KR20210010215A - Organic light emitting device and composition for organic layer of organic light emitting device - Google Patents

Abstract

As an organic light emitting element comprising a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode, the present invention relates to an organic light emitting element in which one or more of the organic material layers include a heterocyclic compound represented by chemical formula 1, and a heterocyclic compound represented by chemical formula 2, and a composition for the organic material layer of the organic light emitting element. Therefore, the organic light emitting element can have excellent life, efficiency and driving voltage.

Description

Composition for organic light emitting device and organic material layer of organic light emitting device {ORGANIC LIGHT EMITTING DEVICE AND COMPOSITION FOR ORGANIC LAYER OF ORGANIC LIGHT EMITTING DEVICE}

The present specification relates to an organic light-emitting device and a composition for an organic material layer of the organic light-emitting device.

An electroluminescent device is a type of self-luminous display device, and has advantages in that it has a wide viewing angle, excellent contrast, and a fast response speed.

The organic light-emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light-emitting device having such a structure, electrons and holes injected from the two electrodes are combined in the organic thin film to form a pair and then emit light while disappearing. The organic thin film may be composed of a single layer or multiple layers as necessary.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of constituting an emission layer by itself may be used, or a compound capable of serving as a host or a dopant of the host-dopant-based emission layer may be used. In addition, as the material of the organic thin film, a compound capable of performing a role of hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, life, or efficiency of an organic light-emitting device, development of a material for an organic thin film is continuously required.

U.S. Patent 4,356,429

The present specification is to provide an organic light-emitting device and a composition for an organic material layer of the organic light-emitting device.

An exemplary embodiment of the present application is an organic light emitting device comprising a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode,

It provides an organic light-emitting device in which at least one of the organic material layers includes a heterocyclic compound represented by Formula 1 below and a heterocyclic compound represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

X ₁ is N or CR ₁ ,

X ₂ is N or CR ₂ ,

Y is O; S; CRR'; Or NR",

L is a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,

m is an integer from 0 to 5,

N-Het is a substituted or unsubstituted, monocyclic or polycyclic C2 to C60 heterocyclic group containing at least one N,

R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to To form a C60 aliphatic or aromatic heterocycle,

Ar ₁ is a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

R ₅₁ to R ₅₈ , R _a to R _c , R, R'and R" are the same as or different from each other, and each independently hydrogen; deuterium; halogen; cyano group; substituted or unsubstituted C1 to C60 alkyl group; substituted Or an unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; substituted or unsubstituted A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And A substituted or unsubstituted aryl group. Two or more groups selected from the group consisting of amine groups or adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or aromatic hetero ring, and , n and q are each an integer of 0 to 4, when n is 2 or more, R _a is the same as or different from each other, when q is 2 or more, R _c is the same or different from each other, and p is an integer of 0 to 2, When p is an integer of 2, R _b is the same as or different from each other,

n+p+q≤9.

In addition, another exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2.

Finally, an exemplary embodiment of the present application, the step of preparing a substrate; Forming a first electrode on the substrate; Forming one or more organic material layers on the first electrode; And forming a second electrode on the organic material layer, wherein the forming of the organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to the present application. Provides a manufacturing method.

The compound described herein can be used as a material for an organic material layer of an organic light emitting device. The compound may serve as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, and the like in the organic light emitting device. In particular, the compound can be used as a material for the light emitting layer of the organic light emitting device. For example, the compound may be used alone as a light-emitting material or as a host material for a light-emitting layer.

In particular, Formula 1 has a characteristic of improving efficiency, resulting in a more stable structure by substituting a specific substituent having a hole transport ability in N-Het, thereby showing the lifespan and stability of the driving of the organic light emitting device, and improving the efficiency. Together with 2, as it is included in the organic light-emitting device, it has excellent characteristics in lifespan, efficiency, and driving voltage.

1 to 3 are diagrams each schematically showing a stacked structure of an organic light emitting diode according to an exemplary embodiment of the present application.

Hereinafter, the present application will be described in detail.

In the present specification, the term "substitution" 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 at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted, When two or more are substituted, two or more substituents may be the same or different from each other.

In the present specification, "substituted or unsubstituted" refers to C1 to C60 straight or branched alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 linear or branched alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R"; -P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; And C2 to C60 monocyclic or polycyclic heteroarylamine selected from the group consisting of It means substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent to which two or more substituents selected from the aforementioned substituents are linked.

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

In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, more specifically 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but are not limited thereto.

In the present specification, the alkenyl group includes a linear or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkenyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20. Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(Naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, and styrenyl group, but are not limited thereto.

In the present specification, the alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.

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 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, 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. May be, but is not limited thereto.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic refers to a group in which a cycloalkyl group is directly connected or condensed with another ring group. Here, the other cyclic group may be a cycloalkyl group, but may be a different type of cyclic group, such as a heterocycloalkyl group, an aryl group, or a heteroaryl group. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, a cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 ,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but are not limited thereto.

In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a hetero atom, includes a monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heterocycloalkyl group is directly connected or condensed with another ring group. Here, the other cyclic group may be a heterocycloalkyl group, but may be a different type of cyclic group, such as a cycloalkyl group, an aryl group, or a heteroaryl group. The number of carbon atoms of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

In the present specification, the aryl group includes monocyclic or polycyclic having 6 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which an aryl group is directly connected or condensed with another ring group. Here, the other cyclic group may be an aryl group, but may be another type of cyclic group such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include phenyl group, biphenyl group, triphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, pyre Nyl group, tetrasenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, condensed ring groups thereof And the like, but are not limited thereto.

In the present specification, the phosphine oxide group is represented by -P(=O)R ₁₀₁ R ₁₀₂ , R ₁₀₁ and R ₁₀₂ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Alkyl group; Alkenyl group; Alkoxy group; Cycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specifically, the phosphine oxide group includes a diphenylphosphine oxide group and a dinaphthylphosphine oxide, but is not limited thereto.

In the present specification, the silyl group is a substituent including Si and the Si atom is directly connected as a radical, represented by -SiR ₁₀₄ R ₁₀₅ R ₁₀₆ , R ₁₀₄ to R ₁₀₆ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Alkyl group; Alkenyl group; Alkoxy group; Cycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. It is not limited.

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

,

,

,

,

,

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

,

,

,

,

,

And the like, but is not limited thereto.

In the present specification, the heteroaryl group includes S, O, Se, N or Si as a hetero atom, and includes a monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other cyclic group may be a heteroaryl group, but may be another type of cyclic group such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, and the like. The number of carbon atoms of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of the heteroaryl group include a pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl Group, isothiazolyl group, triazolyl group, furazinyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , Thiazinyl group, dioxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridyl Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindenyl group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azasilinyl, pyrazolo[1,5-c]quinazolinyl group , Pyrido[1,2-b]indazolyl group, pyrido[1,2-a]imidazo[1,2-e]indolinyl group, 5,11-dihydroindeno[1,2-b ] Carbazolyl group, and the like, but are not limited thereto.

In the present specification, the amine group is a monoalkylamine group; Monoarylamine group; Monoheteroarylamine group; -NH ₂ ; Dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; And it may be selected from the group consisting of an arylheteroarylamine group, carbon number 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, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluore There are nilamine group, phenyltriphenylenylamine group, biphenyltriphenylenylamine group, and the like, but are not limited thereto.

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 addition, the heteroarylene group refers to a heteroaryl group having two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aforementioned heteroaryl group may be applied.

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" to each other.

The aliphatic hydrocarbon rings that can be formed by adjacent groups may be the structures exemplified by the cycloalkyl groups described above except that they are not monovalent groups, and the structures exemplified by the aryl groups except that the aromatic hydrocarbon rings are not monovalent groups. Structures exemplified by the aforementioned heterocycloalkyl groups can be applied except that the aliphatic heterocycle is not a monovalent group, and the aromatic heterocycle is a structure exemplified by the aforementioned heteroaryl group except that it is not a monovalent group. Can be applied.

An exemplary embodiment of the present application is an organic light-emitting device comprising a first electrode, a second electrode, and one or more organic material layers provided between the first and second electrodes, wherein at least one of the organic material layers is It provides an organic light-emitting device comprising a heterocyclic compound represented by and a heterocyclic compound represented by Chemical Formula 2.

In the exemplary embodiment of the present application, Formula 1 may be represented by any one of Formulas 3 to 5 below.

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,

R ₁ , R ₂ , and R ₁₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And it is selected from the group consisting of a substituted or unsubstituted amine group,

The definitions of R _a to R _c , Y, N-Het, L, m, n, p and q are the same as those defined in Chemical Formula 1.

In the exemplary embodiment of the present application, X ₁ may be N or CR ₁ .

In the exemplary embodiment of the present application, X ₁ may be N.

In the exemplary embodiment of the present application, X ₁ may be CR ₁ .

In the exemplary embodiment of the present application, X ₂ may be N or CR ₂ .

In the exemplary embodiment of the present application, X ₂ may be N.

In the exemplary embodiment of the present application, X ₂ may be CR ₂ .

In the exemplary embodiment of the present application, R ₁ and R ₂ is the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a C2 to C60 hetero ring Can be formed.

In another exemplary embodiment, the R ₁ and R ₂ is the same as or different from each other, and each independently hydrogen; And a substituted or unsubstituted C6 to C60 aryl group, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring.

In another exemplary embodiment, the R ₁ and R ₂ is the same as or different from each other, and each independently hydrogen; And a substituted or unsubstituted C6 to C40 aryl group, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted C6 to C40 aromatic hydrocarbon ring.

In another exemplary embodiment, the R ₁ and R ₂ is the same as or different from each other, and each independently hydrogen; And a C6 to C40 aryl group, or two or more groups adjacent to each other may be bonded to each other to form a C6 to C40 aromatic hydrocarbon ring.

In another exemplary embodiment, the R ₁ and R ₂ is the same as or different from each other, and each independently hydrogen; And selected from the group consisting of a phenyl group, or two or more groups adjacent to each other may be bonded to each other to form a benzene ring.

In the exemplary embodiment of the present application, Y is O; S; CRR'; Or NR".

In another exemplary embodiment, Y is O; Or S.

In the exemplary embodiment of the present application, L is a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or it may be a substituted or unsubstituted C2 to C60 heteroarylene group.

In another exemplary embodiment, L is a direct bond; Or it may be a substituted or unsubstituted C6 to C60 arylene group.

In another exemplary embodiment, L is a direct bond; Or it may be a substituted or unsubstituted C6 to C40 arylene group.

In another exemplary embodiment, L is a direct bond; Or it may be a C6 to C40 arylene group.

In another exemplary embodiment, L is a direct bond; Or it may be a C6 to C40 monocyclic arylene group.

In another exemplary embodiment, L is a direct bond; Or it may be a phenylene group.

In the exemplary embodiment of the present application, the R _a to R _c , R, R'and R" are the same as or different from each other, and each independently hydrogen; deuterium; halogen; cyano group; substituted or unsubstituted C1 to C60 Alkyl group; substituted or unsubstituted C2 to C60 alkenyl group; substituted or unsubstituted C2 to C60 alkynyl group; substituted or unsubstituted C1 to C60 alkoxy group; substituted or unsubstituted C3 to C60 cycloalkyl group ; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; substituted or unsubstituted C6 to C60 aryl group; substituted or unsubstituted C2 to C60 heteroaryl group; substituted or unsubstituted phosphine oxide group; And It may be selected from the group consisting of substituted or unsubstituted amine groups.

In another exemplary embodiment, the R _a to R _c , R, R'and R" are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C6 to C60 aryl group; And substituted or unsubstituted It may be selected from the group consisting of a cyclic C2 to C60 heteroaryl group.

In another exemplary embodiment, the R _a to R _c , R, R'and R" are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C6 to C40 aryl group; And substituted or unsubstituted It may be selected from the group consisting of a cyclic C2 to C40 heteroaryl group.

In another exemplary embodiment, R _a to R _c may be hydrogen.

In another exemplary embodiment, R, R'and R" are the same as or different from each other, and each independently hydrogen; or a phenyl group.

In the exemplary embodiment of the present application, R ₁₁ to R ₁₄ may be hydrogen.

In the exemplary embodiment of the present application, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocycle containing one or more N.

In the exemplary embodiment of the present application, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocycle containing 1 or more and 3 or less N.

In the exemplary embodiment of the present application, N-Het is a C1 to C60 alkyl group, a substituted or unsubstituted C6 to C60 aryl group; It is a monocyclic or polycyclic heterocyclic substituted or unsubstituted with one or more substituents selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group and a substituted or unsubstituted amine group, and includes one N.

In the exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of Chemical Formulas 6 to 8.

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 6 to 8,

R ₁ , R ₂ , and R ₁₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And it is selected from the group consisting of a substituted or unsubstituted amine group,

R ₂₁ to R ₂₈ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or aromatic Form a hetero ring,

The definitions of R _a to R _c , Y, L, m, n, p and q are the same as those defined in Formula 1.

In the exemplary embodiment of the present application, R ₂₁ to R ₂₈ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or aromatic Can form hetero rings.

In another exemplary embodiment, the R ₂₁ to R ₂₈ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; And selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 hetero ring. I can.

In another exemplary embodiment, the R ₂₁ to R ₂₈ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; And two or more groups selected from the group consisting of a diarylamine group or adjacent to each other may be bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aromatic hetero ring. .

In another exemplary embodiment, the R ₂₁ to R ₂₈ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C6 to C40 aryl group; A substituted or unsubstituted C2 to C40 heteroaryl group; And two or more groups selected from the group consisting of a diarylamine group or adjacent to each other may be bonded to each other to form a substituted or unsubstituted C6 to C40 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C40 aromatic hetero ring. .

In another exemplary embodiment, the R ₂₁ to R ₂₈ are the same as or different from each other, and each independently hydrogen; C6 to C40 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a C6 to C40 aryl group and a diarylamine group; C2 to C40 heteroaryl group unsubstituted or substituted with a C6 to C40 aryl group; And two or more groups selected from the group consisting of a diarylamine group, or two or more groups adjacent to each other bond to each other and unsubstituted or substituted with a C6 to C40 aromatic hydrocarbon ring unsubstituted or substituted with a C1 to C40 alkyl group or a C6 to C40 aryl group A C2 to C40 aromatic hetero ring may be formed.

In another exemplary embodiment, the R ₂₁ to R ₂₈ are the same as or different from each other, and each independently hydrogen; A phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a carbazole group and an arylamine group; Naphthyl group; A carbazole group unsubstituted or substituted with a phenyl group; And an arylamine group, or two or more groups adjacent to each other are bonded to each other to form a benzene ring; An indene ring unsubstituted or substituted with a methyl group; Benzofuran ring; Benzothiophene ring; Alternatively, an indole ring substituted or unsubstituted with a phenyl group may be formed.

는 하기 화학식 9로 표시될 수 있다. 여기서,

은 상기 L에 연결되는 부위이다.In the exemplary embodiment of the present application, the

May be represented by the following Formula 9. here,

Is a site connected to the L.

[Formula 9]

In Formula 9,

R ₂₁ to R ₂₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or aromatic Form a hetero ring,

Y1 is O, S, CR ₄₁ R ₄₂ ; Or NR ₄₃ ,

R ₃₁ , R ₃₂ and R ₄₁ to R ₄₃ are the same as or different from each other and are hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a C2 to C60 hetero ring, f is It is an integer of 0 to 4, when f is 2 or more, R ₃₂ is the same as or different from each other, g is an integer of 0 to 2, and when g is 2 or more, R ₃₁ is the same or different from each other.

In another exemplary embodiment, Chemical Formula 9 may be selected from the following structural formulas.

In the above structural formula,

The definition of the substituent is the same as the definition in Chemical Formula 9.

는

에 하기와 같이 결합될 수 있다.In an exemplary embodiment of the present application, the formula 1

Is

Can be combined as follows.

의

로 표시되는 위치와 하기 구조식의

로 표시되는 위치가 서로 결합됨을 의미한다.remind

of

Of the position represented by and the following structural formula

It means that the positions indicated by are combined with each other.

In the above structural formula,

The definition of each substituent is the same as that in Chemical Formula 1.

In an exemplary embodiment of the present application, Formula 2 may be represented by any one of Formulas 10 to 12 below.

[Formula 10]

[Formula 11]

[Formula 12]

In Formulas 10 to 12,

R ₆₁ to R ₇₀ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And it is selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group,

R ₇₁ to R ₇₄ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to To form a C60 aliphatic or aromatic hetero ring,

Ar ₂ and Ar ₃ are the same as or different from each other, and each independently, a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

A ₁ is O; S; NAr ₄ ; Or CR _d R _e ,

R _d and R _e are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; Or a substituted or unsubstituted C6 to C60 aryl group,

Ar ₄ is a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

h and i are integers from 0 to 3,

j is an integer from 0 to 2.

In the exemplary embodiment of the present application, Chemical Formula 10 may be represented by Chemical Formula 10-1 or 10-2 below.

[Formula 10-1]

[Formula 10-2]

In Formulas 10-1 and 10-2,

The definition of each substituent is the same as the definition in Formula 10 above.

In the exemplary embodiment of the present application, Formula 11 may be represented by any one of Formulas 11-1 to 11-3 below.

[Chemical Formula 11-1]

[Formula 11-2]

[Chemical Formula 11-3]

In Formulas 11-1 to 11-3,

The definition of each substituent is the same as the definition in Formula 11.

In the exemplary embodiment of the present application, Formula 12 may be represented by any one of Formulas 12-1 to 12-4 below.

[Chemical Formula 12-1]

[Formula 12-2]

[Chemical Formula 12-3]

[Chemical Formula 12-4]

In Formulas 12-1 to 12-4,

The definition of Ar ₂ and A ₁ is the same as in Chemical Formula 12,

R ₈₁ and R ₈₂ are the same as or different from each other, and each independently a substituted or unsubstituted C10 or more aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

R ₈₃ is a substituted or unsubstituted C10 or less aryl group.

In the exemplary embodiment of the present application, Ar ₂ to Ar ₄ are the same as or different from each other, and each independently, a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, Ar ₂ to Ar ₄ are the same as or different from each other, and each independently, a substituted or unsubstituted C1 to C40 alkyl group; A substituted or unsubstituted C6 to C40 aryl group; Or it may be a substituted or unsubstituted C2 to C40 heteroaryl group.

In another exemplary embodiment, Ar ₂ to Ar ₄ are the same as or different from each other, and each independently selected from the group consisting of a C1 to C20 alkyl group, a C6 to C40 aryl group, and a C2 to C40 heteroaryl group. C6 to C40 aryl group unsubstituted or substituted with one or more substituents; Or it may be a C2 to C40 heteroaryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a C6 to C40 aryl group and a C2 to C40 heteroaryl group.

In the exemplary embodiment of the present application, R ₆₁ to R ₇₀ are the same as or different from each other, and each independently, hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And it may be selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, R ₆₁ to R ₇₀ may be hydrogen.

In the exemplary embodiment of the present application, R ₇₁ to R ₇₄ are the same as or different from each other, and each independently, hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or aromatic heterocycles may be formed.

In another exemplary embodiment, R ₇₁ to R ₇₄ are the same as or different from each other and are each independently hydrogen, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or A substituted or unsubstituted C2 to C60 aliphatic or aromatic hetero ring may be formed.

In another exemplary embodiment, R ₇₁ to R ₇₄ are the same as or different from each other and are each independently hydrogen, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring. I can.

In another exemplary embodiment, R ₇₁ to R ₇₄ are the same as or different from each other and are each independently hydrogen, or two or more groups adjacent to each other may be bonded to each other to form a C6 to C60 aromatic hydrocarbon ring.

In another exemplary embodiment, R ₇₁ to R ₇₄ are the same as or different from each other and are each independently hydrogen, or two or more groups adjacent to each other may be bonded to each other to form a C6 to C40 aromatic hydrocarbon ring.

In another exemplary embodiment, R ₇₁ to R ₇₄ are the same as or different from each other and are each independently hydrogen, or two or more groups adjacent to each other may be bonded to each other to form a benzene ring.

In the exemplary embodiment of the present application, R _d and R _e are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; Or it may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R _d and R _e may be the same as or different from each other, and may each independently be a substituted or unsubstituted C1 to C60 alkyl group.

In another exemplary embodiment, R _d and R _e may be the same as or different from each other, and may each independently be a C1 to C40 alkyl group.

In another exemplary embodiment, R _d and R _e may be a methyl group.

In the exemplary embodiment of the present application, R ₈₁ and R ₈₂ are the same as or different from each other, and each independently, a substituted or unsubstituted C10 or more aryl group; Or it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R ₈₁ and R ₈₂ are the same as or different from each other, and each independently, a substituted or unsubstituted C10 or more and C60 or less aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, R ₈₁ and R ₈₂ are the same as or different from each other, and each independently, a substituted or unsubstituted C10 or more and C40 or less aryl group; Or it may be a substituted or unsubstituted C2 to C40 heteroaryl group.

In another exemplary embodiment, R ₈₁ and R ₈₂ are the same as or different from each other, and each independently, a C10 or more and C40 or less aryl group unsubstituted or substituted with a C1 to C20 alkyl group; Or it may be a C2 to C40 heteroaryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a C6 to C40 aryl group and a C2 to C40 heteroaryl group.

In another exemplary embodiment, R ₈₁ and R ₈₂ may be represented by the following Chemical Formula 13.

[Formula 13]

In Formula 13,

A ₂ is NR ₉₆ ; O; S; Or CR ₉₇ R ₉₈ ,

R ₉₁ to R ₉₅ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or Form an aromatic heterocycle,

R ₉₆ to R ₉₈ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

k is an integer of 0 to 3.

In the exemplary embodiment of the present application, R ₈₃ is a substituted or unsubstituted aryl group of less than C10.

In another exemplary embodiment, R ₈₃ is an aryl group of less than C10 unsubstituted or substituted with a C6 to C10 aryl group or a C2 to C20 heteroaryl group.

In another exemplary embodiment, R ₈₃ is a phenyl group unsubstituted or substituted with a phenyl group or a dibenzofuran group; Biphenyl group; Or it may be a naphthyl group.

In the exemplary embodiment of the present application, R ₉₁ to R ₉₅ are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted C6 to C60 aryl group, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring.

In the exemplary embodiment of the present application, R ₉₁ to R ₉₅ are the same as or different from each other, and each independently hydrogen, or two or more groups adjacent to each other may be bonded to each other to form a benzene ring.

In the exemplary embodiment of the present application, R ₉₆ to R ₉₈ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R ₉₆ to R ₉₈ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C20 alkyl group; A substituted or unsubstituted C6 to C40 aryl group; Or it may be a substituted or unsubstituted C2 to C40 heteroaryl group.

In another exemplary embodiment, R ₉₆ to R ₉₈ are the same as or different from each other, and each independently hydrogen; C1 to C20 alkyl group; It may be a C6 to C40 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a C1 to C20 alkyl group, a C6 to C40 aryl group, and a C2 to C40 heteroaryl group.

According to an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

According to an exemplary embodiment of the present application, Formula 2 may be represented by any one of the following compounds, but is not limited thereto.

In addition, by introducing various substituents into the structures of Formulas 1 and 2, a compound having the inherent characteristics of the introduced substituent can be synthesized. For example, a hole injection layer material, a hole transport material, a light emitting layer material, an electron transport layer material, and a substituent mainly used for the charge generation layer material used in manufacturing an organic light emitting device are introduced into the core structure to meet the conditions required by each organic material layer. It is possible to synthesize a material that makes it possible.

In addition, by introducing various substituents into the structures of Formulas 1 and 2, it is possible to finely control the energy band gap, while improving the properties at the interface between organic materials, and various uses of the material. .

On the other hand, the heterocyclic compound has a high glass transition temperature (Tg) and has excellent thermal stability. This increase in thermal stability becomes an important factor providing driving stability to the device.

The heterocyclic compound according to an exemplary embodiment of the present application may be prepared by a multi-step chemical reaction. Some intermediate compounds are prepared first, and a compound of Formula 1 or 2 may be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application may be prepared based on Preparation Examples described below.

In addition, another exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2.

Details of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are the same as described above.

The heterocyclic compound represented by Formula 1 in the composition: the weight ratio of the heterocyclic compound represented by Formula 2 may be 1: 10 to 10: 1, 1: 8 to 8: 1, and 1: 5 To 5: 1, may be 1: 2 to 2: 1, but is not limited thereto.

The composition may be used when forming an organic material of an organic light-emitting device, and particularly, may be more preferably used when forming a host of an emission layer.

In the composition, two or more compounds are simply mixed, and a powdery material may be mixed before the organic material layer of the organic light-emitting device is formed, or a liquid compound may be mixed at an appropriate temperature or higher. The composition is in a solid state below the melting point of each material, and can be maintained in a liquid state by adjusting the temperature.

The composition may further contain materials known in the art, such as solvents and additives.

The organic light-emitting device according to an exemplary embodiment of the present application is a conventional organic material layer, except that one or more organic material layers are formed using the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2. It can be manufactured by the manufacturing method and material of the light emitting device.

The heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 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, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic light emitting device of the present invention 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 light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light-emitting device is not limited thereto, and may include a smaller number of organic material layers.

Specifically, the organic light-emitting device according to an exemplary embodiment of the present application includes a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode, and at least one of the organic material layers is And a heterocyclic compound represented by Chemical Formula 1, and a heterocyclic compound represented by Chemical Formula 2.

In the exemplary embodiment of the present application, the first electrode may be an anode, and the second electrode may be a cathode.

In another exemplary embodiment, the first electrode may be a cathode, and the second electrode may be an anode.

In the exemplary embodiment of the present application, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound according to Formula 1 and the heterocyclic compound according to Formula 2 may be used as a material of the blue organic light-emitting device. .

In the exemplary embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as a material of the green organic light emitting device. .

In the exemplary embodiment of the present application, the organic light-emitting device may be a red organic light-emitting device, and the compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as a material of the red organic light-emitting device. .

The organic light emitting device of the present invention is a light emitting layer, a hole injection layer, a hole transport layer. It may further include one or two or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

In the exemplary embodiment of the present application, the organic material layer includes at least one of a hole blocking layer, an electron injection layer, and an electron transport layer, and at least one of the hole blocking layer, the electron injection layer, and the electron transport layer is represented by Formula 1 above. It provides an organic light-emitting device comprising a heterocyclic compound represented by, and a heterocyclic compound represented by Formula 2.

When the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 are simultaneously included in the organic material layer of the organic light-emitting device, it can be seen that driving voltage, efficiency, and life can be remarkably improved. This result can be expected that when both compounds are included at the same time, an exciplex phenomenon occurs. The exciplex phenomenon is a phenomenon in which energy of a HOMO level of a donor (p-host) and an LUMO level of an acceptor (n-host) is released through electron exchange between two molecules. When an exciplex phenomenon occurs between two molecules, Reverse Intersystem Crossing (RISC) occurs, which can increase the internal quantum efficiency of fluorescence to 100%. When a donor (p-host) with good hole transport capability and an acceptor (n-host) with good electron transport capability are used as hosts of the emission layer, holes are injected into p-host and electrons are injected into n-host. It can help you improve.

In the exemplary embodiment of the present application, the organic material layer includes an emission layer, and the emission layer includes a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2 do.

In the exemplary embodiment of the present application, the organic material layer includes an emission layer, the emission layer includes a host material, and the host material is a heterocyclic compound represented by Formula 1, and a heterocyclic compound represented by Formula 2 It provides an organic light emitting device comprising a.

1 to 3 illustrate a stacking order of an electrode and an organic material layer of an organic light emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and the structure of the organic light emitting device known in the art may be applied to the present application.

Referring to FIG. 1, an organic light-emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, the structure is not limited thereto, and an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented as shown in FIG.

3 illustrates a case in which the organic material layer is a multilayer. The organic light emitting diode according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a lamination structure, and other layers other than the light emitting layer may be omitted, or other necessary functional layers may be further added as necessary.

In an exemplary embodiment of the present application, preparing a substrate; Forming a first electrode on the substrate; Forming one or more organic material layers on the first electrode; And forming a second electrode on the organic material layer, wherein the forming of the organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to an exemplary embodiment of the present application. It provides a method of manufacturing an organic light emitting device.

In the exemplary embodiment of the present application, the forming of the organic material layer is formed using a thermal vacuum deposition method by pre-mixing the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 It provides a method of manufacturing a phosphorus organic light emitting device.

The pre-mixed refers to mixing the materials of the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 before depositing on the organic material layer and mixing them in one park.

The premixed material may be referred to as the composition for an organic material layer according to an exemplary embodiment of the present application.

In the organic light-emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 are exemplified below, but these are only for illustration and the scope of the present application It is not intended to be limiting, and materials known in the art may be substituted.

Materials having a relatively large work function may be used as the cathode material, and transparent conductive oxides, metals, or conductive polymers may be used. Specific examples of the anode material 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; 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.

Materials having a relatively low work function may be used as the cathode material, and metal, metal oxide, or conductive polymer may be used. 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 multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

As the hole injection material, a known hole injection material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429, or a phthalocyanine compound disclosed in Advanced Material, 6, p.677 (1994) is described. Starburst type amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid (Polyaniline/Dodecylbenzenesulfonic acid) or poly( 3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), polyaniline/camphor sulfonic acid or polyaniline/ Poly(4-styrene-sulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) can be used.

As the hole transport material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. may be used, and low molecular weight or high molecular weight materials may be used.

Electron transport materials include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone Derivatives, diphenyl dicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like may be used, and not only low-molecular substances but also high-molecular substances may be used.

As the electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.

Red, green, or blue light emitting materials may be used as the light emitting material, and if necessary, two or more light emitting materials may be mixed and used. In this case, two or more light-emitting materials may be deposited as separate sources and used, or pre-mixed and premixed, and then deposited as one source. Further, a fluorescent material may be used as the light emitting material, but may also be used as a phosphorescent material. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used, but materials in which the host material and the dopant material are both involved in light emission may be used.

When a host of light-emitting materials is mixed and used, hosts of the same series may be mixed and used, or hosts of different types may be mixed and used. For example, any two or more of an n-type host material or a p-type host material may be selected and used as the host material of the light emitting layer.

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

The heterocyclic compound according to the exemplary embodiment of the present application may act on a principle similar to that applied to an organic light-emitting device in organic electronic devices including organic solar cells, organic photoreceptors, and organic transistors.

Hereinafter, the present specification will be described in more detail through examples, but these are only intended to illustrate the present application and are not intended to limit the scope of the present application.

< Manufacturing example 1>- Synthesis of E1 and E2 compounds

Synthesis of C1 compound

Add A1 (20g, 142.9 mmol), B1 (31.9g, 142.9 mmol), Pd(PPh ₃ ) ₄ (8.2g, 7.15 mmol), Na ₂ CO ₃ (30.3g, 285.8 mmol) to 500 mL of a round bottom flask. , Toluene (200 mL), EtOH (40 mL), and H ₂ O (40 mL) were added to dissolve and then refluxed at 120°C. When the reaction was completed, the temperature was lowered to room temperature, and then water was added and extracted with methylene chloride (Mc). The organic layer was dried over Mg ₂ SO ₄ , concentrated, and then purified by a silica-gel column to obtain a C1 compound (18g, 75.5mmol, 53%).

Synthesis of D1 compound

C1 (18g, 75.5mmol) was put in a 250 mL round bottom flask, dissolved in dimethylacetamide (DMA) (150 mL), and then Cs ₂ CO ₃ (49g, 151 mmol) was added. After stirring at a reaction temperature of 140°C, after the reaction was completed, the temperature was lowered to room temperature, and Cs ₂ CO ₃ was removed by paper filter. The filtered solid was washed with water and MeOH, and then dried to obtain a D1 compound (16g, 73.3 mmol, 97%).

Synthesis of E1 compound

D1 (8g, 36.6 mmol) was put into a 250 mL round bottom flask, replaced with a nitrogen atmosphere, and then THF (150 mL) was added to dissolve it. After lowering the external temperature of the reaction vessel to -78°C, n-BuLi (2.5M solution in Hx, 15 mL) was added and stirred for 1 hour (external temperature: -30°C). After lowering the external temperature to -78°C again, B(OMe) ₃ (54.9 mmol) was added and stirred at room temperature for 4 hours. After the reaction was completed, cold water was added and extracted with Mc. The extracted organic layer was dried over Mg ₂ SO ₄ and then concentrated. Silica-gel column (Silica-gel column) and recrystallized to obtain an E1 compound (25.6 mmol, 70%).

Synthesis of E2 compound

D1 (20g, 85.35 mmol) was put into a 500 mL round bottom flask, and dissolved in CHCl ₃ (250 mL). Br ₂ (4.6 mL, 84.6 mmol)) was slowly added dropwise to the reaction vessel. After the reaction was completed, MeOH (150 mL) was added to precipitate a solid and then filtered through a filter paper. MeOH (50 mL x 3) was washed several times. The filtered solid was vacuum dried. Put the dried solid in a 500 mL round-bottom flask, dissolve in dioxane (300 mL), and then PdCl ₂ (dppf) (2.5g, 3.46 mmol), 4,4,4',4',5,5, 5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane)(4,4,4',4',5,5,5',5'-octamethyl- 2,2'-bi(1,3,2-dioxaborolane)) (21.1g, 83.14 mmol), KOAc (20g, 207.6 mmol) were added and stirred at 120°C. After the second reaction was completed, the reaction temperature was lowered to room temperature, water was added, and extraction was performed with Mc. The extracted organic solvent was dried over Mg ₂ SO ₄ and then concentrated. Purification was performed on a silica-gel column to obtain an E2 (21.5g, 59.7 mmol) compound.

< Manufacturing example 2>- Synthesis of E3 and E4 compounds

Synthesis of E3 compound

Except for using D2 instead of D1 as a starting material, the E3 compound was obtained in the same manner as the synthesis method of E1 of Preparation Example 1.

Synthesis of E4 compound

Except for using D2 instead of D1 as a starting material, the E4 compound was obtained in the same manner as the synthesis method of E2 of Preparation Example 1.

< Manufacturing example 3>- E6 compound synthesis

Synthesis of C3 compound

Except for using A2 instead of A1 as a starting material, it proceeded in the same manner as the synthesis method of C1 of Preparation Example 1 to obtain a C3 compound.

Synthesis of D4 compound

Except for using C3 instead of C1 as a starting material, the D4 compound was obtained in the same manner as the synthesis method of D1 of Preparation Example 1.

Synthesis of E6 compound

D4 was used instead of D1 as a starting material, and Pd(dba) ₂ as a catalyst and a ligand, respectively, and XPhos were excluded.

Hereinafter, the following compounds were synthesized, and the compounds of E5, E7 and E8 were synthesized accordingly.

Synthesis of C2 compound

Except for using B2 instead of B1 as a starting material, it proceeded in the same manner as the synthesis method of C1 of Preparation Example 1 to obtain a C2 compound (50%).

[Compound B2]

[Compound C2]

Synthesis of C4 compound

A C4 compound (64%) was obtained in the same manner as the synthesis method of C1 of Preparation Example 1, except that A3 was used instead of A1 as a starting material.

[Compound A3]

[Compound C4]

Synthesis of C5 compound

Except for using A4 instead of A1 as a starting material, it proceeded in the same manner as the synthesis method of C1 of Preparation Example 1 to obtain a C5 compound.

[Compound A4]

[Compound C5]

Synthesis of E5 compound

Except that D3 was used instead of D1 as a starting material, and Pd(dba) ₂ , and XPhos were used as a catalyst and a ligand, respectively, and proceeded in the same manner as the synthesis method of E2 of Preparation Example 1, and the E5 (60%) compound was prepared. Got it.

[Compound D3]

[Compound E5]

Synthesis of E7 compound

Except that D5 was used instead of D1 as a starting material, and Pd(dba) ₂ and XPhos were used as a catalyst and a ligand, respectively, proceed in the same manner as the synthesis method of E2 of Preparation Example 1, and the E7 compound (74%) was prepared. Got it.

[Compound D5]

[Compound E7]

Synthesis of E8 compound

Except that D6 was used instead of D1 as a starting material, and Pd(dba) ₂ , and XPhos were used as a catalyst and a ligand, respectively, and proceeding in the same manner as the synthesis method of E2 of Preparation Example 1, the E8 (80%) compound was prepared. Got it.

[Compound D6]

[Compound E8]

< Manufacturing example 4>- G1 compound synthesis

Synthesis of G1 compound

Put E1 (10g, 38.1 mmol), F1 (8.6g, 38.1 mmol), Pd(PPh ₃ ) ₄ (,2.2g, 1.90 mmol), K ₂ CO ₃ (10.5g, 76.2 mmol) into a 100 mL round bottom flask , THF (120 mL) and water (30 mL) were added and then stirred at 80°C. After the reaction was completed, the temperature was lowered to room temperature, and water was added and extracted with Mc. The extracted organic solvent was dried over Mg ₂ SO ₄ and then concentrated. Silica-gel column (Silica-gel column) and recrystallized to obtain a G1 (8g, 19.8 mmol, 52%) compound.

The synthesis method of the G1 compound of Preparation Example 4, except that any one of E1 to E8 of Table 1 below was used instead of E1 in Preparation Example 4, and any one of F1 to F7 of Table 1 below was used instead of F1, and Synthesis was performed in the same manner to obtain the target compound.

E F G G yield E1 F1 G1 52% E1 F2 G2 59% E1 F3 G3 88% E2 F2 G4 71% E2 F3 G5 93% E3 F1 G6 66% E3 F2 G7 64% E3 F3 G8 97% E4 F2 G9 67% E4 F3 G10 94% E5 F1 G11 47% E5 F2 G12 48% E5 F3 G13 90% E6 F1 G14 60% E6 F2 G15 66% E6 F3 G16 94% E7 F2 G17 66% E7 F3 G18 92% E8 F2 G19 70% E8 F3 G20 94% E7 F4 G21 72% E7 F5 G22 80% E8 F4 G23 79% E4 F5 G24 81% E8 F5 G25 76% E2 F5 G26 88% E8 F6 G27 65% E4 F7 G28 80%

< Manufacturing example 5>- 1-1 compound synthesis

Synthesis of 1-1 compound

G1 (5g, 12.3 mmol) and H1 (2.66g, 12.3 mmol) were added to a 100 mL round bottom flask and dissolved in DMF (60 mL). NaH 60% in mineral oil (1.2g, 18.45 mmol) was added portionwise to the mixture and stirred at 50°C. After the reaction was completed, the resulting solid was filtered through a filter paper, washed with water and MeOH (40 mL), and dried under vacuum. The dried solid was recrystallized in toluene to obtain an I1 compound (7.0g, 11.9 mmol, 97%).

The same as the synthesis method of the compound 1-1 of Preparation Example 5, except that any one of G1 to G20 in Table 2 below was used instead of G1 in Preparation Example 5, and any one of the following H1 to F46 was used instead of H1. Synthesized to obtain the target compound.

entry G H Target compound yield One G1 H1 1-1 97% 2 G1 H2 1-2 96% 3 G1 H4 1-4 80% 4 G1 H5 1-5 84% 5 G1 H11 1-6 88% 6 G2 H4 1-10 86% 7 G2 H5 1-11 86% 8 G2 H11 1-12 90% 9 G2 H27 1-17 76% 10 G2 H22 1-18 69% 11 G2 H24 1-19 74% 12 G6 H5 1-27 94% 13 G6 H7 1-28 88% 14 G7 H7 1-29 90% 15 G7 H12 1-31 68% 16 G7 H25 1-32 59% 17 G7 H14 1-33 69% 18 G7 H26 1-34 69% 19 G7 H27 1-35 59% 20 G7 H30 1-37 88% 21 G7 H33 1-38 88% 22 G7 H35 1-39 94% 23 G7 H37 1-40 89% 24 G7 H38 1-41 80% 25 G7 H39 1-42 93% 26 G4 H3 1-43 88% 27 G4 H5 1-45 92% 28 G4 H6 1-46 77% 29 G4 H7 1-47 78% 30 G4 H11 1-48 88% 31 G4 H28 1-54 86% 32 G4 H31 1-55 73% 33 G4 H33 1-56 96% 34 G4 H35 1-57 94% 35 G9 H10 1-61 49% 36 G9 H9 1-62 89% 37 G9 H8 1-63 60% 38 G9 H4 1-64 71% 39 G9 H5 1-65 88% 40 G9 H12 1-67 90% 41 G9 H25 1-68 66% 42 G9 H40 1-76 59% 43 G9 H45 1-77 84% 44 G12 H9 1-79 88% 45 G12 H8 1-80 76% 46 G12 H10 1-81 60% 47 G11 H5 1-82 94% 48 G12 H5 1-83 90% 49 G12 H13 1-85 92% 50 G12 H16 1-86 75% 51 G12 H14 1-87 77% 52 G12 H19 1-88 89% 53 G12 H24 1-89 94% 54 G12 H25 1-90 96% 55 G12 H26 1-91 70% 56 G12 H27 1-92 89% 57 G12 H28 1-93 94% 58 G12 H29 1-94 79% 59 G12 H33 1-95 90% 60 G12 H35 1-96 93% 61 G14 H3 1-101 88% 62 G14 H7 1-102 90% 63 G15 H7 1-107 89% 64 G16 H35 1-117 94% 65 G16 H41 1-118 88% 66 G16 H38 1-119 89% 67 G16 H39 1-120 89% 68 G17 H12 1-127 89% 69 G17 H25 1-128 90% 70 G17 H26 1-130 68% 71 G17 H24 1-132 92% 72 G19 H9 1-142 70% 73 G19 H5 1-143 95% 74 G19 H11 1-144 93% 75 G19 H12 1-145 88% 76 G12 H32 1-152 77% 77 G3 H9 1-158 74% 78 G3 H5 1-160 92% 79 G3 H11 1-162 88% 80 G3 H12 1-163 90% 81 G3 H25 1-164 69% 82 G3 H35 1-171 78% 83 G3 H43 1-172 82% 84 G3 H38 1-173 89% 85 G3 H44 1-174 88% 86 G8 H15 1-179 60% 87 G8 H17 1-180 90% 88 G8 H33 1-186 88% 89 G8 H42 1-189 77% 90 G8 H32 1-191 69% 91 G8 H44 1-192 81% 92 G5 H5 1-195 91% 93 G5 H7 1-196 96% 94 G5 H12 1-198 90% 95 G5 H23 1-199 76% 96 G5 H14 1-200 90% 97 G5 H22 1-204 79% 98 G5 H34 1-206 80% 99 G10 H5 1-214 88% 100 G10 H18 1-218 79% 101 G10 H24 1-222 77% 102 G13 H5 1-229 80% 103 G13 H25 1-230 72% 104 G13 H18 1-232 77% 105 G13 H21 1-233 68% 106 G13 H12 1-235 86% 107 G16 H5 1-244 90% 108 G16 H7 1-245 88% 109 G16 H11 1-246 95% 110 G16 H12 1-247 90% 111 G16 H25 1-248 88% 112 G16 H16 1-249 72% 113 G16 H26 1-250 69% 114 G16 H22 1-252 79% 115 G16 H39 1-258 64% 116 G18 H11 1-261 78% 117 G18 H24 1-262 88% 118 G18 H25 1-263 85% 119 G18 H32 1-266 77% 120 G20 H4 1-267 78% 121 G20 H5 1-268 70% 122 G20 H26 1-274 89% 123 G20 H20 1-275 74% 124 G20 H23 1-276 90% 125 G20 H33 1-278 70% 126 G20 H35 1-279 88% 127 G20 H36 1-281 57% 128 G20 H44 1-282 79% 129 G16 H46 1-283 77% 130 G18 H46 1-285 82% 131 G18 H45 1-286 83% 132 G3 H46 1-290 90% 133 G8 H46 1-293 88% 134 G8 H45 1-294 79%

Compounds 1-1 to 1-295 other than the compounds described in the above Preparation Example were also prepared in the same manner as the method described in the above Preparation Example.

Synthesis confirmation data of the compounds prepared above are as described in [Table 3] and [Table 4] below.

In Table 3, compounds 1 to 294 are the same as compounds 1-1 to 1-294 of Formula 1, and I1 to I294 in Table 4 are the same as compounds 1-1 to 1-294 of Formula 1 herein.

compound FD-Mass compound FD-Mass One m/z= 587.6820 (C42H25N3O, 587.1998) 2 m/z= 663.7800 (C48H29N3O, 663.2311) 3 m/z= 713.8400 (C52H31N3O, 713.2467) 4 m/z= 637.7420 (C46H27N3O, 637.2154) 5 m/z= 637.7420 (C46H27N3O, 637.2154) 6 m/z= 789.9380 (C58H35N3O, 789.2780) 7 m/z= 588.6780 (C41H24N4O, 588.1950) 8 m/z= 664.7680 (C47H28N4O, 664.2263) 9 m/z= 714.8280 (C51H30N4O, 714.2420) 10 m/z= 638.7300 (C45H26N4O, 638.2107) 11 m/z= 638.7300 (C45H26N4O, 638.2107) 12 m/z= 790.9260 (C57H34N4O, 790.2733) 13 m/z= 779.9030 (C55H33N5O, 779.2685) 14 m/z= 829.9630 (C59H35N5O, 829.2842) 15 m/z= 703.8050 (C49H29N5O, 703.2372) 16 m/z= 753.8650 (C53H31N5O, 753.2529) 17 m/z= 755.8810 (C53H33N5O, 755.2685) 18 m/z= 805.9410 (C57H35N5O, 805.2842) 19 m/z= 781.9190 (C55H35N5O, 781.2841) 20 m/z= 703.8050 (C49H29N5O, 703.2372) 21 m/z= 703.8050 (C49H29N5O, 703.2372) 22 m/z= 628.6910 (C43H24N4O2, 628.1899) 23 m/z= 644.7520 (C43H24N4OS, 644.1671) 24 m/z= 694.8120 (C47H26N4OS, 694.1827) 25 m/z= 680.8290 (C47H28N4S, 680.2035) 26 m/z= 730.8890 (C51H1N4S, 730.2191) 27 m/z= 653.8030 (C46H27N3S, 653.1926) 28 m/z= 729.9010 (C52H31N3S, 729.2239) 29 m/z= 730.8890 (C51H31N4S, 730.2191) 30 m/z= 806.9870 C57H34N4S, 806.2904) 31 m/z= 795.9460 (C55H33N5S, 795.2457) 32 m/z= 846.0240 (C59H35N5S, 845.2613) 33 m/z= 719.8660 (C49H29N5S, 719.2144) 34 m/z= 769.9260 (C53H31N5S, 769.2300) 35 m/z= 771.9420 (C53H33N5S, 771.2457) 36 m/z= 822.0020 (C57H35N5S, 821.2613) 37 m/z= 670.8340 (C46H30N4S, 670.2191) 38 m/z= 719.8660 (C49H29N5S, 719.2144) 39 m/z= 719.8660 (C49H29N5S, 719.2144) 40 m/z= 644.7520 (C43H24N4OS, 644.1671) 41 m/z= 660.8130 (C43H24N4S2, 660.1442) 42 m/z= 710.8730 (C47H26N4S2, 710.1599) 43 m/z= 714.8280 (C51H30N4O, 714.2420) 44 m/z= 638.7300 (C45H26N4O, 638.2107) 45 m/z= 638.7300 (C45H26N4O, 638.2107) 46 m/z= 714.8280 (C51H30N4O, 714.2420) 47 m/z= 714.8280 (C51H30N4O, 714.2420) 48 m/z= 790.9260 (C57H34N4O, 790.2733) 49 m/z= 779.9030 (C55H33N5O, 779.2685) 50 m/z= 829.9630 (C59H35N5O, 829.2842) 51 m/z= 703.8050 (C49H29N5O, 703.2372) 52 m/z= 753.8650 (C53H31N5O, 753.2529) 53 m/z=755.8810 (C53H33N5O, 755.2685) 54 m/z= 805.9410 (C57H35N5O, 805.2842) 55 m/z= 654.7730 (C46H30N4O, 654.2420) 56 m/z= 703.8050 (C49H29N5O, 703.2372) 57 m/z= 703.8050 (C49H29N5O, 703.2372) 58 m/z= 628.6910 (C43H24N4O2, 628.1899) 59 m/z= 644.7520 (C43H24N4OS, 644.1671) 60 m/z= 694.8120 (C47H26N4OS, 694.1827) 61 m/z= 653.8030 (C46H27N3S, 653.1926) 62 m/z= 653.8030 (C46H27N3S, 653.1926) 63 m/z= 653.8030 (C46H27N3S, 653.1926) 64 m/z= 653.8030 (C46H27N3S, 653.1926) 65 m/z= 653.8030 (C46H27N3S, 653.1926) 66 m/z= 806.9870 C57H34N4S, 806.2904) 67 m/z= 795.9460 (C55H33N5S, 795.2457) 68 m/z= 846.0240 (C59H35N5S, 845.2613) 69 m/z= 719.8660 (C49H29N5S, 719.2144) 70 m/z= 769.9260 (C53H31N5S, 769.2300) 71 m/z= 771.9420 (C53H33N5S, 771.2457) 72 m/z= 822.0020 (C57H35N5S, 821.2613) 73 m/z= 670.8340 (C46H30N4S, 670.2191) 74 m/z= 719.8660 (C49H29N5S, 719.2144) 75 m/z= 719.8660 (C49H29N5S, 719.2144) 76 m/z= 710.8730 (C47H26N4S2, 710.1599) 77 m/z= 769.9260 (C53H31N5S, 769.2300) 78 m/z= 710.8730 (C47H26N4S2, 710.1599) 79 m/z= 638.7300 (C45H26N4O, 638.2107) 80 m/z= 638.7300 (C45H26N4O, 638.2107) 81 m/z= 638.7300 (C45H26N4O, 638.2107) 82 m/z= 637.7420 (C46H27N3O, 637.2154) 83 m/z= 638.7300 (C45H26N4O, 638.2107) 84 m/z= 790.9260 (C57H34N4O, 790.2733) 85 m/z= 779.9030 (C55H33N5O, 779.2685) 86 m/z= 779.9030 (C55H33N5O, 779.2685) 87 m/z= 779.9030 (C55H33N5O, 779.2685) 88 m/z= 779.9030 (C55H33N5O, 779.2685) 89 m/z= 781.9190 (C55H35N5O, 781.2842) 90 m/z= 829.9630 (C59H35N5O, 829.2842) 91 m/z= 753.8650 (C53H31N5O, 753.2529) 92 m/z= 755.8810 (C53H33N5O, 755.2685) 93 m/z= 805.9410 (C57H35N5O, 805.2842) 94 m/z= 654.7730 (C46H30N4O, 654.2420) 95 m/z= 703.8050 (C49H29N5O, 703.2372) 96 m/z= 703.8050 (C49H29N5O, 703.2372) 97 m/z= 628.6910 (C43H24N4O2, 628.1899) 98 m/z= 644.7520 (C43H24N4OS, 644.1671) 99 m/z= 694.8120 (C47H26N4OS, 694.1827) 100 m/z= 663.7800 (C48H29N3O, 663.2311) 101 m/z= 713.8400 (C52H31N3O, 713.2467) 102 m/z= 713.8400 (C52H31N3O, 713.2467) 103 m/z= 588.6780 (C41H24N4O, 588.1950) 104 m/z= 664.7680 (C47H28N4O, 664.2263) 105 m/z= 714.8280 (C51H30N4O, 714.2420) 106 m/z= 638.7300 (C45H26N4O, 638.2107) 107 m/z= 714.8280 (C51H30N4O, 714.2420) 108 m/z= 790.9260 (C57H34N4O, 790.2733) 109 m/z= 779.9030 (C55H33N5O, 779.2685) 110 m/z= 829.9630 (C59H35N5O, 829.2842) 111 m/z= 703.8050 (C49H29N5O, 703.2372) 112 m/z= 753.8650 (C53H31N5O, 753.2529) 113 m/z=755.8810 (C53H33N5O, 755.2685) 114 m/z= 805.9410 (C57H35N5O, 805.2842) 115 m/z= 654.7730 (C46H30N4O, 654.2420) 116 m/z= 703.8050 (C49H29N5O, 703.2372) 117 m/z= 703.8050 (C49H29N5O, 703.2372) 118 m/z= 628.6910 (C43H24N4O2, 628.1899) 119 m/z= 644.7520 (C43H24N4OS, 644.1671) 120 m/z= 694.8120 (C47H26N4OS, 694.1827) 121 m/z= 588.6780 (C41H24N4O, 588.1950) 122 m/z= 664.7680 (C47H28N4O, 664.2263) 123 m/z= 714.8280 (C51H30N4O, 714.2420) 124 m/z= 638.7300 (C45H26N4O, 638.2107) 125 m/z= 714.8280 (C51H30N4O, 714.2420) 126 m/z= 790.9260 (C57H34N4O, 790.2733) 127 m/z= 779.9030 (C55H33N5O, 779.2685) 128 m/z= 829.9630 (C59H35N5O, 829.2842) 129 m/z= 703.8050 (C49H29N5O, 703.2372) 130 m/z= 753.8650 (C53H31N5O, 753.2529) 131 m/z= m/z= 805.9410 (C57H35N5O, 805.2842) 132 m/z= 781.9190 (C55H35N5O, 781.2841) 133 m/z= 654.7730 (C46H30N4O, 654.2420) 134 m/z= 703.8050 (C49H29N5O, 703.2372) 135 m/z= 703.8050 (C49H29N5O, 703.2372) 136 m/z= 628.6910 (C43H24N4O2, 628.1899) 137 m/z= 644.7520 (C43H24N4OS, 644.1671) 138 m/z= 694.8120 (C47H26N4OS, 694.1827) 139 m/z= 588.6780 (C41H24N4O, 588.1950) 140 m/z= 664.7680 (C47H28N4O, 664.2263) 141 m/z= 714.8280 (C51H30N4O, 714.2420) 142 m/z= 638.7300 (C45H26N4O, 638.2107) 143 m/z= 638.7300 (C45H26N4O, 638.2107) 144 m/z= 790.9260 (C57H34N4O, 790.2733) 145 m/z= 779.9030 (C55H33N5O, 779.2685) 146 m/z= 829.9630 (C59H35N5O, 829.2842) 147 m/z= 703.8050 (C49H29N5O, 703.2372) 148 m/z= 753.8650 (C53H31N5O, 753.2529) 149 m/z= 755.8810 (C53H33N5O, 755.2685) 150 m/z= 805.9410 (C57H35N5O, 805.2842) 151 m/z= 654.7730 (C46H30N4O, 654.2420) 152 m/z= 703.8050 (C49H29N5O, 703.2372) 153 m/z= 703.8050 (C49H29N5O, 703.2372) 154 m/z= 628.6910 (C43H24N4O2, 628.1899) 155 m/z= 644.7520 (C43H24N4OS, 644.1671) 156 m/z= 694.8120 (C47H26N4OS, 694.1827) 157 m/z= 611.7040 (C44H25N3O, 611.1998) 158 m/z= 611.7040 (C44H25N3O, 611.1998) 159 m/z= 611.7040 (C44H25N3O, 611.1998) 160 m/z= 611.7040 (C44H25N3O, 611.1998) 161 m/z= 687.8020 (C50H29N3O, 687.2311) 162 m/z= 763.9000 (C56H33N3O, 763.2624) 163 m/z= 752.8770 (C54H32N4O, 752.2576) 164 m/z= 802.9370 (C58H34N4O, 802.2733) 165 m/z= 676.7790 (C48H28N4O, 676.2263) 166 m/z= 726.8390 (C52H30N4O, 726.2420) 167 m/z= 728.8550 (C52H32N4O, 728.2576) 168 m/z= 778.9150 (C56H34N4O, 778.2733) 169 m/z= 627.7470 (C45H29N3O, 627.2311) 170 m/z= 676.7790 (C48H28N4O, 676.2263) 171 m/z= 676.7790 (C48H28N4O, 676.2263) 172 m/z= 617.7260 (C42H23N3OS, 617.1562) 173 m/z= 617.7260 (C42H23N3OS, 617.1562) 174 m/z= 667.7860 (C46H25N3OS, 667.1718) 175 m/z= 627.7650 (C44H25N3S, 627.1769) 176 m/z= 779.9610 (C56H33N3S, 779.2395) 177 m/z= 768.9380 (C54H32N4S, 768.2348) 178 m/z= 818.9980 (C58H34N4S, 828.2504) 179 m/z= 692.8400 (C48H28N4S, 692.2035) 180 m/z= 768.9380 (C54H32N4S, 768.2348) 181 m/z= 742.9000 (C52H30N4S, 742.2191) 182 m/z= 818.9980 (C58H34N4S, 828.2504) 183 m/z= 744.9160 (C52H32N4S, 744.2348) 184 m/z= 794.9760 (C56H34N4S, 794.2504) 185 m/z= 856.0010 (C61H37N5O, 855.2998) 186 m/z= 692.8400 (C48H28N4S, 692.2035) 187 m/z= 692.8400 (C48H28N4S, 692.2035) 188 m/z= 617.7260 (C42H23N3OS, 617.1562) 189 m/z= 667.7860 (C46H25N3OS, 667.1718) 190 m/z= 683.8470 (C46H25N3S2, 683.1490) 191 m/z= 742.9000 (C52H30N4S, 742.2191) 192 m/z= 683.8470 (C46H25N3S2, 683.1490) 193 m/z= 561.6440 (C40H23N3O, 561.1841) 194 m/z= 687.8020 (C50H29N3O, 687.2311) 195 m/z= 611.7040 (C44H25N3O, 611.1998) 196 m/z= 687.8020 (C50H29N3O, 687.2311) 197 m/z= 763.9000 (C56H33N3O, 763.2624) 198 m/z= 752.8770 (C54H32N4O, 752.2576) 199 m/z= 802.9370 (C58H34N4O, 802.2733) 200 m/z= 676.7790 (C48H28N4O, 676.2263) 201 m/z= 752.8770 (C54H32N4O, 752.2576) 202 m/z= 726.8390 (C52H30N4O, 726.2420) 203 m/z= 728.8550 (C52H32N4O, 728.2576) 204 m/z= 778.9150 (C56H34N4O, 778.2733) 205 m/z= 627.7470 (C45H29N3O, 627.2311) 206 m/z= 676.7790 (C48H28N4O, 676.2263) 207 m/z= 676.7790 (C48H28N4O, 676.2263) 208 m/z= 601.6650 (C42H23N3O2, 601.1790) 209 m/z= 617.7260 (C42H23N3OS, 617.1562) 210 m/z= 667.7860 (C46H25N3OS, 667.1718) 211 m/z= 577.7050 (C40H23N3S, 577.1613) 212 m/z= 627.7650 (C44H25N3S, 627.1769) 213 m/z= 627.7650 (C44H25N3S, 627.1769) 214 m/z= 627.7650 (C44H25N3S, 627.1769) 215 m/z= 779.9610 (C56H33N3S, 779.2395) 216 m/z= 768.9380 (C54H32N4S, 768.2348) 217 m/z= 818.9980 (C58H34N4S, 828.2504) 218 m/z= 692.8400 (C48H28N4S, 692.2035) 219 m/z= 768.9380 (C54H32N4S, 768.2348) 220 m/z= 744.9160 (C52H32N4S, 744.2348) 221 m/z= 794.9760 (C56H34N4S, 794.2504) 222 m/z= 821.0140 (C58H36N4S, 821.0140) 223 m/z= 643.8080 (C45H29N3S, 643.2082) 224 m/z= 692.8400 (C48H28N4S, 692.2035) 225 m/z= 692.8400 (C48H28N4S, 692.2035) 226 m/z= 617.7260 (C42H23N3OS, 617.1562) 227 m/z= 633.7870 (C42H23N3S2, 633.1333) 228 m/z= 683.8470 (C46H25N3S2, 683.1490) 229 m/z= 611.7040 (C44H25N3O, 611.1998) 230 m/z= 763.9000 (C56H33N3O, 763.2624) 231 m/z= 676.7790 (C48H28N4O, 676.2263) 232 m/z= 802.9370 (C58H34N4O, 802.2733) 233 m/z= 728.8550 (C52H32N4O, 728.2576) 234 m/z= 778.9150 (C56H34N4O, 778.2733) 235 m/z= 752.8770 (C54H32N4O, 752.2576) 236 m/z= 802.9370 (C58H34N4O, 802.2733) 237 m/z= 752.8770 (C54H32N4O, 752.2576) 238 m/z= 752.8770 (C54H32N4O, 752.2576) 239 m/z= 728.8550 (C52H32N4O, 728.2576) 240 m/z= 778.9150 (C56H34N4O, 778.2733) 241 m/z= 561.6440 (C40H23N3O, 561.1841) 242 m/z= 637.7420 (C46H27N3O, 737.2154) 243 m/z= 687.8020 (C50H29N3O, 687.2311) 244 m/z= 611.7040 (C44H25N3O, 611.1998) 245 m/z= 687.8020 (C50H29N3O, 687.2311) 246 m/z= 763.9000 (C56H33N3O, 763.2624) 247 m/z= 752.8770 (C54H32N4O, 752.2576) 248 m/z= 802.9370 (C58H34N4O, 802.2733) 249 m/z= 752.8770 (C54H32N4O, 752.2576) 250 m/z= 802.9370 (C58H34N4O, 802.2733) 251 m/z= 728.8550 (C52H32N4O, 728.2576) 252 m/z= 778.9150 (C56H34N4O, 778.2733) 253 m/z= 627.7470 (C45H29N3O, 627.2311) 254 m/z= 676.7790 (C48H28N4O, 676.2263) 255 m/z= 676.7790 (C48H28N4O, 676.2263) 256 m/z= 601.6650 (C42H23N3O2, 601.1790) 257 m/z= 617.7260 (C42H23N3OS, 617.1562) 258 m/z= 667.7860 (C46H25N3OS, 667.1718) 259 m/z= 611.7040 (C44H25N3O, 611.1998) 260 m/z= 611.7040 (C44H25N3O, 611.1998) 261 m/z= 763.9000 (C56H33N3O, 763.2624) 262 m/z= 752.8770 (C54H32N4O, 752.2576) 263 m/z= 802.9370 (C58H34N4O, 802.2733) 264 m/z= 728.8550 (C52H32N4O, 728.2576) 265 m/z= 676.7790 (C48H28N4O, 676.2263) 266 m/z= 667.7860 (C46H25N3OS, 667.1718) 267 m/z= 611.7040 (C44H25N3O, 611.1998) 268 m/z= 611.7040 (C44H25N3O, 611.1998) 269 m/z= 763.9000 (C56H33N3O, 763.2624) 270 m/z= 752.8770 (C54H32N4O, 752.2576) 271 m/z= 802.9370 (C58H34N4O, 802.2733) 272 m/z= 676.7790 (C48H28N4O, 676.2263) 273 m/z= 752.8770 (C54H32N4O, 752.2576) 274 m/z= 726.8390 (C52H30N4O, 726.2420) 275 m/z= 728.8550 (C52H32N4O, 728.2576) 276 m/z= 778.9150 (C56H34N4O, 778.2733) 277 m/z= 627.7470 (C45H29N3O, 627.2311) 278 m/z= 676.7790 (C48H28N4O, 676.2263) 279 m/z= 676.7790 (C48H28N4O, 676.2263) 280 m/z= 667.7860 (C46H25N3OS, 667.1718) 281 m/z= 617.7260 (C42H23N3OS, 617.1562) 282 m/z= 667.7860 (C46H25N3OS, 667.1718) 283 m/z= 717.8460 (C50H27N3OS, 717.1875) 284 m/z= 701.7850 (C50H27N3O2, 701.2103) 285 m/z= 717.8460 (C50H27N3OS, 717.1875) 286 m/z= 701.7850 (C50H27N3O2, 701.2103) 287 m/z= 717.8460 (C50H27N3OS, 717.1875) 288 m/z= 701.7850 (C50H27N3O2, 701.2103) 289 m/z= 717.8460 (C50H27N3OS, 717.1875) 290 m/z= 701.7850 (C50H27N3O2, 701.2103) 291 m/z= 717.8460 (C50H27N3OS, 717.1875) 292 m/z= 701.7850 (C50H27N3O2, 701.2103) 293 m/z= 733.9070 (C50H27N3S2, 733.1646) 294 m/z= 717.8460 (C50H27N3OS, 717.1875)

Example ¹ H NMR (CDCl ₃ , 200Mz) I1 δ = 8.91(d, 1H), 8.88(d, 1H), 8.76(s, 1H), 8.73(d, 1H), 8.59(d, 1H), 8.18(d, 1H), 7.94~7.74(m, 7H), 7.59~7.38(m, 8H), 7.30~7.21(m, 4H). I2 δ = 8.90(d, 1H), 8.88(d, 1H), 8.76(s, 1H), 8.71(d, 1H), 8.60(d, 1H), 7.81~7.69(m, 9H), 7.52~7.28 ( m, 10H), 7.28 to 7.15 (m, 5H). I4 δ = 8.91(s, 1H), 8.65(d, 2H), 8.59(d, 2H), 8.18~7.90(m, 5H), 7.82~7.64(m, 4H), 7.59~7.53(m, 8H), 7.41~7.36 (m, 5H). I5 δ = 8.9(s, 1H), 8.69(d, 2H), 8.58(d, 2H), 8.24~8.11 (m, 3H), 7.76~7.54 (m, 6H), 7.59~7.34 (m, 7H), 7.29-7.17 (m, 6H). I6 δ = 8.85 (s, 1H), 8.69(s, 2H), 8.38~8.24(m, 7H), 8.22~8.11(m, 8H), 7.76~7.54(m, 6H), 7.44~7.39(m, 5H) ), 7.37 (t, 2H), 7.32-7.27 (m, 4H). I10 δ = 8.64 (d, 2H), 8.59(d, 2H), 8.30~8.15(m, 5H), 7.78~7.64(m, 4H), 7.52~7.40(m, 8H), 7.30~7.20(m, 5H) ). I11 δ = 9.18 (d, 2H), 9.14(d, 2H), 8.83~8.81(m, 3H), 7.90~7.79(m, 10H), 7.59~7.54(m, 3H), 7.43~7.40 (m, 6H) ). I12 δ = 9.20(s, 2H), 9.14(d, 2H), 8.48~8.44(m, 5H), 8.29~8.18(m, 8H), 7.80~7.76(m, 6H), 7.54~7.51(m, 5H) ), 7.39(t, 2H), 7.24~7.18(m, 4H). I17 δ = 8.59(d, 1H), 8.40(d, 2H), 8.27~8.18(m, 6H), 7.82~7.69(m, 11H), 7.59~7.34(m, 6H), 7.29~7.17(m, 6H) ). 6.71 (d, 1H). I18 δ = 8.59(d, 1H), 8.37(d, 2H), 8.27~8.16(m, 7H), 8.12(s, 1H), 7.81~7.66(m, 12H), 7.57~7.30(m, 6H), 7.29-7.17 (m, 5H). 6.71 (d, 1H). I19 δ = 8.7(s, 1H), 8.49 (d, 2H), 8.24~8.11 (m, 5H), 7.76 (d, 2H), 7.60~7.51 (m, 11H), 7.50~7.35 (m, 8H), 7.29~7.16 (m, 6H). I27 δ = 8.9(s, 1H), 8.82(d, 2H), 8.79(d, 2H), 8.27~8.25(m, 3H), 7.77~7.65(m, 6H), 7.54~7.45(m, 7H), 7.31-7.27 (m, 6H). I28 δ = 8.88(s, 1H), 8.62(d, 2H), 8.59 (d, 2H), 8.42(d, 2H), 8.27~8.25(m, 3H), 7.77(d, 2H), 7.67~7.59 ( m, 6H), 7.62-7.53 (m, 7H), 7.27-7.19 (m, 6H). I29 δ = 8.66(d, 2H), 8.52(d, 2H), 8.41(d, 2H), 8.35~8.18(m, 3H), 7.9(d, 2H), 7.77~7.61(m, 6H), 7.72~ 7.43(m, 7H), 7.29~7.15(m, 5H), 7.11~7.09(m, 1H). I31 δ = 9.20(dd, 2H), 9.04(d, 3H), 8.62(s, 1H), 8.58 (s, 1H), 8.27(s, 1H), 8.19~8.15(m, 4H), 8.11(d, 1H), 8.05~8.00(m, 2H), 8.00~7.88(m, 4H), 7.79~7.51(m, 14H), 7.47(d, 1H), 7.41~7.39(m, 1H). I32 δ = 9.19(dd, 2H), 9.08(d, 3H), 8.61(s, 1H), 8.58 (s, 1H), 8.56(d, 1H), 8.28(s, 1H), 8.19~8.15(m, 4H), 8.11(d, 1H), 8.05~8.00(m, 2H), 7.90~7.79(m, 5H), 7.74~7.60(m, 14H), 7.48(d, 1H), 7.40(t, 1H) . I33 δ = 8.86(d, 1H), 8.59(d, 2H), 8.36(s, 1H), 8.27~8.19(m, 5H), 7.88~7.72(m, 9H), 7.57(d, 2H), 7.49~ 7.40(m, 4H), 7.38(d, 2H), 7.27~7.17(m, 4H). 6.71(d, 1H) I34 δ = 8.87(d, 1H), 8.66(d, 2H), 8.48(d, 1H), 8.36(s, 1H), 8.30~8.19 (m, 6H), 7.81~7.68(m, 9H), 7.58( d, 2H), 7.51~7.44 (m, 4H), 7.39 (d, 2H), 7.33~7.22 (m, 4H). 6.84 (d, 1H) I35 δ = 8.65(d, 1H), 8.48(d, 2H), 8.29~8.20(m, 6H), 7.91~7.77(m, 11H), 7.60~7.36(m, 6H), 7.28~7.18(m, 6H) ). 6.89(d, 1H) I37 δ = 8.55 (d, 1H), 8.46 (d, 1H), 8.43 (d, 2H), 8.29 to 8.17 (m, 4H), 7.76 (d, 1H), 7.7 (s, 1H), 7.59 (d, 1H), 7.48~7.38 (m, 8H), 7.28 (s, 1H), 7.36~7.31 (m, 3H), 7.20 (t, 1H), 1.77 (s, 6H). I38 δ = 8.55(d, 1H), 8.47(d, 1H), 8.40(d, 2H), 8.27~8.16 (m, 4H), 7.73(d, 1H), 7.9(s, 1H), 7.59(d, 1H), 7.48~7.38(m, 8H), 7.36~7.27(m, 7H), 7.24(s, 1H), 7.20~7.18(m, 2H). I39 δ = 8.57(d, 2H), 8.48(d, 1H), 8.38(d, 2H), 8.16~8.09(m, 5H), 7.56~7.41(m, 14H), 7.33(t, 2H), 7.21 ( d, 1H), 7.19-7.18 (m, 2H). I40 δ = 8.55(d, 1H), 8.48(d, 1H), 8.37(d, 2H), 8.07~7.99(m, 3H), 7.97(d, 2H), 7.66(d, 1H), 7.59~7.52 ( m, 7H), 7.48~7.44(m, 4H), 7.29~7.23(m, 3H). I41 δ = 8.54(d, 1H), 8.49(d, 1H), 8.37(dd, 2H), 8.07~7.99(m, 3H), 7.98(d, 2H), 7.89(d, 1H), 7.60~7.55 ( m, 7H), 7.49~7.43(m, 4H), 7.30~7.24(m, 3H). I42 δ = 8.49(d, 1H), 8.38(d, 1H), 8.38(dd, 2H), 8.07~7.80(m, 3H), 7.98(d, 2H), 7.89(d, 1H), 7.60~7.52 ( m, 8H), 7.48~7.40 (m, 5H), 7.29~7.25(m, 3H). I43 δ = 9.0(d, 1H), 8.9(d, 1H), 8.56(d, 1H), 8.55(d, 1H), 8.42(d, 1H), 8.39(d, 2H), 8.20~8.13(d, 3H), 8.07~8.01(m, 3H), 7.94(s, 1H), 7.88(s, 1H), 7.79-7.78(m, 1H), 7.47~7.44 (m, 11H), 7.36~7.32(m, 3H). I45 δ = 8.56 (d, 2H), 8.43 (d, 2H), 8.34 to 8.29 (m, 3H), 7.91 to 7.84 (m, 6H), 7.67 (s, 1H), 7.59 to 7.48 (m, 6H), 7.33-7.21 (m, 6H). I46 δ = 8.39(d, 2H), 8.36(d, 2H), 8.27(d, 2H), 8.18~7.95(m, 3H), 7.92(d, 2H), 7.82~7.66(m, 4H), 7.59~ 7.49 (m, 5H), 4.46 (s, 2H), 7.44-7.37 (m, 3H), 7.28-7.15 (m, 5H). I47 δ = 8.54(d, 2H), 8.42(d, 2H), 8.34~8.30(m, 3H), 8.27(d, 2H), 7.91~7.84(m, 6H), 7.67(s, 1H), 7.59( d, 2H), 7.52~7.38(m, 6H), 7.33~7.21(m, 6H). I48 δ = 8.55(d, 2H), 8.42(d, 2H), 8.36~8.31(m, 3H), 8.26(d, 2H), 7.90~7.85(m, 6H), 7.68(s, 1H), 7.54( d, 2H), 7.52~7.33(m, 9H), 7.31~7.19(m, 9H), 7.17(t, 2H). I54 δ = 8.58(d, 1H), 8.33(d, 2H), 8.27~8.16(m, 7H), 8.05~8.01(m, 4H), 7.77~7.64(m, 9H), 7.42~7.36(m, 4H) ), 7.29~7.25(m, 2H), 7.29~7.17(m, 5H). 6.69(d, 1H) I55 δ = 8.55(d, 1H), 8.46(d, 1H), 8.43(d, 2H), 8.29~8.16(m, 4H), 7.76(d, 1H), 7.58(s, 1H), 7.57(d, 1H), 7.46~7.37(m, 8H), 7.27(s, 1H), 7.36~7.31(m, 3H), 7.20~7.19(m, 1H), 1.77(s, 6H). I56 δ = 8.54(d, 1H), 8.44(d, 1H), 8.40(d, 2H), 8.19~8.14 (m, 4H), 7.71(d, 1H), 7.79(s, 1H), 7.56(d, 1H), 7.47~7.36(m, 8H), 7.36~7.26(m, 7H), 7.23(s, 1H), 7.21~7.18(m, 2H). I57 δ = 8.55(d, 2H), 8.47(d, 1H), 8.38(d, 2H), 8.14~8.09(m, 5H), 7.56~7.51(m, 8H), 7.50~7.44(m, 6H), 7.33 (t, 2H), 7.20 (d, 1H), 7.19-7.18 (m, 2H). I61 δ = 8.59(d, 2H), 8.48(s, 1H), 8.44(d, 2H), 8.39(d, 2H), 7.76~7.70(m, 5H), 7.39(d, 2H), 7.33(d, 2H), 7.32~7.26(m, 5H), 7.24~7.20(m, 4H), 7.14(t, 1H). I62 δ = 8.59(d, 2H), 8.46(s, 1H), 8.43(d, 1H), 8.36(d, 1H), 8.22(d, 1H), 8.19(d, 1H), 7.72~7.66(m, 5H), 7.36(d, 2H), 7.35~7.31(m, 7H), 7.28~7.23(m, 4H), 7.17(t, 1H). I63 δ = 8.59 (d, 2H), 8.46 (s, 1H), 8.45 (d, 1H), 8.43 (d, 1H), 8.33 (d, 1H), 8.22 (d, 1H), 8.19 (d, 1H) , 7.77(d, 2H), 7.49~7.42(m, 3H), 7.72~7.66(m, 4H), 7.38(d, 2H), 7.36(d, 2H), 7.35~7.31(m, 4H), 7.22 ~7.20 (m, 1H). I64 δ = 8.66 (d, 2H), 8.54 (s, 1H), 8.49 (s, 2H), 8.49 (d, 2H), 8.38 (s, 2H), 8.03 (d, 4H), 7.76 (d, 4H) , 7.49~7.45 (m, 5H), 7.42~7.38(m, 3H), 7.19~7.17(m, 1H). I65 δ = 9.31 (d, 2H), 9.24 (d, 2H), 9.06 (d, 3H), 8.39 (d, 1H), 8.29 (s, 1H), 8.15 (d, 1H), 8.11 (d, 2H) , 8.04 (t, 1H), 8.00-7.89 (m, 4H), 7.80-7.61 (m, 8H), 7.56 (t, 1H). I67 δ = 9.33(d, 1H), 9.21(dd, 2H), 9.09(d, 3H), 8.62(s, 1H), 8.56(s, 1H), 8.17~8.15(m, 4H), 8.11(d, 1H), 8.04~8.00 (m, 2H), 8.00~7.89(m, 4H), 7.80~7.51(m, 13H), 7.41~7.39(m, 1H). I68 δ = 9.24 (dd, 2H), 9.02 (d, 3H), 8.64 (d, 1H), 8.59 (s, 1H), 8.56 (s, 1H), 8.19 to 8.16 (m, 4H), 8.12 (d, 1H), 8.09~8.04(dd, 2H), 8.01~7.89(m, 4H), 7.80~8.64(m, 8H), 7.60~7.51(m, 6H), 7.43~7.39(m, 2H). I76 δ = 9.42(d, 2H), 9.32(s, 1H), 9.28(d, 1H), 9.15(d, 1H), 8.9(d, 1H), 8.71(d, 1H), 8.52~8.49(m, 2H), 8.39~8.37(m, 1H), 8.04(d, 1H), 7.87~7.83(m, 2H), 7.83~7.75(m, 4H), 7.66(d, 1H), 7.64~7.49(m, 10H), 7.38 (t, 2H). I77 δ = 9.38(d, 2H), 9.3(s, 1H), 9.27(d, 1H), 9.11(d, 1H), 8.87(d, 1H), 8.74(d, 1H), 8.54~8.49(m, 2H), 8.40~8.38(m, 1H), 8.04(d, 1H), 7.87~7.84(m, 2H), 7.83~7.75(m, 4H), 7.61~7.49(m, 8H), 7.36(t, 1H). I79 δ = 8.76(d, 1H), 8.55(d, 1H), 8.46(d, 2H), 8.36(d, 1H), 8.34(d, 1H), 8.29(d, 1H), 7.90~7.86(m, 6H), 7.77(s, 1H), 7.62~7.51(m, 6H), 7.35~7.26(m, 6H). I80 δ = 8.74(d, 1H), 8.71(d, 1H), 8.55(d, 2H), 8.46(d, 2H), 8.36(d, 1H), 8.34~8.30(m, 3H), 7.90~7.84( m, 6H), 7.70(s, 1H), 7.52~7.48(m, 4H), 7.31~7.26(m, 5H). I81 δ = 8.76(d, 2H), 8.71(d, 2H), 8.46(d, 2H), 8.34~8.29(m, 3H), 7.93~7.85(m, 6H), 7.66(s, 1H), 7.50~ 7.46(m, 4H), 7.27~7.22(m, 6H). I82 δ = 8.55(d, 2H), 8.46(d, 2H), 8.34~8.29(m, 3H), 7.93~7.88(m, 6H), 7.73(s, 1H), 7.62~7.48(m, 6H), 7.34-7.27 (m, 6H). I83 δ = 8.78(s, 1H), 8.52(d, 2H), 8.40(d, 2H), 8.33~8.28(m, 3H), 7.93~7.87(m, 6H), 7.70(s, 1H), 7.61~ 7.51 (m, 6H), 7.34-7.27 (m, 6H). I85 δ = 9.36 (s, 1H), 8.71 (d, 1H), 8.68 (d, 1H), 8.46 (d, 1H), 8.29 (d, 1H), 8.27 (d, 2H), 8.24 to 8.11 (m, 5H), 7.76(d, 1H), 7.49~7.44(m, 7H), 7.39~7.36(m, 9H), 7.28~7.23(m, 6H), 7.18~7.16(m, 2H). I86 δ = 9.34 (s, 1H), 8.89 (d, 1H), 8.85 (d, 1H), 8.43 (d, 1H), 8.28 (d, 1H), 8.27 (d, 2H), 8.24 to 8.19 (m, 3H), 7.76(d, 1H), 7.49~7.44(m, 5H), 7.39(s, 1H), 7.38~7.28(m, 9H), 7.26~7.20(m, 6H), 7.18~7.16(m, 2H). I87 δ = 9.34 (s, 1H), 8.89 (d, 1H), 8.85 (d, 1H), 8.42 (s, 1H), 8.29 (d, 1H), 8.27 (d, 2H), 8.15 to 8.11 (m, 3H), 7.77(d, 1H), 7.47~7.43(m, 5H), 7.38~7.27(m, 9H), 7.26~7.20(m, 6H), 7.18~7.17(m, 2H). I88 δ = 9.30(s, 1H), 8.82(d, 1H), 8.88(d, 1H), 8.44(s, 1H), 8.26(d, 1H), 8.25(d, 2H), 8.18~8.11(m, 3H), 7.72(d, 1H), 7.47~7.43(m, 5H), 7.38~7.27(m, 6H), 7.28~7.23(m, 8H), 7.20(d, 2H), 7.18(t, 1H) . I89 δ = 9.30(s, 1H), 8.89(d, 1H), 8.86(d, 1H), 8.79(s, 1H), 8.32(d, 1H), 8.17~8.13(m, 3H), 7.66(d, 1H), 7.42~7.36(m, 5H), 7.35~7.30(m, 6H), 7.28~7.21(m, 12H), 7.14~7.11(m, 3H). I90 δ = 9.27 (s, 1H), 8.95 (d, 2H), 8.87 (d, 1H), 8.74 (d, 1H), 8.77 (d, 1H), 8.75 (d, 1H), 8.58 (d, 2H) , 8.56(d, 1H), 8.22(d, 1H), 8.19~8.15(m, 4H), 8.12(d, 1H), 8.05~8.00(m, 2H), 7.90~7.79(m, 5H), 7.74 ~7.59 (m, 10H), 7.44 (d, 1H), 7.36 (t, 1H). I91 δ = 9.29 (s, 1H), 8.87 (d, 1H), 8.86 (d, 2H), 8.70 (d, 2H), 8.68 (s, 1H), 8.48 (d, 1H), 8.24 to 8.19 (m, 5H), 7.81~7.68(m, 7H), 7.58(d, 2H), 7.51~7.44 (m, 4H), 7.39 (d, 2H), 7.33~7.29(m, 2H), 7.22 (t, 1H) . I92 δ = 9.26 (s, 1H), 8.85 (d, 1H), 8.81 (d, 2H), 8.66 (d, 2H), 8.46 (d, 1H), 8.24 to 8.19 (m, 5H), 8.07 (s, 1H), 7.81~7.72(m, 6H), 7.46~7.41 (m, 4H), 7.33~7.29(m, 8H), 7.17(t, 2H). I93 δ = 9.26(s, 1H), 8.86(d, 1H), 8.83(d, 2H), 8.65(d, 2H), 8.46(d, 1H), 8.31(d, 1H), 8.25~8.19(m, 4H), 8.04(s, 1H), 7.76(d, 1H), 7.64(d, 1H), 7.59(d, 1H), 7.48~7.47(m, 2H), 7.46~7.41(m, 7H), 7.33 ~7.27 (m, 10H), 7.19 (t, 1H). I94 δ = 8.76(d, 1H), 8.45(d, 2H), 8.29~8.17(m, 4H), 7.76(d, 1H), 7.81(s, 1H), 7.59(d, 1H), 7.56(s, 1H), 7.53~7.51(m, 3H), 7.48~7.42(m, 6H), 7.40~7.38(m, 3H), 7.30(s, 1H), 1.75(s, 6H). I95 δ = 9.12(d, 1H), 9.08(s, 1H), 8.89(d, 2H), 8.40(d, 2H), 8.26(d, 2H), 8.25(s, 1H), 8.24~8.16 (m, 4H), 7.73(d, 1H), 7.59(d, 1H), 7.48~7.38(m, 6H), 7.36~7.27(m, 5H), 7.24(s, 1H), 7.20~7.17(m, 2H) . I96 δ = 9.14 (d, 1H), 9.08 (s, 1H), 8.90 (d, 2H), 8.68 (d, 2H), 8.41 (d, 2H), 8.28 (d, 2H), 8.26 (s, 1H) , 8.24~8.21(m, 2H), 7.61(d, 1H), 7.59(d, 1H), 7.46~7.38(m, 6H), 7.36~7.27(m, 5H), 7.23(s, 1H), 7.20 ~7.18 (m, 2H). I101 δ = 8.98(s, 1H), 8.87(d, 1H), 8.79(d, 1H), 8.64(d, 2H), 8.62(s, 1H), 8.34~8.30(m, 3H), 8.27(d, 2H), 8.02(d, 1H), 7.77(d, 1H), 7.70~7.61(m, 6H), 7.59(d, 2H), 7.52~7.43(m, 4H), 7.27~7.21(m, 6H) . I102 δ = 8.98(s, 1H), 8.85~8.83(m, 3H), 8.60(d, 2H), 8.49(d, 2H), 8.26~8.22(m, 3H), 8.21(d, 2H), 7.71~ 7.61(m, 6H), 7.59(d, 2H), 7.52~7.43(m, 4H), 7.27~7.20(m, 6H). I107 δ = 8.87~8.86(m, 3H), 8.64(d, 2H), 8.62(d, 2H), 8.34~8.30(m, 3H), 8.27(d, 2H), 7.71~7.61(m, 6H), 7.59(d, 2H), 7.52~7.43(m, 4H), 7.27~7.21(m, 6H). I117 δ = 8.67 (d, 2H), 8.59 (s, 1H), 8.58 (d, 1H), 8.38 (d, 2H), 8.27 (d, 1H), 8.24 (d, 1H), 8.16 (d, 1H) , 7.51~7.40(m, 14H), 7.33~7.29(m, 3H), 7.21 (d, 1H), 7.19-7.18(m, 2H). I118 δ = 8.69 (d, 2H), 8.61 (s, 1H), 8.58 (d, 1H), 8.40 (d, 2H), 8.18 (d, 1H), 8.16 (d, 1H), 8.12 (d, 1H) , 7.48~7.44(m, 5H), 7.39~7.31(m, 8H), 7.29(d, 1H), 7.24(t, 1H). I119 δ = 8.89 (d, 2H), 8.80 (s, 1H), 8.68 (d, 1H), 8.60 (d, 2H), 8.32 (d, 1H), 8.24 (d, 1H), 8.21 (d, 1H) , 7.56~7.50(m, 5H), 7.49~7.39(m, 8H), 7.32(d, 1H), 7.28(t, 1H). I120 δ = 8.86(d, 2H), 8.77(s, 1H), 8.58(d, 2H), 8.32(d, 1H), 8.30(d, 1H), 8.26(d, 1H), 7.55~7.48(m, 6H), 7.50~7.39 (m, 10H), 7.30 (d, 1H), 7.24 (t, 1H). I127 δ = 9.18 (dd, 2H), 8.72 (d, 1H), 8.65 (d, 1H), 8.51 (s, 1H), 8.42 (s, 1H), 8.34 (s, 1H), 8.28 (d, 1H) , 8.26~8.20(m, 3H), 8.14~8.08(m, 2H), 8.03(d, 1H), 7.97-7.90(m, 2H), 7.86~7.78(m, 3H), 7.63~7.41 (m, 12H), 7.32(t, 1H) I128 δ = 9.16 (dd, 2H), 8.70 (d, 1H), 8.59 (d, 1H), 8.46 (s, 1H), 8.40 (s, 1H), 8.33 (s, 1H), 8.19 (d, 1H) , 8.27~8.22(m, 4H), 8.14~8.06(m, 2H), 8.01(d, 1H), 7.97-7.92(m, 2H), 7.88~7.79(m, 4H), 7.65~7.41 (m, 14H), 7.34-7.30 (m, 1H) I130 δ = 8.92 (d, 1H), 8.87 (d, 1H), 8.86 (d, 2H), 8.70 (d, 1H), 8.69 (d, 1H), 8.66 (s, 1H), 8.60 (s, 1H) , 8.48(d, 1H), 8.29(d, 2H), 8.24~8.20(m, 3H), 7.83~7.66(m, 6H), 7.57(d, 2H), 7.50~7.45(m, 4H), 7.39 (d, 2H), 7.33-7.30 (m, 2H), 7.19 (t, 1H). I132 δ = 8.90 (d, 1H), 8.86 (d, 1H), 8.84 (d, 2H), 8.69 (d, 1H), 8.66 (d, 1H), 8.64 (s, 1H), 8.59 (s, 1H) , 8.48(d, 1H), 8.29(d, 2H), 8.17~8.13(m, 3H), 7.66(d, 1H), 7.42~7.36(m, 4H), 7.35~7.30(m, 4H), 7.28 ~7.21(m, 9H), 7.14~7.11(m, 3H). I142 δ = 9.23 (d, 2H), 9.17 (d, 1H), 8.90 (s, 1H), 8.82 (d, 2H), 8,76 (d, 2H), 8.60 (s, 1H), 8.54 (d, 1H), 8.26(s, 1H), 7.71~7.63(m, 8H), 7.40~7.37(m, 3H), 7.33~7.28(m, 4H). I143 δ = 9.23(d, 2H), 9.17(d, 2H), 8.82(d, 3H), 8.80(s, 1H), 8.26(d, 1H), 8.25(d, 2H), 7.77~7.65(m, 10H), 7.42 to 7.39 (m, 2H), 7.38 to 7.35 (m, 4H). I144 δ = 9.20(s, 2H), 9.16(d, 2H), 8.80(d, 3H), 8.79(s, 1H), 8.24(d, 1H), 8.22(d, 2H), 7.78~7.67(m, 13H), 7.42 to 7.38 (m, 4H), 7.37 to 7.33 (m, 6H). I145 δ = 9.19 (dd, 2H), 8.73 (d, 1H), 8.62 (d, 1H), 8.57 (s, 1H), 8.42 (s, 1H), 8.34 (s, 1H), 8.28 (d, 1H) , 8.26~8.20(m, 3H), 8.14~8.08(m, 2H), 8.03(d, 1H), 7.95-7.89(m, 2H), 7.87~7.76(m, 3H), 7.61~7.40 (m, 12H), 7.32(t, 1H) I152 δ = 9.15 (d, 2H), 9.11 (s, 1H), 9.09 (d, 1H), 8.92 (s, 1H), 8.90 (d, 1H), 8.45 (d, 1H), 8.43 (d, 1H) , 7.65~7.61(m, 5H), 7.56~7.51(m, 7H), 7.48(d, 1H), 7.36~7.32(m, 5H), 7.28(s, 1H), 7.27~7.25(m, 2H) I158 δ = 9.03(d, 2H), 8.97(s, 1H), 8.72(d, 1H), 8.70(d, 2H), 8.52(s, 1H), 8.49~8.47(m, 2H), 8.23(d, 2H), 7.74~7.67(m, 6H), 7.44~7.37(m, 5H), 7.34~7.31 (m, 4H). I160 δ = 8.88 (d, 2H), 8.74 (d, 2H), 8.33 to 8.21 (m, 3H), 8.16 (d, 1H), 7.70 to 7.59 (m, 8H), 7.49 to 7.44 (m, 5H), 7.38~7.31 (m, 6H). I162 δ = 8.89 (s, 2H), 8.71 (d, 2H), 8.32 to 8.21 (m, 3H), 8.19 (d, 1H), 7.69 to 7.64 (m, 5H), 7.59 to 7.56 (m, 3H), 7.49~7.44(m, 7H), 7.36~7.30 (m, 8H), 7.27(t, 2H). I163 δ = 9.19(dd, 2H), 8.73(d, 1H), 8.67(d, 1H), 8.49(s, 1H), 8.41(s, 1H), 8.29(d, 1H), 8.25~8.20(m, 3H), 8.15~8.07(m, 3H), 8.03(d, 1H), 7.98-7.91(m, 2H), 7.85~7.78(m, 3H), 7.66~7.42 (m, 12H), 7.34-7.30 ( m, 1H) I164 δ = 9.16 (dd, 2H), 8.70 (d, 1H), 8.59 (d, 1H), 8.46 (s, 1H), 8.40 (s, 1H), 8.33 (s, 1H), 8.19 (d, 1H) , 8.27~8.22(m, 4H), 8.14~8.06(m, 2H), 8.01(d, 1H), 7.97-7.92(m, 2H), 7.88~7.79(m, 4H), 7.65~7.41 (m, 14H), 7.34-7.30 (m, 1H) I171 δ = 8.92(d, 1H), 8.80(d, 1H), 8.79(d, 1H), 8.68(s, 1H), 8.43(d, 1H), 8.34(d, 2H), 8.30~8.28(m, 2H), 7.66~7.58(m, 10H), 7.54~7.52(m, 2H), 7.29(t, 1H). I172 δ = 8.94(d, 1H), 8.69(s, 1H), 8.67(d, 1H), 8.43(d, 1H), 8.28(dd, 2H), 8.24(d, 2H), 8.20~8.18(m, 3H), 7.70~7.64(m, 7H), 7.49~7.44(m, 5H). I173 δ = 8.99 (d, 1H), 8.84 (d, 1H), 8.71 (s, 1H), 8.62 (d, 1H), 8.40 (d, 1H), 8.35 (d, 1H), 8.23 (d, 2H) , 8.22~8.18(m, 3H), 7.70~7.64(m, 7H), 7.42~7.39(m, 4H). I174 δ = 9.26(d, 1H), 9.15(d, 1H), 8.96(d, 1H), 8.61(s, 1H), 8.47~8.44(m, 1H), 8.39~8.37(m, 1H), 8.21~ 8.18(m, 2H), 8.05(d, 1H), 7.86(t, 1H), 7.84~7.63(m, 3H), 7.62~7.51(m, 9H), 7.34~7.28(m, 3H). I179 δ = 9.18 (d, 2H), 9.15 (d, 1H), 8.89 (d, 1H), 8.80 (s, 1H), 8.79-8.78 (m, 2H), 8.63 (s, 1H), 8.59 (d, 1H), 8.26(dd, 2H), 8.24(d, 1H), 7.76~7.65(m, 10H), 7.49~7.44 (m, 6H). I180 δ = 9.18 (d, 2H), 9.14 (d, 1H), 8.87 (d, 1H), 8.80 (s, 1H), 8.79-8.77 (m, 2H), 8.63 (s, 1H), 8.62 (d, 1H), 8.25(dd, 2H), 8.22(d, 1H), 7.75~7.54 (m, 12H), 7.49~7.43 (m, 8H), 7.31(t, 1H). I186 δ = 9.11(s, 1H), 8.82(d, 1H), 8.80(d, 1H), 8.67(s, 1H), 8.59(d, 1H), 8.46(d, 1H), 8.38~8.36(m, 2H), 7.57~7.54 (m, 8H), 7.44~7.40(m ,4H), 7.36~7.30(m, 6H), 7.28(s, 1H), 7.11(t, 1H). I189 δ = 8.99(d, 1H), 8.82(d, 2H), 8.77(s, 1H), 8.49~8.47(m, 3H), 8.26(d, 1H), 7.78~7.74(m, 5H), 7.56~ 7.51(m, 6H), 7.39~7.33(m, 6H). I191 δ = 8.82(d, 1H), 8.62(d, 1H), 8.44(s, 1H), 8.37(d, 1H), 8.26~8.11(m, 3H), 8.09(d, 1H), 7.76~7.62 ( m, 3H), 7.59~7.50(m, 12H), 7.29~7.26(m, 6H), 7.20(t, 1H). I192 δ = 8.78(d, 2H), 8.70(d, 2H), 8.46(d, 2H), 8.23~8.22(m, 2H), 8.21(d, 2H), 8.14(s, 1H), 8.16(d, 1H), 7.89(d, 1H), 7.44~7.38(m, 6H), 7.29~7.24 (m, 5H), 7.19~7.17(m, 2H). I195 δ = 9.08(d, 2H), 8.92(d, 2H), 8.33~8.32(m, 2H), 8.21(d, 2H), 8.19(s, 1H), 8.17(d, 1H), 7.92(d, 1H), 7.46~7.39(m, 7H), 7.29~7.24 (m, 5H), 7.19~7.17(m, 2H). I196 δ = 8.78(d, 2H), 8.70(d, 2H), 8.46(d, 2H), 8.23~8.22(m, 2H), 8.21(d, 2H), 8.14(s, 1H), 8.16(d, 1H), 7.89(d, 1H), 7.48(d, 2H), 7.46~7.41(m, 8H), 7.31~7.26 (m, 5H), 7.16~7.15(m, 2H). I198 δ = 9.19(dd, 2H), 8.73(d, 1H), 8.67(d, 1H), 8.49(s, 1H), 8.41(s, 1H), 8.29(d, 1H), 8.25~8.20(m, 3H), 8.15~8.07(m, 3H), 8.03(d, 1H), 7.98-7.91(m, 2H), 7.85~7.78(m, 3H), 7.66~7.42 (m, 12H), 7.34-7.30 ( m, 1H) I199 δ = 9.16 (dd, 2H), 8.70 (d, 1H), 8.59 (d, 1H), 8.46 (s, 1H), 8.40 (s, 1H), 8.19 (s, 1H), 8.19 (d, 1H) , 8.27~8.22(m, 4H), 8.14~8.06(m, 2H), 8.01(d, 1H), 7.97-7.92(m, 2H), 7.88~7.79(m, 4H), 7.65~7.41 (m, 14H), 7.34-7.30 (m, 1H) I200 δ = 9.08(d, 2H), 9.01(d, 1H), 8.82(d, 1H), 8.77~8.76(m, 2H), 8.62(s, 1H), 8.59(d, 1H), 8.58(s, 1H), 8.23(dd, 2H), 8.20(d, 1H), 7.74~7.66(m, 8H), 7.39~7.34(m, 8H). I204 δ = 8.89(d, 2H), 8.64 (d, 1H), 8.52(s, 1H), 8.44(s, 1H), 8.29~8.25(m, 5H), 8.15(d, 1H), 8.11(d, 2H), 8.04(d, 1H), 8.00(d, 1H), 7.97(d, 1H), 7.92(s, 1H), 7.89(d, 1H), 7.80~7.61(m, 9H), 7.56~7.54 (m, 3H), 7.45~7.43 (m, 3H), 7.37 (t, 1H). I206 δ = 9.02(s, 1H), 8.80(d, 1H), 8.79(d, 1H), 8.57(d, 1H), 8.49(s, 1H), 8.46(d, 1H), 8.38~8.36(m, 2H), 7.49~7.42(m, 8H), 7.40~7.36(m ,5H), 7.36~7.30(m, 5H), 7.20(s, 1H), 7.06(t, 1H). I214 δ = 9.29 (d, 1H), 9.24 (d, 2H), 9.06 (d, 3H), 8.39 (d, 1H), 8.29 (s, 1H), 8.15 (d, 1H), 8.11 (d, 2H) , 8.04 (t, 1H), 8.00-7.89 (m, 4H), 7.80-7.61 (m, 8H), 7.56 (t, 1H). I218 δ = 9.18 (d, 2H), 9.15 (d, 1H), 8.90 (d, 1H), 8.80 (d, 1H), 8.79 to 8.78 (m, 2H), 8.66 (s, 1H), 8.59 (d, 1H), 8.26(dd, 2H), 8.23(d, 1H), 7.76~7.67 (m, 11H), 7.47~7.41 (m, 6H). I222 δ = 8.88 (d, 2H), 8.87 (d, 1H), 8.69 (d, 1H), 8.46 (s, 1H), 8.31 to 8.29 (m, 4H), 8.23 (d, 1H), 7.46 (d, 2H), 7.44~7.37 (m, 14H), 7.27~7.24(m, 6H), 7.21(t, 2H). I229 δ = 9.23(d, 2H), 8.91(d, 2H), 8.73~8.70(m, 3H), 8.68(s, 1H), 8.49(d, 2H), 8.32~8.29(m, 3H), 8.28~ 8.25(m, 2H), 7.59~7.56(m, 2H), 7.49~7.44(m, 5H), 7.40~7.38(m, 3H). I230 δ = 9.16(s, 2H), 8.74~8.71(m, 3H), 8.70(d, 2H), 8.61(s, 1H), 8.41(d, 1H), 8.26(d, 1H), 8.22~8.21( m, 2H), 7.90~7.84(m, 5H), 7.38~7.32(m, 9H), 7.27~7.23(m, 5H), 7.14(t, 2H). I232 δ = 9.08(d, 2H), 9.04(d, 1H), 8.82(d, 1H), 8.76~8.75(m, 2H), 8.71~8.69(m, 3H), 8.68(d, 1H), 8.61( s, 1H), 8.44(d, 1H), 8.38~8.33(m, 4H), 7.80~7.72(m, 9H), 7.48~7.44(m, 3H), 7.33~7.31(m, 2H). I233 δ = 8.82(d, 2H), 8.69(d, 1H), 8.68~8.67(m, 3H), 8.64(d, 1H), 8.58(s, 1H), 8.38(d, 1H), 8.29~8.25( m, 5H), 7.64~7.55 (m, 11H), 7.38~7.34(m, 4H), 7.29 (t, 2H). I235 δ = 9.19(dd, 2H), 8.73(d, 1H), 8.61(d, 1H), 8.58(d, 1H), 8.46(s, 1H), 8.28(d, 1H), 8.26~8.22(m, 3H), 8.12~8.10(m, 2H), 8.03(d, 1H), 7.95-7.93(m, 3H), 7.87~7.76(m, 3H), 7.58~7.44(m, 12H), 7.30(t, 1H) I244 δ = 9.22(d, 2H), 8.91(d, 2H), 8.74~8.72(m, 3H), 8.48(d, 2H), 8.32~8.29(m, 3H), 8.26~8.24(m, 2H), 7.58(d, 1H), 7.49~7.44(m, 6H), 7.39~7.35(m, 4H). I245 δ = 8.82(d, 2H), 8.74~8.72(m, 3H), 8.62(d, 2H), 8.36(d, 2H), 8.26(d, 1H), 8.23~8.22(m, 2H), 7.88~ 7.85(m, 3H), 7.38~7.33(m, 8H), 7.39~7.36(m, 6H). I246 δ = 9.18(s, 2H), 8.76~8.73(m, 3H), 8.72(d, 2H), 8.38(d, 1H), 8.29(d, 1H), 8.26~8.24(m, 2H), 7.90~ 7.85(m, 5H), 7.39~7.31(m, 12H), 7.29~7.26(m, 3H), 7.18(t, 2H). I247 δ = 8.59(d, 2H), 8.32(d, 1H), 8.20~8.12(m, 4H), 7.99~7.79(m, 9H), 7.60~7.34(m, 13H), 7.23(t, 1H), 7.10 (t, 2H). I248 δ = 8.69(d, 2H), 8.36(d, 2H), 8.24~8.12(m, 5H), 7.99(d, 1H), 7.86~7.79(m, 4H), 7.74(d, 1H), 7.59~ 7.34(m, 10H), 7.23~7.11(m, 7H). I249 δ = 8.79(d, 2H), 8.39(d, 1H), 8.24~8.11(m, 5H), 7.99(d, 2H), 7.86~7.72(m, 11H), 7.57~7.34(m, 12H), 7.20 (t, 1H). I250 δ = 8.88(d, 3H), 8.24~8.11(m, 3H), 7.99~7.87(m, 3H), 7.79~7.61 (m, 9H), 7.54~7.45 (m, 8H), 7.35(t, 1H) ) 7.16 (t, 2H). I252 δ = 8.81(d, 2H), 8.67~8.49(m, 5H), 8.38~8.29(m, 10H), 8.24~8.11(m, 10H), 7.54(t, 2H), 7.44~7.34 (m, 2H) ), 6.78 (d, 1H). I258 δ = 8.91(d, 1H), 8.61(d, 1H), 8.54(d, 1H), 8.34~8.21(m, 8H), 7.89(d, 1H), 7.70~7.54(m, 10H), 7.41( t, 2H), 7.35 (d, 1H), 7.22 (d, 1H). I261 δ = 9.21(d, 4H), 8.91(d, 1H), 8.58(d, 1H), 8.44(d, 1H), 8.13(t, 1H), 7.79~7.64(m, 8H), 7.51~7.37( m, 7H). 7.22~7.15(m, 8H). 7.03 (s, 2H). I262 δ = 9.20(d, 1H), 9.16(d, 1H), 8.72(d, 1H), 8.65(d, 1H), 8.51(s, 1H), 8.42(s, 1H), 8.34(s, 1H) , 8.29(d, 1H), 8.26~8.20(m, 3H), 8.12(d, 1H), 8.09(d, 1H), 8.03(d, 1H), 7.97~7.90(m, 2H), 7.86~7.78 (m, 3H), 7.63~7.41(m, 12H), 7.34~7.30(m, 1H). I263 δ = 9.01(d, 2H), 8.72(d, 2H), 8.58(d, 1H), 8.45(d, 4H), 8.37(d, 2H), 8.27~8.19(m, 7H), 8.11~8.02( m, 8H), 7.94-7.89 (m, 8H), 7.67-7.56 (m, 1H). I266 δ = 8.59(d, 2H), 8.52(d, 2H), 8.45(d, 1H), 8.31(d, 1H), 8.16~8.02(m, 4H), 7.79~7.64(m, 4H), 7.68~ 7.46 (m, 5H), 7.35 (t, 1H), 7.16 (t, 1H). I267 δ = 8.65(d, 1H), 8.48(d, 2H), 8.25(d, 2H), 8.11(d, 1H), 7.89~7.71(m, 8H), 7.65~7.48(m, 8H), 7.17( s, 2H). I268 δ = 8.85(d, 2H), 8.76(d, 1H), 8.27(d, 1H), 8.10~7.94(m, 4H), 7.81~7.70(m, 6H), 7.58~7.36(m, 6H), 7.29-7.17 (m, 5H). I274 δ = 8.7(d, 3H), 8.19~8.14(m, 3H), 7.90~7.82(m, 7H), 7.75~7.67(m, 8H), 7.59~7.50(m, 6H), 7.35(t, 1H) ), 7.20 (t, 2H). I275 δ = 8.60(d, 1H), 8.57(d, 1H), 8.20(d, 1H), 8.11(s, 1H), 7.98(d, 2H), 7.93~7.89(m, 3H), 7.70~7.59( m, 6H), 7.50~7.37 (m, 9H), 7.24 (t, 2H), 7.01 (d, 6H), 6.54 (d, 1H). I276 δ = 8.56(d, 1H), 8.54(d, 1H), 8.19(d, 1H), 8.11(s, 1H), 7.99(d, 2H), 7.90~7.79(m, 10H), 7.61~7.49( m, 11H), 7.24 (t, 2H), 7.10 to 7.02 (m, 4H), 6.55 (d, 1H). I278 δ = 8.71(d, 1H), 8.69(d, 1H), 8.19(d, 1H), 8.13(d, 1H), 7.99~7.91(m, 3H), 7.82~7.78(m, 4H), 7.61~ 7.55(m, 7H), 7.51~7.45(m, 6H), 7.40(s, 1H), 7.35(t, 1H), 7.20(t, 1H), 7.12(t, 1H). I279 δ = 8.55(d, 1H), 8.54(d, 2H), 8.13(d, 1H), 7.99~7.89(m, 6H), 7.85~7.79(m, 4H), 7.62~7.56(m, 7H), 7.52~7.47(m, 6H), 7.35(t, 1H), 7.21(d, 1H), 7.16(t, 1H). I281 δ = 9.1(d, 1H), 9.08(d, 1H), 8.86(d, 1H), 8.67(d, 1H), 8.59(d, 1H), 8.47(d, 1H), 8.23~8.19(m, 3H), 8.17~8.15(m, 2H), 7.96(d, 2H), 7.89~7.87(m 3H), 7.59~7.46(m,5H), 7.40(s, 1H), 7.36~7.35(m, 1H) ) I282 δ = 8.76(d, 1H), 8.75(d, 1H), 8.73~8.71(m, 3H), 8.21(d, 1H), 8.19(d, 1H), 7.99~7.92(m, 7H), 7.66~ 7.59(m, 5H), 7.48(d, 1H), 7.39(s, 1H), 7.29~7.26 (m, 3H), 7.18~7.16(m, 3H). I283 δ = 9.18 (d, 1H), 8.79 (d, 1H), 8.64 (d, 1H), 8.60 (d, 1H), 8.36 (d, 2H), 8.28 to 8.19 (m, 5H), 8.14 (d, 1H), 7.87~7.74(m, 5H), 7.72~7.68(m, 4H), 7.58~7.42(m, 4H), 7.37~7.34(m, 2H). I285 δ = 9.20(d, 1H), 8.82(d, 1H), 8.66(d, 1H), 8.58(s, 1H), 8.36(d, 2H), 8.31~8.24(m, 5H), 8.10(d, 1H), 7.84~7.74(m, 5H), 7.72~7.68(m, 4H), 7.54~7.44(m, 4H), 7.38~7.35(m, 2H). I286 δ = 9.14(d, 1H), 8.75(d, 1H), 8.61(d, 1H), 8.50(s, 1H), 8.38(d, 2H), 8.29~8.20(m, 5H), 8.13(d, 1H), 7.79~7.72(m, 5H), 7.69~7.64(m, 4H), 7.60~7.49(m, 4H), 7.36~7.32(m, 2H). I290 δ = 9.14(d, 1H), 8.75(d, 1H), 8.61(d, 1H), 8.53(d, 1H), 8.40(d, 2H), 8.29(d, 1H), 8.28~8.20(m, 4H), 8.12(d, 1H), 7.79~7.75(m, 2H), 7.74~7.70(m, 3H), 7.69~7.63(m, 4H), 7.60~7.51(m, 4H), 7.36~7.34( m, 2H). I293 δ = 9.27 (d, 1H), 9.08 (d, 1H), 8.72 (d, 1H), 8.62 (d, 1H), 8.56 (d, 2H), 8.31 (d, 1H), 8.29 (d, 1H) , 8.27~8.24(m, 3H), 8.16(d, 1H), 7.85~7.74(m, 5H), 7.73~7.68(m, 4H), 7.57~7.52(m, 4H), 7.38~7.35(m, 2H). I294 δ = 9.22(d, 1H), 8.98(d, 1H), 8.69(d, 1H), 8.59(d, 1H), 8.55(d, 2H), 8.34(d, 1H), 8.29~8.24(m, 3H), 8.11(d, 1H), 7.79~7.71(m, 5H), 7.70(d, 2H), 7.69~7.66(m, 3H), 7.57~7.50(m, 4H), 7.40~7.37(m, 2H).

< Manufacturing example 6> Synthesis of compound 2-2

<General formula>

<Synthesis>

Synthesis of 2-2-1 compound

Compound 2-2-2 (1eq), 4-iodo-1,1'-biphenyl (1eq), CuI (1eq), trans-1,2-cyclo Hexediamine (trans-1,2-cyclohexanediamine) (1ea) and K ₃ PO ₄ (2eq) were put into a round bottom flask, and dioxane (10v/w) was added and stirred at 100°C. When the reaction is complete, the organic layer is concentrated by extraction with MC and H ₂ O. Recrystallized from MC and MeOH to obtain a 2-2-1 compound (yield: 72%).

Synthesis of I1-1 compound

3-bromo-9H-carbazole (1eq), 3-iodo-1,1'-biphenyl (3-iodo-1,1'-biphenyl) (1eq), CuI (1eq), trans-1,2-cyclohexanediamine (1ea), and K ₃ PO ₄ (2eq) were added to a round bottom flask, and Dioxane (10v/w) was added. And stirred at 100°C. When the reaction is complete, the organic layer is concentrated by extraction with MC and H2O. Recrystallized from MC and MeOH to obtain I1-1 compound (yield: 76%)

Synthesis of I1 compound

I1-1 (1eq), Bis (pinacolato) diboron (1.2eq), Pd(dppf)Cl ₂ (0.05eq), and KOAc (2eq) were added to a round bottom flask, and Add dioxane (10v/w) and stir at 110°C. Upon completion of the reaction, extraction was performed with MC and H ₂ O, followed by column separation to obtain an I1 compound (yield: 80%).

Synthesis of 2-2 compound

2-2-1 (1eq), I1(1eq), Pd(pph ₃ ) ₄ (0.05eq), K ₂ CO ₃ (2eq) were added to a round bottom flask, Toluene/H ₂ O/Ethanol (10v/w , 5:1:1) was added and stirred at 110°C. The solid formed by the completion of the reaction was filtered and washed with MeOH and H ₂ O to obtain a 2-2 compound (yield: 60%).

< Manufacturing example 7> Synthesis of compound 3-47

<General formula>

<Synthesis>

Synthesis of 3-47-3 compound

3-47-4 (1eq), iodobenzene (1eq), CuI (1eq), trans-1,2-cyclohexanediamine (1ea), K ₃ PO ₄ (2eq) was placed in a round bottom flask, and dioxane (10v/w) was added, followed by stirring at 100°C. When the reaction is complete, the organic layer is concentrated by extraction with MC and H ₂ O. Recrystallized from MC and MeOH to obtain a 3-47-3 compound (yield: 86%).

Synthesis of 3-47-2 compound

3-47-3 (1eq), 4,4,5,5-tetramethyl-2-(2-nitrophenyl)-1,3,2-dioxaborolane (1.1eq), Pd(dba) ₂ (0.05eq), Xphos (0.1eq), NaOH (2eq) was added to a round bottom flask, and Dioxane/H ₂ O (10v/w, 5:1) was added and stirred at 100°C. Upon completion of the reaction, extraction was performed with MC and H ₂ O, followed by column separation to obtain a compound 3-47-2 (yield: 90%).

Synthesis of 3-47-1 compound

Add 3-47-2 (1eq), pph ₃ (2.5eq) to a round bottom flask, add 1,2-DCB (10v/w), and stir at 180°C. When the reaction was completed, column separation was performed to obtain a 3-47-1 compound (yield: 88%).

The following compounds J1-J5 were synthesized in the same manner as in the preparation of the 3-47-1 compound.

Synthesis of compound 3-47

3-47-1 (1eq), 2-bromotriphenylene (1eq), Pd ₂ (dba) ₃ (0.05eq), P(t-Bu) ₃ (0.1eq), NaOtBu( 2eq) was placed in a round bottom flask, and Toluene (10v/w) was added and stirred at 110°C. When the reaction was complete, extraction was performed with MC and H ₂ O, followed by column separation to obtain a compound 3-47 (yield: 67%).

< Manufacturing example 8> Synthesis of compound 3-58

<General formula and synthesis>

Synthesis of 3-58-4 compound

Synthesis was carried out in the same manner as in the above synthesis method 3-47-1 to synthesize a compound 3-58-4.

Synthesis of 3-58-3 compound

3-58-4 (1eq), bromobenzene (1eq), Pd ₂ (dba) ₃ (0.05eq), P(t-Bu) ₃ (0.1eq), NaOtBu(2eq) in a round bottom flask And toluene (10v/w) and stirred at 110℃. When the reaction was completed, extraction was performed with MC and H ₂ O, followed by column separation to obtain a compound 3-58-3 (yield: 67%).

Synthesis of 3-58-2 compound

3-58-3 (1eq) was placed in a round bottom flask, DMF (10v/w) was added and stirred at 0°C. Add N-bromosuccinimide (NBS) (1eq). When the reaction was completed, an excess of MeOH was added, stirred, and filtered to obtain a compound 3-58-2 (yield: 85%).

3-58- 1 compound synthesis

3-58-2 (1eq), Bis (pinacolato) diboron (1.2eq), Pd (dppf) Cl ₂ (0.05eq), and KOAc (2eq) into a round bottom flask , Dioxane (10v/w) was added and stirred at 110°C. Upon completion of the reaction, extraction was performed with MC and H ₂ O, followed by column separation to obtain a compound 3-58-1 (yield: 87%).

Synthesis of Compound 3-58

3-58-1 (1eq), I2 (1eq), Pd(pph ₃ ) ₄ (0.05eq), K ₂ CO ₃ (2eq) were added to a round bottom flask, Dioxane/H ₂ O/ (10v/w, 5:1) was added and stirred at 110°C. After the reaction is complete, the resulting solid is filtered and washed with MeOH and H ₂ O. The dried solid was purified by silica to obtain a compound 3-58 (yield: 60%).

< Manufacturing example 9> Synthesis of compound 4-1

<General formula>

<Synthesis>

Synthesis of 4-1-2 compound

3-1-3 (1eq), I3 (1eq), CuI (1eq), trans-1,2-cyclohexanediamine (1ea), K ₃ PO ₄ (2eq) Into a round bottom flask, add Dioxane (10v/w) and stir at 100°C. When the reaction was completed, the mixture was extracted with MC and H ₂ O and column-separated to obtain a 4-1-2 compound (yield: 85%).

4-1- 1 compound synthesis

Put 4-1-2 (1eq) into a round bottom flask, add THF (10v/w), and stir at -78°C. 2.5M n-BuLi (1eq) was added dropwise and stirred at room temperature for 1 hour. B(OMe) ₃ (1.2eq) was stirred at room temperature for 2 hours. When the reaction was complete, extraction was performed with MC and H ₂ O, followed by column separation to obtain a 4-1-1 compound (yield: 70%).

Synthesis of 4-1 compound

4-1-1 (1eq), iodobenzene (1eq), Pd(pph ₃ ) ₄ (0.05eq), and K ₂ CO ₃ (2eq) were added to a round bottom flask, and Toluene/H ₂ O/ Add ethanol (10v/w, 5:1:1) and stir at 110°C. When the reaction was completed, the mixture was extracted with MC and H ₂ O and separated by column to obtain a 4-1 compound (yield: 70%).

< Manufacturing example 10> Synthesis of compound 5-37

<General formula>

<Synthesis>

Synthesis of 5-37-5 compound

5-37-6 (1eq), 4,4,5,5-tetramethyl-2-(2-nitrophenyl)-1,3,2-dioxaborolane (1.1eq), Pd(dba) ₂ (0.05eq), Xphos (0.1eq), NaOH (2eq) was added to a round bottom flask, and Dioxane/H ₂ O (10v/w, 5:1) was added and stirred at 100°C. When the reaction was completed, extraction was performed with MC and H2O, followed by column separation to obtain a 5-37-5 compound (yield: 65%).

Synthesis of 5-37-4 compound

Put 5-37-5 (1eq), pph ₃ (2.5eq) into a round bottom flask, add 1,2-DCB (10v/w), and stir at 180°C. The solid produced by the completion of the reaction was filtered to obtain a 5-37-4 compound (yield: 75%).

Synthesis of 5-37-3 compound

5-37-4 (1eq), iodobenzene (1eq), CuI (1eq), trans-1,2-cyclohexanediamine (1ea), K ₃ PO ₄ (2eq) was placed in a round bottom flask, and Dioxane (10v/w) was added and stirred at 110°C. When the reaction was completed, MeOH was added thereto, stirred, and filtered to obtain a 5-37-3 compound (yield: 86%).

Synthesis of 5-37-2 compound

Put 5-37-3 (1eq) into a round bottom flask, add DMF (10v/w), and stir at 0°C. Add NBS (1eq). When the reaction was completed, an excessive amount of MeOH was added, stirred, and filtered to obtain a 5-37-2 compound (yield: 85%).

Synthesis of 5-37-1 compound

5-37-2 (1eq), Bis(pinacolato) diboron (1.2eq), Pd(dppf)Cl ₂ (0.05eq), and KOAc(2eq) were added to a round bottom flask. , Dioxane (10v/w) was added and stirred at 110°C. When the reaction was complete, extraction was performed with MC and H ₂ O, followed by column separation to obtain a 5-37-1 compound (yield: 72%).

Synthesis of compound 5-37

5-37-1 (1eq), I4(1eq), Pd(pph ₃ ) ₄ (0.05eq), K ₂ CO ₃ (2eq) were added to a round bottom flask, Dioxane/H ₂ O/ (10v/w, 5:1) was added and stirred at 110°C. After the reaction is complete, the resulting solid is filtered and washed with MeOH and H ₂ O. The dried solid was purified by silica to obtain a compound 5-37 (yield: 55%).

In Preparation Examples 6 to 10, R1 to R9 may be selected from one of the following substituents.

Synthesis confirmation data of the compounds prepared above are as described in [Table 5] and [Table 6].

compound FD-Mass compound FD-Mass 2-1 m/z= 636.26 (C48H32N2=636.80) 2-2 m/z= 636.26 (C48H32N2=636.80) 2-3 m/z= 636.26 (C48H32N2=636.80) 2-4 m/z= 636.26 (C48H32N2=636.80) 2-5 m/z= 634.24 (C48H30N2=634.78) 2-6 m/z= 788.32 (C60H40N2=788.99) 2-7 m/z= 788.32 (C60H40N2=788.99) 2-8 m/z= 712.29 (C54H36N2=712.90) 2-9 m/z= 712.29 (C54H36N2=712.90) 2-10 m/z= 710.27 (C54H34N2=710.88) 2-11 m/z= 676.29 (C51H36N2=676.86) 2-12 m/z= 736.29 (C56H36N2=736.92) 2-13 m/z= 610.24 (C46H30N2=610.76) 2-14 m/z= 684.26 (C52H32N2=684.86) 2-15 m/z= 726.30 (C55H38N2=726.92) 2-16 m/z= 700.25 (C52H32N2O=700.84) 2-17 m/z= 690.21 (C50H30N2S=690.86) 2-18 m/z= 726.27 (C54H34N2O=726.88) 2-19 m/z= 740.23 (C54H32N2S=740.92) 2-20 m/z= 650.27 (C49H34N2=650.83) 2-21 m/z= 686.27 (C52H34N2=686.86) 2-22 m/z= 726.27 (C54H34N2O=726.88) 2-23 m/z= 700.25 (C52H32N2O=700.84) 2-24 m/z= 636.26 (C48H32N2=636.80) 2-25 m/z= 660.26 (C50H32N2=660.82) 2-26 m/z= 684.26 (C52H32N2=684.86) 2-27 m/z= 736.29 (C56H36N2=736.92) 2-28 m/z= 700.25 (C52H32N2O=700.84) 2-29 m/z= 700.25 (C52H32N2O=700.84) 2-30 m/z= 740.23 (C54H32N2S=740.92) 2-31 m/z= 712.29 (C54H36N2=712.90) 2-32 m/z= 712.29 (C54H36N2=712.90) 2-33 m/z= 650.27 (C49H34N2=650.83) 2-34 m/z= 742.24 (C54H34N2S=742.94) 2-35 m/z= 776.28 (C58H36N2O=776.94) 2-36 m/z= 660.26 (C50H32N2=660.82) 2-37 m/z= 660.26 (C50H32N2=660.82) 2-38 m/z= 650.27 (C49H34N2=650.83) 2-39 m/z= 700.25 (C52H32N2O=700.84) 2-40 m/z= 710.27 (C54H34N2=710.88) 3-1 m/z= 560.23 (C42H28N2=560.73) 3-2 m/z= 560.23 (C42H28N2=560.73) 3-3 m/z= 636.26 (C48H32N2=636.80) 3-4 m/z= 610.24 (C46H30N2=610.76) 3-5 m/z= 584.23 (C44H28N2=584.72) 3-6 m/z= 740.25 (C54H32N2O2=740.86) 3-7 m/z= 660.26 (C50H32N2=660.82) 3-8 m/z= 650.27 (C49H34N2=650.83) 3-9 m/z= 624.22 (C46H28N2O=624.77) 3-10 m/z= 738.28 (C54H34N4=738.89) 3-11 m/z= 738.28 (C54H34N4=738.89) 3-12 m/z= 623.24 (C46H29N3=623.76) 3-13 m/z= 620.14 (C42H24N2S2=620.79) 3-14 m/z= 560.23 (C42H28N2=560.73) 3-15 m/z= 712.29 (C54H36N2=712.90) 3-16 m/z= 712.29 (C54H36N2=712.90) 3-17 m/z= 738.28 (C54H34N4=738.89) 3-18 m/z= 660.26 (C50H32N2=660.82) 3-19 m/z= 636.26 (C48H32N2=636.80) 3-20 m/z= 649.25 (C48H31N3=649.80) 3-21 m/z= 686.27 (C52H34N2=686.86) 3-22 m/z= 623.24 (C46H29N3=623.76) 3-23 m/z= 624.22 (C46H28N2O=624.77) 3-24 m/z= 623.24 (C46H29N3=623.76) 3-25 m/z= 560.23 (C42H28N2=560.73) 3-26 m/z= 660.26 (C50H32N2=660.82) 3-27 m/z= 700.25 (C52H32N2O=700.84) 3-28 m/z= 738.28 (C54H34N4=738.89) 3-29 m/z= 699.27 (C52H33N3=699.86) 3-30 m/z= 775.30 (C58H37N3=775.95) 3-31 m/z= 649.25 (C48H31N3=649.80) 3-32 m/z= 699.27 (C52H33N3=699.86) 3-33 m/z= 725.28 (C54H35N3=725.89) 3-34 m/z= 610.24 (C46H30N3=610.76) 3-35 m/z= 666.21 (C48H32N2S=666.84) 3-36 m/z= 649.25 (C48H31N3=649.80) 3-37 m/z= 574.24 (C43H30N2=574.73) 3-38 m/z= 610.24 (C46H30N3=610.76) 3-39 m/z= 574.20 (C42H26N2O=574.68) 3-40 m/z= 610.24 (C46H30N3=610.76) 3-41 m/z= 636.26 (C48H32N2=636.80) 3-42 m/z= 560.23 (C42H28N2=560.70) 3-43 m/z= 740.25 (C54H32N2O2=740.86) 3-44 m/z= 566.18 (C40H26N2S=566.72) 3-45 m/z= 660.26 (C50H32N2=660.82) 3-46 m/z= 534.21 (C40H26N2=534.66) 3-47 m/z= 558.21 (C42H26N2=558.68) 3-48 m/z= 649.25 (C48H31N3=649.80) 3-49 m/z= 699.27 (C52H33N3=699.86) 3-50 m/z= 610.24 (C46H30N3=610.76) 3-51 m/z= 684.26 (C52H32N2=684.86) 3-52 m/z= 660.26 (C50H32N2=660.82) 3-53 m/z= 674.24 (C50H30N2O=674.80) 3-54 m/z= 626.22 (C46H28N2O=624.74) 3-55 m/z= 679.21 (C48H29N3O=679.84) 3-56 m/z= 725.28 (C54H35N3=725.89) 3-57 m/z= 649.25 (C48H31N3=649.80) 3-58 m/z= 699.27 (C52H33N3=699.86) 3-59 m/z= 749.28 (C56H35N3=749.92) 3-60 m/z= 650.24 (C48H30N2O=650.78) 3-61 m/z= 624.26 (C47H32N2=624.79) 3-62 m/z= 585.25 (C45H31N=585.75) 3-63 m/z= 485.21 (C37H27N=485.63) 3-64 m/z= 625.24 (C47H31NO=625.77) 3-65 m/z= 585.25 (C45H31N=585.75) 3-66 m/z= 725.31 (C56H39N=725.93) 3-67 m/z= 585.25 (C45H31N=585.75) 3-68 m/z= 591.20 (C43H29NS=591.77) 3-69 m/z= 700.29 (C53H36N2=700.88) 3-70 m/z= 651.26 (C49H33NO=651.81) 3-71 m/z= 726.30 (C55H38N2=726.90) 3-72 m/z= 650.27 (C49H34N2=650.83) 3-73 m/z= 726.30 (C55H38N2=726.90) 3-74 m/z= 717.25 (C53H35NS=717.93) 3-75 m/z= 752.32 (C57H40N2=752.96) 3-76 m/z= 739.26 (C54H33N3O=739.88) 3-77 m/z= 725.28 (C54H35N3=725.89) 4-1 m/z= 666.21 (C48H30N2S=666.84) 4-2 m/z= 742.24 (C54H34N2S=742.94) 4-3 m/z= 742.24 (C54H34N2S=742.94) 4-4 m/z= 742.24 (C54H34N2S=742.94) 4-5 m/z= 716.23 (C52H32N2S=716.90) 4-6 m/z= 716.23 (C52H32N2S=716.90) 4-7 m/z= 792.26 (C58H36N2S=793.00) 4-8 m/z= 818.28 (C51H31N5O=819.04) 4-9 m/z= 792.26 (C58H36N2S=793.00) 4-10 m/z= 792.26 (C58H36N2S=793.00) 4-11 m/z= 782.28 (C57H38N2S=783.00) 4-12 m/z= 782.28 (C57H38N2S=783.00) 4-13 m/z= 772.20 (C54H32N2S2=772.98) 4-14 m/z= 772.20 (C54H32N2S2=772.98) 4-15 m/z= 756.22 (C54H32N2OS=756.92) 4-16 m/z= 756.22 (C54H32N2OS=756.92) 4-17 m/z= 756.22 (C54H32N2OS=756.92) 4-18 m/z= 666.21 (C48H30N2S=666.84) 4-19 m/z= 742.24 (C54H34N2S=742.94) 4-20 m/z= 782.28 (C57H38N2S=783.00) 4-21 m/z= 772.20 (C54H32N2S2=772.98) 4-22 m/z= 716.23 (C52H32N2S=716.90) 4-23 m/z= 716.23 (C52H32N2S=716.90) 4-24 m/z= 792.26 (C58H36N2S=793.00) 4-25 m/z= 654.71 (C45H26N4O2=654.21) 4-26 m/z= 716.23 (C52H32N2S=716.90) 4-27 m/z= 792.26 (C58H36N2S=793.00) 4-28 m/z= 792.26 (C58H36N2S=793.00) 4-29 m/z= 716.23 (C52H32N2S=716.90) 4-30 m/z= 742.24 (C54H34N2S=742.94) 4-31 m/z= 766.24 (C56H34N2S=766.96) 4-32 m/z= 716.23 (C52H32N2S=716.90) 4-33 m/z= 590.18 (C42H26N2S=590.74) 4-34 m/z= 640.20 (C46H28N2S=640.80) 4-35 m/z= 666.21 (C48H30N2S=666.84) 4-36 m/z= 716.23 (C52H32N2S=716.90) 4-37 m/z= 716.23 (C52H32N2S=716.90) 5-1 m/z= 641.18 (C46H27NOS=641.79) 5-2 m/z= 716.23 (C52H32N2S=716.90) 5-3 m/z= 715.23 (C53H33NS=715.91) 5-4 m/z= 641.18 (C46H27NOS=641.79) 5-5 m/z= 724.25 (C54H32N2O=724.86) 5-6 m/z= 700.25 (C52H32N2O=700.84) 5-7 m/z= 700.25 (C52H32N2O=700.84) 5-8 m/z= 641.18 (C46H27NOS=641.79) 5-9 m/z= 666.21 (C48H32N2S=666.84) 5-10 m/z= 742.24 (C54H34N2S=742.94) 5-11 m/z= 716.23 (C52H32N2S=716.90) 5-12 m/z= 667.23 (C49H33NS=667.87) 5-13 m/z= 724.25 (C54H32N2O=724.86) 5-14 m/z= 726.27 (C54H34N2O=726.88) 5-15 m/z= 641.18 (C46H27NOS=641.79) 5-16 m/z= 681.16 (C48H27N2S=681.87) 5-17 m/z= 716.23 (C52H32N2S=716.90) 5-18 m/z= 625.20 (C46H27NO2=625.73) 5-19 m/z= 724.25 (C54H32N2O=724.86) 5-20 m/z= 750.27 (C56H34N2O=750.90) 5-21 m/z= 657.16 (C46H27NS2=657.85) 5-22 m/z= 716.23 (C52H32N2S=716.90) 5-23 m/z= 716.23 (C52H32N2S=716.90) 5-24 m/z= 742.24 (C54H34N2S=742.94) 5-25 m/z= 716.23 (C52H32N2S=716.90) 5-26 m/z= 742.24 (C54H34N2S=742.94) 5-27 m/z= 715.23 (C53H33NS=715.91) 5-28 m/z= 625.20 (C46H27NO2=625.73) 5-29 m/z= 700.25 (C52H32N2O=700.84) 5-30 m/z= 726.27 (C54H34N2O=726.88) 5-31 m/z= 700.25 (C52H32N2O=700.84) 5-32 m/z= 774.27 (C58H34N2O=774.92) 5-33 m/z= 774.27 (C58H34N2O=774.92) 5-34 m/z= 649.24 (C49H31NO=649.79) 5-35 m/z= 750.27 (C56H34N2O=750.90) 5-36 m/z= 641.18 (C46H27NOS=641.79) 5-37 m/z= =590.18 (C42H26N2S1=590.74) 5-38 m/z= 716.23 (C52H32N2S=716.90) 5-39 m/z= 766.24 (C56H34N2S=766.96) 5-40 m/z= 742.24 (C54H34N2S=742.94) 5-41 m/z= 806.24 (C58H34N2OS=806.98) 5-42 m/z= 700.25 (C52H32N2O=700.84) 5-43 m/z= 700.25 (C52H32N2O=700.84) 5-44 m/z= 725.24 (C54H31NO2=725.85) 5-45 m/z= 750.27 (C56H34N2O=750.90) 5-46 m/z= 726.27 (C54H34N2O=726.88) 5-47 m/z= 651.26 (C49H33NO=651.81) 5-48 m/z= 667.20 (C48H29NOS=667.83) 5-49 m/z= 792.26 (C53H35N3O=793.00) 5-50 m/z= 691.23 (C51H33NS=691.89) 5-51 m/z= 766.24 (C56H34N2S=766.96) 5-52 m/z= 640.20 (C46H28N2S=640.80) 5-53 m/z= 792.26 (C53H35N3O=793.00) 5-54 m/z= 651.20 (C48H29NS=651.83) 5-55 m/z= 691.23 (C51H33NS=691.89) 5-56 m/z= 756.22 (C54H32N2OS=756.92) 5-57 m/z= 700.25 (C52H32N2O=700.84) 5-58 m/z= 700.25 (C52H32N2O=700.84) 5-59 m/z= 624.22 (C46H28N2O=624.74) 5-60 m/z= 664.22 (C48H28N2O2=664.76) 5-61 m/z= 650.24 (C48H30N2O=650.78) 5-62 m/z= 730.21 (C52H30N2OS=730.88) 5-63 m/z= 674.24 (C50H30N2O=674.80) 5-64 m/z= 700.25 (C52H32N2O=700.84) 5-65 m/z= 650.24 (C48H30N2O=650.78) 5-66 m/z= 677.27 (C51H35NO=677.85) 5-67 m/z= 674.24 (C50H30N2O=674.80) 5-68 m/z= 716.23 (C52H32N2S=716.90) 5-69 m/z= 746.19 (C52H30N2S2=746.95) 5-70 m/z= 690.21 (C50H30N2S=690.86) 5-71 m/z= 742.24 (C54H34N2S=742.94) 5-72 m/z= 706.24 (C51H34N2S=706.91) 5-73 m/z= 640.20 (C46H28N2S=640.80) 5-74 m/z= 730.21 (C52H30N2S=730.88) 5-75 m/z= 740.23 (C54H32N2S=740.92) -

Example ¹ H NMR (CDCl ₃ , 200Mz) 2-1 δ = 8.55(d, 1H), 8.30(d, 1H), 8.19~8.13(d, 2H), 7.94~7.89(m, 12H), 7.77~7.75(d, 4H), 7.50~7.31(m, 8H) ), 7.20~7.16(t, 2H) 2-2 δ = 8.55(d, 1H), 8.31~8.30(d, 3H), 8.19~8.13(d, 2H), 7.99~7.89(m, 5H), 7.77~7.75(m, 5H), 7.62~7.35(m , 14H), 7.20~7.16(t, 2H) 2-4 δ = 8.55(d, 1H), 8.31~8.30(m, 3H), 8.19~8.13(m, 2H), 7.99~7.89(m, 5H), 7.77~7.75(m, 5H), 7.62~7.41(m , 14H), 7.20~7.16(t, 2H) 2-5 δ = 8.55(d, 1H), 8.55(d, 1H), 8.33~8.13(m, 7H), 7.99~7.89(m, 5H), 7.70~7.50(m, 13H), 7.35(t, 1H), 7.20~7.16(t, 2H) 2-7 δ = 8.55(d, 1H), 8.30(d, 1H), 8.19~8.13(m, 2H), 7.94~7.89(m, 15H), 7.77~7.73(m, 7H), 7.61~7.58(m, 5H) ), 7.50~7.35(m, 8H), 7.20~7.16(t, 2H) 2-10 δ = 9.05(d, 1H), 8.55(d, 1H), 8.33~8.13(m, 7H), 7.99~7.89(m, 9H), 7.77~7.35(m, 14H), 7.20~7.16(t, 2H) ) 2-12 δ = 8.95(d, 2H), 8.55~8.50(m, 3H), 8.30(d, 1H), 8.20~8.09(m, 6H), 7.99~7.89(m, 12H), 7.77(t, 3H), 7.58~7.50(m, 4H), 7.39~7.35(m, 3H), 7.20~7.16(t, 2H) 2-13 δ = 8.55(d, 1H), 8.30(d, 1H), 8.21~8.13(m, 3H), 8.03~7.35(m, 23H),, 7.20~7.16(t, 2H) 2-14 δ = 9.05(d, 2H), 8.84(d, 2H), 8.55(d, 1H), 8.30~8.13(m, 5H), 7.99~7.89(m, 7H), 7.77~7.50(m, 11H), 7.35(t, 1H), 7.20~7.16(t, 2H) 2-16 δ = 8.95(d, 2H), 8.55~8.50(m, 2H), 8.30(d, 1H), 8.20~8.09(m, 4H), 7.99~7.89(m, 9H), 7.77~7.74(m, 3H) ), 7.61~7.50(m, 5H), 7.39~7.31(m, 5H), 7.20~7.16(t, 2H) 2-18 δ = 8.55(d, 1H), 8.31~8.30(m, 3H), 8.19~8.13(m, 2H), 7.99~7.89(m, 7H), 7.77~7.75(m, 5H), 7.50~7.16(m , 16H) 2-21 δ = 8.55(d, 1H), 8.30(d, 1H), 8.21~7.89(m, 14H), 7.77~7.35(m, 16H), 7.20~7.16(m, 2H) 2-24 δ = 8.62~8.55(m, 2H), 8.22~8.19(m, 3H), 7.99~7.91(m, 7H), 7.77~7.35(m, 18H), 7.20~7.16(m, 2H) 2-27 δ = 8.95(d, 2H), 8.62~8.50(m, 4H), 8.22~8.19(m, 5H), 8.09(d, 2H), 7.99~7.91(m, 7H), 7.77~7.35(m, 14H) ), 7.20~7.16(m, 2H) 2-32 δ = 8.62(d, 1H), 8.55(d, 1H), 8.31(d, 2H), 8.22~8.19(m, 3H), 7.99~7.89(m, 4H), 7.77~7.68(m, 9H), 7.60~7.35(m, 14H), 7.20~7.16(m, 2H) 2-36 δ = 8.54(d, 1H), 8.30(d, 1H), 8.19~8.13(m, 2H), 8.03~7.75(m, 17H), 7.61~7.41(m, 10H), 7.20(t, 1H) 2-37 δ = 8.95 (d, 1H), 8.54 to 8.50 (m, 2H), 8.30 (d, 1H), 8.20 to 8.09 (m, 4H), 7.99 to 7.89 (m, 10H), 7.77 (d, 2H). 7.62~7.50(m, 10H), 7.39(t, 1H), 7.20(t, 1H) 2-39 δ = 8.54(d, 1H), 8.30(d, 1H), 8.19~8.13(m, 2H), 7.99~7.82(m, 13H), 7.69~7.50(m, 12H), 7.39~7.31(m, 2H) ), 7.20 (t, 1H), 3-1 δ = 8.55(d, 1H), 8.19(d, 1H), 7.94~7.91(m, 9H), 7.75(d, 4H), 7.58~7.35(m, 11H), 7.20~7.18(t, 2H) 3-4 δ = 8.95(d, 1H), 8.55~8.50(m, 2H), 8.20~8.19(m, 2H), 8.09(d, 2H), 7.94~7.91(m, 9H), 7.77~7.75(m, 3H) ), 7.58~7.35(m, 10H), 7.20~7.18(t, 2H) 3-5 δ = 9.27(d, 1H), 8.85(d, 1H), 8.55(d, 1H), 8.37~8.35(m, 2H), 8.19(d, 1H), 7.94~7.90(m, 6H), 7.75~ 7.50(m, 12H), 7.40~7.35(m, 2H), 7.20~7.16(t, 2H) 3-7 δ = 8.95(d, 2H), 8.55~8.50(m, 3H), 8.20~8.19(m, 3H), 8.09(d, 2H), 7.94~7.91(m, 9H), 7.77(d, 2H), 7.58~7.50(m, 5H), 7.40~7.35(m, 4H), 7.20~7.16(t, 2H) 3-10 δ = 8.55(d, 1H), 8.19(d, 3H), 8.08(d, 2H), 7.94(d, 1H), 7.74~7.50(m, 21H), 7.40~7.35(m, 2H), 7.20~ 7.16(m, 4H) 3-18 δ = 8.55(d, 2H), 8.09~7.91(m, 16H), 7.84(d, 2H), 7.60~7.55(m, 6H), 7.38~7.35(m, 4H), 7.16(t, 2H) 3-25 δ = 8.55(d, 1H), 8.19(d, 1H), 7.94~7.91(m, 9H), 7.75(d, 4H), 7.50~7.35(m, 11H), 7.20~7.16(t, 2H) 3-26 δ = 8.95(d, 2H), 8.55~8.50(m, 3H), 8.20~8.19(m, 3H), 8.09(d, 2H), 7.94~7.91(m, 9H), 7.77(d, 2H), 7.58~7.47(m, 6H), 7.39~7.35(m, 3H), 7.20~7.16(t, 2H) 3-28 δ = 8.55(d, 3H), 8.26~8.19(m, 3H), 7.94(d, 2H), 7.62~7.47(m, 16H), 7.35~7.30(m, 5H), 7.20~7.16(m, 4H) ) 3-31 δ = 8.55(d, 1H), 8.30(d, 1H), 8.19~8.13(m, 2H), 7.99~7.89(m, 4H), 7.77(d, 1H), 7.62~7.50(m, 18H), 7.40~7.35(m, 2H), 7.20~7.16(m, 2H) 3-32 δ = 8.55(d, 1H), 8.30(d, 1H), 8.03~7.89(m, 7H), 7.83~7.77(m, 2H), 7.62~7.50(m, 15H), 7.40~7.35(m, 3H) ), 7.20~7.16(m, 2H) 3-33 δ = 8.55(d, 1H), 8.30(d, 1H), 8.19~8.13(m, 2H), 7.99~7.89(m, 8H), 7.77~7.75(m, 3H), 7.62~7.35(m, 18H) ), 7.20~7.16(m, 2H) 3-36 δ = 8.55(d, 3H), 8.12(d, 1H), 7.94~7.91(m, 7H), 7.75~7.35(m, 16H), 7.18~7.16(m, 4H) 3-42 δ = 8.55(d, 2H), 8.21(d, 1H), 8.12(d, 1H), 7.94~7.91(m, 6H), 7.75~7.68(m, 6H), 7.49~7.35(m, 9H), 7.18~7.16(m, 3H) 3-45 δ = 8.95(d, 2H), 8.55~8.50(m, 4H), 8.20(d, 2H), 8.12~8.09(m, 3H), 7.94~7.91(m, 10H), 7.77(d, 2H), 7.52(d, 2H), 7.39~7.35(m, 4H), 7.16(t, 3H) 3-47 δ = 9.08~9.05(m, 2H), 8.55(d, 2H), 8.33(d, 1H), 8.25(d, 1H), 7.94(d, 3H), 7.70~7.50(m, 11H), 7.35~ 7.26(m, 3H), 7.16(t, 2H) 3-49 δ = 8.55(d, 3H), 8.03~7.91(m, 10H), 7.83(d, 1H), 7.75~7.67(m, 4H), 7.69~7.35(m, 11H), 7.26(d, 1H), 7.16(t, 3H) 3-57 δ = 8.55(d, 2H), 8.30(d, 1H), 8.13(d, 1H), 7.99~7.89(m, 5H), 7.77(d, 1H), 7.62~7.50(m, 16H), 7.35( d, 2H), 7.26 (d, 1H), 7.16 (t, 2H) 3-58 δ = 8.55(d, 2H), 8.30(d, 1H), 8.13(d, 1H), 8.03~7.89(m, 8H), 7.83~7.77(m, 2H), 7.62~7.50(m, 13H), 7.36~7.35(m, 3H), 7.26(d, 1H), 7.16(t, 2H) 3-63 δ = 8.55(d, 1H), 8.24(d, 1H), 8.09~7.88(m, 9H), 7.74(d, 1H), 7.63~7.55(m, 3H), 7.49(d, 1H), 7.38~ 7.35(m, 3H), 7.16(t, 1H) 3-72 δ = 8.30~8.13(m, 7H), 8.03(d, 3H), 7.89(d, 2H), 7.83(d, 1H), 7.74~7.73(m, 2H), 7.62~7.50(m, 10H), 7.38-7.36 (m, 2H), 7.20 (t, 1H). 4-1 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.19~8.13(m, 2H), 7.99~7.89(m, 6H), 7.77(d, 2H), 7.62~ 7.41(m, 15H), 7.20~ 7.16(m, 2H) 4-7 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.19~7.89(m, 11H), 7.77(d, 2H), 7.63~7.49(m, 12H), 7.38~ 7.35(m, 2H), 7.25~7.16(m, 6H) 4-10 δ = 8.95(d, 1H), 8.55~8.45(m, 3H), 8.30(d, 1H), 8.20~8.09(m, 4H), 8.00~7.89(m, 6H), 7.77(m, 3H), 7.62~7.35(m, 12H), 7.25~7.16(m, 6H) 4-15 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.19~8.13(m, 2H), 8.00~7.77(m, 12H), 7.62~7.35(m, 13H), 7.20~ 7.16(m, 2H) 4-18 δ = 8.55(d, 1H), 8.45(d, 1H), 8.31~8.30(d, 2H), 8.19~8.13(m, 2H), 8.00~7.89(m, 5H), 7.77~7.74(m, 2H) ), 7.62~7.35(m, 15H), 7.20~ 7.16(m, 2H) 4-23 δ = 8.55~8.54(d, 2H), 8.45(d, 1H), 8.30(d, 1H), 8.13(d, 1H), 8.00~7.89(m, 7H), 7.77(d, 2H), 7.62~ 7.35(m, 17H), 7.16(t, 1H) 4-26 δ = 8.54(d, 1H), 8.45(d, 1H), 8.30(d, 2H), 8.19~8.13(m, 3H), 8.00~7.89(m, 5H), 7.77(d, 1H), 7.65~ 7.41(m, 18H), 7.20(t, 1H) 4-33 δ = 8.55(d, 1H), 8.45(d, 1H), 8.19(d, 1H), 8.00~7.93(m, 3H), 7.77(d, 1H), 7.62~7.35(m, 17H), 7.20~ 7.16(m, 2H) 4-35 δ = 8.55(d, 1H), 8.45(d, 1H), 8.19(d, 1H), 8.00~7.93(m, 3H), 7.77~7.75(m, 3H), 7.62~7.35(m, 15H), 7.25~ 7.16(m, 6H) 4-37 δ = 8.95(d, 1H), 8.55~8.50(m, 3H), 8.20~8.19(d, 2H), 8.09(d, 1H), 8.00~7.93(m, 3H), 7.77(d, 2H), 7.62~7.35(m, 14H), 7.25~ 7.16(m, 6H) 5-4 δ = 8.95(d, 1H), 8.55(d, 1H), 8.45(d, 1H), 8.32~8.30(m, 2H), 8.17~8.13(m, 2H), 7.98~7.89(m, 3H), 7.79~7.70(m, 4H), 7.56~7.31(m, 13H) 5-5 δ = 9.08~9.05(m, 2H), 8.85(d, 1H), 8.33~8.25(m, 3H), 8.13(d, 1H), 7.99~7.89(m, 6H), 7.77~7.31(m, 18H) ), 7.16 (t, 1H). 5-7 δ = 8.55(d, 1H), 8.30(d, 1H), 8.13~7.89(m, 13H), 7.77(d, 1H), 7.63~7.49(m, 10H), 7.42~7.31(m, 5H), 7.16(t, 6H) 5-10 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.21(d, 1H), 8.13(d, 1H), 7.99~7.89(m, 10H), 7.78~7.41( m, 18H), 7.16 (t, 6H) 5-13 δ = 9.08~9.05(d, 2H), 8.55(d, 1H), 8.33~8.25(m, 4H), 8.13(d, 1H), 7.94~7.89(m, 5H), 7.70~7.31(m, 18H) ), 7.16 (t, 1H). 5-17 δ = 8.95(d, 1H), 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.17~8.13(m, 2H), 8.05~7.89(m, 6H), 7.79~ 7.77(m, 4H), 7.62~7.35(m, 15H), 7.16(t, 1H) 5-19 δ = 9.05(d, 1H), 8.55(d, 1H), 8.33~8.25(m, 5H), 8.13(d, 1H), 7.99~7.31(m, 23H), 7.16(t, 1H). 5-21 δ = 8.45(d, 2H), 8.30(d, 1H), 8.13~7.89(m, 14H), 7.80(d, 1H), 7.68~7.49(m, 8H), 7.38(t, 1H) 5-23 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.13~7.89(m, 14H), 7.80~7.77(m, 2H), 7.63~7.49(m, 10H), 7.38~7.35(m, 2H), 7.16(t, 6H) 5-26 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.21(d, 1H), 8.13~8.08(m, 2H), 7.99~7.89(m, 9H), 7.80~ 7.35(m, 18H), 7.16(t, 6H) 5-29 δ = 8.55(d, 1H), 8.30(d, 1H), 8.13~7.89(m, 13H), 7.77(d, 1H), 7.63~7.35(m, 15H), 7.16(t, 2H) 5-37 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.13(d, 1H), 7.96~7.89(m, 6H), 7.77(d, 1H), 7.62~7.49( m, 12H), 7.35~7.31(m, 2H), 7.16(t, 1H) 5-39 δ = 8.95(d, 1H), 8.55~8.45(m, 3H), 8.30(d, 1H), 8.20~7.77(m, 19H), 7.59~7.49(m, 5H), 7.39~7.31(m, 4H) ), 7.16(t, 1H) 5-43 δ = 8.55(d, 1H), 8.30(d, 1H), 8.13(d, 1H), 8.03~7.75(m, 16H), 7.60~7.35(m, 11H), 7.19~7.16(t, 2H) 5-49 δ = 8.95(d, 1H), 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.17~8.13(d, 2H), 8.05~7.89(m, 10H), 7.79~ 7.75(m, 6H), 7.56~7.33(m, 13H), 7.16(t, 1H) 5-52 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.13(d, 1H), 8.03~7.77(m, 11H), 7.62~7.49(m, 9H), 7.36~ 7.31(m, 3H), 7.16(t, 1H) 5-53 δ = 8.95(d, 1H), 8.55~8.50(m, 3H), 8.30(d, 1H), 8.21~8.09(m, 4H), 7.99~7.89(m, 10H), 7.77~7.35(m, 16H) ), 7.16(t, 1H) 5-57 δ = 8.55(d, 1H), 8.30(d, 1H), 8.13~7.89(m, 13H), 7.77(d, 1H), 7.63~7.50(m, 10H), 7.39~7.31(m, 4H), 7.19~7.16(t, 2H) 5-61 δ = 8.55(d, 1H), 8.30(d, 1H), 8.13(d, 1H), 7.99~7.31(m, 24H), 7.16~7.13(t, 2H) 5-64 δ = 8.55(d, 1H), 8.30(d, 1H), 8.13~7.77(m, 11H), 7.63~7.31(m, 16H), 7.16~7.13(t, 2H) 5-68 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.13~7.89(m, 14H), 7.77(d, 1H), 7.63~7.49(m, 10H), 7.38~ 7.33(m, 3H), 7.16(t, 1H) 5-71 δ = 8.55(d, 1H), 8.45(d, 1H), 8.31~8.30(d, 3H), 8.13(d, 1H), 8.05~7.89(m, 7H), 7.77~7.75(m, 5H), 7.62~7.35(m, 15H), 7.16(t, 1H) 5-74 δ = 8.55(d, 1H), 8.45(d, 1H), 8.30(d, 1H), 8.05~7.74(m, 14H), 7.61~7.31(m, 12H), 7.16(t, 1H)

< Example >

1) Fabrication of organic light emitting device (red host)

A glass substrate coated with a thin film of indium tin oxide (ITO) to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with a solvent such as acetone, methanol, or isopropyl alcohol, dried, and UVO treated for 5 minutes using UV in a UV scrubber. Thereafter, the substrate was transferred to a plasma cleaner (PT), followed by plasma treatment to remove the ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation equipment for organic deposition.

Hole injection layer 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino] triphenylamine) as a common layer on the ITO transparent electrode (anode) and a hole transport layer NPB (N,N'-Di( 1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

The light emitting layer was thermally vacuum deposited thereon as follows. The light-emitting layer by using a compound, a red phosphorescent dopant, the host according to Table _{7 (piq) 2 (Ir)} (acac) by the _{(piq) 2 (Ir) (} acac) was deposited to a host doped with 3% 500Å. After that, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited as an electron transport layer thereon.

After that, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited as an electron transport layer thereon. Finally, lithium fluoride (LiF) was deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. An electroluminescent device was manufactured.

On the other hand, all organic compounds required for OLED device fabrication were vacuum-sublimated and purified under 10 ^-6 ~10 ^-8 torr for each material, and used for OLED fabrication.

2) organic Electric field Driving voltage and luminous efficiency of light-emitting elements

For the organic electroluminescent device manufactured as described above, electroluminescence (EL) characteristics were measured with the M7000 of McScience, and the reference luminance was 6,000 through the life equipment measuring equipment (M6000) manufactured by McScience. When cd/m ² , T90 was measured. The characteristics of the organic electroluminescent device of the present invention are shown in Tables 7 and 8 below.

The comparative example in Table 7 is an example in which a single host material is applied, and the example in Table 7 is an example in which two host compounds are deposited as one source, and Table 8 is an example in which the two light emitting layer compounds of Table 7 are mixed at different ratios. This is an example of vapor deposition.

Host 1 2nd host Driving voltage
(V) efficiency
(cd/A) Color coordinates
(x, y) life span
(T90) Comparative Example 1 1-5 - 4.67 15.2 (0.662, 0.353) 70 Comparative Example 2 1-35 4.12 16.0 (0.663, 0.350) 65 Comparative Example 3 1-48 4.87 18.9 (0.660, 0.351) 84 Comparative Example 4 1-68 4.69 17.9 (0.661, 0.351) 71 Comparative Example 5 1-128 4.66 15.8 (0.661, 0.351) 65 Comparative Example 6 1-130 4.24 16.9 (0.662, 0.352) 59 Comparative Example 7 1-145 4.78 17.6 (0.664, 0.352) 46 Comparative Example 8 1-186 4.15 18.4 (0.660, 0.349) 68 Comparative Example 9 1-204 4.26 14.9 (0.663, 0.351) 73 Comparative Example 10 1-282 4.22 16.6 (0.661, 0.352) 69 Comparative Example 11 - 2-12 5.47 12.1 (0.662, 0.353) 20 Comparative Example 12 3-4 6.55 16.1 (0.663, 0.350) 12 Comparative Example 13 4-37 5.21 14.5 (0.660, 0.351) 16 Comparative Example 14 3-31 6.17 10.6 (0.661, 0.351) 5 Comparative Example 15 5-53 7.15 12.7 (0.661, 0.351) 31 Comparative Example 16 2-39 4.98 11.6 (0.662, 0.352) 19 Comparative Example 17 5-17 5.05 13.4 (0.664, 0.352) 25 Comparative Example 18 3-42 6.16 14.8 (0.660, 0.349) 16 Comparative Example 19 4-26 6.78 10.6 (0.663, 0.351) 11 Comparative Example 20 2-39 7.91 15.7 (0.661, 0.352) 8 Comparative Example 21 1-186 B 4.08 18.4 (0.660, 0.350) 70 Comparative Example 22 E 2-12 5.20 13.1 (0.661, 0.353) 35 Comparative Example 23 F 3-4 6.00 16.2 (0.662, 0.351) 55 Comparative Example 24 G 4-37 5.02 16.0 (0.660, 0.349) 49 Comparative Example 25 H 5-29 4.26 13.5 (0.661, 0.351) 82 Example 1 1-128 A 4.51 16.0 (0.659 0.352) 80 Example 2 1-263 C 4.31 16.7 (0.662, 0.351) 68 Example 3 2-282 D 4.43 14.1 (0.660, 0.349) 61 Example 4 1-5 2-12 4.11 18.3 (0.661, 0.352) 110 Example 5 3-10 4.02 19.5 (0.661, 0.351) 100 Example 6 3-18 4.05 19.8 (0.662, 0.351) 107 Example 7 4-26 4.18 17.5 (0.662, 0.353) 120 Example 8 5-39 4.24 19.5 (0.661, 0.351) 91 Example 9 1-17 2-1 4.14 19.5 (0.662, 0.351) 115 Example 10 2-27 4.20 19.8 (0.662, 0.352) 110 Example 11 3-4 4.13 20.1 (0.662, 0.352) 125 Example 12 4-18 4.41 17.5 (0.663, 0.351) 130 Example 13 5-17 4.38 19.5 (0.660, 0.351) 110 Example 14 1-27 2-16 4.00 19.5 (0.659, 0.352) 98 Example 15 3-18 3.98 19.8 (0.660, 0.351) 115 Example 16 3-31 3.90 20.5 (0.661, 0.351) 118 Example 17 4-1 4.05 17.2 (0.659, 0.350) 120 Example 18 5-53 4.10 18.9 (0.658, 0.351) 112 Example 19 1-29 2-4 3.88 19.5 (0.660, 0.350) 111 Example 20 3-42 3.81 20.1 (0.661, 0.352) 104 Example 21 4-23 4.08 17.5 (0.661, 0.351) 120 Example 22 4-37 4.02 17.1 (0.660, 0.352) 128 Example 23 5-29 4.00 19.5 (0.661, 0.351) 121 Example 24 1-35 2-13 3.80 20.4 (0.662, 0.351) 97 Example 25 3-4 3.88 19.5 (0.661, 0.352) 105 Example 26 3-72 3.81 20.1 (0.661, 0.350) 100 Example 27 4-18 4.05 17.6 (0.662, 0.351) 112 Example 28 5-5 3.98 20.1 (0.661, 0.352) 95 Example 29 1-39 2-27 3.94 20.5 (0.661, 0.352) 99 Example 30 3-36 3.87 21.5 (0.661, 0.351) 100 Example 31 4-10 4.10 18.4 (0.662, 0.351) 105 Example 32 4-37 4.09 17.9 (0.661, 0.350) 100 Example 33 5-61 4.08 20.6 (0.662, 0.349) 102 Example 34 1-48 2-10 4.05 21.5 (0.661, 0.351) 121 Example 35 2-24 3.99 21.5 (0.662, 0.350) 135 Example 36 3-25 3.84 22.1 (0.661, 0.351) 118 Example 37 4-26 4.08 20.5 (0.660, 0.350) 120 Example 38 5-4 4.11 21.5 (0.661, 0.352) 121 Example 39 1-55 2-16 3.88 20.5 (0.659, 0.351) 110 Example 40 3-18 3.84 19.6 (0.660, 0.352) 140 Example 41 3-63 3.86 20.0 (0.659, 0.351) 141 Example 42 4-1 4.02 17.5 (0.660, 0.353) 148 Example 43 5-29 4.03 19.5 (0.661, 0.351) 144 Example 44 1-57 2-1 3.87 21.5 (0.661, 0.353) 106 Example 45 2-27 3.85 22.8 (0.660, 0.351) 104 Example 46 3-4 3.82 22.3 (0.661, 0.352) 120 Example 47 4-18 4.02 19.2 (0.662, 0.351) 125 Example 48 5-17 4.05 21.8 (0.662, 0.352) 124 Example 49 1-68 2-1 4.00 21.5 (0.661, 0.351) 100 Example 50 3-28 3.98 22.8 (0.661, 0.350) 108 Example 51 3-49 4.01 21.9 (0.660, 0.352) 100 Example 52 4-7 4.15 20.5 (0.661, 0.350) 102 Example 53 5-43 4.17 21.4 (0.662, 0.351) 99 Example 54 1-77 2-39 3.78 23.5 (0.661, 0.353) 95 Example 55 3-1 3.75 23.8 (0.662, 0.353) 110 Example 56 4-1 4.00 19.5 (0.659, 0.351) 115 Example 57 5-5 3.99 23.5 (0.661, 0.351) 110 Example 58 5-43 4.02 23.1 (0.662, 0.352) 112 Example 59 1-82 2-12 4.00 21.4 (0.661, 0.351) 92 Example 60 3-10 3.98 22.1 (0.662, 0.351) 110 Example 61 3-18 4.02 22.0 (0.662, 0.351) 115 Example 62 4-26 4.30 19.6 (0.661, 0.350) 120 Example 63 5-39 4.22 23.1 (0.662, 0.350) 118 Example 64 1-88 2-39 3.89 22.0 (0.661, 0.350) 87 Example 65 3-7 3.84 22.5 (0.660, 0.350) 108 Example 66 3-32 3.91 24.0 (0.661, 0.352) 112 Example 67 4-15 4.05 19.6 (0.660, 0.349) 110 Example 68 5-21 4.10 23.1 (0.662, 0.351) 109 Example 69 1-96 2-4 3.78 20.7 (0.662, 0.351) 104 Example 70 3-42 3.64 22.4 (0.661, 0.351) 131 Example 71 4-23 4.10 17.2 (0.661, 0.352) 128 Example 72 4-37 4.00 18.7 (0.662, 0.351) 131 Example 73 5-29 4.05 22.5 (0.661, 0.352) 117 Example 74 1-102 2-10 3.88 20.8 (0.662, 0.352) 101 Example 75 2-24 3.79 21.8 (0.661, 0.352) 108 Example 76 3-25 3.84 22.5 (0.660, 0.351) 133 Example 77 4-26 4.05 18.7 (0.662, 0.351) 135 Example 78 5-4 4.08 21.4 (0.662, 0.351) 128 Example 79 1-119 2-13 4.00 20.5 (0.659, 0.351) 101 Example 80 2-21 3.98 21.6 (0.660, 0.352) 109 Example 81 3-5 3.84 22.8 (0.659, 0.350) 141 Example 82 4-15 4.15 19.9 (0.660, 0.351) 142 Example 83 5-52 4.11 23.1 (0.660, 0.349) 148 Example 84 1-120 2-39 3.84 23.4 (0.660, 0.352) 108 Example 85 3-1 3.87 24.1 (0.659, 0.351) 135 Example 86 3-28 3.91 23.7 (0.659, 0.352) 130 Example 87 4-23 4.05 20.1 (0.661, 0.351) 136 Example 88 5-19 4.00 23.2 (0.660, 0.352) 130 Example 89 1-128 2-16 4.05 19.5 (0.661, 0.351) 122 Example 90 3-18 4.00 20.5 (0.662, 0.351) 128 Example 91 3-63 3.94 22.1 (0.660, 0.351) 130 Example 92 4-1 4.01 18.8 (0.661, 0.352) 131 Example 93 5-29 3.97 20.5 (0.659, 0.351) 128 Example 94 1-130 2-27 3.88 20.1 (0.662, 0.351) 99 Example 95 3-36 3.91 24.9 (0.661, 0.351) 111 Example 96 4-10 3.92 25.5 (0.660 0.349) 112 Example 97 4-37 3.90 21.1 (0.661, 0.352) 100 Example 98 5-61 4.03 23.9 (0.662, 0.351) 104 Example 99 1-142 2-21 3.77 23.5 (0.662, 0.352) 90 Example 100 3-42 3.67 24.5 (0.661, 0.351) 115 Example 101 4-1 3.95 19.5 (0.661, 0.352) 100 Example 102 4-18 3.99 19.0 (0.662, 0.350) 105 Example 103 5-17 4.02 23.1 (0.661, 0.352) 110 Example 104 1-145 2-18 3.88 20.3 (0.662, 0.351) 107 Example 105 3-1 3.84 22.6 (0.663, 0.352) 135 Example 106 4-16 4.00 17.6 (0.662, 0.351) 133 Example 107 4-33 3.97 18.6 (0.663, 0.350) 131 Example 108 5-29 3.91 21.7 (0.661, 0.351) 128 Example 109 1-160 2-27 3.80 22.5 (0.662, 0.352) 80 Example 110 3-42 3.78 23.4 (0.661, 0.351) 116 Example 111 3-45 3.69 21.6 (0.660, 0.352) 109 Example 112 4-10 3.92 20.8 (0.662, 0.352) 121 Example 113 5-37 3.94 21.9 (0.662, 0.350) 101 Example 114 1-171 2-13 3.89 23.4 (0.660, 0.352) 108 Example 115 2-21 3.83 23.1 (0.659, 0.352) 105 Example 116 3-5 3.76 24.8 (0.659, 0.351) 120 Example 117 4-15 4.13 20.7 (0.660, 0.351) 117 Example 118 5-52 4.09 23.3 (0.659, 0.352) 121 Example 119 1-174 2-10 3.98 22.1 (0.660, 0.352) 95 Example 120 2-24 3.90 21.0 (0.660, 0.351) 100 Example 121 3-25 3.96 23.2 (0.661, 0.350) 112 Example 122 4-26 4.11 19.4 (0.659, 0.352) 110 Example 123 5-4 4.09 21.1 (0.660, 0.352) 116 Example 124 1-186 2-13 4.08 21.6 (0.660, 0.349) 127 Example 125 3-4 3.99 20.9 (0.661, 0.350) 115 Example 126 3-72 3.87 22.7 (0.660, 0.351) 123 Example 127 4-18 4.09 19.4 (0.660, 0.349) 120 Example 128 5-5 4.10 22.1 (0.660, 0.352) 118 Example 129 1-199 2-39 3.92 18.5 (0.662, 0.351) 101 Example 130 3-7 3.88 20.1 (0.661, 0.350) 118 Example 131 3-32 3.90 19.4 (0.662, 0.351) 116 Example 132 4-15 4.07 17.3 (0.660, 0.351) 120 Example 133 5-21 4.10 20.7 (0.662, 0.349) 116 Example 134 1-204 2-39 4.05 19.9 (0.661, 0.351) 124 Example 135 3-7 3.99 20.1 (0.662, 0.351) 116 Example 136 3-32 3.99 21.7 (0.663, 0.351) 115 Example 137 4-15 3.81 18.9 (0.662, 0.351) 120 Example 138 5-21 3.89 22.1 (0.662, 0.350) 110 Example 139 1-218 2-21 3.90 21.1 (0.661, 0.351) 85 Example 140 3-42 3.88 23.1 (0.661, 0.351) 100 Example 141 4-1 4.00 19.5 (0.660, 0.351) 116 Example 142 4-18 3.96 19.9 (0.661, 0.351) 113 Example 143 5-17 3.97 22.2 (0.661, 0.350) 111 Example 144 1-222 2-39 3.91 20.2 (0.661, 0.351) 95 Example 145 3-1 3.89 21.0 (0.661, 0.350) 104 Example 146 4-1 3.96 18.8 (0.662, 0.351) 111 Example 147 5-5 3.96 21.8 (0.661, 0.351) 107 Example 148 5-43 3.99 21.7 (0.661, 0.350) 104 Example 149 1-233 2-1 3.90 22.0 (0.661, 0.351) 86 Example 150 2-27 3.84 22.8 (0.662, 0.351) 86 Example 151 3-4 3.91 21.9 (0.662, 0.349) 100 Example 152 4-18 3.99 21.1 (0.659, 0.351) 108 Example 153 5-17 3.99 22.1 (0.660, 0.351) 101 Example 154 1-245 2-36 3.88 22.1 (0.662, 0.352) 97 Example 155 3-10 3.80 22.4 (0.662, 0.351) 102 Example 156 3-28 3.82 23.0 (0.661, 0.352) 107 Example 157 4-37 3.89 22.0 (0.662, 0.352) 111 Example 158 5-61 3.91 23.2 (0.662, 0.352) 106 Example 159 1-248 2-12 3.97 22.1 (0.660, 0.351) 108 Example 160 3-10 3.84 23.4 (0.660, 0.350) 116 Example 161 3-18 3.87 23.1 (0.659, 0.351) 120 Example 162 4-26 3.98 22.0 (0.660, 0.351) 124 Example 163 5-39 4.00 23.0 (0.660, 0.352) 117 Example 164 1-258 2-1 4.00 21.9 (0.661, 0.351) 104 Example 165 3-28 4.02 22.4 (0.661, 0.352) 123 Example 166 3-49 4.00 23.1 (0.660, 0.353) 121 Example 167 4-7 4.10 20.9 (0.661, 0.353) 130 Example 168 5-43 4.11 21.5 (0.661, 0.352) 124 Example 169 1-263 2-16 4.03 19.2 (0.660, 0.352) 102 Example 170 3-18 3.99 20.1 (0.662, 0.351) 127 Example 171 3-31 4.00 19.6 (0.661, 0.351) 130 Example 172 4-1 4.11 18.7 (0.660, 0.353) 131 Example 173 5-53 4.12 21.8 (0.659, 0.353) 128 Example 174 1-267 2-18 3.91 20.0 (0.660, 0.352) 98 Example 175 3-1 3.84 21.2 (0.661, 0.351) 111 Example 176 4-16 4.00 19.0 (0.660, 0.352) 115 Example 177 4-33 4.02 18.7 (0.659, 0.352) 116 Example 178 5-29 4.00 22.0 (0.660, 0.351) 118 Example 179 1-279 2-4 3.91 19.5 (0.661, 0.352) 100 Example 180 3-42 3.89 20.1 (0.662, 0.351) 116 Example 181 4-23 3.99 19.0 (0.661, 0.351) 121 Example 182 4-37 4.00 18.9 (0.661, 0.351) 125 Example 183 5-29 3.99 20.8 (0.662, 0.350) 117 Example 184 1-282 2-1 3.89 23.6 (0.660, 0.352) 76 Example 185 2-27 3.79 23.4 (0.661, 0.351) 77 Example 186 3-4 3.74 24.5 (0.662, 0.350) 98 Example 187 4-18 3.91 22.6 (0.661, 0.352) 100 Example 188 5-17 3.92 24.9 (0.660, 0.352) 91 Example 189 1-286 2-4 3.89 24.0 (0.660, 0.349) 118 Example 190 3-42 3.77 23.9 (0.660, 0.351) 101 Example 191 4-23 3.92 23.8 (0.661, 0.349) 109 Example 192 4-37 3.95 22.7 (0.660, 0.352) 110 Example 193 5-29 3.90 24.7 (0.660, 0.349) 96 Example 194 1-293 2-14 3.84 22.5 (0.661, 0.350) 88 Example 195 3-18 3.79 22.9 (0.660, 0.349) 104 Example 196 3-31 3.86 22.0 (0.659, 0.349) 100 Example 197 4-1 3.90 21.9 (0.660, 0.349) 110 Example 198 5-53 3.95 24.1 (0.662, 0.350) 106

Host 1 2nd host Mixing ratio (host 1: host 2) Driving voltage
(V) efficiency
(cd/A) Color coordinates
(x, y) life span
(T ₉₅ ) Example 196 1-271 2-13 3:1 4.21 16.3 (0.589, 0.350) 35 Example 197 2:1 4.10 17.9 (0.661, 0.350) 66 Example 198 1:1 4.01 22.9 (0.659, 0.352) 112 Example 199 1:2 3.98 18.1 (0.661, 0.351) 116 Example 200 1:3 3.65 21.0 (0.660, 0.350) 118 Example 201 1:4 3.52 22.1 (0.661, 0.349) 120 Example 202 1-29 3-7 3:1 4.21 16.3 (0.589, 0.350) 35 Example 203 2:1 4.10 17.9 (0.661, 0.350) 66 Example 204 1:1 3.97 18.0 (0.661, 0.351) 118 Example 205 1:2 3.98 18.1 (0.661, 0.351) 116 Example 206 1:3 3.65 21.0 (0.660, 0.350) 118 Example 207 1:4 3.52 22.1 (0.661, 0.349) 120 Example 208 1-255 4-26 3:1 4.34 16.8 (0.661, 0.350) 85 Example 209 2:1 4.10 17.5 (0.660, 0.349) 88 Example 210 1:1 4.01 19.2 (0.658, 0.350) 109 Example 211 1:2 3.99 19.8 (0.660, 0.352) 110 Example 212 1:3 3.62 20.9 (0.661, 0.352) 120 Example 213 1:4 3.48 22.6 (0.661, 0.350) 121 Example 214 1-266 5-37 3:1 4.10 19.6 (0.661, 0.350) 77 Example 215 2:1 3.93 21.5 (0.662, 0.351) 80 Example 216 1:1 3.91 22.6 (0.659, 0.350) 95 Example 217 1:2 3.90. 22.6 (0.659, 0.351) 100 Example 218 1:3 3.87 23.0 (0.660, 0.351) 102 Example 219 1:4 3.77 23.2 (0.661, 0.352) 115

Table 7 shows that when the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 are simultaneously included in the organic material layer of an organic light-emitting device, driving voltage, efficiency, and life can be remarkably improved. This result can be expected that when both compounds are included at the same time, an exciplex phenomenon occurs. The exciplex phenomenon is a phenomenon in which energy of a HOMO level of a donor (p-host) and an LUMO level of an acceptor (n-host) is released through electron exchange between two molecules. When an exciplex phenomenon occurs between two molecules, Reverse Intersystem Crossing (RISC) occurs, which can increase the internal quantum efficiency of fluorescence to 100%. When a donor (p-host) with good hole transport capability and an acceptor (n-host) with good electron transport capability are used as hosts of the emission layer, holes are injected into p-host and electrons are injected into n-host. It can help you improve.

As shown in Table 8 above, the mixture of the present invention was measured by fabricating a device in each ratio (3:1, 2:1, 1:1, 1:2, 1:3, 1:4). As the ratio of the first host increased, it was confirmed that the results of driving voltage, efficiency, and life were gradually falling, whereas when the ratio of the second host with strong hole characteristics increased, the results of driving voltage, efficiency and life were improved. This is because the charge balance in the light emitting layer is maximized.

100: substrate
200: anode
300: organic material layer
301: hole injection layer
302: hole transport layer
303: light emitting layer
304: hole blocking layer
305: electron transport layer
306: electron injection layer
400: cathode

Claims (17)

An organic light-emitting device comprising a first electrode, a second electrode, and at least one organic material layer provided between the first electrode and the second electrode,
An organic light-emitting device in which at least one of the organic material layers includes a heterocyclic compound represented by the following formula (1) and a heterocyclic compound represented by the following formula (2):
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
X ₁ is N or CR ₁ ,
X ₂ is N or CR ₂ ,
Y is O; S; CRR'; Or NR",
L is a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,
m is an integer from 0 to 5,
N-Het is a substituted or unsubstituted, monocyclic or polycyclic C2 to C60 heterocyclic group containing at least one N,
R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to To form a C60 aliphatic or aromatic heterocycle,
Ar ₁ is a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
R ₅₁ to R ₅₈ , R _a to R _c , R, R'and R" are the same as or different from each other, and each independently hydrogen; deuterium; halogen; cyano group; substituted or unsubstituted C1 to C60 alkyl group; substituted Or an unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; substituted or unsubstituted A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And A substituted or unsubstituted aryl group. Two or more groups selected from the group consisting of amine groups or adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or aromatic hetero ring, and , n and q are each an integer of 0 to 4, when n is 2 or more, R _a is the same as or different from each other, when q is 2 or more, R _c is the same or different from each other, and p is an integer of 0 to 2, When p is an integer of 2, R _b is the same as or different from each other,
n+p+q≤9. The organic light-emitting device of claim 1, wherein Formula 1 is represented by any one of the following Formulas 3 to 5:
[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,
R ₁ , R ₂ , and R ₁₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And it is selected from the group consisting of a substituted or unsubstituted amine group,
The definitions of R _a to R _c , Y, N-Het, L, m, n, p and q are the same as those defined in Chemical Formula 1. The organic light-emitting device of claim 1, wherein Formula 1 is represented by any one of the following Formulas 6 to 8:
[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 6 to 8,
R ₁ , R ₂ , and R ₁₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And it is selected from the group consisting of a substituted or unsubstituted amine group,
R ₂₁ to R ₂₈ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; A substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or aromatic Form a hetero ring,
The definitions of R _a to R _c , Y, L, m, n, p and q are the same as those defined in Formula 1. The organic light-emitting device of claim 1, wherein Formula 2 is represented by any one of the following Formulas 10 to 12:
[Formula 10]

[Formula 11]

[Formula 12]

In Formulas 10 to 12,
R ₆₁ to R ₇₀ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And it is selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group,
R ₇₁ to R ₇₄ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to To form a C60 aliphatic or aromatic hetero ring,
Ar ₂ and Ar ₃ are the same as or different from each other, and each independently, a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
A ₁ is O; S; NAr ₄ ; Or CR _d R _e ,
R _d and R _e are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; Or a substituted or unsubstituted C6 to C60 aryl group,
Ar ₄ is a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
h and i are integers from 0 to 3,
j is an integer from 0 to 2. The organic light-emitting device of claim 4, wherein Formula 10 is the following Formula 10-1 or 10-2:
[Formula 10-1]

[Formula 10-2]

In Formulas 10-1 and 10-2,
The definition of each substituent is the same as the definition in Formula 10 above. The organic light-emitting device of claim 4, wherein the formula 11 is any one of the following formulas 11-1 to 11-3:
[Chemical Formula 11-1]

[Formula 11-2]

[Chemical Formula 11-3]

In Formulas 11-1 to 11-3,
The definition of each substituent is the same as the definition in Formula 11. The organic light-emitting device of claim 4, wherein the formula 12 is represented by any one of the following formulas 12-1 to 12-4:
[Chemical Formula 12-1]

[Formula 12-2]

[Chemical Formula 12-3]

[Chemical Formula 12-4]

In Formulas 12-1 to 12-4,
The definition of Ar ₂ and A ₁ is the same as in Chemical Formula 12,
R ₈₁ and R ₈₂ are the same as or different from each other, and each independently a substituted or unsubstituted C10 or more aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
R ₈₃ is a substituted or unsubstituted C10 or less aryl group. The organic light-emitting device of claim 1, wherein Formula 1 is represented by any one of the following compounds:

. The organic light-emitting device of claim 1, wherein Formula 2 is represented by any one of the following compounds:

The method according to claim 1, wherein the organic material layer comprises at least one of a hole blocking layer, an electron injection layer, and an electron transport layer, and at least one of the hole blocking layer, the electron injection layer and the electron transport layer is a heterocycle represented by Formula 1 An organic light-emitting device comprising a compound, and a heterocyclic compound represented by Chemical Formula 2. The organic light-emitting device of claim 1, wherein the organic material layer includes an emission layer, and the emission layer includes a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2. The method according to claim 1, wherein the organic material layer includes an emission layer, the emission layer includes a host material, and the host material includes a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2 Phosphorus organic light emitting device. The method according to claim 1, wherein the organic light emitting device is a light emitting layer, a hole injection layer, a hole transport layer. An organic light-emitting device further comprising one or two or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer. A composition for an organic material layer of an organic light-emitting device comprising a heterocyclic compound represented by the following formula (1) and a compound represented by the following formula (2):
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
X ₁ is N or CR ₁ ,
X ₂ is N or CR ₂ ,
Y is O; S; CRR'; Or NR",
L is a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,
m is an integer from 0 to 5,
N-Het is a substituted or unsubstituted, monocyclic or polycyclic C2 to C60 heterocyclic group containing at least one N,
R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to To form a C60 aliphatic or aromatic heterocycle,
Ar ₁ is a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
R ₅₁ to R ₅₈ , Ra To R _c , R, R'and R" are the same as or different from each other, and each independently hydrogen; deuterium; halogen; cyano group; substituted or unsubstituted C1 to C60 alkyl group; substituted or unsubstituted C2 to C60 Alkenyl group; substituted or unsubstituted C2 to C60 alkynyl group; substituted or unsubstituted C1 to C60 alkoxy group; substituted or unsubstituted C3 to C60 cycloalkyl group; substituted or unsubstituted C2 to C60 heterocyclo Alkyl group; substituted or unsubstituted C6 to C60 aryl group; substituted or unsubstituted C2 to C60 heteroaryl group; substituted or unsubstituted phosphine oxide group; and substituted or unsubstituted amine group , Two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 aliphatic or aromatic hetero ring, and n and q are each 0 to It is an integer of 4, when n is 2 or more, R _a is the same as or different from each other, when q is 2 or more, R _c is the same as or different from each other, p is an integer of 0 to 2, and when p is an integer of 2, R _b Are the same or different from each other,
n+p+q≤9. The composition for an organic material layer of an organic light emitting device according to claim 14, wherein a weight ratio of the heterocyclic compound represented by Formula 1 in the composition: the heterocyclic compound represented by Formula 2 is 1:10 to 10:1. Preparing a substrate;
Forming a first electrode on the substrate;
Forming one or more organic material layers on the first electrode; And
Including the step of forming a second electrode on the organic material layer,
The step of forming the organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to claim 14. The organic light emitting device of claim 16, wherein the forming of the organic material layer is formed by using a thermal vacuum deposition method by pre-mixing the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 Manufacturing method.

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