KR102291545B1 - Compounds for organic optoelectronic device and organic optoelectronic device including the same - Google Patents

Abstract

상기 화학식 1에서,
Ar¹ 및 Ar²은 각각 독립적으로 치환 또는 비치환된 C5 내지 C20 아릴기 또는 치환 또는 비치환된 C3 내지 C20 헤테로아릴기에서 선택되거나, 서로 연결되어 융합링을 형성하고,
R¹ 내지 R³는 각각 독립적으로 수소, 중수소, C1 내지 C6의 알킬기 또는 C1 내지 C6의 플루오로알킬기이고,
a, b 및 c는 각각 독립적으로 0 내지 4의 정수이고,
-N(Ar¹)(Ar²)는 페난트로록사졸릴기(phenanthroxazolyl group)와 페닐렌 링커의 결합에 대하여 오르쏘 또는 메타 위치에 결합된다.A compound for an organic optoelectronic device represented by the following Chemical Formula 1 and an organic optoelectronic device including the same are provided.
[Formula 1]

In Formula 1,
Ar ¹ and Ar ² are each independently selected from a substituted or unsubstituted C5 to C20 aryl group or a substituted or unsubstituted C3 to C20 heteroaryl group, or are connected to each other to form a fused ring,
R ¹ to R ³ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b and c are each independently an integer of 0 to 4,
-N(Ar ¹ )(Ar ² ) is bonded to the ortho or meta position with respect to the bonding between the phenanthroxazolyl group and the phenylene linker.

Description

A compound for an organic optoelectronic device and an organic optoelectronic device comprising the same

It relates to a compound for an organic optoelectronic device and an organic optoelectronic device comprising the same.

An organic optoelectronic device is a device capable of converting electrical energy and optical energy.

Organic optoelectronic devices can be roughly divided into two types according to their operating principles. One is a photoelectric device in which excitons formed by light energy are separated into electrons and holes, and the electrons and holes are transferred to different electrodes, respectively, to generate electrical energy. It is a light emitting device that generates light energy from energy.

Examples of the organic optoelectronic device include an organic photoelectric device, an organic light emitting device, and an organic solar cell.

Among them, organic light emitting diodes (OLEDs) have recently attracted great attention due to an increase in demand for flat panel display devices. The organic light emitting device is a device that converts electric energy into light by applying a current to an organic light emitting material, and typically has a structure in which an organic layer is inserted between an anode and a cathode. The emission wavelength and performance of the organic light emitting device are greatly affected by the characteristics of the organic layer, and among them, the host material included in the organic layer is greatly affected.

One embodiment provides a compound applicable to an organic optoelectronic device.

Another embodiment provides an organic optoelectronic device including the compound.

According to one embodiment, there is provided a compound for an organic optoelectronic device represented by the following formula (1).

[Formula 1]

In Formula 1,

Ar ¹ and Ar ² are each independently selected from a substituted or unsubstituted C5 to C20 aryl group or a substituted or unsubstituted C3 to C20 heteroaryl group, or are connected to each other to form a fused ring,

R ¹ to R ³ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b and c are each independently an integer of 0 to 4,

-N(Ar ¹ )(Ar ² ) is bonded to the ortho or meta position with respect to the bonding between the phenanthroxazolyl group and the phenylene linker.

The compound may be represented by the following Chemical Formula 1A or Chemical Formula 1B.

[Formula 1A]

[Formula 1B]

In Formula 1A and Formula 1B,

R ^{1 To} R ⁶ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and f are each independently an integer of 0 to 4,

e is an integer from 0 to 3.

The compound may be represented by the following Chemical Formula 1C.

[Formula 1C]

In Formula 1C,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.}

The compound may be represented by the following Chemical Formula 1D.

[Formula 1D]

In Formula 1D,

R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

e is an integer from 0 to 3,

X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.}

The compound may be represented by the following Chemical Formula 1E.

[Formula 1E]

In Formula 1E,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and e are each independently an integer of 0 to 4,

X ¹ to X ⁷ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), at least one of ^{X 1} to X ^{7 is N.}

The compound may be represented by the following Chemical Formula 1F.

[Formula 1F]

In Formula 1F,

R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and e are each independently an integer of 0 to 4.

The compound may be represented by the following Chemical Formula 2A or Chemical Formula 2B.

[Formula 2A]

[Formula 2B]

In Formula 2A and Formula 2B,

R ¹ to R ⁷ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and f are each independently an integer of 0 to 4,

e is an integer from 0 to 3.

The compound may be represented by the following Chemical Formula 2C.

[Formula 2C]

In Formula 2C,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.}

The compound may be represented by the following Chemical Formula 2D.

[Formula 2D]

In Formula 2D,

R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

e is an integer from 0 to 3,

X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.}

The compound may be represented by the following Chemical Formula 2E.

[Formula 2E]

In Formula 2E,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

X ¹ to X ⁷ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), at least one of ^{X 1} to X ^{7 is N.}

The compound may be represented by the following Chemical Formula 2F.

[Formula 2F]

In Formula 2F,

R ¹ to R ⁷ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and e are each independently an integer of 0 to 4.

More specific examples of the compound represented by Formula 1 may include compounds of Formulas A-1 to B-6 below.

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

[Formula A-4] [Formula A-5] [Formula A-6]

[Formula B-1] [Formula B-2] [Formula B-3]

[Formula B-4] [Formula B-5] [Formula B-6]

In the compounds of Formulas A-1 to B-6,

A hydrogen of the aromatic ring may be substituted with deuterium, a C1 to C6 alkyl group or a C1 to C6 fluoroalkyl group.

According to another embodiment, there is provided an organic optoelectronic device comprising an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, wherein the organic layer includes the compound.

The organic layer may include an emission layer, and the emission layer may include the compound as a phosphorescent host.

The compound has excellent light emitting properties in the red light emitting region, and can improve efficiency and lifespan when applied to an organic optoelectronic device.

1 is a cross-sectional view schematically illustrating a configuration of an organic light emitting device according to an exemplary embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

As used herein, unless otherwise defined, at least one hydrogen in a substituent or compound is deuterium, NH ₂ , C1 to C4 amine group, nitro group, C1 to C4 silyl group, C1 to C4 alkyl group, C1 to It means substituted with a C4 alkylsilyl group, a C1 to C4 alkoxy group, a fluoro group, a C1 to C4 trifluoroalkyl group, or a cyano group.

As used herein, the term "fused ring" may be a C6 to C30 aryl group or a C3 to C30 heteroaryl group.

In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, P and Si.

According to one embodiment, there is provided a compound for an organic optoelectronic device represented by the following formula (1).

[Formula 1]

In Formula 1,

Ar ¹ and Ar ² are each independently selected from a substituted or unsubstituted C5 to C20 aryl group or a substituted or unsubstituted C3 to C20 heteroaryl group, or are connected to each other to form a fused ring,

R ¹ to R ³ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b and c are each independently an integer of 0 to 4,

The arylamine group (-N(Ar ¹ )(Ar ² )) is bonded to the ortho or meta position with respect to the bonding between the phenanthroxazolyl group and the phenylene linker.

When the phenanthrooxazolyl group and the arylamine group (-N(Ar ¹ )(Ar ² )) are directly bonded, an overlapping region of electron density does not exist, so energy transfer may not be easy.

In the compound having the structure of Formula 1, the arylamine group (-N(Ar ¹ )(Ar ² )) is bonded to the para position with respect to the bonding between the phenanthroxazolyl group and the phenylene linker. It has excellent luminescent properties as well as excellent thermal properties.

The compound may be represented by the following Chemical Formula 1A or Chemical Formula 1B.

[Formula 1A]

[Formula 1B]

In Formula 1A and Formula 1B,

R ^{1 To} R ⁶ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and f are each independently an integer of 0 to 4,

e is an integer from 0 to 3.

The compound may be represented by the following Chemical Formula 1C.

[Formula 1C]

In Formula 1C,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.}

The compound may be represented by the following Chemical Formula 1D.

[Formula 1D]

In Formula 1D,

R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

e is an integer from 0 to 3,

X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.}

The compound may be represented by the following Chemical Formula 1E.

[Formula 1E]

In Formula 1E,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and e are each independently an integer of 0 to 4,

X ¹ to X ⁷ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), at least one of ^{X 1} to X ^{7 is N.}

The compound may be represented by the following Chemical Formula 1F.

[Formula 1F]

In Formula 1F,

R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and e are each independently an integer of 0 to 4.

The compound may be represented by the following Chemical Formula 2A or Chemical Formula 2B.

[Formula 2A]

[Formula 2B]

In Formula 2A and Formula 2B,

R ¹ to R ⁷ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and f are each independently an integer of 0 to 4,

e is an integer from 0 to 3.

The compound may be represented by the following Chemical Formula 2C.

[Formula 2C]

In Formula 2C,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.}

The compound may be represented by the following Chemical Formula 2D.

[Formula 2D]

In Formula 2D,

R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

e is an integer from 0 to 3,

X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.}

The compound may be represented by the following Chemical Formula 2E.

[Formula 2E]

In Formula 2E,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c and d are each independently an integer of 0 to 4,

X ¹ to X ⁷ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), at least one of ^{X 1} to X ^{7 is N.}

The compound may be represented by the following Chemical Formula 2F.

[Formula 2F]

In Formula 2F,

R ¹ to R ⁷ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,

a, b, c, d and e are each independently an integer from 0 to 4.

More specific examples of the compound represented by Formula 1 may include compounds of Formulas A-1 to B-6 below.

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

[Formula A-4] [Formula A-5] [Formula A-6]

[Formula B-1] [Formula B-2] [Formula B-3]

[Formula B-4] [Formula B-5] [Formula B-6]

In the compounds of Formulas A-1 to B-6,

A hydrogen of the aromatic ring may be substituted with deuterium, a C1 to C6 alkyl group or a C1 to C6 fluoroalkyl group.

_{The compound may exhibit a maximum absorption wavelength (UV max} ) in a solution state from about 300 nm to about 400 nm, for example from about 310 nm to about 380 nm, and a maximum light in the blue region, for example from 380 nm to 460 nm. It may represent the emission wavelength (PL _{max ).}

The compound may have a bandgap of about 2.2 eV to about 3.2 eV, preferably about 2.3 eV to about 3.1 eV, and may exhibit a triplet energy of about 2.3 eV or more.

The above-described compounds can be applied to various organic optoelectronic devices, for example, can be used as a phosphorescent host. The compound may be formed into a thin film using a dry film deposition method such as chemical vapor deposition or a solution process.

Hereinafter, an organic optoelectronic device to which the above-described compound is applied will be described.

The organic optoelectronic device is not particularly limited as long as it is a device capable of converting electrical energy and optical energy, and examples thereof include an organic photoelectric device, an organic light emitting device, and an organic solar cell.

The organic optoelectronic device may include an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, and the organic layer may include the compound.

Herein, an organic light emitting device, which is an example of an organic optoelectronic device, will be described with reference to the drawings.

1 is a cross-sectional view illustrating an organic light emitting diode according to an exemplary embodiment.

Referring to FIG. 1 , an organic light emitting diode 100 according to an exemplary embodiment includes a first electrode 110 and a second electrode 120 facing each other, and between the first electrode 110 and the second electrode 120 . and an organic layer 105 located in

One of the first electrode 110 and the second electrode 120 may be a cathode and the other may be an anode.

At least one of the first electrode 110 and the second electrode 120 may be a transparent electrode. For example, when the first electrode 110 is a transparent electrode, bottom emission emits light toward the first electrode 110 . ) and, when the second electrode 120 is a transparent electrode, it may be a top emission that emits light toward the second electrode 120 . In addition, when both the first electrode 110 and the second electrode 120 are transparent electrodes, light may be emitted from both sides.

The organic layer 105 may include the above-described compound. The organic layer 105 may include at least one layer or more, and may include an emission layer.

The emission layer may include the above-described compound as a phosphorescent host. The light emitting layer may further include a dopant. This dopant may be a red, green or blue dopant. The dopant is a material that emits light by being mixed in a small amount with the host, and in general, a material such as a metal complex that emits light by multiple excitation excitation to a triplet state or higher may be used. The dopant may be, for example, an inorganic, organic, or organic-inorganic compound, and may include one or two or more kinds. The dopant may be included in an amount of about 0.1 to 20 wt% based on the total amount of the emission layer. Examples of the dopant include a phosphorescent dopant, and examples of the phosphorescent dopant include Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. and organometallic compounds containing them. The phosphorescent dopant may be, for example, a compound represented by the following Chemical Formula 3, but is not limited thereto.

[Formula 3]

L ₂ MX

In Formula 3, M is a metal, and L and X are the same as or different from each other and are ligands forming a complex with M.

M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or a combination thereof, wherein L and X are, for example, bidentate It may be a ligand.

The organic layer 105 may further include an auxiliary layer in addition to the emission layer. The auxiliary layer is for improving light emitting efficiency, and may be located at least one of between the first electrode 110 and the light emitting layer and between the second electrode 120 and the light emitting layer. The auxiliary layer includes an electron transport layer and a hole transport layer for balancing electrons and holes, and an electron injection layer and a hole injection layer for enhancing electron and hole injection. injection layer) and the like, and may include one or two or more layers selected from among them.

The above-described organic light emitting device may be applied to an organic light emitting display device.

Hereinafter, specific embodiments of the present invention are presented. However, the examples described below are only for specifically illustrating or explaining the present invention, and the present invention is not limited thereto.

Synthesis Example A-1: Synthesis of the compound represented by compound A-1

(1) Synthesis of compound A-1a

[Scheme A-1a]

9,10-Phenanthrenequinone 1.23g (5.91mmol), 2-bromobenzylamine 1.0g (5.37mmol), silver carbonate 2.96g (10.7mmol) ) into a 100 mL three-necked round flask and substituted with nitrogen. After adding 20 mL of 1,4-dioxane (anhydrous), the mixture is stirred at 50° C. for 12 hours. After the reaction is completed, the reaction solution is filtered and washed several times with methylene chloride (MC). After extraction using MC and distilled water, the solvent is removed. Column purification is performed using ethyl acetate and hexane. (yield rate: 41%)

¹ H NMR (300 MHz, CDCl ₃ ) δ (ppm) 8.79-8.74 (t, 2H), 8.67-8.64 (d, 1H), 8.38-8.35 (t, 1H), 8.28-8.25 (d, 1H), 7.84-7.69 (m, 5H), 7.55-7.50 (t, 1H), 7.42-7.36 (t, 1H)

(2) Synthesis of compound A-1

[Scheme A-1]

2- (2-bromophenyl) phenanthro [9,10] oxazole (2- (2-bromophenyl) phenanthro [9,10] oxazole, compound A-1a) 0.6 g (1.6 mmol), diphenylamine ( Diphenylamine) 0.28g (1.68mmol), Pd ₂ (dba) ₃ 0.058g (0.06mmol), and sodium tert-butoxide 0.46g were placed in a 100mL three-necked round flask and substituted with nitrogen. Add 30 mL of toluene (anhydrous) and 0.08 mL of tri-t-butylphosphine. Stir at 110°C for 3 hours. After the reaction is completed, the solvent is removed after extraction using MC and distilled water. Column purification is performed using ethyl acetate and hexane. (yield rate: 60%)

¹ H NMR (300 MHz, DMSO) δ (ppm) 8.90-8.86 (t, 2H), 8.36-8.32 (d, 1H), 8.29-8.26 (d, 1H), 7.94-7.91 (d, 1H), 7.76 -7.65(m, 5H), 7.53-7.48(t, 1H), 7.36-7.34(d, 1H), 7.16-7.11(t, 4H), 7.04-7.01(d, 4H), 6.83-6.78(t, 2H)

Synthesis Example A-2: Synthesis of the compound represented by compound A-2

[Scheme A-2]

2- (2-bromophenyl) phenanthro [9,10] oxazole (2- (2-bromophenyl) phenanthro [9,10] oxazole, compound 1-1) 0.29 g (0.74 mmol), N-phenylpyridin- 2-amine 0.14g (0.85mmol), Pd(oac) ₂ 0.007g (0.03mmol), BINAP 0.04g (0.062mmol), sodium tert-butoxide 0.23g (2.22mmol) in a 100mL 3-neck round flask and nitrogen substituted do. Add 24 mL of toluene (anhydrous) and stir at 110°C for 4 hours. After the reaction is completed, the solvent is removed after extraction using MC and distilled water. Column purification is performed using ethyl acetate and hexane. (yield rate: 27%)

¹ H NMR (300 MHz, DMSO) δ (ppm) 8.88-8.86 (d, 2H), 8.38-8.32 (t, 2H), 7.88-7.87 (d, 2H), 7.78-7.64 (m, 5H), 7.56 -7.51(t, 1H), 7.43-7.32(m, 6H), 7.15-7.14(d, 1H)

Synthesis Example A-3: Synthesis of the compound represented by compound A-3

[Scheme A-3]

2- (2-bromophenyl) phenanthro [9,10] oxazole (2- (2-bromophenyl) phenanthro [9,10] oxazole, compound A-1a) 0.51 g (1.36 mmol), carbazole 0.24 g ( 1.43mmol), CuI 0.28g (1.63mmol), potassium carbonate 0.56g (4.08mmol), 18-crown-6 ether 0.036g (0.136mmol) into a 100mL three-necked round flask, and nitrogen is substituted. Add 40 mL of 1,2-Dicholrobenzene (anhydrous) and stir at 180°C for 48 hours. After the reaction is completed, the solvent is removed after extraction using MC and distilled water. Column purification is performed using ethyl acetate and hexane. (yield rate: 51%)

¹ H NMR (300 MHz, DMSO) δ (ppm) 8.78-8.74 (q, 2H), 8.67-8.64 (d, 1H), 8.33-8.31 (d, 2H), 8.18-8.15 (d, 1H), 8.01 -7.92(q, 2H), 7.90-7.88(d, 1H), 7.73-7.65(q, 2H), 7.62-7.57(d, 1H), 7.52-7.47(t, 1H), 7.33-7.28(t, 2H), 7.25-7.20 (t, 2H), 7.10-7.08 (d, 2H), 6.83-6.80 (d, 1H)

Synthesis Example B-1: Synthesis of the compound represented by compound B-1

(1) Synthesis of compound B-1a

[Scheme B-1a]

9,10-Phenanthrenequinone 0.84g (4.03mmol), 3-bromobenzylamine 0.5g (2.68mmol), and silver carbonate 1.48g (5.37mmol) were placed in a 100mL three-necked round flask and purged with nitrogen. After adding 15 mL of 1,4-dioxane (anhydrous), the mixture is stirred at 50° C. for 12 hours. After the reaction is completed, the reaction solution is filtered and washed several times with methylene chloride (MC). After extraction using MC and distilled water, the solvent is removed. Column purification is performed using ethyl acetate and hexane. (yield rate: 49%)

¹ H NMR (300 MHz, CDCl ₃ ) δ(ppm) 8.83-8.74(t, 2H), 8.64-8.61(d, 1H), 8.54(s, 1H), 8.39-8.35(d, 1H), 8.34 8.31 (d, 1H), 7.80-7.66 (m, 5H), 7.48-7.43 (t, 1H)

(2) Synthesis of compound B-1

[Scheme B-1]

2- (3-bromophenyl) phenanthro [9,10] oxazole (2- (3-bromophenyl) phenanthro [9,10] oxazole, compound B-1a) 0.3 g (0.8 mmol), diphenylamine 0.15 g ( 0.88mmol), Pd ₂ (dba) ₃ 0.03g (0.03mmol), sodium tert-butoxide 0.23g (2.4mmol) into a 100mL three-necked round flask, and nitrogen is substituted. Add 20 mL of toluene (anhydrous) and 0.08 mL of tri-t-butylphosphine. Stir at 110°C for 4 hours. After the reaction is completed, the solvent is removed after extraction using MC and distilled water. Column purification is performed using ethyl acetate and hexane. (yield rate: 62%)

¹ H NMR (300 MHz, THF) δ (ppm) 8.87-8.82 (t, 2H), 8.54-8.51 (d, 1H), 8.29-8.26 (d, 1H), 8.12 (s, 1H), 8.06-8.02 (d, 1H), 7.72-7.65 (m, 4H), 7.48-7.43 (t, 1H), 7.35-7.26 (t, 4H), 7.24-7.21 (d, 1H), 7.19-7.15 (d, 4H) , 7.08-7.03(t, 2H)

Synthesis Example B-2: Synthesis of the compound represented by compound B-2

[Scheme B-2]

2- (3-bromophenyl) phenanthro [9,10] oxazole (2- (3-bromophenyl) phenanthro [9,10] oxazole, compound B-1a) 0.42 g (1.12 mmol), N-phenylpyridin- 2-amine 0.21g (1.23mmol), Pd(oac) ₂ 0.01g (0.045mmol), BINAP 0.06g (0.089mmol), and sodium tert-butoxide 0.32g (3.36mmol) were placed in a 100mL 3-neck round flask and replaced with nitrogen. do. Add 30 mL of toluene (anhydrous) and stir at 110°C for 4 hours. After the reaction is completed, the solvent is removed after extraction using MC and distilled water. Column purification is performed using ethyl acetate and hexane. (yield rate: 65%)

¹ H NMR (300 MHz, THF) δ (ppm) 8.84-8.81 (t, 2H), 8.55-8.52 (d, 1H), 8.28-8.24 (d, 1H), 8.23 (s, 1H), 8.18-8.16 (d, 1H), 8.15-8.12 (d, 1H), 7.71-7.66 (m, 4H), 7.54-7.49 (t, 2H), 7.40-7.29 (m, 5H), 7.26-7.17 (t, 1H) , 6.85-6.79 (t, 2H)

Synthesis Example B-3: Synthesis of the compound represented by compound B-3

[Scheme B-3]

2- (3-bromophenyl) phenanthro [9,10] oxazole (2- (3-bromophenyl) phenanthro [9,10] oxazole, compound B-1a) 0.2 g (0.53 mmol), carbazole 0.1 g ( 0.57mmol), Pd ₂ (dba) ₃ 0.02g (0.02mmol), and sodium tert-butoxide 0.15g (1.6mmol) into a 100mL 3-neck round flask and nitrogen-substituted. Add 20 mL of toluene (anhydrous) and add 0.05 mL of tri-t-butylphosphine. Stir at 110°C for 4 hours. After the reaction is completed, the solvent is removed after extraction using MC and distilled water. Column purification is performed using ethyl acetate and hexane. (yield rate: 69%)

¹ H NMR (300 MHz, THF) δ (ppm) 8.90-8.84 (t, 2H), 8.63-8.52 (m, 3H), 8.38-8.35 (t, 1H), 8.21-8.18 (d, 2H), 7.91 -7.88(t, 1H), 7.86-7.85(d, 1H), 7.74-7.69(m, 4H), 7.52-7.49(d, 2H), 7.45-7.39(t, 2H), 7.31-7.26(t, 2H)

Evaluation 1: Evaluation of optical properties of compounds

A solution obtained by dissolving the compounds of Synthesis Examples A-1 to B-3 at a ^{concentration of 10 -5} M using a tetrahydrofuran solvent was subjected to UV-Vis. The evaluation was performed using a spectrometer (Lamda 1050 UV-Vis.-NIR spectrometer, PerkinElmer).

The luminescence characteristics (UV _max and PL _max ) of a solution in which the compounds of Synthesis Examples A-1 to B-3 ^{were dissolved in tetrahydrofuran at a concentration of 10 -5} M were measured using a PL spectrometer (PerkinEler luminescence spectrometer LS50 (Xenon flash tube)) was evaluated using Low temperature PL _max was measured at 77K. The results are shown in Table 1 below.

UV _max (nm) PL _max (nm) low temperature PL _max (nm) Synthesis Example A-1 360 455 545 Synthesis Example A-2 359 439 543 Synthesis Example A-3 363 416 508 Synthesis Example B-1 316 437 546 Synthesis Example B-2 319 414 542 Synthesis Example B-3 335 397 540

Referring to Table 1, it can be seen that all of the compounds of Synthesis Examples A-1 to B-3 exhibit light absorption characteristics in a region of 316 nm to 363 nm and emit light in a blue region. The HOMO level, LUMO level, bandgap energy and triplet energy of the compounds of Synthesis Examples A-1 to B-3 are shown in Table 2 below.

The HOMO level was measured using AC-II equipment, and the LUMO level was calculated by adding the bandgap energy to the HOMO level. Triplet energy was obtained from low-temperature PL spectra. The results are shown in Table 2.

HOMO (eV) LUMO (eV) Band gap energy
(eV) Triplet Energy
(eV) Synthesis Example A-1 -5.69 -2.76 2.93 2.34 Synthesis Example A-2 -5.78 -2.77 3.01 2.35 Synthesis Example A-3 -5.85 -2.83 3.02 2.37 Synthesis Example B-1 -5.53 -2.58 2.95 2.44 Synthesis Example B-2 -5.41 -2.47 2.94 2.45 Synthesis Example B-3 -5.89 -2.91 2.98 2.46

Referring to Table 3, it can be seen that the compounds of Synthesis Examples A-1 to B-3 have triplet energy of 2.34 eV or more, so they are suitable for use as a phosphorescent host and energy transfer to a dopant can easily occur.

Evaluation 2: Evaluation of thermal properties

The compounds of Synthesis Examples A-1 to B-3 were subjected to thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) by glass transition temperature (Tg), melting point (Tm) and decomposition temperature ( Td) was measured. The results are shown in Table 3 below.

Tg (℃) Tm (℃) Td (℃) Synthesis Example A-1 ND 212 332 Synthesis Example A-2 ND 224 318 Synthesis Example A-3 ND 273 346 Synthesis Example B-1 ND 235 356 Synthesis Example B-2 ND 244 376 Synthesis Example B-3 ND 255 389

ND: Not detected

Referring to Table 3, the glass transition temperature (Tg) of the compounds of Synthesis Examples A-1 to B-3 is not observed, meaning that the compound is stable without thermal deformation, and the melting point (Tm) and decomposition temperature (Td) ), it can be seen that the thermal stability is excellent.

Example A-1: Fabrication of an organic light emitting device

On a glass substrate, ITO was sputtered to a thickness of 150 nm, and DNTPD 40 nm and NPB 20 nm were sequentially deposited thereon to form a hole auxiliary layer. Then, 96 wt% of compound A-1 obtained in Synthesis Example A-1 and 3 wt% of Ir(mphmq)2(tmd) (CAS: 1228537-80-1) as a dopant were co-deposited on the hole auxiliary layer to form a thickness of 35 nm. A light emitting layer was formed. Then, Alq ₃ 20 nm and LiF 1 nm are sequentially deposited on the emission layer to form an electron auxiliary layer. Then, Al was deposited to a thickness of 200 nm on the electron auxiliary layer to fabricate an organic light emitting diode.

Examples A-2 to B-3: Fabrication of an organic light emitting device

An organic light emitting diode was manufactured in the same manner as in Example A-1, except that the compounds obtained in Synthesis Examples A-2 to B-3 were respectively used instead of Compound A-1 obtained in Synthesis Example A-1.

Evaluation 3: Device Performance Evaluation

_{The luminous efficiency, external quantum efficiency, color coordinates and emission wavelength (EL max} ) of the organic light emitting diodes according to Examples A-1 to B-3 were evaluated. The results are shown in Table 4.

Luminous Efficiency
(cd/A) External quantum efficiency (%) color coordinates
(x,y) Thin film EL _max
(nm) Example A-1 13.1 8.9 (0.64, 0.35) 610 Example A-2 12.2 8.8 (0.64, 0.35) 610 Example A-3 10.9 7.2 (0.64, 0.35) 610 Example B-1 25.5 17.5 (0.64, 0.35) 610 Example B-2 26.2 19.0 (0.64, 0.35) 610 Example B-3 24.3 17.4 (0.64, 0.35) 610

Referring to Table 4, it can be seen that the organic light emitting devices of Examples A-1 to B-3 emit _{red light from color coordinates and thin film EL max} , and have excellent luminous efficiency and external quantum efficiency.

The present invention is not limited to the above embodiments, but can be manufactured in a variety of different forms, and those of ordinary skill in the art to which the present invention pertains can take other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that it can be implemented as Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

110: first electrode
120: second electrode
130: organic layer
100: organic light emitting device

Claims (13)

A compound for an organic optoelectronic device represented by the following formula (1):
[Formula 1]

In Formula 1,
Ar ¹ and Ar ² are each independently selected from a substituted or unsubstituted C5 to C20 aryl group or a substituted or unsubstituted C3 to C20 heteroaryl group, or are connected to each other to form a fused ring,
R ¹ to R ³ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b and c are each independently an integer of 0 to 4,
-N(Ar ¹ )(Ar ² ) is bonded to the ortho or meta position with respect to the bonding between the phenanthroxazolyl group and the phenylene linker. According to claim 1,
The compound is a compound for an organic optoelectronic device, which is represented by the following Chemical Formula 1A or Chemical Formula 1B:
[Formula 1A]

[Formula 1B]

In Formula 1A and Formula 1B,
R ^{1 To} R ⁶ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c, d and f are each independently an integer of 0 to 4,
e is an integer from 0 to 3. According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following Chemical Formula 1C:
[Formula 1C]

In Formula 1C,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c and d are each independently an integer of 0 to 4,
X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.} According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following Chemical Formula 1D:
[Formula 1D]

In Formula 1D,
R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c and d are each independently an integer of 0 to 4,
e is an integer from 0 to 3,
X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.} According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following Chemical Formula 1E:
[Formula 1E]

In Formula 1E,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c, d and e are each independently an integer of 0 to 4,
X ¹ to X ⁷ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), at least one of ^{X 1} to X ^{7 is N.} According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following formula 1F:
[Formula 1F]

In Formula 1F,
R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c, d and e are each independently an integer of 0 to 4. According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following Chemical Formula 2A or Chemical Formula 2B:
[Formula 2A]

[Formula 2B]

In Formula 2A and Formula 2B,
R ¹ to R ⁷ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c, d and f are each independently an integer of 0 to 4,
e is an integer from 0 to 3. According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following Chemical Formula 2C:
[Formula 2C]

In Formula 2C,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c and d are each independently an integer of 0 to 4,
X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.} According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following Chemical Formula 2D:
[Formula 2D]

In Formula 2D,
R ¹ to R ⁵ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c and d are each independently an integer of 0 to 4,
e is an integer from 0 to 3,
X ¹ to X ⁵ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), and at least one of ^{X 1} to X ^{5 is N.} According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following Chemical Formula 2E:
[Formula 2E]

In Formula 2E,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c and d are each independently an integer of 0 to 4,
X ¹ to X ⁷ are each independently N or CR ^a (wherein R ^a is each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group, or adjacent R ^a are connected to each other to form a fused ring may form), at least one of ^{X 1} to X ^{7 is N.} According to claim 1,
The compound is a compound for an organic optoelectronic device represented by the following formula 2F:
[Formula 2F]

In Formula 2F,
R ¹ to R ⁷ are each independently hydrogen, deuterium, a C1 to C6 alkyl group, or a C1 to C6 fluoroalkyl group,
a, b, c, d and e are each independently an integer of 0 to 4. positive and negative poles facing each other, and
at least one organic layer positioned between the anode and the cathode
including,
The organic layer is an organic optoelectronic device comprising the compound according to any one of claims 1 to 11. 13. The method of claim 12,
The organic layer includes a light emitting layer,
The light emitting layer is an organic optoelectronic device comprising the compound according to any one of claims 1 to 11.

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