WO2014104704A1 - Novel organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

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

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WO2014104704A1
WO2014104704A1 PCT/KR2013/012078 KR2013012078W WO2014104704A1 WO 2014104704 A1 WO2014104704 A1 WO 2014104704A1 KR 2013012078 W KR2013012078 W KR 2013012078W WO 2014104704 A1 WO2014104704 A1 WO 2014104704A1
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substituted
unsubstituted
organic electroluminescent
alkyl
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Doo-Hyeon Moon
Hee-Choon Ahn
Kyung-Joo Lee
Tae-Jin Lee
Hyuck-Joo Kwon
Bong-Ok Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Definitions

  • the present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as material for forming a light-emitting layer [see Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminescent efficiency of an organic EL device is a light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • developing phosphorescent materials is one of the best methods to theoretically enhance luminescent efficiency by four (4) times compared to fluorescent materials.
  • 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.
  • R 1 and R 2 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are fused to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
  • X represents -O-, -S- or -N(R 3 )-;
  • R 3 to R 7 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 5- 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 10 R 11 , -SiR 12 R 13 R 14 , -SR 15 , -OR 16 , a cyano group, a nitro group or a hydroxyl group;
  • R 10 to R 16 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 5- 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) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • a, c and d each independently represent an integer of 1 to 4; where a, c or d is an integer of 2 or more, each R 4 , each R 6 or each R 7 is the same or different;
  • b represents an integer of 1
  • L 1 to L 3 each independently represent a single bond, a substituted or unsubstituted (C2-C30)alkylene group, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
  • Ar 1 to Ar 6 each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group; or Ar 1 and Ar 2 , Ar 3 and Ar 4 , or Ar 5 and Ar 6 are fused to form a substituted or unsubstituted mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and
  • l, m and n each independently represent 0 or 1 and l+m+n is 1 or more.
  • the organic electroluminescent compounds according to the present invention have excellent luminescent property. Furthermore, OLED devices comprising the organic electroluminescent compounds according to the present invention provide excellent luminescent property and current efficiency.
  • the present invention relates to an organic electroluminescent compound represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the material.
  • the organic electroluminescent compound represented by formula 1 is described in detail below.
  • X, R 3 to R 7 , R 10 to R 16 , L 1 to L 3 , Ar 1 to Ar 6 , a, c, d and b are as defined in formula 1 above;
  • R 8 is as defined in R 3 of formula 1 above;
  • Ar 7 and Ar 8 are as defined in Ar 1 of formula 1 above;
  • L 4 is as defined in L 1 of formula 1 above;
  • l, m, n and o each independently represent 0 or 1 and l+m+n+o is 1 or more;
  • L 1 to L 4 each independently represent a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
  • (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 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
  • the compounds according to the present invention include the following compounds, but are not limited thereto:
  • organic electroluminescent compounds according to the present invention can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction schemes 1 and 2:
  • L 1 , L 4 , Ar 1 , Ar 2 , Ar 7 , Ar 8 , R 1 to R 9 , X, a to f are as defined in formulae 1 and 2 above, and Hal represents a halogen.
  • the light-emitting layer may comprise known light-emitting materials or other compounds of the present invention which are not the compounds used as the hole transport material as the light-emitting material.
  • the known light-emitting materials may be known host materials and may comprise at least one dopant.
  • the known host materials may be known fluorescent or phosphorescent host materials.
  • the second host material can be any of the known phosphorescent hosts and preferably, is selected from the group consisting of the compounds of the following formulae 3 to 5 in view of luminescent efficiency:
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
  • M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group;
  • h and i each independently represent an integer of 1 to 3;
  • the second host material includes the following:
  • TPS represents triphenylsilyl
  • L is selected from the following structures:
  • R 100 represents hydrogen, or a substituted or unsubstituted (C1-C30) alkyl group
  • R 101 to R 109 and R 111 to R 123 each independently represent hydrogen, deuterium, a halogen; a (C1-C30) alkyl group unsubstituted or substituted with halogen(s); a cyano group, or a substituted or unsubstituted (C1-C30) alkoxy group
  • R 120 to R 123 are linked to an adjacent substituent(s) to form a fused ring, for example, a quinoline ring
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30) alkyl group, or a substituted or unsubstituted (C6-C30) aryl group; when R 124 to R 127 are aryl groups, they are linked to an adjacent substituent(s) to form
  • the organic electroluminescent device of the present invention comprises the compounds of formula 1 in the organic layer and may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the mixture was reflux stirred for 8 hours. After cooling the mixture to room temperature, the mixture was extracted with ethyl acetate (100.0 mL) and the obtained organic layer was washed with distilled water (50.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with methanol, filtered and dried. The obtained product was separated through column chromatography on silica gel and recrystallization to obtain 4-(10,10-dimethyl-10 H -benzofuro[3,2- b ]indolo[3,2,1- de ]-acridine-8-yl)phenyl)-N-phenyl-[1,1’-biphenyl]-4-amine(4.8 g, 46 %).
  • compound C-3 was introduced into another cell of the 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, 9-(4,6-diphenyl-1,3,5-triazine-2-yl)-7,9’-diphenyl-9H,9’H-3,3’-bicarbazole as a host was introduced into one cell of the vacuum vapor depositing apparatus, and compound D-1 as a dopant was introduced into another cell.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed green emission having a luminance of 3980 cd/m 2 and a current density of 8.6 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except that compound C-57 was deposited as a hole transport layer having a thickness of 20 nm; and 9-phenyl-3-(4-(9-(4-phenylquinazoline-2-yl)-9H-carbazole-3-yl)phenyl)-9H-carbazole as a host was introduced into one cell of the vacuum vapor depositing apparatus, and compound D-37 as a dopant was introduced into another cell, and the two materials were evaporated at different rates and the dopant was deposited in a doping amount of 3 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • the produced OLED device showed red emission having a luminance of 1100 cd/m 2 and a current density of 8.0 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except that compound C-142 was deposited as a hole transport layer having a thickness of 20 nm.
  • the produced OLED device showed green emission having a luminance of 1500 cd/m 2 and a current density of 3.0 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 2, except that compound C-144 was deposited as a hole transport layer having a thickness of 20 nm.
  • the produced OLED device showed red emission having a luminance of 3500 cd/m 2 and a current density of 27.3 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 2, except that compound C-212 was deposited as a hole transport layer having a thickness of 20 nm.
  • the produced OLED device showed red emission having a luminance of 700 cd/m 2 and a current density of 4.9 mA/cm 2 .
  • the produced OLED device showed green emission having a luminance of
  • Comparative Example 1 Production of an OLED device by using conventional
  • An OLED device was produced in the same manner as in Device Example 1, except that compound R-1 was deposited as a hole transport layer having a thickness of 20 nm; 4,4’-N,N’-dicarbazole-biphenyl as a host and compound D-15 as a dopant were used as light-emitting materials to form a light-emitting layer having a thickness of 30 nm on the hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was deposited as a hole blocking layer having a thickness of 10 nm.
  • the produced OLED device showed green emission having a luminance of 3350 cd/m 2 and a current density of 10.2 mA/cm 2 .
  • Comparative Example 2 Production of an OLED device by using conventional
  • An OLED device was produced in the same manner as in Device Example 1, except that compound R-1 was deposited as a hole transport layer having a thickness of 20 nm; CBP as a host and compound D-15 as a dopant and compound D-50 as a dopant were used as light-emitting materials to form a light-emitting layer having a thickness of 30 nm on the hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was deposited as a hole blocking layer having a thickness of 10 nm.
  • the produced OLED device showed red emission having a luminance of 1180 cd/m 2 and a current density of 17.4 mA/cm 2 .
  • the organic electroluminescent compounds of the present invention have higher luminescent efficiency than conventional materials. Furthermore, the organic electroluminescent devices comprising the organic electroluminescent compounds of the present invention have high current efficiency.

Abstract

The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same. The organic electroluminescent compounds of the present invention have higher luminescent efficiency than conventional materials. Furthermore, the organic electroluminescent devices comprising the organic electroluminescent compounds of the present invention have high current efficiency.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as material for forming a light-emitting layer [see Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminescent efficiency of an organic EL device is a light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, developing phosphorescent materials is one of the best methods to theoretically enhance luminescent efficiency by four (4) times compared to fluorescent materials. Until now, 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.
A mixed system of a host/light-emitting material (dopant) can be used as a light-emitting material to improve color purity, luminescent efficiency and stability. If the light-emitting material (dopant)/host material system is used, the selection of the host material is important because the host material greatly influences on efficiency and property of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known as phosphorescent host material. Pioneer (Japan) et al., currently developed a high performance organic EL device by employing bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq), which were used in a hole blocking layer, as host materials.
Although these phosphorescent host materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperatures 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 voltage. An organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) and has a higher driving voltage than one comprising fluorescent host materials. Thus, the EL device using conventional phosphorescent materials has no advantage in terms of power efficiency (lm/W). (3) Furthermore, the operating lifespan and luminous efficiency of the organic EL device are not satisfactory.
Meanwhile, copper phthalocyanine (CuPc), 4,4’-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N’-diphenyl-N,N’-bis(3-methylphenyl)-(1,1’-biphenyl)-4,4’-diamine (TPD), 4,4’,4”-tris(3-methylphenylphenylamino)triphenylamine (MTDATA), etc., have been used as hole injection and transport materials in the organic EL device. However, the organic EL device comprising the materials has low quantum efficiency and a short operating lifespan, because, when the organic EL device is driven at a high current, thermal stress is generated between an anode and a hole injection layer, thereby rapidly reducing the operating lifespan of the device. Furthermore, holes greatly move in organic materials used in a hole injection layer, and thus the hole-electron charge balance is broken and quantum efficiency (cd/A) is reduced.
Korean Patent Application Laid-open Nos. 10-2011-0066763 and 10-2012-0015883 disclose, as compounds for an organic EL device, indoloacridine-based compounds and spiroindoloacridine-based compounds, respectively. However, the organic EL device comprising said compounds are not still satisfactory in view of power efficiency, quantum efficiency and lifespan.
The objective of the present invention is to provide an organic electroluminescent compound having higher luminescent efficiency than the conventional material, and to provide an organic electroluminescent device high current efficiency by using the organic electroluminescent compound.
The present inventors found that the above objective can be achieved by an amine derivative compound represented by the following formula 1 wherein benzofuran, benzothiophene or indole is fused to indoloacridine or spiroindoloacridine:
Figure PCTKR2013012078-appb-I000001
wherein
R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C3-C30)cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are fused to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
X represents -O-, -S- or -N(R3)-;
R3 to R7 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 5- 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, -NR10R11, -SiR12R13R14, -SR15, -OR16, a cyano group, a nitro group or a hydroxyl group;
R10 to R16 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 5- 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) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
a, c and d each independently represent an integer of 1 to 4; where a, c or d is an integer of 2 or more, each R4, each R6 or each R7 is the same or different;
b represents an integer of 1;
the heteroaryl(ene) group and heterocycloalkyl group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P;
L1 to L3 each independently represent a single bond, a substituted or unsubstituted (C2-C30)alkylene group, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
Ar1 to Ar6 each independently represent a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group; or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 are fused to form a substituted or unsubstituted mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and
l, m and n each independently represent 0 or 1 and l+m+n is 1 or more.
The organic electroluminescent compounds according to the present invention have excellent luminescent property. Furthermore, OLED devices comprising the organic electroluminescent compounds according to the present invention provide excellent luminescent property and current efficiency.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention relates to an organic electroluminescent compound represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the material.
The organic electroluminescent compound represented by formula 1 is described in detail below.
The amine derivative of formula 1 is represented by the following formula 2:
Figure PCTKR2013012078-appb-I000002
wherein
X, R3 to R7, R10 to R16, L1 to L3, Ar1 to Ar6, a, c, d and b are as defined in formula 1 above;
R8 is as defined in R3 of formula 1 above;
R9 represents hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- 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, -NR10R11, -SiR12R13R14, -SR15, -OR16, a cyano group, a nitro group or a hydroxyl group; or is linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
Ar7 and Ar8 are as defined in Ar1 of formula 1 above;
L4 is as defined in L1 of formula 1 above;
l, m, n and o each independently represent 0 or 1 and l+m+n+o is 1 or more; and
e and f each independently represent an integer of 1 to 4; where e or f is an integer of 2 or more, each R8 or each R9 is the same or different.
Preferably, in formulae 1 and 2, R1 and R2 each independently represent hydrogen, or a substituted or unsubstituted (C1-C30)alkyl group; or are fused to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
R3 to R8 each independently represent hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, more preferably a (C6-C30)aryl group substituted with a 5- to 30-membered heteroaryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or -NR10R11;
R9 is linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic ring;
R10 and R11 each independently represent a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, more preferably a (C6-C30)aryl group substituted with a (C1-C30)alkyl group, a halogen, a 5- to 30-membered heteroaryl group or a cyano group, or a 5- to 30-membered heteroaryl group substituted with a (C6-C30)aryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
L1 to L4 each independently represent a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group; and
Ar1 to Ar8 each independently represent a (C6-C30)aryl group substituted with a (C1-C30)alkyl group or a (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “(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 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “5- to 30-membered heteroaryl(ene)” is an aryl group having at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, and 5 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; has preferably 5 to 15 ring backbone atoms; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. “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 (C1-C30) alkyl group, the substituted (C2-C30) alkenyl group, the substituted (C3-C30) cycloalkyl group, the substituted (C3-C30) cycloalkenyl group, the substituted 3- to 7-membered heterocycloalkyl group, the substituted (C6-C30) aryl(ene) group, the substituted 5- to 30-membered heteroaryl(ene) group and the substituted mono- or polycyclic (C3-C30) alicyclic or aromatic ring in L1 to L4, Ar1 to Ar8, and R1 to R16 of formulae 1 and 2 each independently are at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 5- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a (C6-C30)aryl group which is unsubstituted or substituted with a 5- to 30-membered heteroaryl 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; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30)alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl group; 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; and a (C1-C30)alkyl(C6-C30)aryl group.
The compounds according to the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2013012078-appb-I000003
Figure PCTKR2013012078-appb-I000004
Figure PCTKR2013012078-appb-I000005
Figure PCTKR2013012078-appb-I000006
Figure PCTKR2013012078-appb-I000007
Figure PCTKR2013012078-appb-I000008
Figure PCTKR2013012078-appb-I000009
Figure PCTKR2013012078-appb-I000010
Figure PCTKR2013012078-appb-I000011
Figure PCTKR2013012078-appb-I000012
Figure PCTKR2013012078-appb-I000013
Figure PCTKR2013012078-appb-I000014
Figure PCTKR2013012078-appb-I000015
Figure PCTKR2013012078-appb-I000016
Figure PCTKR2013012078-appb-I000017
Figure PCTKR2013012078-appb-I000018
Figure PCTKR2013012078-appb-I000019
Figure PCTKR2013012078-appb-I000020
Figure PCTKR2013012078-appb-I000021
Figure PCTKR2013012078-appb-I000022
Figure PCTKR2013012078-appb-I000023
Figure PCTKR2013012078-appb-I000024
Figure PCTKR2013012078-appb-I000025
Figure PCTKR2013012078-appb-I000026
Figure PCTKR2013012078-appb-I000027
Figure PCTKR2013012078-appb-I000028
Figure PCTKR2013012078-appb-I000029
Figure PCTKR2013012078-appb-I000030
Figure PCTKR2013012078-appb-I000031
Figure PCTKR2013012078-appb-I000032
Figure PCTKR2013012078-appb-I000033
The organic electroluminescent compounds according to the present invention can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction schemes 1 and 2:
[Reaction Scheme 1]
Figure PCTKR2013012078-appb-I000034
[Reaction Scheme 2]
Figure PCTKR2013012078-appb-I000035
wherein L1, L4, Ar1, Ar2, Ar7, Ar8, R1 to R9, X, a to f are as defined in formulae 1 and 2 above, and Hal represents a halogen.
The present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material. The 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.
The organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1.
One of the first electrodes and the second electrodes can be an anode and the other can be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, and a hole blocking layer.
At least one of the light-emitting layer or the hole transport layer can include the organic electroluminescent compound of the present invention. If the organic electroluminescent compound of the present invention is used in the hole transport layer, it may be included as the hole transport material. If the organic electroluminescent compound of the present invention is used in the light-emitting layer, it may be included as the host material.
If the organic electroluminescent compound of the present invention is included as the hole transport material, the light-emitting layer may comprise known light-emitting materials or other compounds of the present invention which are not the compounds used as the hole transport material as the light-emitting material. The known light-emitting materials may be known host materials and may comprise at least one dopant. The known host materials may be known fluorescent or phosphorescent host materials.
The second host material can be any of the known phosphorescent hosts and preferably, is selected from the group consisting of the compounds of the following formulae 3 to 5 in view of luminescent efficiency:
Figure PCTKR2013012078-appb-I000036
Figure PCTKR2013012078-appb-I000037
Figure PCTKR2013012078-appb-I000038
wherein
Cz represents the following structure:
Figure PCTKR2013012078-appb-I000039
R21 to R24 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- or 30-membered heteroaryl group, or R25R26R27Si-; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- or 30-membered heteroarylene group;
M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group;
Y1 and Y2 each independently represent -O-, -S-, -N(R31)- or -C(R32)(R33)-; and Y1 and Y2 are not simultaneously present;
R31 to R33 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and R32 and R33 may be the same or different;
h and i each independently represent an integer of 1 to 3;
j, k, l and m each independently represent an integer of 0 to 4;
where h, i, j, k, l or m is an integer of 2 or more, each (Cz-L4), each (Cz), each R21, each R22, each R23 or each R24 is the same or different;
Specifically, the second host material includes the following:
Figure PCTKR2013012078-appb-I000040
Figure PCTKR2013012078-appb-I000041
Figure PCTKR2013012078-appb-I000042
Figure PCTKR2013012078-appb-I000043
Figure PCTKR2013012078-appb-I000044
Figure PCTKR2013012078-appb-I000045
Figure PCTKR2013012078-appb-I000046
Figure PCTKR2013012078-appb-I000047
Figure PCTKR2013012078-appb-I000048
Figure PCTKR2013012078-appb-I000049
Figure PCTKR2013012078-appb-I000050
Figure PCTKR2013012078-appb-I000051
Figure PCTKR2013012078-appb-I000052
Figure PCTKR2013012078-appb-I000053
Figure PCTKR2013012078-appb-I000054
Figure PCTKR2013012078-appb-I000055
Figure PCTKR2013012078-appb-I000056
Figure PCTKR2013012078-appb-I000057
Figure PCTKR2013012078-appb-I000058
wherein TPS represents triphenylsilyl.
The dopants applied to the organic electroluminescent device of the present invention are preferably one or more phosphorescent dopants. The phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not specifically limited, but preferably may be selected from complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably ortho metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopant may be selected from the group consisting of the compounds represented by the following formulae 6 to 8:
Figure PCTKR2013012078-appb-I000059
Figure PCTKR2013012078-appb-I000060
Figure PCTKR2013012078-appb-I000061
wherein
L is selected from the following structures:
Figure PCTKR2013012078-appb-I000062
R100 represents hydrogen, or a substituted or unsubstituted (C1-C30) alkyl group; R101 to R109 and R111 to R123 each independently represent hydrogen, deuterium, a halogen; a (C1-C30) alkyl group unsubstituted or substituted with halogen(s); a cyano group, or a substituted or unsubstituted (C1-C30) alkoxy group; R120 to R123 are linked to an adjacent substituent(s) to form a fused ring, for example, a quinoline ring; R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30) alkyl group, or a substituted or unsubstituted (C6-C30) aryl group; when R124 to R127 are aryl groups, they are linked to an adjacent substituent(s) to form a fused ring, for example, a fluorene ring; R201 to R211 each independently represent hydrogen, deuterium, a halogen, or a (C1-C30)alkyl group unsubstituted or substituted with halogen(s); o and p each independently represent an integer of 1 to 3; where o or p is an integer of 2 or more, each R100 may be the same or different; and n represents an integer of 1 to 3.
The phosphorescent dopant material includes the following:
Figure PCTKR2013012078-appb-I000063
Figure PCTKR2013012078-appb-I000064
Figure PCTKR2013012078-appb-I000065
Figure PCTKR2013012078-appb-I000066
Figure PCTKR2013012078-appb-I000067
Figure PCTKR2013012078-appb-I000068
Figure PCTKR2013012078-appb-I000069
Figure PCTKR2013012078-appb-I000070
Figure PCTKR2013012078-appb-I000071
Figure PCTKR2013012078-appb-I000072
Figure PCTKR2013012078-appb-I000073
Figure PCTKR2013012078-appb-I000074
The present invention further provides the material for the organic electroluminescent device. The material comprises the compounds of the present invention as a host material. If the compound of the present invention is included as a host material, the material may further comprise a second host material. The first host material and the second host material may be in the range of 1:99 to 99:1 in a weight ratio.
Furthermore, the organic electroluminescent device of the present invention comprises a first electrode, a second electrode, and at least one organic layer between said first and second electrodes, wherein the organic layer comprises the material for the organic electroluminescent device of the present invention.
The organic electroluminescent device of the present invention comprises the compounds of formula 1 in the organic layer and may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present invention, the organic layer may further comprise, in addition to the compounds of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides, and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising the metal. Furthermore, the organic layer may further comprise a light-emitting layer and a charge-generating layer.
In addition, the organic electroluminescent device of the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound, or a green electroluminescent compound, besides the compound of the present invention; and may further include a yellow or orange light-emitting layer, if necessary.
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 a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer. The surface layer provides operating stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
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 a light-emitting 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 a light-emitting 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 light-emitting layers and emitting white light.
In order to form each layer constituting the organic electroluminescent device according to the present invention, dry film-forming methods, such as vacuum deposition, sputtering, plasma, ion plating methods, etc., or wet film-forming methods, such as spin coating, dip coating, flow coating methods, etc., can be used.
When using a wet film-forming method, a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
Hereinafter, the organic electroluminescent compound of the present invention, the preparation method of the compound, and the luminescent properties of the device comprising the compound will be explained in detail with reference to the following examples:
Example 1: Preparation of compound C-57
Figure PCTKR2013012078-appb-I000075
1-1. Preparation of compound 3
5H-Benzofuran[3,2-c]carbazole (10.3 g, 40.10 mmol), methyl 2-bromo-5-chlorobenzoate (15.0 g, 60.01 mmol), CuI (3.8 g, 20.05 mmol), diaminocyclohexyl (9.6 mL, 80.20 mmol) and potassium phosphate (17.0 g, 80.20 mmol) were dissolved in xylene (200.0 mL). The mixture was reflux stirred for 12 hours. After cooling the mixture to room temperature, the mixture was extracted with ethyl acetate (200.0 mL) and the obtained organic layer was washed with distilled water (100.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with methanol, filtered and dried. The obtained product was separated through column chromatography on silica gel and recrystallization to obtain methyl 2-(5H-benzofuran[3,2-c]carbazole 5-yl)-5-chlorobenzoate (9.8 g, 57 %).
1-2. Preparation of compound 4
Methyl 2-(5H-benzofuran[3,2-c]carbazole 5-yl)-5-chlorobenzoate (8.2 g, 19.30 mmol) was dissolved in tetrahydrofuran (100.0 mL). The mixture was stirred for 10 minutes at 0 ℃, and methyl magnesium bromide solution (16.1 mL, 48.30 mmol) was slowly added to the mixture. After stirring the mixture for 12 hours at room temperature, the reaction was quenched with water. The mixture was extracted with ethyl acetate (100.0 mL) and the obtained organic layer was washed with distilled water (100.0 mL). The organic solvent was removed under the reduced pressure. The obtained liquid was separated through column chromatography on silica gel and recrystallization to obtain 2-(2-(5H-benzofuran[3,2-c]carbazole 5-yl)-5- chlorophenyl)propane-2-ol (6.4 g, 84 %).
1-3. Preparation of compound 5
2-(2-(5H-Benzofuran[3,2-c]carbazole 5-yl)-5-chlorophenyl)propane-2-ol (6.4 g, 16.30 mmol), polyphosphoric acid (16.5 g, 48.90 mmol) and methanesulfonic acid (15.7 g, 163.00 mmol) were dissolved in toluene (410.0 mL). The mixture was reflux stirred for 3 hours. After cooling the mixture to room temperature, the mixture was extracted with ethyl acetate (400.0 mL) and the obtained organic layer was washed with distilled water (200.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with methanol, filtered and dried. The obtained product was separated through column chromatography on silica gel and recrystallization to obtain 8-chloro-10,10-dimethyl-10H-benzofuro[3,2-b]indolo[3,2,1-de]-acridine (4.2 g, 63 %).
1-4. Preparation of compound C-57
8-Chloro-10,10-dimethyl-10H-benzofuro[3,2-b]indolo[3,2,1-de]-acridine (4.2 g, 10.30 mmol), (4-(diphenylamino)phenyl)boronic acid (3.6 g, 12.36 mmol), palladium acetate (0.05 g, 0.21 mmol), 2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl (0.5 g, 1.24 mmol) and potassium phosphate (5.5 g, 25.75 mmol) were dissolved in toluene (100.0 mL). The mixture was reflux stirred for 8 hours. After cooling the mixture to room temperature, the mixture was extracted with ethyl acetate (100.0 mL) and the obtained organic layer was washed with distilled water (50.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with methanol, filtered and dried. The obtained product was separated through column chromatography on silica gel and recrystallization to obtain 4-(10,10-dimethyl-10H-benzofuro[3,2-b]indolo[3,2,1-de]-acridine-8-yl)-N,N-diphenylaniline (1.3 g, 20 %).
Example 2: Preparation of compound C-3
Figure PCTKR2013012078-appb-I000076
Figure PCTKR2013012078-appb-I000077
2-1. Preparation of compound 8
N-Phenyl-[1,1-biphenyl]-4-amine (15.0 g, 61.1 mmol), 1-bromo-4-iodobenzene (21.0 g, 73.32 mmol), tris(dibenzylideneacetone)dipalladium(O) (1.1 g, 1.22 mmol), tris(ortho-toluyl)phosphine (1.5 g, 4.89 mmol) and sodium tert-butoxide (8.8 g, 91.65 mmol) were dissolved in toluene (300.0 mL). The mixture was stirred for 3 hours at 120 ℃. After cooling the mixture to room temperature, the mixture was extracted with ethyl acetate (200.0 mL) and the obtained organic layer was washed with distilled water (200.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with methanol, filtered and dried. The obtained product was separated through column chromatography on silica gel and recrystallization to obtain N-(4-bromophenyl)-N-phenyl-[1,1’-biphenyl]-4-amine (15.0 g, 61 %).
2-2. Preparation of compound 10
N-(4-bromophenyl)-N-phenyl-[1,1’-biphenyl]-4-amine (15.0 g, 37.5 mmol) was dissolved in tetrahydrofurane (190.0 mL) and n-butyl lithium (2.5 M in hexane) (22.0 mL) was added to the mixture at -78 ℃. The mixture was stirred for 1 hour and trimethoxyborane (6.3 mL, 56.21 mmol) was added thereto. After stirring the whole mixture for 4 hours at room temperature, the mixture was extracted with ethyl acetate (200.0 mL) and the obtained organic layer was washed with distilled water (100.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with hexane, filtered and dried to obtain (4-([1,1-biphenyl]-4-yl(phenyl)amino)phenyl)boronic acid (10.0 g, 73%).
2-3. Preparation of compound C-3
8-Chloro-10,10-dimethyl-10H-benzofuro[3,2-b]indolo[3,2,1-de]-acridine (6.2 g, 15.20 mmol), (4-([1,1-biphenyl]-4-yl(phenyl)amino)phenyl)boronic acid (6.7 g, 18.24 mmol), palladium acetate (0.2 g, 0.76 mmol), 2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl (0.8 g, 1.82 mmol) and potassium phosphate (8.1 g, 38.0 mmol) were dissolved in toluene (150.0 mL). The mixture was reflux stirred for 8 hours. After cooling the mixture to room temperature, the mixture was extracted with ethyl acetate (100.0 mL) and the obtained organic layer was washed with distilled water (50.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with methanol, filtered and dried. The obtained product was separated through column chromatography on silica gel and recrystallization to obtain 4-(10,10-dimethyl-10H-benzofuro[3,2-b]indolo[3,2,1-de]-acridine-8-yl)phenyl)-N-phenyl-[1,1’-biphenyl]-4-amine(4.8 g, 46 %).
Example 3: Preparation of compound C-142
Figure PCTKR2013012078-appb-I000078
3-1. Preparation of compound 3-1
A mixture of 1-bromo-2-iodobenzene (44.0 g, 155.47 mmol), 5H-benzofuro[3,2-c]carbazole (20.0 g, 77.73 mmol), copper (2.8 g, 38.87 mmol), potassium carbonate (21.5 g, 155.47 mmol) and 1,2-dichlorobenzene in a reaction vessel was reflux stirred for 7 hours. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate. After removing the solvent by a rotary evaporator, the product was purified through column to obtain compound 3-1 (26.0 g, 81 %).
3-2. Preparation of compound 3-3
A mixture of compound 3-1 (26.0 g, 63.06 mmol) and tetrahydrofuran (210.0 mL) in a reaction vessel was cooled to -78 ℃ under nitrogen condition. N-butyl lithium (33.0 mL, 2.5 M, 81.98 mmol) was slowly added thereto. After stirring the mixture at -78 ℃ for 2 hours, a solution of fluorenone (14.8 g, 81.98 mmol) dissolved in tetrahydrofuran (210.0 mL) was slowly added to the mixture. After adding, the mixture was slowly warmed to room temperature and was stirred for 30 min. After completing the reaction by adding an aqueous solution of ammonium chloride to the reaction solution, the mixture was extracted with ethyl acetate and the obtained organic layer was dried over magnesium sulfate. After removing the solvent by a rotary evaporator, acetic acid (520.0 mL) and HCl (52.0 mL) were added to the obtained compounds 3-2 and the mixture was stirred at 120 ℃ overnight. After removing the solvent by a rotary evaporator, the product was purified through column to obtain compound 3-3 (23.4 g, 65 %).
3-3. Preparation of compound C-142
A mixture of compound 3-3 (5.0 g, 8.70 mmol), diphenylamine (1.8 g, 10.44 mmol), palladium (II) acetate (0.1 g, 0.44 mmol), tri-tert-butyl phosphine (0.4 mL, 50%, 0.87 mmol), sodium tert-butoxide (1.7 g, 17.40 mmol) and toluene (44.0 mL) in a reaction vessel was refluxed for 3 hours. After cooling the mixture to room temperature, the solid was filtered and was washed with methylene chloride (MC). The filtered solution was distilled under the reduced pressure and was purified through column to obtain compound C-142 (2.0 g 34 %).
Example 4: Preparation of compound C-144
Figure PCTKR2013012078-appb-I000079
4-1. Preparation of compound C-144
A mixture of compound 3-3 (6.0 g, 10.44 mmol), N-phenyl-[1,1’-biphenyl]-4-amine (2.8 g, 11.49 mmol), palladium (II) acetate (0.12 g, 0.52 mmol), tri-tert-butyl phosphine (0.6 mL, 50%, 1.04 mmol), sodium tert-butoxide (2.0 g, 20.88 mmol) and toluene (55.0 mL) in a reaction vessel was refluxed for 3 hours. After cooling the mixture to room temperature, the solid was filtered and was washed with MC. The filtered solution was distilled under the reduced pressure and was purified through column to obtain compound C-144 (2.2 g 29 %).
Example 5: Preparation of compound C-212
Figure PCTKR2013012078-appb-I000080
5-1. Preparation of compound C-212
A mixture of compound 3-3 (6.0 g, 10.44 mmol), 4-(naphthalene-2-yl)-N-phenylaniline (3.4 g, 11.49 mmol), palladium (II) acetate (0.12 g, 0.52 mmol), tri-tert-butyl phosphine (0.6 mL, 50%, 1.04 mmol), sodium tert-butoxide (2.0 g, 20.88 mmol) and toluene (55.0 mL) in a reaction vessel was refluxed for 3 hours. After cooling the mixture to room temperature, the solid was filtered and was washed with MC. The filtered solution was distilled under the reduced pressure and was purified through column to obtain compound C-212 (2.2 g 27 %).
Example 6: Preparation of compound C-213
Figure PCTKR2013012078-appb-I000081
6-1. Preparation of compound 6-1
A mixture of 1-bromo-4-chloro-2-nitrobenzene (24.0 g, 101.05 mmol), 5H-benzofuro[3,2-c]carbazole (20.0 g, 77.73 mmol), copper (2.8 g, 38.87 mmol), potassium carbonate (21.5 g, 155.47 mmol) and 1,2-dichlorobenzene in a reaction vessel was reflux stirred for 7 hours. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate. After removing the solvent by a rotary evaporator, the product was purified through column to obtain compound 6-1 (30.0 g, 94 %).
6-2. Preparation of compound 6-2
A mixture of compound 6-1 (30.0 g, 72.87 mmol), tin (II) chloride (53.0 g, 232.55 mmol) and ethyl acetate (775 mL) in a reaction vessel was reflux stirred for 4 hours. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate. After removing the solvent by a rotary evaporator, the product was purified through column to obtain compound 6-2 (20.0 g, 68 %).
6-3. Preparation of compound 6-3
To a mixture of compound 6-2 (20.0 g, 52.24 mmol) and para toluene sulfonic acid (30.0 g, 156.72 mmol) dissolved in acetonitrile in a reaction vessel, sodium nitrite (7.2 g, 104.48 mmol) and potassium iodide (21.7 g, 130.60 mmol) dissolved in water was added at 0 ℃. After stirring the mixture for 6 hours, the mixture was washed with distilled water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate. After removing the solvent by a rotary evaporator, the product was purified through column to obtain compound 6-3 (9.4 g, 37 %).
6-4. Preparation of compound 6-5
A mixture of compound 6-3 (9.4 g, 19.04 mmol) and tetrahydrofuran (65.0 mL) in a reaction vessel was cooled to -78 ℃ under nitrogen condition. N-butyl lithium (10.0 mL, 2.5 M, 24.75 mmol) was slowly added thereto. After stirring the mixture at -78 ℃ for 2 hours, a solution of fluorenone (4.1 g, 22.85 mmol) dissolved in tetrahydrofuran (65.0 mL) was slowly added to the mixture. After adding, the mixture was slowly warmed to room temperature and was stirred for 30 min. After completing the reaction by adding an aqueous solution of ammonium chloride to the reaction solution, the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate. After removing the solvent by a rotary evaporator, acetic acid (127.0 mL) and HCl (13.0 mL) were added to the obtained compounds 6-4 and the mixture was stirred at 120 ℃ overnight. After removing the solvent by a rotary evaporator, the product was purified through column to obtain compound 6-5 (5.8 g, 57 %).
6-5. Preparation of compound C-213
A mixture of compound 6-5 (5.8 g, 10.94 mmol), (4-(diphenylamino)phenyl) boronic acid (3.8 g, 13.13 mmol), palladium (II) acetate (0.05 g, 0.22 mmol), 2-dicyclohexylphosphino-2’,6’-dimentoxybephenyl (0.5 g, 1.32 mmol) and potassium phosphate (5.8 g, 27.35 mmol) was dissolved in a mixture of toluene (100.0 mL), 1,4-dioxane (28.0 mL) and distilled water (28.0 mL) in a reaction vessel. The mixture was refluxed for 4 hours. After cooling the mixture to room temperature, the mixture was extracted with ethyl acetate (100.0 mL) and the obtained organic layer was washed with distilled water (50.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with methanol, filtered and dried. The product was separated through column chromatography on silica gel and recrystallization to obtain compound C-213 (3.0 g 38 %).
Figure PCTKR2013012078-appb-I000082
Device Example 1: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced using the organic electroluminescent compound according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(naphthalene-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, compound C-3 was introduced into another cell of the 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, 9-(4,6-diphenyl-1,3,5-triazine-2-yl)-7,9’-diphenyl-9H,9’H-3,3’-bicarbazole as a host was introduced into one cell of the vacuum vapor depositing apparatus, and compound D-1 as a dopant was introduced into another cell. The two materials were evaporated at different rates and the dopant was deposited in a doping amount of 15 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, compound E-1 was introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rates and were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed green emission having a luminance of 3980 cd/m2 and a current density of 8.6 mA/cm2.
Figure PCTKR2013012078-appb-I000083
Device Example 2: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound C-57 was deposited as a hole transport layer having a thickness of 20 nm; and 9-phenyl-3-(4-(9-(4-phenylquinazoline-2-yl)-9H-carbazole-3-yl)phenyl)-9H-carbazole as a host was introduced into one cell of the vacuum vapor depositing apparatus, and compound D-37 as a dopant was introduced into another cell, and the two materials were evaporated at different rates and the dopant was deposited in a doping amount of 3 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
The produced OLED device showed red emission having a luminance of 1100 cd/m2 and a current density of 8.0 mA/cm2.
Device Example 3: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound C-142 was deposited as a hole transport layer having a thickness of 20 nm.
The produced OLED device showed green emission having a luminance of 1500 cd/m2 and a current density of 3.0 mA/cm2.
Device Example 4: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 2, except that compound C-144 was deposited as a hole transport layer having a thickness of 20 nm.
The produced OLED device showed red emission having a luminance of 3500 cd/m2 and a current density of 27.3 mA/cm2.
Device Example 5: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 2, except that compound C-212 was deposited as a hole transport layer having a thickness of 20 nm.
The produced OLED device showed red emission having a luminance of 700 cd/m2 and a current density of 4.9 mA/cm2.
Device Example 6: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound C-213 was deposited as a hole transport layer having a thickness of 20 nm.
The produced OLED device showed green emission having a luminance of
800 cd/m2 and a current density of 1.6 mA/cm2.
Comparative Example 1: Production of an OLED device by using conventional
light-emitting materials
An OLED device was produced in the same manner as in Device Example 1, except that compound R-1 was deposited as a hole transport layer having a thickness of 20 nm; 4,4’-N,N’-dicarbazole-biphenyl as a host and compound D-15 as a dopant were used as light-emitting materials to form a light-emitting layer having a thickness of 30 nm on the hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was deposited as a hole blocking layer having a thickness of 10 nm.
The produced OLED device showed green emission having a luminance of 3350 cd/m2 and a current density of 10.2 mA/cm2.
Comparative Example 2: Production of an OLED device by using conventional
light-emitting materials
An OLED device was produced in the same manner as in Device Example 1, except that compound R-1 was deposited as a hole transport layer having a thickness of 20 nm; CBP as a host and compound D-15 as a dopant and compound D-50 as a dopant were used as light-emitting materials to form a light-emitting layer having a thickness of 30 nm on the hole transport layer; and aluminum(III) bis(2-methyl-8-quinolinato)-4-phenylphenolate was deposited as a hole blocking layer having a thickness of 10 nm.
The produced OLED device showed red emission having a luminance of 1180 cd/m2 and a current density of 17.4 mA/cm2.
Figure PCTKR2013012078-appb-I000084
The organic electroluminescent compounds of the present invention have higher luminescent efficiency than conventional materials. Furthermore, the organic electroluminescent devices comprising the organic electroluminescent compounds of the present invention have high current efficiency.

Claims (5)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2013012078-appb-I000085
    wherein
    R1 and R2 each independently represent hydrogen, deuterium, a halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C3-C30) cycloalkyl group, a substituted or unsubstituted (C3-C30) cycloalkenyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are fused to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
    X represents -O-, -S- or -N(R3)-;
    R3 to R7 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 5- 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, -NR10R11, -SiR12R13R14, -SR15, -OR16, a cyano group, a nitro group or a hydroxyl group;
    R10 to R16 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 5- 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) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    a, c and d each independently represent an integer of 1 to 4; where a, c or d is an integer of 2 or more, each R4, each R6 or each R7 is the same or different;
    b represents an integer of 1;
    the heteroaryl(ene) group and heterocycloalkyl group contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P;
    L1 to L3 each independently represent a single bond, a substituted or unsubstituted (C2-C30) alkylene group, a substituted or unsubstituted (C6-C30) arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
    Ar1 to Ar6 each independently represent a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or Ar1 and Ar2, Ar3 and Ar4, or Ar5 and Ar6 are fused to form a substituted or unsubstituted mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and
    l, m and n each independently represent 0 or 1 and the sum of l+m+n is 1 or more.
  2. The organic electroluminescent compound according to claim 1, wherein the amine derivative represented by formula 1 is represented by the following formula 2:
    Figure PCTKR2013012078-appb-I000086
    wherein
    X, R3 to R7, R10 to R16, L1 to L3, Ar1 to Ar6, a, c, d and b are as defined in claim 1;
    R8 is as defined in R3 of claim 1;
    R9 represents hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted 5- 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, -NR10R11, -SiR12R13R14, -SR15, -OR16, a cyano group, a nitro group or a hydroxyl group; or is linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    Ar7 and Ar8 are as defined in Ar1 of claim 1;
    L4 is as defined in L1 of claim 1;
    l, m, n and o each independently represent 0 or 1 and the sum of l+m+n+o is 1 or more; and
    e and f each independently represent an integer of 1 to 4; where e or f is an integer of 2 or more, each R8 or each R9 is the same or different.
  3. The organic electroluminescent compound according to claim 1 or 2, wherein the substituents of the substituted (C1-C30) alkyl group, the substituted (C2-C30) alkenyl group, the substituted (C3-C30) cycloalkyl group, the substituted (C3-C30) cycloalkenyl group, the substituted 3- to 7-membered heterocycloalkyl group, the substituted (C6-C30) aryl(ene) group, the substituted 5- to 30-membered heteroaryl(ene) group and the substituted mono- or polycyclic (C3-C30) alicyclic or aromatic ring in L1 to L4, Ar1 to Ar8, and R1 to R16 each independently are at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30) alkyl group; a halo(C1-C30) alkyl group; a (C2-C30) alkenyl group; a (C2-C30) alkynyl group; a (C1-C30) alkoxy group; a (C1-C30) alkylthio group; a (C3-C30) cycloalkyl group; a (C3-C30) cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryloxy group; a (C6-C30) arylthio group; a 5- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30) aryl group; a (C6-C30) aryl group which is unsubstituted or substituted with a 5- to 30-membered heteroaryl 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; an amino group; a mono- or di(C1-C30) alkylamino group; a mono- or di(C6-C30) arylamino group; a (C1-C30) alkyl (C6-C30) arylamino group; a (C1-C30) alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30) arylcarbonyl group; 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; and a (C1-C30) alkyl (C6-C30) aryl group.
  4. The organic electroluminescent compound according to claim 1, wherein the amine derivative represented by formula 1 is selected from the group consisting of the following compounds:
    Figure PCTKR2013012078-appb-I000087
    Figure PCTKR2013012078-appb-I000088
    Figure PCTKR2013012078-appb-I000089
    Figure PCTKR2013012078-appb-I000090
    Figure PCTKR2013012078-appb-I000091
    Figure PCTKR2013012078-appb-I000092
    Figure PCTKR2013012078-appb-I000093
    Figure PCTKR2013012078-appb-I000094
    Figure PCTKR2013012078-appb-I000095
    Figure PCTKR2013012078-appb-I000096
    Figure PCTKR2013012078-appb-I000097
    Figure PCTKR2013012078-appb-I000098
    Figure PCTKR2013012078-appb-I000099
    Figure PCTKR2013012078-appb-I000100
    Figure PCTKR2013012078-appb-I000101
    Figure PCTKR2013012078-appb-I000102
    Figure PCTKR2013012078-appb-I000103
    Figure PCTKR2013012078-appb-I000104
    Figure PCTKR2013012078-appb-I000105
    Figure PCTKR2013012078-appb-I000106
    Figure PCTKR2013012078-appb-I000107
    Figure PCTKR2013012078-appb-I000108
    Figure PCTKR2013012078-appb-I000109
    Figure PCTKR2013012078-appb-I000110
    Figure PCTKR2013012078-appb-I000111
    Figure PCTKR2013012078-appb-I000112
    Figure PCTKR2013012078-appb-I000113
    Figure PCTKR2013012078-appb-I000114
    Figure PCTKR2013012078-appb-I000115
    Figure PCTKR2013012078-appb-I000116
    Figure PCTKR2013012078-appb-I000117
  5. An organic electroluminescent device comprising the compound according to claim 1.
PCT/KR2013/012078 2012-12-24 2013-12-24 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same WO2014104704A1 (en)

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US9859507B2 (en) 2014-05-02 2018-01-02 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
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EP3357912A4 (en) * 2015-09-30 2019-04-03 LG Chem, Ltd. Spiro compound and organic light emitting element comprising same
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KR101910498B1 (en) 2016-06-08 2018-10-22 (주)씨엠디엘 The novel organic electroluminescent compounds and organic electroluminescent device including the same
CN107216330A (en) * 2017-06-13 2017-09-29 中节能万润股份有限公司 A kind of new OLED material, its preparation method and application

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