;
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 R4 and R5 each independently are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or a substituted or unsubstituted (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 heteroatom 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 a substituted or unsubstituted (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 heteroatom 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 heteroatom selected from B, N, O, S, P(=O), Si and P.
he organic electroluminescent compounds 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 organic electroluminescent compounds 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 characteristics 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 represented by the above formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent 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., but are not limited thereto.
Herein, “(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.
Herein, “(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.
Herein, “(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.
Herein, “(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.
Herein, “(C3-C30)cycloalkylene” is one formed by removing a hydrogen from cycloalkyl having 3 to 30, preferably 3 to 20, more preferably 3 to 7 carbon atoms.
Herein, “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.
Herein, “halogen” includes F, Cl, Br and I.
Herein, “(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. The naphthyl includes 1-naphthyl, 2-naphthyl, etc.; the anthracenyl includes 1-anthracenyl, 2- anthracenyl, 9-anthracenyl, etc.; the phenanthrenyl includes 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, etc.; the naphthacenyl includes 1-naphthacenyl, 2-naphthacenyl, 9-naphthacenyl, etc.; the pyrenyl includes 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, etc.; the biphenyl includes 2-biphenyl, 3-biphenyl, 4- biphenyl, etc.; the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, etc.; the fluorenyl includes 1-fluorenyl, 2- fluorenyl, 3-fluorenyl, 4-fluorenyl, 9-fluorenyl, etc.
Herein, “3- to 30-membered heteroaryl(ene)” is an aryl having at least one, preferably 1 to 4 heteroatoms 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). The heteroaryl(ene) includes a divalent aryl group, which forms an N-oxide, a quaternary salt, etc., by oxidation or quaternarization of a heteroatom existing in a ring. The heteroaryl(ene) 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., a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc., and N-oxides (for example, pyridyl N-oxide and quinolyl N-oxide) and quaternary salts thereof, but are not limited thereto. The pyrrolyl includes 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, etc.; the pyridyl includes 2-pyridyl, 3-pyridyl, 4-pyridyl, etc.; the indolyl includes 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, etc.; the isoindolyl includes 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, etc.; the furyl includes 2-furyl, 3-furyl, etc.; the benzofuranyl includes 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, etc.; isobenzofuranyl includes 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, etc.; quinolyl includes 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, etc.; the isoquinolyl includes 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, etc.; the quinoxalinyl includes 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, etc.; the carbazolyl includes 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl, etc.; the phenanthridinyl includes 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, etc.; the acridinyl includes 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, etc.; the phenanthrolinyl includes 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,7-phenanthroline-5-yl, 1,7-phenanthroline-6-yl, 1,7-phenanthroline-8-yl, 1,7-phenanthroline-9-yl, 1,7-phenanthroline-10-yl, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4-yl, 1,8-phenanthroline-5-yl, 1,8-phenanthroline-6-yl, 1,8-phenanthroline-7-yl, 1,8-phenanthroline-9-yl, 1,8-phenanthroline-10-yl, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthroline-4-yl, 1,9-phenanthroline-5-yl, 1,9-phenanthroline-6-yl, 1,9-phenanthroline-7-yl, 1,9-phenanthroline-8-yl, 1,9-phenanthroline-10-yl, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1,10-phenanthroline-5-yl, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4-yl, 2,9-phenanthroline-5-yl, 2,9-phenanthroline-6-yl, 2,9-phenanthroline-7-yl, 2,9-phenanthroline-8-yl, 2,9-phenanthroline-10-yl, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2,8-phenanthroline-5-yl, 2,8-phenanthroline-6-yl, 2,8-phenanthroline-7-yl, 2,8-phenanthroline-9-yl, 2,8-phenanthroline-10-yl, 2,7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7-phenanthroline-5-yl, 2,7-phenanthroline-6-yl, 2,7-phenanthroline-8-yl, 2,7-phenanthroline-9-yl, 2,7-phenanthroline-10-yl, etc.; the phenazinyl includes 1-phenazinyl, 2-phenazinyl, etc.; the phenothiazinyl includes 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, 10-phenothiazinyl, etc.; the phenoxazinyl includes 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, etc.; the oxazolyl includes 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, etc.; the oxadiazolyl includes 2-oxadiazolyl, 5-oxadiazolyl, etc.; the furazanyl includes 3-furazanyl, etc.; the dibenzofuranyl includes 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl, etc.; and the dibenzothiophenyl includes 1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl, 4-dibenzothiophenyl, etc.
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 cycloalkyl(ene) group, the substituted heterocycloalkyl group, the substituted aryl(ene) group, the substituted heteroaryl(ene) group, the substituted arylalkyl group and the substituted aromatic ring in L1, L2, R1 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, a 3- to 30-membered heteroaryl group substituted with a (C1-C30)alkyl, a 3- to 30-membered heteroaryl group substituted 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 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; more preferably at least one selected from the group consisting of deuterium, a halogen, a (C1-C20)alkyl group substituted or unsubstituted with a halogen and a (C6-C20)aryl group; even more preferably at least one selected from the group consisting of deuterium, fluorine, methyl, phenyl and naphthyl.
Specifically, in the above formula 1, 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 and Y2 each independently represent -O-, -S-, -CR6R7- or -NR8-; R1 to R5 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group, a (C6-C30)aryl group, a 3- to 30-membered heteroaryl group, a N-carbazolyl group, -NR11R12, or -SiR13R14R15; or R4 and R5 each independently are linked to an adjacent substituent(s) via a (C3-C30)alkylene or a (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 heteroatom selected from nitrogen, oxygen and sulfur; R6 to R8 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; R11 to R15 each independently represent a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group; and the arylene group, the heteroarylene group and the cycloalkylene group in L1 and L2, and the alkyl group, the aryl group and the heteroaryl group in R1 to R8 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, a 3- to 30-membered heteroaryl group substituted with a (C6-C30)aryl, a (C3-C30)cycloalkyl group and a (C6-C30)aryl(C1-C30)alkyl group.
In the above formula 1, L1 and L2 each independently are preferably selected from the group consisting of a single bond, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, phenylene, methylphenylene, naphthylene, biphenylene, terphenylene, anthracenylene, indenylene, fluorenylene, phenanthrenylene, triphenylenylene, pyrenylene, phenylenylene, crycenylene, naphthacenylene, fluoranthenyl, 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, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenanthridinylene, benzodioxolylene, dibenzofuranylene and dibenzothiophenylene, and the L1 and L₂ can be substituted with at least one selected from the group consisting of deuterium, a halogen, (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, a 3- to 30-membered heteroaryl group substituted with a (C6-C30)aryl, a (C3-C30)cycloalkyl group and a (C6-C30)aryl(C1-C30)alkyl. In the above formula 1, L1 and L2 each independently are more preferably selected from the group consisting of a single bond, phenylene, methylphenylene and cyclohexylene.
In the above formula 1, Y1 and Y2 each independently selected from the following structures:
Figure PCTKR2012007008-appb-I000004
Figure PCTKR2012007008-appb-I000005
In the above formula 1, R1 to R5 each independently are preferably a (C6-C20)aryl group, an 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 a substituted or unsubstituted (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring, more preferably phenyl, carbazolyl, diphenylamino or methyldiphenylsilyl; or are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or a substituted or unsubstituted (C3-C30)alkenylene group to form a mono- or polycyclic, alicyclic or aromatic ring. The R11 to R15 each independently are preferably a (C1-C6)alkyl group or a (C6-C20)aryl group, more preferably methyl or phenyl.
In the above formula 1, R6 to R8 each independently are preferably hydrogen, a (C1-C6)alkyl group, a substituted or unsubstituted (C6-C20)aryl group, or a substituted or unsubstituted 5- to 21-membered heteroaryl group, more preferably hydrogen; methyl; phenyl; biphenyl; naphthyl; phenyl substituted with deuterium; phenyl substituted with fluorine; fluorenyl substituted with methyl; or naphthylphenyl.
In the above formula 1,
Figure PCTKR2012007008-appb-I000006
is selected from the following structures, but are not limited thereto:
Figure PCTKR2012007008-appb-I000007
Figure PCTKR2012007008-appb-I000008
Figure PCTKR2012007008-appb-I000009
Figure PCTKR2012007008-appb-I000010
Figure PCTKR2012007008-appb-I000011
Figure PCTKR2012007008-appb-I000012
The representative organic electroluminescent compounds of the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2012007008-appb-I000013
Figure PCTKR2012007008-appb-I000014
Figure PCTKR2012007008-appb-I000015
Figure PCTKR2012007008-appb-I000016
Figure PCTKR2012007008-appb-I000017
Figure PCTKR2012007008-appb-I000018
Figure PCTKR2012007008-appb-I000019
Figure PCTKR2012007008-appb-I000020
Figure PCTKR2012007008-appb-I000021
Figure PCTKR2012007008-appb-I000022
Figure PCTKR2012007008-appb-I000023
Figure PCTKR2012007008-appb-I000024
Figure PCTKR2012007008-appb-I000025
Figure PCTKR2012007008-appb-I000026
Figure PCTKR2012007008-appb-I000027
Figure PCTKR2012007008-appb-I000028
Figure PCTKR2012007008-appb-I000029
Figure PCTKR2012007008-appb-I000030
The organic electroluminescent compounds according to the present invention can be prepared according to the following reaction scheme.
[Reaction Scheme 1]
Figure PCTKR2012007008-appb-I000031
wherein L1, L2, X1, Y1, Y2, R1 to R5, a, b, c, d and e are as defined in formula 1 above, and Hal represents a halogen.
In addition, the present invention provides an organic electroluminescent material comprising the compound of formula 1 and an organic electroluminescent device comprising the material. The above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials. 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 organic electroluminescent compound of formula 1 according to the present invention. Further, said organic layer comprises a light-emitting layer in which the organic electroluminescent 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 PCTKR2012007008-appb-I000032
wherein M1 is selected from the group consisting of Ir, Pt, Pd and Os; and
L101, L102 and L103 are each independently selected from the following structures:
Figure PCTKR2012007008-appb-I000033
Figure PCTKR2012007008-appb-I000034
Figure PCTKR2012007008-appb-I000035
Figure PCTKR2012007008-appb-I000036
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 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 3- 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 PCTKR2012007008-appb-I000037
,
Figure PCTKR2012007008-appb-I000038
or
Figure PCTKR2012007008-appb-I000039
; 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 PCTKR2012007008-appb-I000040
Figure PCTKR2012007008-appb-I000041
Figure PCTKR2012007008-appb-I000042
Figure PCTKR2012007008-appb-I000043
Figure PCTKR2012007008-appb-I000044
Figure PCTKR2012007008-appb-I000045
The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent 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 organic electroluminescent 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 organic electroluminescent 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 C-18
Figure PCTKR2012007008-appb-I000046
Preparation of compound 1-1
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 purified water (200 mL), Pd(PPh3)4 (14.5 g, 12.5 mmol) and Na2CO3 (80 g, 755 mmol) was added to the mixture. The mixture was stirred for 20 hours at 80°C. The reaction mixture was cooled to room temperature, and the reaction was terminated with ammonium chloride aqueous solution (200 mL). The reaction mixture was extracted with ethyl acetate (EA) 1 L and an aqueous layer was further 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 EA (100 mL) to obtain compound 1-1 (50 g, 74%).
Preparation of compound 1-2
After dissolving 9-phenyl-9H-carbazol-3-yl boronic acid (30 g, 149 mmol), 1-bromo-2-nitrobenzene (51 g, 178.8 mmol), K2CO3 (52 g, 372.5 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 and triturated with methylene chloride (MC), and then was filtered to obtain compound 1-2 (50 g, 92%).
Preparation of compound 1-3
After dissolving compound 1-2 (50 g, 137 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 and extracted with EA. Then, the organic layer was concentrated and purified through silica column to obtain compound 1-3 (32 g, 70%).
Preparation of compound C-18
After suspending compound 1-1 (5.5 g, 16.5 mmol) and compound 1-3 (5.0 g, 15 mmol) in dimethyl formamide (DMF) 80mL, 60% NaH (930 mg, 23.2 mmol) was added to the mixture at room temperature. The reaction mixture was stirred for 12 hours. After adding purified water (1 L), 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 and was filtered through silica. Then, it was triturated with MeOH/EA to obtain compound C-18 (4.6 g, 48.9%).
MS/FAB found 627; calculated 626.70
Device Example 1: Production of an organic light-emitting diode (OLED) device using the organic electroluminescent 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 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 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 C-18 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% of dopant with respect to the total amount of the host material and the dopant 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 the same rates and were deposited in a doping amount of 50 wt% for each material to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 1 to 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.
The produced OLED device showed red emission having a luminance of 3,400 cd/m2 and a current density of 44.7 mA/cm2 at a driving voltage of 5.6 V.
Comparative Example 1: Production of an OLED device using conventional
electroluminescent material
An OLED device was produced in the same manner as that of Device Example 1, except that a light-emitting layer 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 between the light-emitting layer and a electron transport layer 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 8.2 V.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2012007008-appb-I000047
    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 (C3-C30)cycloalkylene group;
    X1 represents CH or N;
    Y1 and Y2 each independently represent -O-, -S-, -CR6R7- or -NR8-;
    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 R4 and R5 each independently are linked to an adjacent substituent(s) via a substituted or unsubstituted (C3-C30)alkylene or a substituted or unsubstituted (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 heteroatom 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 a substituted or unsubstituted (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 heteroatom 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 heteroatom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein substituents of the substituted alkyl(ene) group, the substituted alkenylene group, the substituted cycloalkyl(ene) group, the substituted heterocycloalkyl group, the substituted aryl(ene) group, the substituted heteroaryl(ene) group, the substituted arylalkyl group and the substituted aromatic ring in said L1 and L2, R1 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, a 3- to 30-membered heteroaryl group substituted with a (C1-C30)alkyl, a 3- to 30-
    membered heteroaryl group substituted 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 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.
  3. The organic electroluminescent 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 and Y2 each independently represent -O-, -S-, -CR6R7- or -NR8-;
    R1 to R5 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group, a (C6-C30)aryl group, a 3- to 30-membered heteroaryl group, a N-carbazolyl group, -NR11R12, or -SiR13R14R15; or R4 and R5 each independently are linked to an adjacent substituent(s) via a (C3-C30)alkylene or a (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 heteroatom selected from nitrogen, oxygen and sulfur;
    R6 to R8 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;
    R11 to R15 each independently represent a (C1-C30)alkyl group, a (C6-C30)aryl group, or a 3- to 30-membered heteroaryl group; and
    the arylene group, the heteroarylene group and the cycloalkylene group in L1 and L2, and the alkyl group, the aryl group and the heteroaryl group in R1 to R8 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, a 3- to 30-membered heteroaryl group substituted with a (C6-C30)aryl, a (C3-C30)cycloalkyl group and a (C6-C30)aryl(C1-C30)alkyl group.
  4. The organic electroluminescent compound according to claim 1, wherein
    the moiety:
    Figure PCTKR2012007008-appb-I000048
    in formula 1 is selected from the following structures:
    Figure PCTKR2012007008-appb-I000049
    Figure PCTKR2012007008-appb-I000050
    Figure PCTKR2012007008-appb-I000051
    Figure PCTKR2012007008-appb-I000052
    Figure PCTKR2012007008-appb-I000053
    Figure PCTKR2012007008-appb-I000054
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2012007008-appb-I000055
    Figure PCTKR2012007008-appb-I000056
    Figure PCTKR2012007008-appb-I000057
    Figure PCTKR2012007008-appb-I000058
    Figure PCTKR2012007008-appb-I000059
    Figure PCTKR2012007008-appb-I000060
    Figure PCTKR2012007008-appb-I000061
    Figure PCTKR2012007008-appb-I000062
    Figure PCTKR2012007008-appb-I000063
    Figure PCTKR2012007008-appb-I000064
    Figure PCTKR2012007008-appb-I000065
    Figure PCTKR2012007008-appb-I000066
    Figure PCTKR2012007008-appb-I000067
    Figure PCTKR2012007008-appb-I000068
    Figure PCTKR2012007008-appb-I000069
    Figure PCTKR2012007008-appb-I000070
    Figure PCTKR2012007008-appb-I000071
    Figure PCTKR2012007008-appb-I000072
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2012/007008 2011-09-01 2012-08-31 Novel organic electroluminescent compounds and organic electroluminescent device using the same Ceased WO2013032284A1 (en)

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