KR101338253B1 - Cyclopentaphenanthrene-based compound and organoelectroluminescent device employing the same - Google Patents

Abstract

The present invention provides a cyclopentaphenanthrene-based compound and an organic electroluminescent device using the same. The cyclopentaphenanthrene-based compound according to the present invention is easy to prepare and has excellent solubility, excellent color purity and color stability, and excellent thermal stability. The cyclopentaphenanthrene-based compound is not only useful as an organic film, particularly a charge transport layer and a light emitting layer forming material of an organic electroluminescent device, but also may be used as an electronic material such as organic dyes and nonlinear optical materials.

Organic electroluminescence, cyclopentaphenanthrene

Description

Cyclopentaphenanthrene-based compound and organic electroluminescent device using same {Cyclopentaphenanthrene-based compound and organoelectroluminescent device employing the same}

1A to 1C are schematic diagrams illustrating a laminated structure of an organic EL device according to an embodiment of the present invention.

2A and 2B are graphs showing voltage-efficiency characteristics of an organic EL device according to an embodiment of the present invention.

The present invention relates to a cyclopentaphenanthrene-based compound and an organic electroluminescent device using the same, and more particularly, to an organic electroluminescent device having a cyclopentaphenanthrene-based compound and an organic film formed using the same.

The organic electroluminescent device is an active light emitting display device using a phenomenon in which light is generated while electrons and holes are combined in an organic film when a current flows through a thin film of fluorescent or phosphorescent organic compound (hereinafter referred to as an organic film). It is possible, and the parts are simple, the manufacturing process is simple, and has the advantage of ensuring a wide viewing angle in high quality. In addition, video can be fully realized, high color purity can be realized, and low power consumption and low voltage can be driven to have electrical characteristics suitable for portable electronic devices.

Eastman Kodak Co. has developed a multi-layered organic electroluminescent device using an aluminum quinolinol complex layer and a triphenylamine derivative layer (US Pat. No. 4,885,211). As the low molecular weight is used in forming the organic light emitting layer, various light emission from the ultraviolet ray to the infrared ray region is possible. (US Pat. No. 5,151,629).

The light emitting device is a self-luminous device and has a wide viewing angle, excellent contrast, and fast response time. The light emitting device includes an inorganic light emitting device using an inorganic compound and an organic light emitting device using an organic compound (OLED) in the light emitting layer, and the organic light emitting device has higher luminance and driving than the inorganic light emitting device. Much research has been conducted in that the voltage and response speed characteristics are excellent and multicoloring is possible.

The organic light emitting device generally has a stack structure of an anode / an organic light emitting layer / a cathode and includes an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / an electron injecting layer / a cathode or an anode / a hole injecting layer / a hole transporting layer / Blocking layer / electron transporting layer / electron injecting layer / cathode, and the like.

The material used for the organic light emitting device may be classified into a vacuum deposition material and a solution coating material according to the method of manufacturing an organic film. The vacuum evaporable material should have a vapor pressure of 10 ⁻⁶ torr or more under 500 ° C., and preferably a low molecular weight material having a molecular weight of 1200 or less. The solution coatable material is highly soluble in a solvent and must be able to be prepared as a solution, and mainly includes an aromatic or heterocyclic ring.

When manufacturing an organic EL device using a vacuum deposition method, the manufacturing cost is increased by using a vacuum system, and when a shadow mask is used to manufacture pixels for a color display, it is difficult to manufacture high resolution pixels. On the other hand, solution coating methods such as inkjet printing, screen printing, and spin coating are easy to manufacture, inexpensive to manufacture, and have a relatively higher resolution than shadow masks.

However, in the case of materials that can be used for solution coating, the performance of the light emitting molecules was inferior to those that can be used for vacuum deposition in terms of thermal stability and color purity. In addition, even when the performance is excellent, after the organic film is manufactured and gradually crystallized, the crystal size may be visible light scattering by scattering the visible light corresponding to the range of the visible light wavelength, pin holes (pin hole) is formed to form There was a problem that it is easy to cause deterioration.

Japanese Patent Laid-Open No. 1999-003782 discloses anthracene substituted with two naphthyl groups as a compound that can be used in the light emitting layer or the hole injection layer. However, the compound was not satisfactory in solvent solubility, and the characteristics of the organic electroluminescent device employing the compound did not reach satisfactory levels.

Therefore, there is still a need for the development of an organic EL device having excellent thermal stability and improved driving voltage, brightness, efficiency, and color purity characteristics.

Accordingly, the present invention has been made in an effort to provide a compound having a cyclopentaphenanthrene structure having dry and wet processing, excellent thermal stability, excellent charge transfer characteristics, and luminescent properties, and an organic electroluminescent device employing the same. .

In order to achieve the first technical problem, the present invention provides a cyclopentaphenanthrene-based compound represented by Formula 1 below.

In Formula 1,

Y is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group,

Q is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group,

Q and Y are the same or different from each other;

m is an integer from 0 to 5;

n is an integer from 0 to 5;

when m and n are integers of 2 or more, each Q and Y may be different;

R ₁ and R ₂ are the same or different and each is hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 -C 20 alkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted Or an unsubstituted C 5 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C An aralkyl group of 30, a substituted or unsubstituted C 2 -C 30 heteroaryl group;

R ₃ to R ₈ are the same or different, hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 ~ C 20 alkyl group, substituted or unsubstituted C 3 ~ C 20 cycloalkyl group, substituted Or an unsubstituted C 5 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C 30 aralkyl group, substituted or unsubstituted C 2 ~ C 30 heteroaryl group, -N (G ₁ ) (G ₂ ) or -Si (G ₃ ) (G ₄ ) (G ₅ ), the G ₁ , G ₂ , G ₃ , G ₄ and G ₅ are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 5 to C 20 cycloalkyl group or a substituted or unsubstituted C 5 to C 30 heterocycloalkyl group;

Z ₁ to Z ₄ are the same or different and each substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 5 to C 30 heterocyclo Alkyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl group, substituted or unsubstituted C 6 ~ C 30 Aralkyl group, substituted or unsubstituted C 8 ~ C 30 Allylaryl group, substituted or unsubstituted C 1 ~ C 20 Alkylene group, substituted or unsubstituted C 6 ~ C 30 Arylene group , A substituted or unsubstituted C 2 ~ C 30 heteroarylene group;

X is a single bond, -CH = CH-, -O-, -S-, -Se-, -C (R'R ")-, wherein R 'and R" are the same as R ₃ , or-( CH ₂ ) _p − and p is an integer from 1 to 10;

o is 0 or 1;

When R ₁ and R ₂ together form a ring, a substituted or unsubstituted C 3 to C 20 aliphatic ring, a substituted or unsubstituted C 5 to C 30 heteroaliphatic ring, a substituted or unsubstituted C 6 to C 30 aromatic rings, substituted or unsubstituted C 2 to C 30 heteroaromatic rings.

When R ₁ and R ₂ together form a ring in Formula 1 may be a ring of Formula 2 to 5:

Wherein R ₉ is the same or different and is hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 ~ C 20 alkyl group, substituted or unsubstituted C 3 ~ C 20 cycloalkyl group, substituted Or an unsubstituted C 5 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C 30 aralkyl group, substituted or unsubstituted C 2 ~ C 30 heteroaryl group, -N (G ₁ ) (G ₂ ) or -Si (G ₃ ) (G ₄ ) (G ₅ ), the G ₁ , G ₂ , G ₃ , G ₄ and G ₅ are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 5 to C 20 cycloalkyl group or a substituted or unsubstituted C 5 to C 30 heterocycloalkyl group;

A represents a single bond or -O-, -S-,-(CH ₂ ) _s -where s is an integer from 1 to 5.

According to an embodiment of the present invention the compound of Formula 1 may be a compound of Formula 6 to:

In Chemical Formulas 6 to 8

Y is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group;

Q is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group,

Q and Y are the same or different from each other;

m is an integer from 0 to 5;

n is an integer from 0 to 5;

when m and n are integers of 2 or more, each Q and Y may be different;

R ₁ ^′ and R ₂ ^′ are the same or different and each represents a hydrogen, a halogen, a cyano group, a hydroxyl group, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group , Substituted or unsubstituted C 5 -C 30 heterocycloalkyl group, substituted or unsubstituted C 1 ~ C 20 alkoxy group, substituted or unsubstituted C 6 ~ C 30 aryl group, substituted or unsubstituted C 6 A C 30 to C 30 aralkyl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group;

Z ₁ to Z ₄ are the same or different and each substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 5 to C 30 heterocyclo Alkyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl group, substituted or unsubstituted C 6 ~ C 30 Aralkyl group, substituted or unsubstituted C 2 ~ C 30 Allylaryl group, substituted or unsubstituted C 1 ~ C 20 Alkylene group, substituted or unsubstituted C 6 ~ C 30 Aryl A ethylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group;

X is a single bond, -CH = CH-, -O-, -S-, -Se-, -C (R'R ")-, wherein R 'and R" are the same as R ₃ , or-( CH ₂ ) _p − and p is an integer from 1 to 10;

o is 0 or 1;

R ₁₀ is the same or different and is hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 3 to C 20 cycloalkyl group, substituted or unsubstituted, respectively A C 5 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C 30 aral A kill group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, -N (G ₁ ) (G ₂ ) or -Si (G ₃ ) (G ₄ ) (G ₅ ), wherein G ₁ , G ₂ , G ₃ , G ₄ and G ₅ are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C A 30 heteroaryl group, a substituted or unsubstituted C 5 to C 20 cycloalkyl group, or a substituted or unsubstituted C 5 to C 30 heterocycloalkyl group.

In the present invention to solve the second technical problem; A second electrode; And an organic electroluminescent device comprising at least one organic film between the first electrode and the second electrode, wherein the organic film includes an organic light emitting compound as described above.

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

The present invention provides a cyclopentaphenanthrene-based compound of Formula 1 below:

[Formula 1]

In Formula 1,

Y is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group;

Q is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group,

Q and Y are the same or different from each other;

m is an integer from 0 to 5, preferably an integer from 0 to 2;

n is an integer from 0 to 5, preferably an integer from 0 to 2;

when m and n are integers of 2 or more, each Q and Y may be different;

R ₁ and R ₂ are the same or different and each is hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 -C 20 alkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted Or an unsubstituted C 5 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C An aralkyl group of 30, a substituted or unsubstituted C 2 -C 30 heteroaryl group;

R ₃ to R ₈ are the same or different, hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 ~ C 20 alkyl group, substituted or unsubstituted C 3 ~ C 20 cycloalkyl group, substituted Or an unsubstituted C 5 -C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C 30 aralkyl group, substituted or unsubstituted C 2 ~ C 30 heteroaryl group, -N (G ₁ ) (G ₂ ) or -Si (G ₃ ) (G ₄ ) (G ₅ ), the G ₁ , G ₂ , G ₃ , G ₄ and G ₅ are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 5 to C 20 cycloalkyl group or a substituted or unsubstituted C 5 to C 30 heterocycloalkyl group;

Z ₁ to Z ₄ are the same or different and each substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 5 to C 30 hetero Cycloalkyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl group, substituted or unsubstituted A C 6 to C 30 aralkyl group, a substituted or unsubstituted C 8 to C 30 allylaryl group, a substituted or unsubstituted C 1 to C 20 alkylene group, a substituted or unsubstituted C 6 to C 30 aryl A ethylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group;

X is a single bond, -CH = CH-, -O-, -S-, -Se-, -C (R'R ")-, wherein R 'and R" are the same as R ₃ , or-( CH ₂ ) _p − and p is an integer from 1 to 10;

o is 0 or 1;

When R ₁ and R ₂ together form a ring, a substituted or unsubstituted C 3 to C 20 aliphatic ring, a substituted or unsubstituted C 5 to C 30 heteroaliphatic ring, a substituted or unsubstituted C 6 to C To form an aromatic ring of 30, a substituted or unsubstituted C 2 to C 30 heteroaromatic ring.

When R ₁ and R ₂ together form a ring in Formula 1 may be a ring of Formula 2 to 5:

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formula

R ₉ is the same or different and is hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 -C 20 alkyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl group, substituted or unsubstituted, respectively A C 5 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C 30 aral A kill group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, -N (G ₁ ) (G ₂ ) or -Si (G ₃ ) (G ₄ ) (G ₅ ), wherein G ₁ , G ₂ , G ₃ , G ₄ and G ₅ are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C A 30 heteroaryl group, a substituted or unsubstituted C 5 to C 20 cycloalkyl group, or a substituted or unsubstituted C 5 to C 30 heterocycloalkyl group;

A represents a single bond or O, S, (CH ₂ ) _s -where s is an integer from 1 to 10.

In particular, in Formulas 1 to 5, R ₁ to R ₉ serves to improve the film proccesibility by increasing the solubility and amorphous properties of the compound.

The compound of Formula 1 according to the present invention may be a compound of Formulas 6 to 8:

[Chemical Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 6 to 8

Y is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group;

Q is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group,

Q and Y are the same or different from each other;

m is an integer from 0 to 5, preferably an integer from 0 to 2;

n is an integer from 0 to 5, preferably an integer from 0 to 2;

when m and n are integers greater than or equal to 2, each of Q and Y may be different;

R ₁ ^′ and R ₂ ^′ are the same or different and each represents a hydrogen, a halogen, a cyano group, a hydroxyl group, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 3 -C 20 cycloalkyl group , Substituted or unsubstituted C 5 -C 30 heterocycloalkyl group, substituted or unsubstituted C 1 ~ C 20 alkoxy group, substituted or unsubstituted C 6 ~ C 30 aryl group, substituted or unsubstituted C 6 A C 30 to C 30 aralkyl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group;

Z ₁ to Z ₄ are the same or different and each substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 5 to C 30 heterocyclo Alkyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl group, substituted or unsubstituted C 6 ~ C 30 Aralkyl group, substituted or unsubstituted C 2 ~ C 30 Allylaryl group, substituted or unsubstituted C 1 ~ C 20 Alkylene group, substituted or unsubstituted C 6 ~ C 30 Aryl A ethylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group;

X is a single bond, -CH = CH-, -O-, -S-, -Se-, -C (R'R ")-, wherein R 'and R" are the same as R ₃ , or-( CH ₂ ) _p − and p is an integer from 1 to 10;

o is 0 or 1;

R ₁₀ independently or identically to each other is hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 3 to C 20 cycloalkyl group, substituted or unsubstituted A substituted C 5 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C 30 Aralkyl group, a substituted or unsubstituted C 2 ~ C 30 heteroaryl group, -N (G ₁ ) (G ₂ ) or -Si (G ₃ ) (G ₄ ) (G ₅ ), the G ₁ , G ₂ , G ₃ , G ₄ and G ₅ are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to A C 30 heteroaryl group, a substituted or unsubstituted C 5 to C 20 cycloalkyl group, or a substituted or unsubstituted C 5 to C 30 heterocycloalkyl group.

The aryl group in the above formulas may be a monovalent group having an aromatic ring system and may include two or more ring systems, and the two or more ring systems may exist in a bonded or fused form to each other. The heteroaryl group refers to a group in which at least one of the aryl groups is substituted with at least one member selected from the group consisting of N, O, S, and P.

On the other hand, the cycloalkyl group refers to an alkyl group having a ring system, and the heterocycloalkyl group refers to a group in which at least one carbon in the cycloalkyl group is substituted with at least one member selected from the group consisting of N, O, S and P.

In the above formulas, when an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a cycloalkyl group and a heterocycloalkyl group are substituted, their substituents are -F; -Cl; -Br; -CN; -NO ₂ ; -OH; A C 1 -C 20 alkyl group substituted by unsubstituted or -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C 1 -C 20 alkoxy group unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C 6 -C 30 aryl group substituted with an unsubstituted or C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C 2 -C 30 heteroaryl group unsubstituted or substituted by a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; Unsubstituted or C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or a C 5 ~ C 20 cycloalkyl group substituted with -OH; Unsubstituted or substituted C 1 to C 20 alkyl group, C 1 to 20 alkoxy group, C 5 to C 30 heterocycloalkyl group substituted with —F, —Cl, —Br, —CN, —NO ₂ or —OH and —N It may be at least one selected from the group consisting of a group represented by (G ₆ ) (G ₇ ). Wherein G ₆ and G ₇ are the same or different and each is hydrogen; A C 1 -C 10 alkyl group; Or a C 6 -C 30 aryl group substituted with a C 1 -C 10 alkyl group.

More specifically, R ₁ to R ₁₀ are the same or different and are each hydrogen, halogen, cyano group, hydroxyl group, C 1 to C 10 alkyl group, C 1 to C 10 alkoxy group, substituted or unsubstituted as follows: It may be selected from the group consisting of derivatives: phenyl group, biphenyl group, pentarenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, azurenyl group, heptarenyl group, acenaphthylenyl group, phenenalenyl group , Fluorenyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, ethyl-crisenyl group, pisenyl group, peryllenyl group, chloroperylenyl group, pentaphenyl group, pentacenyl Group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, fluorenyl group, pyrantrenyl group, ovarenyl group, carbazolyl group , Thiophenyl group, indolyl group, furinyl group, benzimidazolyl group , Quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrroyl group, pyrazolyl group, imidazolyl group, imidazolinyl group, oxazolyl group, thiazolyl group, triazolyl group, tetrazolyl group, oxadiazolyl Group, pyridinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, thianthrenyl group, thianthrenyl group, cyclopentyl group, cyclohexyl group, oxiranyl group, pyrrolidinyl group, pyrazolidinyl group, imida Zolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, di (C 6 -C 30 aryl) amino group, tri (C 6 -C 30 aryl) silyl group and derivatives thereof.

As used herein, the term "derivative" refers to a group in which one or more hydrogens of the groups listed above are substituted with a substituent as described above.

The compound according to the present invention may have the following Chemical Formulas 9 to 46, but is not limited thereto:

 [Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[Formula 14]

[Formula 15]

 [Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

 [Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

[Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

[Formula 37]

(38)

[Chemical Formula 39]

[Formula 40]

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

The compound according to the present invention represented by Chemical Formula 1 may be synthesized by using a conventional synthetic method, and for a more detailed synthesis route of the compound, refer to the scheme of the following Synthesis Example.

The organic electroluminescent device of the present invention,

A first electrode;

A second electrode; And

And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises at least one compound represented by the formula (1).

The compound of Formula 1 is suitable for use in an organic film, particularly a light emitting layer, a hole injection layer or a hole transport layer of an organic electroluminescent device.

The organic electroluminescent device according to the present invention includes a compound capable of forming a stable organic film while having excellent solubility and thermal stability, unlike a conventional organic electroluminescent device having low stability of an organic film when manufactured by a solution coating method. Thus, it is possible to provide improved light emission characteristics such as excellent driving voltage and color purity.

The structure of the organic electroluminescent device according to the present invention can be very various. That is, one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, an electron transport layer and an electron injection layer may be further included between the first electrode and the second electrode.

More specifically, specific examples of the organic EL device according to the present invention refer to FIGS. 1A, 1B and 1C. The organic electroluminescent device of FIG. 1A has a structure consisting of a first electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / second electrode, and the organic electroluminescent device of FIG. 1B includes a first electrode / hole It has a structure consisting of an injection layer / light emitting layer / electron transport layer / electron injection layer / second electrode. In addition, the organic EL device of FIG. 1C has a structure of a first electrode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / second electrode. At this time, one or more of the light emitting layer, the hole injection layer and the hole transport layer may include a compound according to the present invention.

The light emitting layer of the organic electroluminescent device according to the present invention may include a phosphorescent or fluorescent dopant including red, green, blue or white. The phosphorescent dopant may be an organometallic compound containing at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb and Tm.

Hereinafter, a method of manufacturing an organic EL device according to the present invention will be described with reference to the organic EL device illustrated in FIG. 1C.

First, a first electrode material having a high work function is formed on a substrate by a vapor deposition method, a sputtering method, or the like to form a first electrode. The first electrode may be an anode. Herein, a substrate used in a conventional organic electroluminescent device is used, and a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the material for the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like which is transparent and excellent in conductivity is used.

Next, a hole injection layer (HIL) may be formed on the first electrode by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method.

In the case of forming the hole injection layer by vacuum deposition, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the hole injection layer, and the like. It is preferable that a vacuum degree of 10 ^-8 to 10 ^-3 torr, a deposition rate of 0.01 to 100 mW / sec, and a film thickness are usually appropriately selected in the range of 10 mV to 5 m.

When the hole injection layer is formed by the spin coating method, the coating conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal properties of the desired hole injection layer, but the coating speed is preferably from about 2000 rpm to 5000 rpm , And the heat treatment temperature for removing the solvent after coating is suitably selected within a temperature range of about 80 캜 to 200 캜.

The hole injection layer material may be a compound having the formula (1) as described above. Or phthalocyanine compounds such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 or the starburst type amine derivatives described in Advanced Material, 6, p.677 (1994), for example, TCTA, m-MTDATA, m-. MTDAPB, Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): Poly (3,4) -Ethylenedioxythiophene) / poly (4-styrenesulfonate)), Pani / CSA (Polyaniline / Camphor sulfonicacid: polyaniline / camphorsulfonic acid) or PANI / PSS (Polyaniline) / Poly (4-styrenesulfonate): polyaniline) / poly Known hole injection materials such as (4-styrenesulfonate)) and the like can be used.

Pani / DBSA

PEDOT / PSS

The thickness of the hole injection layer may be about 100 Å to 10000 Å, preferably 100 Å to 1000 Å. If the thickness of the hole injection layer is less than 100 angstroms, the hole injection characteristics may be degraded. If the thickness of the hole injection layer exceeds 10000 angstroms, the driving voltage may increase.

Next, a hole transport layer (HTL) may be formed on the hole injection layer by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. In the case of forming the hole transporting layer by the vacuum deposition method and the spin coating method, the deposition conditions and the coating conditions vary depending on the compound used, but they are generally selected from substantially the same conditions as the formation of the hole injection layer.

The hole transport layer material may be a compound having Formula 1 as described above. Or carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole and the like, N, N'-bis (3-methylphenyl) -N, N'- diphenyl- [ Amine having an aromatic condensed ring such as N, N'-tetramethyldisiloxane, -4,4'-diamine (TPD) and N, N'-di (naphthalen- The same known hole transport materials can be used.

The thickness of the hole transporting layer may be about 50 Å to 1000 Å, preferably 100 Å to 600 Å. When the thickness of the hole transporting layer is less than 50 Å, the hole transporting property may be degraded. When the thickness of the hole transporting layer is more than 1000 Å, the driving voltage may increase.

Next, a light emitting layer (EML) may be formed on the hole transporting layer by a method such as a vacuum evaporation method, a spin coating method, a casting method, or an LB method. When a light emitting layer is formed by a vacuum deposition method and a spin coating method, the deposition conditions vary depending on the compound used, but generally, the conditions are substantially the same as those for forming the hole injection layer.

The light emitting layer may include a compound of Formula 1 according to the present invention as described above. At this time, a known fluorescent host material suitable for the compound of Formula 1 may be used together, or a known dopant material may be used together. The compound of Formula 1 may be used alone or in combination with CBP (4,4'-N, N'-dicarbazole-biphenyl), PVK (poly (n-vinylcarbazole)) and the like. As the phosphorescent dopant, a red phosphorescent dopant PtOEP, an RD 61 manufactured by UDC, a green phosphorescent dopant Ir (PPy) 3 (PPy = 2-phenylpyridine), an F ₂ Irpic which is a blue phosphorescent dopant, a red phosphorescent dopant RD 61 manufactured by UDC, and the like can be used.

When the compound of Formula 1 is used as a dopant, the doping concentration is not particularly limited, but the content of the dopant is generally 0.01 to 15 parts by weight based on 100 parts by weight of the host. In addition, when the compound of Formula 1 is used as a single host, the doping concentration is not particularly limited, but the content of the dopant is generally 0.01 to 15 parts by weight based on 100 parts by weight of the host, and the The host is 30 to 99 parts by weight based on 100 parts by weight of the whole host.

The thickness of the light emitting layer may be about 100 Å to 1000 Å, preferably 200 Å to 600 Å. When the thickness of the light emitting layer is less than 100 angstroms, the luminescent characteristics may be degraded, and when the thickness of the light emitting layer is more than 1000 angstroms, the driving voltage may increase

In the case of using the phosphorescent dopant in the light emitting layer, in order to prevent the triplet excitons or holes from diffusing into the electron transport layer, a method such as vacuum deposition, spin coating, cast method, LB method, etc. is used on the hole transport layer. The hole blocking layer HBL may be formed. In the case of forming the hole blocking layer by the vacuum deposition method and the spin coating method, the conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer. Known hole blocking materials which can be used, for example, oxadiazole derivatives or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

Phenanthroline-containing organic compounds Imidazole-containing organic compounds

Triazole-containing organic compound

Oxadiazole-containing compound

BAlq

The thickness of the hole blocking layer may be about 50 Å to 1000 Å, preferably 100 Å to 300 Å. This is because when the thickness of the hole blocking layer is less than 50 kV, the hole blocking property may be deteriorated. When the thickness of the hole blocking layer is more than 1000 kV, the driving voltage may increase.

Next, the electron transport layer (ETL) is formed using various methods such as vacuum deposition, spin coating, and casting. In the case of forming the electron transporting layer by the vacuum deposition method and the spin coating method, the conditions vary depending on the compound used, but generally, the conditions are substantially the same as those for forming the hole injection layer. The electron transport layer material functions to stably transport electrons injected from an electron injection electrode (Cathode), an oxazole compound, an isoxazole compound, a triazole compound, an isothiazole compound, an oxadiazole compound , Thiadiazole compounds, perylene compounds, aluminum complexes such as Alq3 (tris (8-quinolinolato) -aluminum) BAlq, SAlq, Known materials such as Almq3, gallium complexes (e.g., Gaq'2OPiv, Gaq'2OAc, 2 (Gaq'2)) and the like can also be used.

       Perylene-Based Compound

     Alq3 BAlq

    SAlq Almq3

Gaq'2OPiv Gaq'2Oac

2 (Gaq'2)

The thickness of the electron transporting layer may be about 100 ANGSTROM to 1000 ANGSTROM, preferably 200 ANGSTROM to 500 ANGSTROM. When the thickness of the electron transporting layer is less than 100 angstroms, the electron transporting characteristics may be deteriorated. When the thickness of the electron transporting layer exceeds 1000 angstroms, the driving voltage may increase.

Further, an electron injection layer (EIL), which is a material having a function of facilitating the injection of electrons from the cathode, may be laminated on the electron transport layer, which is not particularly limited.

As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li ₂ O, BaO, or the like can be used. The deposition conditions of the electron injection layer vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The thickness of the electron injection layer may be about 1 A to 100 A, preferably 5 A to 50 A. If the thickness of the electron injection layer is less than 1 angstrom, the electron injection characteristics may be deteriorated. If the thickness of the electron injection layer exceeds 100 angstroms, the driving voltage may increase.

Finally, the second electrode can be formed on the electron injection layer by a vacuum evaporation method, a sputtering method, or the like. The second electrode may be used as a cathode. As the metal for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, or a mixture thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- . Also, a transmissive cathode using ITO or IZO may be used to obtain a front light emitting element.

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

Example

Synthesis Example 1

1) Synthesis of 8,9-dihydro-4H-cyclopenta [def] phenanthrene (8,9-Dihydro-4H-cyclopenta [def] phenanthrene)

4H-cyclopenta [def] phenanthrene (4.75 g, 25 mmol) was placed in a Par reactor bottle followed by EtOH (200 ml). 5% Pd / C (3.99 g) was added to the reaction solution and reacted for 24 hours while maintaining the hydrogen pressure at 40 psi. After the reaction was completed, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure to obtain a white target product (4.32 g, 90%).

¹ H NMR (300MHz, CDCl ₃ , δ): 7.36 (2H, d), 7.21 (2H, t), 7.12 (2H, d), 3.90 (2H, s), 3.16 (4H, s)

2) Synthesis of 2,6-Dibromo-8,9-dihydro-4H-cyclopenta [def] phenanthrene (2,6-Dibromo-8,9-dihydro-4H-cyclopenta [def] phenanthrene)

8,9-dihydro-4H-cyclopenta [def] phenanthrene (4.42 g, 23 mmol) was added to a 250 ml round bottom flask (RBF), and CCl ₄ (100 ml) was added thereto and dissolved. The reaction solution was cooled to 0 ^° C. and Br ₂ (7.72 g, 48 mmol) was added dropwise to the reaction solution. After reacting for 4 hours, 10% NaSO ₃ solution was added and the organic layer was separated. The separated organic layer was concentrated under reduced pressure, and then recrystallized with n-hexane to obtain the target product (4.45 g, 55%).

¹ H NMR (300MHz, CDCl ₃ , δ): 7.48 (2H, s), 7.28 (2H, s), 3.85 (2H, s), 3.10 (4H, s)

3) Synthesis of Compound 1

In a 250 ml round bottom flask, 2,6-dibromo-8,9-dihydro-4H-cyclopenta [def] phenanthrene (4.45 g, 12.7 mmol) was dissolved in xylene and o-chloranil (o-) at room temperature. Chloranil) (4.15 g) was added. The reaction was carried out for 72 hours while refluxing using an oil bath. After the reaction was completed, the reaction solution was cooled and concentrated under reduced pressure. The residue obtained by concentration was subjected to silica gel column chromatography using n-hexane as a developing solvent, to obtain Compound 1 (3.6 g, 81%).

_{^{1 H NMR (300MHz, CDCl 3}} , δ): 7.98 (2H, s), 7.79 (2H, s), 7.73 (2H, s), 4.28 (2H, s)

4) Synthesis of Compound 2

2.6g (7.7mmol) and t-BuOK (20.8g) in 2,6-dibromo-4H-cyclopenta [def] phenanthrene in a 50 ml round bottom flask , 61.6 mmol), DMSO (20 ml) and HMPA (20 ml) were added by syringe, stirred at room temperature for 50 minutes, and the reaction temperature was lowered to 0 ^o C. At _{^{0 o C CH 3 I (3.75}} ml, 61.6mmol) was added dropwise by syringe and the mixture was stirred for 30 minutes at 0 ^o C. Thereafter, water (50 ml) and methylene chloride (50 ml) were added to the reaction solution, and the organic layer was separated and subjected to silica gel column chromatography to obtain Compound 2 (3.6 g, 80%). ¹ H NMR (300 MHz, CDCl ₃ , δ): 7.98 (2H, s), 7.79 (2H, s), 7.73 (2H, s), 1.93 (m, 6H).

5) Synthesis of Material 1 (Formula 9)

0.65g (1.747mmol) of compound 2, 1.40g (4.37mmol) of bis (4-biphenyl) amine (TCI), 50g of sodium tert-butoxide (0.5mmol), Pd (dba) in a 50ml round bottom flask ₂ [(Tris (dibenzylidine acetone) dipalladium (0))] 0.08 g (0.087 mmol), and 0.017 g (0.087 mmol) tri (tert-butyl) phosphine were dissolved in 10 mL of toluene, followed by reflux for 12 hours. I was. After the reaction was completed, the reaction mixture was cooled to room temperature, 100 ml of distilled water was added to extract the organic layer. The combined organic layers were dried over MgSO ₄ , concentrated, and silica gel column chromatography was performed. The eluate thus obtained was concentrated and dried to obtain 1.1 g (yield: 75%) of material 1 represented by the formula (9).

¹ H NMR (300 MHz, CDCl ₃ , δ): 7.90 (2H, s), 7.75 (2H, s), 7.72 (2H, s), 7.48-6.62 (m, 36H), 1.92 (m, 6H).

Synthesis Example 2

1) Synthesis of Compound 3

In a 50 ml round bottom flask, 2.6 g (7.7 mmol) of 2,6-dibromo-4H-cyclopenta [def] phenanthrene and 3.6 g (18.5 mmol) of octylbromide were dissolved in 10 ml of toluene and TBAB (tetrabutyl ammonium bromide) 0.125 g (0.385 mmol) was added. To the reaction mixture was added a solution of 3.1 g (77 mmol) of NaOH in 50 ml of water, followed by reflux for 2 days. After the reaction was completed, the mixture was extracted with chloroform, and the organic layer obtained therefrom was dried and concentrated with MgSO ₄ , and silica gel column chromatography was performed using n-hexane as eluent. The eluate thus obtained was evaporated under reduced pressure to remove unreacted octyl bromide to give compound 2 (3.6 g, 80%).

¹ H NMR (300MHz, CDCl ₃ , δ): 7.98 (2H, s), 7.79 (2H, s), 7.73 (2H, s), 1.93 (m, 4H), 1.21 (m, 20H), 0.87 (m , 6H), 0.65 (broad s, 4H)

2) Synthesis of Material 2 (Formula 10)

In a 50 ml round bottom flask, 1 g (1.747 mmol) of compound 2, 0.88 g (5.241 mmol) of diphenylamine, 0.51 g (0.5 mmol) of sodium tert-butoxide, Pd (dba) ₂ [(Tris (dibenzylidine acetone) dipalladium ( 0))] 0.08 g (0.087 mmol) and 0.017 g (0.087 mmol) tri (tert-butyl) phosphine were dissolved in 10 mL of toluene and refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100 ml of distilled water was added to extract the organic layer. The combined organic layers were dried over MgSO ₄ , concentrated, and silica gel column chromatography was performed. The eluate thus obtained was concentrated and dried to obtain 10.9 g (yield: 70%) of material 1 represented by the formula (9).

¹ H NMR (300 MHz, CDCl ₃ , δ): 7.98-6.74 (m, 26H), 1.93 (m, 4H), 1.21 (m, 20H), 0.87 (m, 6H), 0.65 (broad s, 4H).

Synthesis Example 3

1) Synthesis of 2,6-Dibromo-cyclopenta [def] phenanthren-4-one (2,6-Dibromo-cyclopenta [def] phenanthren-4-one)

Benzene (200 ml) was added to a 250 ml round bottom flask, and compound 1 (3.6 g, 10.4 mmol) was added thereto. After adding MnO ₂ (150 g) to the reaction solution, the reaction mixture was reacted for 18 hours under reflux using an oil bath. After the reaction was completed, the reaction solution was filtered to remove MnO ₂ , and the mixture was washed with CHCl ₃ , THF, and MeOH in order. The residue obtained after the filtrate was concentrated under reduced pressure was recrystallized with acetone to obtain the target product (1.45 g, 39%).

¹ H NMR (300 MHz, CDCl ₃ , δ): 8.08 (2H, s), 7.89 (2H, s), 7.74 (2H, s)

2) Synthesis of intermediate A

2-bromo biphenyl (0.68 g, 2.95 mmol) was dissolved in 10 ml of anhydrous THF and the reaction temperature was cooled to -78 ^° C. Then, 3.5 ml of t-BuLi was slowly added dropwise and stirred for 1 hour, followed by 2,6-dibromo-cyclopenta [def] phenanthren-4-one (1 g, 2.95 mmol) in 5 ml of dry THF. The solution dissolved in was added dropwise to the reaction solution for 30 minutes. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the residue was added with ethyl acetate and brine to separate the organic layer. The residue obtained by concentration was subjected to silica gel column chromatography to obtain Intermediate A Compound 1 (3.6 g).

3) Synthesis of Compound 4

The intermediate A compound obtained above was dissolved in 30 ml of acetic acid, and then the temperature of the reaction solution was cooled to 0 ^° C. Thereafter, 1 ml of concentrated sulfuric acid was added dropwise to the reaction solution and reacted for 2 hours. After completion of the reaction, the white solid produced during the reaction was filtered and washed with acetic acid and methanol to give a white solid 2 g (80%).

4) Synthesis of Material 3 (Formula 13)

Synthesis of Material 1 of Synthesis Example 1 The same method as the synthesis of Material 1 of Synthesis Example 1 was used except that Compound 4 instead of Compound 2 and 9H-carbazole were used instead of bis (4-biphenyl) amine. To synthesize a material 3 represented by the formula (13).

¹ H NMR (300MHz, CDCl ₃ , δ): 8.10-6.82 (m, 30H)

5) Synthesis of Material 4 (Formula 14)

1 g (1.747 mmol) of Compound 4 in a 50 ml round bottom flask, di-naphthalen-2-yl- [4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolane- 2-yl) -phenyl] -amine 1.81 g (3.843 mmol), K ₂ CO ₃ 1.935 g (0.014 mmol), tetrakis (triphenylphosphine) palladium (0) 0.4 g (0.35 mmol), and tetrabutylammonium 1.13 g (3.49 mmol) of bromide was dissolved in 10 ml of toluene and 10 ml of THF, and then refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100 ml of distilled water was added to extract the organic layer. The combined organic layers were dried over MgSO ₄ , concentrated, and silica gel column chromatography was performed. The eluate thus obtained was concentrated and dried to obtain 0.8 g (yield: 45%) of material 4 represented by the formula (14).

¹ H NMR (300MHz, CDCl ₃ , δ): 8.15-6.54 (m, 50H)

Synthesis Example 4

1) Synthesis of Intermediate B

2,6-dibromo-cyclopenta [def] phenanthren-4-one 1.0 g (2.76 mmol) was dissolved in dry ether (30 ml) and THF (10 ml), and slowly added phenylmagnesium bromide (3.0 M in ether) under nitrogen gas and refluxed for 3 hours. The reaction was terminated by adding water, brought to pH 3-4 with 1N-HCl solution, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The solid obtained was purified by silica gel column chromatography to obtain 0.79 g (65%) of the title compound in a solid state.

2) Synthesis of Compound 5

0.79 g (1.79 mmol) of an intermediate B compound was dissolved in 20 ml of dry benzene, and 0.48 ml (5.38 mmol, 3eq.) Of trifluoromethane sulfonic acid was added dropwise, followed by reaction at 80 ^° C. for 2 hours. The reaction solution was diluted with water, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The obtained solid was purified by silica gel column chromatography, and the obtained solid was recrystallized with EtOAc-Hex mixed solvent to obtain a solid. 0.65 g (63%) of the title compound were obtained. ¹ H NMR (300 MHz, CDCl ₃ , δ) : 7.22-7.26 (m, 10H), 7.70 (s, 2H), 7.80 (s, 3H), 8.00 (s, 2H)

3) Synthesis of Material 5 (Formula 15)

Synthesis of Material 1 of Synthesis Example 1 The same method as the synthesis of Material 1 of Synthesis Example 1 was used except that Compound 5 instead of Compound 2 and 9H-carbazole were used instead of bis (4-biphenyl) amine. To synthesize a material 5 represented by the formula (15).

¹ H NMR (300MHz, CDCl ₃ , δ): 8.02-6.89 (m, 32H)

4) Synthesis of Material 6 (Formula 27)

A material 6 represented by Chemical Formula 27 was synthesized in the same manner as in the synthesis of Material 1 of Synthesis Example 1, except that Compound 5 was used instead of Compound 2 in the synthesis of Material 1 of Synthesis Example 1.

¹ H NMR (300 MHz, CDCl ₃ , δ): 8.05-7.75 (6H, m), 7.55-6.68 (m, 36H).

5) Synthesis of Material 7 (Formula 35)

In a 500 ml round bottom flask, 7.6 g (23.45 mmol) of 4-bromo triphenylamine, 21.85 g (0.235 mol) of aniline, 6.76 g (70 mmol) of sodium tert-butoxide, Pd (dba) ₂ [(Tris (dibenzylidine acetone) dipalladium (0))] 0.86 g (0.938 mmol), and 0.23 g (1.173 mmol) tri (tert-butyl) phosphine were dissolved in 200 mL of toluene and refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and 200 ml of distilled water was added to extract the organic layer. The combined organic layers were dried over MgSO ₄ , concentrated, and silica gel column chromatography was performed. The eluate obtained here was concentrated and dried to give 6.71 g (85%) of N, N, N'-triphenyl-p-phenyldiamine.

3.36 g (10.0 mmol) of the obtained N, N, N'-triphenyl-p-phenyldiamine, 2.0 g (4.0 mmol) of the compound 5, 1.15 g (12 mmol) of sodium tert-butoxide, and Pd (dba) ₂ [(Tris (dibenzylidine acetone) dipalladium (0))] 0.14 g (0.16 mmol), and 0.04 g (0.2 mmol) tri (tert-butyl) phosphine were placed in a 100 ml round bottom flask, dissolved in 50 mL of toluene. It was refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 ml of distilled water was added to extract the organic layer. The combined organic layers were dried over MgSO ₄ , concentrated, and silica gel column chromatography was performed. The eluate thus obtained was concentrated and dried to obtain 2.91 g (yield: 72%) of the material 7 represented by the formula (35).

¹ H NMR (300 MHz, CDCl ₃ , δ): 7.86-7.71 (6H, m), 7.32-6.64 (m, 48H).

Synthesis Example 5

1) Synthesis of Intermediate C

To a 250 ml three-necked round bottom flask was added 2,6-dibromo-cyclopenta [def] phenanthren-4-one (0.95 g, 2.62 mmol) and phenol (30 ml). In the heated state, the reaction was carried out for 5 hours while passing HCl gas through the reaction solution. After the reaction was completed, the unreacted phenol was removed by concentration under reduced pressure. Concentration was performed by silica gel column chromatography to isolate Intermediate B (0.59 g, 42%).

2) Synthesis of Compound 6

Intermediate C (0.95 g, 2.62 mmol) was added to a 100 ml round bottom flask, and DMF (5 ml) and acetonitrile (20 ml) were added thereto. K ₂ CO ₃ (1.52 g) and octyl bromide (2.11 g) were added to the reaction solution in this order and reacted for 18 hours under reflux conditions. After completion of the reaction, the organic layer was separated, and the separated organic layer was subjected to silica gel column chromatography to obtain 0.68 g (82%) of compound 4.

¹ H NMR (300 MHz, CDCl ₃ , δ): 7.78 (2H, d) 7.79 (2H, s) 7.67 (2H, d) 7.11 (4H, dd) 3.89 (4H, t) 1.74 (4H, q) 1.28 ( 20H, m) 0.88 (6H, m)

3) Synthesis of Material 8 (Formula 38)

The same method as the synthesis of Material 1 of Synthesis Example 1 was performed except that Compound 6 and 9H-carbazole were used instead of Bis (4-biphenyl) amine in the synthesis of Material 1 of Synthesis Example 1. To synthesize a material 8 represented by the formula (38).

¹ H NMR (300 MHz, CDCl ₃ , δ): 7.85- 6.92 (30H, m) (4H, dd) 3.89 (4H, t) 1.74 (4H, q) 1.28 (20H, m) 0.88 (6H, m)

5) Synthesis of Material 9 (Formula 39)

A material 9 represented by Chemical Formula 39 was synthesized by the same method as the synthesis of material 4 of synthesis example 3, except that compound 6 was used instead of compound 4 in the synthesis of material 4 of synthesis example 3.

¹ H NMR (300MHz, CDCl ₃ , δ): 7.95-6.75 (50H, m) (4H, dd) 3.89 (4H, t) 1.74 (4H, q) 1.28 (20H, m) 0.88 (6H, m)

Evaluation example  : Evaluation of Optical Properties of Materials

The luminescence properties of each compound were evaluated by evaluating the PL (photoluminescence) spectra of the material in the solution phase and the film phase.

To evaluate the optical properties of the solution phase, the material was diluted in toluene at a concentration of 10 mM and photoluminecscence (PL) spectra were measured using an ISC PC1 Spectrofluorometer equipped with a Xenon lamp. In addition, in order to evaluate the optical properties on the film, a quartz substrate was prepared and washed with acetone and pure water. Thereafter, the material was spin-coated on the substrate, and then heat-treated at a temperature of 110 ° C. for 30 minutes to form a film having a thickness of 1000 μs. PL spectra were measured for the film. The results are shown in Table 1 below. Thus, it can be seen that the material according to the present invention has a luminescent property suitable for application to the organic electroluminescent device.

material Solution (λ _max ) (nm) Film (λ _max ) (nm) 3 390 397 4 420 445 8 395 398 9 420 450

Example 1

[Formula 47]

(48)

(49)

Using the material 1 as a hole transport layer, the formula 47 as a hole injection layer, and the compounds of formula 48 and 49 as a host and a dopant of the light emitting layer, respectively, an organic light emitting device having the following structure was manufactured: ITO / Chemical Formula 47 (200 Hz) / Material 1 (300 Hz) / Chemical Formula 48: Chemical Formula 49 (300 Hz) / Alq3 (40 Hz) / LiF (10 Hz) / Al (2000 Hz).

The anode was cut into 50 mm x 50 mm x 0.7 mm sized 15 Ω / cm ² (1000 Å) ITO glass substrate, sonicated for 15 minutes in acetone isopropyl alcohol and pure water, followed by UV ozone cleaning for 30 minutes. Formula 47 (hole injection layer) and material 1 (hole transport layer) were vacuum deposited on the substrate, and Formula 48 and Formula 49 were vacuum deposited at a weight ratio of 100: 5 to form a light emitting layer. Thereafter, an Alq3 compound was vacuum deposited on the light emitting layer to a thickness of 40 Å to form an electron transporting layer. LiF 10 Å (electron injection layer) and Al 2000 Å (cathode) were sequentially vacuum-deposited on the electron transport layer to form an organic light emitting device as shown in FIG. 1A. In this device, blue light emission of 14,000 cd / m ² was obtained at a voltage of 6.0 V, and the efficiency was 5.45 cd / A.

Example 2

(50)

Using the material 3 as a host of the light emitting layer and using the compound of Formula 50 as a dopant of the light emitting layer, an organic light emitting device having the following structure was manufactured: ITO / Formula 47 (200kV) / α-NPD ) / Material 3: Chemical formula 50 (300 kPa) / Alq3 (40 kPa) / LiF (10 kPa) / Al (2000 kPa).

The light emitting layer was formed by vacuum depositing Chemical Formula 47 (hole injection layer) and α-NPD (hole transport layer) on the substrate, and vacuum depositing Material 3 and RD15 (Formula 50) at a weight ratio of 100: 10. . Thereafter, an Alq3 compound was vacuum deposited on the light emitting layer to a thickness of 40 Å to form an electron transporting layer. LiF 10 Å (electron injection layer) and Al 2000 Å (cathode) were sequentially vacuum-deposited on the electron transport layer to form an organic light emitting device as shown in FIG. 1A. In this device, red light emission of 1200 cd / m ² was obtained at a voltage of 10 V, the efficiency was 4.32 cd / A, and voltage-efficiency characteristics are shown in FIG. 2A.

Example 3

In the same manner as in Example 1, except that α-NPD was used as the hole transport layer and the compound of Material 4 was used as the dopant of the light emitting layer in Example 1: ITO / Formula 47 (200 ′) / α-NPD An organic light emitting device having a structure of (300 Hz) / Chemical Formula 48: Material 4 (300 Hz) / Alq3 (40 Hz) / LiF (10 Hz) / Al (2000 Hz) was manufactured. In this device, blue light emission of 4600 cd / m ² was obtained at a voltage of 8V, and the efficiency was 5.4 cd / A.

Example 4

In Example 2, the same method as in Example 2, except that the compound of Material 5 was used instead of the Material 3 as the host of the light emitting layer: ITO / Formula 47 (200 Å) / α-NPD (300 Å) / Material 5: An organic light emitting device was manufactured having a structure of Formula 50 (300 mV) / Alq 3 (40 mV) / LiF (10 mV) / Al (2000 mV). In this device, red light emission of 6500 cd / m ² was obtained at a voltage of 10 V, and the efficiency was 7.48 cd / A.

Example 5

In the same manner as in Example 1, except that Material 6 was used as the hole transport layer in Example 1: ITO / Formula 47 (200 ′) / Material 6 (300 ′) / Formula 48: Formula 49 (300 ′) / Alq3 An organic light emitting device having a structure of (40 Hz) / LiF (10 Hz) / Al (2000 Hz) was manufactured. In this device, blue light emission of 15,800 cd / m ² was obtained at a voltage of 6.5 V, and the efficiency was 7.66 cd / A.

Example 6

In Example 1, except that Material 7 was used as the hole injection layer and α-NPD was used as the hole transport layer, the same method as in Example 1 was used: ITO / Material 7 (200 Hz) / α-NPD (300 Hz) / Formula 48: An organic light emitting device having a structure of Formula 49 (300 ms) / Alq3 (40 ms) / LiF (10 ms) / Al (2000 ms) was prepared. In this device, blue light emission of 15,000 cd / m ² was obtained at a voltage of 6.0 V, and the efficiency was 6.48 cd / A.

Example 7

Using the material 8 as the host of the light emitting layer and using the compound of Formula 50 as the dopant of the light emitting layer, an organic light emitting device having the following structure was manufactured: ITO / PEDOT (400 kV) / material 8: (300 Hz) / Alq3 (40 Hz) / LiF (10 Hz) / Al (2000 Hz).

The anode was cut into 15 mm / cm ² (1000 mmW) ITO glass substrates of 50 mm × 50 mm × 0.7 mm size, ultrasonically cleaned for 15 minutes in acetone isopropyl alcohol and pure water, followed by UV ozone cleaning for 30 minutes. Bayer's PEDOT-PSS (AI4083) was coated on the substrate and heat-treated at 110 ° C. for 5 minutes in air and at 200 ° C. for 5 minutes in a nitrogen atmosphere to form a hole injection layer of 400 μs. On top of the hole injection layer, spin-coated a mixture of 0.1 g of host material 8 and 0.01 g of a compound of dopant formula 50 (the compound of formula 50 is 10 parts by weight per 100 parts by weight of material 8), followed by 100 ° C After heat treatment for 30 minutes to form a light emitting layer of 300 Å thickness. Thereafter, an Alq3 compound was vacuum deposited on the light emitting layer to a thickness of 40 Å to form an electron transporting layer. LiF 10kV (electron injection layer) and Al 2000kV (cathode) were sequentially vacuum deposited on the electron transport layer to prepare an organic light emitting device as shown in FIG. In this device, red light emission of 1500 cd / m ² was obtained at a voltage of 9 V, the efficiency was 4.1 cd / A, and voltage-efficiency characteristics are shown in FIG. 2B.

Example 8

In Example 7, ITO / PEDOT (400 ′) / Form 48: Material 9 was used in the same manner as in Example 7, except that Chemical Formula 48 was used as the host of the light emitting layer and Material 9 was used as the dopant of the light emitting layer. An organic light emitting device having a structure of 300 Hz) / Alq 3 (40 Hz) / LiF (10 Hz) / Al (2000 Hz) was manufactured. In this device, blue light emission of 3700 cd / m ² was obtained at a voltage of 6 V, and the efficiency was 4.2 cd / A.

From the above examples, it was found that the material of the present invention has excellent EL light emission characteristics as phosphorescent and fluorescent materials.

The compound represented by Formula 1 according to the present invention is capable of dry and wet processing and has excellent luminescence properties and thermal stability. Therefore, by using the compound according to the present invention it is possible to obtain an organic EL device having a low driving voltage, excellent color purity and efficiency.

Claims (7)

Compounds, characterized in that any one of the compounds of formulas (6) to (8): [Chemical Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 6 to 8 Y is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group; Q is a substituted or unsubstituted C 2 to C 30 alkylene group, a substituted or unsubstituted C 6 to C 30 cycloalkylene group, a substituted or unsubstituted C 6 to C 30 arylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group, substituted or unsubstituted C 2 to C 30 alkenylene group, Q and Y are the same or different from each other; m is an integer from 0 to 5; n is an integer from 0 to 5; when m and n are integers of 2 or more, each Q and Y may be different; R ₁ ^{`and</sup> R <sup><sub>2`</sub>} which may be the same or different and each is hydrogen, halogen, a cyano group, a hydroxyl group, a substituted or unsubstituted C cycloalkyl group of 1 ~ C 20 alkyl group, a substituted or unsubstituted C 3 ~ C 20 ring , Substituted or unsubstituted C 5 -C 30 heterocycloalkyl group, substituted or unsubstituted C 1 ~ C 20 alkoxy group, substituted or unsubstituted C 6 ~ C 30 aryl group, substituted or unsubstituted C 6 A C 30 to C 30 aralkyl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group; Z ₁ to Z ₄ are the same or different and each substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 5 to C 30 heterocyclo Alkyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted C 2 to C 30 heteroaryl group, substituted or unsubstituted C 6 ~ C 30 Aralkyl group, substituted or unsubstituted C 2 ~ C 30 Allylaryl group, substituted or unsubstituted C 1 ~ C 20 Alkylene group, substituted or unsubstituted C 6 ~ C 30 Aryl A ethylene group, a substituted or unsubstituted C 2 to C 30 heteroarylene group; X is a single bond, -CH = CH-, -O-, -S-, -Se-, -C (R'R ")-, wherein R 'and R" are the same as R ₃ , or-( CH ₂ ) _p − and p is an integer from 1 to 10; o is 0 or 1; R ₁₀ independently or identically to each other is hydrogen, halogen, cyano group, hydroxyl group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 3 to C 20 cycloalkyl group, substituted or unsubstituted A substituted C 5 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 6 to C 30 Aralkyl group, a substituted or unsubstituted C 2 ~ C 30 heteroaryl group, -N (G ₁ ) (G ₂ ) or -Si (G ₃ ) (G ₄ ) (G ₅ ), the G ₁ , G ₂ , G ₃ , G ₄ and G ₅ are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to A C 30 heteroaryl group, a substituted or unsubstituted C 5 to C 20 cycloalkyl group, or a substituted or unsubstituted C 5 to C 30 heterocycloalkyl group, The substituted C2 to C30 alkylene group, substituted C6 to C30 cycloalkylene group, substituted C 6 to C 30 arylene group, substituted C2 to C30 heteroarylene group, substituted C2 to C30 alkenylene group , Substituted C 1 to C 20 alkyl group, substituted C 3 to C 20 cycloalkyl group, substituted C 5 -C 30 heterocycloalkyl group, substituted C 1 to C 20 alkoxy group, substituted C 6 to C 30 aryl group, substitution At least one substituent of the C6 to C30 aralkyl group and the substituted C 2 to C 30 heteroaryl group is -F; -Cl; -Br; -CN; -NO ₂ ; -OH; A C 1 -C 20 alkyl group substituted by unsubstituted or -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C 1 -C 20 alkoxy group unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C 6 -C 30 aryl group substituted with an unsubstituted or C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C 2 -C 30 heteroaryl group unsubstituted or substituted by a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; Unsubstituted or C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or a C 5 ~ C 20 cycloalkyl group substituted with -OH; Unsubstituted or C 1 ~ C 20 alkyl group, C 1 ~ 20 alkoxy group, a C 5 ~ C 30 substituted with -F, -Cl, -Br, -CN, -NO 2 or -OH heterocycloalkyl alkyl, and -N ( G ₆ ) (G ₇ ), G ₆ and G ₇ are the same or different and each is hydrogen; A C 1 -C 10 alkyl group; Or a C 6 -C 30 aryl group substituted with a C 1 -C 10 alkyl group. The compound of claim 1, wherein any one of the compounds of Formula 6 to Formula 8 is any one of the compounds of Formula: [Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

 [Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

[Formula 37]

(38)

[Chemical Formula 39]

[Formula 40] (41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

A first electrode; A second electrode; And An organic electroluminescent device comprising at least one organic film between the first electrode and the second electrode, wherein the organic film comprises the compound of any one of claims 1 and 2. device. The organic electroluminescent device according to claim 3, wherein the organic film is a light emitting layer, a hole injection layer, or a hole transport layer. The method of claim 3, further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer between the first electrode and the second electrode. An organic electroluminescent device characterized by. delete delete

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