KR20140125061A - An organoelectro luminescent compound and an organoelectroluminescent device using the same - Google Patents

Abstract

The present invention relates to an organic light-emitting compound represented by chemical formula 1 and an organic electroluminescent device including the same. The organic electroluminescent device including an organic light-emitting compound according to the present invention reduces driving voltage and improves current efficiency.

Description

[0001] The present invention relates to an organic electroluminescent compound and an organic electroluminescent compound using the same,

More particularly, the present invention relates to a bipolar compound containing a benzocarbazole-based compound and an organic electroluminescent compound capable of being driven at a low voltage and having excellent luminous efficiency, luminance, thermal stability, Emitting device.

Organic electroluminescent devices (OLEDs) are devices that inject electrons and holes into organic materials to recombine / excite / emit electrons in organic materials, and can realize characteristics such as self-emission and low power consumption. It is expected. Particularly, the organic electroluminescent device can not only form a device on a transparent substrate that can be made like a plastic but also can operate at a voltage as low as 10 V or less as compared with a plasma display panel or an inorganic electroluminescent display, It has the advantage of being excellent in color. In addition, organic electroluminescent devices are capable of displaying three colors of green, blue, and red, and thus are attracting much attention as next-generation rich color display devices.

The OLED is composed of two electrodes, an anode, a cathode and a multilayer organic layer including a light emitting layer. In general, the organic layer is formed by a hole injection layer (HIL), a hole transport layer (HTL) ), An electron transport layer (ETL), and an electron injection layer (EIL).

Organic electroluminescent devices have been increasingly applied to display and illumination fields of various electronic products. However, efficiency and lifetime characteristics are limiting the expansion of application fields. In order to improve efficiency and lifetime characteristics, Many studies are under way. Particularly, as a light emitting material, a host / dopant system is used as a luminescent material in order to improve the color purity and efficiency at present, the most important factor for determining the luminescent efficiency in the organic electroluminescent device. The principle is that a dopant having a small amount of light emitting efficiency is added to a light emitting layer, and a host having a light emitting layer as a main component has a larger energy band gap than a dopant, and excitons generated in the host are transported to a dopant to produce highly efficient light. Since the wavelength generated by the host moves to the wavelength band of the dopant, the wavelength of light that can be obtained varies depending on the type of dopant.

In addition, although a fluorescent material is currently widely used as a light emitting material, development of a phosphorescent material on a light emitting mechanism is one of the methods that can improve the light emitting efficiency theoretically. Accordingly, various phosphorescent materials have been developed In particular, CBP (4,4'-N, N'-dicarbazolbiphenyl), which is a phosphorescent host compound capable of maximizing the luminescent properties of a dopant, and materials in which various substituents are introduced into carbazole (Japanese Patent Application Laid-Open No. 2008-214244, Japanese Patent Laid-Open No. 2003-133075), and BALq derivatives and the like are also known.

However, when a material such as BAlq or CBP is used as a host of a phosphorescent material, the driving voltage is higher than that of a device using a fluorescent material, so there is no significant advantage in terms of power efficiency, and the lifetime of the device is not satisfactory have. In addition, when the transport of electrons or holes is shifted to either side, the recombination of excitons in the light emitting layer is unevenly performed, thereby adversely affecting the lifetime and efficiency of the device.

Therefore, further improvement is demanded in terms of efficiency and lifetime in order to realize a more stable organic electroluminescent device, high efficiency, long life, and large size of the device.

Accordingly, an object of the present invention is to solve the above-described problems, and it is an object of the present invention to provide an organic electroluminescent compound capable of improving the driving voltage, luminous efficiency, brightness, thermal stability, and device lifetime by making the recombination of excitons uniform using a bipolar compound. .

Also, the present invention is to provide an organic electroluminescent device which can be driven at a low voltage by employing the organic electroluminescent compound as a light emitting material, and which has high efficiency, brightness, and lifetime characteristics.

In order to solve the above problems, the present invention provides an organic luminescent compound represented by the following formula (1).

[Chemical Formula 1]

Further, the present invention is a liquid crystal display device comprising a first electrode, a second electrode facing the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, The organic electroluminescent device includes at least one organic electroluminescent compound to be displayed.

Specific substituents of the organic luminescent compound represented by the formula (1) according to the present invention will be described later.

The bipolar organic electroluminescent compound comprising a benzocarbazole derivative represented by the formula (1) according to the present invention simultaneously contains a substituent having an electron-transporting property and a substituent having a hole-transporting property, When employed, the mobility of electrons and holes is increased and the recombination efficiency is improved. Therefore, various characteristics such as luminous efficiency, luminance, thermal stability, driving voltage and lifetime of the organic electroluminescent device can be improved.

Hereinafter, the present invention will be described in more detail.

The present invention is an organic luminescent compound employed in an organic layer of an organic electroluminescent device, characterized by being represented by the following formula (1) and being a bipolar compound having a hole transporting unit and an electron transporting unit simultaneously in the molecule.

[Chemical Formula 1]

In the above formula (1)

Z ₁ , Z ₂ and Z ₃ are each independently CH or N, and Z ₁ To Z ₃ At least one of them is N.

X and Y each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms.

L is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 6 to 30 carbon atoms, and n is an integer of 0 to 3.

The * -HTU (Hole Transportation Unit) is a benzocarbazole-based hole transporting unit and is characterized by being represented by the following formula (2).

(2)

In the above formula (2)

R ₁ , R ₂ , R ₃ And R ₄ are the same or different from each other and each independently represents hydrogen, deuterium, halogen, a nitro group, a substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted alkenyl group having 2-40 carbon atoms, A substituted or unsubstituted amino group having 1-40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted C1- Or an unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms.

In addition, the R ₁ To R ₄ May be bonded to each other to form at least one fused ring.

Q is selected from the group consisting of hydrogen, deuterium, a halogen, a nitro group, a substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted alkenyl group having 2-40 carbon atoms, a substituted or unsubstituted alkoxy group having 1-40 carbon atoms, Or an unsubstituted amino group having 1-40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted aryl group having 6-40 carbon atoms And a substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms, m is an integer of 1 to 5, and when m is 2 or more, the plurality of Qs may be the same or different from each other.

The Q may also be bonded to adjacent substituents to form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring.

The 'substituted' in the 'substituted or unsubstituted' may be a hydrogen, a deuterium, a halogen, a nitro group, an alkyl group having 1-40 carbon atoms, an alkenyl group having 2-40 carbon atoms, an alkoxy group having 1-40 carbon atoms, Substituted with at least one substituent selected from an amino group of -40, a cycloalkyl group of 3-40 carbon atoms, a heterocycloalkyl group of 3-40 carbon atoms, an aryl group of 6-40 carbon atoms, and a heteroaryl group of 5-40 carbon atoms. The X, Y, L, R < _{1 >} To R ₄ And Q may each independently be further substituted with the substituents described above.

On the other hand, the aryl group contained in the organic light emitting compound according to the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and is a single or fused ring system containing 5 to 7 atoms, preferably 5 or 6 atoms And when a substituent is present in the aryl group, it may be fused with an adjacent substituent to further form a ring.

Specific examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, an o- Naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, anthryl group, phenanthryl group, naphthyl group, An aromatic group such as a fluorenyl group, a pyrenyl group, an indenyl group, a fluorenyl group, a tetrahydronaphthyl group, a pyrenyl group, a perylene group, a crycenyl group, a naphthacenyl group and a fluoranthenyl group.

The at least one hydrogen atom of the aryl group may be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ' , An alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, , A heteroaryl group having 2 to 24 carbon atoms, or a heteroarylalkyl group having 2 to 24 carbon atoms.

On the other hand, the heteroaryl group contained in the organic light emitting compound according to the present invention is a heteroaromatic group having 2 to 24 carbon atoms which may contain 1 to 4 hetero atoms selected from N, O, P or S in each ring in the aryl group Refers to an organic radical, which rings can be fused to form a ring. And at least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as the aryl group.

When X and Y are each independently an aryl group or a heteroaryl group, they may be more specifically selected from the group consisting of the following structural formula (1).

[Structural formula 1]

In the above formula 1,

Q ₁ is the same as the definition of Q in the above formula 2, 1 is an integer of 1 to 9, and when 1 is 2 or more, the plurality of Qs are the same or different from each other and combine with adjacent substituents to form a condensed aliphatic ring , Condensed aromatic rings, condensed heteroaliphatic rings or condensed heteroaromatic rings.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. The atom may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group used as the substituent in the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy and hexyloxy. At least one hydrogen atom of the group may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the halogen group which is a substituent used in the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the alkenyl group used in the present invention include straight or branched chain alkenyl groups, and examples thereof include a 3-pentenyl group, a 4-hexenyl group, a 5-heptenyl group, a 4-methyl- Dimethyl-pentenyl group, 6-methyl-5-heptenyl group and 2,6-dimethyl-5-heptenyl group.

According to a preferred embodiment of the present invention, the organic electroluminescent compound represented by the formula (1) may be more specifically selected from the following compounds represented by the following formulas (3) to (162).

[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 7]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]

[Chemical Formula 23]

[Chemical Formula 25]

[Chemical Formula 27]

[Chemical Formula 30]

(32)

[Chemical Formula 33]

[Chemical Formula 35]

[Chemical Formula 37]

[Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 43]

[Chemical Formula 45]

[Chemical Formula 47]

[Chemical Formula 49]

[Chemical Formula 51]

(54)

[Chemical Formula 55]

[Chemical Formula 57]

[Chemical Formula 60]

[Chemical Formula 61]

(63)

[Chemical Formula 65]

[Chemical Formula 67]

(70)

[Chemical Formula 71]

[Chemical Formula 73]

[Chemical Formula 75]

[Formula 77]

[Formula 79]

[Formula 81]

[Chemical Formula 83]

[Chemical Formula 85]

[Chemical Formula 87]

(90)

[Chemical Formula 91]

[Chemical Formula 93]

[Chemical Formula 95]

(98)

(100)

(101)

[Chemical Formula 103]

(106)

(108)

(110)

(111)

[Formula 113]

(115)

(118)

(120)

[Formula 121]

(124)

[Formula 125]

(128)

[Formula 130]

[Formula 131]

[Formula 133]

[Chemical Formula 135]

[Chemical Formula 137]

[Formula 140]

(141)

(144)

[Chemical Formula 145]

[Chemical Formula 147]

[Formula 150]

[Formula 152]

(154)

[Chemical Formula 155]

(158)

[Formula 15]

[Formula 161]

Further, the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, And an organic electroluminescent device comprising at least one luminescent compound.

The organic layer containing the organic luminescent compound represented by Formula 1 may be at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, . ≪ / RTI >

When the compound represented by Formula 1 is included in the organic electroluminescent device as a material of the electron injecting layer, the electron transporting layer, the hole injecting layer, and the hole transporting layer, the electron injecting / transporting ability of the organic electroluminescent device, Ability can be maximized.

In addition, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, and the light emitting layer may specifically include a host and a dopant, and the organic light emitting compound of the present invention may be used as a host, The luminous efficiency and lifetime characteristics of the organic electroluminescent device are maximized.

In the present invention, a dopant material may be used for the light emitting layer, in addition to the host. When the light emitting layer comprises a host and a dopant, the dopant content may be selected in the range of about 0.01 to about 20 parts by weight, based on 100 parts by weight of the host.

A specific example of the structure of the organic electroluminescent device according to the present invention is described below.

At least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer may be formed by sequentially laminating a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, Lt; RTI ID = 0.0 > 1, < / RTI > In addition, an electron injection layer may be disposed on the electron transport layer, and the electron injection layer may include a compound represented by the formula (1).

In addition, the organic electroluminescent device according to the present invention may have an insulating layer or an adhesive layer interposed 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 deposition 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 may be formed by using materials and methods known in the art, except that at least one layer of one or more organic layers is formed to include an organic light emitting compound represented by Formula 1 of the present invention Thereby forming 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); A combination of a metal and an oxide such as ZnO: Al or SnO2: 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 LiO2 / Al, but are not limited thereto.

In addition, materials such as a hole injection layer, a hole transport layer, and an electron injection layer are not particularly limited, and ordinary materials known in the art can be used.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It will be clear to those who have knowledge.

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by Formula 9

Synthesis Example 1-1 Synthesis of Compound a

[Reaction Scheme 1-1]

50 g of trichlorotriazine (CNC) is dissolved in 500 mL of THF, cooled to 5 ° C, and 570 mL of 1.0 M THF solution of phenylmagnesium bromide is added dropwise. The mixture was further stirred at 5 DEG C for 6 hours, 500 mL of a 1% hydrochloric acid aqueous solution was added, stirred for 30 minutes, and then allowed to stand to collect the organic layer. The collected organic layer is washed twice with 250 mL of water and concentrated. To the concentrated reaction solution was added 250 mL of methanol, and the mixture was stirred vigorously for 24 hours. 43.2 g (yield: 65%) of a white solid precipitated by filtration was obtained.

Synthesis Example 1-2 Synthesis of Compound b

[Reaction Scheme 1-2]

40 g of the compound a obtained in Synthesis Example 1-1 and 28.4 g of 3-boromophenylboronic acid were dissolved in 1.4 L of toluene, and 4.95 g of tetrakis (triphenylphosphine) palladium (0) and 2 N of potassium carbonate L was added. The reaction was refluxed and stirred for 12 hours, and then cooled to room temperature to separate the organic layer and the water layer. The organic layer separated from the water layer was concentrated and purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 27.5 g (yield: 50%) of a white solid compound b.

Synthesis Example 1-3 Synthesis of Compound Represented by Formula 9

[Reaction 1 - 3]

The compound obtained in the above Synthesis Example 1-2 b 25 g, benzo [1,2 ] carbazole 15.4 g, Bis (dibenzylideneacetone) palladium (0) 1.11 g, tri- t -butylphosphine 0.4 g and sodium tertbutoxide 12.4 g Toluene 250 mL And the mixture was stirred under reflux conditions for 15 hours, cooled to room temperature, 200 mL of water was added, stirred for 30 minutes, and the organic layer was separated. The organic layer separated from the water layer was concentrated and purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 26.3 g (yield: 78%) of a compound represented by the formula (9) as a white solid.

_{1H NMR (500 MHz, CDCl 3} ) 7.16 (dd, 1H), 7.35 (dd, 1H), 7.50-7.57 (m, 7H), 7.60-7.72 (m, 4H), 7.94 (d, 1H), 8.11- 8.12 (m, 2H), 8.21-8.24 (m, 2H), 8.36 (d, 4H), 8.55

Synthesis Example 2 Synthesis of Compound Represented by Formula (32)

Synthesis Example 2-1 Synthesis of Compound c

[Reaction Scheme 2-1]

6.3 g of magnesium and 0.2 g of iodine were added to 120 mL of THF and stirred at reflux for 3 hours. After cooling to 60 ° C, 53.9 g of 2-bromonaphthalene was dissolved in 76 mL of THF, and the mixture was stirred for 1 hour under reflux After cooling to room temperature, 20 g of trichlorotriazine was added, and the mixture was stirred at reflux for 2 hours. The mixture was cooled to room temperature, and the mixture was stirred at room temperature for 15 hours. The mixture was filtered to obtain 27.5 g of brownish compound c (yield: 69% ).

Synthesis Example 2-2 Synthesis of Compound (d)

[Reaction Scheme 2-2]

25 g of the compound c obtained in Synthesis Example 2-1 and 14.0 g of 4-boromophenylboronic acid were dissolved in 1 L of toluene, and then 2.5 g of tetrakis (triphenylphosphine) palladium (0) and 2 N of potassium carbonate L was added. The reaction was refluxed and stirred for 12 hours, and then cooled to room temperature to separate the organic layer and the water layer. The organic layer separated from the water layer was concentrated and then purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 13.6 g (yield: 43%) of a white solid compound d.

Synthesis Example 2-3 Synthesis of Compound Represented by Formula 32

[Reaction Scheme 2-3]

The compound obtained in the above Synthesis Example 2-2 d 12 g, benzo [1,2 ] carbazole 5.9 g, Bis (dibenzylideneacetone) palladium (0) 0.4 g, tri- t -butylphosphine 0.15 g and 4.7 g sodium tertbutoxide in toluene 120 mL And the mixture was stirred at reflux for 15 hours. After cooling to room temperature, 100 mL of water was added, stirred for 30 minutes, and the organic layer was separated. The organic layer separated from the water layer was concentrated and purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 26.3 g (yield: 78%) of a compound represented by the general formula (32) as a white solid.

_{1H NMR (500 MHz, CDCl 3} ) 7.15 (dd, 1H), 7.36 (dd, 1H), 7.57-7.61 (m, 5H), 7.67-7.72 (m, 2H), 7.91 (s, 4H), 7.94 ( (m, 4H), 8.12-8.16 (m, 4H), 8.49-8.55 (m, 4H), 9.11

Synthesis Example 3 Synthesis of Compound Represented by Chemical Formula 54

Synthesis Example 3-1 Synthesis of Compound e

[Reaction Scheme 3-1]

10 g of the compound b obtained in the above Synthesis Example 1-2 and 4.4 g of 4-chlorophenylboronic acid were dissolved in 100 mL of toluene, 1.5 g of tetrakis (triphenylphosphine) palladium (0) and 2 N of potassium carbonate (K2CO3) mL. The reaction was refluxed and stirred for 12 hours, and then the organic layer and the water layer were separated. The organic layer separated from the water layer was cooled to room temperature and filtered to obtain 9.3 g (yield: 86%) of a white solid compound e.

Synthesis Example 3-2 Synthesis of Compound Represented by Chemical Formula 54

[Reaction Scheme 3-2]

The compound obtained in the above Synthesis Example 3-1 e 5.0 g, benzo [1,2 ] carbazole 2.8 g, Bis (dibenzylideneacetone) palladium (0) 0.2 g, tri- t -butylphosphine 0.07 g sodium tertbutoxide and 2.3 g of toluene 50 mL And the mixture was stirred at reflux for 15 hours. After cooling to room temperature, 25 mL of water was added, stirred for 30 minutes, and the organic layer was separated. The organic layer separated from the water layer was concentrated and purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 5.8 g (yield: 81%) of a compound represented by Chemical Formula 54 as a white solid.

_{1H NMR (500 MHz, CDCl 3} ) 7.12 (dd, 1H), 7.32 (t, 1H), 7.50-7.57 (m, 7H), 7.67-7.73 (m, 4H), 7.91-7.94 (m, 6H), 8.11 (d, 1H), 8.12 (d, 1H), 8.36-8.39 (m, 5H), 8.50-8.56

Synthesis Example 4 Synthesis of Compound Represented by Formula 80

Synthesis Example 4-1 Synthesis of Compound f

[Reaction Scheme 4-1]

0.63 g of magnesium and 0.02 g of iodine were added to 12 mL of THF and stirred at reflux for 3 hours. After cooling to 60 DEG C, 6.69 g of 9-bromoanthracene was dissolved in 7.6 mL of THF, and the mixture was stirred at reflux for 1 hour. After cooling to room temperature, 2.0 g of trichlorotriazine was added, and the mixture was stirred under reflux for 2 hours. After cooling to room temperature, the mixture was added to 18 L of methanol, stirred at room temperature for 15 hours and filtered to obtain 3.1 g of a brown compound (yield: 61% ).

Synthesis Example 4-2 Synthesis of Compound g

[Reaction Scheme 4-2]

After 3.0 g of the compound obtained in Synthesis Example 4-1 and 1.6 g of 4'-Chloro-4-biphenyl boronic acid were dissolved in 10 mL of toluene, 0.4 g of tetrakis (triphenyl phosphine) palladium (0) Of potassium carbonate (K2CO3) (6 mL). The reaction was refluxed and stirred for 12 hours, and then the organic layer and the water layer were separated. The organic layer separated from the water layer was cooled to room temperature and filtered to obtain 3.8 g (yield: 89%) of a white solid compound e.

Synthesis Example 4-3 Synthesis of Compound Represented by Formula 80

[Reaction Scheme 4-3]

The compound obtained in the above Synthesis Example 4-2 e 3.5 g, benzo [1,2 ] carbazole 1.3 g, Bis (dibenzylideneacetone) palladium (0) 0.1 g, tri- t -butylphosphine 0.03 g sodium tertbutoxide and 1.0 g of toluene 35 mL And the mixture was stirred under reflux conditions for 15 hours, cooled to room temperature, 20 mL of water was added, stirred for 30 minutes, and the organic layer was separated. The organic layer separated from the aqueous layer was concentrated and purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 2.2 g (yield: 70%) of a compound represented by the general formula (80) as a white solid.

_{1H NMR (500 MHz, CDCl 3} ) 7.10 (dd, 1H), 7.22 (d, 2H), 7.37 (dd, 1H), 7.45-7.50 (m, 8H), 7.57 (d, 1H), 7.69-7.73 ( 2H), 7.94-7.98 (m, 7H), 8.06-8.11 (m, 6H), 8.21 (d, 4H), 8.46-8.

Synthesis Example 5 Synthesis of Compound Represented by Formula 100

Synthesis Example 5-1 Synthesis of Compound h

[Reaction Scheme 5-1]

After 4.0 g of the compound a obtained in Synthesis Example 1-1 and 2.8 g of 4-boromophenylboronic acid were dissolved in 140 mL of toluene, 0.5 g of tetrakis (triphenylphosphine) palladium (0) and 2 N of potassium carbonate (K2CO3) 120 mL. The reaction was refluxed and stirred for 12 hours, and then cooled to room temperature to separate the organic layer and the water layer. The organic layer separated from the water layer was concentrated and then purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 2.7 g of a white solid compound h (yield: 51%).

Synthesis Example 5-2 Synthesis of Compound i

[Reaction Scheme 5-2]

2.5 g of the compound h obtained in Synthesis Example 5-1 and 1.1 g of 4-chlorophenylboronic acid were dissolved in 25 mL of toluene, 0.4 g of tetrakis (triphenylphosphine) palladium (0) and 2 N of potassium carbonate (K2CO3) mL. The reaction was refluxed and stirred for 12 hours, and then the organic layer and the water layer were separated. The organic layer separated from the water layer was concentrated and purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 2.2 g (yield: 85%) of Compound e as a white solid.

Synthesis Example 5-3 Synthesis of Compound Represented by Formula 100

[Reaction Scheme 5-3]

The compound obtained in the above Synthesis Example 5-1 h 2.0 g, benzo [1,2 ] carbazole 1.1 g, Bis (dibenzylideneacetone) palladium (0) 0.08 g, tri- t -butylphosphine 0.03 g sodium tertbutoxide and 0.9 g of toluene 20 mL And the mixture was stirred at reflux for 15 hours, cooled to room temperature, added with 15 mL of water, stirred for 30 minutes, and the organic layer was separated. The organic layer separated from the water layer was concentrated and purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 2.3 g (yield: 79%) of a compound represented by Chemical Formula 100 as a white solid.

_{1H NMR (500 MHz, CDCl 3} ) 7.11 (dd, 1H), 7.24 (d, 2H), 7.35 (dd, 1H), 7.45 (d, 1H), 7.47-7.51 (m, 6H), 7.56-7.60 ( 2H), 8.38 (dd, 4H), 8.55-8.58 (m, 2H), 7.64-7.70 (m,

Synthesis Example 6 Synthesis of Compound Represented by Formula 123

Synthesis Example 6-1 Synthesis of Compound j

[Reaction Scheme 6-1]

A solution of 0.6 g of Copper (I) iodide, 0.4 g of trans-1,2-diaminocyclohexane, 12.6 g of photocatalyst phosphate, 25.8 g of benzo [1,2] carbazole and 20 g of 9,10-dibromoanthracene were placed in 240 mL of toluene, After stirring for an hour, the reaction mixture was filtered to remove insolubles, and the filtrate was concentrated and purified by column chromatography (n-hexane / dichloromethane = 2/1) to obtain 8.8 g (yield: 31%) of compound j as a white solid.

Synthesis Example 6-2 Synthesis of Compound k

[Reaction Scheme 6-2]

Compound (7.3 g) obtained in Synthesis Example 6-1 was dispersed in 70 mL of 1,4-dioxane together with 4.7 g of bis (pinacolato) diboron, followed by addition of [1,1'- 0.3 g of bis (diphenylphosphino) ferrocene] dichloropalladium (II) and 4.6 g of potassium acetate (KOAc) were added. The mixture was refluxed for 24 hours and cooled to room temperature. 70 ml of distilled water was added thereto and stirred. Then, 70 ml of dichloromethane And the organic layer and the water layer were separated. Thereafter, the organic layer separated from the water layer was concentrated and then purified by column chromatography (n-hexane / dichloromethane = 2/1) to obtain 5.4 g (yield: 68%) of compound k as a white solid.

Synthesis Example 6-3 Synthesis of Compound represented by Formula 123

[Reaction Scheme 6-3]

2.8 g of the compound a obtained in the above Synthesis Example 1-1 and 5.0 g of the compound k obtained in the above Synthesis Example 6-2 were dissolved in 50 mL of toluene, to which 0.5 g of tetrakis (triphenyl phosphine) palladium (0) 30 mL of potassium carbonate (K2CO3) was added. The reaction was refluxed and stirred for 12 hours, and then the organic layer and the water layer were separated. The organic layer separated from the water layer was concentrated and then purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 4.7 g (yield: 77%) of a white solid.

_{1H NMR (500 MHz, CDCl 3} ) 7.17 (dd, 1H), 7.36 (t, 1H), 7.45-7.51 (m, 10H), 7.57 (d, 2H), 7.69-7.72 (m, 2H), 7.95 ( (m, 2H), 8.36 (d, 4H), 8.51-8.55 (m, 2H)

Synthesis Example 7 Synthesis of Compound Represented by Formula 146

Synthesis Example 7-1 Synthesis of Compound 1

[Reaction Scheme 7-1]

0.2 g of Copper (I) iodide, 0.2 g of trans-1,2-diaminocyclohexane, 7.4 g of photosium phosphate, 15.2 g of benzo [1,2] carbazole and 10 g of 1,4-dibromonaphthalene were placed in 120 mL of toluene. After stirring for an hour, the reaction mixture was filtered to remove insolubles. The filtrate was concentrated and purified by column chromatography (n-hexane / dichloromethane = 2/1) to obtain 4.8 g (yield: 29%) of Compound 1 as a white solid.

Synthesis Example 7-2 Synthesis of Compound (m)

[Reaction Scheme 7-2]

4.5 g of the compound l obtained in the above Synthesis Example 6-1 was dispersed in 50 mL of 1,4-dioxane together with 3.2 g of bis (pinacolato) diboron, followed by the addition of [1,1'- 0.3 g of bis (diphenylphosphino) ferrocene] dichloropalladium (II) and 4.6 g of potassium acetate (KOAc) were added. The mixture was refluxed for 24 hours and cooled to room temperature. 70 ml of distilled water was added thereto and stirred. Then, 70 ml of dichloromethane And the organic layer and the water layer were separated. Thereafter, the organic layer separated from the water layer was concentrated and then purified by column chromatography (n-hexane / dichloromethane = 2/1) to obtain 3.5 g (yield: 71%) of compound k as a white solid.

Synthesis Example 7-3 Synthesis of Compound Represented by Formula 146

[Reaction Scheme 7-3]

1.9 g of the compound a obtained in the above Synthesis Example 1-1 and 3.5 g of the compound obtained in the above Synthesis Example 7-2 were dissolved in 35 mL of toluene, 0.4 g of tetrakis (triphenyl phosphine) palladium (0) 30 mL of potassium carbonate (K ₂ CO ₃ ) was added. The reaction was refluxed and stirred for 12 hours, and then the organic layer and the water layer were separated. The organic layer separated from the water layer was concentrated and then purified by column chromatography (n-hexane / dichloromethane = 4/1) to obtain 3.1 g (yield: 84%) of a white solid.

_{1H NMR (500 MHz, CDCl 3} ) 7.16 (t, 1H), 7.35 (t, 1H), 7.49-7.51 (m, 6H), 7.56-7.58 (m, 3H), 7.69-7.72 (m, 3H), 2H), 9.00 (m, 1H), 7.95 (d, 1H), 8.11-8.12 (m, 3H), 8.34

&Lt; Examples 1 to 7 > Manufacture of organic electroluminescent device

OLED devices were fabricated using the organic light emitting compounds according to the present invention. The transparent electrode ITO thin film (1500 Å) was ultrasonically washed with trichlorethylene, acetone, ethanol, and distilled water sequentially, and stored in isopropanol before use. Next, an ITO substrate was placed on a substrate folder of a vacuum deposition apparatus, and NPB [ N , N- di (naphthalene-1-yl) -N , N- diphenylbenzidine] The transport layer was deposited.

Subsequently, organic light emitting compounds according to the present invention synthesized in Synthesis Examples 1 to 7 were used as hosts, and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium III) acetylacetonate] was doped in a thickness of 30 nm to form a light emitting layer. Subsequently, BPhen [bathophenanthroline] was deposited as an electron transport layer on the light emitting layer to a thickness of 30 nm, lithium fluoride was deposited to a thickness of 1 nm as an electron injection layer, and an Al cathode was deposited to a thickness of 100 nm to form an OLED device .

&Lt; Comparative Example 1 &

Except that CBP (4,4'-di (9H-carbazol-9-yl) biphenyl) was used as a host instead of the compound represented by the formula (9) as a host material in the formation of the light emitting layer in Example 1 The organic light emitting device was fabricated in the same manner as in Example 1, and the structure of CBP was as follows.

<Experimental Example 1>

The driving voltage and the current efficiency were measured for each of the organic light emitting devices manufactured in Examples 1 to 7 and Comparative Example 1, and the results are shown in Table 1 below.

 division The driving voltage (V) Current efficiency (cd / A) Current efficiency (lm / W) Example 1 6.7 7.5 4.8 Example 2 4.5 7.8 5.3 Example 3 5.8 8.2 6.3 Example 4 6.1 8.6 5.9 Example 5 5.3 7.7 4.5 Example 6 4.7 7.3 4.4 Example 7 4.5 7.6 5.5 Comparative Example 1 6.8 7.2 4.3

Claims (8)

An organic light-emitting compound represented by the following Formula 1:
[Chemical Formula 1]

In the above formula (1)
Z ₁ , Z ₂ and Z ₃ are each independently CH or N, and Z ₁ To Z ₃ Is at least N,
X and Y are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms,
L is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 6 to 30 carbon atoms, n is an integer of 0 to 3,
* -HTU is represented by the following formula (2)
(2)

In the above formula (2)
R ₁ , R ₂ , R ₃ And R ₄ are the same or different from each other and each independently represents hydrogen, deuterium, halogen, a nitro group, a substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted alkenyl group having 2-40 carbon atoms, A substituted or unsubstituted amino group having 1-40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted C1- Or an unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms,
The R ₁ To R ₄ Are bonded to each other to form at least one fused ring,
Q is selected from the group consisting of hydrogen, deuterium, a halogen, a nitro group, a substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted alkenyl group having 2-40 carbon atoms, a substituted or unsubstituted alkoxy group having 1-40 carbon atoms, Or an unsubstituted amino group having 1-40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted aryl group having 6-40 carbon atoms And a substituted or unsubstituted heteroaryl group having 5 to 40 carbon atoms, m is an integer of 1 to 5, and when m is 2 or more, plural Qs are the same or different from each other,
The Q may combine with adjacent substituents to form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring. The method according to claim 1,
The X, Y, L, R ₁ To R ₄ And Q are each independently selected from the group consisting of hydrogen, deuterium, a halogen, a nitro group, an alkyl group having 1-40 carbon atoms, an alkenyl group having 2-40 carbon atoms, an alkoxy group having 1-40 carbon atoms, an amino group having 1-40 carbon atoms, An aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 5 to 40 carbon atoms, wherein the substituent is selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, The method according to claim 1,
And X and Y are each independently any one selected from the group consisting of the following structural formula 1:
[Structural formula 1]

In the above formula 1,
Q ₁ is the same as the definition of Q in the above formula 2, 1 is an integer of 1 to 9, and when 1 is 2 or more, the plurality of Qs are the same or different from each other and combine with adjacent substituents to form a condensed aliphatic ring , Condensed aromatic rings, condensed heteroaliphatic rings or condensed heteroaromatic rings. The method according to claim 1,
The organic luminescent compound according to claim 1, wherein the compound represented by formula (1) is selected from compounds represented by the following formulas (3) to (162)
[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 7]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]

[Chemical Formula 23]

[Chemical Formula 25]

[Chemical Formula 27]

[Chemical Formula 30]

(32)

[Chemical Formula 33]

[Chemical Formula 35]

[Chemical Formula 37]

[Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 43]

[Chemical Formula 45]

[Chemical Formula 47]

[Chemical Formula 49]

[Chemical Formula 51]

(54)

[Chemical Formula 55]

[Chemical Formula 57]

[Chemical Formula 60]

[Chemical Formula 61]

(63)

[Chemical Formula 65]

[Chemical Formula 67]

(70)

[Chemical Formula 71]

[Chemical Formula 73]

[Chemical Formula 75]

[Formula 77]

[Formula 79]

[Formula 81]

[Chemical Formula 83]

[Chemical Formula 85]

[Chemical Formula 87]

(90)

[Chemical Formula 91]

[Chemical Formula 93]

[Chemical Formula 95]

(98)

(100)

(101)

[Chemical Formula 103]

(106)

(108)

(110)

(111)

[Formula 113]

(115)

(118)

(120)

[Formula 121]

(124)

[Formula 125]

(128)

[Formula 130]

[Formula 131]

[Formula 133]

[Chemical Formula 135]

[Chemical Formula 137]

[Formula 140]

(141)

(144)

[Chemical Formula 145]

[Chemical Formula 147]

[Formula 150]

[Formula 152]

(154)

[Chemical Formula 155]

(158)

[Formula 15]

[Formula 161]

A first electrode; A second electrode facing the first electrode; And at least one organic layer interposed between the first electrode and the second electrode,
Wherein the organic layer comprises at least one organic electroluminescent compound represented by Formula 1 according to Claim 1. 6. The method of claim 5,
Wherein the organic layer comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer and an electron injection layer. The method according to claim 6,
Wherein the light emitting layer comprises at least one host compound and at least one dopant compound, and the host compound is an organic light emitting compound represented by the following formula (1). 6. The method of claim 5,
Wherein the organic layer further comprises one or more organic light emitting layers emitting red, green, or blue light to emit white light.