KR102156562B1 - Asymmetric pyrene derivatives comprising aryl amine group and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to an asymmetric pyrene derivative represented by the following [Chemical Formula A] or [Chemical Formula B] and an organic light emitting device including the same, wherein the substituents Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Z and m are Same as defined in the description.
[Formula A] [Formula B]

Description

Asymmetric pyrene derivatives comprising aryl amine group and organic light-emitting diode including the same

The present invention relates to an asymmetric pyrene derivative containing an aryl amine group and an organic light emitting device including the same, and includes an aryl group as a substituent of the amine, and when used as an organic light emitting material, the color purity is improved and the device characteristics of a long life are improved. It relates to an asymmetric pyrene derivative and an organic light emitting device comprising the same.

Recently, as display devices have become larger, there is an increasing demand for display devices that occupy less space or bendable display devices due to a flat panel structure, and liquid crystal displays, which are representative flat display devices, are lighter than conventional CRT (cathode ray tubes). Although there is an advantage that it is possible, it has disadvantages such as a limited viewing angle and a need for back light. On the other hand, organic light emitting diodes (OLEDs), which are new flat display devices, are displays using a self-luminous phenomenon, and have advantages such as a large viewing angle, lightness and compactness compared to liquid crystal displays, and fast response speed. And, in recent years, applications to full-color displays or lighting are expected.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.

An organic light emitting device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground. These organic light-emitting devices are known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

Materials used as the organic material layer in the organic light-emitting device can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. The light-emitting material may be classified into a high-molecular-type and a low-molecular-type according to its molecular weight, and may be classified into a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron according to the light emitting mechanism . In addition, the light-emitting material may be classified into blue, green, and red light-emitting materials and yellow and orange light-emitting materials necessary for realizing better natural colors according to the light-emitting color.

When a 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 are recombined in the emission layer through the hole transport layer and the electron transport layer to form a light emitting exciter. The light-emitting excitons thus formed emit light while transitioning to the ground state. The light may be divided into fluorescence using singlet excitons and phosphorescence using triplet excitons according to an emission mechanism, and the fluorescence and phosphorescence may be used as a light emitting source of an organic light emitting device.

On the other hand, when only one material is used as a light-emitting material, the maximum light-emitting wavelength shifts to a long wavelength due to the interaction between molecules, and the color purity decreases, or the efficiency of the device decreases due to the light-emitting attenuation effect. In order to increase the luminous efficiency through transition, a host-dopant system may be used as a light emitting material.

The principle is that when a small amount of a dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, 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 moves to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

In recent years, there is an increasing need for a blue organic light emitting material having high brightness and high color purity for application to a full-color display or lighting. As the blue organic light-emitting material, Korean Patent Publication No. 10-2006-0006760 (2006.01.19) discloses an organic light-emitting device using a substituted pyrene-based derivative, and Korean Patent Publication No. 10-2011-0072041 (2011.06) 29) discloses an organic light emitting device using a pyrene-based derivative containing heteroaryl.

However, despite the above efforts, organic light-emitting materials manufactured by the prior art, including the prior art, have low color purity, leaving room for improvement because it is difficult to realize vivid colors.Therefore, the necessity of developing new organic light-emitting materials is It is a situation that is constantly being demanded.

Unexamined Patent Publication No. 10-2006-0006760 (2006.01.19) Unexamined Patent Publication No. 10-2011-0072041 (2011.06.29)

Accordingly, the first technical problem to be achieved by the present invention is to provide a novel organic light-emitting compound that can be used in the light-emitting layer of an organic light-emitting device, and has long life characteristics and high color purity.

A second technical problem to be achieved by the present invention is to provide an organic light-emitting device including the organic light-emitting compound.

The present invention provides an asymmetric pyrene derivative represented by the following [Chemical Formula A] or [Chemical Formula B] in order to achieve the first technical problem.

[Formula A] [Formula B]

In the above [Formula A] and [Formula B],

Substituents Ar ₁ to Ar ₄ are each the same or different, and independently of each other, 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 carbon number of 5 to It is one selected from 50 aryl groups,

The substituent Z is 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 A substituted or unsubstituted alkynyl group having 2 to 20 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 heteroatom O, N, S and P A C2-C50 heteroaryl group having any one or more selected from, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted carbon number 1 to 30 alkylthio groups, substituted or unsubstituted arylthioxy groups having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine groups having 1 to 30 carbon atoms, substituted or unsubstituted arylamine groups having 5 to 30 carbon atoms, It is any one selected from a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a cyano group, a nitro group, a halogen group, and is bonded to each other with a neighboring substituent. Can form saturated or unsaturated rings;

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

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

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

In [Formula B], m is an integer of 1 to 9, and when m is 2 or more, each of Z may be the same or different from each other independently.

In addition, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, and the organic layer is It provides an organic light-emitting device comprising at least one organic light-emitting compound of the invention.

According to the present invention, the organic light-emitting compound represented by [Chemical Formula A] or [Chemical Formula B] has characteristics of high color purity and excellent luminous efficiency compared to conventional materials, and thus can be used in devices for manufacturing full color displays. I can.

1 is a schematic diagram of an organic light-emitting device according to an embodiment of the present invention.
2 is a graph showing the life evaluation of the devices of Example 1, Comparative Example 1, and Comparative Example 2 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 [Chemical Formula A] or [Chemical Formula B] as an organic light emitting compound that can be used in an emission layer of an organic light emitting device.

[Formula A] [Formula B]

In the above [Formula A] and [Formula B],

Substituents Ar ₁ to Ar ₄ are each the same or different, and independently of each other, 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 carbon number of 5 to It is one selected from 50 aryl groups,

The substituent Z is 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 A substituted or unsubstituted alkynyl group having 2 to 20 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 heteroatom O, N, S and P A C2-C50 heteroaryl group having any one or more selected from, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted carbon number 1 to 30 alkylthio groups, substituted or unsubstituted arylthioxy groups having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine groups having 1 to 30 carbon atoms, substituted or unsubstituted arylamine groups having 5 to 30 carbon atoms, It is any one selected from a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a cyano group, a nitro group, a halogen group, and is bonded to each other with a neighboring substituent. Can form saturated or unsaturated rings;

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

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

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

In [Formula B], m is an integer of 1 to 9, and when m is 2 or more, each Z is independently the same or different from each other;

'Substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 1 to 24 carbon atoms , C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group, C2-C24 heteroarylalkyl group , C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, C1-C24 arylsilyl It means substituted with one or more substituents selected from the group consisting of a group and an aryloxy group having 1 to 24 carbon atoms.

In addition, in the present invention, considering the range of the alkyl group 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", the carbon number The range of carbon number of the alkyl group of 1 to 30 and the aryl group having 5 to 50 carbon atoms means the total number of carbon atoms constituting the alkyl moiety or aryl moiety when the substituent is considered to be unsubstituted 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 4 carbon atoms.

The present invention is an asymmetric pyrene derivative compound represented by Formula A or Formula B, wherein each of the two amine groups bonded to the pyrene of Formula A includes a substituted or unsubstituted aryl group, wherein the amine groups are different from each other. The pyrene derivative of is characterized by having an asymmetric structure.

As in the present invention, when an aryl group is asymmetrically bonded to the amine group as a substituent, the color purity can be improved, and the organic light emitting compound having an asymmetric pyrene structure of the present invention is an organic light emitting material according to the prior art. Since the color purity of the organic light-emitting device is improved and excellent device characteristics of high luminance can be shown, an organic light-emitting device having improved characteristics can be manufactured compared to the prior art.

On the other hand, the aryl group used in the compound of the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, In addition, when the aryl group has a substituent, it may be fused with neighboring substituents to further form a ring.

Specific examples of the aryl include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluorane. Including tenil, etc., but is not limited thereto.

At least one hydrogen atom in the aryl group is 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')(R''), R'and R" are each independently an alkyl group having 1 to 10 carbon atoms, and in this case, referred to as "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, 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, an arylalkyl group having 6 to 24 carbon atoms Can be substituted.

The heteroaryl group as a substituent used in the compound of the present invention is a heteroaromatic organic radical 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. Means, and the rings may be fused to form a ring. And at least one hydrogen atom in the heteroaryl group may be substituted with the same substituent as in the case of 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, and at least one hydrogen atom in the alkyl group is The atom may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group that is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like, 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 as a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclo Butylsilyl, dimethylfurylsilyl, and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.

In the present invention, the substituent Z is deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted and hetero atom having at least one selected from O, N, S, and P having 2 to 30 carbon atoms. It may be any one selected from a heteroaryl group, 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, but is not limited thereto.

Further, the one of Ar ₁ and Ar ₂ in the formula (A) in the present invention is the Ar ₃ substituents and the other amine And Ar ₄ and one of the same as each other, or the Ar ₁ and Ar ₂ They are identical to each other, or all of Ar ₁ to Ar ₄ in Formula A may be different substituents.

In the present invention, A r ₁ to Ar ₄ in Formula A and Ar ₁ and Ar ₂ in Formula B may be any one selected from the following [Substituent 801] to [Substituent 809], respectively.

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

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

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

Wherein the R, R'and R" are each the same or different and independently of each other, hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or its A salt, a sulfonic acid group or a salt thereof, phosphoric acid or a 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 alkoxy group having 1 to 60 carbon atoms, 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 C6 group To 60 aryl groups, substituted or unsubstituted aryloxy groups having 5 to 60 carbon atoms, substituted or unsubstituted arylthio groups having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl groups having 2 to 60 carbon atoms, substituted or Unsubstituted C1-C60 (alkyl) amino group, di(substituted or unsubstituted C1-C60 alkyl) amino group, or (substituted or unsubstituted C6-C60 aryl) amino group, di(substituted or unsubstituted It may be selected from a substituted or 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 of the substituents may be fused with groups adjacent to each other to form a ring,

n is an integer from 1 to 9,

When the substituent R is not bonded to the carbon of the aromatic ring in the aryl group of the substituents 801 to 809, hydrogen is bonded, and one of R is a single bond bonded to the nitrogen atom bonded to pyrene in Formula A,

'Substitution' in the'substituted or unsubstituted' is the same as defined above.

In addition, in the present invention, the pyrene derivative of Formula A may have an amine bonded at positions 1 and 6 or at positions 2 and 7 respectively.

In addition, in the present invention, in the [Chemical Formula A], any one or more of Ar ₁ to Ar ₄ bonded to the amine includes deuterium; In [Chemical Formula B], Ar ₁ or Ar ₂ bonded to the amine may contain deuterium.

In addition, in the present invention, in the [Chemical Formula A], at least two of Ar ₁ to Ar ₄ bonded to the amine contain deuterium; In [Chemical Formula B], Ar ₁ and Ar ₂ bonded to the amine may contain deuterium.

In this case, deuterium is substituted at the hydrogen site in the aromatic ring of the substituents Ar ₁ to Ar ₄ in the [Formula A] or [Formula B], or the'substituent' bonded to the substituents Ar ₁ to Ar ₄ is deuterium Can include.

In general, the deuterium-substituted compound exhibits a lower zero point energy and a lower vibration energy level as the atomic mass of deuterium is twice that of hydrogen compared to the compound bound to hydrogen. In addition, the physicochemical properties, such as the length of chemical bonds related to deuterium, appear different from those of hydrogen, and in particular, the elongation amplitude of the CD bond is smaller than that of the CH bond, so the Van der Waals radius of deuterium is smaller than that of hydrogen, and in general, CD It indicates that the bond is shorter and stronger than the CH bond.

In addition, when substituted with deuterium, the energy in the ground state is lowered, and as the bond length of deuterium and carbon is shortened, the molecular hardcore volume decreases, and accordingly, the electrical polarizability can be reduced. It is known that the volume of the thin film can be increased by weakening the intermolecular interaction. Such a characteristic may be effective in lowering the crystallinity of the thin film, that is, an amorphous state, and in general, it may be effective to increase the life and driving characteristics of the organic light emitting device, and the heat resistance may be further improved.

In addition, in the present invention, the substituent substituted on Ar ₁ and Ar ₄ is a cyano group, a halogen group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl having 1 to 6 carbon atoms, and An aryl group, a C6-C18 arylalkyl group, a C3-C18 heteroaryl group, a C6-C18 aryloxy group, a C1-C18 alkylsilyl group, and a C6-C18 arylsilyl group I can.

In addition, in the present invention, Formula A or Formula B may be any one asymmetric pyrene derivative selected from Compounds 1 to 73 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]

[Compound 13] [Compound 14] [Compound 15]

[Compound 16] [Compound 17] [Compound 18]

[Compound 19] [Compound 20] [Compound 21]

[Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27]

[Compound 28] [Compound 29] [Compound 30]

[Compound 31] [Compound 32] [Compound 33]

[Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39]

[Compound 40] [Compound 41] [Compound 42]

[Compound 43] [Compound 44] [Compound 45]

[Compound 46] [Compound 47] [Compound 48]

[Compound 49] [Compound 50] [Compound 51]

[Compound 52] [Compound 53] [Compound 54]

[Compound 55] [Compound 56] [Compound 57]

[Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62] [Compound 63]

[Compound 64] [Compound 65] [Compound 67]

[Compound 68] [Compound 69] [Compound 70]

[Compound 71] [Compound 72] [Compound 73]

In addition, the present invention is 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 may provide an organic light-emitting device including at least one kind of the organic light-emitting compound in the present invention.

In the present invention, "(organic layer) includes one or more organic compounds" means, "(organic layer) one organic compound belonging to the scope of the present invention or two or more different compounds belonging to the category of the organic compound. It can be interpreted as".

In addition, the organic layer containing the organic light emitting compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, an emission layer, an electron transport layer, and an electron injection layer. have. In this case, the organic layer interposed between the first electrode and the second electrode may include an emission layer, the emission layer is composed of a host and a dopant, and the organic emission compound of the present invention may be used as a dopant.

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

Meanwhile, in the present invention, a known electron transport material may be used as the material for the electron transport layer to stably transport electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinorate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10-noate) (beryllium bis(benzoquinolin-10-). olate: Bebq2), ADN, compound 201, compound 202, BCP, oxadiazole derivatives such as PBD, BMD, BND, etc. may be used, but the present invention is not limited thereto.

TAZ BAlq

<Compound 201> <Compound 202> BCP

In addition, as for the electron transport layer used in the present invention, an organometallic compound represented by Formula C may be used alone or in combination with the electron transport layer material.

[Formula C]

In [Chemical Formula C],

Y is a portion in which any one selected from C, N, O, and S is directly bonded to the M to form a single bond, and a portion in which any one selected from C, N, O, and S forms a coordination bond to the M. And is a ligand chelated by the single bond and the coordination bond

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

O is oxygen,

A is 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 An alkynyl group, 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 at least one selected from O, N, S and P It is any one selected from a C2-C50 heteroaryl group having,

When M is one metal selected from alkali metals, m = 1, n = 0,

When M is one metal selected from alkaline earth metals, m=1, n=1, or m=2, n=0,

When M is boron or aluminum, m is any one of 1 to 3, and n is any one of 0 to 2, which satisfies m + n = 3;

'Substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, It means substituted with one or more substituents selected from the group consisting of aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

In the present invention, Y is the same or different, and may be any one independently selected from the following [Structural Formula C1] to [Structure 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 [Structural Formula C1] to [Structural Formula C39],

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or Unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl It is selected from groups, and may be connected to an adjacent substituent with 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.

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, and if necessary, the hole injection layer 30 and the electron The injection layer 70 may be further included, and in addition, one or two intermediate layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, an organic light-emitting device of the present invention and a method of manufacturing the same are as follows. First, an anode 20 is formed by coating a material for an anode electrode on the substrate 10. Here, as the substrate 10, a substrate used in a typical organic EL device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproofness is preferable. In addition, as a material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum thermal evaporation or spin coating on the anode 20 electrode. Then, a hole transport layer material is vacuum thermally evaporated or spin coated on the hole injection layer 30 to form the hole transport layer 40.

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, for example, 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ], etc. However, the present invention is not necessarily limited thereto.

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

Subsequently, an organic light-emitting layer 50 is stacked on the hole transport layer 40 and 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. can do. The hole blocking layer serves to prevent this problem by using a material having a very low level of Highest Occupied Molecular Orbital (HOMO) because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . In this case, the hole blocking material to be used is not particularly limited, but must have an electron transport ability and an ionization potential higher than that of the light emitting compound, and representatively, BAlq, BCP, TPBI, etc. may be used.

After depositing the electron transport layer 60 on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode-forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form the cathode 80 electrode. Here, the cathode-forming metal is lithium (Li), magnesium (Mg), aluminum (Al), aluminum-ridium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) or the like may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

In addition, the emission layer may be formed 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 Å.

In this case, the host used in the emission layer may be a compound represented by the following Formulas 1A to 1D.

[Formula 1A]

In Formula 1A,

The Ar _{7 ,} Ar ₈ and Ar ₉ are the same as or different from each other, and each independently, a single bond, a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ heteroaromatic linking group;

The R ₂₁ to R ₃₀ are the same or different from each other, and each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or A salt thereof, phosphoric acid or a 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 A substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group (alkylthio), a substituted or unsubstituted C3-C60 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl Group, substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, substituted or unsubstituted carbon number 1 to 60 (alkyl) amino group, di(substituted or unsubstituted C 1 to C 60 alkyl) amino group, or (substituted or unsubstituted C 6 to C 60 aryl) amino group, di(substituted or unsubstituted C 6 To 60 aryl) 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, and each substituent is May form a condensed ring with a group adjacent to each other;

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

The two sites marked with * of the anthracene may be the same or different from each other, and each independently combine with the P or Q structure to form an anthracene derivative selected from Formulas 1Aa-1 to 1Aa-3 below.

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

Here, the'substituted' in the'substituted or unsubstituted' refers to deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, and having 1 to 24 carbon atoms. Alkenyl group, alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms or heteroaryl having 2 to 24 carbon atoms Arylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 heteroarylamino group, C1-C24 alkylsilyl group, C1-C24 It means substituted with at least one substituent selected from the group consisting of an arylsilyl group and an aryloxy group having 1 to 24 carbon atoms.

[Formula 1B]

In Formula 1B,

The Ar ₁₇ to Ar ₂₀ are the same as or different from each other and each independently consists of the same substituent as defined in Ar ₇ to Ar ₈ in Formula 1A, and R ₆₀ to R ₆₃ are defined in R ₂₁ to R ₃₀ of Formula 1A. It consists of the same substituents as.

The w and ww are the same as or different from each other, the x and xx are the same as or different from each other, and the w+ww and x+xx values are the same or different from each other, and are each independently an integer of 0-3. Further, y and yy are the same as or different from each other, z and zz are the same or different from each other, y+yy to z+zz values are 2 or less, and are integers of 0 to 2, respectively.

[Formula 1C]

In Formula 1C,

The Ar ₂₁ to Ar ₂₄ are the same as or different from each other, and each independently consists of the same substituent as defined in Ar ₇ to Ar ₈ of Formula 1A, and R ₆₄ to R ₆₇ are in R ₂₁ to R ₃₀ of Formula 1A. It consists of the same substituents as defined.

In addition, ee to hh are the same as or different from each other, and each independently an integer of 1 to 4, and ii to ll are the same or different from each other, and each independently an integer of 0 to 4.

[Formula 1D]

In Formula 1D,

The Ar ₂₅ to Ar ₂₇ are the same as or different from each other, and each independently consists of the same substituent as defined in Ar ₇ to Ar ₈ of Formula 1A, and R ₆₈ to R ₇₃ are the same as or different from each other, and each independently the above formula It consists of the same substituents as defined for R ₂₁ to R ₃₀ in 1A, and each of the substituents may form a saturated or unsaturated cyclic structure between adjacent ones. In addition, the mm to ss are the same as or different from each other, and each independently an integer of 0 to 4.

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

[Host1] [Host2] [Host3] [Host4]

[Host5] [Host6] [Host7] [Host8]

[Host9] [Host10] [Host11] [Host12]

[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]

In addition, the emission layer may further include various hosts and various dopant materials in addition to the dopant and host.

In addition, in the present invention, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule 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 layer through heating in a vacuum or low pressure state, and the solution process is used to form each layer. It refers to a method of forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, etc. by mixing a material used as a material for use with a solvent.

In addition, the organic light emitting device in the present invention includes a flat panel display device; Flexible display device; Monochrome or white flat lighting devices; And a single color or white flexible lighting device; may be used in any one device selected from.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for explaining the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereto.

(Example)

Synthesis example 1. Synthesis of [Compound 1]

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

[Intermediate 1-a]

6-bromo-1-hydroxypyrene (20.8 g, 0.07 mol) was added to 200 mL of dichloromethane and stirred. Pyridine (7 g, 0.09 mol) was added, and the reaction mixture was cooled to 0° C., trifluoromethane sulphonic anhydride (21.1 g, 0.075 mol) was slowly added dropwise, followed by stirring at room temperature for about 1 hour. Separated by column chromatography to give [Intermediate 1-a] 22.2 g (74% yield).

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

[Intermediate 1-b]

(4-chlorophenyl) trimethylsilane (18.5 g, 0.1 mol), benzeneamine (9.3 g, 0.1 mol), palladium acetate (0.08 g, 0.32 mmol), 2,2'-bis(diphenylphosphino)-1 -1'-Binaphthyl (0.26 g, 0.42 mmol) and sodium tertiarybutoxide (15.2 g, 0.16 mol) were added to 150 mL of toluene and refluxed for 12 hours. After cooling to room temperature, it was washed with methanol, and recrystallized with dichloromethane and methanol to give [Intermediate 1-b] 18.1 g (75% yield).

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

[Intermediate 1-c]

[Intermediate 1-b] (6.5 g, 27 mmol) synthesized in [Scheme 1-2], [Intermediate 1-a] (9.6 g, 22.5 mmol) synthesized in [Scheme 1-1], 2, 2'-bis(diphenylphosphino)-1-1'-binaphthyl (0.28 g, 0.45 mmol), sodium turretoxide (4.3 g, 45 mmol), palladium acetate (0.1 g, 0.45 mmol) Put in 100 mL of toluene and refluxed for 24 hours. After extraction with ethyl acetate, it was washed with methanol. Separated by column chromatography to give 4.8 g (yield 57%) of [Intermediate 1-c].

[Scheme 1-4] Synthesis of [Intermediate 1-d]

[Intermediate 1-d]

3-Aminophenylboronic acid (10.0 g, 0.073 mol), 5-terstributyl-2-iodobenzonitrile (17.4 g, 0.061 mol), tetrakis (triphenylphosphine) palladium (3.62 g, 0.003 mol) ), potassium carbonate (16.9 g, 0.122 mol) was added to 150 mL of 1,4-dioxane, 150 mL of toluene, and 60 mL of distilled water, and refluxed for 12 hours. After cooling to room temperature, extraction with ethyl acetate, and separation by column chromatography to give [Intermediate 1-d] 11.9 g (yield 78%).

[Scheme 1-5] Synthesis of [Intermediate 1-e]

[Intermediate 1-e]

Using chlorobenzene instead of (4-chlorophenyl)trimethylsilane used in [Scheme 1-2], and [Intermediate 1-d] synthesized in [Scheme 1-4] instead of benzeneamine, [ Intermediate 1-e] (yield 74%) was obtained.

[Scheme 1-6] Synthesis of [Compound 1]

[Compound 1]

[Intermediate 1-c] (4.5 g, 7.6 mmol) synthesized in [Scheme 1-3], [Intermediate 1-e] (3.7 g, 11.4 mmol) synthesized in [Scheme 1-5], sodium tursher Reviewoxide (1.1 g, 11.4 mmol), palladium acetate (0.03 g, 0.152 mmol), and BINAP (0.35 g, 0.57 mmol) were added to 500 mL of toluene, stirred at room temperature for 30 minutes, and then heated to 110 °C. Refluxed for 24 hours. After lowering the temperature to room temperature, extraction was performed with dichloromethane and separated by column chromatography to obtain 3.0 g (51% yield) of [Compound 1].

MS (MALDI-TOF): m/z 765.35 [M] ⁺

Synthesis example 2. Synthesis of [Compound 2]

In the above [Scheme 1-2], 2-biphenyl bromide was used instead of (4-chlorophenyl) trimethylsilane, 1-amino-4-methylbenzene was used instead of benzeneamine, and chlorobenzene in [Scheme 1-5] [Compound 2] (yield 52%) was prepared in the same manner as in Synthesis Example 1, except that 3-bromo-1-methylnaphthalene was used instead, and 3-fluorobenzeneamine was used instead of [Intermediate 1-d]. Got it.

MS (MALDI-TOF): m/z 708.29 [M] ⁺

Synthesis Example 3. Synthesis of [Compound 3]

In the above [Scheme 1-2], 1-bromo-3,5-diphenylbenzene was used instead of (4-chlorophenyl)trimethylsilane, and 3-bromo-1- instead of chlorobenzene in [Scheme 1-5] [Compound 3] (yield 52%) was obtained in the same manner as in Synthesis Example 1, except that methylnaphthalene was used, and 3-fluorobenzeneamine was used instead of [Intermediate 1-d].

MS (MALDI-TOF): m/z 770.31 [M] ⁺

Synthesis Example 4. Synthesis of [Compound 4]

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

[Intermediate 4-a]

In the above [Scheme 1-4], phenylboronic acid was used instead of 3-aminophenylboronic acid, and 3-bromo-4-methylbenzeneamine was used instead of 5-tertiaryl-2-iodobenzonitrile. [Intermediate 4-a] (yield 77%) was obtained by the method.

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

[Intermediate 4-b]

In the above [Scheme 1-4], 4-bromophenylboronic acid was used instead of 3-aminophenylboronic acid, and 4-bromopyrimidine was used instead of 5-tertiary-2-iodobenzonitrile. [Intermediate 4-b] (yield 78%) was obtained by the method.

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

[Intermediate 4-c]

[Intermediate 4-b] synthesized in [Scheme 4-2] was used instead of (4-chlorophenyl) trimethylsilane used in [Scheme 1-2], and synthesized in [Scheme 4-1] instead of benzeneamine [Intermediate 4-c] (75% yield) was obtained by the same method using one [Intermediate 4-a].

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

[Intermediate 4-c] synthesized in [Scheme 4-3] was used instead of [Intermediate 1-b] in [Scheme 1-2], and 6-bromo- instead of chlorobenzene in [Scheme 1-5] [Compound 4] (yield 53%) was obtained in the same manner as in Synthesis Example 1, except that 2-cyanonaphthalene was used, and 4-methyl-1-naphthalenamine was used instead of [Intermediate 1-d].

MS (MALDI-TOF): m/z 845.35 [M] ⁺

Synthesis Example 5. Synthesis of [Compound 5]

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

[Intermediate 5-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 stirred. Recrystallized from methanol to give [Intermediate 5-a] 139 g (yield 78%).

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

[Intermediate 5-b]

[Intermediate 5-a] (139.7 g, 0.347 mol) obtained in [Scheme 5-1] was added to 2 L of ethanol, and 1 L of 12 M hydrochloric acid was added thereto, followed by stirring. The temperature was lowered to 0° C., and tin powder (165 g, 1.39 mol) was slowly added dropwise over 20 minutes. Refluxed at 100° C. for 3 hours. When the reaction was completed, the temperature was lowered to 0° C., and 1 L of 12 M aqueous sodium hydroxide solution was slowly added thereto for basicization. Extracted with ethyl acetate and separated by column chromatography to give [Intermediate 5-b] 87.7 g (74% yield).

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

[Intermediate 5-c]

[Intermediate 5-b] (87.7 g, 0.256 mol) synthesized in [Scheme 5-2] 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) was added to distilled water at 0 °C. It was dissolved in 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° C. and stirred for 3 hours. Extracted with ethyl acetate and separated by column chromatography to give 42.1 g (29% yield) of [Intermediate 5-c].

[Scheme 5-4] Synthesis of [Intermediate 5-d]

[Intermediate 5-d]

[Intermediate 5-c] (19.7 g, 35 mmol) synthesized in [Scheme 5-3], tetrakis (triphenylphosphine) palladium (0.8 g, 0.5 mmol), copper iodide (0.54 g, 1 mmol) Was added to 50 mL of triethylamine, stirred at room temperature, and then phenylacetylene (3.6 mL, 35 mmol) was slowly added. After stirring at room temperature for about 1 hour, 300 mL of hexane was added and the reaction was terminated. Separated by column chromatography to give [Intermediate 5-d] 13.2 g (74% yield).

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

[Intermediate 5-e]

[Intermediate 5-d] (12.3 g, 0.024 mol) synthesized in [Scheme 5-4] was dissolved in 120 mL of dichloromethane. Iron trifluoromethanesulfonate (1.2 g, 0.002 mol) was added and refluxed for 12 hours. After hot filtering, it was recrystallized to obtain 2.0 g (yield 16%) of [Intermediate 5-e].

[Scheme 5-6] Synthesis of [Intermediate 5-f]

[Intermediate 5-f]

In the above [Scheme 1-4], benzene boronic acid was used instead of 3-aminophenylboronic acid, and 2,4-dibromoaniline was used instead of 5-tertiaryl-2-iodobenzonitrile. [Intermediate 5-f] (yield 90%) was obtained.

[Scheme 5-7] Synthesis of [Intermediate 5-g]

[Intermediate 5-g]

[Intermediate 5-f] synthesized in [Scheme 5-6] instead of (4-chlorophenyl) trimethylsilane used in [Scheme 1-2], and 1-cyano-4-chlorobenzene was used instead of benzeneamine [Intermediate 5-g] (yield 72%) was obtained by the same method using.

[Scheme 5-8] Synthesis of [Intermediate 5-h]

[Intermediate 5-h]

[Intermediate 5-g] synthesized in [Scheme 5-7] was used instead of [Intermediate 1-b] used in [Scheme 1-3], and [Scheme 5-5] was used instead of [Intermediate 1-a] [Intermediate 5-e] synthesized in was used to obtain [Intermediate 5-h] (yield 42%) by the same method.

[Scheme 5-9] Synthesis of [Intermediate 5-i]

[Intermediate 5-i]

[Intermediate 5-i] in the same manner using pentadeutereo chlorobenzene instead of (4-chlorophenyl)trimethylsilane used in [Scheme 1-2], and 1-amino-4-methylbenzene instead of benzeneamine (Yield 75%) was obtained.

[Scheme 5-10] Synthesis of [Compound 5]

[Compound 5]

[Intermediate 5-i] synthesized in [Scheme 5-9] is used instead of [Intermediate 1-b] used in [Scheme 1-3], and [Scheme 5-8] is used instead of [Intermediate 1-a] [Compound 5] (yield 40%) was obtained by the same method using [Intermediate 5-h] synthesized in

MS (MALDI-TOF): m/z 904.46 [M] ⁺

Synthesis Example 6. Synthesis of [Compound 6]

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

[Intermediate 6-a]

In the above [Scheme 1-4], 3-bromophenylboronic acid was used instead of 3-aminophenylboronic acid, and 1-chloronaphthalene was used instead of 5-tertiary-2-iodobenzonitrile. [Intermediate 6-a] (yield 80%) was obtained.

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

[Intermediate 6-b]

[Intermediate 6-a] synthesized in [Scheme 6-1] was used instead of (4-chlorophenyl) trimethylsilane used in [Scheme 1-2], and 1-amino-4-methoxybenzene was used instead of benzeneamine [Intermediate 6-b] (yield 73%) was obtained by the same method using.

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

[Intermediate 6-b] synthesized in [Scheme 6-2] was used instead of [Scheme 5-7], and 6-bromo-2-cyano instead of pentadeutereochlorobenzene in [Scheme 5-9] [Compound 6] (Yield 54) in the same manner as in Synthesis Example 5, except that naphthalene (4-chlorophenyl) trimethylsilane was used, and 4-amino-tertiary benzene was used instead of 1-amino-4-methylbenzene. %).

MS (MALDI-TOF): m/z 972.45 [M] ⁺

Synthesis Example 7. Synthesis of [Compound 7]

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

[Intermediate 7-a]

3-methylphenylboronic acid (17.4 g, 0.128 mol), 1,6-dibromopyrene (21.9 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 refluxed for 12 hours. After cooling to room temperature, extraction with ethyl acetate, and separation by column chromatography to give [Intermediate 7-a] 18.2 g (78% yield).

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

[Intermediate 7-b]

[Intermediate 7-a] (19.1 g, 0.05 mol) obtained in [Scheme 7-1] was dissolved in 200 mL of dimethylformamide and stirred at 0 °C. N-bromosuccinimide (20.1 g, 0.11 mol) was dissolved in 100 mL of dimethylformamide and slowly added dropwise for 1 hour. After raising to room temperature, it was stirred for 12 hours. Filtered with an excess of distilled water, washed with methanol, and recrystallized with toluene and methanol to give [Intermediate 7-b] 23.8 g (88% yield).

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

[Intermediate 7-c]

In the above [Scheme 1-4], 4-bromo-2,5-dimethylphenylboronic acid was used instead of 3-aminophenylboronic acid, and pentadeutereoio was used instead of 5-tertiary-2-iodobenzonitrile. [Intermediate 7-c] (yield 77%) was obtained by the same method using dobenzene.

[Scheme 7-4] Synthesis of [Intermediate 7-d]

[Intermediate 7-d]

[Intermediate 7-c] synthesized in [Scheme 7-3] was used instead of (4-chlorophenyl)trimethylsilane in [Scheme 1-2], and 4-(trifluoromethyl)benzeneamine was used instead of benzeneamine [Intermediate 7-d] (yield 75%) was obtained by the same method using.

[Scheme 7-5] Synthesis of [Intermediate 7-e]

[Intermediate 7-e]

Instead of [Intermediate 1-b] used in [Scheme 1-3], [Intermediate 7-d] synthesized in [Scheme 7-4] is used, and instead of [Intermediate 1-a], the above Reaction Scheme [Scheme 7-2] [Intermediate 7-b] synthesized in [Intermediate 7-e] (yield 43%) was obtained.

[Scheme 7-6] Synthesis of [Intermediate 7-f]

[Intermediate 7-f]

In the above [Scheme 1-4], 1-bromonaphthalene-4-boronic acid was used instead of 3-aminophenylboronic acid, and 3-iodopyridine was used instead of 5-tertiaryl-2-iodobenzonitrile. Then, [Intermediate 7-f] (79% yield) was obtained in the same manner.

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

[Intermediate 7-g]

Instead of (4-chlorophenyl)trimethylsilane in [Scheme 1-5], [Intermediate 7-e] synthesized in [Scheme 7-5] was used, and 3,5-dimethylbenzeneamine was used instead of benzeneamine. [Intermediate 7-g] (74% yield) was obtained by the same method.

[Scheme 7-8] Synthesis of [Compound 7]

[Compound 7]

Instead of [Intermediate 1-b] used in [Scheme 1-3], [Intermediate 7-g] synthesized in [Scheme 7-7] was used, and [Scheme 7-5] above instead of [Intermediate 1-a] [Compound 7] (yield 40%) was obtained by the same method using [Intermediate 7-e] synthesized in

MS (MALDI-TOF): m/z 1068.54 [M] ⁺

Synthesis Example 8. Synthesis of [Compound 8]

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

In [Scheme 1-4], 2-amino-5-methylphenylboronic acid was used instead of 3-aminophenylboronic acid, and 2-bromonaphthalene was used instead of 5-tertiaryl-2-iodobenzonitrile. [Intermediate 8-a] (yield 77%) was obtained by the method.

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

[Intermediate 8-b] (yield 75%) was obtained by the same method using [Intermediate 8-a] synthesized in [Scheme 8-1] instead of benzeneamine in [Scheme 1-2].

[Scheme 8-3] Synthesis of [Compound 8]

[Intermediate 8] synthesized in [Scheme 8-2] instead of [Intermediate 7-d] used in [Scheme 7-5] and [Intermediate 8] using cyclohexaneboronic acid instead of 3-methylphenylboronic acid used in [Scheme 7-1] -b] was used, and 1-bromo-2-fluoro-4-(trifluoromethyl)benzene was used instead of [intermediate 7-c] in [Scheme 7-4], and 4-(trifluoromethyl) ) [Compound 8] (yield 50%) was obtained in the same manner as in Synthesis Example 7, except that 4-methyl-1-naphthalenamine was used instead of benzeneamine.

MS (MALDI-TOF): m/z 1062.49 [M] ⁺

Synthesis example 9. Synthesis of [Compound 9]

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

In [Scheme 1-4], cyclohexaneboronic acid was used instead of 3-aminophenylboronic acid, and 4-bromo-2-naphthylamine was used instead of 5-tertiaryl-2-iodobenzonitrile. [Intermediate 9-a] (yield 79%) was obtained by the method.

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

In [Scheme 1-2], 2-biphenyl bromide was used instead of (4-chlorophenyl) trimethylsilane, and [Intermediate 9-a] synthesized in [Scheme 9-1] was used instead of benzeneamine. Thus, [intermediate 9-b] (yield 73%) was obtained.

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

In [Reaction Scheme 1-4], 4-bromophenylboronic acid was used instead of 3-aminophenylboronic acid, and 1-chloronaphthalene was used instead of 5-tertiary-2-iodobenzonitrile. Intermediate 9-c] (yield 80%) was obtained.

[Scheme 9-4] Synthesis of [Intermediate 9-d]

[Intermediate 9-d] (yield 76%) using [Intermediate 9-c] synthesized in [Scheme 9-3] instead of (4-chlorophenyl)trimethylsilane in [Scheme 1-2] Got it.

[Scheme 9-5] Synthesis of [Compound 9]

[0043] [Scheme 9-2] was synthesized instead of [Intermediate 7-d] used in [Scheme 7-5], and 3-pyridylboronic acid was used instead of 3-methylphenylboronic acid used in [Scheme 7-1]. The same as in Synthesis Example 7 except that intermediate 9-b] was used and [intermediate 9-d] synthesized in [Scheme 9-4] was used instead of [Intermediate 7-g] in [Scheme 7-8]. By the method [Compound 9] (yield 52%) was obtained.

MS (MALDI-TOF): m/z 1026.47 [M] ⁺

Hereinafter, the structures of the synthesized [Compound 1] to [Compound 9] are shown.

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

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

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

Example 1 to 9

Fabrication of organic light emitting diodes

The ITO glass was patterned and washed so that the light emitting area was 2 mm x 2 mm in size. After mounting the substrate in a vacuum chamber, the base pressure is 1x10 ^-6 torr, and then the organic material is placed on the ITO with DNTPD (700Å), α-NPD (300Å), BH1 as a host for the emission layer, and compound 1 prepared by the present invention. One of the compounds 9 (3 wt%) was co-deposited (300 Å), and then Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed in order, and the measurement was performed at 0.4 mA.

[DNTPD] [α-NPD]

[BH1] [Alq ₃ ]

Comparative Examples 1 to 2

The organic light emitting devices for Comparative Examples 1 to 2 were manufactured in the same manner, except that the following [Compound 101] and [Compound 102] were used instead of the compounds prepared by the invention in the device structures of Examples 1 to 9, The structure is as follows.

[Compound 101] [Compound 102]

For the organic light-emitting devices manufactured according to Examples 1 to 9 and Comparative Examples 1 to 2, voltage, luminance, color coordinates and lifetime were measured, and the results are shown in Table 1 below. T97 refers to the time it takes for the luminance to decrease from the initial luminance (2000nit) to 97%.

In addition, Fig. 2 shows the life evaluation results (T97) of the devices in Example 1 and Comparative Examples 1 and 2 of the present invention.

division Host Dopant Voltage(V) Luminance (Cd/m ² ) CIEx CIEy T ₉₇ Example 1
BH1 Compound 1 3.8 824 0.131 0.118 85 Example 2
BH1 Compound 2 3.8 818 0.133 0.117 83 Example 3
BH1 Compound 3 3.8 809 0.132 0.119 81 Example 4
BH1 Compound 4 3.9 805 0.133 0.117 79 Example 5
BH1 Compound 5 3.8 798 0.132 0.119 82 Example 6
BH1 Compound 6 3.9 800 0.135 0.109 79 Example 7
BH1 Compound 7 3.7 797 0.134 0.113 81 Example 8
BH1 Compound 8 3.8 786 0.133 0.117 82 Example 9
BH1 Compound 9 3.9 790 0.134 0.113 80 Comparative Example 1
BH1 Compound 101 6.4 515 0.149 0.166 41 Comparative Example 2
BH1 Compound 102 6.0 653 0.175 0.225 52

As shown in Tables 1 and 2, the asymmetric pyrene derivative according to the present invention has a much improved color purity and long lifespan than the case of using a symmetric pyrene-based arylamine compound according to the prior art, thereby realizing full color. It shows high applicability as an organic light emitting device for the following.

Claims (14)

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

In the above [Formula A],
Substituents Ar ₁ to Ar ₄ are each the same or different, and independently of each other, any one selected from the following [substituent 801] to [substituent 804], [substituent 806] and [substituent 807],
[Substituent 801] [Substituent 802] [Substituent 803]

[Substituent 804] [Substituent 806]

[Substituent 807]

Wherein R, R'and R" are each the same or different, and hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, substituted or unsubstituted C 3 to C 60 Cycloalkyl group, substituted or unsubstituted aryl group having 6 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 40 carbon atoms, substituted or unsubstituted carbon number It may be selected from 6 to 30 arylsilyl groups,
n is an integer from 1 to 9,
When the substituent R is not bonded to the carbon of the aromatic ring in the aryl group of the substituent 801 to the substituent 804, the substituent 806, and the substituent 807, hydrogen is bonded,
One of R is a single bond bonded to a nitrogen atom bonded to pyrene in Formula A,
The substituent Z is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted A C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a cyano group, a nitro group, a halogen group;
Each carbon atom in the pyrene ring is bonded to hydrogen when it is not bonded to the nitrogen atom of the amine or the substituent Z;
In [Formula A], m is an integer of 1 to 8, and when m is 2 or more, each Z is independently the same or different from each other,
Since the two amine groups bonded to the pyrene are different from each other, the pyrene has an asymmetric structure,
In the pyrene derivative of Formula A, an amine is bonded to positions 1, 6 or 2,7, respectively,
'Substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, carbon number At least one substituent selected from the group consisting of an arylalkyl group of 6 to 24, a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, and an arylsilyl group having 1 to 24 carbon atoms Means to be substituted with.
However, compound 19 and compound 25 below are excluded.

The method of claim 1,
The substituent Z is any one 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, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms. Asymmetric pyrene derivatives characterized by. The method of claim 1,
One of said Ar ₁ and Ar ₂ in the formula (A) is the Ar ₃ substituents and the other amine And Ar ₄ and one of the same as each other, or the Ar ₁ and Ar ₂ Are the same as each other, or
Or the asymmetric pyrene derivative, characterized in that all of Ar ₁ to Ar ₄ in the formula (A) are different substituents delete delete The method according to any one of claims 1 to 3,
In the [Formula A], any one or more of Ar ₁ to Ar ₄ bonded to the amine contains deuterium; an asymmetric pyrene derivative, characterized in that. The method of claim 6,
In the [Chemical Formula A], at least two of Ar ₁ to Ar ₄ bonded to the amine contain deuterium; an asymmetric pyrene derivative, characterized in that. The method according to any one of claims 1 to 3,
The substituents substituted for Ar ₁ and Ar ₄ are cyano group, halogen group, alkyl group having 1 to 6 carbon atoms, halogenated alkyl having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms, arylalkyl group having 6 to 18 carbon atoms, 3 carbon atoms An asymmetric pyrene derivative, characterized in that it is any one selected from the group consisting of a heteroaryl group having 1 to 18 carbon atoms, an alkylsilyl group having 1 to 18 carbon atoms, and an arylsilyl group having 6 to 18 carbon atoms. The following [Compound 1] to [Compound 8], [Compound 14], [Compound 16] to [Compound 23], [Compound 25] to [Compound 30], [Compound 32] to [Compound 47], [Compound 50] To [Compound 62], [Compound 65] to [Compound 73].
[Compound 1] [Compound 2] [Compound 3]

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

[Compound 7] [Compound 8]

[Compound 14]

[Compound 16] [Compound 17] [Compound 18]

[Compound 19] [Compound 20] [Compound 21]

[Compound 22] [Compound 23]

[Compound 25] [Compound 26] [Compound 27]

[Compound 28] [Compound 29] [Compound 30]

[Compound 32] [Compound 33]

[Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39]

[Compound 40] [Compound 41] [Compound 42]

[Compound 43] [Compound 44] [Compound 45]

[Compound 46] [Compound 47]

[Compound 50] [Compound 51]

[Compound 52] [Compound 53] [Compound 54]

[Compound 55] [Compound 56] [Compound 57]

[Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62]

[Compound 65] [Compound 67]

[Compound 68] [Compound 69] [Compound 70]

[Compound 71] [Compound 72] [Compound 73]

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 contains at least one organic light-emitting compound of any one selected from claims 1 to 3 and 9. device. The method of claim 10,
The organic layer is an organic light emitting device comprising at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer. The method of claim 10,
The organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The light-emitting layer is an organic light-emitting device comprising a host and a dopant, and the organic light-emitting compound is used as a dopant. The method of claim 11,
An organic light-emitting device, characterized in that at least one layer selected from each of the layers is formed by a deposition process or a solution process. The method of claim 10,
The organic light emitting device may include a flat panel display device; Flexible display device; Monochrome or white flat lighting devices; And, a single color or white flexible lighting device; Organic light emitting device, characterized in that used in any one device selected from.

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