KR101452577B1 - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Organic light-emitting compound and organic electroluminescent device using the same Download PDF

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KR101452577B1
KR101452577B1 KR1020120079560A KR20120079560A KR101452577B1 KR 101452577 B1 KR101452577 B1 KR 101452577B1 KR 1020120079560 A KR1020120079560 A KR 1020120079560A KR 20120079560 A KR20120079560 A KR 20120079560A KR 101452577 B1 KR101452577 B1 KR 101452577B1
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엄민식
김태형
백영미
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주식회사 두산
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Abstract

The present invention relates to a novel cyclic compound having a closed ring structure which is excellent in hole injection and transport ability, light emitting ability, etc. and contains at least one carbazole ring in a molecule, and a novel cyclic compound having at least one carbazole ring in the molecule, And an organic electroluminescent device having improved characteristics.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent compound, and an organic electroluminescent device using the same. BACKGROUND ART [0002]

The present invention relates to a novel organic light emitting compound and an organic electroluminescent device using the same. More particularly, the present invention relates to a novel compound having excellent hole injection and transport ability, And lifetime of the organic electroluminescent device.

A study on organic electroluminescent (EL) devices (hereinafter simply referred to as "organic EL devices") led to blue electroluminescence using anthracene single crystals in 1965 based on observation of the organic thin film emission of Bernanose in the 1950s, (Tang) and a functional layer of a light emitting layer. In order to produce high efficiency and high number of organic EL devices, the organic EL device has been developed to introduce each characteristic organic material layer in the device, leading to the development of specialized materials used therefor.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. The material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on its function.

The light emitting layer forming material of the organic EL device can be classified into blue, green and red light emitting materials depending on the luminescent color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such a phosphorescent material can theoretically improve the luminous efficiency up to 4 times as compared with that of fluorescence, and attention is focused on phosphorescent host materials as well as phosphorescent dopants.

Up to now, hole injecting layer, hole transporting layer. As the hole blocking layer and the electron transporting layer, NPB, BCP and Alq 3 represented by the following formulas are widely known, and an anthracene derivative as a luminescent material has been reported as a fluorescent dopant / host material. In particular Firpic, Ir as a phosphorescent material that has a great advantage in improving the efficiency aspects of the light-emitting material (ppy) 3, (acac) Ir (btp) 2 Ir metal complex compound is a blue, green and red host material that includes such as . So far, CBP has shown excellent properties as a phosphorescent host material.

Figure 112012058306863-pat00001

Figure 112012058306863-pat00002

However, existing materials have advantages in terms of light emitting properties, but their glass transition temperature is low and their thermal stability is not very good, which is not satisfactory in terms of lifetime in organic EL devices.

It is an object of the present invention to provide a novel organic compound which can be applied to an organic electroluminescent device and which has excellent hole injecting, transporting ability, and light emitting ability.

It is another object of the present invention to provide an organic electroluminescent device including the novel organic compound and exhibiting a low driving voltage and a high luminous efficiency and having an improved lifetime.

In order to accomplish the above object, the present invention relates to a carbazole ring system comprising at least one carbazole ring in a molecule; Or one or more carbazole-based rings and one or more linking groups, wherein the at least one carbazole-based ring or the carbazole-based ring and the linking group are bonded to each other to form a closed cyclic structure, and the molecular weight is 500 ≪ / RTI > to < RTI ID = 0.0 > 3000. ≪ / RTI >

Here, the linker may use a conventional linker, i.e., a divalent group of functional groups known in the art.

The present invention also provides an organic electroluminescent device comprising at least one organic material layer interposed between (i) an anode, (ii) a cathode, and (iii) an anode and a cathode, wherein at least one of the one or more organic layers One of the organic electroluminescent devices includes the cyclic compound.

At this time, the compound may be used as a phosphorescent host or a hole transport layer of the light emitting layer.

The compound of the present invention can exhibit excellent heat resistance, hole injection and transport ability, and light emitting ability

Therefore, an organic EL device including the above compound as a phosphorescent / fluorescent host or dopant in a hole injection / transport layer or a light emitting layer can be greatly improved in terms of light emitting performance, driving voltage, lifetime, efficiency, Can be effectively applied.

Hereinafter, the present invention will be described in detail.

<Novel compound>

Conventional biomimetic molecules, such as phthalocyanine or porphyrin derivatives, are typical structures of dyes or pigments. Compounds having such a closed ring-like molecular structure are thermochemical and electrochemical stable. Therefore, they are the most ideal form of the material in a device where an oxidation-reduction reaction is repeated like an OLED.

Thus, the present invention has the above-mentioned molecular structure in the form of a closed loop, and has a higher molecular weight than conventional organic EL device materials (for example, 4,4-dicarbazolybiphenyl (hereinafter referred to as CBP) Lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt;

The novel compounds according to the present invention comprise at least one carbazole ring in the molecule; Or one or more carbazole-based rings and at least one linking group, and the at least one carbazole-based ring or the carbazole-based ring and the linking group are bonded to each other to form a closed cyclic structure. Due to such a molecular structure, stability can be shown thermochemically and electrochemically.

Further, the cyclic compound has a wide band gap (sky blue to red) by controlling the energy level by introducing various substituents into one molecular structure. As a result, it is possible to improve the phosphorescence characteristics of the device and improve the electron and / or hole transporting ability, luminous efficiency, driving voltage, lifetime characteristics, and the like. And the like.

On the other hand, since the molecular weight of the compound is significantly increased, the glass transition temperature is improved, and thus, it can have higher thermal stability than conventional CBP. Accordingly, the organic electroluminescent device including the compound of the present invention can greatly improve durability and lifetime characteristics. In particular, when the number of the carbazole groups forming the closed ring structure is large, the molecular weight is significantly increased and the closed ring structure is stabilized, so that the thermal stability of the compound can be enhanced.

In addition, when the compound of the present invention is used as a hole injecting / transporting layer of an organic electroluminescence (EL) device, a blue, green and / or red phosphorescent host material or a fluorescent host material, . Therefore, the compounds according to the present invention can greatly contribute to improvement of the performance and lifetime of the organic EL device.

The novel cyclic compound according to the present invention can be further compounded by any one of the compounds represented by the following general formulas (1) to (5).

Figure 112012058306863-pat00003

Figure 112012058306863-pat00004

Figure 112012058306863-pat00005

Figure 112012058306863-pat00006

Figure 112012058306863-pat00007

In this formula,

Ar 1 to Ar 4 are the same or different and each independently represents hydrogen, a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 2 to C 40 alkenyl group, a substituted or unsubstituted C 2 ~ C 40 of the alkynyl group, a substituted or unsubstituted C 3 ~ C 40 cycloalkyl group, a substituted or unsubstituted C of 3 ~ C 40 heterocycloalkyl group, a substituted or unsubstituted C 6 ~ C 60 unsubstituted aryl A substituted or unsubstituted C 1 -C 40 alkyloxy group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, An unsubstituted C 1 to C 40 alkylsilyl group, a substituted or unsubstituted C 6 to C 60 arylsilyl group, and a substituted or unsubstituted C 6 to C 60 arylamine group,

L 1 to L 4 are the same or different and each independently represents a substituted or unsubstituted C 1 to C 40 alkylene group, a substituted or unsubstituted C 3 to C 40 cycloalkylene group, a substituted or unsubstituted C 3 ~ C 40 heterocycloalkyl group, the substituted or unsubstituted C 6 ~ C 60 aryl group, a substituted or unsubstituted be unsubstituted nuclear atoms of 5 to 60 heteroaryl group, a substituted or non-substituted of unsubstituted C 1 ~ C A substituted or unsubstituted C 1 to C 40 arylalkylene group, a substituted or unsubstituted C 1 to C 40 silylalkylene group, and a substituted or unsubstituted C 6 to C 60 arylamine group,

X is Ar 1 or a single bond, and wherein if is a single bond connected to a direct bond and Ar 1,

Wherein Ar 1 ~ Ar 4, L 1 ~ at L 4, substituents described the term "substituted or unsubstituted", more specifically, C 1 ~ alkenyl group of the C 40 alkyl group, C 2 ~ C 40 of, C 2 ~ for C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, C 3 ~ C 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 of the heteroaryl group, C 1 ~ C 40 C 6 -C 60 aryloxy groups, C 1 -C 40 alkylsilyl groups, C 6 -C 60 arylsilyl groups, C 6 -C 60 arylamine groups, C 1 -C 40 alkyl groups, A C 3 to C 40 cycloalkylene group, a C 3 to C 40 heterocycloalkylene group, a C 6 to C 60 arylene group, a heteroarylene group having 5 to 60 nuclear atoms, a C 1 to C 40 The C 1 to C 40 silylalkylene groups are each independently selected from the group consisting of deuterium, halogen, cyano, C 1 to C 40 alkyl, C 2 to C 40 alkenyl, C 2 to C 40 alkenyl, A C 6 to C 40 aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C 6 to C 40 aryl group, The aryloxy group, C 1 ~ C 40 of the alkyloxy group, C 6 ~ C 40 aryl amine group, C 6 ~ C 40 aryl group, C of 3 ~ C 40 cycloalkyl group, C of 3 ~ C 40 heteroaryl A C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkylboron group, a C 6 to C 60 arylboron group, a C 6 to C 60 aryl phosphine group may be substituted with one or more substituents selected from C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ C 60 aryl group consisting of amine groups of the.

In the compounds represented by formulas (1) to (5) according to the present invention, when considering the triplet energy level, Ar 1 to Ar 4 are the same or different and each independently represents a substituted or unsubstituted C6 to C60 aryl Substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms. In one example, the C 6 ~ C 40 aryl group or a nuclear atoms groups are heteroaryl of 5 to 60, phenyl, naphthyl, indene, anthracene, phenanthrene, pyrene, triphenylene, pyridine, pyrimidine, pyrazine, tri- And examples thereof include azine, quinoline, isoquinoline, quinoxaline, fluorene, carbazole, dibenzothiophene, dibenzofuran, acridine, indole, benzofuran, benzothiophene, benzimidazole, benzothiazole, It can be Lin.

L 1 to L 4 are divalent group functional groups which are the same or different from each other, and each independently represents a substituted or unsubstituted C6 to C60 arylene group, a substituted or unsubstituted 5 to 60 And a substituted or unsubstituted C 6 to C 60 arylamine group. More preferably, L 1 to L 4 may be selected from phenylene, pyridinylene, pyrimidylene, pyrazinylene, and triazinylene, and each of phenylene, pyridylene, pyrimidylene, pyrazinylene , Triazinylene may be substituted with one or more of the same or different substituents described above.

In the above Ar 1 to Ar 4 , L 1 to L 4 , A C6 ~ C60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, a group arylamine of C6 ~ C60 aryl group, a number of nuclear atoms of 5 to 60 heteroaryl group, a C 6 ~ C 60 each independently represents deuterium , a halogen, a nitrile group, a nitro group, a cyano group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, an alkoxy group of C 1 ~ C 40, C 1 ~ C 40 of the amino group, C 3 ~ C A C 3 to C 40 heterocycloalkyl group, a C 6 to C 40 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyloxy group, a C 6 to C 60 A C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group, a C 1 to C 40 alkylboron group, a C 6 to C 60 arylboron group, a C 6 to C 60 An aryl phosphine group of C 6 to C 60, an aryl phosphine oxide group of C 6 to C 60 , and an arylamine group of C 6 to C 60 , or may be unsubstituted.

As used herein, "unsubstituted alkyl" refers to straight or branched chain saturated hydrocarbons having 1 to 40 carbon atoms, including but not limited to methyl, ethyl, propyl, isobutyl, sec- - Amyl, hexyl and the like.

"Unsubstituted aryl" means an aromatic moiety having from 6 to 60 carbon atoms, either alone or in combination with at least two rings. Where two or more rings may be attached to each other in a simple attached or condensed form.

"Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety having 5 to 60 nuclear atoms in which at least one carbon, preferably one to three carbons, of the ring is replaced by N, O , S, or Se. In this case, two or more rings may be attached to each other in a form of simple attachment or condensation, and further, it may be interpreted as including a condensed form with an aryl group.

Further, "condensed rings" means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.

According to the present invention described above, the compounds represented by the formulas (1) to (5) can be further specified by the following illustrated formulas. However, the compounds represented by the general formulas (1) to (5) of the present invention are not limited by the following examples.

Figure 112012058306863-pat00008

Figure 112012058306863-pat00009

Figure 112012058306863-pat00010

Figure 112012058306863-pat00011

Figure 112012058306863-pat00012

Figure 112012058306863-pat00013

Figure 112012058306863-pat00014

According to the present invention, the compounds represented by the general formulas (1) to (5) can be synthesized according to a general synthetic method. Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later. However, it is not limited by the following synthesis examples.

&Lt; Organic electroluminescent device &

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a compound represented by any of Formulas 1 to 5 according to the present invention.

More specifically, the organic electroluminescent device according to the present invention comprises at least one organic layer interposed between (i) an anode, (ii) a cathode, and (iii) an anode and a cathode, One of them is characterized by containing one or more compounds represented by the above Chemical Formulas (1) to (5).

Here, the organic compound layer containing the compound of the present invention may be at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In this case, the organic electroluminescent device can improve the luminous efficiency, the luminance, the thermal efficiency of the power efficiency, and the lifetime of the device.

In particular, according to the present invention, the compounds represented by the general formulas (1) to (5) can be used as a phosphorescent host or a fluorescent host or a dopant material of the light emitting layer. Preferably, the compound represented by Formula 1 may be included in the organic light emitting device as a blue, green, and / or red phosphorescent host or hole transport material.

Non-limiting examples of the structure of the organic electroluminescent device according to the present invention include a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode sequentially laminated. At this time, at least one of the hole injection layer, the hole transporting layer and the light emitting layer may contain at least one compound represented by the above Chemical Formulas 1 to 5. Further, the compound of the present invention can be used as a phosphorescent host or a hole transporting material of the light emitting layer. An electron injection layer may be disposed on the electron transport layer.

In addition, the organic EL device according to the present invention may have an insulating layer or an adhesive layer inserted into the interface between the electrode and the organic layer as well as the structure in which the anode, one or more organic layers and the cathode are sequentially stacked, as described above.

In the organic electroluminescent device according to the present invention, the organic material layer containing the compound represented by Formula 1 may be formed by a vacuum evaporation method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The organic electroluminescent device according to the present invention can be formed by using materials and methods known in the art, except that one or more of the organic material layers are formed so as to include the compounds represented by the general formulas (1) to (5) An organic layer and an electrode.

For example, a silicon wafer, quartz or glass plate, a metal plate, a plastic film or a sheet can be used as the substrate.

Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but are not limited thereto.

Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Layer structure materials such as LiF / Al or LiO 2 / Al, but are not limited thereto.

The hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer are not particularly limited, and conventional materials known in the art can be used.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[ Synthetic example  One] Macrocycle Preparation of -I

Figure 112012058306863-pat00015

Step 1) Compound One Manufacturing

1 equiv. (20 g, 40.49 mmol), 3-bromo-3-methylbenzoic acid A mixed solution of 9-phenylcarbazole, 2 eq (26 g, 81 mmol), K 2 CO 3 33.5 g, toluene 800 ml and water 200 ml was added to a 2 L 2-neck round bottom flask and stirred for 30 minutes at room temperature It was added to give put Pd (PPh 3) 4 (1.4 g, 1.21 mmol) and then to the mixture was refluxed for 24 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO 4 and filtered. After removing the solvent of the obtained organic layer, it was purified by column chromatography to obtain intermediate compound 1 (24.80 g, yield 82%).

GC-Mass (calculated: 725.88 g / mol, measured: 725 g / mol)

Step 2) Compound 2 Manufacturing

The compound 1 (20.0 g, 27.55 mmol) obtained above was dissolved in 300 ml of DMF under a nitrogen stream, 5.40 g (30.31 mol) of N-bromosuccinimide was added thereto, stirred at 60 ° C for 8 hours, . The reaction mixture was extracted with ethyl acetate and water, and the obtained organic layer was filtered with MgSO 4 . The solvent was removed by distillation under reduced pressure and then purified by column chromatography to obtain a yellow intermediate compound 2 (15.58 g, yield 64%).

GC-Mass (calculated: 883.67 g / mol, measured: 883 g / mol)

Step 3) Macrocycle-I  Manufacturing

Compound obtained in the above 2 (15.0 g, 16.98 mmol) and 3,6-bis (4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl) -9-phenylcarbazole 8.15g (16.98 mmol ), 14.0 g of anhydrous K 2 CO 3 , 800 ml of toluene and 200 ml of water was added to a 2-liter 2-neck round bottom flask, stirred at room temperature for 30 minutes, and further treated with Pd (PPh 3 ) 4 g, 0.52 mmol) and refluxed for 24 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO 4 and filtered. After the solvent of the obtained organic layer was removed, the residue was purified by column chromatography to obtain the target compound Macrocycle-I (4.42 g, yield 27%).

GC-Mass (calculated: 965.15 g / mol, measured: 965 g / mol)

[ Synthetic example  2] Macrocycle -II

Figure 112012058306863-pat00016

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9-phenylcarbazole (10.0 g, 20.19 mmol) and 4- (3,5- -phenyl) -2,6-diphenyl-pyrimidine A mixture of 9.41 g (20.19 mmol) of K 2 CO 3, 16.7 g of K 2 CO 3 , 800 ml of toluene and 200 ml of water was placed in a 2-liter 2-neck round bottom flask, to put the Pd (PPh 3) with stirring and then added 4 (70 mg, 0.61 mmol) at room temperature and refluxed for 18 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO 4 and filtered. The solvent of the obtained organic layer was removed, and the residue was purified by column chromatography to obtain the target compound Macrocycle-II (4.93 g, yield 22.3%).

GC-Mass (calculated: 1095.29 g / mol, measured: 1095 g / mol)

[ Synthetic example  3] Macrocycle -III

Figure 112012058306863-pat00017

Step 1) Compound 3 Manufacturing

20 g (23.86 mmol) of 2,8-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) 23.86 mmol), K 2 CO 3 19.8 g, toluene 800 ml, and a mixed solution of water 200 ml of the following additional stirring at room temperature for 30 minutes to put a 2-neck round bottom flask of 2L Pd (PPh 3) 4 ( 0.83 g, 0.72 mmol) and refluxed for 24 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO 4 and filtered. The solvent of the obtained organic layer was removed and then purified by column chromatography to obtain intermediate compound 3 (2.14 g, yield 18.5%).

GC-Mass (calculated: 484.55 g / mol, measured: 484 g / mol)

Step 2) Manufacture of Macrocycle-III

Compound obtained in the above 3 (2.0 g, 4.13 mmol) and 1,4-diiodobenzene 2.72 g (8.26 mmol ), anhydrous K 2 CO 3 3.42 g, Cu powder 52 mg (0.83 mmol) and Na 2 SO 4 1.2 g (8.26 mmol) were added to 50 ml of nitrobenzene and refluxed for 24 hours. After the reaction was completed, nitrobenzene was removed, and the mixture was extracted with methylene chloride, and then filtered through MgSO 4 to remove moisture. The solvent of the obtained organic layer was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain the target compound Macrocycle-III (1.22 g, yield 53%).

GC-Mass (calculated: 558.63 g / mol, measured: 558 g / mol)

[ Synthetic example  4] Macrocycle -IV production

Figure 112012058306863-pat00018

Step 1) Compound 4 Manufacturing

9,9'-diphenyl-6,6'-bis- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H, 9'H-3,3 (27.16 mmol) of 6'-dibromo-9H, 9'H-3,3'-bicarbazolyl, 22.5 g of K 2 CO 3 , 800 ml of toluene and 200 ml of water (PPh 3 ) 4 (0.94 g, 0.81 mmol) was added thereto, followed by refluxing for 24 hours. The resulting mixture was stirred at room temperature for 30 minutes. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO 4 and filtered. The solvent of the obtained organic layer was removed and then purified by column chromatography to obtain an intermediate compound 4 (4.11 g, yield 18.6%).

GC-Mass (calculated: 812.95 g / mol, measured: 812 g / mol)

Step 2) Manufacture of Macrocycle-IV

Compound obtained in the above 4 (4.0 g, 4.92 mmol) and 2-bromo-4,6-diphenylpyridine 3.05 g (9.84 mmol), anhydrous K 2 CO 3 4.08 g, Cu powder 63 mg (0.98 mmol), and Na 2 SO 4 1.4 g (9.84 mmol) was added to 50 ml of nitrobenzene and refluxed for 24 hours. After the reaction was completed, nitrobenzene was removed, and the mixture was extracted with methylene chloride, and then filtered through MgSO 4 to remove moisture. The solvent of the obtained organic layer was removed by distillation under reduced pressure and then purified by column chromatography to obtain the target compound Macrocycle-IV (3.32 g, yield 53%).

GC-Mass (calculated: 1,271.51 g / mol, measured: 1,271 g / mol)

[ Synthetic example  5] Macrocycle Manufacturing of -V

Figure 112012058306863-pat00019

Since the Macrocycle-Ⅱ manufacturing Macrocycle-V compound is also produced with the, the Macrocycle -V compound of the aimed compound by further column chromatography Isolated and purified. (1.15 g, 2.6% yield)

GC-Mass (theory: 2,190.59 g / mol, measured: 2,190 g / mol)

[Examples 1 to 5] Fabrication of organic EL device (1)

The compounds Macrocycle-I to Macrocycle-V synthesized in Synthesis Examples 1 to 5 were subjected to high purity sublimation purification by a known method, and then an organic EL device was fabricated according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

On this ITO transparent electrode, m-MTDATA (60 nm) / TCTA (80 nm) / Macrocycle-I to Macrocycle-V The respective compounds of + 10% Ir (ppy) stacked in 3 (300nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) in order to prepare a organic EL device .

The structures of m-MTDATA, TCTA, Ir (ppy) 3 , CBP and BCP are as follows.

Figure 112012058306863-pat00020

Figure 112012058306863-pat00021

[Comparative Example 1] Fabrication of organic EL device

A green organic EL device was fabricated in the same manner as in Example 1, except that CBP was used instead of the compound Macrocycle-I as a luminescent host material in forming the light emitting layer.

[Evaluation Example 1]

The driving voltage, current efficiency and emission peak at current densities of 10 mA / cm 2 were measured for each of the organic EL devices manufactured in Example 1-5 and Comparative Example 1, and the results are shown in Table 1 below.

Host Driving voltage
(V)
EL peak
(nm)
Current efficiency
(cd / A)
Example 1 Macrocycle-I 6.44 519 40.5 Example 2 Macrocycle-II 6.60 518 41.3 Example 3 Macrocycle-III 6.65 520 42.2 Example 4 Macrocycle-Ⅳ 6.55 520 41.0 Example 5 Macrocycle-V 6.50 521 41.5 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, the organic EL device of Example 1-5 using the compound (Macrocycle-I to Macrocycle-V) according to the present invention as the light emitting layer was compared with the organic EL device of Comparative Example 1 using the conventional CBP It can be seen that it shows superior performance in terms of efficiency and driving voltage.

[Example 6 - 7] Fabrication of organic EL device (2)

The compounds Macrocycle-I and Macrocycle-III synthesized in Synthesis Examples 1 and 3 were subjected to high purity sublimation purification by a conventionally known method, and then an organic EL device was fabricated according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

DS-205 (Doosan) was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 800 Å to form a hole injecting layer, and Macrocycle-I or Macrocycle-III Each of them was vacuum deposited at a thickness of 150 ANGSTROM to form a hole transport layer.

Doped with 5% of DS-405 (Doosan) as a dopant and vacuum-deposited to a thickness of 300 Å to form a light emitting layer. Alq3, which is an electron transporting material, was vacuum deposited on the light emitting layer to a thickness of 250 A to form an electron transporting layer. Then, LiF, an electron injecting material, was deposited to a thickness of 10 Å to form an electron injecting layer, and aluminum was vacuum deposited thereon to a thickness of 2000 Å to form a cathode. Thus, an organic electroluminescent device was fabricated.

The structures of ADN and NPB are as follows.

Figure 112012058306863-pat00022

[Comparative Example 2] Fabrication of organic EL device

An organic EL device was fabricated in the same manner as in Example 6, except that NPB was used instead of the compound Macrocycle-I as a hole transport material in the formation of the light emitting layer.

[ Evaluation example  2]

The driving voltage, current efficiency and emission peak at current densities of 10 mA / cm 2 were measured for each of the organic EL devices manufactured in Example 6-7 and Comparative Example 2, and the results are shown in Table 2 below.

Hole transport material Driving voltage
(V)
EL peak
(nm)
Current efficiency
(cd / A)
Example 6 Macrocycle-I 4.50 _ 6.6 Example 7 Macrocycle-III 4.92 _ 6.8 Comparative Example 2 NPB 5.60 _ 4.8

As shown in Table 2 above, the organic EL device of Example 6-7 using the compound (Macrocycle-I, Macrocycle-III) according to the present invention as a hole transporting layer of an organic EL device had a comparative example 2 shows superior performance in terms of efficiency and driving voltage.

Claims (11)

  1. delete
  2. At least one carbazole ring in the molecule; Or one or more carbazole-based rings and one or more linking groups, wherein the at least one carbazole-based ring or the carbazole-based ring and the linking group are bonded to each other to form a closed cyclic structure, and the molecular weight is 500 To &lt; RTI ID = 0.0 &gt; 3000,
    A cyclic compound represented by the following formula (4) or (5):
    [Chemical Formula 4]
    Figure 112014022627558-pat00026

    [Chemical Formula 5]
    Figure 112014022627558-pat00027


    In this formula,
    Ar 1 to Ar 4 are the same or different and each independently selected from the group consisting of a substituted or unsubstituted C 6 to C 60 aryl group and a substituted or unsubstituted heteroaryl group having 5 to 60 nucleus atoms And,
    L 1 to L 4 are the same or different and are each independently selected from the group consisting of a substituted or unsubstituted C 6 to C 60 arylene group and a substituted or unsubstituted heteroarylene group having 5 to 60 ring atoms Selected,
    Here, the C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, a group heteroarylene of C 6 ~ C 60 arylene group, the number of nuclear atoms of 5 to 60, and each independently C 6 ~ A C 40 aryl group, and a heteroaryl group having 5 to 40 nuclear atoms.
  3. delete
  4. delete
  5. delete
  6. delete
  7. 3. The compound according to claim 2, wherein the compound represented by the formula (4) is selected from the group of compounds represented by the following formula:
    Figure 112012058306863-pat00032

    Figure 112012058306863-pat00033

    Figure 112012058306863-pat00034
  8. The compound according to claim 2, wherein the compound represented by the formula (5) is selected from the group of compounds represented by the following formula:
    Figure 112012058306863-pat00035
  9. An organic electroluminescent device comprising: (i) a cathode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode,
    Wherein at least one of the one or more organic compound layers comprises the cyclic compound according to any one of claims 2 to 7.
  10. 10. The organic electroluminescent device according to claim 9, wherein the organic material layer is selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer.
  11. The organic electroluminescent device according to claim 9, wherein the cyclic compound is used as a phosphorescent host or a hole transport layer of the light emitting layer.
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