KR102216402B1 - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound of Formula 1 and an organic light emitting device including the same.

Description

Heterocyclic compound and organic light-emitting device including the same TECHNICAL FIELD

The present invention claims the benefit of the filing date of Korean Patent Application No. 10-2018-0033703 filed with the Korean Intellectual Property Office on March 23, 2018, the entire contents of which are incorporated herein.

The present specification relates to a heterocyclic compound and an organic light emitting device including the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

Development of a new material for the organic light emitting device as described above is continuously required.

US Patent Application Publication No. 2004-0251816

The present specification provides a heterocyclic compound and an organic light emitting device including the same.

An exemplary embodiment of the present specification provides a heterocyclic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

Any one of G1 and G2 is -L2-Ar2, the rest are hydrogen,

L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

Ar1 and Ar2 are different from each other, and each electron donor (EDG); Or an electron aspirator (EWG),

R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl thioxy group; A substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent groups combine with each other to form a substituted or unsubstituted ring,

m and n are each an integer of 1 to 4,

When m is 2 or more, 2 or more R1s are the same as or different from each other,

When n is 2 or more, 2 or more R2s are the same as or different from each other.

In addition, another exemplary embodiment of the present specification is a first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the aforementioned heterocyclic compound.

According to an exemplary embodiment of the present specification, the heterocyclic compound represented by Formula 1 is both polarity having both n-type (electron withdrawing group (EWG)) and p-type (electron donating group (EDG)) substituents in one molecule ( Since it is an ambipolar) compound, an organic light-emitting device including the same has features of low voltage, high efficiency, and long life.

1 illustrates an organic light-emitting device 10 according to an exemplary embodiment of the present specification.
2 shows an organic light-emitting device 11 according to another exemplary embodiment of the present specification.

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

The present specification provides a heterocyclic compound represented by Chemical Formula 1.

Specifically, the spiro-type structure composed of only carbon may interfere with the movement of electrons between molecules due to steric hindrance and cause an increase in the driving voltage, but as in the exemplary embodiment of the present specification, a spiro-type structure including a heteroatom of a sulfur atom The structure can expect a low driving voltage. In addition, Formula 1 is an ambipolar compound having both n-type (electron withdrawing group (EWG)) and p-type (electron donating group (EDG)) substituents in one molecule, thus preventing electron transfer within and between molecules. An organic light-emitting device including it as an organic material layer by constant control exhibits low voltage, high efficiency, and long life.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be located "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

Examples of the substituents in the present specification are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Ester group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl thioxy group; A substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heteroaryl group substituted with one or two or more substituents selected from the group consisting of, or two or more of the substituents exemplified above are substituted with a connected substituent, or does not have any substituents. For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

Means a site bonded to another substituent or a bonding portion.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the nitrogen of the amide group may be substituted with hydrogen, a straight-chain, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto. It is not.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc., but It is not limited.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkylarylamine group; Arylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group, and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine group , Diphenylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-biphenylnaphthylamine group, N- Naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenanthrenylflu Orenylamine group, N-biphenylfluorenylamine group, and the like, but are not limited thereto.

In the present specification, the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group.

In the present specification, the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, examples of the alkylamine group include a substituted or unsubstituted monoalkylamine group, or a substituted or unsubstituted dialkylamine group. The alkyl group in the alkylamine group may be a linear or branched alkyl group. The alkylamine group containing two or more alkyl groups may include a straight-chain alkyl group, a branched-chain alkyl group, or a straight-chain alkyl group and a branched-chain alkyl group at the same time. For example, the alkyl group in the alkylamine group may be selected from the examples of the alkyl group described above.

In the present specification, the alkyl group in the N-alkylarylamine group, the alkylthioxy group, the alkylsulfoxy group, and the N-alkylheteroarylamine group is the same as the exemplary alkyl group described above. Specifically, the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group, and the alkyl sulfoxy group is a methyl sulfoxy group, an ethyl sulfoxy group, a propyl sulfoxy group, and butyl. There are sulfoxy groups, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group may be -BR ₁₀₀ R ₁₀₁ , the R ₁₀₀ and R ₁₀₁ are the same or different, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted C 1 to C 30 linear or branched alkyl group; A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

In the present specification, the phosphine oxide group specifically includes an alkylphosphine oxide group, an arylphosphine oxide group, and the like, and more specifically, a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, etc., but is limited thereto. It is not.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracene group, a phenanthryl group, a triphenylene group, a pyrene group, a phenalene group, a perylene group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may be bonded to each other to form a ring.

,

,

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

And

Etc. However, it is not limited thereto.

In the present specification, the "adjacent" group means a substituent substituted on an atom directly connected to the atom where the corresponding substituent is substituted, a substituent positioned three-dimensionally closest to the corresponding substituent, or another substituent substituted on the atom where the corresponding substituent is substituted. I can. For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups to each other.

In the present specification, the aryl group among the aryloxy group, arylthioxy group, arylsulfoxy group, N-arylalkylamine group, N-arylheteroarylamine group, and arylphosphine group is the same as the example of the aryl group described above. Specifically, the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, and 9-phenanthryloxy group, and the arylthioxy group includes a phenylthioxy group, 2- There are a methylphenyl thioxy group, a 4-tert-butylphenyl thioxy group, and the like, and the aryl sulfoxy group includes a benzene sulfoxy group and a p-toluene sulfoxy group, but is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, or a substituted or unsubstituted diarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group includes one or more atoms and heteroatoms other than carbon, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenane Tridin group, phenanthridine group (phenanthridine), phenanthroline group (phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, dibenzofuran group, and the like, but are not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, or a substituted or unsubstituted diheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as those of the aforementioned heteroaryl group.

In the present specification, an arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.

In the present specification, in a substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" is a substituted or unsubstituted hydrocarbon ring; Or it means a substituted or unsubstituted heterocycle.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic, or condensed ring of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or the aryl group, except for the non-monovalent one.

In the present specification, the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group except that it is not monovalent.

In the present specification, the heterocycle includes one or more atoms and heteroatoms other than carbon, and specifically, the heterocycle may include one or more atoms selected from the group consisting of O, N, Se, and S. The heterocycle may be monocyclic or polycyclic, and may be an aromatic, aliphatic, or condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group or heterocyclic group except that it is not monovalent.

In the present specification, an electron donative group (EDG) is a substituent having a negatively charged or unshared electron pair, and means donating an electron to a portion lacking a positive charge or an electron pair. In addition, the electron donor in the present specification is an electron with a large electron attractor due to the rich electron retention property of the molecule itself when light is received in a state mixed with an electron withdrawing group, even if it has a negative charge but does not have an unshared electron pair. Includes a substituent capable of delivering.

In the present specification, the electron withdrawing group (EWG) refers to all substituents that accept electrons from an electron donor.

According to an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 1-1 or 1-2.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

The definitions of L1, L2, Ar1, Ar2, R1, R2, m and n are the same as those defined in Chemical Formula 1.

According to an exemplary embodiment of the present specification, in Chemical Formula 1, R1 is hydrogen.

According to an exemplary embodiment of the present specification, in Formula 1, R2 is hydrogen.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Or an arylene group.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a phenylene group.

According to an exemplary embodiment of the present specification, L1 is a direct bond.

According to an exemplary embodiment of the present specification, L1 is a phenylene group.

According to an exemplary embodiment of the present specification, L2 is a direct bond.

According to an exemplary embodiment of the present specification, L2 is a phenylene group.

According to an exemplary embodiment of the present specification, Ar1 is an electron donor (EDG).

According to an exemplary embodiment of the present specification, Ar2 is an electron aspirator (EWG).

According to an exemplary embodiment of the present specification, Ar1 is an electron aspirator (EWG).

According to an exemplary embodiment of the present specification, Ar2 is an electron donor (EDG).

According to the exemplary embodiment of the present specification, Ar1 and Ar2 are different from each other, Ar1 is an electron donor (EDG), and Ar2 is an electron withdrawing group (EWG).

According to the exemplary embodiment of the present specification, Ar1 and Ar2 are different from each other, Ar1 is an electron withdrawing group (EWG), and Ar2 is an electron donating group (EDG).

According to an exemplary embodiment of the present specification, the electron donating group (EDG) is a substituted or unsubstituted indole group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted indolocarbazole group; A substituted or unsubstituted amine group; A substituted or unsubstituted hexahydropyridoquinoline group; And a substituted or unsubstituted silyl group.

According to an exemplary embodiment of the present specification, the electron donating group (EDG) is a carbazole group unsubstituted or substituted with an aryl group; An indolocarbazole group unsubstituted or substituted with an aryl group; Hexahydropyridoquinoline group; And a silyl group unsubstituted or substituted with an aryl group.

According to an exemplary embodiment of the present specification, the electron donor (EDG) is an indole; A carbazole group unsubstituted or substituted with a phenyl group; An indolocarbazole group unsubstituted or substituted with a phenyl group; Hexahydropyridoquinoline group; And triphenylsilyl group.

According to an exemplary embodiment of the present specification, the electron donor (EDG) is an indole; A carbazole group unsubstituted or substituted with a phenyl group; An indolocarbazole group substituted with a phenyl group; Hexahydropyridoquinoline group; And triphenylsilyl group.

According to an exemplary embodiment of the present specification, the electron donating group (EDG) is selected from groups represented by Formulas A-1 to A-8, but is not limited thereto.

[Formula A-1]

[Formula A-2]

[Formula A-3]

[Formula A-4]

[Formula A-5]

[Formula A-6]

[Formula A-7]

[Formula A-8]

In the formulas A-1 to A-8,

Q1 to Q14 and Q101 to Q103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl thioxy group; A substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

q1, q4 and q6 are each an integer of 1 to 6,

q2 is an integer from 1 to 8,

q3 is an integer from 1 to 7,

q5 and q7 are each an integer of 1 to 4,

q10 is 1 or 2,

q11 is an integer from 1 to 12,

q12 to q14 are each an integer of 1 to 5,

When each of q1 to q7 and q11 to q14 is 2 or more, the structures in the two or more parentheses are the same or different from each other,

When q10 is 2, Q10 of 2 is the same as or different from each other,

는 상기 화학식 1에 결합되는 부위이다.

Is a moiety bonded to Formula 1 above.

According to an exemplary embodiment of the present specification, the electron donor (EDG) is selected from groups represented by the following structure, but is not limited thereto.

In the above structure,

는 상기 화학식 1에 결합되는 부위이다.The definitions of Q8, Q9 and Q101 to Q103 are as described above,

Is a moiety bonded to Formula 1 above.

According to an exemplary embodiment of the present specification, the electron donor (EDG) is selected from groups represented by the following structure, but is not limited thereto.

In the above structure,

는 상기 화학식 1에 결합되는 부위이다.

Is a moiety bonded to Formula 1 above.

According to an exemplary embodiment of the present specification, the electron aspirator (EWG) is a cyano group; An aryl group substituted with one or more cyano groups; A substituted or unsubstituted N-containing monocyclic heteroaryl group; Including O or S, a substituted or unsubstituted tricyclic heteroaryl group; And two or more of N, O and S, and is selected from a substituted or unsubstituted tricyclic heteroaryl group.

According to an exemplary embodiment of the present specification, the electron aspirator (EWG) is a cyano group; An aryl group substituted with one or more cyano groups; N-containing monocyclic heteroaryl group unsubstituted or substituted with an aryl group; A tricyclic heteroaryl group including O or S and unsubstituted or substituted with a cyano group; And two or more of N, O and S, and is selected from a tricyclic heteroaryl group substituted or unsubstituted with a cyano group.

According to an exemplary embodiment of the present specification, the electron aspirator (EWG) is a cyano group; A phenyl group substituted with one or more cyano groups; A pyridine group substituted with an aryl group; A pyrimidine group substituted with an aryl group; A triazine group substituted with an aryl group; Dibenzofuran group unsubstituted or substituted with a cyano group; And a dibenzothiophene group unsubstituted or substituted with a cyano group.

According to an exemplary embodiment of the present specification, the electron aspirator (EWG) is a cyano group; A phenyl group substituted with one or more cyano groups; A pyridine group substituted with one or more substituents selected from a phenyl group and a biphenyl group; A pyrimidine group substituted with one or more substituents selected from a phenyl group and a biphenyl group; A triazine group substituted with one or more substituents selected from a phenyl group and a biphenyl group; Dibenzofuran group unsubstituted or substituted with a cyano group; And a dibenzothiophene group unsubstituted or substituted with a cyano group.

According to an exemplary embodiment of the present specification, the electron withdrawing group (EWG) is selected from groups represented by Formulas B-1 to B-4 below, but is not limited thereto.

[Formula B-1]

[Formula B-2]

[Formula B-3]

[Formula B-4]

In the formulas B-1 to B-4,

At least one of X1 to X3 is N, the rest are CH,

X4 is N or CT4, X5 is N or CT5, X6 is N or CT6, X7 is N or CT7,

Y1 is O or S,

T1 to T7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl thioxy group; A substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

q is an integer from 1 to 5,

t3 is an integer from 1 to 3,

When t3 is 2 or more, the two or more T3s are the same as or different from each other,

는 상기 화학식 1에 결합되는 부위이다.

Is a moiety bonded to Formula 1 above.

According to an exemplary embodiment of the present specification, the electron aspirator (EWG) is selected from groups represented by the following structure, but is not limited thereto.

In the above structure,

The definitions of q, T1, T2 and T4 to T7 are as described above,

는 상기 화학식 1에 결합되는 부위이다.

Is a moiety bonded to Formula 1 above.

According to an exemplary embodiment of the present specification, q is 1 or 2.

According to an exemplary embodiment of the present specification, T1 and T2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present specification, T1 and T2 are the same as or different from each other, and each independently an aryl group.

According to an exemplary embodiment of the present specification, T1 and T2 are the same as or different from each other, and each independently a phenyl group; Or a biphenyl group.

According to an exemplary embodiment of the present specification, T1 and T2 are phenyl groups.

According to an exemplary embodiment of the present specification, T1 is a phenyl group, and T2 is a biphenyl group.

According to an exemplary embodiment of the present specification, T1 is a biphenyl group, and T2 is a phenyl group.

According to an exemplary embodiment of the present specification, T1 and T2 are biphenyl groups.

According to an exemplary embodiment of the present specification, the T4 to T7 are the same as or different from each other, and each independently hydrogen; Or it is a cyano group.

According to an exemplary embodiment of the present specification, T4 to T7 are hydrogen.

According to an exemplary embodiment of the present specification, at least one of the T4 to T7 is a cyano group, and the other is hydrogen.

According to an exemplary embodiment of the present specification, the electron aspirator (EWG) is selected from groups represented by the following structure, but is not limited thereto.

According to an exemplary embodiment of the present specification, Formula 1 is selected from the following compounds.

The present specification provides an organic light-emitting device including the aforementioned heterocyclic compound.

According to an exemplary embodiment of the present specification, the first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a heterocyclic compound represented by Formula 1 above.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a hole control layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron controlling layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. have. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

For example, the structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.

1 illustrates a structure of an organic light emitting diode 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20. 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.

2 shows a first electrode 30, a hole injection layer 60, a hole transport layer 70, a light emitting layer 40, an electron transport layer 80, an electron injection layer 90, and a second electrode on the substrate 20. 50) is illustrated in the structure of the organic light-emitting device stacked in sequence. 2 is an exemplary structure according to the exemplary embodiment of the present specification, and may further include another organic material layer. The compound represented by Formula 1 may be included in the hole injection layer 60, the hole transport layer 70, the light emitting layer 40, the electron transport layer 80, and the electron injection layer 90, and preferably included in the light emitting layer. I can.

According to the exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes a heterocyclic compound represented by Formula 1 above.

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes a heterocyclic compound represented by Formula 1 as a host of the emission layer.

According to the exemplary embodiment of the present specification, the emission layer may include the heterocyclic compound represented by Formula 1 as a host of the emission layer, and may further include a dopant.

According to the exemplary embodiment of the present specification, the emission layer may include the heterocyclic compound represented by Chemical Formula 1 as a host of the emission layer, and may further include a delayed fluorescent material.

According to the exemplary embodiment of the present specification, the emission layer may use a metal complex such as an iridium-based dopant as a dopant.

According to the exemplary embodiment of the present specification, the emission layer may include a host and a dopant in a weight ratio of 99:1 to 30:70.

According to an exemplary embodiment of the present specification, the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, and the electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons is the It includes a heterocyclic compound represented by Formula 1.

According to an exemplary embodiment of the present specification, the organic material layer includes a hole blocking layer, and the hole blocking layer includes a heterocyclic compound represented by Formula 1 above.

According to an exemplary embodiment of the present specification, the organic material layer includes an electron controlling layer, and the electron controlling layer includes a heterocyclic compound represented by Formula 1 above.

According to an exemplary embodiment of the present specification, the organic material layer further includes a hole injection layer or a hole transport layer including a compound including an arylamino group, a carbazole group, or a benzocarbazole group in addition to the organic material layer including the heterocyclic compound represented by Formula 1 Include.

The organic light emitting device of the present specification is to be manufactured by materials and methods known in the art, except that at least one of the organic material layers contains the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by Formula 1 above. I can.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device of the present specification may be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or a conductive metal oxide or an alloy thereof is deposited on the substrate. It can be manufactured by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, an emission layer, and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. In addition, the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

According to an exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

According to another exemplary embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode 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); A combination of a metal and an oxide such as ZnO:Al or SnO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are a multilayered material such as LiF/Al or LiO ₂ /Al, and Mg/Ag, but are not limited thereto.

The hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer, and the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The electron blocking layer is a layer capable of improving the life and efficiency of the device by preventing holes injected from the hole injection layer from entering the electron injection layer through the emission layer. Using known materials, the emission layer and the electron injection layer It can be formed in an appropriate part between.

As the light-emitting material of the light-emitting layer, 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 for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzothiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or hetero ring-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted A compound in which at least one arylvinyl group is substituted on the arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The electron transport material of the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. The electron transport material is a material that can receive electrons from the cathode and transfer them to the emission layer. This large material is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or light emitting material, and injects holes of excitons generated from the light emitting layer. A compound that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

The hole blocking layer is a layer that prevents holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc., but are not limited thereto.

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

According to the exemplary embodiment of the present specification, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

<Typical Manufacturing Example>

The compound according to an exemplary embodiment of the present specification may be prepared by a manufacturing method described below.

For example, the compounds of Formulas 1-1 and 1-2 may be combined with a substituent from a core structure having a halogen element by a method known in the art (Suzuki reaction, Borylation reaction, Buchwald reaction, etc.). The type, location, or number may be changed according to techniques known in the art.

The manufacturing method of the compound of Formula 1 and the manufacturing of an organic light emitting device using them will be described in detail in the following manufacturing examples. However, the following preparation examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

<Production Example>

-Preparation example of compound 1

Core A 10g(21.74mmol), bis(pinacolato)diboron 7.2g(28.26mmol), potassium acetate 4.3g(43.48mmol) and [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium [ (1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)) 4mol% was added to 60ml dioxane and stirred at 100°C for 12 hours. After the reaction was terminated, the mixture was cooled to room temperature, anhydrous magnesium sulfate was added thereto, stirred, filtered with a silica pad, and concentrated under reduced pressure. After column purification, 8.3 g (75% yield) of Intermediate 1-1 was obtained.

Intermediate 1-1 8.3g (16.33mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.4g (16.33mmol) and tetrakis triphenylphosphine palladium (Tetrakis (triphenylphosphine) palladium) ) 3 mol% was added to 50 ml of tetrahydrofuran and 48.99 mmol of potassium carbonate was dissolved in 25 ml of water and mixed. After stirring at 80 °C for 12 hours, the reaction was terminated, cooled to room temperature, and water and an organic layer were separated. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad, the solution was concentrated under reduced pressure, followed by column purification, and 6.8 g (68% yield) of Intermediate 1-2 was obtained.

Intermediate 1-2 6.8g (11.09mmol), 9H-carbazole 1.9g (11.09mmol) and sodium terbutoxide 1.3g (13.31mmol) was added to 50ml of toluene and the temperature was raised while stirring.

At 100°C, 2 mol% of bis(dibenzylideneacetone)palladium(0) and 4 mol% of xantphos were added, stirred for 10 hours, and the reaction was terminated and cooled to room temperature to separate water and organic layers. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad, the solution was concentrated under reduced pressure, followed by column purification, and 5.9g (72% yield) of Compound 1 was obtained.

MS: [M+H]+= 745

-Preparation example of compound 2

Except for using 10g (19.68mmol) of Intermediate 1-1 and 6.1g (19.68mmol) of 2-bromo-4,6-diphenylpyridine, reacted and purified in the same manner as in the synthesis of Intermediate 1-2. Intermediate 2-1 was obtained in yield.

Intermediate 2-1 9.7g (15.87mmol) and 9H-carbazole 2.7g (15.87mmol) was reacted and purified in the same manner as the synthesis of compound 1, except that the compound 2 was obtained 8.0g (68% yield). .

MS: [M+H]+= 743

-Preparation example of compound 3

Intermediate 1-1 10g (19.68mmol) and 3-bromobenzonitrile 3.6g (19.68mmol), except for using the same method as the synthesis of Intermediate 1-2, purified by the same method as the intermediate 3-1 in a yield of 79% Was obtained.

Intermediate 3-1 7.5g (15.53mmol) and 9H-carbazole 2.6g (15.53mmol) was reacted and purified in the same manner as the synthesis of compound 1, except that 6.3g (66% yield) was obtained. .

MS: [M+H]+= 615

-Preparation example of compound 4

Except for using Intermediate 1-1 10g (19.68mmol) and 4-bromodibenzo[b,d]furan 4.8g (19.68mmol), reacted and purified in the same manner as in the synthesis of Intermediate 1-2, yielding 80% To obtain the intermediate 4-1.

Intermediate 4-1 8.6g (15.69mmol) and 9H-carbazole 2.6g (15.69mmol) was reacted and purified in the same manner as the synthesis of compound 1, except that 7.6g (71% yield) of compound 4 was obtained. .

MS: [M+H]+= 680

-Preparation example of compound 5

Intermediate 1-2 10g (16.31mmol), bis (pinacolato) diboron 5.4g (21.20mmol), potassium acetate 3.2g (32.62mmol) and bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium) 4 mol% and 8 mol% of tricyclohexylphosphine were added to 50 ml dioxane and stirred at 100 °C for 12 hours. After the reaction was terminated, the mixture was cooled to room temperature, anhydrous magnesium sulfate was added thereto, stirred, filtered with a silica pad, and concentrated under reduced pressure. After column purification, intermediate 5-1 was obtained in 64% yield.

Intermediate 5-1 7.4 g (10.49 mmol), 2-bromo-9-phenyl-9H-carbazole 3.4 g (10.49 mmol) and tetrakistriphenylphosphine palladium (Tetrakis (triphenyl phosphine) palladium) 3 mol% Into 50 ml of hydrofuran, 31.47 mmol of potassium carbonate was dissolved in 25 ml of water and mixed. After stirring at 80 °C for 12 hours, the reaction was terminated, cooled to room temperature, and water and an organic layer were separated. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad, the solution was concentrated under reduced pressure, followed by column purification, and 6.6 g (77% yield) of compound 5 was obtained.

MS: [M+H]+= 821

-Preparation example of compound 6

Except for using 7.4g (10.49mmol) of Intermediate 5-1 and 3.4g (10.49mmol) of 3-bromo-9-phenyl-9H-carbazole, the compound 6 was reacted and purified in the same manner as in the synthesis of compound 5 above. 6.2 g (72% yield) were obtained.

MS: [M+H]+= 821

-Preparation example of compound 7

.

.

Intermediate 5-1 7.4g (10.49mmol) and bromotriphenylsilene 3.5g (10.49mmol) was reacted and purified in the same manner as the synthesis of compound 5, except that 5.8g (66% yield) was obtained. I did.

MS: [M+H]+= 838

-Preparation example of compound 8

Except for using 7.4g (10.49mmol) of Intermediate 5-1 and 4.3g (10.49mmol) of (4-bromophenyl)triphenylsilene, it was reacted and purified in the same manner as in the synthesis of compound 5, and 7.0g ( 73% yield).

MS: [M+H]+= 914

-Preparation example of compound 9

Core B 10g(21.74mmol), bis(pinacolato)diboron 7.2g(28.26mmol), potassium acetate 4.3g(43.48mmol) and [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium [ (1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)) 4mol% was added to 60ml dioxane and stirred at 100°C for 12 hours. After the reaction was terminated, the mixture was cooled to room temperature, anhydrous magnesium sulfate was added thereto, stirred, filtered with a silica pad, and concentrated under reduced pressure. After column purification, 7.8g (71% yield) of Intermediate 9-1 was obtained.

Intermediate 9-1 7.8g (15.35mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.1g (15.35mmol) and tetrakis triphenylphosphine palladium (Tetrakis (triphenylphosphine) palladium) ) 3 mol% was added to 50 ml of tetrahydrofuran and 46.05 mmol of potassium carbonate was dissolved in 25 ml of water and mixed. After stirring at 80 °C for 12 hours, the reaction was terminated, cooled to room temperature, and water and an organic layer were separated. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad, the solution was concentrated under reduced pressure, followed by column purification, and 6.0 g (64% yield) of Intermediate 9-2 was obtained.

Intermediate 9-2 6.0g (9.79mmol), 9H-carbazole 1.6g (9.79mmol) and sodium terbutoxide 1.1g (11.75mmol) were added to 50ml of toluene and the temperature was raised while stirring.

At 100°C, 2 mol% of bis(dibenzylideneacetone)palladium(0) and 4 mol% of xantphos were added, stirred for 10 hours, and the reaction was terminated and cooled to room temperature to separate water and organic layers. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad, the solution was concentrated under reduced pressure, followed by column purification, and 5.1g (70% yield) of compound 9 was obtained.

MS: [M+H]+= 745

-Preparation example of compound 10

Intermediate 9-1 10g (19.68mmol) and 2-bromo-4,6-diphenylpyridine 6.1g (19.68mmol) was reacted in the same manner as in the synthesis of Intermediate 9-2, and purified to 77% Intermediate 10-1 was obtained in yield.

Intermediate 10-1 9.3g (15.22mmol) and 9H-carbazole 2.5g (15.22mmol) was reacted and purified in the same manner as in the synthesis of compound 9, except that 7.3g (65% yield) of compound 10 was obtained. .

MS: [M+H]+= 743

-Preparation example of compound 11

Intermediate 9-1 10g (19.68mmol) and 3-bromobenzonitrile 3.6g (19.68mmol), except for using the same method as the synthesis of Intermediate 9-2, and purified by the same method as the intermediate 11-1 in a yield of 73% Was obtained.

Except for using 6.9g (14.28mmol) of Intermediate 11-1 and 2.4g (14.28mmol) of 9H-carbazole, reacted and purified in the same manner as the synthesis of compound 9 to obtain 5.9g (68% yield) of compound 11. .

MS: [M+H]+= 615

-Preparation example of compound 12

Intermediate 9-1 10g (19.68mmol) and 4-bromo dibenzo[b,d]furan 4.8g (19.68mmol) was reacted in the same manner as in the synthesis of Intermediate 9-2, except for using a purified 77% Intermediate 12-1 was obtained in yield.

Except for using 8.3g (15.23mmol) of Intermediate 12-1 and 2.5g (15.23mmol) of 9H-carbazole, it was reacted and purified in the same manner as in the synthesis of compound 9 to give 7.0g (68% yield) of compound 12. .

MS: [M+H]+= 680

-Preparation example of compound 13

Intermediate 9-2 10g (16.31mmol), bis (pinacolato) diboron 5.4g (21.20mmol), potassium acetate 3.2g (32.62mmol) and bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium) 4 mol% and 8 mol% of tricyclohexylphosphine were added to 50 ml dioxane and stirred at 100 °C for 12 hours. After the reaction was terminated, the mixture was cooled to room temperature, anhydrous magnesium sulfate was added thereto, stirred, filtered with a silica pad, and concentrated under reduced pressure. After column purification, intermediate 13-1 was obtained in 69% yield.

Intermediate 13-1 7.9g (11.20mmol), 2-bromo-9-phenyl-9H-carbazole 3.6g (11.20mmol) and tetrakistriphenylphosphine palladium (Tetrakis (triphenyl phosphine) palladium) 3 mol% Into 50 ml of hydrofuran, 33.60 mmol of potassium carbonate was dissolved in 25 ml of water and mixed. After stirring at 80 °C for 12 hours, the reaction was terminated, cooled to room temperature, and water and an organic layer were separated. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad, the solution was concentrated under reduced pressure, followed by column purification, and 6.9 g (75% yield) of compound 13 was obtained.

MS: [M+H]+= 821

-Preparation example of compound 14

Except for using 7.4 g (10.49 mmol) of Intermediate 13-1 and 3.4 g (10.49 mmol) of 3-bromo-9-phenyl-9H-carbazole, the compound 14 was reacted and purified in the same manner as in the synthesis of compound 13 above. 6.3g (73% yield) was obtained.

MS: [M+H]+= 821

-Preparation example of compound 15

Except for using 7.4g (10.49mmol) of Intermediate 13-1 and 3.5g (10.49mmol) of bromotriphenylsilene, it was reacted and purified in the same manner as in the synthesis of compound 13 to obtain 6.2g (71% yield) of compound 15. I did.

MS: [M+H]+= 838

-Preparation example of compound 16

Except for using 7.4g (10.49mmol) of Intermediate 13-1 and 4.3g (10.49mmol) of (4-bromophenyl)triphenylsilene, reacted and purified in the same manner as in the synthesis of compound 13, and 6.8g of compound 16 ( 71% yield) was obtained.

MS: [M+H]+= 914

[Example]

<Experimental Example 1-1>

A glass substrate coated with a thin film of ITO (Indium tin oxide) to a thickness of 1,000Å was placed in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the prepared ITO transparent electrode, m-MTDATA(60nm) / TCTA(80 nm) / Host + 10% Ir(ppy) ₃ (300nm)/ BCP(10 nm)/ Alq ₃ (30 nm) / LiF(1 nm) / Al (200 nm), a light-emitting device was constructed in that order, and an organic EL device was manufactured using Compound 1 as the host.

The structures of m-MTDATA, TCTA, Ir(ppy)3 and BCP are as follows, respectively.

<Experimental Example 1-2>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 2 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-3>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 3 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-4>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 4 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-5>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 5 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-6>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 6 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-7>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 7 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-8>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 8 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-9>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 9 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-10>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 10 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-11>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 11 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-12>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 12 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-13>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 13 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-14>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 14 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-15>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 15 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-16>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 16 was used instead of Compound 1 in Experimental Example 1-1.

<Comparative Example 1-1>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that GH 1 was used instead of Compound 1 in Experimental Example 1-1.

<Comparative Example 1-2>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that GH 2 was used instead of Compound 1 in Experimental Example 1-1.

<Comparative Example 1-3>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that GH 3 was used instead of Compound 1 in Experimental Example 1-1.

When a current was applied to the organic light-emitting devices manufactured according to Experimental Examples 1-1 to 1-16 and Comparative Examples 1-1 and 1-3, the results of Table 1 were obtained.

compound
(Host) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) EL peak
(nm) Experimental Example 1-1 Compound 1 3.63 44.93 417 Experimental Example 1-2 Compound 2 3.86 42.64 416 Experimental Example 1-3 Compound 3 3.85 43.62 418 Experimental Example 1-4 Compound 4 3.75 42.75 417 Experimental Example 1-5 Compound 5 3.88 42.51 415 Experimental Example 1-6 Compound 6 3.79 42.53 416 Experimental Example 1-7 Compound 7 3.77 44.52 416 Experimental Example 1-8 Compound 8 3.68 42.54 417 Experimental Example 1-9 Compound 9 3.88 42.58 418 Experimental Example 1-10 Compound 10 3.78 43.14 418 Experimental Example 1-11 Compound 11 3.72 44.08 418 Experimental Example 1-12 Compound 12 3.71 43.48 418 Experimental Example 1-13 Compound 13 3.70 42.92 418 Experimental Example 1-14 Compound 14 3.69 43.08 418 Experimental Example 1-15 Compound 15 3.73 44.31 418 Experimental Example 1-16 Compound 16 3.80 43.74 418 Comparative Example 1-1 GH 1 5.78 38.47 388 Comparative Example 1-2 GH 2 5.90 37.21 391 Comparative Example 1-3 GH 3 5.67 36.11 398

As a result of the experiment, the green organic EL devices of Experimental Examples 1-1 to 1-16 using the compounds represented by compounds 1 to 16 according to the present invention as a host material of the emission layer were Comparative Examples 1-1 to 1 using conventional GH. It showed superior performance in terms of current efficiency and driving voltage than the green organic EL device of -3.

< Experimental example 2-1>

An organic light-emitting diode was prepared in which Compound 1 was applied as a host of a light emitting material layer. First, a glass substrate with an ITO (including a reflector) electrode having a thickness of 40 mm x 40 mm x 0.5 mm was subjected to ultrasonic cleaning with isopropyl alcohol, acetone, and DI water for 5 minutes, and then dried in an oven at 100°C. After cleaning the substrate, it was subjected to O ₂ plasma treatment in a vacuum state for 2 minutes, and then transferred to the deposition chamber to deposit other layers thereon. The organic material layer was deposited in the following order by evaporation from a heating boat under a vacuum of about 10 ^-7 Torr. At this time, the deposition rate of the organic material was set to 1 Å/s.

A hole injection layer (HIL; HAT-CN, 70 Å), a hole transport layer (HTL; NPB, 780 Å), an electron blocking layer (EBL; mCBP, 150 Å), a light emitting material layer (EML; compound 1 is used as a host) 4CzIPN doped 30% by weight with a fluorescent material, 350 Å), hole blocking layer (HBL; B3PYMPM; 100 Å), electron transport layer (ETL: TPBi, 250 Å), electron injection layer (EIL; LiF, 8 Å), cathode (Al; 1000 Å).

After the CPL (capping layer) was formed, it was encapsulated with glass. After the deposition of these layers, they were transferred from the deposition chamber into a drying box for film formation, and subsequently encapsulated using UV curing epoxy and moisture getter.

<Experimental Example 2-2>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 2 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-3>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 3 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-4>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 4 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-5>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 5 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-6>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 6 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-7>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 7 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-8>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 8 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-9>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 9 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-10>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 10 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-11>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 11 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-12>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 12 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-13>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 13 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-14>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 14 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-15>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 15 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-16>

An organic light emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 16 was used instead of Compound 1 in Experimental Example 2-1.

<Comparative Example 2-1>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that GH 1 was used instead of Compound 1 in Experimental Example 2-1.

<Comparative Example 2-2>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that GH 2 was used instead of Compound 1 in Experimental Example 2-1.

<Comparative Example 2-3>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that GH 3 was used instead of Compound 1 in Experimental Example 2-1.

When an electric current was applied to the organic light-emitting devices manufactured according to Experimental Examples 2-1 to 2-16 and Comparative Examples 2-1 and 2-3, the results of Table 2 were obtained.

compound
(Host) Voltage
(V@10mA/cm ² ) EQE
(%) CIE x CIE y Experimental Example 2-1 Compound 1 3.35 16.7 0.33 0.59 Experimental Example 2-2 Compound 2 3.35 16.3 0.33 0.59 Experimental Example 2-3 Compound 3 3.29 16.0 0.34 0.59 Experimental Example 2-4 Compound 4 3.33 16.8 0.34 0.58 Experimental Example 2-5 Compound 5 3.30 16.1 0.35 0.58 Experimental Example 2-6 Compound 6 3.37 15.9 0.34 0.59 Experimental Example 2-7 Compound 7 3.40 16.3 0.33 0.59 Experimental Example 2-8 Compound 8 3.38 16.6 0.34 0.58 Experimental Example 2-9 Compound 9 3.31 15.9 0.33 0.58 Experimental Example 2-10 Compound 10 3.28 16.0 0.33 0.59 Experimental Example 2-11 Compound 11 3.29 16.1 0.35 0.58 Experimental Example 2-12 Compound 12 3.34 15.9 0.34 0.59 Experimental Example 2-13 Compound 13 3.41 16.3 0.33 0.59 Experimental Example 2-14 Compound 14 3.50 16.6 0.34 0.58 Experimental Example 2-15 Compound 15 3.34 15.9 0.33 0.58 Experimental Example 2-16 Compound 16 3.50 16.0 0.33 0.59 Comparative Example 2-1 GH 1 4.38 13.0 0.34 0.58 Comparative Example 2-2 GH 2 4.41 12.8 0.32 0.57 Comparative Example 2-3 GH 3 4.24 13.4 0.33 0.56

When the organic compound synthesized according to the present invention is used as the host of the light emitting material layer, compared to the case where the compounds of Comparative Examples 2-1 to 2-3 are used as the host of the light emitting material layer, the driving voltage is lowered and the external quantum efficiency ( EQE) was improved. As a result, it was confirmed that the organic compound of the present invention was applied to the organic light-emitting layer to lower the driving voltage of the light-emitting diode, improve luminous efficiency, and improve color purity. Accordingly, the organic light-emitting diode to which the organic compound of the present invention is applied can be used in light-emitting devices such as an organic light-emitting diode display device and/or a lighting device with lower power consumption and improved luminous efficiency and device life.

10, 11: organic light emitting device
20: substrate
30: first electrode
40: light emitting layer
50: second electrode
60: hole injection layer
70: hole transport layer
80: electron transport layer
90: electron injection layer

Claims (14)

Heterocyclic compound represented by the following Formula 1:
[Formula 1]

In Formula 1,
Any one of G1 and G2 is -L2-Ar2, the rest are hydrogen,
L1 and L2 are the same as or different from each other, and each independently a direct bond; Or an arylene group,
Ar1 is a triazine substituted with an aryl group, pyrimidine substituted with an aryl group, pyridine substituted with an aryl group, CN, dibenzofuran, dibenzothiophene, dibenzofuran substituted with CN, or dibenzothiophene substituted with CN. ,
Ar2 is a carbazole group unsubstituted or substituted with an aryl group, a silyl group substituted with an aryl group,
R1 and R2 are hydrogen,
m and n are each 4. The method according to claim 1, wherein the formula 1 is a heterocyclic compound represented by the following formula 1-1 or 1-2:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
The definitions of L1, L2, Ar1, Ar2, R1, R2, m and n are the same as those defined in Formula 1 above. delete delete delete delete delete The heterocyclic compound of claim 1, wherein Formula 1 is selected from the following compounds:

A first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the heterocyclic compound of any one of claims 1, 2 and 8. Organic light emitting device. The organic light-emitting device of claim 9, wherein the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound. The organic light-emitting device of claim 9, wherein the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound as a host of the emission layer. The method according to claim 9, wherein the organic material layer comprises an electron injection layer, an electron transport layer, or a layer for simultaneously injecting and transporting electrons, and the layer for simultaneously injecting and transporting electrons, an electron injection layer, an electron transport layer, or the heterocyclic compound Organic light-emitting device comprising. The organic light-emitting device of claim 9, wherein the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound. The organic light-emitting device of claim 9, wherein the organic material layer includes an electron controlling layer, and the electron controlling layer includes the heterocyclic compound.

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