WO2015050391A1 - An organic electroluminescent compound and an organic electroluminescent device comprising the same - Google Patents

An organic electroluminescent compound and an organic electroluminescent device comprising the same Download PDF

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WO2015050391A1
WO2015050391A1 PCT/KR2014/009308 KR2014009308W WO2015050391A1 WO 2015050391 A1 WO2015050391 A1 WO 2015050391A1 KR 2014009308 W KR2014009308 W KR 2014009308W WO 2015050391 A1 WO2015050391 A1 WO 2015050391A1
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substituted
unsubstituted
aryl
alkyl
organic electroluminescent
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PCT/KR2014/009308
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French (fr)
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Ji-Song JUN
Doo-Hyeon Moon
Hee-Choon Ahn
Tae-Jin Lee
Chi-Sik Kim
Young-Jun Cho
Kyung-Joo Lee
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority to JP2016516043A priority Critical patent/JP6478978B2/en
Priority to CN201480052354.9A priority patent/CN105579551B/en
Publication of WO2015050391A1 publication Critical patent/WO2015050391A1/en

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Definitions

  • the present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
  • An electroluminescent device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in an organic EL device is the light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • an organic EL device has a structure of a multilayer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.
  • the selection of a compound comprised in the hole transport layer is known as a method for improving the characteristics of a device such as hole transport efficiency to the light-emitting layer, luminous efficiency, lifespan, etc.
  • CuPc copper phthalocyanine
  • NPB 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum efficiency (cd/A
  • JP Patent No. 3065125 B discloses a compound wherein the 2-position of a fluorene is substituted with a diarylamine as a compound for an organic EL device.
  • the above reference does not disclose a compound wherein the 9-position of a fluorene is substituted with both a diarylamine or heteroarylamine, and a fluorene, dibenzothiophene, or dibenzofuran.
  • the objective of the present invention is to provide an organic electroluminescent compound having excellent current and power efficiencies and long lifespan.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; 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;
  • X represents -O-, -S-, or -C(R 5 )(R 6 )-;
  • R 1 to R 4 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (3- to 30-membered)hetero
  • R 5 to R 16 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
  • n is an integer of 0 to 2;
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
  • L 1 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
  • a, b and d each independently represent an integer of 1 to 4, where a, b or d is an integer of 2 or more, each of R 1 , each of R 2 , and each of R 4 can be the same or different;
  • c represents an integer of 1 to 3, where c is an integer of 2 or more, each of R 3 can be the same or different;
  • organic electroluminescent compound according to the present invention By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device having excellent current and power efficiencies and long lifespan.
  • the present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
  • the present invention was invented to provide a hole transport material used in an organic EL device which can solve the problems of conventional technology.
  • An ideal hole transport material requires high glass transition temperature, hole injection ability and hole transport ability, and suitable triplet energy and LUMO energy.
  • glass transition temperature is low, crystallization may occur due to thermal stress applied during or after the formation of a thin film, which can directly influence the lifespan of the device.
  • arylamine derivatives show excellent hole transport ability and low driving voltage, many arylamine derivatives need to have an increased molecular weight by introducing a large amount of substituents in order to obtain suitable glass transition temperature. In this case however, pi-conjugation gets longer to shorten the triplet energy or LUMO energy, and thus the performance of the device deteriorates. It is because high triplet energy contributes to blocking the excitons transporting from the host to the hole transport layer, and high LUMO energy contributes to blocking the electrons transporting from the electron transport layer through the host to the hole transport layer.
  • the present invention proposes as a solution to introduce arylamine and selected heteroaryl or fluorene to the 9-position of a fluorene.
  • the reason for introducing arylamine to the 9-position rather than the 2-position is to obtain relatively high triplet energy by short conjugation. In order to obtain high triplet energy, it is best not to introduce any substituent. However, although the triplet energy gets a little lower, it is possible to obtain excellent hole injection ability/transport ability, high power efficiency, long lifespan, etc., by introducing arylamine. In addition, by introducing heteroaryl or fluorene to the 9-position rather than the 2-position, it is possible to obtain appropriate glass transition temperature without increasing the deposition temperature too high in spite of high molecular weight due to the decrease of the linearity of the molecules.
  • the organic electroluminescent compound represented by the above formula 1 will be described in detail.
  • (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, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.;
  • (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl is meant to be a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably
  • 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.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; 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, preferably, each independently, represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl, and more preferably, each independently, represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C12)aryl; or
  • R 1 to R 4 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (3- to 30-membered)hetero
  • R 5 to R 16 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring, preferably, each independently, represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring, and more preferably, each independently, represent an unsubstituted (C1-C6)alkyl, or an unsubstitute
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene, preferably represents a single bond or a substituted or unsubstituted (C6-C20)arylene, and more preferably represents an unsubstituted (C6-C20)arylene.
  • L 1 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl, preferably represents a substituted or unsubstituted (C6-C20)aryl, and more preferably represents an unsubstituted (C6-C20)aryl.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl;
  • X represents -O-, -S-, or -C(R 5 )(R 6 )-;
  • R 1 to R 4 each independently represent hydrogen or -NR 7 R 8 , or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C6-C20) alicyclic or aromatic ring;
  • R 5 to R 8 each independently represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl, or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) ali
  • Ar 1 and Ar 2 each independently represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C12)aryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl;
  • X represents -O-, -S-, or -C(R 5 )(R 6 )-;
  • R 1 to R 4 each independently represent hydrogen or -NR 7 R 8 , or are linked to an adjacent substituent(s) to form an unsubstituted, monocyclic (C6-C20)aromatic ring;
  • R 5 to R 8 each independently represent an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C20)aryl, or are linked to an adjacent substituent(s) to form an unsubstituted, poly
  • the specific compounds of the present invention include the following compounds, but are not limited thereto:
  • organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction scheme.
  • R 1 to R 4 , X, Ar 1 , Ar 2 , L 1 , n, and a to d are as defined in formula 1 above, and Hal represents a halogen.
  • the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the 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.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer may comprise at least one organic electroluminescent compound of formula 1.
  • the organic layer comprises 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, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound represented by formula 1 can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound represented by formula 1 can be comprised as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as host materials, and can further comprise one or more dopants.
  • the organic electroluminescent compound according to the present invention is comprised as a host material (first host material)
  • the other compound may be comprised as a second host material.
  • the ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
  • the host material other than the organic electroluminescent compound according to the present invention can be from any of the known phosphorescent hosts. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulae 11 to 13 below is preferable in view of luminous efficiency.
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -SiR 25 R 26 R 27 ;
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )- or -C(R 32 )(R 33 )-, provided that Y 1 and Y 2 do not simultaneously exist;
  • R 31 to R 33 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, and R 32 and R 33 may be the same or different;
  • h and i each independently represent an integer of 1 to 3;
  • j, k, p and q each independently represent an integer of 0 to 4.
  • each of (Cz-L 4 ), each of (Cz), each of R 21 , each of R 22 , each of R 23 or each of R 24 may be the same or different.
  • preferable examples of the host material are as follows:
  • the dopant comprised in the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant.
  • the dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopants may be preferably selected from compounds represented by the following formulae 101 to 103.
  • L is selected from the following structures:
  • R 100 represents hydrogen, or a substituted or unsubstituted (C1-C30)alkyl
  • R 101 to R 109 , and R 111 to R 123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen(s); a cyano; a substituted or unsubstituted (C1-C30)alkoxy; or a substituted or unsubstituted (C3-C30)cycloalkyl; and R 120 to R 123 may be linked to an adjacent substituent(s) to form a mono- or polycyclic (3- to 30-membered) alicyclic or aromatic ring, e.g. quinoline;
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R 124 to R 127 are aryl groups, they may be linked to an adjacent substituent(s) to form a mono- or polycyclic (3- to 30-membered) alicyclic or aromatic ring, e.g. fluorene;
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, or a (C1-C30)alkyl unsubstituted or substituted with a halogen(s);
  • r and s each independently represent an integer of 1 to 3; where r or s is an integer of 2 or more, each of R 100 may be the same or different; and
  • e represents an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • compositions for preparing an organic electroluminescent device comprises the compound according to the present invention as a host material or a hole transport material.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for preparing the organic electroluminescent device according to the present invention.
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound 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 further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device according to 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 known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
  • a surface layer is preferably placed on an inner surface(s) of one or both electrode(s); selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • said chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and said metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably 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.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • UV 360 nm (in toluene), PL: 396 nm (in toluene), MP: 270°C, MW: 727.89, Tg: 140°C
  • UV 324 nm (in toluene), PL: 407 nm (in toluene), MP: 145°C, MW: 701.27, Tg: 134°C
  • UV 382 nm (in toluene), PL: 405 nm (in toluene), MP: 230°C, MW: 717.92, Tg: 140°C
  • UV 322 nm (in toluene), PL: 398 nm (in toluene), MP: 242°C, MW: 767.95, Tg: 151°C
  • UV 344 nm (in toluene), PL: 387 nm (in toluene), MP: 225°C, MW: 691.86, Tg: 137°C
  • UV 344 nm (in toluene), PL: 397 nm (in toluene), MP: 255°C, MW: 727.29, Tg: 141°C
  • UV 378 nm (in toluene), PL: 395 nm (in toluene), MP: 178°C, MW: 753.34, Tg: 143°C
  • UV 376 nm (in toluene), PL: 389 nm (in toluene), MP: 175°C, MW: 842.08, Tg: 150°C
  • UV 370 nm (in toluene), PL: 391 nm (in toluene), MP: 153°C, MW: 677.87, Tg: 129°C
  • An OLED device was produced using the light emitting material according to the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropan alcohol, sequentially, and then was stored in isopropan alcohol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1' -([1,1'-biphenyl]-4,4'-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzen-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.
  • compound C-6 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. 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 rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was 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 a green emission having a luminance of 900 cd/m 2 and a current density of 1.9 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 15,000 nit was 250 hours or more.
  • An OLED device was produced in the same manner as in Device Example 1, except for forming a hole transport layer having a thickness of 20 nm by using compound C-9 ; introducing 7-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-7H-benzo[c]carbazole into one cell of the vacuum vapor depositing apparatus as a host, introducing compound D-87 into another cell as a dopant, and evaporating the two materials at different rates and depositing them in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 1000 cd/m 2 and a current density of 6.7 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 5,000 nit was 200 hours or more.
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound C-8 for the hole transport layer; compound H-1 as below for the host; and compound FD-1 as below for the dopant.
  • the produced OLED device showed a blue emission having a luminance of 800 cd/m 2 and a current density of 16.3 mA/cm 2 .
  • the time period for the luminance to decrease to 50% at 2,000 nit was 170 hours or more.
  • An OLED device was produced in the same manner as in Device Example 2, except for evaporating compound C-78 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a red emission having a luminance of 1700 cd/m 2 and a current density of 11.7 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 5,000 nit was 210 hours or more.
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-79 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 3000 cd/m 2 and a current density of 4.2 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 15,000 nit was 240 hours or more.
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-12 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 1500 cd/m 2 and a current density of 3.2 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 15,000 nit was 270 hours or more.
  • An OLED device was produced in the same manner as in Device Example 3, except for evaporating compound C-81 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a blue emission having a luminance of 1200 cd/m 2 and a current density of 22.6 mA/cm 2 .
  • the time period for the luminance to decrease to 50% at 2,000 nit was 130 hours or more.
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-80 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 1500 cd/m 2 and a current density of 2.84 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 15,000 nit was 230 hours or more.
  • An OLED device was produced in the same manner as in Device Example 2, except for evaporating compound C-107 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a red emission having a luminance of 2000 cd/m 2 and a current density of 12.64 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 5,000 nit was 200 hours or more.
  • An OLED device was produced in the same manner as in Device Example 2, except for evaporating compound C-108 to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a red emission having a luminance of 700 cd/m 2 and a current density of 4.29 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 5,000 nit was 180 hours or more.
  • Comparative Example 1 Production of an OLED device using a
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 12000 cd/m 2 and a current density of 32.6 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 15,000 nit was 230 hours or more.
  • Comparative Example 2 Production of an OLED device using a
  • An OLED device was produced in the same manner as in Device Example 3, except for evaporating N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a blue emission having a luminance of 5000 cd/m 2 and a current density of 138.1 mA/cm 2 .
  • the time period for the luminance to decrease to 50% at 2,000 nit was 130 hours or more.
  • Comparative Example 3 Production of an OLED device using a
  • An OLED device was produced in the same manner as in Device Example 2, except for evaporating N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a red emission having a luminance of 10000 cd/m 2 and a current density of 131.6 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 5,000 nit was 180 hours or more.
  • Comparative Example 4 Production of an OLED device using a
  • the produced OLED device showed a green emission having a luminance of 9000 cd/m 2 and a current density of 20.8 mA/cm 2 .
  • the time period for the luminance to decrease to 80% at 15,000 nit was 25 hours or more.
  • an organic electroluminescent device using the organic electroluminescent compound according to the present invention has excellent luminous characteristics, especially current and power efficiencies.

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention has excellent thermal stability due to a high glass transition temperature. By using the organic electroluminescent compound according to the present invention, it is possible to produce an organic electroluminescent device having excellent current/power efficiency and long lifespan.

Description

AN ORGANIC ELECTROLUMINESCENT COMPOUND AND AN ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
An electroluminescent device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic EL device is the light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host materials. Recently, Pioneer (Japan) et al. developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc. as host materials, which were known as hole blocking layer materials.
Though these materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum, and the lifespan of the device decreases. (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. Although an organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Further, the operational lifespan of an organic EL device is short and luminous efficiency is still required to be improved.
Meanwhile, in order to enhance its efficiency and stability, an organic EL device has a structure of a multilayer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. The selection of a compound comprised in the hole transport layer is known as a method for improving the characteristics of a device such as hole transport efficiency to the light-emitting layer, luminous efficiency, lifespan, etc.
Accordingly, 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. were used as a hole injection and transport material. However, an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum efficiency (cd/A) may decrease.
Therefore, a hole transport layer for improving durability of an organic EL device still needs to be developed.
JP Patent No. 3065125 B discloses a compound wherein the 2-position of a fluorene is substituted with a diarylamine as a compound for an organic EL device. However, the above reference does not disclose a compound wherein the 9-position of a fluorene is substituted with both a diarylamine or heteroarylamine, and a fluorene, dibenzothiophene, or dibenzofuran.
The objective of the present invention is to provide an organic electroluminescent compound having excellent current and power efficiencies and long lifespan.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2014009308-appb-I000001
wherein
Ar1 and Ar2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; 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;
X represents -O-, -S-, or -C(R5)(R6)-;
R1 to R4 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, -NR7R8, -SiR9R10R11, -SR12, -OR13, -COR14, or -B(OR15)(OR16); or are linked to an adjacent substituent(s) 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;
R5 to R16 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
n is an integer of 0 to 2;
where n is 1 or 2, L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
where n is 0, L1 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
a, b and d each independently represent an integer of 1 to 4, where a, b or d is an integer of 2 or more, each of R1, each of R2, and each of R4 can be the same or different;
c represents an integer of 1 to 3, where c is an integer of 2 or more, each of R3 can be the same or different; and
the heterocycloalkyl and the heteroaryl(ene) each independently contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device having excellent current and power efficiencies and long lifespan.
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 of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
The present invention was invented to provide a hole transport material used in an organic EL device which can solve the problems of conventional technology. An ideal hole transport material requires high glass transition temperature, hole injection ability and hole transport ability, and suitable triplet energy and LUMO energy. When the glass transition temperature is low, crystallization may occur due to thermal stress applied during or after the formation of a thin film, which can directly influence the lifespan of the device. Although arylamine derivatives show excellent hole transport ability and low driving voltage, many arylamine derivatives need to have an increased molecular weight by introducing a large amount of substituents in order to obtain suitable glass transition temperature. In this case however, pi-conjugation gets longer to shorten the triplet energy or LUMO energy, and thus the performance of the device deteriorates. It is because high triplet energy contributes to blocking the excitons transporting from the host to the hole transport layer, and high LUMO energy contributes to blocking the electrons transporting from the electron transport layer through the host to the hole transport layer.
Another problem of the hole transport material having high molecular weight by introducing a large amount of substituents is that deposition does not occur well. As the molecular weight gets higher, the deposition temperature also gets higher, and the molecules are likely to decompose to many shapes or get damaged. Hence, retaining appropriate glass transition temperature by introducing a suitable amount of substituents, and maintaining low deposition temperature for high molecular weight are important. Therefore, the present invention proposes as a solution to introduce arylamine and selected heteroaryl or fluorene to the 9-position of a fluorene.
Introducing arylamine and selected heteroaryl or fluorene to the 9-position of a fluorene increases the glass transition temperature, but increases the deposition temperature less compared to introducing the substituents to the 2-position. This is because the linearity of the molecules is relatively low. As the linearity of the molecules gets higher, the intermolecular forces get stronger, and the deposition temperature gets higher.
Meanwhile, the reason for introducing arylamine to the 9-position rather than the 2-position is to obtain relatively high triplet energy by short conjugation. In order to obtain high triplet energy, it is best not to introduce any substituent. However, although the triplet energy gets a little lower, it is possible to obtain excellent hole injection ability/transport ability, high power efficiency, long lifespan, etc., by introducing arylamine. In addition, by introducing heteroaryl or fluorene to the 9-position rather than the 2-position, it is possible to obtain appropriate glass transition temperature without increasing the deposition temperature too high in spite of high molecular weight due to the decrease of the linearity of the molecules.
The organic electroluminescent compound represented by the above formula 1 will be described in detail.
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, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.; “(C2-C30)alkynyl” is meant to be a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.; “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(3- to 7- membered)heterocycloalkyl” is a cycloalkyl having 3 to 7 ring backbone atoms including at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably O, S and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “(5- to 30-membered)heteroaryl(ene)” is an aryl having 5 to 30 ring backbone atoms including at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Further, “halogen” includes F, Cl, Br and I.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. The substituents of the substituted (C1-C30)alkyl, the substituted (C2-C30)alkenyl, the substituted (C2-C30)alkynyl, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), and the substituted (3- to 30-membered)heteroaryl(ene) in Ar1, Ar2, R1 to R16, and L1 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di- (C1-C30)alkylamino, a mono- or di- (C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl, and preferably each independently are at least one selected from the group consisting of a (C1-C6)alkyl and a (C6-C15)aryl.
In formula 1 above, Ar1 and Ar2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; 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, preferably, each independently, represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl, and more preferably, each independently, represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C12)aryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl.
R1 to R4 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, -NR7R8, -SiR9R10R11, -SR12, -OR13, -COR14, or -B(OR15)(OR16); or are linked to an adjacent substituent(s) 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, preferably, each independently, represent hydrogen or -NR7R8, or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C6-C20) alicyclic or aromatic ring, and more preferably, each independently, represent hydrogen or -NR7R8, or are linked to an adjacent substituent(s) to form an unsubstituted, monocyclic (C6-C20)aromatic ring.
R5 to R16 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring, preferably, each independently, represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring, and more preferably, each independently, represent an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C20)aryl; or are linked to an adjacent substituent(s) to form an unsubstituted, polycyclic (C3-C30) aromatic ring.
Where n is 1 or 2, L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene, preferably represents a single bond or a substituted or unsubstituted (C6-C20)arylene, and more preferably represents an unsubstituted (C6-C20)arylene.
Where n is 0, L1 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl, preferably represents a substituted or unsubstituted (C6-C20)aryl, and more preferably represents an unsubstituted (C6-C20)aryl.
According to one embodiment of the present invention, in formula 1 above, Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; X represents -O-, -S-, or -C(R5)(R6)-; R1 to R4 each independently represent hydrogen or -NR7R8, or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C6-C20) alicyclic or aromatic ring; R5 to R8 each independently represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl, or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring; where n is 1 or 2, L1 represents a single bond or a substituted or unsubstituted (C6-C20)arylene; and where n is 0, L1 represents a substituted or unsubstituted (C6-C20)aryl.
According to another embodiment of the present invention, in formula 1 above, Ar1 and Ar2 each independently represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C12)aryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; X represents -O-, -S-, or -C(R5)(R6)-; R1 to R4 each independently represent hydrogen or -NR7R8, or are linked to an adjacent substituent(s) to form an unsubstituted, monocyclic (C6-C20)aromatic ring; R5 to R8 each independently represent an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C20)aryl, or are linked to an adjacent substituent(s) to form an unsubstituted, polycyclic (C3-C30) aromatic ring; where n is 1 or 2, L1 represents an unsubstituted (C6-C20)arylene; and where n is 0, L1 represents an unsubstituted (C6-C20)aryl.
The specific compounds of the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2014009308-appb-I000002
Figure PCTKR2014009308-appb-I000003
Figure PCTKR2014009308-appb-I000004
Figure PCTKR2014009308-appb-I000005
Figure PCTKR2014009308-appb-I000006
Figure PCTKR2014009308-appb-I000007
Figure PCTKR2014009308-appb-I000008
Figure PCTKR2014009308-appb-I000009
Figure PCTKR2014009308-appb-I000010
Figure PCTKR2014009308-appb-I000011
Figure PCTKR2014009308-appb-I000012
Figure PCTKR2014009308-appb-I000013
Figure PCTKR2014009308-appb-I000014
Figure PCTKR2014009308-appb-I000015
Figure PCTKR2014009308-appb-I000016
Figure PCTKR2014009308-appb-I000017
Figure PCTKR2014009308-appb-I000018
Figure PCTKR2014009308-appb-I000019
Figure PCTKR2014009308-appb-I000020
The organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction scheme.
[Reaction Scheme 1]
Figure PCTKR2014009308-appb-I000021
wherein R1 to R4, X, Ar1, Ar2, L1, n, and a to d are as defined in formula 1 above, and Hal represents a halogen.
The present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
The 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.
The organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes is an anode, and the other is a cathode. The organic layer comprises 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, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound represented by formula 1 can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound represented by formula 1 can be comprised as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as host materials, and can further comprise one or more dopants.
Where the organic electroluminescent compound according to the present invention is comprised as a host material (first host material), the other compound may be comprised as a second host material. Herein, the ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
The host material other than the organic electroluminescent compound according to the present invention can be from any of the known phosphorescent hosts. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulae 11 to 13 below is preferable in view of luminous efficiency.
Figure PCTKR2014009308-appb-I000022
Figure PCTKR2014009308-appb-I000023
Figure PCTKR2014009308-appb-I000024
wherein Cz represents the following structure;
Figure PCTKR2014009308-appb-I000025
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -SiR25R26R27;
R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
Y1 and Y2 each independently represent -O-, -S-, -N(R31)- or -C(R32)(R33)-, provided that Y1 and Y2 do not simultaneously exist;
R31 to R33 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, and R32 and R33 may be the same or different;
h and i each independently represent an integer of 1 to 3;
j, k, p and q each independently represent an integer of 0 to 4; and
where h, i, j, k, p or q is an integer of 2 or more, each of (Cz-L4), each of (Cz), each of R21, each of R22, each of R23 or each of R24 may be the same or different.
Specifically, preferable examples of the host material are as follows:
Figure PCTKR2014009308-appb-I000026
Figure PCTKR2014009308-appb-I000027
Figure PCTKR2014009308-appb-I000028
Figure PCTKR2014009308-appb-I000029
Figure PCTKR2014009308-appb-I000030
Figure PCTKR2014009308-appb-I000031
Figure PCTKR2014009308-appb-I000032
Figure PCTKR2014009308-appb-I000033
Figure PCTKR2014009308-appb-I000034
Figure PCTKR2014009308-appb-I000035
Figure PCTKR2014009308-appb-I000036
Figure PCTKR2014009308-appb-I000037
Figure PCTKR2014009308-appb-I000038
[wherein TPS represents triphenylsilyl]
The dopant comprised in the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant. The dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopants may be preferably selected from compounds represented by the following formulae 101 to 103.
Figure PCTKR2014009308-appb-I000039
Figure PCTKR2014009308-appb-I000040
Figure PCTKR2014009308-appb-I000041
wherein L is selected from the following structures:
Figure PCTKR2014009308-appb-I000042
R100 represents hydrogen, or a substituted or unsubstituted (C1-C30)alkyl;
R101 to R109, and R111 to R123 each independently represent hydrogen; deuterium; a halogen; a (C1-C30)alkyl unsubstituted or substituted with a halogen(s); a cyano; a substituted or unsubstituted (C1-C30)alkoxy; or a substituted or unsubstituted (C3-C30)cycloalkyl; and R120 to R123 may be linked to an adjacent substituent(s) to form a mono- or polycyclic (3- to 30-membered) alicyclic or aromatic ring, e.g. quinoline;
R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; where R124 to R127 are aryl groups, they may be linked to an adjacent substituent(s) to form a mono- or polycyclic (3- to 30-membered) alicyclic or aromatic ring, e.g. fluorene;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, or a (C1-C30)alkyl unsubstituted or substituted with a halogen(s);
r and s each independently represent an integer of 1 to 3; where r or s is an integer of 2 or more, each of R100 may be the same or different; and
e represents an integer of 1 to 3.
Specifically, the phosphorescent dopant materials include the following:
Figure PCTKR2014009308-appb-I000043
Figure PCTKR2014009308-appb-I000044
Figure PCTKR2014009308-appb-I000045
Figure PCTKR2014009308-appb-I000046
Figure PCTKR2014009308-appb-I000047
Figure PCTKR2014009308-appb-I000048
Figure PCTKR2014009308-appb-I000049
Figure PCTKR2014009308-appb-I000050
Figure PCTKR2014009308-appb-I000051
Figure PCTKR2014009308-appb-I000052
Figure PCTKR2014009308-appb-I000053
Figure PCTKR2014009308-appb-I000054
Figure PCTKR2014009308-appb-I000055
Figure PCTKR2014009308-appb-I000056
Figure PCTKR2014009308-appb-I000057
Figure PCTKR2014009308-appb-I000058
Figure PCTKR2014009308-appb-I000059
Figure PCTKR2014009308-appb-I000060
Figure PCTKR2014009308-appb-I000061
Figure PCTKR2014009308-appb-I000062
Figure PCTKR2014009308-appb-I000063
In another embodiment of the present invention, a composition for preparing an organic electroluminescent device is provided. The composition comprises the compound according to the present invention as a host material or a hole transport material.
In addition, the organic electroluminescent device according to the present invention comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for preparing the organic electroluminescent device according to the present invention.
The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound 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 further comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device according to 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 known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
According to the present invention, at least one layer (hereinafter, "a surface layer”) is preferably placed on an inner surface(s) of one or both electrode(s); selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide(includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, 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.
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 is preferably 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.
In order to form each layer of the organic electroluminescent device according to the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the organic electroluminescent compound, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound C-6
Figure PCTKR2014009308-appb-I000064
Preparation of compound 1-1
After introducing dibenzofuran (30 g, 178 mmol) and tetrahydrofuran 500 mL in a reaction container, the container was cooled to -78°C under nitrogen atmosphere. N-butyl lithium 71 mL (2.5 M, 178 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 30 minutes at -78°C, it was stirred at room temperature for 3 hours, and cooled to -78°C. Thereafter, fluorenone (32 g, 178 mmol) dissolved in tetrahydrofuran 500 mL was slowly added dropwise to the mixture. After adding, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 16 hours. Ammonium chloride aqueous solution was then added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-1 (43 g, 70%).
Preparation of compound 1-2
After introducing compound 1-1 (10 g, 28.7 mmol), 4-bromodiphenylamine (7.4 g, 30.1 mmol), and methylenechloride (MC) 570 mL in a reaction container, the container was introduced to nitrogen atmosphere. Thereafter, borontrifluoride diethylether (3.8 mL, 30.1 mmol) dissolved in methylenechloride 120 mL was slowly added dropwise to the mixture. After stirring the mixture at room temperature for 2 hours, ethanol and distilled water were added thereto to complete the reaction, and the mixture was extracted with methylenechloride. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-2 (15 g, 95%).
Preparation of compound 1-3
After introducing compound 1-2 (15 g, 26.9 mmol), phenylboronic acid (3.6 g, 29.6 mmol), tetrakis(triphenylphosphine)palladium (1.5 g, 1.34 mmol), potassium carbonate (8.9 g, 64.7 mmol), toluene 160 mL, ethanol 40 mL, and distilled water 40 mL in a reaction container, the mixture was stirred at 120°C for 1 hour. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-3 (12.3 g, 80%).
Preparation of compound C-6
After introducing compound 1-3 (8 g, 13.8 mmol), 4-bromobiphenyl (3.4 g, 14.5 mmol), palladiumacetate (0.12 g, 0.55 mmol), S-phos (0.57 g, 1.38 mmol), sodium tert-butoxide (3.3 g, 34.7 mmol), and toluene 70 mL in a reaction container, the mixture was stirred for 1 hour under reflux. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with methylenechloride (MC). The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-6 (8.2 g, 81%).
UV: 360 nm (in toluene), PL: 396 nm (in toluene), MP: 270°C, MW: 727.89, Tg: 140°C
Example 2: Preparation of compound C-8
Figure PCTKR2014009308-appb-I000065
Preparation of compound 2-2
After introducing compound 2-1 (30 g, 86.1 mmol), 4-bromotriphenylamine (84 g, 259 mmol), and methylenechloride (MC) 600 mL in a reaction container, the container was introduced to nitrogen atmosphere. Thereafter, Eaton’s reagent 3 mL was slowly added dropwise to the mixture. After stirring the mixture at room temperature for 2 hours, ethanol and distilled water were added thereto to complete the reaction, and the mixture was extracted with methylenechloride. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-2 (42 g, 74%).
Preparation of compound C-8
After introducing compound 2-2 (10 g, 26.9 mmol), 2-naphthylboronic acid (3.2 g, 18.4 mmol), tetrakis(triphenylphosphine)palladium (0.7 g, 1.08 mmol), potassium carbonate (5.3 g, 38.3 mmol), toluene 60 mL, ethanol 20 mL, and distilled water 20 mL in a reaction container, the mixture was stirred at 120°C for 3 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-8 (7.7 g, 72%).
UV: 324 nm (in toluene), PL: 407 nm (in toluene), MP: 145°C, MW: 701.27, Tg: 134°C
Example 3: Preparation of compound C-38
Figure PCTKR2014009308-appb-I000066
Preparation of compound 3-1
After introducing 2-bromodibenzothiophene (27 g, 103 mmol) and tetrahydrofuran 340 mL in a reaction container, the container was cooled to -78°C under nitrogen atmosphere. N-butyl lithium 33 mL (2.5 M, 82 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 2 hours at -78°C, 9H-fluoren-9-one (19 g, 103 mmol) dissolved in tetrahydrofuran 340 mL was slowly added dropwise to the mixture. After adding, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 30 minutes. Ammonium chloride aqueous solution was then added to the reaction solution to complete the reaction, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 3-1 (23 g, 61%).
Preparation of compound 3-2
After dissolving compound 3-1 (23 g, 63 mmol) and 4-bromotriphenylamine (41 g, 126 mmol) in dichloromethane 315 mL in a reaction container, Eaton’s reagent 1.4 mL (0.9 M, 1.3 mmol) was slowly added dropwise to the mixture. After stirring the mixture for 30 minutes at room temperature, the reaction was completed with sodium hydrogen carbonate, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 3-2 (27 g, 65%).
Preparation of compound C-38
After introducing compound 3-2 (10 g, 14.91 mmol), 2-naphthylboronic acid (3.1 g, 17.89 mmol), tetrakis(triphenylphosphine)palladium (0.5 g, 0.45 mmol), sodium carbonate (4 g, 37.28 mmol), toluene 76 mL, ethanol 19 mL, and distilled water 19 mL in a reaction container, the mixture was stirred at 120°C for 6 hours. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-38 (1.2 g, 11%).
UV: 382 nm (in toluene), PL: 405 nm (in toluene), MP: 230°C, MW: 717.92, Tg: 140°C
Example 4: Preparation of compound C-9
Figure PCTKR2014009308-appb-I000067
Preparation of compound 4-1
After introducing dibenzothiophene (30 g, 163 mmol) and tetrahydrofuran 400 mL in a reaction container, the container was cooled to -78°C under nitrogen atmosphere. N-butyl lithium 65 mL (2.5 M, 163 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 2 hours at -78°C, 9H-fluoren-9-one (29 g, 163 mmol) dissolved in tetrahydrofuran 400 mL was slowly added dropwise to the mixture. After adding, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 30 minutes. Ammonium chloride aqueous solution was then added to the reaction solution to complete the reaction, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 4-1 (20 g, 34%).
Preparation of compound 4-2
After dissolving compound 4-1 (7 g, 19 mmol) and 4-bromotriphenylamine (16 g, 48 mmol) in dichloromethane 96 mL in a reaction container, Eaton’s reagent 0.5 mL (0.9 M, 0.4 mmol) was slowly added dropwise to the mixture. After stirring the mixture for 30 minutes at room temperature, the reaction was completed with sodium hydrogen carbonate, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 4-2 (8 g, 62%).
Preparation of compound C-9
After introducing compound 4-2 (8 g, 11.93 mmol), 2-naphthylboronic acid (2.5 g, 14.31 mmol), tetrakis(triphenylphosphine)palladium (0.4 g, 0.36 mmol), sodium carbonate (3.2 g, 29.83 mmol), toluene 60 mL, ethanol 15 mL, and distilled water 15 mL in a reaction container, the mixture was stirred at 120°C for 6 hours. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-9 (4.3 g, 50%).
UV: 390 nm (in toluene), PL: 407 nm (in toluene), MP: 215°C, MW: 717.92, Tg: 151°C
Example 5: Preparation of compound C-78
Figure PCTKR2014009308-appb-I000068
Preparation of compound C-78
After introducing compound 1-3 (5.6 g, 9.72 mmol), 2-bromo-9,9-dimethylfluorene (2.9 g, 10.7 mmol), palladiumacetate (0.08 g, 0.38 mmol), S-phos (0.39 g, 0.97 mmol), sodium tert-butoxide (2.3 g, 24.3 mmol), and toluene 50 mL in a reaction container, the mixture was stirred for 1 hour under reflux. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with methylenechloride (MC). The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-78 (6.2 g, 83%).
UV: 322 nm (in toluene), PL: 398 nm (in toluene), MP: 242°C, MW: 767.95, Tg: 151°C
Example 6: Preparation of compound C-12
Figure PCTKR2014009308-appb-I000069
Preparation of compound 5-2
After introducing compound 1-1 (10 g, 28.7 mmol), diphenylamine (14 g, 86.1 mmol), and methylenechloride (MC) 570 mL in a reaction container, the container was introduced to nitrogen atmosphere. Thereafter, borontrifluoride diethylether (3.8 mL, 30.1 mmol) dissolved in methylenechloride 120 mL was slowly added dropwise to the mixture. After stirring the mixture at room temperature for 2 hours, ethanol and distilled water were added thereto to complete the reaction, and the mixture was extracted with methylenechloride. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 5-2 (11 g, 78%).
Preparation of compound C-12
After introducing compound 5-2 (11 g, 22.1 mmol), 2-bromo-9,9-dimethylfluorene (6.6 g, 24.4 mmol), palladiumacetate (0.19 g, 0.88 mmol), S-phos (0.91 g, 2.21 mmol), sodium tert-butoxide (5.3 g, 55.4 mmol), and toluene 110 mL in a reaction container, the mixture was stirred for 1 hour under reflux. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with methylenechloride (MC). The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-12 (12 g, 79%).
UV: 344 nm (in toluene), PL: 387 nm (in toluene), MP: 225°C, MW: 691.86, Tg: 137°C
Example 7: Preparation of compound C-79
Figure PCTKR2014009308-appb-I000070
Preparation of compound C-79
After introducing compound 2-2 (6.7 g, 10.2 mmol), 4-biphenylboronic acid (2.4 g, 12.2 mmol), tetrakis(triphenylphosphine)palladium (0.47 g, 0.41 mmol), potassium carbonate (3.5 g, 25.5 mmol), toluene 45 mL, ethanol 15 mL, and distilled water 15 mL in a reaction container, the mixture was stirred at 120°C for 3 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-79 (5.0 g, 67%).
UV: 344 nm (in toluene), PL: 397 nm (in toluene), MP: 255°C, MW: 727.29, Tg: 141°C
Example 8: Preparation of compound C-80
Figure PCTKR2014009308-appb-I000071
Preparation of compound 6-1
After introducing 2-bromo-9,9'-dimethylfluorene (40 g, 146 mmol) and tetrahydrofuran 500 mL in a reaction container, the container was cooled to -78°C under nitrogen atmosphere. N-butyl lithium 60 mL (2.5 M, 146 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 90 minutes at -78°C, fluorenone (26 g, 146 mmol) dissolved in tetrahydrofuran 500 mL was slowly added dropwise to the mixture. After adding, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 16 hours. Ammonium chloride aqueous solution was then added to the reaction solution to complete the reaction, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 6-1 (41 g, 72%).
Preparation of compound C-80
After introducing compound 6-1 (10 g, 26.7 mmol), compound 6-2 (CAS no.: 122215-84-3) (10.6 g, 26.7 mmol), and methylenechloride (MC) 134 mL in a reaction container, the container was introduced to nitrogen atmosphere. Thereafter, Eaton’s reagent 0.6 mL was slowly added dropwise to the mixture. After stirring the mixture at room temperature for 2 hours, ethanol and distilled water were added thereto to complete the reaction, and the mixture was extracted with methylenechloride. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-80 (17 g, 85%).
UV: 378 nm (in toluene), PL: 395 nm (in toluene), MP: 178°C, MW: 753.34, Tg: 143°C
Example 9: Preparation of compound C-107
Figure PCTKR2014009308-appb-I000072
Preparation of compound 7-1
After dissolving 2-bromo-9,9-diphenyl-9H-fluorene (15 g, 37.75 mmol) in tetrahydrofuran 125 mL in a reaction container, n-butyl lithium 15 mL (2.5 M, 37.75 mmol) was then slowly added dropwise to the mixture at -78°C, and the mixture was stirred for 2 hours. Thereafter, 9-fluoren-one (6.2 g, 34.32 mmol) was dissolved in tetrahydrofuran 125 mL, and slowly added dropwise to the mixture. The mixture was then stirred for 5 hours. After the reaction, the mixture was washed with distilled water, and extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 7-1 (11.7 g, 62%).
Preparation of compound C-107
After dissolving compound 7-1 (10 g, 20.06 mmol) and 9,9-dimethyl-N,N-diphenyl-9H-fluoren-2-amine (14.5 g, 40.12 mmol) in dichloromethane 100 mL in a reaction container, Eaton’s reagent (0.4 mL, 0.40 mmol) was slowly added dropwise thereto, and stirred for 2 hours. After the reaction, the mixture was washed with distilled water, and extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-107 (6.5 g, 38%).
UV: 376 nm (in toluene), PL: 389 nm (in toluene), MP: 175°C, MW: 842.08, Tg: 150°C
Example 10: Preparation of compound C-81
Figure PCTKR2014009308-appb-I000073
Preparation of compound 8-1
After introducing 2-bromofluorene (40 g, 146 mmol) and tetrahydrofuran 500 mL in a reaction container, the container was cooled to -78°C under nitrogen atmosphere. N-butyl lithium (60 mL, 146 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 2 hours, 9H-fluoren-9-one (26 g, 146 mmol) dissolved in tetrahydrofuran 500 mL was slowly added dropwise to the mixture. After adding, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 30 minutes. Ammonium chloride aqueous solution was then added to the reaction solution to complete the reaction, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 8-1 (41 g, 75%).
Preparation of compound 8-2
After dissolving compound 8-1 (16 g, 43 mmol) and 4-bromotriphenylamine (28 g, 86 mmol) in dichloromethane 213 mL in a reaction container, Eaton’s reagent (1 mL, 0.9 mmol) was slowly added dropwise to the mixture. After stirring the mixture for 30 minutes at room temperature, the reaction was completed with sodium hydrogen carbonate, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 8-2 (20 g, 69%).
Preparation of compound C-81
After introducing compound 8-2 (10 g, 15 mmol), 2-naphthylboronic acid (3 g, 18 mmol), tetrakis(triphenylphosphine)palladium (0.5 g, 0.4 mmol), sodium carbonate (4 g, 37 mmol), toluene 76 mL, and ethanol 19 mL in a reaction container, distilled water 19 mL was added thereto, and the mixture was stirred at 120°C for 2 hours. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-81 (5.3 g, 50%).
UV: 388 nm (in toluene), PL: 405 nm (in toluene), MP: 152°C, MW: 727.93, Tg: 136°C
Example 11: Preparation of compound C-108
Figure PCTKR2014009308-appb-I000074
Preparation of compound 9-1
After introducing 2-bromofluorene (40 g, 146 mmol) and tetrahydrofuran 500 mL in a reaction container, the container was cooled to -78°C under nitrogen atmosphere. N-butyl lithium (60 mL, 146 mmol) was then slowly added dropwise to the mixture. After stirring the mixture for 2 hours, 9H-fluoren-9-one (26 g, 146 mmol) dissolved in tetrahydrofuran 500 mL was slowly added dropwise to the mixture. After adding, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 30 minutes. Ammonium chloride aqueous solution was then added to the reaction solution to complete the reaction, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 9-1 (41 g, 75%).
Preparation of compound C-108
After dissolving compound 9-1 (10 g, 26.70 mmol) and N,N-diphenyl-[1,1'-biphenyl]-4-amine (17.2 g, 53.40 mmol) in dichloromethane 130 mL in a reaction container, Eaton’s reagent (0.6 mL, 0.53 mmol) was slowly added dropwise to the mixture. After stirring the mixture for 30 minutes at room temperature, the reaction was completed with sodium hydrogen carbonate, and the mixture was extracted with ethylacetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-108 (6.7 g, 37%).
UV: 370 nm (in toluene), PL: 391 nm (in toluene), MP: 153°C, MW: 677.87, Tg: 129°C
Device Example 1: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced using the light emitting material 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 (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropan alcohol, sequentially, and then was stored in isopropan alcohol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1'-([1,1'-biphenyl]-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzen-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, compound C-6 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. 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 rate and were deposited in a doping amount of 50 wt% each 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 a green emission having a luminance of 900 cd/m2 and a current density of 1.9 mA/cm2.
The time period for the luminance to decrease to 80% at 15,000 nit was 250 hours or more.
Device Example 2: Production of an OLED device 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 for forming a hole transport layer having a thickness of 20 nm by using compound C-9; introducing 7-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-7H-benzo[c]carbazole into one cell of the vacuum vapor depositing apparatus as a host, introducing compound D-87 into another cell as a dopant, and evaporating the two materials at different rates and depositing them in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
The produced OLED device showed a red emission having a luminance of 1000 cd/m2 and a current density of 6.7 mA/cm2.
The time period for the luminance to decrease to 80% at 5,000 nit was 200 hours or more.
Device Example 3: Production of an OLED device 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 for using compound C-8 for the hole transport layer; compound H-1 as below for the host; and compound FD-1 as below for the dopant.
The produced OLED device showed a blue emission having a luminance of 800 cd/m2 and a current density of 16.3 mA/cm2.
The time period for the luminance to decrease to 50% at 2,000 nit was 170 hours or more.
Figure PCTKR2014009308-appb-I000075
Device Example 4: Production of an OLED device 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 for evaporating compound C-78 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a red emission having a luminance of 1700 cd/m2 and a current density of 11.7 mA/cm2.
The time period for the luminance to decrease to 80% at 5,000 nit was 210 hours or more.
Device Example 5: Production of an OLED device 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 for evaporating compound C-79 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 3000 cd/m2 and a current density of 4.2 mA/cm2.
The time period for the luminance to decrease to 80% at 15,000 nit was 240 hours or more.
Device Example 6: Production of an OLED device 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 for evaporating compound C-12 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 1500 cd/m2 and a current density of 3.2 mA/cm2.
The time period for the luminance to decrease to 80% at 15,000 nit was 270 hours or more.
Device Example 7: Production of an OLED device using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 3, except for evaporating compound C-81 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a blue emission having a luminance of 1200 cd/m2 and a current density of 22.6 mA/cm2.
The time period for the luminance to decrease to 50% at 2,000 nit was 130 hours or more.
Device Example 8: Production of an OLED device 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 for evaporating compound C-80 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 1500 cd/m2 and a current density of 2.84 mA/cm2.
The time period for the luminance to decrease to 80% at 15,000 nit was 230 hours or more.
Device Example 9: Production of an OLED device 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 for evaporating compound C-107 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a red emission having a luminance of 2000 cd/m2 and a current density of 12.64 mA/cm2.
The time period for the luminance to decrease to 80% at 5,000 nit was 200 hours or more.
Device Example 10: Production of an OLED device 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 for evaporating compound C-108 to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a red emission having a luminance of 700 cd/m2 and a current density of 4.29 mA/cm2.
The time period for the luminance to decrease to 80% at 5,000 nit was 180 hours or more.
Comparative Example 1: Production of an OLED device using a
conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 1, except for evaporating N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 12000 cd/m2 and a current density of 32.6 mA/cm2.
The time period for the luminance to decrease to 80% at 15,000 nit was 230 hours or more.
Comparative Example 2: Production of an OLED device using a
conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 3, except for evaporating N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a blue emission having a luminance of 5000 cd/m2 and a current density of 138.1 mA/cm2.
The time period for the luminance to decrease to 50% at 2,000 nit was 130 hours or more.
Comparative Example 3: Production of an OLED device using a
conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 2, except for evaporating N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a red emission having a luminance of 10000 cd/m2 and a current density of 131.6 mA/cm2.
The time period for the luminance to decrease to 80% at 5,000 nit was 180 hours or more.
Comparative Example 4: Production of an OLED device using a
conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 1, except for evaporating 9,9-dimethyl-N,N-diphenyl-9H-fluoren-2-amine (Tg=43°C) to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 9000 cd/m2 and a current density of 20.8 mA/cm2.
The time period for the luminance to decrease to 80% at 15,000 nit was 25 hours or more.
It is verified that the glass transition temperature of the organic electroluminescent compound according to the present invention is high, and the current efficiency is higher than the conventional compounds. In addition, an organic electroluminescent device using the organic electroluminescent compound according to the present invention has excellent luminous characteristics, especially current and power efficiencies.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014009308-appb-I000076
    wherein
    Ar1 and Ar2 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; 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;
    X represents -O-, -S-, or -C(R5)(R6)-;
    R1 to R4 each independently represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, -NR7R8, -SiR9R10R11, -SR12, -OR13, -COR14, or -B(OR15)(OR16); or are linked to an adjacent substituent(s) 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;
    R5 to R16 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring;
    n is an integer of 0 to 2;
    where n is 1 or 2, L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
    where n is 0, L1 represents a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    a, b and d each independently represent an integer of 1 to 4, where a, b or d is an integer of 2 or more, each of R1, each of R2, and each of R4 can be same or different;
    c represents an integer of 1 to 3, where c is an integer of 2 or more, each of R3 can be same or different; and
    the heterocycloalkyl and the heteroaryl(ene) each independently contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl, the substituted (C2-C30)alkenyl, the substituted (C2-C30)alkynyl, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), and the substituted (3- to 30-membered)heteroaryl(ene) in Ar1, Ar2, R1 to R16, and L1 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di- (C1-C30)alkylamino, a mono- or di- (C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl.
  3. The organic electroluminescent compound according to claim 1, wherein Ar1 and Ar2 each independently represent a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; X represents -O-, -S-, or -C(R5)(R6)-; R1 to R4 each independently represent hydrogen or -NR7R8, or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C6-C20) alicyclic or aromatic ring; R5 to R8 each independently represent a substituted or unsubstituted (C1-C6)alkyl, or a substituted or unsubstituted (C6-C20)aryl, or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic (C3-C30) alicyclic or aromatic ring; where n is 1 or 2, L1 represents a single bond or a substituted or unsubstituted (C6-C20)arylene; and where n is 0, L1 represents a substituted or unsubstituted (C6-C20)aryl.
  4. The organic electroluminescent compound according to claim 1, wherein Ar1 and Ar2 each independently represent a (C6-C20)aryl unsubstituted or substituted with a (C1-C6)alkyl or a (C6-C12)aryl; or a (5- to 20-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; X represents -O-, -S-, or -C(R5)(R6)-; R1 to R4 each independently represent hydrogen or -NR7R8, or are linked to an adjacent substituent(s) to form an unsubstituted, monocyclic (C6-C20)aromatic ring; R5 to R8 each independently represent an unsubstituted (C1-C6)alkyl, or an unsubstituted (C6-C20)aryl, or are linked to an adjacent substituent(s) to form an unsubstituted, polycyclic (C3-C30) aromatic ring; where n is 1 or 2, L1 represents an unsubstituted (C6-C20)arylene; and where n is 0, L1 represents an unsubstituted (C6-C20)aryl.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2014009308-appb-I000077
    Figure PCTKR2014009308-appb-I000078
    Figure PCTKR2014009308-appb-I000079
    Figure PCTKR2014009308-appb-I000080
    Figure PCTKR2014009308-appb-I000081
    Figure PCTKR2014009308-appb-I000082
    Figure PCTKR2014009308-appb-I000083
    Figure PCTKR2014009308-appb-I000084
    Figure PCTKR2014009308-appb-I000085
    Figure PCTKR2014009308-appb-I000086
    Figure PCTKR2014009308-appb-I000087
    Figure PCTKR2014009308-appb-I000088
    Figure PCTKR2014009308-appb-I000089
    Figure PCTKR2014009308-appb-I000090
    Figure PCTKR2014009308-appb-I000091
    Figure PCTKR2014009308-appb-I000092
    Figure PCTKR2014009308-appb-I000093
    Figure PCTKR2014009308-appb-I000094
    Figure PCTKR2014009308-appb-I000095
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
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