KR20140121123A - Asymmetric pyrene derivatives comprising amine group including heteroaryl group and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a pyrene derivative represented by [chemical formula A] or [chemical formula B], and an organic light emitting diode comprising the same, wherein substituents Py_1, Py_2, Ar_1, Ar_2, Z, and m are defined in the detailed description of the invention.

Description

[0001] The present invention relates to an asymmetric pyrene derivative substituted with an amine group including a heteroaryl group and an organic light emitting device comprising the same.

The present invention relates to an asymmetric pyrene derivative substituted with an amine group containing a heteroaryl group and an organic light emitting device including the amine group. More particularly, the present invention relates to an asymmetric pyrene derivative substituted with an amine group having a heteroaryl group, And an organic light emitting device including the asymmetric pyrene derivative.

Recently, as the size of a display device has been increased, a demand for a display device or a bendable display device having little space occupation due to a flat plate structure has been increasing. The liquid crystal display, which is a typical flat display device, is lighter than a conventional CRT However, it is disadvantageous in that a viewing angle is limited and a back light is necessarily required. In contrast, an organic light emitting diode (OLED), a new flat display device, is a display using an auto-luminescent phenomenon and has advantages such as a large viewing angle, a light weight and a small size compared to a liquid crystal display, In recent years, application to a full-color display or illumination is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layered structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

When current is applied to the organic light emitting device, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons recombine in the light emitting layer through the respective hole transporting layers and electron transporting layers to form luminescent excitons. The thus formed luminescent excitons emit light while transitioning to the ground state. The light may be divided into fluorescence using a singlet exciton and phosphorescent triplet exciton according to a light emitting mechanism, and the fluorescence and phosphorescence may be used as a light source of an organic light emitting device.

On the other hand, when only one material is used as the light emitting material, there arises a problem that the maximum light emitting wavelength shifts to a long wavelength due to intermolecular interaction, the color purity drops, or the efficiency of the device decreases due to the light emission attenuating effect. A host-dopant system can be used as a light emitting material to increase the efficiency of light emission through the transition.

When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the light of the desired wavelength can be obtained according to the type of the dopant used.

In recent years, there is an increasing need for high-luminance and high-purity blue organic light emitting materials for applications in full-color displays or lighting. As the blue organic luminescent material, Patent Document 10-2006-0006760 (Jan. 19, 2006) discloses an organic luminescent device using a substituted pyrene-based derivative, and Japanese Unexamined Patent Application Publication No. 10-2011-0072041 .29) discloses an organic light emitting device using a pyrene-based derivative containing heteroaryl.

However, despite the above efforts, it is difficult to realize a full-color display of full color because the organic light emitting materials manufactured by the prior art including the prior art have low color purity of blue and it is difficult to realize a clear blue color. There is a need to develop new organic light emitting materials continuously.

Japanese Patent Application Laid-Open No. 10-2006-0006760 (2006.01.19) Japanese Patent Application Laid-Open No. 10-2011-0072041 (June 29, 2011)

Accordingly, a first technical object of the present invention is to provide a novel organic luminescent compound which can be used in a luminescent layer of an organic luminescent device, and has high luminance and color purity of blue.

A second object of the present invention is to provide an organic light emitting device including the organic light emitting compound.

In order to achieve the first technical object, the present invention provides an organic luminescent compound represented by the following formula (A) or (B).

[Chemical Formula A]

In the above formulas (A) and (B)

Each of Py ₁ and Py ₂ is the same or different and independently of each other, a substituted or unsubstituted pyridinyl group, or a substituted or unsubstituted 6-membered aromatic heteroaryl group, two of which are nitrogen atoms And the remainder is a heteroaryl group which is a carbon atom,

Ar ₁ and Ar ₂ are the same or different and independently represent a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted 5 to 50 Or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms and having at least one heteroatom selected from O, N, S and Si,

The substituent Z is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N, S, and Si A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 hetero aryl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 30 carbon atoms An arylamine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group, To form a saturated or unsaturated ring;

Each carbon atom in the pyrene ring is bonded to the nitrogen atom of the amine or, when not bonded to the substituent Z, to hydrogen;

In formula [A], m is an integer of 1 to 8, and when m is 2 or more, each Z is independently the same as or different from each other,

The two amine groups bonded to the pyrene are different from each other, so that the pyrene has an asymmetric structure.

In the formula (B), m is an integer of 1 to 9, and when m is 2 or more, each Z is independently the same as or different from each other.

According to another aspect of the present invention, there is provided a plasma display panel comprising a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, An organic light emitting device including at least one organic light emitting compound of the present invention is provided.

According to the present invention, the organic luminescent compound represented by the formula (A) or (B) has characteristics of high color purity and excellent luminescence efficiency as compared with the existing materials, and is used for a device for producing a full color display .

1 is a schematic view of an organic light emitting device according to an embodiment of the present invention.

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

The present invention provides an asymmetric pyrene derivative represented by the following formula (A) or (B) as an organic luminescent compound that can be used in a luminescent layer of an organic luminescent device.

 [Chemical Formula A]

In the above formulas (A) and (B)

Each of Py ₁ and Py ₂ is the same or different and independently of each other, a substituted or unsubstituted pyridinyl group, or a substituted or unsubstituted 6-membered aromatic heteroaryl group, two of which are nitrogen atoms And the remainder is a heteroaryl group which is a carbon atom,

Ar ₁ and Ar ₂ are the same or different and independently represent a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted 5 to 50 Or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms and having at least one heteroatom selected from O, N, S and Si,

The substituent Z is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N, S, and Si A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 hetero aryl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 30 carbon atoms An arylamine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group, To form a saturated or unsaturated ring;

Each carbon atom in the pyrene ring is bonded to the nitrogen atom of the amine or, when not bonded to the substituent Z, to hydrogen;

In formula [A], m is an integer of 1 to 8, and when m is 2 or more, each Z is independently the same as or different from each other,

The two amine groups bonded to the pyrene are different from each other, so that the pyrene has an asymmetric structure.

In the formula (B), m is an integer of 1 to 9, and when m is 2 or more, each Z is independently the same as or different from each other;

The 'substituted' in the above 'substituted or unsubstituted' means a group selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl 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, an arylalkyl 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 , An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, Group, and an aryloxy group having 1 to 24 carbon atoms.

In consideration of the range of the alkyl or aryl group in the "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms" and "substituted or unsubstituted aryl group having 5 to 50 carbon atoms", it is preferable that the number of carbon atoms is 1 to 30 And the number of carbon atoms of the aryl group having 5 to 50 carbon atoms means the total number of carbon atoms constituting the alkyl moiety or aryl moiety when it is considered that the substituent is not substituted without considering the substituted moiety. For example, a phenyl group substituted with a butyl group at the para position should be considered to correspond to an aryl group having 6 carbon atoms substituted with a butyl group having a carbon number of 4.

The present invention relates to an asymmetric pyrene derivative compound represented by the above formula (A) or (B), wherein each of the two amine groups bonded to the pyrene is at least one substituted or unsubstituted pyridinyl group or a substituted or unsubstituted six- The heteroaryl group includes a heteroaryl group in which two of the six-membered rings are nitrogen atoms and the other is a carbon atom, and the pyrene derivative to which the amine group is bonded has an asymmetric structure.

Here, the aromatic heteroaryl group of the above-mentioned six-membered ring may be any heteroaryl group selected from pyridazine, pyrimidine and pyrazine having the following structural formula as the heteroaryl group having two nitrogen atoms and the remaining carbon atoms, An aryl group can be selected.

In the present invention, each Py ₁ and Py ₂ When the substituent is a pyridinyl group, the position of the nitrogen included in the pyridinyl group may have an ortho, meta, or para position based on the position of the nitrogen of the amine. That is, the nitrogen atom of the pyridinyl group and the amine may be bonded so as to be represented by the following structures (1) to (3).

In the case where each of the Py ₁ and Py ₂ substituents is a heteroaryl group selected from pyridazine, pyrimidine and pyrazine, the position of nitrogen contained in Py ₁ and Py ₂ is determined based on the position of nitrogen of amine May be combined so as to be represented by any one of the following structures (4) to (9).

As in the present invention, the organic light emitting device in which the pyridinyl group as the substituent group or the aromatic heteroaryl group of the 6-membered ring as the substituent in the amine group is bonded to the heteroaryl group having two nitrogen atoms in the 6-membered ring and the remainder being the carbon atom, The organic luminescent compound having the asymmetric pyrene structure of the present invention can improve the blue color purity of the organic light emitting device compared to the organic luminescent material according to the prior art and exhibit excellent device characteristics with high luminance, An organic light emitting device having characteristics of the present invention can be manufactured.

On the other hand, the aryl group used in the compound of the present invention includes an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and includes a single or fused ring system containing 5 to 7 atoms, preferably 5 or 6 atoms, When a substituent is present in the aryl group, the adjacent substituent may be fused with each other to form a ring.

Specific examples of the aryl include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluororan And the like, but are not limited thereto.

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 hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ' R 'and R "are independently an alkyl group having 1 to 10 carbon atoms, and in this case, they are referred to as" alkylamino group "), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, , 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, an arylalkyl 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.

The heteroaryl group which is a substituent used in the compounds of 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, Si or S in each ring in the aryl group. Radical, and the rings may 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.

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. May be substituted with the same substituents as those in the aryl group.

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

Specific examples of the silyl group used as the substituent in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, Butylsilyl, dimethylpurylsilyl and the like, and at least one hydrogen atom of the silyl group may be substituted with the same substituent as the aryl group.

In the present invention, the above-mentioned formula A may be any one selected from the following formulas A-1 to A-3, and the above formula B may be an asymmetric pyrene derivative represented by the following formula A-4 or A- .

[Formula A-1] [Formula A-2] [Formula A-3]

[Chemical formula A-4] [Chemical formula A-5]

The substituents Ar ₁₁ and Ar ₂₁ are the same or different and are each independently a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and the substituents Het ₁ and Het ₂ are the same Or a heteroaryl group having 2 to 50 carbon atoms having at least one heteroatom selected from O, N, S and Si, which is substituted or unsubstituted independently of each other.

In one embodiment, in which is Het ₁ with Het ₁ and Het ₂ of the present invention the formula A-1 to A-3 of the formula A-4) and (A-5 is selected from the structural formulas A to Structure F, respectively one Or a heteroaryl group.

[Structural Formula A]

[Structural formula B]

[Structural formula C]

[Structural formula D]

[Structural formula E]

[Structural formula F]

In Formulas A to F,

T ₁ to T ₈ are the same or different and independently selected from the group consisting of C (R ₁₁ ), C (R ₁₁ ) (R ₁₂ ), N, N (R ₁₃ ), O and S, _{C (R 11), C (} R 11) (R 12), N (R 13) of any of the structural formulas a to Structure F each C (R ₁₁₎ containing a plurality of the case that includes a plurality in, C (R ₁₁ ) (R ₁₂ ) and N (R ₁₃ ) may be the same or different,

Wherein R ₁ to R ₁₃ are the same or different from each other and independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms and having at least one heteroatom selected from O, N, S and Si,

In each of the structural formulas A to F, one of R ₁ to R ₁₃ is a single bond bonding to the nitrogen atom bonded to the pyrene in the above formulas A-1 to A-5,

The structural formulas A to F each include at least one nitrogen atom, a sulfur atom, a silicon atom or an oxygen atom, and the 'substitution' in the 'substituted or unsubstituted' is the same as defined above.

In the present invention, Het ₁ and Het ₂ in the formulas A-1 to A-5 may be represented by any one of substituent groups 101 to 612 shown below.

[Substituent 101] [Substituent 102] [Substituent 103]

[Substituent group 104] [Substituent group 105] [Substituent group 106]

[Substituent 107] [Substituent 108]

 [Substituent group 109] [Substituent group 110] [Substituent group 111]

 [Substituent group 112] [Substituent group 113] [Substituent group 114] [Substituent group 115]

[Substituent group 201] [Substituent group 202] [Substituent group 203]

[Substituent group 204] [Substituent group 205]

[Substituent group 301] [Substituent group 302] [Substituent group 303]

[Substituent group 304] [Substituent group 305] [Substituent group 306]

[Substituent group 307] [Substituent group 308] [Substituent group 309] [Substituent group 310]

[Substituent 401] [Substituent 402] [Substituent 403]

[Substituent group 404] [Substituent group 405] [Substituent group 406]

[Substituent group 407] [Substituent group 408] [Substituent group 409]

[Substituent group 410] [Substituent group 411] [Substituent group 412] [Substituent group 413]

[Substituent group 501] [Substituent group 502] [Substituent group 503] [Substituent group 504]

[Substituent group 505] [Substituent group 506] [Substituent group 507]

[Substituent 601] [Substituent 602] [Substituent 603]

[Substituent 604] [Substituent 605] [Substituent 606]

[Substituent 607] [Substituent 608] [Substituent 609]

[Substituent 610] [Substituent 611] [Substituent 612]

Wherein R is the same or different and is independently selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted C1- A substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, Or an unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, (Substituted or unsubstituted alkyl having 1 to 60 carbon atoms) amino group, or a substituted or unsubstituted (having 6 to 60 carbon atoms) amino group, a di (substituted or unsubstituted) alkyl group having 1 to 60 carbon atoms, A substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, and boron, and each of May be fused to adjacent groups to form a ring,

n is an integer of 1 to 9, hydrogen is bonded when the substituent R is not bonded to the carbon of the aromatic ring in the heteroaryl group of the substituents 101 to 612,

One of the Rs is a single bond bonding to the nitrogen atom bonded to the pyrene in the formulas A-1 to A-5, and the 'substitution' in the 'substituted or unsubstituted' is the same as defined above.

In one embodiment, Het ₁ and Het ₂ in the above formulas A-1 to A-5 are as follows: [substituent 101], [substituent 201], [substituent 402], [substituent 403] 407], [Substituent group 409], [Substituent group 409], [Substituent group 502]

Substituents Ar ₁₁ and Ar ₂₁ in the above Formulas A-1 to A-5 may be represented by any one of the following Substituents 801 to 809.

[Substituent 101] [Substituent 201] [Substituent 402] [Substituent 403]

[Substituent group 406] [Substituent group 407] [Substituent group 409] [Substituent group 502]

[Substituent group 503] [Substituent group 504] [Substituent group 601]

[Substituent 602]

[Substituent group 801] [Substituent group 802] [Substituent group 803]

[Substituent 804] [Substituent 805] [Substituent 806]

[Substituent 807] [Substituent 808] [Substituent 809]

Wherein R, R 'and R "are the same as defined above for substituent R.

In this case, the substituent Z is selected from deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms But the present invention is not limited thereto.

In the present invention, Py ₁ and Py ₂ in formula (A) are different from each other, and Ar ₁ and Ar ₂ are the same substituent group;

Or Py ₁ and Py ₂ in Formula A are the same substituent, and Ar ₁ and Ar ₂ may be different substituents.

In the present invention, the pyrene derivative of the formula (A) may be represented by the form in which the respective amines are bonded to the 1, 6 position or the 2 7 position, respectively.

In the present invention, in the above formula (A), at least one of Ar ₁ and Ar ₂ bonded to the amine may contain deuterium; Or at least one of Py ₁ and Py ₂ includes deuterium, and in the above formula (B), Ar ₁ bonded to the amine includes deuterium; Or Py ₁ may contain deuterium.

That is, in the above-mentioned formula (A), deuterium is substituted for hydrogen in the aromatic ring of each Py ₁ group or Py ₂ group, or a substituent group bonded to the Py ₁ group or Py ₂ group is substituted with a substituent containing deuterium In another case, the hydrogen sites in the aromatic rings of Ar ₁ and Ar ₂ may be substituted with deuterium, or the 'substituents' of Ar ₁ and Ar ₂ may include deuterium.

This can be similarly applied to the above-mentioned formula (B).

In general, the deuterium-substituted compound exhibits a lower zero energy and lower vibration energy level because the atomic mass of deuterium is two times larger than that of hydrogen, as compared to a compound bonded with hydrogen. In addition, physicochemical properties such as chemical bond lengths related to deuterium appear to be different from hydrogen, and in particular, the CD bond elongation amplitude is smaller than that of CH bonds, so that the van der Waals radius of deuterium is smaller than hydrogen, Indicating that the bond is shorter and stronger than the CH bond.

In addition, when substituted with deuterium, the energy of the bottom state is lowered. As the bond length of deuterium and carbon becomes shorter, the molecular hardcore volume is reduced, and thus, the electro polar polarizability can be reduced, It is known that the thin film volume can be increased by weakening the intermolecular interaction. Such characteristics can make the effect of lowering the crystallinity of the thin film, that is, amorphous state, and can generally be effective for increasing the lifetime and driving characteristics of the organic light emitting device, and the heat resistance can be further improved.

In the present invention, the substituent substituted on the Py ₁ , Py ₂ , Ar ₁ and Ar ₂ may be a cyano group, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 6 to 18 carbon atoms , A heteroaryl group having 3 to 18 carbon atoms, an alkylsilyl group having 1 to 12 carbon atoms, and an arylsilyl group having 6 to 18 carbon atoms.

As an embodiment of the present invention, the formula (A) or (B) of the present invention may be any one of the asymmetric pyrene derivatives selected from the following compounds 1 to 12.

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes at least one organic electroluminescent compound according to the present invention.

In the present invention, the phrase "(organic layer) contains at least one organic compound" means that one organic compound belonging to the category of the present invention (organic layer) or two or more different compounds belonging to the category of organic compound May be included.

The organic layer containing the organic luminescent compound of the present invention may include 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, have. At this time, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, and the organic light emitting compound of the present invention may be used as a dopant.

In the present invention, a host material may be used for the light emitting layer, in addition to a dopant. When the light emitting layer includes a host and a dopant, the dopant may be selected from the range of about 0.01 to about 20 parts by weight based on 100 parts by weight of the host, but is not limited thereto.

In the present invention, as the electron transporting layer material, a known electron transporting material can be used as a material that stably transports electrons injected from an electron injection electrode (cathode). Examples of known electron transporting materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10- but are not limited to, materials such as olate: Bebq2), ADN, compound 201, compound 202, BCP, oxadiazole derivative PBD, BMD, BND and the like.

TAZ BAlq

&Lt; Compound 201 > < Compound 202 > BCP

In addition, the electron transporting layer used in the present invention can be used alone or in combination with the electron transporting layer material as the organometallic compound represented by the formula (C).

&Lt; RTI ID = 0.0 &

In the above formula (C)

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M And is a ligand chelated by coordination bond with the single bond,

Wherein M is an alkali metal, an alkaline earth metal, an aluminum (Al), or a boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination bond with M,

O is oxygen,

A represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted C2 to C20 A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, and a substituted or unsubstituted hetero atom selected from O, N, S and Si And a heteroaryl group having 2 to 50 carbon atoms,

M is 1 and n is 0 when M is a metal selected from an alkali metal,

M = 1, n = 1, or m = 2 and n = 0 when M is a metal selected from alkaline earth metals,

M is from 1 to 3 when M is boron or aluminum, and n is any of from 0 to 2, and m + n = 3;

The 'substituted' in the 'substituted or unsubstituted' may be a substituent selected from the group consisting of deuterium, cyano, halogen, hydroxy, nitro, alkyl, alkoxy, alkylamino, arylamino, heteroarylamino, alkylsilyl, An aryl group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

In the present invention, Y may be the same or different and independently of each other may be any one selected from the following formulas [C1] to [C39], but is not limited thereto.

[Structural formula C1] [Structural formula C2] [Structural formula C3]

[Structural formula C4] [Structural formula C5] [Structural formula C6]

[Structural formula C7] [Structural formula C8] [Structural formula C9] [Structural formula C10]

[Structural formula C11] [Structural formula C12] [Structural formula C13]

[Structural formula C14] [Structural formula C15] [Structural formula C16]

[Structural formula C17] [Structural formula C18] [Structural formula C19] [Structural formula C20]

[Structural formula C21] [Structural formula C22] [Structural formula C23]

[Structural formula C24] [Structural formula C25] [Structural formula C26]

[Structural formula C27] [Structural formula C28] [Structural formula C29] [Structural formula C30]

[Structural formula C31] [Structural formula C32] [Structural formula C33]

[Structural formula C34] [Structural formula C35] [Structural formula C36]

[Structural formula C37] [Structural formula C38] [Structural formula C39]

In the above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

Hereinafter, the organic light emitting device of the present invention will be described with reference to FIG.

1 is a cross-sectional view showing the structure of an organic light emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode 80, An injection layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic light emitting device of the present invention and a method of manufacturing the same will be described below. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

The hole injection layer material is not particularly limited as long as it is conventionally used in the art. For example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- ], Etc. However, the present invention is not limited thereto.

The material for the hole transport layer is not particularly limited as long as it is commonly used in the art and includes, for example, N, N'-bis (3-methylphenyl) -N, N'- -Biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine (a-NPD). However, the present invention is not necessarily limited thereto.

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

The light emitting layer may be made of a host and a dopant.

Further, according to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM.

Here, the host used in the light emitting layer may be a compound represented by the following Chemical Formulas 1A to 1D.

&Lt; EMI ID =

In the above formula (1A)

Ar _7, Ar ₈ and Ar ₉ are the same or different and each independently represents a single bond, a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ A heteroaromatic linking group;

R ₂₁ to R ₃₀ are the same or different from each other and each independently represents a hydrogen atom, a heavy hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted aryl group, A substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, A substituted or unsubstituted (alkyl) amino group having 1 to 60 carbon atoms, a di (substituted or unsubstituted alkyl having 1 to 60 carbon atoms) amino group, a substituted or unsubstituted amino group having 6 to 60 carbon atoms, Or an unsubstituted aryl group having 6 to 60 carbon atoms) amino group, a substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, boron Each substituent may form a fused ring with the adjacent groups;

E, f and g are the same as or different from each other and each independently 0 or an integer of 1 to 4;

The two sites indicated by * in the anthracene may be the same as or different from each other, and may independently form an anthracene derivative selected from the following formulas (1Aa-1) to (1Aa-3) in combination with the P or Q structure.

[Chemical Formula 1Aa-1] [Chemical Formula 1Aa-2] Chemical Formula 1Aa-3]

The 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group, 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, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, An alkyl group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, An aryloxy group having 1 to 24 carbon atoms, an arylsilyl group, and an aryloxy group having 1 to 24 carbon atoms.

&Lt; RTI ID = 0.0 &

In the above formula (1B)

Wherein Ar ₁₇ to Ar ₂₀ are the same or different from each other and each independently represent a substituent group as defined in Ar ₇ to Ar ₈ in Formula 1A, and R ₆₀ to R ₆₃ are the same as defined in R ₂₁ to R ₃₀ in Formula 1A Lt; / RTI &gt;

W and ww are the same as or different from each other, x and xx are the same as or different from each other, w + ww and x + xx are the same or different from each other and independently an integer of 0 to 3; Y and yy are the same or different, and z and zz are the same or different from each other, y + yy to z + zz are not more than 2, and each is an integer of 0 to 2;

[Chemical Formula 1C]

In the above formula (1C)

Wherein Ar ₂₁ to Ar ₂₄ are the same or different and are made of the same substituents as defined for Ar ₇ to Ar ₈ in the (1A) each independently from each other, wherein R ₆₄ to R ₆₇ is at R ₂₁ to R ₃₀ of Formula 1A Lt; / RTI &gt; is as defined above.

The above ee to hh are the same as or different from each other, and each independently is an integer of 1 to 4, and the above-mentioned II to 11 are the same or different and independently an integer of 0 to 4.

[Chemical Formula 1D]

In the above formula (1D)

Wherein Ar ₂₅ to Ar ₂₇ are the same or different from each other and each independently represent a substituent group as defined in Ar ₇ to Ar ₈ in formula (1A), and R ₆₈ to R ₇₃ are the same or different from each other, The substituent groups are the same as defined in R ₂₁ to R ₃₀ of 1 A, and each substituent may form a saturated or unsaturated cyclic structure adjacent to each other. In addition, the mm to ss are the same or different from each other and each independently an integer of 0 to 4.

More specifically, the host may be represented by any one selected from the group consisting of the following [host 1] to [host 56], but is not limited thereto.

[Host 1] [Host 2] [Host 3] [Host 4]

[Host 5] [Host 6] [Host 7] [Host 8]

[Host 9] [Host 10] [Host 11] [Host 12]

[호스트13] [호스트14] [호스트15] [호스트16]

[Host 13] [Host 14] [Host 15] [Host 16]

[Host 17] [Host 18] [Host 19] [Host 20]

[Host 21] [Host 22] [Host 23] [Host 24]

[Host 25] [Host 26] [Host 27] [Host 28]

[Host 29] [Host 30] [Host 31] [Host 32]

[Host 33] [Host 34] [Host 35] [Host 36]

[Host 37] [Host 38] [Host 39] [Host 40]

[Host 41] [Host 42] [Host 43] [Host 44]

[Host 45] [host 46] [host 47] [host 48]

[Host 49] [host 50] [host 51] [host 52]

[Host 53] [Host 54] [Host 55] [Host 56]

The light emitting layer may further include various dopants and various hosts as well as the dopant and the host.

In the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer may be formed by a single molecular deposition method or a solution process. Here, the deposition method refers to a method of forming a thin film by evaporating a material used as a material for forming each of the layers through heating or the like under vacuum or low pressure, Refers to a method of mixing a material used as a material with a solvent and forming the thin film by a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating or the like.

Further, the organic light emitting device of the present invention may be a flat panel display device; A flexible display device; Monochrome or white flat panel illumination devices; And a single-color or white-colored flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

( Example )

Synthesis Example 1. Synthesis of [Compound 1]

Synthesis of [Reaction Scheme 1-1] [Intermediate 1-a]

                                      [Intermediate 1-a]

(17.3 g, 0.1 mol), 1-amino-4-methylbenzene (10.7 g, 0.1 mol), palladium acetate (0.08 g, 0.32 mmol), 2,2'-bis (0.26 g, 0.42 mmol) and sodium tertiary butoxide (15.2 g, 0.16 mol) were added to 200 mL of toluene and refluxed for 12 hours. The reaction mixture was cooled to room temperature, washed with methanol, and recrystallized from dichloromethane and methanol to obtain 15.5 g (yield 78%) of Intermediate 1-a.

[ Synthesis of Reaction Scheme 1-2] [Intermediate 1-b]

                                          [Intermediate 1-b]

[Synthesis of Intermediate 1-a] (5.4 g, 27 mmol) synthesized in the above Reaction Scheme 1-1, 1,6-dibromopyrene (8.1 g, 22.5 mmol), 2,2'-bis (diphenylphosphino ) Palladium acetate (0.1 g, 0.45 mmol) was added to 70 mL of toluene and refluxed for 24 hours . Extracted with ethyl acetate and washed with methanol. The reaction mixture was separated by column chromatography to obtain 5.9 g (yield 46%) of Intermediate 1-b.

Synthesis of [Scheme 1-3] [Intermediate 1-c]

                                [Intermediate 1-c]

Except that 4-bromopyrimidine was used instead of 2-bromo-6-methylpyrazine used in [Reaction Scheme 1-1], and 3-cyanophenylamine was used instead of 1-amino- [Intermediate 1-c] (yield: 76%).

Synthesis of [Scheme 1-4] [Compound 1]

                                      [Compound 1]

[Intermediate 1-c] synthesized in [Reaction Scheme 1-3] was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6- ] [Compound 1] (yield: 45%) was obtained in the same manner as in [Intermediate 1-b]

MS (MALDI-TOF): m / z 593.23 [M] ^&lt; ^{+ &}

Synthesis Example 2. Synthesis of [Compound 2]

Synthesis of [Reaction Scheme 2-1] [Intermediate 2-a]

                                 [Intermediate 2-a]

Bromo-2,3-dimethylpyrazine instead of 2-bromo-6-methylpyrazine used in [Reaction Scheme 1-1] above, 1-amino-3-methylbenzene [Intermediate 2-a] (yield: 76%) was obtained in the same manner.

Synthesis of [Reaction Scheme 2-2] [Intermediate 2-b]

                                         [Intermediate 2-b]

[Intermediate 2-b] (yield: 45%) was obtained in the same manner as in [Intermediate 2-a] synthesized in the above Reaction Scheme 2-1 instead of Intermediate 1-a used in the above Reaction Scheme 1-2 .

Synthesis of [Reaction 2-3] [Intermediate 2-c]

                                 [Intermediate 2-c]

Bromo-5-methylpyrazine was used in place of 2-bromo-6-methylpyrazine used in [Reaction Scheme 1-1], 1-naphthalenamine was used instead of 1-amino- (Intermediate 2-c) (yield: 75%).

[Reaction formula 2-4] Synthesis of [Compound 2]

                                          [Compound 2]

[Intermediate 2-c] synthesized in the above Reaction Scheme 2-3 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6-dibromopyrene, ] [Compound 2] (yield: 44%) was obtained in the same manner as in [Intermediate 2-b].

MS (MALDI-TOF): m / z 646.28 [M] ^&lt; ^{+ &}

Synthesis Example 3. Synthesis of [Compound 3]

Synthesis of [Reaction Scheme 3-1] [Intermediate 3-a]

                                    [Intermediate 3-a]

Instead of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1, and using 3-amino-6-methylpyridazine instead of 1-amino- [Intermediate 3-a] (yield: 77%) was obtained in the same manner.

Synthesis of [Reaction Scheme 3-2] [Intermediate 3-b]

                                    [Intermediate 3-b]

(17.9 g, 0.128 mol), 1,6-dibromopyrene (21.9 g, 0.061 mol), tetrakis (triphenylphosphine) palladium (3.62 g, 0.003 mol) and potassium carbonate , 0.183 mol) was added to 75 mL of 1,4-dioxane, 75 mL of toluene and 30 mL of distilled water, and the mixture was refluxed for 12 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, and then subjected to column chromatography to obtain 18.2 g of [intermediate 3-b] (yield 78%).

Synthesis of [Reaction Scheme 3-3] [Intermediate 3-c]

                                   [Intermediate 3-c]

[Intermediate 3-b] (19.1 g, 0.05 mol) obtained in the above Reaction Scheme 3-2 was dissolved in 200 mL of dimethylformamide and stirred at 0 ° C. En-Bromosuccinimide (20.1 g, 0.11 mol) was dissolved in 100 mL of dimethylformamide and slowly added dropwise over 1 hour. The mixture was stirred at room temperature for 12 hours. The reaction mixture was filtered with an excess of distilled water, washed with methanol, and recrystallized from toluene and methanol to obtain 23.8 g (yield: 88%) of Intermediate 3-c.

Synthesis of [Reaction Scheme 3-4] [Intermediate 3-d]

                                         [Intermediate 3-d]

[Intermediate 3-a] synthesized in [Reaction Scheme 3-1] above was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, [Intermediate 3-d] (yield: 43%) was obtained in the same manner as in [Intermediate 3-c].

Synthesis of [Reaction Scheme 3-5] [Intermediate 3-e]

                               [Intermediate 3-e]

Except that 2-chloropyrimidine was used instead of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1 and benzeneamine was used instead of 1-amino-4-methylbenzene to obtain Intermediate 3-e ] (Yield: 78%).

[Reaction Scheme 3-6] Synthesis of [Compound 3]

                                            [Compound 3]

[Intermediate 3-e] synthesized in [Reaction Scheme 3-5] was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, ] [Compound 3] (yield: 42%) was obtained in the same manner as in [Intermediate 3-d]

MS (MALDI-TOF): m / z 759.41 [M] ^&lt; ^{+ &}

Synthesis Example 4. Synthesis of [Compound 4]

Synthesis of [Reaction Scheme 4-1] [Intermediate 4-a]

                              [Intermediate 4-a]

2,5-Dibromonitrobenzene (250 g, 0.890 mol) and copper powder (135.74 g, 2.136 mol) were added to 1 L of dimethylformamide, and the mixture was heated to 125 ° C and stirred for 3 hours. The temperature was lowered to room temperature, 500 mL of toluene was added, and the mixture was stirred. And recrystallized from methanol to obtain 139 g (yield 78%) of [intermediate 4-a].

Synthesis of [Reaction Scheme 4-2] [Intermediate 4-b]

                                   [Intermediate 4-b]

[Intermediate 4-a] (139.7 g, 0.347 mol) obtained in the above Reaction Scheme 4-1 was placed in 2 L of ethanol and 1 L of 12 M hydrochloric acid was added and stirred. The temperature was reduced to 0 &lt; 0 &gt; C and tin powder (165 g, 1.39 mol) was slowly added dropwise over 20 minutes. 0.0 &gt; 100 C &lt; / RTI &gt; for 3 hours. When the reaction was completed, the temperature was lowered to 0 ° C and 1 L of a 12 M sodium hydroxide aqueous solution was slowly added to make it basic. The reaction mixture was extracted with ethyl acetate and separated by column chromatography to obtain 87.7 g of [intermediate 4-b] (yield 74%).

Synthesis of [Reaction Scheme 4-3] [Intermediate 4-c]

                                 [Intermediate 4-c]

[Intermediate 4-b] (87.7 g, 0.256 mol) synthesized in the above Reaction Scheme 4-2 was added to 380 mL of 12 M hydrochloric acid and 380 mL of distilled water, and sodium nitrite (44.2 g, 0.641 mol) 220 mL, slowly added dropwise, and stirred for 1 hour. Potassium iodide was dissolved in 850 mL of distilled water, slowly added dropwise, and stirred at room temperature for 1 hour. The temperature was raised to 60 캜 and stirred for 3 hours. Ethyl acetate and separated by column chromatography to obtain 42.1 g of [intermediate 4-c] (yield: 29%).

Synthesis of [Reaction Scheme 4-4] [Intermediate 4-d]

                                        [Intermediate 4-d]

Intermediate 4-c (19.7 g, 35 mmol), tetrakis (triphenylphosphine) palladium (0.8 g, 0.5 mmol), copper iodide (0.54 g, 1 mmol) synthesized in the above Reaction Scheme 4- Was added to 50 mL of triethylamine, stirred at room temperature, and then phenylacetylene (3.6 mL, 35 mmol) was slowly added thereto. After stirring at room temperature for about 1 hour, 300 mL of hexane was added and the reaction was terminated. The resultant product was separated by column chromatography to obtain 13.2 g (yield 74%) of [intermediate 4-d].

Synthesis of [Reaction Scheme 4-5] [Intermediate 4-e]

                                   [Intermediate 4-e]

[Intermediate 4-d] (12.3 g, 0.024 mol) synthesized in the above Reaction Scheme 4-4 was dissolved in 120 mL of dichloromethane. Iron trifluoromethanesulfonate (1.2 g, 0.002 mol) was added and refluxed for 12 hours. After hot filtration and recrystallization, 2.0 g (yield 16%) of Intermediate 4-e was obtained.

Synthesis of [Reaction Scheme 4-6] [Intermediate 4-f]

                              [Intermediate 4-f]

(4-chlorophenyl) trimethylsilane was used in place of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1 and 2-aminopyridine was used instead of 1- [Intermediate 4-f] (yield 75%).

Synthesis of [Reaction Scheme 4-7] [Intermediate 4-g]

                                     [Intermediate 4-g]

[Intermediate 4-f] synthesized in the above Reaction Scheme 4-6 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and [Reaction Scheme 4-5 [Intermediate 4-g] (yield: 44%) was obtained in the same manner as in [Intermediate 4-e].

Synthesis of [Reaction Scheme 4-8] [Intermediate 4-h]

                                [Intermediate 4-h]

[Intermediate 4-h] (yield: 73%) was obtained in the same manner as 2-chloropyrimidine was used in place of 2-bromo-6-methylpyrazine used in [Reaction Scheme 1-1] above.

[Reaction Scheme 4-9] Synthesis of [Compound 4]

                                        [Compound 4]

[Intermediate 4-h] synthesized in the above Reaction Scheme 4-8 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6-dibromopyrene, ] [Compound 4] (yield: 43%) was obtained in the same manner as in [Intermediate 4-g]

MS (MALDI-TOF): m / z 761.35 [M] ^&lt; ⁺ & gt ^;

Synthesis Example 5. Synthesis of [Compound 5]

Synthesis of [Reaction Scheme 5-1] [Intermediate 5-a]

[Intermediate 5-a]

[Intermediate 5-a] (yield: 43%) was obtained in the same manner as Intermediate 3-a synthesized in the above Reaction Scheme 3-1 instead of Intermediate 1-a used in Reaction Scheme 1-2 above .

Synthesis of [Reaction Scheme 5-2] [Intermediate 5-b]

[Intermediate 5-b]

(10.9 g, 0.061 mol), tetrakis (triphenylphosphine) palladium (3.62 g, 0.003 mol), potassium carbonate (25.3 g, , 0.183 mol) was added to 75 mL of 1,4-dioxane, 75 mL of toluene and 30 mL of distilled water, and the mixture was refluxed for 12 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, and then subjected to column chromatography to obtain 10.1 g of [intermediate 5-b] (yield 75%).

[ Synthesis of Reaction Scheme 5-3] [Intermediate 5-c]

[Intermediate 5-c]

6-chloro-3-methylpyridazine was used instead of 2-bromo-6-methylpyrazine used in [Reaction Scheme 1-1], and instead of 1-amino- [Intermediate 5-c] (yield 75%) was obtained in the same manner using [Intermediate 5-b].

[Reaction Scheme 5-4] Synthesis of [Compound 5]

                                         [Compound 5]

[Intermediate 5-c] synthesized in the above Reaction Scheme 5-3 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6-dibromopyrene, ] [Compound 5] (yield: 44%) was obtained in the same manner as in [Intermediate 5-a].

MS (MALDI-TOF): m / z 720.37 [M] ^&lt; ^{+ &}

Synthesis Example 6. Synthesis of [Compound 6]

Synthesis of [Reaction Scheme 6-1] [Intermediate 6-a]

                                      [Intermediate 6-a]

5-bromo-1,10-phenanthroline was used instead of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1 and 2,5-dimethyl- [Intermediate 6-a] (yield: 74%) was obtained in the same manner using 4-pyridinamine.

Synthesis of [Reaction Scheme 6-2] [Intermediate 6-b]

                                           [Intermediate 6-b]

[Intermediate 6-a] synthesized in [Reaction Scheme 6-1] above was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, [Intermediate 6-b] (yield: 42%) was obtained in the same manner as in [Intermediate 4-e].

Synthesis of [Reaction Scheme 6-3] [Intermediate 6-c]

                               [Intermediate 6-c]

[Intermediate 6-c] (yield: 79%) was obtained in the same manner as in the above-mentioned 2-amino-5-chloropyrimidine in place of 3-amino-4-chloroisoquinoline used in the above Reaction Scheme 5-2.

Synthesis of [Reaction Scheme 6-4] [Intermediate 6-d]

                                   [Intermediate 6-d]

Fluoro-1-chlorobenzene was used instead of the 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1 and the synthesis was carried out in the same manner as in [Scheme 6-3] [Intermediate 6-d] (yield 75%) was obtained in the same manner using [Intermediate 6-c].

Synthesis of [Scheme 6-5] [Compound 6]

                                               [Compound 6]

[Intermediate 6-d] synthesized in [Reaction Scheme 6-4] was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6- ] [Compound 6] (yield: 41%) was obtained in the same manner as in [Intermediate 6-b]

MS (MALDI-TOF): m / z 915.35 [M] ^&lt; ⁺ & gt ^;

SYNTHESIS EXAMPLE 7 Synthesis of [Compound 7]

Synthesis of [Reaction Scheme 7-1] [Intermediate 7-a]

                                 [Intermediate 7-a]

Except that 3-chloro-4-methylpyridazine was used instead of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1 and 4-amino-tert-butylbenzene was used instead of 1- [Intermediate 7-a] (yield: 74%) was obtained in the same manner.

Synthesis of [Reaction Scheme 7-2] [Intermediate 7-b]

                                      [Intermediate 7-b]

[Intermediate 7-b] (yield: 42%) was obtained in the same manner as in [Intermediate 7-a] synthesized in the above Reaction Scheme 7-1 instead of Intermediate 1-a used in the above Reaction Scheme 1-2 .

Synthesis of [Reaction Scheme 7-3] [Intermediate 7-c]

                                      [Intermediate 7-c]

Bromo-2-methylpyrazine was used in place of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1 and 2- (3-fluorophenyl) Pyridine-4-amine was used in the same manner as in [Intermediate 7-c] (yield 75%).

Synthesis of [Scheme 7-4] [Compound 7]

                                            [Compound 7]

[Intermediate 7-c] synthesized in the above Reaction Scheme 7-3 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6-dibromopyrene, ] [Compound 7] (yield: 44%) was obtained in the same manner as in [Intermediate 7-b]

MS (MALDI-TOF): m / z 719.32 [M] ^&lt; ^{+ &}

Synthesis Example 8. Synthesis of [Compound 8]

Synthesis of [Reaction Scheme 8-1] [Intermediate 8-a]

                                [Intermediate 8-a]

Chloro-5-methylpyrimidine was used instead of 2-bromo-6-methylpyrazine used in [Reaction Scheme 1-1], and 4-amino-tert- butylbenzene [Intermediate 8-a] (yield: 75%) was obtained in the same manner.

Synthesis of [Reaction Scheme 8-2] [Intermediate 8-b]

                                       [Intermediate 8-b]

[Intermediate 8-b] (yield: 42%) was obtained in the same manner as Intermediate 8-a synthesized in the above Reaction Scheme 8-1 instead of Intermediate 1-a used in Scheme 1-2 above .

Synthesis of [Reaction Scheme 8-3] [Intermediate 8-c]

                                         [Intermediate 8-c]

Instead of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1, 4-bromodibenzofuran was used instead of 2-tertiarybutylpyrimidin-4-amine instead of 1-amino- [Intermediate 8-c] (yield: 73%) was obtained in the same manner.

[Reaction Scheme 8-4] Synthesis of [Compound 8]

                                              [Compound 8]

[Intermediate 8-c] synthesized in the above Reaction Scheme 8-3 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6-dibromopyrene, ] [Compound 8] (yield: 42%) was obtained in the same manner as in [Intermediate 8-b].

MS (MALDI-TOF): m / z 756.36 [M] ^&lt; ^{+ &}

Synthesis Example 9. Synthesis of [Compound 9]

Synthesis of [Synthesis 9-1] [Synthesis of Intermediate 9-a]

                                    [Intermediate 9-a]

Bromoquinoline was used instead of 2-bromo-6-methylpyrazine used in [Reaction Scheme 1-1], 6-methyl-3-pyridinamine was used instead of 1-amino- [Intermediate 9-a] (yield: 75%).

Synthesis of [Reaction Scheme 9-2] [Intermediate 9-b]

                                        [Intermediate 9-b]

[Intermediate 9-a] synthesized in the above Reaction Scheme 9-1 was used in place of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6-dibromopyrene, ] [Intermediate 9-b] (yield: 41%) was obtained in the same manner as in [Intermediate 3-c]

Synthesis of [Synthesis 9-3] [Intermediate 9-c]

                                           [Intermediate 9-c]

5-bromo-1, 10-phenanthroline was used instead of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1 and 2-amino- [Intermediate 9-c] (yield: 73%) was obtained in the same manner as in 6-dimethylpyrazine.

Synthesis of [Synthesis 9-4] [Compound 9]

                                             [Compound 9]

[Intermediate 9-c] synthesized in the above Reaction Scheme 9-3 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6-dibromopyrene, [Compound 9] (yield: 40%) was obtained in the same manner as in [Intermediate 9-b] synthesized in Preparation Example 1.

MS (MALDI-TOF): m / z 914.38 [M] ^&lt; ^{+ &}

Synthesis Example 10. Synthesis of [Compound 10]

Synthesis of [Synthesis 10-1] [Synthesis of Intermediate 10-a]

                              [Intermediate 10-a]

60% Sodium hydride (2.1 g, 52 mmol) was added to 50 mL of dimethylformamide and stirred for about 30 minutes. 3-Bromo-9H-carbazole (10.8 g, 44 mmol) was dissolved in 100 mL of dimethylformamide, followed by further stirring for about 1 hour. Pentaerythritol Iodobenzene (11 g, 52.6 mmol) was dissolved in 100 mL of dimethylformamide, and the mixture was stirred overnight. Filtered through distilled water, and recrystallized from dichloromethane and hexane to obtain 12.2 g (yield 85%) of [intermediate 10-a].

Synthesis of [Reaction Scheme 10-2] [Intermediate 10-b]

                                       [Intermediate 10-b]

[Intermediate 10-a] synthesized in the above Reaction Scheme 10-1 was used instead of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1 and 2- [Intermediate 10-b] (yield: 72%) was obtained in the same manner using amino-5-cyanopyrimidine.

Synthesis of [Reaction Scheme 10-3] [Intermediate 10-c]

                                            [Intermediate 10-c]

[Intermediate 10-c] (yield: 43%) was obtained in the same manner as in [Intermediate 10-b] synthesized in the above Reaction Scheme 10-2 instead of Intermediate 1-a used in Reaction Scheme 1-2 above .

Synthesis of [Scheme 10-4] [Compound 10]

                                          [Compound 10]

[Intermediate 8-c] synthesized in the above Reaction Scheme 8-3 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and instead of 1,6-dibromopyrene, ] [Compound 10] (yield 39%) was obtained in the same manner as in [Intermediate 10-c].

MS (MALDI-TOF): m / z 881.36 [M] ^&lt; ^{+ &}

Synthesis Example 11. Synthesis of [Compound 11]

[Reaction Formula 11-1] Synthesis of [Intermediate 11-a;

                                 [Intermediate 11-a]

Chloro-5-methylpyridazine instead of 2-bromo-6-methylpyrazine used in [Reaction Scheme 1-1], 1-naphthalenamine was used instead of 1-amino- [Intermediate 11-a] (yield: 77%).

Synthesis of [Scheme 11-2] [Compound 11]

                                        [Compound 11]

[Intermediate 11-a] synthesized in the above Reaction Scheme 11-1 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and 1-bromopyrrene instead of 1,6- [Compound 11] (yield: 73%) was obtained in the same manner.

MS (MALDI-TOF): m / z 435.17 [M] ^&lt; ^{+ &}

Synthesis Example 12. Synthesis of [Compound 12]

[ Synthesis of Intermediate 12-a]

                                     [Intermediate 12-a]

Amino-5-chloropyrimidine was used instead of 3-amino-4-chloroisoquinoline used in the above Reaction Scheme 5-2, pentaerythritol iodophenylboronic acid was used instead of phenylboronic acid, [Intermediate 12-a] (yield: 78%).

Synthesis of [Reaction Scheme 12-2] [Intermediate 12-b]

                                      [Intermediate 12-b]

[Intermediate 12-a] synthesized in the above Reaction Scheme 12-1 was used in place of 2-bromo-6-methylpyrazine used in the above Reaction Scheme 1-1 and 4- [Intermediate 12-b] (yield: 74%) was obtained in the same manner using chloro-6,8-dimethylquinoline.

[Reaction Formula 12-3] [Compound 12] Synthesis of

                                              [Compound 12]

[Intermediate 12-b] synthesized in the above Reaction Scheme 12-2 was used instead of [Intermediate 1-a] used in the above Reaction Scheme 1-2, and 2-bromoprene was used instead of 1,6- [Compound 12] (yield: 77%) was obtained by the same method.

MS (MALDI-TOF): m / z 551.31 [M] ^&lt; ^{+ &}

The structures of [compound 1] to [compound 12] are shown below.

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

Example  1 to 10

Manufacture of organic light-emitting diodes

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was allowed to have a pressure of 1 × 10 ^-6 torr, and then DNTPD (700 ANGSTROM), α-NPD (300 ANGSTROM), BH1 as a host for the light emitting layer, and Compound 1 (3 wt%) were deposited by co-deposition (300 Å), followed by deposition of Alq ₃ (350 Å), LiF (5 Å) and Al (1,000 Å) in this order.

        [DNTPD] [[alpha] -NPD]

[BH1] [Alq _3]

Comparative Examples 1 to 2

The organic light emitting devices for Comparative Examples 1 and 2 were fabricated in the same manner except that the following compounds [101] and [102] were used in place of the compounds prepared by the invention in the device structures of Examples 1 to 10, The structure is as follows.

[Compound 101] [Compound 102]

The voltage, the current density, the luminance, the color coordinates, and the lifetime of the organic light emitting device manufactured according to Examples 1 to 10 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 1 below. T80 means the time required for the luminance to decrease from the initial luminance (5000 nits) to 80%.

division Host Dopant Voltage (V) Brightness (Cd / m ² ) CIEx CIEy T ₈₀ Example 1 BH1 Compound 1 3.8 690 0.139 0.099 60 Example 2 BH1 Compound 2 3.9 711 0.137 0.098 63 Example 3 BH1 Compound 3 3.9 727 0.136 0.100 61 Example 4 BH1 Compound 4 3.8 714 0.139 0.097 62 Example 5 BH1 Compound 5 3.9 710 0.138 0.097 64 Example 6 BH1 Compound 6 3.8 695 0.138 0.101 61 Example 7 BH1 Compound 7 3.8 712 0.138 0.099 60 Example 8 BH1 Compound 8 3.7 721 0.137 0.100 62 Example 9 BH1 Compound 9 3.8 738 0.139 0.100 62 Example 10 BH1 Compound 10 3.8 709 0.139 0.097 64 Comparative Example 1 BH1 Compound 101 6.4 515 0.149 0.166 46 Comparative Example 2 BH1 Compound 102 6.0 653 0.175 0.225 57

As shown in Table 1, the asymmetric pyrene derivative according to the present invention shows much improved color purity than the case of using the pyrene-based arylamine compound according to the prior art, And the application is high.

Claims (16)

An asymmetric pyrene derivative represented by the following formula [A] or [B].
[Chemical Formula A]

In the above formulas (A) and (B)
Each of Py ₁ and Py ₂ is the same or different and independently of each other, a substituted or unsubstituted pyridinyl group, or a substituted or unsubstituted 6-membered aromatic heteroaryl group, two of which are nitrogen atoms And the remainder is a heteroaryl group which is a carbon atom,
Ar ₁ and Ar ₂ are the same or different and independently represent a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted 5 to 50 Or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms and having at least one heteroatom selected from O, N, S and Si,
The substituent Z is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N, S, and Si A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 hetero aryl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 30 carbon atoms An arylamine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group, To form a saturated or unsaturated ring;
Each carbon atom in the pyrene ring is bonded to the nitrogen atom of the amine or, when not bonded to the substituent Z, to hydrogen;
In formula [A], m is an integer of 1 to 8, and when m is 2 or more, each Z is independently the same as or different from each other,
The two amine groups bonded to the pyrene are different from each other, so that the pyrene has an asymmetric structure.
In the formula (B), m is an integer of 1 to 9, and when m is 2 or more, each Z is independently the same as or different from each other;
The 'substituted' in the above 'substituted or unsubstituted' means a group selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl 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, an arylalkyl 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 , An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, Group, and an aryloxy group having 1 to 24 carbon atoms. The method according to claim 1,
The formula (A) is any one selected from the following formulas (A-1) to (A-3)
Wherein the formula (B) is represented by the following formula (A-4) or (A-5)
[Formula A-1] [Formula A-2] [Formula A-3]

[Chemical formula A-4] [Chemical formula A-5]

In the above formulas A-1 to A-5, the substituents Ar ₁₁ and Ar ₂₁ are the same or different and independently of each other, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and the substituents Het ₁ and Het ₂ are Or a heteroaryl group having 2 to 50 carbon atoms, which is substituted or unsubstituted, and which has at least one heteroatom selected from O, N, S and Si, independently of each other. 3. The method of claim 2,
And wherein Het ₁ and Het ₂ in formula A-1) to (A-3, Het ₁ in formula A-4) and (A-5 is asymmetric, it characterized in that the display of one selected from the structural formulas A to Structure F, respectively Pyrene derivative.
[Structural Formula A]

[Structural formula B]

[Structural formula C]

[Structural formula D]

[Structural formula E]

[Structural formula F]

In Formulas A to F,
T ₁ to T ₈ are the same or different and independently selected from the group consisting of C (R ₁₁ ), C (R ₁₁ ) (R ₁₂ ), N, N (R ₁₃ ), O and S, _{C (R 11), C (} R 11) (R 12), N (R 13) of any of the structural formulas a to Structure F each C (R ₁₁₎ containing a plurality of the case that includes a plurality in, C (R ₁₁ ) (R ₁₂ ) and N (R ₁₃ ) may be the same or different,
Wherein R ₁ to R ₁₃ are the same or different from each other and independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms and having at least one heteroatom selected from O, N, S and Si,
In each of the structural formulas A to F, the R &lt; _{1 &gt;} To R &lt; ₁₃ &gt; is a single bond bonding to the nitrogen atom bonded to the pyrene in the above formulas A-1 to A-5,
The structural formulas A to F each contain at least one nitrogen atom, a sulfur atom, a silicon atom or an oxygen atom,
The 'substitution' in the 'substituted or unsubstituted' is the same as defined in claim 1. 3. The method of claim 2,
Wherein each of Het ₁ and Het ₂ in the above formulas A-1 to A-5 is any one of substituent groups 101 to 612 shown below.
[Substituent 101] [Substituent 102] [Substituent 103]

[Substituent group 104] [Substituent group 105] [Substituent group 106]

[Substituent 107] [Substituent 108]

[Substituent group 109] [Substituent group 110] [Substituent group 111]

[Substituent group 112] [Substituent group 113] [Substituent group 114] [Substituent group 115]

[Substituent group 201] [Substituent group 202] [Substituent group 203]

[Substituent group 204] [Substituent group 205]

[Substituent group 301] [Substituent group 302] [Substituent group 303]

[Substituent group 304] [Substituent group 305] [Substituent group 306]

[Substituent group 307] [Substituent group 308] [Substituent group 309] [Substituent group 310]

[Substituent 401] [Substituent 402] [Substituent 403]

[Substituent group 404] [Substituent group 405] [Substituent group 406]

[Substituent group 407] [Substituent group 408] [Substituent group 409]

[Substituent group 410] [Substituent group 411] [Substituent group 412] [Substituent group 413]

[Substituent group 501] [Substituent group 502] [Substituent group 503] [Substituent group 504]

[Substituent group 505] [Substituent group 506] [Substituent group 507]

[Substituent 601] [Substituent 602] [Substituent 603]

[Substituent 604] [Substituent 605] [Substituent 606]

[Substituent 607] [Substituent 608] [Substituent 609]

[Substituent 610] [Substituent 611] [Substituent 612]

Wherein R is the same or different and is independently selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted C1- A substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 60 carbon atoms, Or an unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, (Substituted or unsubstituted alkyl having 1 to 60 carbon atoms) amino group, or a substituted or unsubstituted (having 6 to 60 carbon atoms) amino group, a di (substituted or unsubstituted) alkyl group having 1 to 60 carbon atoms, A substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, germanium, phosphorus, and boron, and each of May be fused to adjacent groups to form a ring,
n is an integer of 1 to 9,
When the substituent R is not bonded to the carbon of the aromatic ring in the heteroaryl group of the substituents 101 to 612, hydrogen is bonded,
One of the Rs is a single bond which binds to the nitrogen atom bonded to the pyrene in the above formulas A-1 to A-5,
The 'substitution' in the 'substituted or unsubstituted' is the same as defined in claim 1. 3. The method of claim 2,
Het ₁ and Het ₂ in the above formulas A-1 to A-5 are each independently selected from the following substituents 101, 201, 402, 403, 406, 407, 409], [substituent 502], [substituent 503], [substituent 504], [substituent 601]
The substituents Ar ₁₁ and Ar ₂₁ in the above formulas A-1 to A-5 are any one selected from the following [substituent groups 801] to [substituent group 809]
[Substituent 101] [Substituent 201] [Substituent 402] [Substituent 403]

[Substituent group 406] [Substituent group 407] [Substituent group 409] [Substituent group 502]

[Substituent group 503] [Substituent group 504] [Substituent group 601]

[Substituent 602]

[Substituent group 801] [Substituent group 802] [Substituent group 803]

[Substituent 804] [Substituent 805] [Substituent 806]

[Substituent 807] [Substituent 808] [Substituent 809]

Wherein R, R 'and R "are the same as the definition of substituent R in the above-mentioned fourth claim. 6. The method of claim 5,
The substituent Z is any one selected from the group consisting of deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms Characterized in that the asymmetric pyrene derivative. The method according to claim 6,
The Py Py ₁ and ₂ in the above formula, and A is different from each other, Ar ₁ and Ar ₂ are the same or another substituent;
Or the above Py ₁ and Py ₂ in Formula A are the same substituents, and Ar ₁ and Ar ₂ are different substituents. 8. The method according to any one of claims 1 to 7,
Wherein the pyrene derivative of formula (A) has amines at positions 1, 6, or 2, 7, respectively. 8. The method according to any one of claims 1 to 7,
In the above formula (A), at least one of Ar ₁ and Ar ₂ bonded to the amine may include deuterium; Or at least one of Py ₁ and Py ₂ contains deuterium,
In the above formula (B), Ar ₁ bonded to the amine includes deuterium; Or Py ₁ comprises deuterium. 8. The method according to any one of claims 1 to 7,
The substituent on the Py ₁ , Py ₂ , Ar ₁ and Ar ₂ is preferably a cyano group, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 6 to 18 carbon atoms, An alkylsilyl group having 1 to 18 carbon atoms, and an arylsilyl group having 6 to 18 carbon atoms. Is an asymmetric pyrene derivative selected from the following compounds 1 to 12.
[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

A first electrode;
A second electrode facing the first electrode; And
And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises at least one organic electroluminescent compound selected from the group consisting of the compounds represented by any one of claims 1 to 7. 13. The method of claim 12,
Wherein the organic layer comprises 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, and an electron injecting layer. 13. The method of claim 12,
An organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
Wherein the light emitting layer comprises a host and a dopant, and the organic light emitting compound is used as a dopant. 15. The method of claim 14,
Wherein at least one layer selected from the respective layers is formed by a deposition process or a solution process. 13. The method of claim 12,
The organic light emitting device includes a flat panel display device; A flexible display device; Monochrome or white flat panel illumination devices; And a device for flexible illumination of a single color or a white color.

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