KR101072812B1 - Chemiclal having an asymmetric structure which froms the ring by combining carbazole and fluorine and organic electroric element using the same, terminal thererof - Google Patents

Abstract

The present invention provides a compound having an asymmetric structure in which carbazole and fluorene are bonded to form a ring, an organic electronic device using the same, and a terminal thereof.

Organic electronic devices, carbazole, fluorene

Description

FIELD OF THE INVENTION A compound having an asymmetric structure in which carbazole and fluorene bond to form a ring, and an organic electronic device using the same, and a terminal thereof THEREROF}

The present invention relates to a compound having an asymmetric structure in which carbazole and fluorene are bonded to form a ring, an organic electronic device using the same, and a terminal thereof.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electronic device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic electronic device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

Materials used as the organic material layer in the organic electronic device may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. The principle is that when a small amount of dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high-efficiency light. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to fully exhibit the excellent characteristics of the organic electronic device described above, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electronic device has not been sufficiently achieved, and therefore, the development of a new material is still required.

The inventors have found a derivative having an asymmetric structure in which carbazole and fluorene are bonded to form a ring to have a novel structure, and when the compound is applied to an organic electronic device, the luminous efficiency, stability and lifetime of the device are greatly improved. It turns out that you can.

Accordingly, an object of the present invention is to provide a compound having an asymmetric structure in which a novel carbazole and fluorene are bonded to form a ring, an organic electronic device using the same, and a terminal thereof.

In one aspect, the present invention provides a compound of the formula

At this time, the compound according to an embodiment of the present invention has an asymmetric structure necessarily around A. On the other hand, when A is a single bond, it has an asymmetrical structure around this single bond.

The compound applied to the organic electronic device may be used as one or more of a hole injection material and a hole transport material suitable for phosphorescent devices of all colors, such as red, green, blue, and white, depending on the synthesized compound. Compounds applied to organic electronic devices can be used as phosphorescent dopants and host materials of various colors.

Compounds having an asymmetric structure in which carbazole and fluorene are bonded to form a ring of the present invention may play various roles in organic electronic devices and terminals, and when applied to organic electronic devices and terminals, high efficiency, low voltage, high brightness, Long life can be expected.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

The present invention provides a compound of Formula 1 below.

In the above formula,

(1) A means a single bond, independently of, or a substituted or unsubstituted C _{2 -50} alkenyl group, a substituted or unsubstituted C _{6 -50} aryl group, a substituted or unsubstituted C _{4 -60} ring of the ring of the aryl group , S, N, O, substituted or unsubstituted alkenyl group of _{2 -50} C containing at least one heteroatom of P and Si, S, N, O, containing at least one heteroatom of P and Si substitution of C _{2 -50} or unsubstituted arylene group, S, N, O, P, and it can be one selected from the group consisting of an Si group substituted or unsubstituted aryl group of C _{4 -60} containing at least one heteroatom have.

(2) R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, an alkylthiol group, an arylthiol group, a substituted or unsubstituted C _1-50 alkyl group, a substituted or _{Unsubstituted} C _1-50 alkoxy group, substituted or unsubstituted C _2-50 alkenyl group, substituted or unsubstituted C _6-50 arylene group, substituted or unsubstituted C _4-60 aryl group, substituted or unsubstituted C _4-60 aryloxy group, S, N, O, optionally substituted containing at least one heteroatom of P and Si or unsubstituted alkyl group of C _{1 -50,} S, N, O, alkoxy group substituted with at least contains one or more hetero atoms of P and Si or unsubstituted _{C 1 -50, S, N,} O, optionally substituted C _{2 -50} of including at least one or more hetero atoms of P and Si or unsubstituted alkenyl group, S, N, O, P, and Si of at least a substituted or unsubstituted C _{2 -50} ring containing one or more heteroatoms arylene group, S, N, Substituted or unsubstituted C _{4 -60} aryl group containing at least one hetero atom of O, P and Si Substituted or unsubstituted containing at least one hetero atom of S, N, O, P and Si It may be one selected from the group consisting of a substituted or unsubstituted amino group represented by C _{4 -60} aryloxy group, -N (Ar ₅ ) ₂ or -N (Ar ₅ ) (Ar ₆ ).

(3) Ar ₁ , Ar ₂ , Ar ₃ are the same as or different from each other, each independently represent a substituted or unsubstituted C _6-50 arylene group, a substituted or unsubstituted C _4-60 aryl group, a substituted or unsubstituted hwandoen aryloxy group _{C 4-60, S, N, O} , P , and Si of at least a substituted or non-substituted C _{2 -50} ring containing one or more heteroatoms arylene group, S, N, O, P and an aryl group, a substituted or unsubstituted C _{4 -60} containing at least one heteroatom of Si, S, N, O, substituted or unsubstituted C including at least one or more hetero atoms of P and Si _{4 -60} It may be one selected from the group consisting of an aryloxy group, Ar ₁ , Ar ₂ may be bonded to each other to form a ring.

₍₄₎ Ar 4 are independently hydrogen or a substituted or unsubstituted C _{6 -50} aryl group, an aryloxy group of a substituted or unsubstituted C _{4 -60} aryl group, a substituted or unsubstituted C _{4 -60} ring of the ring, S, N, O, substituted for at least one of P and a substituted or unsubstituted of C _{2 -50} ring containing at least one or more hetero atoms in the arylene group, Si, S, N, O, P, and Si include one or more heteroatoms or unsubstituted C _{4 -60} aryl group, S, N, O, an aryloxy group of a C _4-60 substituted or unsubstituted including at least one or more hetero atoms of P and Si, -N (Ar _{5) It} may be one selected from the group consisting of a substituted or unsubstituted amino group represented by ₂ or -N (Ar ₅ ) (Ar ₆ ).

(5) n is an integer of 0 to 5, Ar ₅ and Ar ₆ may be the same as or different from Ar ₁ to Ar ₃ .

In addition, the compound having the above structural formula can be used in a soluble process. Since the solution process can be carried out at low temperature, the thin film can be easily formed on the plastic substrate, and the process cost can be reduced by minimizing the use of vacuum equipment, and the large area process is possible.

As a result, the compound according to the embodiment has an asymmetric structure in which carbazole and fluorene are bonded to form a ring.

On the other hand, the term "aryl group" used in the examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, naphthasenyl group, pyrenyl group and chrysenyl group, fluorenyl group and the like, preferred aryl groups It may be a phenyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group and pyrenyl group and the like, but is not limited thereto.

In addition, the term "aromatic heterocyclic group containing a hetero atom" used in the examples is pyrrolyl group, pyrazinyl group, pyridinyl group, indolyl group, isoindolyl group, furyl group, benzofuranyl group, isobenzofuranyl group, quinolyl Group, isoquinolyl group, quinoxalineyl group, carbazolyl group, phenanthrizine group, acridinyl group, phenanthrolineyl group, phenazine group, phenoxyazine group, phenoxazineyl group, oxazolyl group, oxadiazolyl The group, furazanyl group, cyenyl group etc. are mentioned. Preferred aromatic heterocyclic groups are pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group , 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindoleyl group, 2-isoindoleyl group, 3-isoindoleyl group, 4-isoindoleyl group, 5 -Isoindoleyl group, 6-isoindoleyl group, 7-isoindoleyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5 -Benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuran Diary, 7-isobenzofuranyl, quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1 Isoquinolyl group, 3-isoquinolyl group, 4-isoquinol group, 5-isoquinolyl group , 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl Group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenantrizinyl group 2-phenanthrylzinyl group, 3-phenanthrylzinyl group, 4-í-nantrizinyl group, 6-phenanyl Trizine diary, 7-phenanthrizine diary, 8-phenanthrizine diary, 9-phenanthrizine diary, 10-phenanthrizine diary, 1-acridinyl group, 2-acridinyl group, 3-acryl Dinyl, 4-acridinyl, 9-acridinyl, 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4 -Diary, 1,7-phenanthroline-5-diary, 1,7-phenanthroline-6-diary, 1,7-phenanthroline-8-diary, 1,7-phenanthroline-9-diary , 1,7-phenanthroline-10- diary, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4-yl, 1 , 8-phenanthroline-5-diary, 1,8-phenanthroline-6-diary, 1,8-phenanthroline-7-diary, 1,8- Phenanthroline-9-diary, 1,8-phenanthroline-10-diary, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthrole Lin-4-yl, 1,9-phenanthroline-5-diary, 1,9-phenanthroline-6-diary, 1,9-phenanthroline-7-diary, 1,9-phenanthroline- 8-diary, 1,9-phenanthroline-10-diary, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4- Diary, 1,10-phenanthroline-5-diary, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4-yl, 2,9-phenanthroline-5-diary, 2,9-phenanthroline-6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthroline-8-diary, 2, 9-phenanthroline-10- diary, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2,8- Phenanthroline-5-diary, 2,8-phenanthroline-6-diary, 2,8-phenanthroline-7-diary, 2,8-phenanthroline-9-diary, 2,8-phenanthrole Lin-10-di, 2,7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7- Nantrolin-5-diary, 2,7-phenanthroline-6-diary, 2,7-phenanthroline-8-diary, 2,7-phenanthroline-9-diary, 2,7-phenanthrole Rin-10- diary, 1-phenazine diary, 2-phenazine diary, 1-phenothiazin diary, 2-phenothiazin diary, 3-phenothiazin diary, 4-phenothiazin diary, 10-phenosai Azinyl group, 1-phenoxazine group, 2-phenoxazine group, 3-phenoxazine group, 4-phenoxazine group, 10-phenoxazine group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group , 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group, 2-methylpyrrole-3-yl group , 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole-4-yl group, 3-methylpyrrole -5-yl group, 2-t-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2- Methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl1-indolyl group, 4-t- Butyl-indolyl group, 2-t-butyl3-indolyl group and 4-t-butyl3-indolyl group.

Further, the terms used in the embodiment examples of the "substituted or unsubstituted C _{1 -50} alkyl group", methyl group, ethyl group, propyl group, isopropyl group, n- views group, a s- views group, isobutoxy group, a t- Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2- Dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2 -Chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl Group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo- t-butyl group, 1, 2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoiso Propyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1, 2-diaminoethyl group, 1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2 -Cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2, 3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 2-nitroisobutyl group, 1,2-dinitroethyl group, 1,3-dinitroisopropyl Flag, 2,3-dyna Low-t-butyl group, 1,2,3-trinitropropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 1-adamantyl group, 2- Adamantyl, 1-norbornyl, 2-norbornyl, and the like, but are not limited thereto.

Further, in terms that are used in for example, "alkoxy group of a substituted or unsubstituted C _{1 -50"} may be represented by -OR, and examples of R, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n- view group , s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group , 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxy Roxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t -Butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3- Dibromoai Propyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1- Aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl group, 2,3-diamino-t-butyl group, 1,2,3 -Triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3- dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 2-nitroisobutyl group, 1 , 2-diethyl ethyl, 1,3-di Bytes, isopropyl group, 2,3-nitro -t- view or the like, but a group profile group, and 1,2,3-tri-nitro not limited to this.

In addition, the term "substituted or unsubstituted aryloxy group of C _{4 -60} " used in the examples may be represented by -OY ', and as examples of Y', a phenyl group, 1-naphthyl group, 2-naphthyl group, 1 -Anthryl group, 2-Anthryl group, 9-Anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphtha Senyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p- Terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2- Diary, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4'-methylbiphenylyl group, 4 "-t-butyl-p-terphenyl-4-yl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridine Diary, 3-pyridinyl, 4-pyridinyl, 2-indolyl , 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindoleyl group, 3-isoindolyl group, 4-isoindolinyl group, 5-iso Soindolyl group, 6-isoindoleyl group, 7-isoindoleyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuran Diary, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7 Isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1- Isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinoline, 2-quinoxaline Diary, 5-quinoxalineyl, 6-quinoxalineyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazole Group, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group , 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,7-phenanthroline-5-diary, 1, 7-phenanthroline-6-diary, 1,7-phenanthroline-8-diary, 1,7-phenanthroline-9-diary, 1,7-phenanthroline-10-diary, 1,8- Phenanthroline-2-yl, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4-yl, 1,8-phenanthroline-5-diary, 1,8-phenanthrole Lin-6-diary, 1,8-phenanthroline-7-diary, 1,8-phenanthroline-9-diary, 1,8-phenanthroline-10-diary, 1,9-phenanthroline- 2-diary, 1,9-phenanthroline-3-yl,

1,9-phenanthroline-4-yl, 1,9-phenanthroline-5-diary, 1,9-phenanthroline-6-diary, 1,9-phenanthroline-7-diary, 1, 9-phenanthroline-8-diary, 1,9-phenanthroline-10-diary, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10- Phenanthroline-4-yl, 1,10-phenanthroline-5-yl, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthrole Lin-4-yl, 2,9-phenanthroline-5-diary, 2,9-phenanthroline-6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthroline- 8-diary, 2,9-phenanthroline-10-diary, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4- Diary, 2,8-phenanthroline-5-diary, 2,8-phenanthroline-6-diary, 2,8-

Phenanthroline-7-diary, 2,8-phenanthroline-9-diary, 2,8-phenanthroline-10-diary, 2,7-phenanthroline-1-diary, 2,7-phenanthrole Lin-3-yl, 2,7-phenanthroline-4-yl, 2,7-phenanthroline-5-diary, 2,7-phenanthroline-6-diary, 2,7-phenanthroline- 8-diary, 2,7-phenanthroline-9-diary, 2,7-phenanthroline-10-diary, 1-phenazineyl group, 2-phenazineyl group, 1-phenothiazinyl group, 2-pheno Thiazin diary, 3-phenothiazin diary, 4-phenothiazin diary, 1-phenoxazine diary, 2-phenoxazine diary, 3-phenoxazine diary, 4-phenoxazine diary, 2-oxazolyl group, 4- Oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group , 2-methylpyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole -4-yl group, 3-methylpyrrole-5-yl group, 2-t-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group , 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl1-indolyl group, 4-t -Butyl 1-indolyl group, 2-t- butyl 3- indolyl group, 4-t- butyl 3- indolyl group and the like, but is not limited thereto.

In addition, the term "alkylthio" used in the examples may be represented by -SR, and R is as defined above.

In addition, "arylthio group" used in the embodiment may be represented by-SY ', Y' is as defined above.

In addition, the "substituted or unsubstituted amino group represented by -N (Ar ₅ ) ₂ or -N (Ar ₅ ) (Ar ₆ )" used in the examples is as defined above with Ar ₁ to Ar ₃ . .

In addition, the term "halogen atom" used in the examples may be, but is not limited to, fluorine, chlorine, bromine and iodine.

As a specific example of the compound according to an embodiment of the present invention, there are compounds of the formula (2) belonging to the formula (1), but the present invention is not limited thereto.

As a specific example of the compound according to an embodiment of the present invention, there are compounds of the formula (3) belonging to the formula (1), but the present invention is not limited thereto.

As a specific example of a compound according to an embodiment of the present invention, there are compounds of the formula (4) belonging to the formula (1), but the present invention is not limited thereto.

Various organic electronic devices exist in which the compounds described with reference to Chemical Formulas 1 to 4 are used as the organic material layer. Examples of the organic electronic device in which the compounds described with reference to Chemical Formulas 1 to 4 may be used include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), and a photodiode. Organic semiconductor materials such as photodiode, organic laser, and laser diode may be used.

As an example, among the organic electronic devices to which the compounds described with reference to Chemical Formulas 1 to 4 may be applied, the organic light emitting diode (OLED) will be described below. The present invention is not limited thereto, and the compounds described above may be applied to various organic electronic devices. Can be.

Another embodiment of the present invention is an organic electronic device comprising a first electrode, a second electrode and an organic material layer disposed between these electrodes, at least one of the organic material layer of the organic electric field comprising the compounds of Formula 1 to 4 Provided is a light emitting device.

An organic light emitting display device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer to form the compound of Formula 1 to 4 to include It can be prepared in a structure known in the art using conventional manufacturing methods and materials in the art. The structure of the organic light emitting display device according to the present invention is illustrated in FIGS. 1 to 5, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer, 104 a hole transport layer, 105 a light emitting layer, 106 an electron injection layer, and 107 a cathode.

Compounds described with reference to Formulas 1 to 4 may be included in one or more of a hole injection layer and a hole transport layer. Specifically, the compounds described with reference to Formulas 1 to 4 may be used in place of one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer described below, or may be used by forming a layer with them. Of course, it is not only used in one layer of the organic material layer but may be used in two or more layers.

In particular, the compounds described with reference to Chemical Formulas 1 to 4 replace the existing materials or form the corresponding layers with one or more of the light emitting layers, for example, blue, green, and red light emitting layers (fluorescent materials), respectively. You may.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation It can be prepared by depositing an oxide or an alloy thereof to form an anode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. .

In addition to the above method, an organic electronic device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

The organic light emitting device according to another embodiment of the present invention may form an organic material layer, for example, a light emitting layer, by the soluble process of the compounds described above.

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene and silicon germanium oxide. Compounds, silicone arylamine compounds and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3) in order to increase blue light emission efficiency. A small amount of '[(1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H A small amount of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) is used. When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer. .

As described above, the compounds described with reference to Chemical Formulas 1 to 4 may replace the existing materials or form the corresponding layers with the existing materials in one or more of the light emitting layers, for example, the blue, green, and red light emitting layers, respectively. have.

As described above, the compounds described with reference to Chemical Formulas 1 to 4 may be used as one or more of a hole injection material and a hole transport material suitable for phosphorescent devices of all colors, such as red, green, blue, and white, depending on the synthesized compound. .

For example, the compounds described with reference to Formulas 1-4 may be used as phosphorescent dopant host materials of various colors.

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The cathode is positioned on the electron transport layer. This cathode serves to inject electrons into the electron transport layer. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

Meanwhile, the present invention includes a display device including the organic electronic device described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, various computers, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Production Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Hereinafter, the preparation or synthesis examples of the compounds belonging to the formulas (2) to (4). However, only one or two of the compounds belonging to Formulas 2 to 4 are described as examples because of the large number of compounds belonging to Formulas 2 to 4. Those skilled in the art, that is, those skilled in the art can prepare the compounds belonging to the present invention not illustrated through the preparation examples described below.

Preparation Example 1 Preparation of the Following Compound 12 of the Group of Formula 2

1. Synthesis of First Intermediates

In a 1000 mL two-necked round bottom flask, 1-iodo-2-nitrobenzene (102.74 mmol, 25.58 g), 2-bromophenylboronic acid (102.74 mmol, 20.63 g), tetrakistriphenylphosphine palladium (0) (3.08 mmol, 3.56 g), potassium cabonate Add (308.21 mmol, 42.60 g), add 300 mL of tetrahydrofuran (THF) and 100 mL of water as a solvent, and stir at 80 ° C. Lower the temperature of the reaction solution to room temperature and extract with dichloromethane. The obtained extract is dried over anhydrous magnesium sulfate and concentrated. The resulting mixture was separated by silica gel column chromatography to obtain 20.00 g of a first intermediate 2-bromo-2'-nitrobiphenyl as a white solid. (Yield: 70%)

¹ H-NMR (CDCl ₃ ) δ 8.00-8.05 (m, 2H), 7.90 (t, 1H), 7.66-7.68 (m, 3H), 7.45 (t, 1H), 7.30 (t, 1H)

2. Synthesis of Second Intermediate

2-bromo-2'-nitrobiphenyl (119.86 mmol, 33.33 g) and Triphenyl phosphine (287.67 mmol, 75.45 g) were added to a 500 mL two-necked round bottom flask filled with nitrogen. 100 mL of o -dichlorobezene was added thereto as a solvent and stirred at 180 ° C. After the reaction, o- dichlorobezene was simply distilled and the obtained mixture was recrystallized from chloroform to obtain 20.0 g of the title compound as a white solid. (Yield: 60%)

¹ H-NMR (CDCl ₃ ) δ 10.10 (s, 1H), 8.12 (d, 1H), 7.50-7.63 (m, 3H), 7.26-7.34 (m, 3H)

3. Synthesis of Third Intermediate

The second intermediate 4-bromo-9H-carbazole (67.19 mmol, 16.53 g) was added to a 500 mL two-necked round bottom flask filled with nitrogen. Add 300 mL of anhydrous Tetrahydrofuran (THF), dissolve, and slowly add n-Butyllithium in Hexane 2.5M (70.55 mmol, 28.22 mL) at -78 ° C. The temperature was allowed to stand at room temperature, followed by stirring for 30 minutes. The temperature was then set to -78 ° C, and 2-bromobenzoyl chloride (67.19 mmol, 14.74 g) was diluted in anhydrous Tetrahydrofuran (THF) and slowly added. The temperature is brought to room temperature and stirred. After completion of the reaction, the mixture is extracted with dichloromethane and the extract is dried over anhydrous magnesium sulfate and concentrated. The resulting mixture was separated by silica gel column chromatography to give 18.02 g of a third intermediate (2-bromophenyl) (9H-carbazol-3-yl) methanone as a yellow solid. (Yield: 77%)

¹ H-NMR (CDCl ₃ ) δ 10.10 (s, 1H), 8.74 (s, 1H) 8.12 (d, 1H), 7.98 (d, 1H), 7.50-7.73 (m, 7H), 7.29 (t, 1H )

4. Synthesis of the fourth intermediate

Into a 1000 mL two-necked round bottom flask, put the third intermediate (2-bromophenyl) (9H-carbazol-4-yl) methanone (85.66 mmol, 27.77 g) and Pd (OAc) 2 (0.86 mmol, 0.19 g) To fill. Add 500 mL of Dimethyformamide as a solvent, add P (o-tol) 3 (1.71 mmol, 0.52 g), and stir at 90 ° C. After the reaction, the reaction solution is cooled to room temperature and ethanol is added to filter the precipitate. The resulting mixture was separated by silica gel column chromatography (eluent-dichloromethane: n-hexane = 3: 7) to give 15.0 g of the fourth intermediate indeno [1,2-c] carbazol-12 (5H) -one as a white solid. To get. (Yield: 50%)

¹ H-NMR (CDCl ₃ ) δ 10.10 (s, 1H), 8.44-7.29 (m, 9H)

5. Synthesis of Fifth Intermediates

In a 500 mL two-necked round bottom flask, the fourth intermediate indeno [1,2-c] carbazol-12 (5H) -one (68.57 mmol, 18.47 g), bromobenzene (68.57 mmol, 10.77 g), Pd2 (dba) 3 (2.06 mmol, 1.88 g) and sodium tert-butoxide (205.72 mmol, 19.77 g) are added and charged with nitrogen. 250 mL of toluene was added thereto as a solvent, tritertbutylphosphine (6.86 mmol, 1.39 g) was added thereto, followed by stirring at 110 ° C. for 3 hours. Lower the temperature of the reaction solution to room temperature and extract with dichloromethane. The obtained extract is dried over anhydrous magnesium sulfate and fractional distillation to remove the solvent. The resulting mixture was separated by silica gel column chromatography (eluent-dichloromethane: n-hexane = 4: 6) to give the fifth intermediate 5-phenylindeno [1,2-c] carbazol-12 (5H) -one as a white solid. 18.0 g is obtained. (Yield: 76%)

¹ H-NMR (CDCl ₃ ) δ 8.55-7.25 (m, 15H)

6. Synthesis of Sixth Intermediate

The fifth intermediate 5-phenylindeno [1,2-c] carbazol-12 (5H) -one (60.28 mmol, 20.82 g) was added to a 500 mL two neck round bottom flask, and charged with nitrogen. Then, add 300 mL of anhydrous diethyl ether, dissolve it, and slowly add Methylmagnesium bromide 3M (63.03 mmol, 25.32 mL) at -78 ° C. Then, slowly bring the temperature to room temperature and stir. After the reaction is completed, the mixture is extracted with dichloromethane, and the extract is dried over anhydrous magnesium sulfate and concentrated. The resulting mixture was separated by silica gel column chromatography to give 19.0 g of a sixth intermediate 12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1,2-c] carbazole as a yellow solid. (Yield: 90%)

¹ H-NMR (CDCl ₃ ) δ 8.09-7.24 (m, 15H), 1.72 (s, 6H)

7. Synthesis of Intermediate

In a 500 mL two-necked round bottom flask, 6th intermediate 12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1,2-c] carbazole (47.26 mmol, 16.99 g) was added and N-bromosuccinimide (96.88 mmol). , 9.80 g), add 300 mL of dichloromethane and stir at room temperature. After the reaction, the mixture was diluted with dichloromethane and extracted. The extract was dried over anhydrous magnesium sulfate and concentrated. The resulting mixture was dissolved in dichloromethane, recrystallized from methanol, and filtered to obtain 22.0 g of 7th intermediate 2,10-dibromo-12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1,2-c] carbazole as a yellow solid. To get. (Yield: 90%)

¹ H-NMR (CDCl ₃ ) δ 7.98-7.25 (m, 13H), 1.72 (s, 6H)

8. Synthesis of 8th Intermediate

In a 500 mL two-necked round bottom flask, 7th intermediate 2,10-dibromo-12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1,2-c] carbazole (59.91 mmol, 30.99 g) was added thereto. Fill with nitrogen. Add 300 mL of anhydrous Tetrahydrofuran (THF), dissolve it, and slowly add n-Butyllithium in Hexane 2.5M (62.91 mmol, 25.16 mL) at -78 ° C. The temperature was allowed to stand at room temperature, followed by stirring for 30 minutes, and then the temperature was set at -78 ° C. Chlorotrimethylsilane (89.87 mmol, 9.76 g) was slowly added thereto. The temperature is brought to room temperature and stirred. After completion of the reaction, the mixture is extracted with dichloromethane and the extract is dried over anhydrous magnesium sulfate and concentrated. The obtained mixture was recrystallized to obtain 26.0 g of the eighth intermediate 10-bromo-12,12-dimethyl-5-phenyl-2- (trimethylsilyl) -5,12-dihydroindeno [1,2-c] carbazole. (Yield: 80%)

¹ H-NMR (CDCl ₃ ) δ 7.98-7.30 (m, 13H), 1.72 (S, 6H), 0.25 (S, 9H)

8. Synthesis of Compound 12

Intermediate 10-bromo-12,12-dimethyl-5-phenyl-2- (trimethylsilyl) -5,12-dihydroindeno [1,2-c] carbazole (38.43 mmol, 19.62 g) in a 1000 mL two-necked round bottom flask , dibiphenyl-4-ylamine (38.43 mmol, 12.35 g), Pd2 (dba) 3 (1.15 mmol, 1.06 g), sodium tert-butoxide (115.28 mmol, 11.08 g) were added and filled with nitrogen. To this was added 500 mL of toluene as a solvent, tritertbutylphosphine (3.84 mmol, 0.78 g) was added, followed by stirring at 90 ° C for 2 hours. Lower the temperature of the reaction solution to room temperature and stir 2 mL 100 mL of 2M-HCl and extract with dichloromethane. The obtained extract is dried over anhydrous magnesium sulfate and fractional distillation to remove the solvent. The resulting mixture was separated by silica gel column chromatography to give 24.0 g of compound 12. (Yield: 92%)

¹ H-NMR (CDCl ₃ ) δ 7.94-7.28 (m, 26H), 6.81-6.69 (m, 5H), 1.72 (s, 6H)

Preparation Example 2 Preparation of the Following Compound 15 belonging to the Group of Formula 3

1.Synthesis of Compound 15

In the process of synthesizing the compound of compound 15, the process of synthesizing the intermediate refers to compound 12 described above.

10-bromo-12,12-dimethyl-5-phenyl-2- (trimethylsilyl) -5,12-dihydroindeno [1,2-c] carbazole (62.23 mmol, 31.77 g), N in a 1000 mL two-necked round bottom flask -(biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine (62.23 mmol, 22.49 g), Pd2 (dba) 3 (1.87 mmol, 1.71 g), sodium tertbutoxide (186.68 mmol , 17.94 g) is charged with nitrogen. To this was added 500 mL of toluene as a solvent, tritertbutylphosphine (6.22 mmol, 1.26 g) was added, followed by stirring at 90 ° C. for 2 hours. Lower the temperature of the reaction solution to room temperature and stir 2 mL 100 mL of 2M-HCl and extract with dichloromethane. The obtained extract is dried over anhydrous magnesium sulfate and fractional distillation to remove the solvent. The resulting mixture was separated by silica gel column chromatography to give 34.0 g of a white solid as compound 15. (Yield: 76%)

¹ H-NMR (CDCl ₃ ) δ 7.94-7.28 (m, 19H), 6.58-6.75 (m, 5H), 1.72 (s, 12H)

Preparation Example 3 Preparation of the Following Compound 42 belonging to the Group of Formula 4

1. Synthesis of First Intermediates

In the synthesis of the intermediate of compound 42, part of the procedure for synthesizing the first intermediate refers to compound 12 described above.

10-bromo-12,12-dimethyl-5-phenyl-2- (trimethylsilyl) -5,12-dihydroindeno [1,2-c] carbazole (45.70 mmol, 23.33 g), N1 in a 1000 mL two-necked round bottom flask , N1, N4-triphenylbenzene-1,4-diamine (45.70 mmol, 15.37 g), Pd2 (dba) 3 (1.37 mmol, 1.26 g), sodium tert-butoxide (137.09 mmol, 13.18 g) were added and filled with nitrogen. . To this was added 500 mL of toluene as a solvent, tritertbutylphosphine (4.57 mmol, 0.92 g) was added, followed by stirring at 90 ° C. for 2 hours. Lower the temperature of the reaction solution to room temperature and stir 2 mL 100 mL of 2M-HCl and extract with dichloromethane. The obtained extract is dried over anhydrous magnesium sulfate and fractional distillation to remove the solvent. The resulting mixture was subjected to silica gel column chromatography to separate the first intermediate N1- (12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1,2-c] carbazol-10-yl) -N1, N4, N4- 26 g of triphenylbenzene-1,4-diamine is obtained as a white solid. (Yield: 82%)

¹ H-NMR (CDCl ₃ ) δ 8.55 (d, 1H), 7.84-7.20 (m, 17H), 6.81-6.38 (m, 13H), 1.72 (s, 6H)

2. Synthesis of Second Intermediate

The first intermediate N1- (12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1,2-c] carbazol-10-yl) -N1, N4, N4- in a 500 mL two-necked round bottom flask Add triphenylbenzene-1,4-diamine (37.57 mmol, 13.50 g), add N-bromosuccinimide (39.45 mmol, 3.99 g), add 300 mL of dichloromethane, and stir at room temperature. After the reaction, the mixture was diluted with dichloromethane and extracted. The extract was dried over anhydrous magnesium sulfate and concentrated. The obtained mixture was recrystallized and filtered to obtain the second intermediate N1- (2-bromo-12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1,2-c] carbazol-10-yl) -N1, N4, 27.0 g of N4-triphenylbenzene-1,4-diamine is obtained as a white solid. (Yield 93%)

¹ H-NMR (CDCl ₃ ) δ 7.84-7.20 (m, 17H), 6.81-6.38 (m, 13H), 1.72 (s, 6H)

3. Synthesis of Compound 42

In a 500 mL two-necked round bottom flask, the second intermediate N1- (2-bromo-12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1,2-c] carbazol-10-yl) -N1, N4, N4-triphenylbenzene-1,4-diamine (22.43 mmol, 17.34 g), diphenylamine (22.43 mmol, 3.8 g) Pd2 (dba) 3 (0.67 mmol, 0.62 g), sodium tertbutoxide (67.30 mmol, 6.47 g ) And fill with nitrogen. 250 mL of toluene was added thereto as a solvent, tritertbutylphosphine (2.24 mmol, 0.42 g) was added thereto, followed by stirring at 90 ° C for 2 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The obtained extract is dried over anhydrous magnesium sulfate and fractional distillation to remove the solvent. The resulting mixture was separated by silica gel column chromatography to give 17 g of compound 42 as a white solid. (Yield: 88%)

¹ H-NMR (CDCl ₃ ) δ 7.79-7.20 (m, 19H), 6.81-6.38 (m, 21H), 5.93 (d, 1H), 1.72 (s, 6H)

Preparation Example 4 Preparation of the Following Compound 43 belonging to the Group of Formula 4

1. Synthesis of First Intermediates

In the synthesis of the intermediate of the compound 43, the steps leading to the process for synthesizing the first intermediate, refer to the compound 12 described above.

10-bromo-12,12-dimethyl-5-phenyl-2- (trimethylsilyl) -5,12-dihydroindeno [1,2-c] carbazole (40.81 mmol, 20.84 g), N in a 1000 mL two-necked round bottom flask , 9-diphenyl-9H-carbazol-3-amine (40.81 mmol, 13.73 g), Pd2 (dba) 3 (1.22 mmol, 1.12 g), sodium tert-butoxide (122.43 mmol, 11.77 g) were added and charged with nitrogen. . To this was added 500 mL of toluene as a solvent, tritertbutylphosphine (4.08 mmol, 0.83 g) was added, followed by stirring at 90 ° C. for 2 hours. Lower the temperature of the reaction solution to room temperature and stir 2 mL 100 mL of 2M-HCl and extract with dichloromethane. The obtained extract is dried over anhydrous magnesium sulfate and fractional distillation to remove the solvent. The resulting mixture was subjected to silica gel column chromatography to separate the first intermediate 12,12-dimethyl-N, 5-diphenyl-N- (9-phenyl-9H-carbazol-3-yl) -5,12-dihydroindeno [1,2- c) 24 g of carbazol-10-amine as a white solid. (Yield: 85%)

¹ H-NMR (CDCl ₃ ) δ 8.55 (d, 1H), 7.84-7.20 (m, 17H), 6.81-6.38 (m, 11H), 1.72 (s, 6H)

2. Synthesis of Second Intermediate

In a 500 mL two-necked round bottom flask, the first intermediate 12,12-dimethyl-N, 5-diphenyl-N- (9-phenyl-9H-carbazol-3-yl) -5,12-dihydroindeno [1,2- c] carbazol-10-amine (30.05 mmol, 20.79 g) was added, N-bromosuccinimide (31.55 mmol, 3.19 g) was added, 300 mL of dichloromethane was added thereto, and the mixture was stirred at room temperature. After the reaction, the mixture was diluted with dichloromethane and extracted. The extract was dried over anhydrous magnesium sulfate and concentrated. The obtained mixture was recrystallized and filtered to obtain the second intermediate 2-bromo-12,12-dimethyl-N, 5-diphenyl-N- (9-phenyl-9H-carbazol-3-yl) -5,12-dihydroindeno [1,2]. 22.0 g of 2-c] carbazol-10-amine is obtained as a white solid. (Yield 95%)

¹ H-NMR (CDCl ₃ ) δ 7.84-7.20 (m, 17H), 6.81-6.38 (m, 11H), 1.72 (s, 6H)

3. Synthesis of Compound 43

In a 500 mL two-necked round bottom flask, the second intermediate 2-bromo-12,12-dimethyl-N, 5-diphenyl-N- (9-phenyl-9H-carbazol-3-yl) -5,12-dihydroindeno [ 1,2-c] carbazol-10-amine (17.71 mmol, 13.65 g), diphenylamine (17.71 mmol, 3.00 g) Pd2 (dba) 3 (0.53 mmol, 0.49 g), sodium tertbutoxide (53.14 mmol, 5.11 g ) And fill with nitrogen. 250 mL of toluene was added thereto as a solvent, tritertbutylphosphine (1.77 mmol, 0.36 g) was added thereto, followed by stirring at 90 ° C. for 2 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The obtained extract is dried over anhydrous magnesium sulfate and fractional distillation to remove the solvent. The resulting mixture was separated by silica gel column chromatography to yield 14 g of compound 43 as a white solid. (Yield: 92%)

¹ H-NMR (CDCl ₃ ) δ 7.79-7.20 (m, 19H), 6.81-6.38 (m, 19H), 5.93 (d, 1H), 1.72 (s, 6H)

Experimental Example

For comparison with compounds 42 and 43 of the present invention, the physical properties of organic light emitting diodes using 2-TNATA as the hole injection layer were measured and compared.

4,4 ', 4 ”-Tris [2-naphthyl (phenyl) amino] -triphenylamine (2-TNATA) was used as a hole injection layer material, and an organic light emitting diode was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer (hole transport layer material: NPB), and 450 Å thickness BD- on the ITO layer (anode) formed on the glass substrate. Light-emitting layer doped with 052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 전자 thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq3)), 10 Å thick electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode The deposition produced an organic light emitting display device.

The driving voltage, current density, efficiency, and color coordinates of the organic light emitting diode fabricated as described above were measured to be 6.95V, 14.31mA / cm ² , 5.21cd / A, and (0.145, 0.143), respectively.

Experimental Example 1 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 42 of the Present Invention as Hole Injection Layer)

Using the compound 42 as the hole injection layer material, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: Compound 70), a 300 Å hole transport layer (hole transport layer material: NPB), and 450 Å thickness BD-052X (on the ITO layer (anode) formed on the glass substrate Idemitsu Co., Ltd., 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 kHz thick Electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq3)), 10 Å thick electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode were sequentially deposited An organic electroluminescent device was manufactured.

The driving voltage, current density, luminous efficiency, and color coordinates of the organic light emitting display device manufactured by Experimental Example 1 were measured as 5.63 V, 13.77 mA / cm ² , 6.54 cd / A, and (0.146, 0.147), respectively.

Experimental Example 2 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 43 of the Present Invention as Hole Injection Layer)

An organic light emitting diode was manufactured according to a conventional method using compound 43 as a hole injection layer material.

First, a 600 Å hole injection layer (hole injection layer material: Compound 92), a 300 Å hole transport layer (hole transport layer material: NPB), 450 Å thickness BD-052X (on the ITO layer (anode) formed on the glass substrate Idemitsu Co., Ltd., 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 kHz thick Electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq3)), 10 Å thick electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode were sequentially deposited An organic electroluminescent device was manufactured.

The driving voltage, current density, luminous efficiency, and color coordinates of the organic light emitting display device manufactured by Experimental Example 2 were measured to be 6.12 V, 13.32 mA / cm ² , 6.28 cd / A, and (0.146, 0.148), respectively.

The physical properties of the organic light emitting device using 2-TNATA as the hole injection layer material and the organic light emitting device of Experimental Examples 1 and 2 are summarized in Table 1 below.

Hole injection layer material Voltage
(V) Currentdensity
(mA / cm ² ) E fficiency
(㏅ / A) CIE
(x, y) Control 1 2-TNATA 6.95 14.31 5.21 (0.145, 0.143) Experimental Example 1 Compound 42 5.63 13.77 6.54 (0.146,
0.147) Experimental Example 2 Compound 43 6.12 13.32 6.28 (0.146,
0.148)

As can be seen from Table 1, the organic light emitting diodes of Experimental Examples 1 and 2 exhibit substantially the same color coordinates as the organic electroluminescent device using 2-TNATA as the hole injection layer material, and have a driving voltage, a current density, It can be seen that the luminous efficiency is improved with a critical significance.

In addition, the physical properties of the organic electroluminescent device using NPB as the hole transport layer was measured for comparison with the compounds 12 and 15 of the present invention.

An organic light emitting diode was manufactured according to a conventional method using NPB (N, N'-Di-1-naphthyl-N, N'-diphenylbenzidine) as a hole transport material.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer (hole transport layer material: NPB), and 450 Å thickness BD- on the ITO layer (anode) formed on the glass substrate. Light-emitting layer doped with 052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 전자 thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), 10 Å thick electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode Evaporation was carried out to produce an organic light emitting display device.

The driving voltage, current density, efficiency, and color coordinates of the organic light emitting diode thus manufactured were measured as 6.73 V, 15.23 mA / cm ² , 5.32 cd / A, and (0.145, 0.147), respectively.

Experimental Example 3 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 12 of the Present Invention as Hole Transport Layer)

Using organic compound 12 as a hole transport material, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer (hole transport layer material: compound 2), and 450 Å thickness BD- are placed on the ITO layer (anode) formed on the glass substrate. Light-emitting layer doped with 052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 Å thickness electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq3)), 10 층 thickness electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode The deposition produced an organic light emitting display device.

The driving voltage, current density, luminous efficiency, and color coordinates of the organic light emitting display device manufactured by Experimental Example 3 were measured as 5.23 V, 14.76 mA / cm ² , 6.62 cd / A, and (0.144, 0.150), respectively.

Experimental Example 4 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 15 of the Present Invention as Hole Transport Layer)

Using the compound 15 as a hole transport material, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole hole transport layer (hole transport layer material: Compound 49), and a 450 Å BD on the ITO layer (anode) formed on the glass substrate. Light-emitting layer doped with 052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 Å thickness electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq3)), 10 층 thickness electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode The deposition produced an organic light emitting display device.

The driving voltage, current density, luminous efficiency, and color coordinates of the organic light emitting display device manufactured by Experimental Example 4 were measured to be 5.55V, 14.21mA / cm ² , 6.52cd / A, (0.144, 0.145), respectively.

The physical properties of the organic light emitting device using NPB as the hole transport layer material and the organic light emitting device of Experimental Examples 3 and 4 are summarized in Table 2 below.

Hole transport material Voltage
(V) Currentdensity
(mA / cm ² ) Efficiency
(㏅ / A) CIE
(x, y) Control 2 2-TNATA 6.73 15.23 5.32 (0.145,
0.147) Experimental Example 3 Compound 12 5.23 14.76 6.62 (0.144,
0.150) Experimental Example 4 Compound 15 5.55 14.21 6.52 (0.144,
0.145)

As can be seen from Table 2, the organic electroluminescent devices of Experimental Examples 3 and 4 exhibit substantially the same color coordinates as the organic electroluminescent device using 2-TNATA as the hole transport layer material, and have the driving voltage, the current density, and the light emission. It can be seen that the efficiency has improved with critical significance.

Based on the above results, the compounds of the present invention can be expected to have high efficiency, low voltage, high brightness, and long life, based on improvements in physical characteristics such as driving voltage, current density, and luminous efficiency when used in an organic light emitting device as a hole injection layer or a hole transport layer material. . On the other hand, even if the compounds of the present invention are used in other organic material layer of the organic light emitting device it is obvious that the same effect can be obtained.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

1 to 5 show examples of organic electronic devices to which the compounds of the present invention can be applied.

Claims (10)

Compound represented by the formula

In the above formula, (1) A is independently a single bond or an arylene group of C _6-10 , (2) R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group of C _1-6 , (3) Ar ₁ , Ar ₂ , Ar ₃ are the same as or different from each other, and each independently an aryl group of C _6-13 , or a C _6-18 aryl group including N, wherein Ar ₁ and Ar ₂ are Together with the N to which they are bound to form a ring, (4) Ar ₄ is independently selected from the group consisting of a hydrogen atom, a C ₆ -C ₁₈ aryl group, an amino group represented by -N (Ar ₅ ) ₂ or -N (Ar ₅ ) (Ar ₆ ), wherein Ar ₅ and Ar ₆ are each independently an aryl group of C _6-18 , (5) n is an integer of 0-5. delete The method of claim 1, The compound is,

,

,

Compounds, characterized in that one selected from the group consisting of. The method according to claim 1 or 3, Said compound being used in a soluble process. An organic electronic device comprising at least one organic material layer comprising a compound of claim 1. The method of claim 5, The organic electronic device is an organic electroluminescent device comprising a first electrode, the at least one organic material layer and the second electrode in a stacked form sequentially. The method of claim 6, The organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer and an electron injection layer, the compound is an organic electronic device, characterized in that included in at least one of the hole injection layer and the hole transport layer. The method of claim 7, wherein The compound is an organic electronic device, characterized in that used as a phosphorescent host material containing red, green, blue, white in the light emitting layer. The method of claim 7, wherein The compound is an organic electronic device, characterized in that to form the light emitting layer by a solution process (soluble process). A display device comprising the organic electronic device of claim 5; And a control unit for driving the display device.

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