KR102683910B1 - Heterocyclic compound and organic light emitting device using same - Google Patents

Abstract

The present application provides a heterocyclic compound that can significantly improve the lifespan, efficiency, electrochemical stability, and thermal stability of an organic light-emitting device, and an organic light-emitting device containing the same in an organic material layer.

Description

Heterocyclic compound and organic light-emitting device using the same {HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING SAME}

This application relates to heterocyclic compounds and organic light-emitting devices using the same.

Electroluminescent devices are a type of self-luminous display devices and have the advantages of a wide viewing angle, excellent contrast, and fast response speed.

Organic light-emitting devices have a structure in which an organic thin film is placed between two electrodes. When voltage is applied to an organic light emitting device with this structure, electrons and holes injected from two electrodes combine in the organic thin film to form a pair and then disappear, emitting light. The organic thin film may be composed of a single layer or multiple layers, depending on need.

The material of the organic thin film may have a light-emitting function as needed. For example, as an organic thin film material, a compound that can independently form a light-emitting layer may be used, or a compound that can act as a host or dopant of a host-dopant-based light-emitting layer may be used. In addition, as a material for the organic thin film, compounds that can perform roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, lifespan, or efficiency of organic light-emitting devices, the development of organic thin film materials is continuously required.

US Patent No. 4,356,429

The present invention seeks to provide an organic light-emitting device containing a heterocyclic compound and .

An exemplary embodiment of the present application provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L1 to L6 are the same or different from each other and are each independently directly bonded; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms, a to f are each an integer of 0 to 3, and when a to f are each an integer of 2 or more, the substituents in parentheses are the same or different from each other,

One of R1 to R6 is -P(=O)R31R32, and the remainder of R1 to R6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

R31 and R32 are the same or different from each other and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

Rn is hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 6 to 60 carbon atoms, n is an integer of 0 to 5, and when n is 2 or more, Rn in parentheses are the same or different from each other.

In addition, another embodiment of the present application is an organic light-emitting device including a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers are An organic light-emitting device comprising a heterocyclic compound represented by Formula 1 is provided.

The heterocyclic compound according to an exemplary embodiment of the present application can be used as an organic layer material of an organic light-emitting device. The heterocyclic compound can be used as a material such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a charge generation layer in an organic light emitting device. In particular, the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 can be used as a material for the light-emitting layer of an organic light-emitting device. In addition, when the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are used in an organic light emitting device, the driving voltage of the device is lowered, the luminous efficiency is improved, and the lifespan of the device is extended due to the thermal stability of the compound. Characteristics can be improved.

1 to 4 are diagrams schematically showing the stacked structure of an organic light-emitting device according to an exemplary embodiment of the present application.

The present application will be described in detail below.

An exemplary embodiment of the present application provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L1 to L6 are the same or different from each other and are each independently directly bonded; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms, a to f are each an integer of 0 to 3, and when a to f are each an integer of 2 or more, the substituents in parentheses are the same or different from each other,

One of R1 to R6 is -P(=O)R31R32, and the remainder of R1 to R6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

R31 and R32 are the same or different from each other and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

Rn is hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 6 to 60 carbon atoms, n is an integer of 0 to 5, and when n is 2 or more, Rn in parentheses are the same or different from each other.

That is, the heterocyclic compound represented by Formula 1 has a structure in which a phosphine oxide group is substituted in the phenanthroline core structure, and thus has the characteristic of being able to have a stable bond with metals.

Because of these characteristics, when the heterocyclic compound represented by Formula 1 is used in the organic material layer, more preferably the electron transport layer, of an organic light-emitting device using a metal as a cathode, decomposition or destruction of the compound does not occur, so that the organic light-emitting device Electron transport characteristics and stability can be improved.

In addition, due to its ability to form a stable bond with a metal, when the heterocyclic compound represented by Formula 1 of the present invention is doped with a metal to use it as an N-type charge generation layer, a gap is formed in the N-type charge generation layer. A (gap) state can be formed stably.

This has the effect of facilitating electron injection of electrons generated from the P-type charge generation layer into the electron transport layer through the gap state generated within the N-type charge generation layer.

Therefore, an organic light-emitting device using the heterocyclic compound represented by Formula 1 in the organic material layer has excellent operation, efficiency, and lifespan.

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

In this specification, the chemical formula means the position where it is combined.

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

In this specification, “substituted or unsubstituted” means deuterium; halogen group; -CN; C1 to C60 alkyl group; C2 to C60 alkenyl group; C2 to C60 alkynyl group; C1 to C60 haloalkyl group; C1 to C60 alkoxy group; Aryloxy group of C6 to C60; C1 to C60 alkylthioxy group; Arylthioxy group of C6 to C60; C1 to C60 alkyl sulfoxy group; C6 to C60 aryl sulfoxy group; C3 to C60 cycloalkyl group; C2 to C60 heterocycloalkyl group; Aryl group of C6 to C60; C2 to C60 heteroaryl group; -SiRR'R"; -P(=O)RR'; means that one or more substituents selected from the group consisting of -NRR', or two or more substituents selected from the above exemplified substituents are substituted or unsubstituted with a connected substituent; , R, R' and R" are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; heterocycloalkyl group; Aryl group; and a substituent consisting of at least one of a heteroaryl group.

In this specification, “Cn” means n carbon atoms.

In this specification, “if a substituent is not indicated in the chemical formula or compound structure” means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( ^2H , Deuterium) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In an exemplary embodiment of the present application, “when a substituent is not indicated in the chemical formula or compound structure” may mean that all positions that can appear as substituents are hydrogen or deuterium. That is, in the case of deuterium, it is an isotope of hydrogen, and some hydrogen atoms may be the isotope deuterium, and in this case, the content of deuterium may be 0% to 100%.

In an exemplary embodiment of the present application, in “cases where substituents are not indicated in the chemical formula or compound structure,” the content of deuterium is 0%, the content of hydrogen is 100%, and all substituents are hydrogen, etc., explicitly excluding deuterium. Otherwise, hydrogen and deuterium can be used together in compounds.

In an exemplary embodiment of the present application, deuterium is one of the isotopes of hydrogen and is an element that has a deuteron, consisting of one proton and one neutron, as its nucleus. Hydrogen- It can be expressed as 2, and the element symbol can also be written as D or ² H.

In an exemplary embodiment of the present application, isotopes refer to atoms having the same atomic number (Z) but different mass numbers (A). Isotopes have the same number of protons but do not contain neutrons. It can also be interpreted as an element with a different number of neutrons.

In an exemplary embodiment of the present application, the meaning of the content T% of a specific substituent means that the total number of substituents that the basic compound can have is defined as T1, and the number of specific substituents among them is defined as T2. It can be defined as /T1×100 = T%.

That is, in one example, The deuterium content of 20% in the phenyl group represented by means that the total number of substituents that the phenyl group can have is 5 (T1 in the formula), and if the number of deuteriums among them is 1 (T2 in the formula), it will be expressed as 20%. You can. That is, the deuterium content of 20% in the phenyl group can be expressed by the following structural formula.

Additionally, in an exemplary embodiment of the present application, “a phenyl group with a deuterium content of 0%” may mean a phenyl group that does not contain deuterium atoms, that is, has 5 hydrogen atoms.

In this specification, 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 another substituent. The carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, and 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, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group Tyl 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-methyl Examples include pentyl group, 4-methylhexyl group, and 5-methylhexyl group, but it is not limited thereto.

In the present specification, the alkenyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms. 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, styrenyl group, etc., but is not limited to these.

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

In this specification, a haloalkyl group refers to an alkyl group substituted with a halogen group, and specific examples include -CF ₃ and -CF ₂ CF ₃ , but are not limited thereto.

In this specification, a haloalkyl group refers to an alkyl group substituted with a halogen group, and specific examples include -CF ₃ and -CF ₂ CF ₃ , but are not limited thereto.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms and may be further substituted by another substituent. Here, polycyclic refers to a group in which a cycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, or a heteroaryl group. The carbon number of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, 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, etc., but is not limited thereto.

In the present specification, the heterocycloalkyl group contains O, S, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which a heterocycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, or a heteroaryl group. The carbon number 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 a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which an aryl group is directly connected to or condensed with another ring group. Here, the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, heteroaryl group, etc. The aryl group includes a spiro group. The carbon number 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, terphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, and phenalenyl group. , pyrenyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, these Condensation ring groups, etc. may be included, but are not limited thereto.

In the present specification, the terphenyl group may be selected from the following structures.

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

When the fluorenyl group is substituted, , , , , , It may be, but is not limited to this.

In the present specification, the heteroaryl group contains S, O, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic refers to a group in which a heteroaryl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, or aryl group. The carbon number 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 pyridine group, pyrrole group, pyrimidine group, pyridazine group, furan group, thiophene group, imidazole group, pyrazole group, oxazole group, isoxazole group, thiazole group, isothiazole group, Triazole group, furazine group, oxadiazole group, thiadiazole group, dithiazole group, tetrazolyl group, pyran group, thiopyran group, diazine group, oxazine group, thiazine group, dioxine group, triazine group, tetrazine group, quinoline group, Isoquinoline group, quinazoline group, isoquinazoline group, quinozoline group, naphthyridine group, acridine group, phenanthridine group, imidazopyridine group, diazanaphthalene group, triazindene group, indole group, indolizine group, Benzothiazole group, benzoxazole group, benzimidazole group, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, carbazole group, benzocarbazole group, dibenzocarbazole group, phenazine group, dibenzo Sylol group, spirobi (dibenzosilol), dihydrophenazine group, phenoxazine group, phenanthridine group, thienyl group, indolo [2,3-a] carbazole group, indolo [2,3-b] carbazole group, Indoline group, 10,11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridine group, phenanthrazine group, phenothiathiazine group, phthalazine group, phenanthroline group, naphthobenzofuran group, naphthobenzothiophene group, benzo[c][1,2,5]thiadiazole group, 2,3-dihydrobenzo[b]thiophene group, 2,3-dihydrobenzofuran group, 5, 10-dihydrodibenzo[b,e][1,4]azacillin group, pyrazolo[1,5-c]quinazoline group, pyrido[1,2-b]indazole group, pyrido[1, Examples include, but are not limited to, 2-a]imidazo[1,2-e]indoline group and 5,11-dihydroindeno[1,2-b]carbazole group.

In this specification, when the substituent is a carbazole group, it means bonding with the nitrogen or carbon of carbazole.

In this specification, when a carbazole group is substituted, an additional substituent may be substituted on the nitrogen or carbon of the carbazole.

In this specification, when a carbazole group is substituted, an additional substituent may be substituted on the nitrogen or carbon of the carbazole.

In the present specification, the benzocarbazole group may have any one of the following structures.

In the present specification, the dibenzocarbazole group may have any one of the following structures.

In the present specification, the naphthobenzofuran group may have any of the following structures.

In the present specification, the naphthobenzothiophene group may have any one of the following structures.

In this specification, the alkoxy group is represented by -O(R101), and examples of the above-described alkyl group may be applied to R101.

In the present specification, the aryloxy group is represented by -O(R102), and examples of the above-described aryl groups may be applied to R102.

In this specification, the alkylthioxy group is represented by -S(R103), and examples of the alkyl groups described above may be applied to R103.

In the present specification, the arylthioxy group is represented by -S(R104), and examples of the above-described aryl groups may be applied to R104.

In the present specification, the alkyl sulfoxy group is represented by -S(=0) ₂ (R105), and examples of the above-described alkyl groups may be applied to R105.

In the present specification, the arylsulfoxy group is represented by -S(=0) ₂ (R106), and examples of the above-described aryl groups may be applied to R106.

In the present specification, the silyl group is a substituent that contains Si and is directly connected to the Si atom as a radical, and is represented by -SiR104R105R106, and R104 to R106 are the same or different from each other, and are 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 silyl groups include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. It is not limited.

For example (trimethylsilyl group), (triethylsilyl group), (t-butyldimethylsilyl group), (vinyldimethylsilyl group), (propyldimethylsilyl group), (triphenylsilyl group), (diphenylsilyl group), (phenylsilyl group), etc., but is not limited thereto.

In the present specification, the phosphine oxide group is represented by -P(=O)(R110)(R111), and R110 and R111 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; heterocycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heteroaryl group. Specifically, it may be substituted with an alkyl group or an aryl group, and the examples described above may be applied to the alkyl group and the aryl group. For example, phosphine oxide groups include dimethylphosphine oxide, diphenylphosphine oxide, and dinaphthylphosphine oxide, but are not limited thereto.

In this specification, the amine group is represented by -N(R112)(R113), and R112 and R113 are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; heterocycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heteroaryl group. The amine group is -NH ₂ ; Monoalkylamine group; monoarylamine group; Monoheteroarylamine group; dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; and an arylheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenyl fluores Examples include a nylamine group, phenyltriphenylenylamine group, and biphenyltriphenylenylamine group, but are not limited to these.

In the present specification, the examples of the aryl group described above may be applied, except that the arylene group is a divalent group.

In the present specification, the examples of the heteroaryl group described above may be applied, except that the heteroarylene group is a divalent group.

As used herein, an “adjacent” group may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located closest to the substituent in terms of structure, or another substituent substituted on the atom on which the substituent is substituted. You can. For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring can be interpreted as “adjacent” groups.

Hydrocarbon rings and heterocycles that can be formed by adjacent groups include aliphatic hydrocarbon rings, aromatic hydrocarbon rings, aliphatic heterocycles, and aromatic heterocycles, and the rings are each of the above-described cycloalkyl groups and aryl groups, except that they are not monovalent. Structures exemplified by groups, heterocycloalkyl groups, and heteroaryl groups can be applied.

In an exemplary embodiment of the present application, L1 to L6 of Formula 1 are the same or different from each other and are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms, a to f are each an integer of 0 to 3, and when a to f are each an integer of 2 or more, the substituents in parentheses are the same or different from each other.

In an exemplary embodiment of the present application, L1 to L6 are the same or different from each other and are each independently directly bonded; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, L1 to L6 are the same or different from each other and are each independently directly bonded; A substituted or unsubstituted arylene group having 6 to 40 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, L1 to L6 are the same or different from each other and are each independently directly bonded; A substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, L1 to L6 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted phenylene group; Substituted or unsubstituted naphthylene group; Substituted or unsubstituted pyridylene group; Substituted or unsubstituted pyrimidylene group; Substituted or unsubstituted purenylene group; Substituted or unsubstituted thiophenylene group; Or a substituted or unsubstituted phenanthrolinene group.

In an exemplary embodiment of the present application, L1 to L6 are the same or different from each other and are each independently directly bonded; A phenylene group substituted or unsubstituted with one or more deuterium; Naphthylene group substituted or unsubstituted with one or more deuterium; A pyridylene group substituted or unsubstituted with one or more deuterium; A pyrimidylene group substituted or unsubstituted with one or more deuterium; A purenylene group substituted or unsubstituted with one or more deuterium; A thiophenylene group substituted or unsubstituted with one or more deuterium; Or it is a phenanthrolinene group substituted or unsubstituted with one or more deuterium.

The pyridylene group; Pyrimidylene group; Purenylene group; thiophenylene group; And the phenanthrolinene group is each a two-valent group of a pyridine group; Two groups of pyrimidine groups; 2 groups of furan group; 2 groups of thiophene groups; and two groups of phenanthroline groups.

In an exemplary embodiment of the present application, a is an integer from 0 to 3, and when a is 2 or more, L1 in parentheses are the same as or different from each other. In one embodiment of the present application, a is 0. In an exemplary embodiment of the present application, a is 1. In an exemplary embodiment of the present application, a is 2. In an exemplary embodiment of the present application, a is 3.

In an exemplary embodiment of the present application, b is an integer from 0 to 3, and when b is 2 or more, L2 in parentheses are the same as or different from each other. In an exemplary embodiment of the present application, b is 0. In an exemplary embodiment of the present application, b is 1. In an exemplary embodiment of the present application, b is 2. In an exemplary embodiment of the present application, b is 3.

In an exemplary embodiment of the present application, c is an integer from 0 to 3, and when c is 2 or more, L3 in parentheses are the same as or different from each other. In an exemplary embodiment of the present application, c is 0. In an exemplary embodiment of the present application, c is 1. In an exemplary embodiment of the present application, c is 2. In an exemplary embodiment of the present application, c is 3.

In an exemplary embodiment of the present application, d is an integer from 0 to 3, and when d is 2 or more, L4 in parentheses are the same as or different from each other. In an exemplary embodiment of the present application, d is 0. In an exemplary embodiment of the present application, d is 1. In an exemplary embodiment of the present application, d is 2. In an exemplary embodiment of the present application, d is 3.

In an exemplary embodiment of the present application, e is an integer from 0 to 3, and when e is 2 or more, L5 in parentheses are the same as or different from each other. In an exemplary embodiment of the present application, e is 0. In an exemplary embodiment of the present application, e is 1. In an exemplary embodiment of the present application, e is 2. In an exemplary embodiment of the present application, e is 3.

In an exemplary embodiment of the present application, f is an integer from 0 to 3, and when f is 2 or more, L6 in parentheses are the same as or different from each other. In an exemplary embodiment of the present application, f is 0. In an exemplary embodiment of the present application, f is 1. In an exemplary embodiment of the present application, f is 2. In an exemplary embodiment of the present application, f is 3.

In an exemplary embodiment of the present application, one of R1 to R6 is -P(=O)R31R32, and the remainder of R1 to R6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, wherein R31 and R32 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, one of R1 to R6 is -P(=O)R31R32, and the remainder of R1 to R6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, one of R1 to R6 is -P(=O)R31R32, and the remainder of R1 to R6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, one of R1 to R6 is -P(=O)R31R32, and the remainder of R1 to R6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted pyridine group; Or a substituted or unsubstituted phenanthroline group.

In an exemplary embodiment of the present application, one of R1 to R6 is -P(=O)R31R32, and the remainder of R1 to R6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with one or more deuterium; Biphenyl group substituted or unsubstituted with one or more deuterium; A naphthyl group substituted or unsubstituted with one or more deuterium; A pyridine group substituted or unsubstituted with one or more deuterium; Or it is a phenanthroline group substituted or unsubstituted with one or more deuterium.

In an exemplary embodiment of the present application, R1 is -P(=O)R31R32, and R2 to R6 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R2 is -P(=O)R31R32, R1, and R3 to R6 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R3 is -P(=O)R31R32, and R1, R2, and R4 to R6 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R4 is -P(=O)R31R32, and R1 to R3, R5, and R6 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R5 is -P(=O)R31R32, and R1 to R4 and R6 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R6 is -P(=O)R31R32, and R1 to R5 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R31 and R32 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R31 and R32 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R31 and R32 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, R31 and R32 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, R31 and R32 are the same as or different from each other, and are each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted pyridine group; Or a substituted or unsubstituted quinoline group.

In an exemplary embodiment of the present application, R31 and R32 are the same as or different from each other, and are each independently a phenyl group substituted or unsubstituted with one or more deuterium; Biphenyl group substituted or unsubstituted with one or more deuterium; A pyridine group substituted or unsubstituted with one or more deuterium; Or it is a quinoline group substituted or unsubstituted with one or more deuterium.

In an exemplary embodiment of the present application, Rn is hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 6 to 60 carbon atoms, n is an integer of 0 to 5, and when n is 2 or more, Rn in parentheses are the same or different.

In an exemplary embodiment of the present application, Rn is hydrogen; Or deuterium.

In an exemplary embodiment of the present application, Rn is hydrogen.

In an exemplary embodiment of the present application, Rn is deuterium.

In an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following Formulas 2 to 7.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 2 to 7,

The definitions of L1 to L6, a to f, R31 and R32 are the same as in Formula 1,

R11 to R16 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R11 to R16 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, R11 to R16 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, R11 to R16 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, R11 to R16 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted pyridine group; Or a substituted or unsubstituted phenanthroline group.

In an exemplary embodiment of the present application, R11 to R16 are the same as or different from each other and are each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with one or more deuterium; Biphenyl group substituted or unsubstituted with one or more deuterium; A naphthyl group substituted or unsubstituted with one or more deuterium; A pyridine group substituted or unsubstituted with one or more deuterium; Or it is a phenanthroline group substituted or unsubstituted with one or more deuterium.

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.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Formula 1 is 0% or more and 100% or less.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Formula 1 may be 0%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is greater than 0% and less than or equal to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Formula 1 is 1% or more and 100% or less.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Formula 1 is 10% or more and 100% or less.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Formula 1 is 20% or more and 100% or less.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound represented by Formula 1 is 40% or more and 100% or less.

Additionally, by introducing various substituents into the structure of Formula 1, it is possible to synthesize compounds having the unique properties of the introduced substituents. For example, the conditions required for each organic material layer are met by introducing substituents mainly used in the hole injection layer material, hole transport material, light emitting layer material, electron transport layer material, and charge generation layer material used in the manufacture of organic light-emitting devices into the core structure. You can synthesize the desired substance.

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

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

Heterocyclic compounds according to an exemplary embodiment of the present application can be produced through a multi-step chemical reaction. Some intermediate compounds are first prepared, and the compound of Formula 1 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application can be prepared based on the production example described later.

In one embodiment of the present specification, a first electrode; second electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes a heterocyclic compound represented by Formula 1.

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

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

Another embodiment of the present application provides an organic light-emitting device containing the heterocyclic compound represented by Formula 1 above. The “organic light emitting device” may be expressed by terms such as “organic light emitting diode,” “OLED (Organic Light Emitting Diodes),” “OLED device,” and “organic electroluminescent device.”

The heterocyclic compound may be formed into 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 application method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

In the organic light emitting device of the present application, the organic material layer includes an electron transport layer, and the electron transport layer may include a heterocyclic compound represented by Formula 1 above. Among the organic material layers, when the electron transport layer includes the heterocyclic compound represented by Formula 1, the luminous efficiency and lifespan of the organic light-emitting device are further improved.

In the organic light-emitting device according to the present application, the organic layer may include a light-emitting layer, and the light-emitting layer may include a host material.

In the organic light emitting device according to the present application, the host material may include two or more host materials, and one of the two or more host materials may be an n-type host material and the other may be a p-type host material.

In the organic light emitting device according to the present application, the host material may include two or more host materials, and the two or more host materials may be pre-mixed before use.

That is, the light emitting layer can be used by pre-mixing two or more host materials. The pre-mixed means that the light emitting layer first mixes two or more host materials into one container before depositing them on the organic layer.

The organic light-emitting device according to an exemplary embodiment of the present application can be manufactured using conventional organic light-emitting device manufacturing methods and materials, except that the organic material layer is formed using the heterocyclic compound described above.

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

1 to 3 illustrate the stacking order of electrodes and organic material layers 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 structures of organic light-emitting devices known in the art may also be applied to the present application.

According to Figure 1, an organic light emitting device is shown in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100. However, it is not limited to this structure, and an organic light-emitting device may be implemented in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate, as shown in FIG. 2.

Figure 3 illustrates the case where the organic material layer is multi-layered. The organic light emitting device 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 this laminated structure, and if necessary, the remaining layers except the light-emitting layer may be omitted, and other necessary functional layers may be added.

In addition, an organic light-emitting device according to an exemplary embodiment of the present application includes a first electrode, a first stack provided on the first electrode and including a first light-emitting layer, a charge generation layer provided on the first stack, and It includes a second stack provided on the charge generation layer and including a second light-emitting layer, and a second electrode provided on the second stack.

At this time, the charge generation layer may include a heterocyclic compound represented by Formula 1 above. When the heterocyclic compound is used in the charge generation layer, the driving, efficiency, and lifespan of the organic light-emitting device can be improved.

In addition, the first stack and the second stack may each independently additionally include one or more of the above-described hole injection layer, hole transport layer, hole blocking layer, electron transport layer, and electron injection layer.

The charge generation layer may be an N-type charge generation layer, and the charge generation layer may further include a dopant known in the art in addition to the heterocyclic compound represented by Formula 1.

As an organic light-emitting device according to an exemplary embodiment of the present application, an organic light-emitting device with a 2-stack tandem structure is exemplarily shown in FIG. 4 below.

At this time, the first electron blocking layer, first hole blocking layer, and second hole blocking layer shown in FIG. 4 below may be omitted in some cases.

In an exemplary embodiment of the present application, the compound of Formula 1 may be doped with an alkali metal or alkaline earth metal. In this case, due to the formation of the gap state, the driving voltage of the organic light emitting device is lowered, and efficiency and lifespan can be further improved.

In an exemplary embodiment of the present application, a composition containing an alkali metal or alkaline earth metal in the compound of Formula 1 is provided. The content of alkali metal or alkaline earth metal in the composition may be 0.01 wt% to 30 wt%, preferably 0.01 wt% to 25 wt%, and more preferably 0.01 wt% to 20 wt%, based on the total weight of the composition.

In an exemplary embodiment of the present application, the alkali metal or alkaline earth metal may be lithium (Li), rubidium (Rb), cesium (Cs), or magnesium (Mg). However, it is not limited to this.

In the organic light-emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Formula 1 are illustrated below, but these are for illustrative purposes only and are not intended to limit the scope of the present application, and are not intended to limit the scope of the present application. It can be replaced with known materials.

As the anode material, materials with a relatively large work function can be used, and transparent conductive oxides, metals, or conductive polymers can 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); Combination of metal and oxide such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

As the cathode material, materials with a relatively low work function can be used, and metals, metal oxides, or conductive polymers can be used. Specific examples of the cathode 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-layer structure materials such as LiF/Al or LiO ₂ /Al, but they are not limited to these.

As the hole injection material, known hole injection materials may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in Advanced Material, 6, p.677 (1994). 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, a soluble conductive polymer, or poly( 3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate), Polyaniline/Camphor sulfonic acid or polyaniline/ Poly(4-styrenesulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) can be used.

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

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

For example, LiF is typically used as an electron injection material in the industry, 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. Additionally, a fluorescent material can be used as a light-emitting material, but it can also be used as a phosphorescent material. As a light-emitting material, a material that emits light by combining holes and electrons injected from an anode and a cathode, respectively, may be used, but materials that participate in light emission together with a host material and a dopant material may also be used.

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

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

Below, the present specification is described in more detail through examples, but these are only for illustrating the present application and are not intended to limit the scope of the present application.

[Preparation Example 1] Preparation of Compound 1

1) Preparation of compound 1-1

Compound 2-bromo-1,10-phenanthroline (A) (20 g, 0.077 mol, 1 eq), 2-(3-bro) in a reaction flask Mo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-(3-bromo-2-nitrophenyl)-4,4,5,5- tetramethyl-1,3,2-dioxaborolane) (B) (27.9 g, 0.173 mol, 1.1 eq), Pd(PPh ₃ ) ₄ (4.6g 0.004 mol, 0.05 eq), K ₃ PO ₄ (49.0 g, 0.231 mol) , 3.0 eq), 1,4-dioxane (240 ml), and water (60 ml) were added and stirred at 100°C for 6 hours (h). Afterwards, water was added to terminate the reaction, and then extraction was performed using methylene chloride (MC) and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 27.4 g of compound 1-1 was obtained with a yield of 93%.

2) Preparation of Compound 1-2

In a reaction flask, compound 1-1 (24 g, 0.063 mol, 1 eq), triphenylphosphine (33.0 g, 0.126 mol, 2.0 eq), and 1,2-dichlorobenzene (1,2 -dichlorobenzene) (240 ml) was added and stirred at 160°C for 24 h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 17.4 g of compound 1-2 was obtained with a yield of 80%.

3) Preparation of Compound 1-3

In a reaction flask, compound 1-2 (14 g, 0.040 mol, 1 eq), 3-iodo-1,1'-biphenyl (3-iodo-1,1'-biphenyl) (C) (16.8 g, 0.060 mol, 1.5 eq), Pd ₂ (dba) ₃ (1.8 g, 0.002 mol, 0.05 eq), P(t-Bu) ₃ (0.8 g, 0.004 mol, 0.1 eq), NaOt-Bu (5.8 g , 0.060 mol, 1.5 eq) and toluene (140 ml) were added and stirred at 100°C for 12h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 18.0 g of compound 1-3 was obtained with a yield of 90%.

4) Preparation of Compound 1

Compound 1-3 (10 g, 0.020 mol, 1 eq), diphenylphosphine oxide (D) (4.4 g, 0.022 mol, 1.1 eq), and Pd(PPh ₃ ) ₄ in a reaction flask. (1.2 g, 0.001 mol, 0.05 eq), Et ₃ N (4.0 g, 0.040 mol, 2.0 eq), and toluene (100 ml) were added and stirred at 110°C. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . By separation using a silica gel column, 8.5 g of compound 1 was obtained with a yield of 68%.

In Preparation Example 1, intermediate A of Table 1 below was used instead of 2-bromo-1,10-phenanthroline (A), and 2-(3-bromo- 2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl- Intermediate B of Table 1 below is used instead of 1,3,2-dioxaborolane) (B), and instead of 3-iodo-1,1'-biphenyl (3-iodo-1,1'-biphenyl) (C) A compound was synthesized in the same manner as Preparation Example 1, except that Intermediate C of Table 1 below was used and Intermediate D of Table 1 below was used instead of diphenylphosphine oxide (D).

[Preparation Example 2] Preparation of Compound 8

1) Preparation of compound 8-1-1

(4-bromophenyl)diphenylphosphine oxide (D) (20 g, 0.056 mol, 1 eq), 4,4,4',4' in a reaction flask. ,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)) (21.3 g, 0.084 mol, 1.5 eq), Pd(dppf)Cl ₂ (2.2g 0.003 mol, 0.05 eq), KOAc ( 16.5 g, 0.168 mol, 3.0 eq), and 1,4-dioxane (200 ml) were added and stirred at 100°C for 6h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 21.0 g of compound 8-1-1 was obtained with a yield of 93%.

2) Preparation of compound 8-1

In the method for preparing compound 1-1 of Preparation Example 1, 2-bromo-9-(naphthalen-2-yl) was used instead of 2-bromo-1,10-phenanthroline (2-bromo-1,10-phenanthroline). Method for producing compound 1-1 of Preparation Example 1, except using -1,10-phenanthroline (2-bromo-9-(naphthalen-2-yl)-1,10-phenanthroline) (A) Compound 8-1 was obtained in the same manner as above. That is, in the preparation of compound 8-1, 2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-di, as in the preparation method of compound 1-1. Oxaborolane (2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (B) was used.

3) Preparation of compound 8-2

Compound 8-2 was obtained in the same manner as the method for preparing compound 1-2 in Preparation Example 1, except that Compound 8-1 was used instead of Compound 1-1 in the preparation method of Compound 1-2 in Preparation Example 1.

4) Preparation of compound 8-3

In the method for preparing compound 1-3 of Preparation Example 1, iodobenzene (C) is used instead of 3-iodo-1,1'-biphenyl, Compound 8-3 was obtained in the same manner as the preparation method of Compound 1-3 in Preparation Example 1, except that Compound 8-2 was used instead of Compound 1-2.

5) Preparation of Compound 8

Compound 8-3 (10 g, 0.018 mol, 1 eq) and diphenyl (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2) were added to the reaction flask. -yl)phenyl)phosphine oxide (diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide) (8.1 g, 0.020 mol, 1.1 eq ), Pd(PPh ₃ ) ₄ (1.2g 0.001 mol, 0.05 eq), K ₃ PO ₄ (11.5 g, 0.054 mol, 3.0 eq), 1,4-dioxane (120 ml) , Water (30 ml) was added and stirred at 100°C for 6h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 10.8 g of compound 8 was obtained with a yield of 80%.

In Preparation Example 2, 2-bromo-9-(naphthalen-2-yl)-1,10-phenanthroline (2-bromo-9-(naphthalen-2-yl)-1,10-phenanthroline) (A ) Instead, use intermediate A of Table 2 below, and 2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2- Instead of (3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (B), intermediate B of Table 2 below is used, and iodobenzene (C ) Instead of using Intermediate C of Table 2 below, and using Intermediate D of Table 2 below instead of (4-bromophenyl)diphenylphosphine oxide (D), The compound was synthesized in the same manner as Preparation Example 2.

[Preparation Example 3] Preparation of compound 113

1) Preparation of compound 113-1

Compound 1-2 of Preparation Example 1 (10 g, 0.029 mol, 1 eq), phenylboronic acid (C) (3.9 g, 0.032 mol, 1.1 eq), and Pd (PPh ₃ ) in a flask. ₄ (1.2g 0.001 mol, 0.05 eq), K ₃ PO ₄ (18.5 g, 0.087 mol, 3.0 eq), 1,4-dioxane (120 ml), and Water ( 30 ml) was added and stirred at 100°C for 6h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 9.0 g of compound 113-1 was obtained with a yield of 90%.

2) Preparation of compound 113

In a flask, compound 113-1 (9 g, 0.026 mol, 1 eq), (4-bromophenyl)diphenylphosphine oxide (D) (13.9 g, 0.039 mol) , 1.5 eq), Pd ₂ (dba) ₃ (0.9 g, 0.001 mol, 0.05 eq), P(t-Bu) ₃ (0.4 g, 0.002 mol, 0.1 eq), NaOt-Bu (3.7 g, 0.039 mol, 1.5 eq), and toluene (90 ml) were added and stirred at 100°C for 12h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . By separation using a silica gel column, 12.9 g of compound 113 was obtained with a yield of 80%.

In Preparation Example 3, intermediate A of Table 3 below was used instead of 2-bromo-1,10-phenanthroline (A), and 2-(3-bromo- 2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl- Intermediate B of Table 3 below is used instead of 1,3,2-dioxaborolane (B), intermediate C of Table 3 below is used instead of phenylboronic acid (C), and (4-bromophenyl)di A compound was synthesized in the same manner as Preparation Example 3, except that Intermediate D of Table 3 below was used instead of (4-bromophenyl)diphenylphosphine oxide (D).

[Preparation Example 4] Preparation of Compound 209

1) Preparation of compound 209-1

2,9-dibromo-1,10-phenanthroline (A) (30 g, 0.089 mol, 1 eq) and diphenyl in a reaction flask. Diphenylphosphine oxide (B) (19.8 g, 0.098 mol, 1.1 eq), Pd(PPh ₃ ) ₄ (4.6 g, 0.004 mol, 0.05 eq), Et ₃ N (18.0 g, 0.178 mol, 2.0 eq) ), and toluene (300 ml) were added and stirred at 110°C. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . By separation using a silica gel column, compound 209-1 (29.8 g) was obtained with a yield of 73%.

2) Preparation of compound 209-2

In a reaction flask, compound 209-1 (29 g, 0.063 mol, 1 eq), 2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3, 2-Dioxaborolane (2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (C) (22.6 g, 0.069 mol, 1.1 eq) , Pd(PPh ₃ ) ₄ (3.5g 0.003 mol, 0.05 eq), K ₃ PO ₄ (40.1 g, 0.189 mol, 3.0 eq), 1,4-dioxane (360 ml), And water (90 ml) was added and stirred at 100°C for 6 hours (h). Afterwards, water was added to terminate the reaction, and then extraction was performed using methylene chloride (MC) and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 33.6 g of compound 209-2 was obtained with a yield of 92%.

3) Preparation of compound 209-3

In a reaction flask, compound 209-3 (33 g, 0.057 mol, 1 eq), triphenylphosphine (29.9 g, 0.114 mol, 2.0 eq), and 1,2-dichlorobenzene (1,2 -dichlorobenzene) (330 ml) was added and stirred at 160°C for 24h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 25.8 g of compound 209-3 was obtained with a yield of 82%.

4) Preparation of compound 209-4

Compound 209-3 (13 g, 0.024 mol, 1 eq), 3-iodo-1,1'-biphenyl (3-iodo-1,1'-biphenyl) (D) (10.1) in a reaction flask g, 0.036 mol, 1.5 eq), Pd ₂ (dba) ₃ (0.9 g, 0.001 mol, 0.05 eq), P(t-Bu) ₃ (0.4 g, 0.002 mol, 0.1 eq), NaOt-Bu (3.5 g) , 0.036 mol, 1.5 eq) and toluene (130 ml) were added and stirred at 100°C for 12h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 15.4 g of compound 209-4 was obtained with a yield of 90%.

5) Preparation of Compound 209

Compound 209-4 (8 g, 0.011 mol, 1 eq), phenylboronic acid (E) (1.5 g, 0.012 mol, 1.1 eq), and Pd(PPh ₃ ) ₄ (1.1g) in a flask. 0.001 mol, 0.05 eq), K ₃ PO ₄ (7.0 g, 0.033 mol, 3.0 eq), 1,4-dioxane (96 ml), and Water (24 ml) and stirred at 100°C for 6h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . By separation using a silica gel column, 6.9 g of compound 209 was obtained with a yield of 89%.

In Preparation Example 4, intermediate A of Table 4 below was used instead of 2,9-dibromo-1,10-phenanthroline (A), and diphenylphos Instead of diphenylphosphine oxide (B), use intermediate B of Table 4 below, and 2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2 -Use intermediate C of Table 4 below instead of dioxaborolane (2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (C), Intermediate D of Table 4 below is used instead of 3-iodo-1,1'-biphenyl (D), and instead of phenylboronic acid (E) The compound was synthesized in the same manner as Preparation Example 4, except that Intermediate E in Table 4 was used.

[Preparation Example 5] Preparation of compound 216

1) Preparation of compound 216-1

2,9-dibromo-1,10-phenanthroline (A) (30 g, 0.089 mol, 1 eq) and diphenyl in a reaction flask. (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide (diphenyl(4-(4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide) (B) (39.6 g, 0.098 mol, 1.1 eq), Pd(PPh ₃ ) ₄ (4.6g 0.004 mol, 0.05 eq), K ₃ PO ₄ (56.7 g, 0.267 mol, 3.0 eq), 1,4-dioxane (360 ml), and water (90 ml) were added and stirred at 100°C for 6 h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 41.2 g of compound 216-1 was obtained with a yield of 87%.

2) Preparation of compound 216-2

In a reaction flask, compound 216-1 (41 g, 0.077 mol, 1 eq), 2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3, 2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (C) (27.9 g, 0.085 mol, 1.1 eq) , Pd(PPh ₃ ) ₄ (4.6g 0.004 mol, 0.05 eq), K ₃ PO ₄ (49.0 g, 0.231 mol, 3.0 eq), 1,4-dioxane (490 ml), And water (120 ml) was added and stirred at 100°C for 6 hours (h). Afterwards, water was added to terminate the reaction, and then extraction was performed using methylene chloride (MC) and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 41.2 g of compound 216-2 was obtained with a yield of 92%.

3) Preparation of compound 216-3

In a reaction flask, compound 216-2 (41 g, 0.071 mol, 1 eq), triphenylphosphine (37.2 g, 0.142 mol, 2.0 eq), and 1,2-dichlorobenzene (1,2 -dichlorobenzene) (410 ml) was added and stirred at 160°C for 24h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . After separation using a silica gel column, 31.2 g of compound 216-3 was obtained with a yield of 80%.

4) Preparation of compound 216-4

In a reaction flask, compound 216-3 (20 g, 0.036 mol, 1 eq), iodobenzene (D) (11.0 g, 0.054 mol, 1.5 eq), Pd ₂ (dba) ₃ (1.8 g) , 0.002 mol, 0.05 eq), P(t-Bu) ₃ (0.8 g, 0.004 mol, 0.1 eq), NaOt-Bu (5.2g, 0.054 mol, 1.5 eq) and toluene (200 ml) were added. It was stirred at 100°C for 12h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . By separation using a silica gel column, 20.6 g of compound 216-4 was obtained with a yield of 92%.

5) Preparation of compound 216

Compound 216-4 (10 g, 0.016 mol, 1 eq), naphthalen-2-ylboronic acid (E) (3.1 g, 0.018 mol, 1.1 eq), and Pd ( PPh ₃ ) ₄ (1.2g 0.001 mol, 0.05 eq), K ₃ PO ₄ (10.2 g, 0.048 mol, 3.0 eq), 1,4-dioxane (120 ml), and water ( Water (30 ml) was added and stirred at 100°C for 6h. Afterwards, water was added to terminate the reaction and extraction was performed using MC and water. Afterwards, moisture was removed with MgSO ₄ . By separation using a silica gel column, 9.4 g of compound 216 was obtained with a yield of 90%.

In Preparation Example 5, intermediate A of Table 5 below was used instead of 2,9-dibromo-1,10-phenanthroline (A), and diphenyl ( 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide (diphenyl(4-(4,4,5,5-tetramethyl- Instead of 1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide) (B), use intermediate B of Table 5 below, and 2-(3-bromo-2-nitrophenyl)-4,4,5 ,5-Tetramethyl-1,3,2-dioxaborolane (2-(3-bromo-2-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (C) Instead, use Intermediate C of Table 5 below, use Intermediate D of Table 5 below instead of iodobenzene (D), and use Intermediate D of Table 5 below instead of naphthalen-2-ylboronic acid (E) The compound was synthesized in the same manner as Preparation Example 5, except that Intermediate E in Table 5 was used.

Compounds were prepared in the same manner as in the above preparation examples, and the synthesis confirmation results are shown in Tables 6 and 7. Table 6 shows the measured values of ¹ H NMR (CDCl ₃ , 200Mz), and Table 7 shows the measured values of FD-MS (Field desorption mass spectrometry).

compound ^1H NMR (CDCl ₃ , 200Mz) One δ= 8.99(1H, d), 8.80(1H, d), 8.45(1H, d), 8.21(1H, s), 8.14(1H, d), 8.00(1H, s), 7.89(1H, d) , 7.77-7.68(7H, m), 7.61-7.56(3H, m), 7.51-7.41(11H, m) 2 δ= 8.99(1H, d), 8.71(1H, d), 8.33(2H, d), 8.14(1H, d), 8.00(1H, s), 7.89(1H, d), 7.77-7.75(4H, m), 7.62-7.55(6H, m), 7.51-7.45(10H, m), 7.29(1H, s) 8 δ= 8.85-8.84(2H, m), 8.71(1H, d), 8.42-8.37(2H, m), 8.14(1H, d), 8.06-7.96(9H, m), 7.77-7.75(4H, m) ), 7.62-7.44(14H, m), 7.29(1H, s) 33 δ= 9.18(1H, d), 8.63(1H, d), 8.55(1H, d), 8.41-8.37(2H, m), 8.14(1H, d), 8.00(1H, s), 7.93-7.89( 2H, m), 7.77-7.74(5H, m), 7.62-7.50(12H, m), 7.23(1H, t) 40 δ= 8.71(1H, d), 8.62(1H, d), 8.43(1H, s), 8.33-8.31(2H, m), 8.22-8.14(3H, m), 8.03-8.00(3H, m), 7.89(1H, d), 7.77-7.74(5H, m), 7.62-7.49(15H, m), 7.38(1H, d), 7.29(1H, d) 44 δ= 8.80(1H, d), 8.62(1H, d), 8.45(1H, d), 8.22(1H, d), 8.14(1H, d), 8.00-7.89(3H, m), 7.77-7.74( 5H, m), 7.62-7.50(12H, m), 7.30(1H, d) 50 δ= 8.80(1H, d), 8.71(1H, d), 8.63(1H, d), 8.45-8.43(2H, m), 8.33-8.31(2H, m), 8.14-8.12(2H, m), 8.03-8.00(2H, m), 7.93-7.89(3H, m), 7.77-7.75(4H, m), 7.56-7.49(11H, m), 7.29(1H, d) 54 δ= 8.71-8.70(2H, m), 8.63(1H, d), 8.43(1H, d), 8.33-8.31(4H, m), 8.14-8.12(2H, m), 8.03-8.00(2H, m) ), 7.93-7.89(3H, m), 7.77-7.75(4H, m), 7.55-7.49(13H, m), 7.29-7.27(2H, m) 63 δ= 8.80(1H, d), 8.45(1H, d), 8.30(1H, d), 8.14-8.13(3H, m), 8.00(1H, s), 7.89-7.87(3H, m), 7.77- 7.74(6H, m), 7.62-7.50(12H, m) 80 δ= 8.71(1H, d), 8.41-8.33(6H, m), 8.14-8.08(4H, m), 8.00(1H, s), 7.89-7.87(2H, m), 7.77-7.75(4H, m) ), 7.62-7.49(15H, m), 7.29(1H, d) 113 δ= 8.84-8.80(2H, m), 8.45-8.42(2H, m), 8.14(1H, s), 8.00(1H, s), 7.93-7.89(5H, m), 7.77-7.75(4H, m) ), 7.56-7.41(9H, m), 7.19-7.17(4H, m) 133 δ= 9.00(1H, d), 8.84-8.80(2H, m), 8.71-8.69(2H, m), 8.45(1H, d), 8.33-8.31(2H, m), 8.20-8.14(2H, m) ), 8.00(1H, s), 7.93-7.89(6H, m), 7.77-7.75(4H, m), 7.56-7.44(11H, m), 7.29-7.27(2H, m) 142 δ= 8.71(1H, d), 8.62(1H, d), 8.33-8.31(2H, m), 8.22-8.12(5H, m), 8.00(1H, d), 7.89(1H, d), 7.80- 7.74(8H, m), 7.59-7.41(14H, m), 7.29(1H, d) 186 δ= 8.71(1H, d), 8.33-8.31(2H, m), 8.22(1H, d), 8.14(1H, d), 8.04-8.00(2H, m), 7.93-7.89(5H, m), 7.79-7.77(6H, m), 7.55-7.46(13H, m), 7.29(1H, d) 209 δ= 8.84(1H, d), 8.66(1H, d), 8.42(1H, d), 8.21(1H, s), 8.14(1H, d), 8.00(1H, s), 7.89(1H, d) , 7.79-7.60(9H, m), 7.51-7.41(12H, m), 7.19-7.17(4H, m) 210 δ= 8.84(1H, d), 8.66(1H, d), 8.42(1H, d), 8.14(1H, d), 8.00(1H, s), 7.89(1H, d), 7.79-7.77(5H, m), 7.62-7.41(13H, m), 7.19-7.17(4H, m) 212 δ= 8.84(1H, d), 8.66(1H, d), 8.42(1H, d), 8.14(1H, d), 8.00(1H, s), 7.89(1H, d), 7.79-7.75(7H, m), 7.62-7.41(15H, m), 7.25-7.23(4H, m) 216 δ= 8.84(1H, d), 8.71(1H, d), 8.42-8.36(3H, m), 8.14-7.89(8H, m), 7.77-7.75(4H, m), 7.63-7.38(16H, m) ), 7.29(1H, s) 229 δ= 8.80-8.74(2H, m), 8.66(1H, d), 8.45-8.43(2H, m), 8.14-8.12(2H, m), 8.03-7.89(5H, m), 7.79-7.77(5H) , m), 7.56-7.51(7H, m), 7.35-7.32(2H, m) 231 δ= 9.00(1H, d), 8.84-8.80(2H, m), 8.71-8.66(2H, m), 8.45(1H, d), 8.20-8.14(2H, m), 8.00(1H, s), 7.90-7.89(2H, m), 7.79-7.77(5H, m), 7.62-7.44(13H, m), 7.29(1H, d) 247 δ= 8.85(1H, s), 8.71(1H, d), 8.62-8.61(2H, m), 8.37-8.35(3H, m), 8.18-8.13(3H, m), 8.06-8.01(3H, m) ), 7.89(1H, d), 7.77-7.75(4H, m), 7.62-7.50(11H, m), 7.38(1H, t), 7.29(1H, d), 7.14(1H, d), 6.90( 1H, t) 249 δ= 9.12(1H, s), 8.98(1H, d), 8.62(1H, d), 8.41-8.37(2H, m), 8.22-8.14(3H, m), 8.00(1H, s), 7.89( 1H, d), 7.77-7.74(7H, m), 7.62-7.41(14H, m) 252 δ= 8.65-8.62(2H, m), 8.22(1H, d), 8.14(1H, m), 8.00(1H, s), 7.94-7.89(2H, m), 7.77-7.74(7H, m), 7.63-7.41(15H, m), 7.30-7.25(5H, m) 326 All D substituents 327 δ= 8.80(1H, d), 8.45-8.37(5H, m), 8.14-8.08(4H, m), 8.00(1H, s), 7.89-7.87(2H, m), 7.62-7.50(7H, m) ) 340 All D substituents 343 δ= 8.66-8.62(2H, m), 8.22(1H, d), 8.14(1H, d), 8.00(1H, s), 7.89(1H, d), 7.79-7.74(2H, m) 344 All D substituents

compound FD-MS compound FD-MS One m/z=621.20 (C42H28N3OP=621.68) 2 m/z=621.20 (C42H28N3OP=621.68) 8 m/z=747.24 (C52H34N3OP=747.84) 33 m/z=622.19 (C41H27N4OP=622.67) 40 m/z=747.24 (C52H34N3OP=747.84) 44 m/z=611.18 (C40H26N3O2P=611.64) 50 m/z=723.22 (C48H30N5OP=723.78) 54 m/z=799.25 (C54H34N5OP=799.87) 63 m/z=621.20 (C42H28N3OP=621.68) 80 m/z=799.25 (C54H34N5OP=799.87) 113 m/z=621.20 (C42H28N3OP=621.68) 133 m/z= 799.25 (C54H34N5OP= 799.87) 142 m/z=747.24(C52H34N3OP=747.84) 186 m/z=697.23 (C48H32N3OP=697.78) 209 m/z=697.23 (C48H32N3OP=697.78) 210 m/z=621.20 (C42H28N3OP=621.68) 212 m/z=697.23 (C48H32N3OP=697.78) 216 m/z=747.24 (C52H34N3OP=747.84) 229 m/z=647.19(C42H26N5OP=647.68) 231 m/z=723.22
(C48H30N5OP= 723.78) 247 m/z=748.24(C51H33N4OP=748.83) 249 m/z=698.22
(C47H31N4OP=698.77) 252 m/z=763.24(C52H34N3O2P=763.84) 326 m/z=649.37 (C42D28N3OP=649.85) 327 m/z= 733.28 (C48H20D10N5OP= 733.84) 340 m/z=729.43
(C48D32N3OP=729.97) 343 m/z=641.32 (C42H8D20N3OP=641.80) 344 m/z=729.43(C48D32N3OP=729.97)

[Experimental Example] <Experimental Example 1>

1) Fabrication of organic light emitting device

The transparent electrode indium tin oxide (ITO) thin film obtained from OLED glass (manufactured by Samsung-Corning) was ultrasonically cleaned for 5 minutes each using trichlorethylene, acetone, ethanol, and distilled water sequentially, and then stored in isopropanol. used. Next, the ITO substrate was installed in the substrate folder of the vacuum deposition equipment, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine ( 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) was added.

Subsequently, the vacuum in the chamber was evacuated until it reached 10 ^-6 torr, and then a current was applied to the cell to evaporate 2-TNATA to deposit a 600Å-thick hole injection layer on the ITO substrate. In another cell in the vacuum deposition equipment, the following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis(α-naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added and evaporated by applying a current to the cell to deposit a 1000Å thick hole transport layer on the hole injection layer.

After forming the hole injection layer and the hole transport layer in this way, a blue light-emitting material with the following structure was deposited thereon as a light-emitting layer. Specifically, H1, a blue light-emitting host material, was vacuum-deposited to a thickness of 200 Å in one cell of the vacuum deposition equipment, and D1, a blue light-emitting dopant material, was vacuum-deposited 5% of the host material on top of it.

Next, a compound of the following structural formula E1 was deposited to a thickness of 300 Å as an electron transport layer.

An OLED device was manufactured by depositing lithium fluoride (LiF) to a thickness of 10 Å as an electron injection layer and using an Al cathode to a thickness of 1,000 Å. Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 ^-8 to 10 ^-6 torr for each material and used for OLED production.

An organic light-emitting device was manufactured in the same manner as Comparative Example 1, except that the compounds shown in Table 8 below were used instead of E1 used in forming the electron transport layer in Comparative Example 1.

2) Driving voltage and luminous efficiency of organic light emitting devices

The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured using McScience's M7000, and the standard luminance was measured to be 3,500 cd/ through the lifespan measurement equipment (M6000) manufactured by McScience using the measurement results. When m ² , T ₉₅ was measured. The results of measuring the driving voltage, luminous efficiency, color coordinate (CIE), and lifespan (T ₉₅ ) of the blue organic electroluminescent device manufactured according to the present invention are shown in Table 8.

compound driving voltage
(V) Luminous efficiency
(cd/A) CIE
(x, y) life span
(T ₉₅ ) Example 1 One 4.83 6.81 (0.133, 0.100) 93 Example 2 2 4.84 6.78 (0.134, 0.100) 91 Example 3 8 4.85 6.80 (0.134, 0.100) 89 Example 4 33 4.80 6.83 (0.134, 0.101) 88 Example 5 40 4.87 6.73 (0.133, 0.101) 85 Example 6 44 4.91 6.85 (0.134, 0.100) 83 Example 7 50 4.85 6.90 (0.133, 0.101) 89 Example 8 54 4.90 6.74 (0.134, 0.102) 84 Example 9 63 4.87 6.88 (0.134, 0.101) 86 Example 10 80 4.86 6.80 (0.134, 0.101) 89 Example 11 113 4.92 6.70 (0.133, 0.100) 82 Example 12 133 4.88 6.85 (0.134, 0.100) 83 Example 13 142 4.82 6.85 (0.134, 0.100) 85 Example 14 186 4.83 6.84 (0.133, 0.100) 85 Example 15 209 4.81 6.86 (0.134, 0.101) 88 Example 16 210 4.85 6.87 (0.134, 0.101) 84 Example 17 212 4.89 6.88 (0.133, 0.100) 84 Example 18 216 4.83 6.85 (0.133, 0.101) 85 Example 19 229 4.86 6.87 (0.134, 0.100) 85 Example 20 231 4.91 6.71 (0.134, 0.100) 81 Example 21 247 4.85 6.90 (0.133, 0.101) 85 Example 22 249 4.84 6.88 (0.134, 0.101) 84 Example 23 252 4.81 6.93 (0.133, 0.101) 86 Example 24 326 4.81 6.95 (0.134, 0.100) 95 Example 25 327 4.83 6.88 (0.133, 0.101) 87 Example 26 340 4.83 6.90 (0.133, 0.100) 93 Example 27 343 4.80 6.85 (0.134, 0.100) 88 Example 28 344 4.85 6.83 (0.134, 0.100) 87 Comparative Example 1 E1 5.51 6.17 (0.134, 0.100) 31 Comparative Example 2 Comparative Compound A 5.28 6.35 (0.134, 0.100) 48 Comparative Example 3 Comparative compound B 5.31 6.38 (0.134, 0.100) 55 Comparative Example 4 Comparative Compound C 5.33 6.34 (0.134, 0.100) 49

Comparative compounds A to C in Table 8 are as follows.

As can be seen from the results in Table 8, Examples 1 to 28, which are organic light-emitting devices using the heterocyclic compound represented by Formula 1 of the present invention as an electron transport layer material of a blue organic light-emitting device, are the organic light-emitting devices of Comparative Examples 1 to 4. It was confirmed that the driving voltage was lower than that of the light emitting device, and the luminous efficiency and lifespan were significantly improved.

This result is believed to be because the heterocyclic compound represented by Formula 1 of the present invention has appropriate length and strength as an electron transport layer material.

In addition, the P=O functional group of the heterocyclic compound represented by Formula 1 of the present invention forms a stable bond with the metals used in the cathode, so that when the device is driven, the heterocyclic compound represented by Formula 1 of the present invention It is believed that this is because electrons can be transferred efficiently because no decomposition or destruction occurs.

thus. It is believed that by using the heterocyclic compound represented by Formula 1 of the present invention in the electron transport layer, the electron-transport characteristics and stability of the device were improved, resulting in excellent operation, efficiency, and lifespan.

<Experimental Example 2>

1) Fabrication of organic light emitting device

A glass substrate coated with a thin film of ITO with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, it was ultrasonic washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UV in a UV cleaner for 5 minutes. Afterwards, the substrate was transferred to a plasma cleaner (PT), then plasma treated in a vacuum to remove the ITO work function and residual film, and then transferred to a thermal evaporation equipment for organic deposition.

An organic material was formed in a two-stack WOLED (White Orgainc Light Device) structure on the ITO transparent electrode (anode). In the first stack, TAPC was first thermally vacuum deposited to a thickness of 300 Å to form a hole transport layer. After forming the hole transport layer, a light emitting layer was thermally vacuum deposited on it as follows. The light-emitting layer was deposited at 300 Å by doping 8% of FIrpic as a blue phosphorescent dopant on TCz1, the host. The electron transport layer was formed to have a thickness of 400 Å using TmPyPB, and then the charge generation layer was formed to have a thickness of 100 Å by doping 20% of Cs ₂ CO ₃ into the compound shown in Table 9 below.

In the second stack, MoO ₃ was first thermally vacuum deposited to a thickness of 50 Å to form a hole injection layer. The hole transport layer, which is a common layer, was formed by doping 20% of MoO ₃ on TAPC to form 100 Å and then depositing 300 Å of TAPC. On top of this, the light emitting layer was formed by doping 8% of Ir(ppy) ₃ , a green phosphorescent topant, into TCz1, the host. After depositing 300Å, 600Å was formed using TmPyPB as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1,200Å on the electron injection layer to form the cathode, thereby forming an organic A light emitting device was manufactured.

Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 ^-8 to 10 ^-6 torr for each material and used for OLED production.

2) Driving voltage and luminous efficiency of organic light emitting devices

The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured using McScience's M7000, and the standard luminance was measured to be 3,500 cd/ through the lifespan measurement equipment (M6000) manufactured by McScience using the measurement results. When m ² , T ₉₅ was measured. The results of measuring the driving voltage, luminous efficiency, color coordinate (CIE), and lifespan (T ₉₅ ) of the white organic electroluminescent device manufactured according to the present invention are shown in Table 9.

compound driving voltage
(V) Luminous efficiency
(cd/A) CIE
(x, y) life span
(T ₉₅ ) Example 29 One 7.03 67.58 (0.214, 0.418) 88 Example 30 2 7.20 69.77 (0.213, 0.417) 84 Example 31 8 7.44 68.68 (0.213, 0.420) 85 Example 32 33 7.32 69.12 (0.215, 0.420) 86 Example 33 40 7.35 69.15 (0.215, 0.420) 86 Example 34 44 7.34 68.88 (0.214, 0.420) 85 Example 35 50 7.33 69.02 (0.214, 0.418) 87 Example 36 54 7.33 68.53 (0.215, 0.419) 86 Example 37 63 7.40 70.03 (0.216, 0,424) 86 Example 38 80 7.38 69.87 (0.214, 0.425) 85 Example 39 113 7.24 68.13 (0.219, 0.426) 86 Example 40 133 7.25 69.00 (0.218, 0.421) 85 Example 41 142 7.30 69.50 (0.215, 0.417) 84 Example 42 186 7.42 67.72 (0.209, 0.422) 85 Example 43 209 7.33 68.58 (0.210, 0.428) 86 Example 44 210 7.35 69.13 (0.209, 0.428) 87 Example 45 212 7.31 68.43 (0.210, 0.430) 85 Example 46 216 7.38 69.84 (0.212, 0.428) 83 Example 47 229 7.42 70.18 (0.219, 0.426) 82 Example 48 231 7.39 70.02 (0.218, 0.424) 84 Example 49 247 7.30 70.42 (0.215, 0.417) 84 Example 50 249 7.37 70.25 (0.214, 0.420) 85 Example 51 252 7.33 69.39 (0.214, 0.418) 86 Example 52 326 7.41 69.88 (0.214, 0.418) 95 Example 53 327 7.31 69.98 (0.215, 0.419) 91 Example 54 340 7.25 68.80 (0.219, 0.426) 96 Example 55 343 7.30 69.22 (0.220, 0.424) 90 Example 56 344 7.28 70.13 (0.219, 0.422) 92 Comparative Example 5 TmPyPB 8.20 57.71 (0.211, 0.430) 60 Comparative Example 6 Comparative compound A 7.99 56.23 (0.213, 0.426) 56 Comparative Example 7 Comparative compound B 7.88 58.31 (0.209, 0.425) 54 Comparative Example 8 Comparative compound C 7.90 58.61 (0.211, 0.428) 54

Comparative compounds A to C in Table 9 are as follows.

As can be seen from the results in Table 9, Examples 29 to 56, which are organic light-emitting devices using the heterocyclic compound represented by Formula 1 of the present invention as a material for the charge generation layer of the 2-stack white organic electroluminescent device, are compared. It was confirmed that the driving voltage was lower and the lifespan and luminous efficiency were improved compared to Examples 5 to 8.

As a result, it is believed that the heterocyclic compound represented by Formula 1 of the present invention has appropriate length and strength as a material for the charge generation layer.

Another reason is believed to be that the heterocyclic compound represented by Formula 1 of the present invention is composed of an appropriate hetero compound structure and a P=O functional group that can stably bind to metal. .

Due to these structural features, when the heterocyclic compound represented by Formula 1 of the present invention used as the N-type charge generation layer is doped with a metal, the gap state within the N-type charge generation layer is stably maintained. It is thought that the electrons formed and generated from the P-type charge generation layer were easily injected into the electron transport layer through the gap state created within the N-type charge generation layer.

Therefore, it is believed that electron injection and electron transfer from the P-type charge generation layer to the N-type charge generation layer can be performed better, thereby lowering the driving voltage of the organic light emitting device and improving efficiency and lifespan.

100: substrate
200: anode
300: Organic 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 (11)

Heterocyclic compound represented by the following formula (1):
[Formula 1]

In Formula 1,
L1 to L6 are the same or different from each other and are each independently directly bonded; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms, a to f are each an integer of 0 to 3, and when a to f are each an integer of 2 or more, the substituents in parentheses are the same or different from each other,
One of R1 to R6 is -P(=O)R31R32, and the remainder of R1 to R6 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
R31 and R32 are the same or different from each other and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms. The heterocyclic compound according to claim 1, wherein the heterocyclic compound represented by Formula 1 has a deuterium content of 10% or more and 100% or less. delete The method according to claim 1, wherein the formula 1 is a heterocyclic compound represented by any one of the following formulas 2 to 7:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 2 to 7,
The definitions of L1 to L6, a to f, R31 and R32 are the same as in Formula 1,
R11 to R16 are the same or different from each other and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it is a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms. The method according to claim 1, wherein Formula 1 is a heterocyclic compound represented by any one of the following compounds:
















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, wherein at least one layer of the organic material layer is any of claims 1, 2, 4, and 5. An organic light-emitting device comprising the heterocyclic compound according to one clause. The organic light-emitting device of claim 6, wherein the organic material layer includes an electron transport layer, and the electron transport layer includes the heterocyclic compound. The method of claim 6, wherein the organic light emitting device comprises one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, an electron injection layer, an electron transport layer, a hole auxiliary layer, and a hole blocking layer. Further comprising an organic light emitting device. The method of claim 6, comprising: a first electrode, a first stack provided on the first electrode and including a first light-emitting layer, a charge generation layer provided on the first stack, and a second light-emitting layer provided on the charge generation layer. An organic light emitting device comprising a second stack including a second stack, and a second electrode provided on the second stack. The organic light emitting device of claim 9, wherein the charge generation layer includes the heterocyclic compound. The organic light emitting device of claim 10, wherein the charge generation layer is an N-type charge generation layer.