Heterocyclic compound, organic light-emitting device, and composition for organic material layer of organic light-emitting device

Abstract

The present specification relates to: a heterocyclic compound of chemical formula 1; an organic light-emitting device comprising same; and a composition for an organic material layer of the organic light-emitting device.

Description

Heterocyclic compound, organic light-emitting device and composition for organic layer of organic light-emitting device

[0001] The present specification relates to a heterocyclic compound, an organic light-emitting device, and a composition for an organic layer of an organic light-emitting device.

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0189779, filed with the Korean Intellectual Property Office on December 22, 2023, the entire contents of which are incorporated herein by reference.

[0003] Electroluminescent elements are a type of self-luminous display element that have the advantages of a wide viewing angle, excellent contrast, and a fast response speed.

[0004] 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 of this structure, electrons and holes injected from the two electrodes combine in the organic thin film, forming pairs and then disappearing, emitting light. The organic thin film may be composed of a single layer or multiple layers, as needed.

[0005] The material of the organic thin film may have a light-emitting function as needed. For example, the organic thin film material may be a compound that can form a light-emitting layer on its own, or a compound that can act as a host or dopant in a host-dopant light-emitting layer. In addition, the material of the organic thin film may be a compound that can perform roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection.

[0006] To improve the performance, lifespan, or efficiency of organic light-emitting devices, the development of materials for organic thin films is continuously required.

[0007] [Prior Art Literature]

[0008] (Patent Document 1) U.S. Patent No. 4,356,429

[0009] The present specification provides a heterocyclic compound and an organic light-emitting device including the same, and a composition for an organic layer of the organic light-emitting device, thereby providing an organic light-emitting device having a low driving voltage and high luminous efficiency and lifespan.

[0010] In one embodiment of the present specification, a heterocyclic compound of the following chemical formula 1 is provided.

[0011] [Chemical Formula 1]

[0012]

[0013] In the above chemical formula 1,

[0014] Y is O or S,

[0015] X1 to X3 are each independently N or CH, and at least one is N,

[0016] Ar1 and Ar2 are each independently a C6 to C60 aryl group; or a C2 to C60 heteroaryl group,

[0017] L is an arylene group of C10 to C30 substituted with deuterium, m is an integer of 1 to 3, and when it is 2 or more, L is the same or different,

[0018] R1 to R8 are each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group, or adjacent groups are bonded to each other to form a ring.

[0019] At least one of R1 to R8 is deuterium,

[0020] D is deuterium, and n is an integer from 0 to 6.

[0021] In another embodiment of the present specification, an organic light-emitting device is provided, comprising: a first electrode; a second electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers includes at least one type of the heterocyclic compound.

[0022] In another embodiment of the present specification, a composition for an organic layer of an organic light-emitting device comprising the heterocyclic compound is provided.

[0023] The heterocyclic compound described herein, when used in an organic light-emitting device, can lower the driving voltage of the device, improve the luminous efficiency, and improve the lifespan characteristics of the device. Specifically, the heterocyclic compound of the present invention is characterized in that it includes dibenzofuran or dibenzothiophene as a core structure as in Chemical Formula 1, an azine group is substituted without a linker as one substituent, and a carbazole group is included as another substituent, but a linker is necessarily included between the core structure and the carbazole group, and the carbazole group and the linker include at least one deuterium, whereas the azine group does not include deuterium.

[0024] As in the heterocyclic compound of the present invention, since deuterium is substituted only at specific positions, the vibrational energy of the HOMO region, which requires hole stability, is reduced, which reduces intermolecular interactions and exhibits excellent lifetime characteristics within the device. In addition, since the azine group does not include a linker and the carbazole group includes a linker, the HOMO region is expanded, thereby synthesizing a compound with a more stable HOMO. The expansion of the HOMO not only ensures molecular stability but also induces smooth charge transfer, which can exhibit excellent efficiency and lifetime characteristics within the device.

[0025] Figures 1 to 3 are diagrams each exemplifying a laminated structure of an organic light-emitting device according to one embodiment of the present specification.

[0026] [Explanation of symbols]

[0027] 100: Substrate

[0028] 200: Bipolar

[0029] 300: Organic layer

[0030] 301: Hole injection layer

[0031] 302: Hole transport layer

[0032] 303: Emissive layer

[0033] 304: Hole blocking layer

[0034] 305: Electron transport layer

[0035] 306: Electron injection layer

[0036] 400: Cathode

[0037] Hereinafter, the present specification will be described in more detail.

[0038] In this specification, when a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0039] In this specification, “N to N'” means N or more and N' or less.

[0040] In this specification, the chemical formula means the position where it is combined.

[0041] The term "substitution" above means that a hydrogen atom bonded to a carbon atom or nitrogen atom of a compound is replaced with another substituent, and the position of substitution is not limited as long as it is a position where a hydrogen atom is replaced, i.e. a position where a substituent can be replaced, and when two or more are replaced, the two or more substituents may be the same or different from each other.

[0042] In this specification, "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a C1 to C60 alkyl group; a C2 to C60 alkenyl group; a C2 to C60 alkynyl group; a C1 to C60 alkoxy group; a C6 to C60 aryloxy group; a C1 to C60 alkylthioxy group; a C6 to C60 arylthioxy group; a C1 to C60 alkylsulfoxy group; a C6 to C60 arylsulfoxy group; a C3 to C60 cycloalkyl group; a C2 to C60 heterocycloalkyl group; a C6 to C60 aryl group; a C2 to C60 heteroaryl group; a silyl group; a phosphine oxide group; and an amine group, or a substituent in which two or more substituents selected from the above substituents are linked, or unsubstituted.

[0043] In this specification, "when no substituent is indicated in the chemical formula or compound structure" means that a hydrogen atom is bonded to a carbon atom. However, deuterium ( 2 H, Deuterium) is an isotope of hydrogen, so some hydrogen atoms may be deuterium.

[0044] In one embodiment of the present application, "when no substituent is indicated in the chemical formula or compound structure" may mean that all positions that can be substituted 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, in which case the deuterium content may be 0% to 100%, and the deuterium content may also be expressed as a deuterium substitution ratio.

[0045] In one embodiment of the present application, deuterium is an element having a deuteron, which is one of the isotopes of hydrogen and is composed of one proton and one neutron, as its nucleus, and can be expressed as hydrogen-2, and its element symbol is D or 2 It can also be written as H.

[0046] In one embodiment of the present application, an isotope means an atom having the same atomic number (Z) but a different mass number (A). An isotope can also be interpreted as an element having the same number of protons but a different number of neutrons.

[0047] In one embodiment of the present application, the meaning of the substitution rate T% of a specific substituent can be defined as T2 / T1Х100 = T%, where 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.

[0048] That is, in one example, In the phenyl group represented by , a deuterium substitution rate of 20% 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 can be expressed as 20%. In other words, a deuterium substitution rate of 20% in the phenyl group can be expressed by the structural formula below.

[0049]

[0050] Additionally, in one embodiment of the present application, the term "phenyl group having a deuterium substitution rate of 0%" may mean a phenyl group that does not contain a deuterium atom as a substituent, i.e., has 5 hydrogen atoms.

[0051] In this specification, halogen may be fluorine, chlorine, bromine or iodine.

[0052] In the present specification, an alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by another substituent. The alkyl group may have 1 to 60 carbon atoms, specifically 1 to 40 carbon atoms, and more specifically 1 to 20 carbon atoms. 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, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, Examples include, but are not limited to, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, and 5-methylhexyl group.

[0053] In the present specification, the alkenyl group includes a straight 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, but are not limited to, a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl-1-yl group, a 2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, a 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, a stilbenyl group, and a styrenyl group.

[0054] In the present specification, an alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The alkynyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms.

[0055] In this specification, an alkoxy group is represented as -O(R101), and examples of the alkyl group described above can be applied to R101.

[0056] In this specification, the aryloxy group is represented as -O(R102), and R102 can be applied to the examples of the aryl group described above.

[0057] In this specification, the alkylthioxy group is represented as -S(R103), and examples of the alkyl group described above can be applied to R103.

[0058] In this specification, the arylthioxy group is represented as -S(R104), and R104 can be applied to the examples of the aryl group described above.

[0059] In this specification, an alkylsulfoxy group is represented as -S(=0)2(R105), and examples of the alkyl group described above can be applied to R105.

[0060] In this specification, an arylsulfoxy group is represented as -S(=0)2(R106), and examples of the aryl group described above can be applied to R106.

[0061] In the present specification, a cycloalkyl group includes a monocyclic or polycyclic group having 3 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic means 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, a heteroaryl group, etc. The cycloalkyl group may have 3 to 60 carbon atoms, specifically 3 to 40 carbon atoms, and more specifically 5 to 20 carbon atoms. Specifically, there are, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc.

[0062] In the present specification, a heterocycloalkyl group includes O, S, Se, N or Si as a heteroatom, and includes a monocyclic or polycyclic group having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic means 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, a heteroaryl group, etc. The heterocycloalkyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 20 carbon atoms.

[0063] In the present specification, an aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic means 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, a heterocycloalkyl group, a heteroaryl group, etc. The aryl group includes a spiro group. The aryl group may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, and more specifically 6 to 25 carbon atoms. Specific examples of the above aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a fluorenyl group, an indenyl group, an acenaphthylenyl group, a benzofluorenyl group, a spirobifluorenyl group, a 2,3-dihydro-1H-indenyl group, and condensed ring groups thereof.

[0064] In this specification, the terphenyl group may be selected from the following structures.

[0065]

[0066] In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be combined with each other to form a ring.

[0067] When the above fluorenyl group is substituted, the structures below can be formed, but are not limited thereto.

[0068]

[0069] In the present specification, a heteroaryl group includes S, O, Se, N or Si as a heteroatom, and includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic ring means 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, a heterocycloalkyl group, an aryl group, etc. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 25 carbon atoms.Specific examples of the above heteroaryl group include a pyridine group, a pyrrole group, a pyrimidine group, a pyridazine group, a furan group, a thiophene group, an imidazole group, a pyrazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, a triazole group, a furazan group, an oxadiazole group, a thiadiazole group, a dithiazole group, a tetrazolyl group, a pyran group, a thiopyran group, a diazine group, an oxazine group, a thiazine group, a dioxin group, a triazine group, a tetrazine group, a quinoline group, an isoquinoline group, a quinazoline group, an isoquinazoline group, a quinozoline group, a naphthyridine group, an acridine group, a phenanthridine group, an imidazopyridine group, a diazanaphthalene group, a triazaindene group, an indole group, an indolizine group, a benzothiazole group, Benzoxazole group, benzimidazole group, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, carbazole group, benzocarbazole group, dibenzocarbazole group, phenazine group, dibenzosilole group, spirobi(dibenzosilole), 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, Examples thereof include, but are not limited to, 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[1,2-a]imidazo[1,2-e]indolin group, and 5,11-dihydroindeno[1,2-b]carbazole group.

[0070] In the present specification, the benzocarbazole group may have any of the following structures.

[0071]

[0072] In the present specification, the dibenzocarbazole group may have any of the following structures.

[0073]

[0074] In the present specification, when the substituent is a carbazole group, a benzocarbazole group, or a dibenzocarbazole group, it means that it is bonded to the nitrogen or carbon of the carbazole group, the benzocarbazole group, or the dibenzocarbazole group.

[0075] In the present specification, when a carbazole group, a benzocarbazole group, or a dibenzocarbazole group is substituted, an additional substituent may be substituted on the nitrogen or carbon of the carbazole group, the benzocarbazole group, or the dibenzocarbazole group.

[0076] In the present specification, the naphthobenzofuran group may have any of the following structures.

[0077]

[0078] In the present specification, the naphthobenzothiophene group may have any of the following structures.

[0079]

[0080] In the present specification, a silyl group is a substituent that contains Si and is directly connected to the Si atom as a radical, and is represented by -Si(R107)(R108)(R109), and R107 to R109 are the same as or different from each other, and may each independently be a substituent composed of at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group.

[0081] The above silyl group may include an alkylsilyl group, an arylsilyl group, a heteroarylsilyl group, an alkylarylsilyl group, an arylheteroarylsilyl group, etc., depending on the substituent bonded to the Si element. An alkylsilyl group, an arylsilyl group, or a heteroarylsilyl group means that the Si element of a silyl group is substituted with an alkyl group, an aryl group, or a heteroaryl group, respectively, an alkylarylsilyl group means that the Si element of a silyl group is substituted with an alkyl group and an aryl group, and an arylheteroarylsilyl group means that the Si element of a silyl group is substituted with an aryl group and a heteroaryl group.

[0082] Specific examples of silyl groups include, but are not limited to, the following structures.

[0083] (trimethylsilyl group), (triethylsilyl group), (t-butyldimethylsilyl group), (vinyldimethylsilyl group), (propyldimethylsilyl group), (triphenylsilyl group), (diphenylsilyl group), (phenylsilyl group)

[0084] In the present specification, a phosphine oxide group is represented by -P(=O)(R110)(R111), and R110 and R111 are the same as or different from each other, and can each independently be a substituent composed of at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group. Specifically, it can be substituted with an alkyl group or an aryl group, and the above-described examples can be applied to the alkyl group and the aryl group. For example, the phosphine oxide group includes, but is not limited to, a dimethylphosphine oxide group, a diphenylphosphine oxide group, and dinaphthylphosphine oxide.

[0085] In the present specification, an amine group is represented by -N(R112)(R113), and R112 and R113 are the same as or different from each other, and can each independently be a substituent composed of at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; a heterocycloalkyl group; an aryl group; and a heteroaryl group. The amine group can be selected from the group consisting of -NH2; a monoalkylamine group; a monoarylamine group; a monoheteroarylamine group; a dialkylamine group; a diarylamine group; a diheteroarylamine group; an alkylarylamine group; an 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 above amine group include, but are not limited to, a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, a biphenylnaphthylamine group, a phenylbiphenylamine group, a biphenylfluorenylamine group, a phenyltriphenylenylamine group, and a biphenyltriphenylenylamine group.

[0086] In this specification, the description of the aryl group described above may be applied, except that the arylene group is divalent.

[0087] In this specification, the description of the heteroaryl group described above may be applied, except that the heteroarylene group is divalent.

[0088] One embodiment of the present specification provides a heterocyclic compound of the following chemical formula 1.

[0089] [Chemical Formula 1]

[0090]

[0091] In the above chemical formula 1,

[0092] Y is O or S,

[0093] X1 to X3 are each independently N or CH, and at least one is N,

[0094] Ar1 and Ar2 are each independently a C6 to C60 aryl group; or a C2 to C60 heteroaryl group,

[0095] L is an arylene group of C10 to C30 substituted with deuterium, m is an integer of 1 to 3, and when it is 2 or more, L is the same or different,

[0096] R1 to R8 are each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group, or adjacent groups are bonded to each other to form a ring.

[0097] At least one of R1 to R8 is deuterium,

[0098] D is deuterium, and n is an integer from 0 to 6.

[0099] In one embodiment of the present specification, Y may be O.

[0100] In one embodiment of the present specification, Y may be S.

[0101] In one embodiment of the present specification, the chemical formula 1 may be represented by the following chemical formula 1-O or 1-S.

[0102] [Chemical formula 1-O]

[0103]

[0104] [Chemical Formula 1-S]

[0105]

[0106] In the above chemical formulas 1-O and 1-S,

[0107] The definition of each substituent is the same as that in the chemical formula 1 above.

[0108] In one embodiment of the present specification, X1 may be N, and X2 and X3 may be CH.

[0109] In one embodiment of the present specification, X2 may be N, and X1 and X3 may be CH.

[0110] In one embodiment of the present specification, at least two of X1 to X3 may be N.

[0111] In one embodiment of the present specification, X1 and X2 may be N, and X3 may be CH.

[0112] In one embodiment of the present specification, X1 and X3 may be N, and X2 may be CH.

[0113] In one embodiment of the present specification, X1 to X3 may be N.

[0114] In one embodiment of the present specification, the chemical formula 1 may be represented by the following chemical formula 1-N.

[0115] [Chemical formula 1-N]

[0116]

[0117] In the above chemical formula 1-N,

[0118] The definition of each substituent is the same as that in the chemical formula 1 above.

[0119] In one embodiment of the present specification, L may be a C10 to C20 arylene group substituted with deuterium.

[0120] In one embodiment of the present specification, L may be a biphenylene group substituted with deuterium; or a terphenylene group substituted with deuterium.

[0121] In one embodiment of the present specification, L may be represented by any one of the following structural formulas.

[0122]

[0123] In the above structural formula,

[0124] is the position that binds to the above chemical formula 1,

[0125] D is deuterium,

[0126] a1, a2, a3, b1, b3, b6 and c3 are integers from 0 to 4, respectively.

[0127] a4, a6 and b2 are integers from 0 to 3,

[0128] b4, b5, c2, c5 and c6 are integers from 0 to 5, respectively.

[0129] a5 is an integer from 0 to 2,

[0130] a1+b1, a2+b2+c2, a3+b3+c3, a4+b4, a5+b5+c5, and a6+b6+c6 are each integers greater than or equal to 1.

[0131] In one embodiment of the present specification, m may be 1.

[0132] In one embodiment of the present specification, Ar1 and Ar2 may each independently be a C6 to C30 aryl group; or a C2 to C30 heteroaryl group.

[0133] In one embodiment of the present specification, Ar1 and Ar2 may each independently be a C6 to C20 aryl group; or a C2 to C20 heteroaryl group.

[0134] In one embodiment of the present specification, Ar1 and Ar2 may each independently be a phenyl group; a biphenyl group; a dibenzofuran group; a dibenzothiophene group; or a carbazole group.

[0135] In one embodiment of the present specification, Ar1 may be a C6 to C20 aryl group, and Ar2 may be a C6 to C20 aryl group; or a C2 to C20 heteroaryl group.

[0136] In one embodiment of the present specification, Ar1 may be a phenyl group, and Ar2 may be a phenyl group; a biphenyl group; a dibenzofuran group; a dibenzothiophene group; or a carbazole group.

[0137] In one embodiment of the present specification, the chemical formula 1 may be represented by the following chemical formula 1-1 or 1-2.

[0138] [Chemical Formula 1-1]

[0139]

[0140] [Chemical Formula 1-2]

[0141]

[0142] In the above chemical formulas 1-1 and 1-2,

[0143] The definition of each substituent is the same as that in the chemical formula 1 above.

[0144] In one embodiment of the present specification, the chemical formula 1 may be represented by any one of the following chemical formulas 1-1-1 to 1-1-4.

[0145] [Chemical Formula 1-1-1]

[0146]

[0147] [Chemical Formula 1-1-2]

[0148]

[0149] [Chemical Formula 1-1-3]

[0150]

[0151] [Chemical Formula 1-1-4]

[0152]

[0153] In the above chemical formulas 1-1-1 to 1-1-4,

[0154] The definition of each substituent is the same as that in the chemical formula 1 above.

[0155] In one embodiment of the present specification, the chemical formula 1 includes structures of the following chemical formulas A to C.

[0156] [Chemical Formula A]

[0157]

[0158] [Chemical Formula B]

[0159]

[0160] [Chemical Formula C]

[0161]

[0162] In the above chemical formulas A to C,

[0163] The definitions of Y, X1 to X3, Ar1, Ar2, L, m and R1 to R8 are the same as those in the above chemical formula 1,

[0164] One of D1 to D8 is a group represented by the above chemical formula B, the other is a group represented by the above chemical formula C, and the rest are hydrogen; or deuterium,

[0165] is the position where the above chemical formulas B and C are bonded to the above chemical formula A.

[0166] In one embodiment of the present specification, the D1 may be a group represented by the chemical formula B, and the D2 may be a group represented by the chemical formula C.

[0167] In one embodiment of the present specification, the D1 may be a group represented by the chemical formula B, and the D3 may be a group represented by the chemical formula C.

[0168] In one embodiment of the present specification, the D1 may be a group represented by the chemical formula B, and the D4 may be a group represented by the chemical formula C.

[0169] In one embodiment of the present specification, the D1 may be a group represented by the chemical formula B, and the D5 may be a group represented by the chemical formula C.

[0170] In one embodiment of the present specification, the D1 may be a group represented by the chemical formula B, and the D6 may be a group represented by the chemical formula C.

[0171] In one embodiment of the present specification, the D1 may be a group represented by the chemical formula B, and the D7 may be a group represented by the chemical formula C.

[0172] In one embodiment of the present specification, the D1 may be a group represented by the chemical formula B, and the D8 may be a group represented by the chemical formula C.

[0173] In one embodiment of the present specification, the D2 may be a group represented by the chemical formula B, and the D5 may be a group represented by the chemical formula C.

[0174] In one embodiment of the present specification, the D2 may be a group represented by the chemical formula B, and the D6 may be a group represented by the chemical formula C.

[0175] In one embodiment of the present specification, the D2 may be a group represented by the chemical formula B, and the D7 may be a group represented by the chemical formula C.

[0176] In one embodiment of the present specification, the D2 may be a group represented by the chemical formula B, and the D8 may be a group represented by the chemical formula C.

[0177] In one embodiment of the present specification, the D3 may be a group represented by the chemical formula B, and the D5 may be a group represented by the chemical formula C.

[0178] In one embodiment of the present specification, the D3 may be a group represented by the chemical formula B, and the D6 may be a group represented by the chemical formula C.

[0179] In one embodiment of the present specification, the D3 may be a group represented by the chemical formula B, and the D7 may be a group represented by the chemical formula C.

[0180] In one embodiment of the present specification, the D3 may be a group represented by the chemical formula B, and the D8 may be a group represented by the chemical formula C.

[0181] In one embodiment of the present specification, the D4 may be a group represented by the chemical formula B, and the D1 may be a group represented by the chemical formula C.

[0182] In one embodiment of the present specification, the D4 may be a group represented by the chemical formula B, and the D2 may be a group represented by the chemical formula C.

[0183] In one embodiment of the present specification, the D4 may be a group represented by the chemical formula B, and the D3 may be a group represented by the chemical formula C.

[0184] In one embodiment of the present specification, the D4 may be a group represented by the chemical formula B, and the D5 may be a group represented by the chemical formula C.

[0185] In one embodiment of the present specification, the D4 may be a group represented by the chemical formula B, and the D6 may be a group represented by the chemical formula C.

[0186] In one embodiment of the present specification, the D4 may be a group represented by the chemical formula B, and the D7 may be a group represented by the chemical formula C.

[0187] In one embodiment of the present specification, the D4 may be a group represented by the chemical formula B, and the D8 may be a group represented by the chemical formula C.

[0188] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula A is 0% to 100%, the deuterium substitution rate of the chemical formula B is 0%, and the deuterium substitution rate of the chemical formula C may be greater than 0% and less than or equal to 100%.

[0189] In this specification, the deuterium substitution rate of the chemical formulas A to C refers to the substitution rate of deuterium with respect to the total number of hydrogens and deuteriums contained in the chemical formulas A to C, respectively.

[0190] That is, the chemical formula B does not contain deuterium at all, and the chemical formula C necessarily contains deuterium.

[0191] With the core structure, chemical formula A, as the center, one substituent contains deuterium and the other does not, thereby maximizing the effects of deuterium substitution and efficiently obtaining a compound through a synthetic method. The azine group, which exhibits electronic properties, not only has a minimal long-life effect due to deuterium substitution, but also reduces the stacking effect, resulting in a decrease in carrier mobility, which can result in an increase in operating voltage.

[0192] In general, compounds substituted with only hydrogen and compounds substituted with deuterium show differences in thermodynamic behavior due to differences in atomic mass, van der Waals radius, etc. Deuterium has lower vibrational energy than hydrogen, and the bond between carbon and deuterium is shorter and has stronger dissociation energy compared to the bond between carbon and hydrogen. Accordingly, compounds substituted with deuterium have the characteristic of having a lower ground state energy than compounds substituted with only hydrogen, and the molecular hardcore volume is reduced, which can reduce electrical polarizability. In addition, it has the effect of increasing the volume of the device thin film by weakening the intermolecular interaction, and lowering the crystallinity by creating an amorphous state of the thin film. Therefore, when the heterocyclic compound of the present invention is used as a material for an OLED device, the device efficiency and lifespan characteristics can be improved.

[0193] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula A is 0%, the deuterium substitution rate of the chemical formula B is 0%, and the deuterium substitution rate of the chemical formula C may be greater than 0% and less than or equal to 100%.

[0194] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula A may be greater than 0% and less than or equal to 100%, the deuterium substitution rate of the chemical formula B may be greater than 0% and less than or equal to 100%, and the deuterium substitution rate of the chemical formula C may be greater than 0% and less than or equal to 100%.

[0195] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula C may be 10% to 100%.

[0196] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula C may be 30% to 100%.

[0197] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula C may be 50% to 100%.

[0198] In one embodiment of the present specification, R1 to R8 are each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group, or adjacent groups may be bonded to each other to form a ring, and at least one of R1 to R8 is deuterium.

[0199] In one embodiment of the present specification, R1 to R8 are each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C3 to C20 cycloalkyl group; a substituted or unsubstituted C2 to C20 heterocycloalkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group, or adjacent groups may be bonded to each other to form a ring, and at least one of R1 to R8 is deuterium.

[0200] In one embodiment of the present specification, R1 to R8 are each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group, and at least one of R1 to R8 is deuterium.

[0201] In one embodiment of the present specification, R1 to R8 are each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C10 alkyl group; a substituted or unsubstituted C3 to C20 cycloalkyl group; a substituted or unsubstituted C2 to C20 heterocycloalkyl group; a substituted or unsubstituted C6 to C20 aryl group; or a substituted or unsubstituted C2 to C20 heteroaryl group, and at least one of R1 to R8 is deuterium.

[0202] In one embodiment of the present specification, R1 to R8 are each independently hydrogen; deuterium; or a substituted or unsubstituted C6 to C30 aryl group, and at least one of R1 to R8 is deuterium.

[0203] In one embodiment of the present specification, R1 to R8 are each independently hydrogen; deuterium; or a substituted or unsubstituted C6 to C20 aryl group, and at least one of R1 to R8 is deuterium.

[0204] In one embodiment of the present specification, R1 to R8 are each independently hydrogen; deuterium; or a C6 to C30 aryl group substituted or unsubstituted with deuterium, and at least one of R1 to R8 is deuterium.

[0205] In one embodiment of the present specification, R1 to R8 are each independently hydrogen; deuterium; or a C6 to C20 aryl group substituted or unsubstituted with deuterium, and at least one of R1 to R8 is deuterium.

[0206] In one embodiment of the present specification, D is deuterium, and n is an integer from 0 to 6.

[0207] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula 1 may be from more than 0% to 90%.

[0208] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula 1 may be 10% to 90%.

[0209] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula 1 may be 20% to 90%.

[0210] In one embodiment of the present specification, the deuterium substitution rate of the chemical formula 1 may be 30% to 80%.

[0211] In this specification, the deuterium substitution rate of the chemical formula 1 refers to the substitution rate of deuterium with respect to the total number of hydrogens and deuteriums contained in the chemical formula 1. For example, if there are 20 hydrogens and 20 deuteriums contained in the chemical formula 1, the substitution rate of 20 deuteriums with respect to the total of 40 hydrogens and deuteriums is 50%.

[0212] In one embodiment of the present specification, when the deuterium substitution rate of the heterocyclic compound of the chemical formula 1 satisfies the above range, the photochemical characteristics of the compound not containing deuterium and the compound containing deuterium are almost similar, but when deposited on a thin film, the material containing deuterium tends to be packed with a narrower intermolecular distance.

[0213] Accordingly, by fabricating an EOD (Electron Only Device) and a HOD (Hole Only Device) and checking the current density according to the voltage, it can be confirmed that the heterocyclic compound of chemical formula 1 of the present invention exhibits much more balanced charge transport characteristics than a compound that does not contain deuterium.

[0214] Additionally, when looking at the surface of the thin film with an atomic force microscope (AFM), it can be confirmed that the thin film made of a compound containing deuterium is deposited with a more uniform surface without any aggregated areas.

[0215] Additionally, since the single bond dissociation energy of carbon and deuterium is higher than the single bond dissociation energy of carbon and hydrogen, in the case of the heterocyclic compound of chemical formula 1 of the present invention, the stability of the entire molecule increases, thereby improving the device lifespan.

[0216] In one embodiment of the present specification, the chemical formula 1 may be represented by any one of the following compounds.

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244] The deuterium substitution rate can be determined from the number of deuterium atoms indicated in the above compound, and the substitution positions may be slightly different.

[0245] That is, when only a portion of the linker or carbazole structure is substituted with deuterium, deuterium is marked at an arbitrary position to indicate the deuterium substitution ratio, and the deuterium substitution position may vary depending on the synthesis.

[0246] In addition, by introducing various substituents into the structure of the above chemical formula 1, compounds having the unique characteristics of the introduced substituents can be synthesized. For example, by introducing substituents mainly used in hole injection layer materials, hole transport layer materials, light-emitting layer materials, electron transport layer materials, and charge generation layer materials used in the manufacture of organic light-emitting devices into the core structure, a material satisfying the conditions required for each organic layer can be synthesized.

[0247] In addition, by introducing various substituents into the structure of the above chemical formula 1, it is possible to finely control the energy band gap, while improving the properties at the interface between organic substances and diversifying the uses of the material.

[0248] In another embodiment of the present specification, an organic light-emitting device is provided, comprising: a first electrode; a second electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one layer of the organic layer comprises at least one heterocyclic compound of the chemical formula 1.

[0249] In one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer may include one or more types of the heterocyclic compound.

[0250] In one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer may include one type of the heterocyclic compound.

[0251] In one embodiment of the present specification, the organic layer includes a light-emitting layer, the light-emitting layer includes a host, and the host may include one or more of the heterocyclic compounds.

[0252] In one embodiment of the present specification, the organic layer includes a light-emitting layer, the light-emitting layer includes a host, and the host may include one type of the heterocyclic compound.

[0253] In one embodiment of the present specification, the organic layer includes a light-emitting layer, the light-emitting layer includes a host, the host includes a green host, and the green host may include one or more of the heterocyclic compounds.

[0254] In one embodiment of the present specification, the organic layer includes a light-emitting layer, the light-emitting layer includes a host, the host includes a red host, and the red host may include one or more of the heterocyclic compounds.

[0255] In one embodiment of the present specification, the organic layer includes a light-emitting layer, the light-emitting layer includes a host, the host includes a blue host, and the blue host may include one or more of the heterocyclic compounds.

[0256] In one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer may include the heterocyclic compound as an N-type host.

[0257] In one embodiment of the present specification, the organic layer including the heterocyclic compound may further include a compound of the following chemical formula 2.

[0258] [Chemical Formula 2]

[0259]

[0260] In the above chemical formula 2,

[0261] At least one of R11 to R18 is a substituted or unsubstituted carbazole group, or adjacent groups of R11 to R18 combine to form a substituted or unsubstituted heterocycle,

[0262] The remainder of R11 to R18 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted phosphine oxide group; or a substituted or unsubstituted amine group,

[0263] L11 is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group,

[0264] l11 is an integer from 1 to 3, and if it is 2 or more, the substituents in the parentheses are the same or different,

[0265] Ar11 is a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0266] In one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer may further include a compound of the chemical formula 2.

[0267] In one embodiment of the present specification, the organic layer includes a light-emitting layer, the light-emitting layer includes a host, and the host may further include a compound of the chemical formula 2.

[0268] In one embodiment of the present specification, the light-emitting layer may further include a compound of the above chemical formula 2 as a P-type host.

[0269] In one embodiment of the present specification, at least one of R11 to R18 is a substituted or unsubstituted carbazole group, or adjacent groups of R11 to R18 combine to form a substituted or unsubstituted heterocycle.

[0270] In one embodiment of the present specification, at least one of R11 to R18 is a substituted or unsubstituted carbazole group, or adjacent groups of R11 to R18 combine to form a substituted or unsubstituted indole ring.

[0271] In one embodiment of the present specification, the remainder of R11 to R18 may each independently be hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0272] In one embodiment of the present specification, the remainder of R11 to R18 may each independently be hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; or a substituted or unsubstituted C6 to C60 aryl group.

[0273] In one embodiment of the present specification, the remainder of R11 to R18 may each independently be hydrogen or deuterium.

[0274] In one embodiment of the present specification, the chemical formula 2 may be represented by the following chemical formula 2-1 or 2-2.

[0275] [Chemical Formula 2-1]

[0276]

[0277] [Chemical Formula 2-2]

[0278]

[0279] In the above chemical formulas 2-1 and 2-2,

[0280] The definitions of L11, l11 and Ar11 are the same as those in the above chemical formula 2,

[0281] R21 and R22 are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted phosphine oxide group; or a substituted or unsubstituted amine group,

[0282] L12 and L13 are each independently a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group,

[0283] Ar12 and Ar13 are each independently a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group,

[0284] r21 and r22 are integers from 1 to 7, respectively,

[0285] r23 is an integer from 1 to 6,

[0286] r24 is an integer from 1 to 4,

[0287] l12 and l13 are integers from 1 to 3, respectively.

[0288] When r21, r22, r23, r24, l12 and l13 are each 2 or more, the substituents in parentheses are the same or different.

[0289] In one embodiment of the present specification, R21 and R22 may each independently be hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0290] In one embodiment of the present specification, R21 and R22 may each independently be hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; or a substituted or unsubstituted C6 to C60 aryl group.

[0291] In one embodiment of the present specification, R21 and R22 may each independently be hydrogen or deuterium.

[0292] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group.

[0293] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a substituted or unsubstituted C6 to C30 arylene group; or a substituted or unsubstituted C2 to C30 heteroarylene group.

[0294] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a substituted or unsubstituted C6 to C20 arylene group; or a substituted or unsubstituted C2 to C20 heteroarylene group.

[0295] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; or a substituted or unsubstituted divalent dibenzofuran group.

[0296] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a substituted or unsubstituted phenylene group; or a substituted or unsubstituted divalent dibenzofuran group.

[0297] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; or a substituted or unsubstituted C6 to C30 arylene group.

[0298] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; or a substituted or unsubstituted C6 to C20 arylene group.

[0299] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a substituted or unsubstituted phenylene group; or a substituted or unsubstituted biphenylene group.

[0300] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; or a substituted or unsubstituted phenylene group.

[0301] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a C6 to C60 arylene group substituted or unsubstituted with deuterium; or a C2 to C60 heteroarylene group substituted or unsubstituted with deuterium.

[0302] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a C6 to C30 arylene group substituted or unsubstituted with deuterium; or a C2 to C30 heteroarylene group substituted or unsubstituted with deuterium.

[0303] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; a C6 to C20 arylene group substituted or unsubstituted with deuterium; or a C2 to C20 heteroarylene group substituted or unsubstituted with deuterium.

[0304] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; or an arylene group having C6 to C60 substituted or unsubstituted with deuterium.

[0305] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; or a C6 to C30 arylene group substituted or unsubstituted with deuterium.

[0306] In one embodiment of the present specification, L11 to L13 may each independently be a direct bond; or a C6 to C20 arylene group substituted or unsubstituted with deuterium.

[0307] In one embodiment of the present specification, Ar11 to Ar13 may each independently be a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.

[0308] In one embodiment of the present specification, Ar11 to Ar13 may each independently be a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted triphenylenyl group; a substituted or unsubstituted dibenzofuran group; or a substituted or unsubstituted dibenzothiophene group.

[0309] In one embodiment of the present specification, Ar11 to Ar13 may each independently be a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted triphenylenyl group; a substituted or unsubstituted dibenzofuran group; or a substituted or unsubstituted dibenzothiophene group.

[0310] In one embodiment of the present specification, Ar11 to Ar13 may each independently be a C6 to C60 aryl group substituted or unsubstituted with deuterium; or a C2 to C60 heteroaryl group substituted or unsubstituted with deuterium or an aryl group.

[0311] In one embodiment of the present specification, Ar11 to Ar13 may each independently be a C6 to C30 aryl group substituted or unsubstituted with deuterium; or a C2 to C30 heteroaryl group substituted or unsubstituted with deuterium or an aryl group.

[0312] In one embodiment of the present specification, the chemical formula 2 may be selected from the following compounds.

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321] The organic layer of the organic light-emitting device of the present invention may be formed as a single-layer structure, but may also be formed as a multi-layer structure in which two or more organic layers are laminated. For example, the organic light-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. as the organic layers. However, the structure of the organic light-emitting device is not limited thereto and may include a smaller number of organic layers.

[0322] In one embodiment of the present specification, the first electrode may be an anode, and the second electrode may be a cathode.

[0323] In another embodiment of the present specification, the first electrode may be a cathode and the second electrode may be an anode.

[0324] An organic light-emitting device according to one embodiment of the present specification can be manufactured using a conventional method and material for manufacturing an organic light-emitting device, except that one or more organic layers are formed using the heterocyclic compound of the above-described chemical formula 1.

[0325] The heterocyclic compound of the above chemical formula 1 can be formed into an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution coating method refers to, but is not limited to, spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc.

[0326] In one embodiment of the present specification, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound of the chemical formula 1 may be used as a material of the blue organic light-emitting device. For example, the heterocyclic compound of the chemical formula 1 may be included in a light-emitting layer of the blue organic light-emitting device.

[0327] In another embodiment of the present specification, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound of the chemical formula 1 may be used as a material of the green organic light-emitting device. For example, the heterocyclic compound of the chemical formula 1 may be included in a light-emitting layer of the green organic light-emitting device.

[0328] In another embodiment of the present specification, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound of the chemical formula 1 may be used as a material of the red organic light-emitting device. For example, the heterocyclic compound of the chemical formula 1 may be included in a light-emitting layer of the red organic light-emitting device.

[0329] The organic light-emitting device of the present invention may further include one or more layers selected from the group consisting of a light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

[0330] The stacking order of electrodes and organic layers of an organic light-emitting device according to one embodiment of the present disclosure is exemplified in Figures 1 to 3. However, the scope of the present application is not intended to be limited by these drawings, and the structure of an organic light-emitting device known in the art may also be applied to the present application.

[0331] According to FIG. 1, an organic light-emitting device is illustrated in which an anode (200), an organic layer (300), and a cathode (400) are sequentially laminated on a substrate (100). However, the present invention is not limited to this structure, and an organic light-emitting device in which a cathode, an organic layer, and an anode are sequentially laminated on a substrate, as shown in FIG. 2, may also be implemented.

[0332] Fig. 3 illustrates a case where the organic layer is multilayered. 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 such a laminated structure, and, if necessary, the remaining layers except for the light-emitting layer may be omitted, and other necessary functional layers may be further added.

[0333] The organic layer containing the heterocyclic compound of the above chemical formula 1 may additionally contain other substances as needed.

[0334] In an organic light-emitting device according to one embodiment of the present specification, materials other than the heterocyclic compound of the above chemical formula 1 are exemplified below, but these are only for exemplification and are not intended to limit the scope of the present application, and may be replaced with materials known in the art.

[0335] Materials having a relatively large work function can be used as the anode material, and transparent conductive oxides, metals, or conductive polymers can be used. Specific examples of the anode material include, but are not limited to, 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); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline.

[0336] Materials with relatively low work functions can be used as cathode materials, and metals, metal oxides, or conductive polymers can be used. Specific examples of the cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayered materials such as LiF / Al or LiO2 / Al.

[0337] As the hole injection material, a known hole injection material may be used, for example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429, or a starburst amine derivative described in the literature [Advanced Material, 6, p. 677 (1994)], 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), a soluble conductive polymer such as polyaniline / dodecylbenzenesulfonic acid, or Poly(3,4-ethylenedioxythiophene) / Poly(4-styrenesulfonate), polyaniline / camphor sulfonic acid, or polyaniline / poly(4-styrenesulfonate) can be used.

[0338] Pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. can be used as hole transport materials, and low molecular weight or high molecular weight materials can also be used.

[0339] As the electron transport material, metal complexes of oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and derivatives thereof, etc. can be used, and not only low molecular weight substances but also high molecular weight substances can be used.

[0340] For example, LiF is a representative material used in the art, but the present application is not limited thereto.

[0341] Red, green, or blue light-emitting materials may be used as the light-emitting material, and if necessary, two or more light-emitting materials may be mixed and used. At this time, two or more light-emitting materials may be deposited and used as individual sources, or may be premixed and deposited and used as a single source. In addition, a fluorescent material may be used as the light-emitting material, but it may also be used as a phosphorescent material. A material that emits light by combining holes and electrons injected from the anode and cathode, respectively, may be used as the light-emitting material, but materials in which both the host material and the dopant material participate in light emission may also be used.

[0342] When using a mixture of hosts for light-emitting materials, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, two or more types of materials, either N-type host materials or P-type host materials, may be selected and used as the host materials for the light-emitting layer.

[0343] An organic light-emitting device according to one embodiment of the present specification may be a front-emitting, back-emitting, or double-sided emitting device depending on the material used.

[0344] The heterocyclic compound according to one embodiment of the present specification can function in organic electronic devices, including organic solar cells, organic photoconductors, organic transistors, etc., by a similar principle to that applied to organic light-emitting devices.

[0345] In addition, by introducing various substituents into the structure of the above chemical formula 1, it is possible to finely control the energy band gap, while improving the properties at the interface between organic substances and diversifying the uses of the material.

[0346] Another embodiment of the present specification provides a composition for an organic layer comprising the heterocyclic compound.

[0347] In one embodiment of the present specification, the composition for the organic layer may further include a compound of the chemical formula 2.

[0348] In one embodiment of the present specification, the composition for the organic layer may include the heterocyclic compound and the compound of the chemical formula 2 in a weight ratio of 1:10 to 10:1.

[0349] In one embodiment of the present specification, the composition for the organic layer may include the heterocyclic compound and the compound of the chemical formula 2 in a weight ratio of 1:8 to 8:1, 1:5 to 5:1, or 1:3 to 3:1.

[0350] In one embodiment of the present specification, the composition for the organic layer may include the heterocyclic compound and the compound of the chemical formula 2 in a weight ratio of 1:1 to 5:1, or 1:1 to 3:1.

[0351] Another embodiment of the present specification provides a method for manufacturing an organic light-emitting device, comprising the steps of: preparing a substrate; forming a first electrode on the substrate; forming one or more organic layers on the first electrode; and forming a second electrode on the organic layer, wherein the step of forming the organic layer includes the step of forming one or more organic layers using the organic layer composition described above.

[0352] In one embodiment of the present specification, the step of forming the organic layer may include a step of premixing a composition for the organic layer of the organic light-emitting device and depositing it using one supply source.

[0353] The above pre-mixing means that the heterocyclic compound of the above chemical formula 1 and the compound of the above chemical formula 2 are mixed in one container before being deposited on the organic layer. In the case of pre-mixing, there is an advantage in that the process is simpler because one deposition source is used instead of two or more deposition sources.

[0354] When premixing the composition for the above organic layer, the inherent thermal properties of each material can significantly affect deposition conditions, such as the deposition rate, when depositing the premixed material. Therefore, the inherent thermal properties of each material to be premixed must be confirmed. If the thermal properties of the materials are not similar, repeatability and reproducibility in the deposition process cannot be maintained, and uniform OLED devices cannot be manufactured.

[0355] To overcome this, the electrical properties of each material can be tuned by appropriately combining the basic structure and substituents of each material, while thermal properties can also be controlled based on the morphology of the molecular structure. By manipulating the thermal properties of each material, a variety of host-to-host premixed deposition processes can be secured. This allows for the creation of diverse premixed deposition processes utilizing not only two compounds as hosts, but also three or more host materials.

[0356] In one embodiment of the present specification, the composition for the organic layer may include a host other than the compound of the chemical formula 2.

[0357] In one embodiment of the present specification, the composition for the organic layer includes the compound of the chemical formula 2 and may further include another host.

[0358] Hereinafter, the present specification will be described in more detail through examples, but these are only intended to illustrate the present application and are not intended to limit the scope of the present application.

[0359] <Manufacturing Example>

[0360] <Manufacturing Example 1> Preparation of compound 10

[0361]

[0362] 1) Preparation of compound P5

[0363] 2-phenyl-9H-carbazole[P6](30g, 123.45mmol), 3-bromo-3'-chloro-1,1'-biphenyl[A](33g, 123.45mmol), and Cs2CO3(80g, 1246.92mmol) were dissolved in 500mL of DMA(Demethylamide), and stirred at a reaction temperature of 150℃ for 5 hours. After completion of the reaction, the solution was cooled to room temperature and inorganic salts were removed by filtration. The filtrate was concentrated using a rotary evaporator, dissolved in an excess of MC(Methylene chloride), and filtered through silica gel. The filtrate was subjected to column chromatography after removing the solvent using a rotary evaporator.<MC / Hexane=1 / 3> Purification under these conditions yielded 41 g of compound P5 as a white solid in 77% yield.

[0364] 2) Preparation of compound P4

[0365] Compound P5 (41 g, 95.34 mmol) was dissolved in 200 mL of D6-Benzene, and then triflic acid (60 mL, 667.44 mmol) was slowly added. The reaction temperature was raised to 60 °C and stirred for 1 hour, then the reaction temperature was lowered to 0 °C to terminate the reaction. A solution of triethylamine (67 mL, 476.11 mmol) dissolved in 40 mL of D2O was slowly added to neutralize the mixture, and the precipitated solid was filtered. The solid was dried, dissolved in an excess of DCM, and filtered through silica gel. The filtrate was used to remove the solvent using a rotary evaporator to obtain 39 g of compound P4 as an ivory solid in a 92% yield (75% D substitution rate).

[0366] 3) Preparation of compound P3

[0367] Compound P4 (39 g, 86.66 mmol), B2Pin2(Bis(pinacolato)diboron) (33 g, 129.99 mol), Pd(dba)2(Bis(dibenzylideneacetone)palladium(0)) (4.9 g, 8.66 mmol), XPhos(2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) (8.8 g, 17.32 mmol), KOAc (17 g, 173.32 mmol) were dissolved in 500 mL of 1,4-dioxane and stirred at a reaction temperature of 100 °C for 14 hours. After completion of the reaction, the solution was cooled to room temperature and the inorganic salt was removed by filtration. The filtrate was concentrated using a rotary evaporator, dissolved in an excess of MC, and filtered through silica gel. The solvent was removed from the residue using a rotary evaporator and the residue was recrystallized from MeOH to obtain 37 g of compound P3 as a white solid in 84% yield.

[0368] 4) Preparation of compound P2

[0369] Compound P3 (37 g, 68.31 mmol), 1-bromo-9-chlorodibenzo[b,d]furan[B](19 g, 68.31 mmol), Pd(PPh3)4(Tetrakis(triphenylphosphine)palladium(0)) (3.9 g, 3.41 mmol), and K2CO3 (19 g, 136.62 mmol) were dissolved in 500 mL of 1,4-dioxane / 100 mL of H2O, and stirred at a reaction temperature of 100 ℃ for 4 hours. After the reaction was completed, the solution was cooled to room temperature and the solvent was removed using a rotary evaporator. The concentrated solution was dissolved in an excess of MC, extracted with H2O, and the organic layer was dried over anhydrous MgSO4 and filtered through silica gel. The solvent was removed from the filtrate using a rotary evaporator, and EA (Ethyl acetate) was recrystallized to obtain 28 g of compound P2 as an ivory-colored solid with a yield of 69%.

[0370] 5) Preparation of compound P1

[0371] Compound P2 (28 g, 46.63 mmol), B2Pin2 (18 g, 69.79 mmol), Pd(dba)2 (2.6 g, 4.66 mmol), XPhos (4.7 g, 9.33 mmol), KOAc (9 g, 93.26 mmol) were dissolved in 400 mL of 1,4-dioxane and stirred at a reaction temperature of 100 °C for 6 hours. After the reaction was completed, the solution was cooled to room temperature and the inorganic salts were removed by filtration. The filtrate was concentrated using a rotary evaporator, dissolved in an excess of MC, and filtered through silica gel. The filtrate was subjected to removal of the solvent using a rotary evaporator and recrystallized with MeOH to obtain 26 g of compound P1 as a white solid in a yield of 79%.

[0372] 6) Preparation of compound 10

[0373] Compound P1 (26 g, 36.77 mmol), 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine[C](13 g, 36.77 mmol), Pd(PPh3)4(2.1 g, 1.84 mmol), and K2CO3(10 g, 73.54 mmol) were dissolved in 300 mL of 1,4-dioxane / 50 mL of H2O, and stirred at a reaction temperature of 100 ℃ for 5 hours. After the reaction was completed, the solution was cooled to room temperature and the solvent was removed using a rotary evaporator. The concentrated solution was dissolved in an excess of MC, extracted with H2O, and the organic layer was dried over anhydrous MgSO4 and filtered through silica gel. The solvent was removed from the residue using a rotary evaporator and recrystallized with CB (Chlorobenzne) to obtain compound 10, 18 g as a pale yellow solid in a yield of 56%.

[0374] The target compound of Table 1 was synthesized in the same manner as in Manufacturing Example 1, except that Intermediate P6, Intermediate A, Intermediate B, and Intermediate C of Table 1 were used instead of Compound [P6], Compound [A], Compound [B], and Compound [C] of Manufacturing Example 1.

[0375]

[0376]

[0377]

[0378] <Manufacturing Example 2> Preparation of compound 21

[0379]

[0380] 1) Preparation of compound S5

[0381] 9H-carbazole[S6](30g, 167.94mmol), 3-bromo-4'-chloro-1,1'-biphenyl[D](44g, 167.94mmol), and Cs2CO3(109g, 335.88mmol) were dissolved in 500mL of DMA and stirred at a reaction temperature of 150℃ for 5 hours. After completion of the reaction, the solution was cooled to room temperature and inorganic salts were removed by filtration. The filtrate was concentrated using a rotary evaporator, dissolved in an excess of MC, and filtered through silica gel. The filtrate was subjected to column chromatography after removing the solvent using a rotary evaporator.<MC / Hexane=1 / 3> Purification under these conditions yielded 41 g of compound S5 as a white solid in 70% yield.

[0382] 2) Preparation of compound S4

[0383] Compound S5 (41 g, 116.15 mmol), B2Pin2 (44 g, 174.229 mol), Pd(dba)2 (3.4 g, 5.81 mmol), XPhos (5.5 g, 11.62 mmol), and KOAc (22 g, 232.31 mmol) were dissolved in 550 mL of 1,4-dioxane and stirred at a reaction temperature of 100 °C for 14 hours. After the reaction was completed, the solution was cooled to room temperature and the inorganic salts were removed by filtration. The filtrate was concentrated using a rotary evaporator, dissolved in an excess of MC, and filtered through silica gel. The filtrate was purified by removing the solvent using a rotary evaporator and recrystallized with MeOH to obtain 37 g of compound S4 as a white solid in a yield of 72%.

[0384] 3) Preparation of compound S3

[0385] Compound S4 (37 g, 83.17 mmol), 1-bromo-8-chlorodibenzo[b,d]furan[E](23 g, 83.17 mmol), Pd(PPh3)4(4.9 g, 4.16 mmol), and K2CO3(23 g, 166.34 mmol) were dissolved in 500 mL of 1,4-dioxane / 100 mL of H2O, and stirred at a reaction temperature of 100 °C for 5 hours. After the reaction was completed, the solution was cooled to room temperature and the solvent was removed using a rotary evaporator. The concentrated solution was dissolved in an excess of MC, extracted with H2O, and the organic layer was dried over anhydrous MgSO4 and filtered through silica gel. The filtrate was subjected to removal of the solvent using a rotary evaporator, and EA was recrystallized to obtain 27 g of compound S3 as an ivory solid in a yield of 62%.

[0386] 4) Preparation of compound S2

[0387] Compound S3 (27 g, 51.92 mmol) was dissolved in 150 mL of D6-Benzene, and then triflic acid (33 mL, 363.44 mmol) was slowly added. The reaction temperature was raised to 60 °C and stirred for 1 hour, then the reaction temperature was lowered to 0 °C to terminate the reaction. A solution of triethylamine (20 mL, 259.11 mmol) dissolved in 30 mL of D2O was slowly added to neutralize the mixture, and the precipitated solid was filtered. The solid was dried, dissolved in an excess of DCM, and filtered through silica gel. The filtrate was used to remove the solvent using a rotary evaporator to obtain 26 g of compound S2 as an ivory solid in a 93% yield (100% D substitution rate).

[0388] 5) Preparation of compound S1

[0389] Compound S2 (26 g, 47.97 mmol), B2Pin2 (18 g, 71.96 mmol), Pd(dba)2 (1.4 g, 2.39 mmol), XPhos (2.3 g, 4.79 mmol), and KOAc (9.5 g, 95.94 mmol) were dissolved in 400 mL of 1,4-dioxane and stirred at a reaction temperature of 100 °C for 5 hours. After the reaction was completed, the solution was cooled to room temperature and the inorganic salts were removed by filtration. The filtrate was concentrated using a rotary evaporator, dissolved in an excess of MC, and filtered through silica gel. The filtrate was subjected to removal of the solvent using a rotary evaporator and recrystallized with MeOH to obtain 21 g of compound S1 as a white solid in a yield of 69%.

[0390] 6) Preparation of compound 21

[0391] Compound S1 (21 g, 33.45 mmol), 1-bromo-8-chlorodibenzo[b,d]furan[F](7.1 g, 33.45 mmol), Pd(PPh3)4(1.9 g, 1.67 mmol), and K2CO3(9.2 g, 66.89 mmol) were dissolved in 300 mL of 1,4-dioxane / 40 mL of H2O, and stirred at a reaction temperature of 100 °C for 7 hours. After the reaction was completed, the solution was cooled to room temperature and the solvent was removed using a rotary evaporator. The concentrated solution was dissolved in an excess of MC, extracted with H2O, and the organic layer was dried over anhydrous MgSO4 and filtered through silica gel. The filtrate was purified by removing the solvent using a rotary evaporator, and xylene was recrystallized to obtain 12 g of compound 21 as a pale yellow solid in a yield of 48%.

[0392] The final compound of Table 2 was synthesized in the same manner as in Manufacturing Example 2, except that Intermediate S6, Intermediate D, Intermediate E, and Intermediate F of Table 2 were used instead of Compound [S6], Compound [D], Compound [E], and Compound [F] of Manufacturing Example 2.

[0393]

[0394]

[0395]

[0396] The compounds synthesized in the above manufacturing examples 1 and 2 were analyzed by FD-mass spectrometry and 1 The synthesis of the desired compound was confirmed through H-NMR. The measured values ​​of FD-mass spectrometry (FD-MS: Field desorption mass spectrometry) are shown in Table 3 below. 1 The measured values ​​of H NMR (CDCl3, 300 MHz) are listed in Table 4 below.

[0397] Compound number FD-MS Compound number FD-MS 1MW = 732.94 (C 51 H 16 D 16 N4O)271MW=813.06(C 57 H 16 D 20 N4O)2MW=732.94(C 51 H 16 D 16 N4O)272MW=736.97(C 51 H 14 D 18 N4O)3MW=809.04(C 57 H 20 D 16 N4O)273MW=813.06(C 57 H 16 D 20 N4O)4MW=808.03(C 57 H 21 D 15 N4O)274MW=811.05(C 57 H 18 D 18 N4O)5MW=812.06(C 57 H 17 D 19 N4O)275MW=813.06(C 57 H 16 D 20 N4O)6MW=810.05(C 57 H 19 D 17 N4O)276MW=732.94(C 51 H 16 D16 N4O)7MW=809.04(C 57 H 20 D 16 N4O)277MW=813.06(C 57 H 16 D 20 N4O)8MW=818.09(C 57 H 11 D 25 N4O)278MW=732.94(C 51 H 16 D 16 N4O)9MW=808.03(C 57 H 21 D 15 N4O)279MW=813.06(C 57 H 16 D 20 N4O)10MW=898.11(C 63 H 23 D 15 N4O2)280MW=813.06(C 57 H 16 D 20 N4O)11MW=808.03(C 57 H 21 D 15 N4O)281MW=826.04(C 57 H 15 D 19 N4O2)12MW=812.06(C 57 H 17 D 19 N4O)282MW=809.04(C 57 H 20 D 16 N4O)13MW=803.00(C 57 H 26 D 10 N4O)283MW=813.06(C 57 H 16 D 20 N4O)14MW=815.08(C 57 H 14 D 22 N4O)284MW=813.06(C 57 H 16 D 20 N4O)15MW=813.06(C 57 H 16 D20 N4O)285MW=817.09(C 57 H 12 D 24 N4O)16MW=731.94(C 51 H 17 D 15 N4O)286MW=735.96(C 51 H 13 D 19 N4O)17MW=812.06(C 57 H 17 D 19 N4O)287MW=809.04(C 57 H 20 D 16 N4O)18MW=729.92(C 51 H 19 D 13 N4O)288MW=734.96(C 51 H 14 D 18 N4O)19MW=820.05(C 58 H 25 D 13 N4O)289MW=732.94(C 51 H 16 D 16 N4O)20MW=813.06(C 57 H 16 D 20 N4O)290MW=813.06(C 57 H 16 D 20 N4O)21MW=738.98(C 51 H 10 D 22 N4O)291MW=813.06(C 57 H 16 D 20 N4O)22MW=732.94(C 51 H 16 D 16 N4O)292MW=734.96(C 51 H 14 D 18 N4O)23MW=808.03(C 57 H 21 D 15 N4O)293MW=813.06(C 57 H 16 D20 N4O)24MW=808.03(C 57 H 21 D 15 N4O)294MW=810.05(C 57 H 19 D 17 N4O)25MW=813.06(C 57 H 16 D 20 N4O)295MW=813.06(C 57 H 16 D 20 N4O)26MW=809.04(C 57 H 20 D 16 N4O)296MW=732.94(C 51 H 16 D 16 N4O)27MW=808.03(C 57 H 21 D 15 N4O)297MW=813.06(C 57 H 16 D 20 N4O)28MW=819.10(C 57 H 10 D 26 N4O)298MW=732.94(C 51 H 16 D 16 N4O)29MW=807.03(C 57 H 22 D 14 N4O)299MW=813.06(C 57 H 16 D 20 N4O)30MW=883.13(C 63 H 26 D 14 N4O)300MW=813.06(C 57 H 16 D 20 N4O)31MW=813.06(C 57 H 16 D 20 N4O)301MW=825.06(C 57 H 16 D 19 N5O)32MW=809.04(C 57 H 20 D16 N4O)302MW=809.04(C 57 H 20 D 16 N4O)33MW=807.03(C 57 H 22 D 14 N4O)303MW=813.06(C 57 H 16 D 20 N4O)34MW=810.05(C 57 H 19 D 17 N4O)304MW=813.06(C 57 H 16 D 20 N4O)35MW=818.09(C 57 H 11 D 25 N4O)305MW=812.06(C 57 H 17 D 19 N4O)36MW=732.94(C 51 H 16 D 16 N4O)306MW=734.96(C 51 H 14 D 18 N4O)37MW=812.06(C 57 H 17 D 19 N4O)307MW=809.04(C 57 H 20 D 16 N4O)38MW=823.02(C 57 H 18 D 16 N4O2)308MW=736.97(C 51 H 12 D 20 N4O)39MW=808.03(C 57 H 21 D 15 N4O)309MW=732.94(C 51 H 16 D 16 N4O)40MW=807.03(C 57 H 22 D 14 N4O)310MW=813.06(C 57 H 16 D20 N4O)41MW=730.93(C 51 H 18 D 14 N4O)311MW=813.06(C 57 H 16 D 20 N4O)42MW=732.94(C 51 H 16 D 16 N4O)312MW=736.97(C 51 H 12 D 20 N4O)43MW=808.03(C 57 H 21 D 15 N4O)313MW=809.04(C 57 H 20 D 16 N4O)44MW=808.03(C 57 H 21 D 15 N4O)314MW=812.06(C 57 H 17 D 19 N4O)45MW=813.06(C 57 H 16 D 20 N4O)315MW=813.06(C 57 H 16 D 20 N4O)46MW=810.05(C 57 H 19 D 17 N4O)316MW=823.02(C 57 H 18 D 16 N4O2)47MW=815.08(C 57 H 14 D 22 N4O)317MW=813.06(C 57 H 16 D 20 N4O)48MW=808.03(C 57 H 21 D 15 N4O)318MW=732.94(C 51 H 16 D 16 N4O)49MW=808.03(C 57 H 21 D15 N4O)319MW=813.06(C 57 H 16 D 20 N4O)50MW=889.16(C 63 H 20 D 20 N4O)320MW=813.06(C 57 H 16 D 20 N4O)51MW=808.03(C 57 H 21 D 15 N4O)321MW=749.00(C 51 H 16 D 16 N4S)52MW=813.06(C 57 H 16 D 20 N4O)322MW=749.00(C 51 H 16 D 16 N4S)53MW=808.03(C 57 H 21 D 15 N4O)323MW=829.13(C 57 H 16 D 20 N4S)54MW=810.05(C 57 H 19 D 17 N4O)324MW=829.13(C 57 H 16 D 20 N4S)55MW=808.03(C 57 H 21 D 15 N4O)325MW=835.16(C 57 H 10 D 26 N4S)56MW=732.94(C 51 H 16 D 16 N4O)326MW=825.10(C 57 H 20 D 16 N4S)57MW=810.05(C 57 H 19 D 17 N4O)327MW=830.13(C 57 H 15 D21 N4S)58MW=814.97(C 57 H 26 D8N4O2)328MW=835.16(C 57 H 10 D 26 N4S)59MW=809.04(C 57 H 20 D 16 N4O)329MW=829.13(C 57 H 16 D 20 N4S)60MW=813.06(C 57 H 16 D 20 N4O)330MW=919.21(C 63 H 18 D 20 N4S)61MW=738.98(C 51 H 10 D 22 N4O)331MW=829.13(C 57 H 16 D 20 N4S)62MW=733.95(C 51 H 15 D 17 N4O)332MW=825.10(C 57 H 20 D 16 N4S)63MW=809.04(C 57 H 20 D 16 N4O)333MW=829.13(C 57 H 16 D 20 N4S)64MW=809.04(C 57 H 20 D 16 N4O)334MW=830.13(C 57 H 15 D 21 N4S)65MW=811.05(C 57 H 18 D 18 N4O)335MW=835.16(C 57 H 10 D 26 N4S)66MW=734.95(C 51 H 14 D 18N4O)336MW=748.00(C 51 H 17 D 15 N4S)67MW=808.03(C 57 H 21 D 15 N4O)337MW=835.16(C 57 H 10 D 26 N4S)68MW=809.04(C 57 H 20 D 16 N4O)338MW=832.04(C 57 H 25 D9N4OS)69MW=813.06(C 57 H 16 D 20 N4O)339MW=829.13(C 57 H 16 D 20 N4S)70MW=884.13(C 63 H 25 D 15 N4O)340MW=829.13(C 57 H 16 D 20 N4S)71MW=810.05(C 57 H 19 D 17 N4O)341MW=825.10(C 57 H 20 D 16 N4S)72MW=809.04(C 57 H 20 D 16 N4O)342MW=831.14(C 57 H 14 D 22 N4S)73MW=813.06(C 57 H 16 D 20 N4O)343MW=829.13(C 57 H 16 D 20 N4S)74MW=808.03(C 57 H 21 D 15 N4O)344MW=829.13(C 57 H 16 D 20 N4S)75MW=807.03(C57 H 22 D 14 N4O)345MW=805.22(C 63 H 20 D 20 N4S)76MW=732.94(C 51 H 16 D 16 N4O)346MW=829.13(C 57 H 16 D 20 N4S)77MW=810.05(C 57 H 19 D 17 N4O)347MW=829.13(C 57 H 16 D 20 N4S)78MW=819.00(C 57 H 22 D 12 N4O2)348MW=829.13(C 57 H 16 D 20 N4S)79MW=808.03(C 57 H 21 D 15 N4O)349MW=831.14(C 57 H 14 D 22 N4S)80MW=813.06(C 57 H 16 D 20 N4O)350MW=829.13(C 57 H 16 D 20 N4S)81MW=731.94(C 51 H 17 D 15 N4O)351MW=755.04(C 51 H 10 D 22 N4S)82MW=728.92(C 51 H 20 D 12 N4O)352MW=755.04(C 51 H 10 D 22 N4S)83MW=813.06(C 57 H 16 D 20 N4O)353MW=829.13(C57 H 16 D 20 N4S)84MW=807.03(C 57 H 22 D 14 N4O)354MW=829.13(C 57 H 16 D 20 N4S)85MW=814.07(C 57 H 15 D 21 N4O)355MW=745.98(C 51 H 19 D 13 N4S)86MW=829.06(C 57 H 12 D 22 N4O2)356MW=832.14(C 57 H 13 D 23 N4S)87MW=808.03(C 57 H 21 D 15 N4O)357MW=832.14(C 57 H 13 D 23 N4S)88MW=806.02(C 57 H 23 D 13 N4O)358MW=839.08(C 57 H 18 D 16 N4OS)89MW=806.02(C 57 H 23 D 13 N4O)359MW=826.11(C 57 H 19 D 17 N4S)90MW=813.06(C 57 H 16 D 20 N4O)360MW=829.13(C 57 H 16 D 20 N4S)91MW=813.06(C 57 H 16 D 20 N4O)361MW=751.01(C 51 H 14 D 18 N4S)92MW=814.07(C57 H 15 D 21 N4O)362MW=749.00(C 51 H 16 D 16 N4S)93MW=807.03(C 57 H 22 D 14 N4O)363MW=829.13(C 57 H 16 D 20 N4S)94MW=809.04(C 57 H 20 D 16 N4O)364MW=829.13(C 57 H 16 D 20 N4S)95MW=732.94(C 51 H 16 D 16 N4O)365MW=835.16(C 57 H 10 D 26 N4S)96MW=729.92(C 51 H 19 D 13 N4O)366MW=861.18(C 57 H 12 D 22 N4S2)97MW=812.06(C 57 H 17 D 19 N4O)367MW=831.14(C 57 H 14 D 22 N4S)98MW=732.94(C 51 H 16 D 16 N4O)368MW=829.13(C 57 H 16 D 20 N4S)99MW=807.03(C 57 H 22 D 14 N4O)369MW=829.13(C 57 H 16 D 20 N4S)100MW=813.06(C 57 H 16 D 20 N4O)370MW=829.13(C57 H 16 D 20 N4S)101MW=732.94(C 51 H 16 D 16 N4O)371MW=829.13(C 57 H 16 D 20 N4S)102MW=727.91(C 51 H 21 D 11 N4O)372MW=829.13(C 57 H 16 D 20 N4S)103MW=807.03(C 57 H 22 D 14 N4O)373MW=829.13(C 57 H 16 D 20 N4S)104MW=818.01(C 57 H 23 D 12 N5O)374MW=831.14(C 57 H 14 D 22 N4S)105MW=814.07(C 57 H 15 D 21 N4O)375MW=829.13(C 57 H 16 D 20 N4S)106MW=821.01(C 57 H 20 D 14 N4O2)376MW=749.00(C 51 H 16 D 16 N4S)107MW=806.02(C 57 H 23 D 13 N4O)377MW=835.16(C 57 H 10 D 26 N4S)108MW=810.05(C 57 H 19 D 17 N4O)378MW=749.00(C 51 H 16 D 16N4S)109MW=808.03(C 57 H 21 D 15 N4O)379MW=825.10(C 57 H 20 D 16 N4S)110MW=807.03(C 57 H 22 D 14 N4O)380MW=829.13(C 57 H 16 D 20 N4S)111MW=807.03(C 57 H 22 D 14 N4O)381MW=860.18(C 57 H 13 D 21 N4S2)112MW=808.03(C 57 H 21 D 15 N4O)382MW=831.14(C 57 H 14 D 22 N4S)113MW=808.03(C 57 H 21 D 15 N4O)383MW=827.11(C 57 H 18 D 18 N4S)114MW=809.04(C 57 H 20 D 16 N4O)384MW=829.13(C 57 H 16 D 20 N4S)115MW=809.04(C 57 H 20 D 16 N4O)385MW=829.13(C 57 H 16 D 20 N4S)116MW=729.92(C 51 H 19 D 13 N4O)386MW=829.13(C 57 H 16 D 20 N4S)117MW=819.10(C 57 H 10 D26 N4O)387MW=825.10(C 57 H 20 D 16 N4S)118MW=729.92(C 51 H 19 D 13 N4O)388MW=829.13(C 57 H 16 D 20 N4S)119MW=807.03(C 57 H 22 D 14 N4O)389MW=831.14(C 57 H 14 D 22 N4S)120MW=808.03(C 57 H 21 D 15 N4O)390MW=829.13(C 57 H 16 D 20 N4S)121MW=727.91(C 51 H 21 D 11 N4O)391MW=749.00(C 51 H 16 D 16 N4S)122MW=729.92(C 51 H 19 D 13 N4O)392MW=749.00(C 51 H 16 D 16 N4S)123MW=826.08(C 58 H 19 D 19 N4O)393MW=829.13(C 57 H 16 D 20 N4S)124MW=813.06(C 57 H 16 D 20 N4O)394MW=829.13(C 57 H 16 D 20 N4S)125MW=810.05(C 57 H 19 D 17 N4O)395MW=829.13(C 57 H 16 D20 N4S)126MW=828.05(C 57 H 13 D 21 N4O2)396MW=749.00(C 51 H 16 D 16 N4S)127MW=815.08(C 57 H 14 D 22 N4O)397MW=829.13(C 57 H 16 D 20 N4S)128MW=808.03(C 57 H 21 D 15 N4O)398MW=749.00(C 51 H 16 D 16 N4S)129MW=809.04(C 57 H 20 D 16 N4O)399MW=829.13(C 57 H 16 D 20 N4S)130MW=813.06(C 57 H 16 D 20 N4O)400MW=829.13(C 57 H 16 D 20 N4S)131MW=813.06(C 57 H 16 D 20 N4O)401MW=745.98(C 51 H 20 D 12 N4S)132MW=813.06(C 57 H 16 D 20 N4O)402MW=745.98(C 51 H 20 D 12 N4S)133MW=813.06(C 57 H 16 D 20 N4O)403MW=828.12(C 57 H 17 D 19 N4S)134MW=815.08(C 57 H 14D 22 N4O)404MW=829.13(C 57 H 16 D 20 N4S)135MW=813.06(C 57 H 16 D 20 N4O)405MW=829.13(C 57 H 16 D 20 N4S)136MW=732.94(C 51 H 16 D 16 N4O)406MW=844.11(C 57 H 13 D 21 N4OS)137MW=819.10(C 57 H 10 D 26 N4O)407MW=825.10(C 57 H 20 D 16 N4S)138MW=732.94(C 51 H 16 D 16 N4O)408MW=828.12(C 57 H 17 D 19 N4S)139MW=810.05(C 57 H 19 D 17 N4O)409MW=829.13(C 57 H 16 D 20 N4S)140MW=732.94(C 51 H 16 D 16 N4O)410MW=829.13(C 57 H 16 D 20 N4S)141MW=732.94(C 51 H 16 D 16 N4O)411MW=829.13(C 57 H 16 D 20 N4S)142MW=732.94(C 51 H 16 D 16 N4O)412MW=754.03(C 51 H11 D 21 N4S)143MW=812.06(C 57 H 17 D 19 N4O)413MW=829.13(C 57 H 16 D 20 N4S)144MW=810.05(C 57 H 19 D 17 N4O)414MW=834.16(C 57 H 11 D 25 N4S)145MW=813.06(C 57 H 16 D 20 N4O)415MW=829.13(C 57 H 16 D 20 N4S)146MW=828.05(C 57 H 13 D 21 N4O2)416MW=749.00(C 51 H 16 D 16 N4S)147MW=815.08(C 57 H 14 D 22 N4O)417MW=829.13(C 57 H 16 D 20 N4S)148MW=813.06(C 57 H 16 D 20 N4O)418MW=749.00(C 51 H 16 D 16 N4S)149MW=813.06(C 57 H 16 D 20 N4O)419MW=829.13(C 57 H 16 D 20 N4S)150MW=819.10(C 57 H 10 D 26 N4O)420MW=824.09(C 57 H 21 D 15 N4S)151MW=813.06(C 57H 16 D 20 N4O)421MW=842.10(C 57 H 15 D 19 N4OS)152MW=813.06(C 57 H 16 D 20 N4O)422MW=825.10(C 57 H 20 D 16 N4S)153MW=813.06(C 57 H 16 D 20 N4O)423MW=753.03(C 51 H 12 D 20 N4S)154MW=815.08(C 57 H 14 D 22 N4O)424MW=749.00(C 51 H 16 D 16 N4S)155MW=819.10(C 57 H 10 D 26 N4O)425MW=829.13(C 57 H 16 D 20 N4S)156MW=732.94(C 51 H 16 D 16 N4O)426MW=829.13(C 57 H 16 D 20 N4S)157MW=815.08(C 57 H 14 D 22 N4O)427MW=753.03(C 51 H 12 D 20 N4S)158MW=732.94(C 51 H 16 D 16 N4O)428MW=829.13(C 57 H 16 D 20 N4S)159MW=813.06(C 57 H 16 D 20 N4O)429MW=829.13(C57 H 16 D 20 N4S)160MW=810.05(C 57 H 19 D 17 N4O)430MW=829.13(C 57 H 16 D 20 N4S)161MW=732.94(C 51 H 16 D 16 N4O)431MW=753.03(C 51 H 12 D 20 N4S)162MW=729.92(C 51 H 19 D 13 N4O)432MW=749.00(C 51 H 16 D 16 N4S)163MW=813.06(C 57 H 16 D 20 N4O)433MW=829.13(C 57 H 16 D 20 N4S)164MW=813.06(C 57 H 16 D 20 N4O)434MW=829.13(C 57 H 16 D 20 N4S)165MW=813.06(C 57 H 16 D 20 N4O)435MW=833.15(C 57 H 12 D 24 N4S)166MW=828.05(C 57 H 13 D 21 N4O2)436MW=749.00(C 51 H 16 D 16 N4S)167MW=809.04(C 57 H 20 D 16 N4O)437MW=829.13(C 57 H 16 D 20N4S)168MW=812.06(C 57 H 17 D 19 N4O)438MW=749.00(C 51 H 16 D 16 N4S)169MW=813.06(C 57 H 16 D 20 N4O)439MW=824.09(C 57 H 21 D 15 N4S)170MW=809.04(C 57 H 20 D 16 N4O)440MW=829.13(C 57 H 16 D 20 N4S)171MW=813.06(C 57 H 16 D 20 N4O)441MW=842.10(C 57 H 15 D 19 N4OS)172MW=813.06(C 57 H 16 D 20 N4O)442MW=825.10(C 57 H 20 D 16 N4S)173MW=813.06(C 57 H 16 D 20 N4O)443MW=748.00(C 51 H 17 D 15 N4S)174MW=815.08(C 57 H 14 D 22 N4O)444MW=749.00(C 51 H 16 D 16 N4S)175MW=813.06(C 57 H 16 D 20 N4O)445MW=829.13(C 57 H 16 D 20 N4S)176MW=732.94(C 51 H 16 D16 N4O)446MW=829.13(C 57 H 16 D 20 N4S)177MW=809.04(C 57 H 20 D 16 N4O)447MW=752.02(C 51 H 13 D 19 N4S)178MW=732.94(C 51 H 16 D 16 N4O)448MW=829.13(C 57 H 16 D 20 N4S)179MW=809.04(C 57 H 20 D 16 N4O)449MW=828.12(C 57 H 17 D 19 N4S)180MW=819.10(C 57 H 10 D 26 N4O)450MW=829.13(C 57 H 16 D 20 N4S)181MW=735.95(C 51 H 13 D 19 N4O)451MW=732.94(C 51 H 16 D 16 N4O)182MW=732.94(C 51 H 16 D 16 N4O)452MW=822.04(C 57 H 19 D 16 N5O)183MW=813.06(C 57 H 16 D 20 N4O)453MW=813.06(C 57 H 16 D 20 N4O)184MW=813.06(C 57 H 16 D 20 N4O)454MW=812.06(C 57 H 17 D19 N4O)185MW=818.06(C 57 H 11 D 25 N4O2)455MW=817.09(C 57 H 11 D 25 N4O)186MW=827.05(C 57 H 14 D 20 N4O2)456MW=814.07(C 57 H 15 D 21 N4O)187MW=809.04(C 57 H 20 D 16 N4O)457MW=812.06(C 57 H 17 D 19 N4O)188MW=737.97(C 51 H 11 D 21 N4O)458MW=818.09(C 57 H 10 D 26 N4O)189MW=808.03(C 57 H 21 D 15 N4O)459MW=808.03(C 57 H 21 D 25 N4O)190MW=813.06(C 57 H 16 D 20 N4O)460MW=903.15(C 63 H 18 D 20 N4O2)191MW=813.06(C 57 H 16 D 20 N4O)461MW=813.06(C 57 H 16 D 20 N4O)192MW=737.97(C 51 H 11 D 21 N4O)462MW=812.06(C 57 H 17 D 19 N4O)193MW=809.04(C 57 H 20D 16 N4O)463MW=813.06(C 57 H 16 D 20 N4O)194MW=814.07(C 57 H 15 D 21 N4O)464MW=813.06(C 57 H 16 D 20 N4O)195MW=813.06(C 57 H 16 D 20 N4O)465MW=816.08(C 57 H 13 D 23 N4O)196MW=732.94(C 51 H 16 D 16 N4O)466MW=731.94(C 51 H 17 D 15 N4O)197MW=813.06(C 57 H 16 D 20 N4O)467MW=813.06(C 57 H 16 D 20 N4O)198MW=732.94(C 51 H 16 D 16 N4O)468MW=823.02(C 57 H 18 D 16 N4O2)199MW=813.06(C 57 H 16 D 20 N4O)469MW=812.06(C 57 H 17 D 19 N4O)200MW=813.06(C 57 H 16 D 20 N4O)470MW=812.06(C 57 H 17 D 19 N4O)201MW=737.97(C 51 H 11 D 21 N4O)471MW=817.09(C 57 H12 D 24 N4O)202MW=732.94(C 51 H 16 D 16 N4O)472MW=813.06(C 57 H 16 D 20 N4O)203MW=813.06(C 57 H 16 D 20 N4O)473MW=813.06(C 57 H 16 D 20 N4O)204MW=813.06(C 57 H 16 D 20 N4O)474MW=812.06(C 57 H 17 D 19 N4O)205MW=814.07(C 57 H 15 D 21 N4O)475MW=884.13 (C 63 H 25 D 15 N4O)206MW=826.04(C 57 H 15 D 19 N4O2)476MW=813.06(C 57 H 16 D 20 N4O)207MW=809.04(C 57 H 20 D 16 N4O)477MW=820.03(C 57 H 21 D 14 N5O)208MW=736.97(C 51 H 12 D 20 N4O)478MW=812.06(C 57 H 17 D 19 N4O)209MW=732.94(C 51 H 16 D 16 N4O)479MW=814.07(C 57 H 15 D 21 N4O)210MW=813.06(C 57H 16 D 20 N4O)480MW=813.06(C 57 H 16 D 20 N4O)211MW=813.06(C 57 H 16 D 20 N4O)481MW=824.03(C 57 H 17 D 17 N4O2)212MW=733.95(C 51 H 15 D 17 N4O)482MW=736.97(C 51 H 12 D 20 N4O)213MW=813.06(C 57 H 16 D 20 N4O)483MW=812.06(C 57 H 17 D 19 N4O)214MW=813.06(C 57 H 16 D 20 N4O)484MW=812.06(C 57 H 17 D 19 N4O)215MW=813.06(C 57 H 16 D 20 N4O)485MW=813.06(C 57 H 16 D 20 N4O)216MW=732.94(C 51 H 16 D 16 N4O)486MW=813.06(C 57 H 16 D 20 N4O)217MW=813.06(C 57 H 16 D 20 N4O)487MW=813.06(C 57 H 16 D 20 N4O)218MW=732.94(C 51 H 16 D 16 N4O)488MW=812.06(C57 H 17 D 19 N4O)219MW=813.06(C 57 H 16 D 20 N4O)489MW=814.07(C 57 H 15 D 21 N4O)220MW=813.06(C 57 H 16 D 20 N4O)490MW=812.06(C 57 H 17 D 19 N4O)221MW=734.95(C 51 H 14 D 18 N4O)491MW=736.97(C 51 H 12 D 20 N4O)222MW=732.94(C 51 H 16 D 16 N4O)492MW=823.02(C 57 H 18 D 16 N4O2)223MW=813.06(C 57 H 16 D 20 N4O)493MW=813.06(C 57 H 16 D 20 N4O)224MW=813.06(C 57 H 16 D 20 N4O)494MW=813.06(C 57 H 16 D 20 N4O)225MW=817.09(C 57 H 12 D 24 N4O)495MW=817.09(C 57 H 12 D 24 N4O)226MW=826.04(C 57 H 15 D 19 N4O2)496MW=810.05(C 57 H 19 D 17N4O)227MW=809.04(C 57 H 20 D 16 N4O)497MW=813.06(C 57 H 16 D 20 N4O)228MW=736.97(C 51 H 12 D 20 N4O)498MW=808.03(C 57 H 21 D 15 N4O)229MW=732.94(C 51 H 16 D 16 N4O)499MW=813.06(C 57 H 16 D 20 N4O)230MW=813.06(C 57 H 16 D 20 N4O)500MW=813.06(C 57 H 16 D 20 N4O)231MW=813.06(C 57 H 16 D 20 N4O)501MW=749.00(C 51 H 16 D 16 N4S)232MW=736.97(C 51 H 12 D 20 N4O)502MW=838.10(C 57 H 19 D 16 N5S)233MW=813.06(C 57 H 16 D 20 N4O)503MW=829.13(C 57 H 16 D 20 N4S)234MW=810.05(C 57 H 19 D 17 N4O)504MW=828.12(C 57 H 17 D 19 N4S)235MW=813.06(C 57 H 16 D 20N4O)505MW=833.15(C 57 H 12 D 24 N4S)236MW=732.94(C 51 H 16 D 16 N4O)506MW=829.13(C 57 H 16 D 20 N4S)237MW=813.06(C 57 H 16 D 20 N4O)507MW=828.12(C 57 H 17 D 19 N4S)238MW=732.94(C 51 H 16 D 16 N4O)508MW=829.13(C 57 H 16 D 20 N4S)239MW=813.06(C 57 H 16 D 20 N4O)509MW=829.13(C 57 H 16 D 20 N4S)240MW=813.06(C 57 H 16 D 20 N4O)510MW=832.15(C 57 H 13 D 23 N4S)241MW=736.97(C 51 H 12 D 20 N4O)511MW=748.00(C 51 H 17 D 15 N4S)242MW=732.94(C 51 H 16 D 16 N4O)512MW=834.16(C 57 H 11 D 25 N4S)243MW=813.06(C 57 H 16 D 20 N4O)513MW=839.08(C 57 H 18 D 16N4OS)244MW=813.06(C 57 H 16 D 20 N4O)514MW=828.12(C 57 H 17 D 19 N4S)245MW=812.06(C 57 H 17 D 17 N4O)515MW=828.12(C 57 H 17 D 19 N4S)246MW=825.03(C 57 H 16 D 18 N4O2)516MW=828.12(C 57 H 17 D 19 N4S)247MW=809.04(C 57 H 20 D 16 N4O)517MW=829.13(C 57 H 16 D 20 N4S)248MW=735.96(C 51 H 13 D 19 N4O)518MW=829.13(C 57 H 16 D 20 N4S)249MW=732.94(C 51 H 16 D 16 N4O)519MW=828.12(C 57 H 17 D 19 N4S)250MW=813.06(C 57 H 16 D 20 N4O)520MW=905.22(C 63 H 20 D 20 N4S)251MW=804.01(C 57 H 25 D 11 N4O)521MW=844.11(C 57 H 13 D 21 N4OS)252MW=733.95(C 51 H 15 D17 N4O)522MW=753.03(C 51 H 12 D 20 N4S)253MW=813.06(C 57 H 16 D 20 N4O)523MW=828.12(C 57 H 17 D 19 N4S)254MW=812.06(C 57 H 17 D 19 N4O)524MW=828.12(C 57 H 17 D 19 N4S)255MW=813.06(C 57 H 16 D 20 N4O)525MW=829.13(C 57 H 16 D 20 N4S)256MW=732.94(C 51 H 16 D 16 N4O)526MW=749.00(C 51 H 16 D 16 N4S)257MW=813.06(C 57 H 16 D 20 N4O)527MW=832.14(C 57 H 13 D 23 N4S)258MW=732.94(C 51 H 16 D 16 N4O)528MW=825.10(C 57 H 20 D 16 N4S)259MW=813.06(C 57 H 16 D 20 N4O)529MW=833.15(C 57 H 12 D 24 N4S)260MW=813.06(C 57 H 16 D 20 N4O)530MW=838.10(C 57 H 19 D16 N5S)261MW=736.97(C 51 H 12 D 20 N4O)531MW=753.03(C 51 H 12 D 20 N4S)262MW=823.02(C 57 H 18 D 16 N4O2)532MW=839.08(C 57 H 18 D 16 N4OS)263MW=813.06(C 57 H 16 D 20 N4O)533MW=829.13(C 57 H 16 D 20 N4S)264MW=813.06(C 57 H 16 D 20 N4O)534MW=829.13(C 57 H 16 D 20 N4S)265MW=817.09(C 57 H 12 D 24 N4O)535MW=833.15(C 57 H 12 D 24 N4S)266MW=736.97(C 51 H 13 D 19 N4O)536MW=829.13(C 57 H 16 D 20 N4S)267MW=809.04(C 57 H 20 D 16 N4O)537MW=824.09(C 57 H 21 D 15 N4S)268MW=736.97(C 51 H 13 D 19 N4O)538MW=828.12(C 57 H 17 D 19 N4S)269MW=732.94(C 51 H 16D 16 N4O)539MW=830.13(C 57 H 15 D 21 N4S)270MW=813.06(C 57 H 16 D 20 N4O)540MW=828.12(C 57 H 17 D 19 N4S)

[0398] Compound number 1H NMR(CDCl3, 300MHz)107.30-7.33 (m, 5H), 7.41-7.42 (m, 3H), 7.75 (dd, 2H), 7.89 (s, 2H), 7.94-7.96 (m, 4H), 8.00-8.03 (m, 2H), 8.11 (d, 2H), 8.30 (d, 1H), 8.55 (dd, 2H)217.46 (d, 1H), 7.55 (d, 1H), 7.60 (dd, 2H), 7.68 (dd, 1H), 7.94 (dd, 2H), 8.19 (d, 1H), 8.41-8.42 (m, 2H)287.49-7.50 (m, 2H), 7.93 (d, 1H), 8.01 (d, 1H), 8.03 (d, 1H), 8.10 (d, 1H), 8.22 (dd, 2H), 8.35-8.36 (m, 2H)387.38 (s, 1H), 7.41-7.43 (m, 4H), 7.75 (dd, 2H), 7.87-7.90 (m, 4H), 7.94-7.96 (m, 2H), 8.00-8.03 (m, 2H), 8.30 (d, 1H), 8.55 (dd, 2H)497.21-7.23 (m, 4H), 7.31-7.39 (m, 3H), 7.41-7.45 (m, 3H), 7.57 (d, 1H), 7.69 (d, 1H), 7.82 (d, 1H), 7.98 (d, 1H), 8.01 (d, 1H), 8.08 (s, 1H), 8.39-8.41 (m, 2H)597.19-7.21 (m, 5H), 7.30 (dd, 2H), 7.34-7.35 (m, 3H), 7.43 (t, 1H), 7.46-7.48 (m, 2H), 7.55 (dd, 2H), 7.77 (s, 1H), 7.89 (s, 1H), 8.10 (s, 1H), 8.35-8.36 (m, 2H)697.19-7.20 (d, 5H), 7.41 (td, 1H), 7.49-7.51 (m, 4H), 7.61 (dd, 1H), 7.73 (t, 1H), 7.94 (s, 1H), 8.01 (d, 1H), 8.08 (s, 1H), 8.11 (dd, 2H), 8.38-8.40 (m, 4H)897.26-7.28 (m, 4H), 7.31 (d, 1H), 7.39 (td, 1H), 7.41-7.43 (m, 2H), 7.49-7.51 (m, 6H), 7.98 (d, 1H), 8.01 (dd, 2H), 8.08 (s, 1H), 8.11 (dd, 1H), 8.36-8.38 (m, 4H)947.40-7.42 (m, 3H), 7.50 (d, 1H), 7.70 (d, 1H), 7.79 (dd, 2H), 8.03 (d, 1H), 8.10 (d, 1H), 8.22 (dd, 1H), 8.35 (m, 2H), 8.40 (s, 1H), 8.55 (d, 1H)1047.20-7.22 (d, 4H), 7.30-7.35 (m, 3H), 7.40-7.43 (m, 5H), 7.50-7.51 (m, 3H), 7.52-7.53 (m, 2H), 7.98 (dd, 1H), 8.01 (s, 1H), 8.10 (d, 1H), 8.25 (d, 1H), 8.36 (dd, 1H), 8.98 (d, 1H)1277.35-7.38 (m, 2H), 7.55 (s, 1H), 7.60 (dd, 2H), 7.94 (dd, 2H), 8.03 (d, 1H), 8.10 (d, 1H), 8.16 (d, 2H), 8.40 (s, 1H), 8.55 (dd, 2H)1487.32-7.39 (m, 2H), 7.41-7.44 (m, 3H), 7.52 (dd, 2H), 7.70 (d, 1H), 7.80 (d, 1H), 7.89-7.90 (m, 2H), 8.18 (s, 1H), 8.26 (dd, 2H), 8.35-8.37 (m, 2H)1637.26-7.28 (m, 3H), 7.30 (d, 1H), 7.34-7.35 (m, 2H), 7.46-7.48 (m, 2H), 7.55 (dd, 2H), 7.70 (d, 1H), 8.10 (s, 1H), 8.14 (dd, 1H), 8.40-8.42 (m, 2H)1797.28-7.30 (m, 4H), 7.38 (dd, 2H), 7.41-7.43 (m, 5H), 7.47 (d, 1H), 7.65 (d, 1H), 7.78 (dd, 1H), 7.90 (d, 1H), 8.01 (d, 1H), 8.08 (s, 1H), 8.11 (d, 1H), 8.36 (dd, 2H)1847.29-7.30 (m, 3H), 7.47 (d, 1H), 7.50-7.52 (m, 2H), 7.66 (d, 1H), 7.77 (s, 1H), 7.80 (d, 1H), 7.89-7.90 (m, 2H), 8.18 (s, 1H), 8.35-8.37 (m, 2H), 8.41 (d, 1H), 8.44 (d, 1H)1877.35 (t, 1H), 7.46 (d, 1H), 7.50-7.52 (m, 4H), 7.50 (dd, 1H), 7.66 (d, 1H), 7.80 (t, 1H), 8.08-8.11 (m, 3H), 8.15 (s, 1H), 8.26 (dd, 2H), 8.35-8.37 (m, 4H), 8.55 (d, 1H)2067.25-7.29 (m, 3H), 7.32 (d, 1H), 7.34-7.35 (m, 2H), 7.47-7.48 (m, 2H), 7.57 (dd, 2H), 8.10 (s, 1H), 8.14 (dd, 1H), 8.40-8.42 (m, 2H)2377.19-7.21 (d, 2H), 7.41 (t, 1H), 7.41-7.44 (m, 3H), 7.49 (s, 1H), 7.52 (dd, 2H), 8.01 (s, 1H), 8.08-8.10 (m, 2H), 8.35-8.37 (m, 4H)2517.19-7.22 (d, 4H), 7.25 (dd, 2H), 7.47 (t, 1H), 7.50-7.52 (m, 4H), 7.55-7.58 (m, 2H), 7.62 (d, 1H), 7.78-7.80 (m, 3H), 7.89-7.90 (m, 2H), 8.11 (s, 1H), 8.16 (dd, 1H), 8.35-8.37 (m, 2H), 8.41-8.42 (m, 2H)2737.35-7.36 (m, 2H), 7.50-7.52 (m, 2H), 7.55-7.58 (m, 2H), 7.61 (dd, 1H), 7.75-7.76 (m, 3H), 7.94 (s, 1H), 8.14 (dd, 1H), 8.35-8.36 (m, 2H), 8.40-8.42 (m, 2H)2817.25 (dd, 4H), 7.60 (dd, 2H), 7.75 (dd, 2H), 7.80 (s, 1H), 7.90 (d, 1H), 7.96 (dd, 2H), 8.10 (d, 1H), 8.35-8.36 (m, 2H)3017.40 (dd, 2H), 7.53 (dd, 1H), 7.93-7.94 (m, 3H), 8.06 (d, 1H), 8.09 (dd, 1H), 8.11 (d, 1H), 8.29 (d, 1H), 8.36-8.37 (m, 4H), 8.40 (s, 1H), 8.55 (d, 1H)3257.25-7.27 (m, 2H), 7.34 (d, 1H), 7.47 (dd, 1H), 8.10 (s, 1H), 8.18 (dd, 1H), 8.35-8.36 (m, 2H), 8.40-8.42 (m, 2H)3387.41-7.43 (m, 4H), 7.49-7.50 (m, 5H), 7.60 (dd, 2H), 7.65 (s, 1H), 7.79 (dd, 2H), 7.96 (dd, 2H), 8.01 (s, 1H), 8.09 (d, 1H), 8.11 (d, 1H), 8.37-8.38 (m, 4H), 8.42 (dd, 2H)4147.41-7.43 (m, 2H), 7.77 (d, 1H7.89 (s, 1H), 7.99 (d, 1H), 8.06 (dd, 1H), 8.34 (s, 1H), 8.36-8.37 (m, 2H), 8.55 (dd, 1H)4207.19-7.20 (m, 4H), 7.28 (d, 1H), 7.33-7.35 (m, 4H), 7.41 (t, 1H), 7.84 (s, 1H), 8.10 (d, 1H), 8.14 (dd, 2H), 8.19-8.22 (m, 3H), 8.35-8.36 (m, 2H), 8.40-8.42 (m, 2H)4627.32-7.33 (m, 3H), 7.49-7.51 (m, 3H), 7.60 (dd, 2H), 7.99 (dd, 2H), 8.01 (d, 1H), 8.08 (s, 1H), 8.11 (d, 1H), 8.36-8.37 (m, 4H)4887.40-7.41 (m, 3H), 7.59-7.61 (m, 4H), 8.02 (d, 1H), 8.10 (d, 1H), 8.18 (dd, 2H), 8.33 (dd, 2H), 8.39 (dd, 2H), 8.49 (dd, 2H)4967.30-7.32 (m, 4H), 7.39-7.41 (m, 2H), 7.57 (dd, 1H), 7.60-7.62 (m, 3H), 7.81 (d, 1H), 8.07 (s, 1H), 8.11 (dd, 1H),8.29 (d, 1H), 8.35-8.36 (m, 2H), 8.40-8.42 (m, 2H), 8.55 (s, 1H)5217.19-7.20 (m, 2H), 7.90 (d, 1H), 8.03 (dd, 1H), 8.10 (dd, 2H), 8.25 (d, 1H), 8.30 (dd, 2H), 8.40 (d, 1H), 8.43 (d, 1H), 8.97 (dd, 2H)5307.25-7.26 (m, 3H), 7.40-7.43 (m, 4H), 7.48-7.49 (m, 2H), 7.55 (d, 1H), 7.58 (dd, 2H), 7.75-7.76 (m, 2H), 7.84 (s, 1H), 8.12 (s, 1H), 8.16 (dd, 1H), 8.37-8.38 (m, 2H), 8.41-8.42 (m, 2H).

[0399] <제조예 3> 화합물 2-2의 제조

[0400]

[0401] 1) 화합물 R1의 제조

[0402] 9H,9'H-3,3'-bicarbazole[R2](20g, 60.16mmol), Bromobenzene[G](9.4g, 60.16mmol), Pd2(dba)3(Tris(dibenzylideneacetone)dipalladium(0))(5.5g, 6.02mmol), XPhos (5.7g, 12.03mmol), K2CO3(12.5g, 90.24mmol) were dissolved in 300mL of 1,4-dioxane and stirred at a reaction temperature of 110℃ for 6 hours. After completion of the reaction, the solution was cooled to room temperature and the solvent was removed using a rotary evaporator. The concentrated solution was dissolved in an excess of MC, extracted with H2O, and the organic layer was dried over anhydrous MgSO4 and filtered through silica gel. The solvent was removed from the residue using a rotary evaporator and EA was recrystallized to obtain 20 g of compound R1 as a white solid with a yield of 81%.

[0403] 2) Preparation of compound 2-2

[0404] Compound R1 (20 g, 49.02 mmol), 4-bromo-1,1'-biphenyl[H](12 g, 49.02 mmol), Pd2(dba)3(4.5 g, 4.9 mmol), P(tBu)3(Tri-tert-butylphosphine) (1.9 g, 9.81 mmol), NaOtBu(Sodium tert-butoxide) (9.5 g, 98.04 mmol) were dissolved in 300 mL of toluene and stirred at a reaction temperature of 110 ℃ for 15 hours. After the reaction was completed, the solution was cooled to room temperature and the solvent was removed using a rotary evaporator. The concentrated solution was dissolved in an excess of MC, extracted with H2O, and the organic layer was dried over anhydrous MgSO4 and filtered through silica gel. The solvent was removed from the residue using a rotary evaporator, and CB was recrystallized to obtain 17 g of compound 2-2 as a white solid in a yield of 63%.

[0405] The final compound of Table 5 below was synthesized by the same method as in Manufacturing Example 3, except that Intermediate R2, Intermediate H, and Intermediate G of Table 5 below were used instead of Compound [R2], Compound [H], and Compound [G] in Manufacturing Example 3 above.

[0406]

[0407]

[0408] <Manufacturing Example 4> Preparation of compound 2-42

[0409]

[0410] 9-([1,1'-biphenyl]-4-yl)-9'-phenyl-9H,9'H-3,3'-bicarbazole[I](20 g, 35.74 mmol) was dissolved in 200 mL of D6-Benzene, and then Triflic acid (22 mL, 250.18 mmol) was slowly added. The reaction temperature was raised to 60 ℃, and the mixture was stirred for 1 hour. Then, a solution of triethylamine (35 mL, 250.18 mmol) dissolved in 50 mL of D2O was added to neutralize the mixture. Excess EA was added to perform extraction, and the organic layer was dried over anhydrous MgSO4 and filtered through silica gel. The solvent was removed from the filtrate using a rotary evaporator to obtain 19 g of compound 2-42 as a white solid in a yield of 92% (100% D substitution rate).

[0411] The final compound of Table 6 below was synthesized by the same method as in Manufacturing Example 4, except that Intermediate I of Table 6 below was used instead of Compound [I] in Manufacturing Example 4 above.

[0412]

[0413]

[0414] The compounds synthesized in the above manufacturing examples 3 and 4 were analyzed by FD-mass spectrometry and 1The synthesis of the desired compound was confirmed through H-NMR. The measured values ​​of FD-mass spectrometry (FD-MS: Field desorption mass spectrometry) are shown in Table 7 below. 1 The measured values ​​of H NMR (CDCl3, 300 MHz) are listed in Table 8 below.

[0415] Compound number FD-MS Compound number FD-MS2-1 m / z = 484.60 (C 36 H 24 N2)2-81m / z=484.60(C 36 H 24 N2)2-2m / z=560.70(C 42 H 28 N2)2-82m / z=560.70(C 42 H 28 N2)2-3m / z=560.70(C 42 H 28 N2)2-83m / z=560.70(C 42 H 28 N2)2-4m / z=636.80(C 48 H 32 N2)2-84m / z=560.70(C 42 H 28 N2)2-5m / z=636.80(C 48 H 32 N2)2-85m / z=560.70(C 42 H 28 N2)2-6m / z=636.80(C 48 H 32 N2)2-86m / z=560.70(C 42 H 28 N2)2-7m / z=634.78(C 48 H 30 N2)2-87m / z=636.80(C 48 H 32 N2)2-8m / z=636.80(C 48 H 32 N2)2-88m / z=636.80(C 48 H 32 N2)2-9m / z=575.68(C 42 H 26 N2)2-89m / z=636.80(C48 H 32 N2)2-10m / z=650.78(C 48 H 30 N2O)2-90m / z=636.80(C 48 H 32 N2)2-11m / z=636.80(C 48 H 32 N2)2-91m / z=560.70(C 42 H 28 N2)2-12m / z=636.80(C 48 H 32 N2)2-92m / z=636.80(C 48 H 32 N2)2-13m / z=712.90(C 54 H 36 N2)2-93m / z=636.80(C 48 H 32 N2)2-14m / z=650.78(C 48 H 30 N2O)2-94m / z=636.80(C 48 H 32 N2)2-15m / z=712.90(C 54 H 36 N2)2-95m / z=636.80(C 48 H 32 N2)2-16m / z=712.90(C 54 H 36 N2)2-96m / z=636.80(C 48 H 32 N2)2-17m / z=636.80(C 48 H 32 N2)2-97m / z=558.68(C 42 H 26 N2)2-18m / z=650.78(C 48 H 30 N2O)2-98m / z=712.90(C 54 H 36 N2)2-19m / z=712.90(C 54 H 36 N2)2-99m / z=498.58(C 36 H 22 N2O)2-20m / z=710.88(C 54 H 34N2)2-100m / z=712.90(C 54 H 36 N2)2-21m / z=636.80(C 48 H 32 N2)2-101m / z=484.60(C 36 H 24 N2)2-22m / z=636.80(C 48 H 32 N2)2-102m / z=560.70(C 42 H 28 N2)2-23m / z=636.80(C 48 H 32 N2)2-103m / z=498.58(C 36 H 22 N2O)2-24m / z=590.74(C 42 H 26 N2S)2-104m / z=560.70(C 42 H 28 N2)2-25m / z=788.99(C 60 H 40 N2)2-105m / z=558.68(C 42 H 26 N2)2-26m / z=712.90(C 54 H 36 N2)2-106m / z=560.70(C 42 H 28 N2)2-27m / z=788.99(C 60 H 40 N2)2-107m / z=636.80(C 48 H 32 N2)2-28m / z=712.90(C 54 H 36 N2)2-108m / z=712.90(C 54 H 36 N2)2-29m / z=788.99(C 60 H 40 N2)2-109m / z=636.80(C 48 H 32 N2)2-30m / z=712.90(C 54 H 36 N2)2-110m / z=636.80(C 48 H 32 N2)2-31m / z=726.88(C54 H 34 N2O)2-111m / z=560.70(C 42 H 28 N2)2-32m / z=560.70(C 42 H 28 N2)2-112m / z=636.80(C 48 H 32 N2)2-33m / z=636.80(C 48 H 32 N2)2-113m / z=636.80(C 48 H 32 N2)2-34m / z=636.80(C 48 H 32 N2)2-114m / z=560.70(C 42 H 28 N2)2-35m / z=712.90(C 54 H 36 N2)2-115m / z=574.68(C 42 H 26 N2O)2-36m / z=636.80(C 48 H 32 N2)2-116m / z=484.60(C 36 H 24 N2)2-37m / z=712.90(C 54 H 36 N2)2-117m / z=560.70(C 42 H 28 N2)2-38m / z=712.90(C 54 H 36 N2)2-118m / z=560.70(C 42 H 28 N2)2-39m / z=574.68(C 42 H 26 N2O)2-119m / z=560.70(C 42 H 28 N2)2-40m / z=788.99(C 60 H 40 N2)2-120m / z=636.80(C 48 H 32 N2)2-41m / z=508.75(C 36 D 24 N2)2-121m / z=508.75(C 36 D24 N2)2-42m / z=587.86(C 42 HD 27 N2)2-122m / z=588.87(C 42 D 28 N2)2-43m / z=588.75(C 42 D 28 N2)2-123m / z=588.87(C 42 D 28 N2)2-44m / z=666.98(C 48 H2D 30 N2)2-124m / z=586.86(C 42 H2D 26 N2)2-45m / z=668.98(C 48 D 32 N2)2-125m / z=588.87(C 42 D 28 N2)2-46m / z=665.98(C 48 H3D 29 N2)2-126m / z=588.87(C 42 D 28 N2)2-47m / z=662.98(C 48 H2D 28 N2)2-127m / z=588.87(C 42 D 28 N2)2-48m / z=668.98(C 48 D 32 N2)2-128m / z=666.98(C 48 H2D 30 N2)2-49m / z=600.84(C 42 D 26 N2O)2-129m / z=665.98(C 48 H3D 29 N2)2-50m / z=678.98(C 48 H2D 28 N2)2-130m / z=668.98(C 48 D 32 N2)2-51m / z=668.98(C 48 D 32 N2)2-131m / z=588.87(C 42 D 28 N2)2-52m / z=667.98(C 48 HD31 N2)2-132m / z=664.98(C 48 H4D 28 N2)2-53m / z=748.12(C 54 HD 35 N2)2-133m / z=663.96(C 48 H5D 27 N2)2-54m / z=680.96(C 48 D 30 N2O)2-134m / z=668.98(C 48 D 32 N2)2-55m / z=747.10(C 54 H2D 34 N2)2-135m / z=667.98(C 48 HD 31 N2)2-56m / z=739.05(C 54 H 10 D 26 N2)2-136m / z=585.87(C 42 H3D 25 N2)2-57m / z=668.98(C 48 D 32 N2)2-137m / z=582.83(C 42 H2D 24 N2)2-58m / z=677.98(C 48 H3D 27 N2O)2-138m / z=749.12(C 54 D 36 N2)2-59m / z=746.10(C 54 H3D 33 N2)2-139m / z=518.71(C 36 H2D 20 N2O)2-60m / z=744.08(C 54 HD 33 N2)2-140m / z=748.12(C 54 HD 35 N2)2-61m / z=668.98(C 48 D 32 N2)2-141m / z=508.75(C 36 D 24 N2)2-62m / z=666.98(C 48 H2D 30 N2)2-142m / z=588.87(C42 D 28 N2)2-63m / z=667.98(C 48 HD 31 N2)2-143m / z=520.72(C 36 D 22 N2O)2-64m / z=614.89(C 42 H2D 24 N2S)2-144m / z=583.84(C 42 H5D 23 N2)2-65m / z=826.22(C 60 H3D 37 N2)2-145m / z=583.84(C 42 HD 25 N2)2-66m / z=747.10(C 54 H2D 34 N2)2-146m / z=588.87(C 42 D 28 N2)2-67m / z=829.24(C 60 D 40 N2)2-147m / z=668.98(C 48 D 32 N2)2-68m / z=746.10(C 54 H3D 33 N2)2-148m / z=746.12(C 54 H3D 33 N2)2-69m / z=829.24(C 60 D 40 N2)2-149m / z=665.97(C 48 H3D 29 N2)2-70m / z=747.10(C 54 H2D 34 N2)2-150m / z=668.98(C 48 D 32 N2)2-71m / z=759.09(C 54 H2D 32 N2)2-151m / z=587.87(C 42 HD 27 N2)2-72m / z=588.75(C 42 D 28 N2)2-152m / z=668.98(C 48 D 32 N2)2-73m / z=668.98(C48 D 32 N2)2-153m / z=666.98(C 48 H2D 30 N2)2-74m / z=668.98(C 48 D 32 N2)2-154m / z=588.87(C 42 D 28 N2)2-75m / z=749.12(C 54 D 36 N2)2-155m / z=596.82(C 42 H4D 22 N2O)2-76m / z=666.98(C 48 H2D 30 N2)2-156m / z=508.75(C 36 D 24 N2)2-77m / z=824.21(C 60 H5D 35 N2)2-157m / z=588.87(C 42 D 28 N2)2-78m / z=829.24(C 60 D 40 N2)2-158m / z=586.86(C 42 H2D 26 N2)2-79m / z=598.83(C 42 H2D 24 N2)2-159m / z=588.87(C 42 D 28 N2)2-80m / z=862.22(C 60 H3D 37 N2)2-160m / z=668.99(C 48 D 32 N2)

[0416] 화합물번호 1<h2 style=";text-align:left;direction:ltr">H NMR(CDCl3, 300MHz)2-27.20-7.24 (m, 4H), 7.30-7.33 (m, 5H), 7.41-7.42 (m, 3H), 7.75 (dd, 2H), 7.89 (s, 2H), 7.94-7.96 (m, 4H), 8.00-8.03 (m, 2H), 8.11 (d, 2H), 8.19 (d, 1H), 8.30 (d, 1H), 8.55 (dd, 2H)2-47.21-7.23 (m, 3H), 7.30-7.33 (m, 6H), 7.38 (s, 1H), 7.41-7.43 (m, 4H), 7.75 (dd, 2H), 7.87-7.90 (m, 4H), 7.94-7.96 (m, 4H), 8.00-8.03 (m, 2H), 8.11 (d, 2H), 8.19 (d, 1H), 8.30 (d, 1H), 8.55 (dd, 2H)2-157.19-7.21 (m, 5H), 7.25-7.27 (m, 3H), 7.30-7.33 (m, 6H), 7.38 (s, 1H), 7.41-7.43 (m, 4H), 7.75 (dd, 2H), 7.87-7.90 (m, 4H), 7.94-7.96(m, 4H), 8.00-8.03 (m, 2H), 8.11 (d, 2H), 8.19 (d, 1H), 8.30 (d, 1H), 8.55 (dd, 2H)2-317.19-7.21 (m, 3H), 7.23-7.25 (m, 3H), 7.30-7.32 (m, 6H), 7.41-7.43 (m, 4H), 7.75 (dd, 2H), 7.87-7.90 (m, 4H), 7.94-7.96 (m, 4H), 8.00-8.03 (m, 2H), 8.11 (d, 2H), 8.19 (d, 1H), 8.25 (s, 1H), 8.30 (d, 1H), 8.55 (dd, 2H)2-42중수소 치환율 100%로<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> H NMR peak 없음2-51중수소 치환율 100%로<h2 style=";text-align:left;direction:ltr"> 1No H NMR peak2-557.49 (s, 1H), 8.52 (s, 1H)2-687.52 (s, 1H), 7.66 (m, 2H)2-867.16 (t, 2H), 7.23-7.26 (m, 3H), 7.35-7.37 (m, 4H), 7.40-7.41 (m, 5H), 7.49 (dd, 2H), 7.65 (dd, 2H), 7.75 (d, 2H), 7.91-7.95 (m, 4H), 7.99 (dd, 2H), 8.56 (dd, 2H)2-1077.19 (t, 2H), 7.20-7.21 (m, 4H), 7.23-7.26 (m, 3H), 7.35-7.37 (m, 4H), 7.40-7.41 (m, 5H), 7.49 (dd, 2H), 7.65 (dd, 2H), 7.75 (d, 2H), 7.91-7.95 (m, 4H), 7.99 (dd, 2H), 8.56 (dd, 2H)2-1177.16 (t, 2H), 7.23-7.26 (m, 3H), 7.35-7.37 (m, 4H), 7.40-7.41 (m, 5H), 7.49 (dd, 2H), 7.65 (dd, 2H), 7.75 (d, 2H), 7.81 (s, 1H), 7.91-7.95 (m, 3H), 7.99 (dd, 2H), 8.56 (dd, 2H)2-123 with 100% deuterium substitution rate 1 No H NMR peak2-1337.21-7.23 (m, 3H), 7.38 (s, 1H), 7.55 (m, 2H)2-1357.50 (s, 1H)2-1447.16 (s, 1H), 7.29 (m, 2H)2-1517.55 (s, 1H)2-1557.26 (s, 1H), 7.52 (m, 2H)

[0417] <Experimental Example>

[0418] Experimental Example 1

[0419] (1) Fabrication of organic light-emitting devices

[0420] A glass substrate coated with a 1,500 Å thick ITO film was ultrasonically cleaned in distilled water. After the distilled water cleaning, it was ultrasonically cleaned with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UVO for 5 minutes in a UV cleaner. The substrate was then transferred to a plasma cleaner (PT), where it was 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.

[0421] A common layer, a hole injection layer 2-TNATA (4,4′,4′′-Tris[2-naphthyl (phenyl)amino]triphenylamine) and a hole transport layer NPB (N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine), were formed on the ITO transparent electrode (anode).

[0422] On top of that, a light-emitting layer was thermally vacuum deposited as follows. The light-emitting layer used the compounds listed in Table 9 as a host, and Ir(mppy)3Tris[2-(p-tolyl)pyridine]iridium(III) as a green phosphorescent dopant. The host was doped with 7% Ir(mppy)3 and deposited to a thickness of 360Å. Then, BCP was deposited to a thickness of 60Å as a hole-blocking layer, and Alq3 was deposited to a thickness of 200Å as an electron-transporting layer thereon. Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron-transporting layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1200Å on the electron injection layer to form a cathode, thereby manufacturing an organic electroluminescent device.

[0423] Meanwhile, all organic compounds required for OLED device production are 10 for each material. -8 ~10 -6 It was purified by vacuum sublimation under 10 torr and used in OLED production.

[0424] The structures of the compounds used in Comparative Examples 1 to 7 are as follows.

[0425]

[0426] 2) Driving voltage and luminous efficiency of organic field effect devices

[0427] The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured using M7000 from Max Science, and the standard luminance was determined to be 6,000 cd / m using the life measurement equipment (M6000) manufactured by Max Science based on the measurement results. 2 At that time, T90 was measured.

[0428] The results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifespan of the organic light-emitting device manufactured according to the present invention are as shown in Table 9 below.

[0429] Compound Driving Voltage (V) Luminous Efficiency (cd / A) Color Coordinate Lifespan (T90) Comparative Example 1 Ref. 15.49 30.5 Green 15 Comparative Example 2 Ref. 25.60 29.7 Green 65 Comparative Example 3 Ref. 35.50 25.5 Green 30 Comparative Example 4 Ref. 45.68 27.6 Green 25 Comparative Example 5 Ref. 55.74 28.8 Green 59 Comparative Example 6 Ref. 65.66 30.5 Green 65 Comparative Example 7 Ref. 75.86 26.8 Green 48 Example 1 104.88 40.5 Green 90 Example 2 214.25 46.8Green133Example 3284.2947.0Green128Example 4384.9241.2Green98Example 5494.4545.0Green135Example 6594.3047.1Green125Example 7694.2844.6Green130Example 8894.2548.5Green159Example 9944.1848.0Green141Example 101044.9040.1Green85Example 111274.3345.9Green120Example 121484.5545.8Gr een125Example131634.4046.2Green119Example141794.2047.2Green133Example151844.2148.9Green138Example161874.2847.0Green129Example172064.5240.8Green88Example182374.1548.1Green150Example192514.2747.2Green146Example202734.3245.5Green134Example212814.6240.8Green99Example223014 .5843.2Green96Example233254.3146.8Green129Example243384.7140.5Green118Example254144.3345.9Green122Example264204.3945.7Green132Example274624.2547.6Green136Example284884.2246.2Green134Example294964.2946.8Green140Example305214.4441.8Green121Example315304.6341.9Green100

[0430] Looking at the results in Table 9 above, it can be seen that the driving voltage of the examples using the heterocyclic compound according to the present invention is lower, the luminous efficiency is higher, and the lifespan is significantly improved compared to Comparative Examples 1 to 7.

[0431] This is because deuterium is heavier than light hydrogen and has lower vibrational energy, so compounds substituted with deuterium show higher lifetime characteristics in devices than compounds that are not substituted. This effect is maximized in the case of the hole transfer unit, and the effect is minimal in the electron transfer unit. This is expected to be because holes have lower stability than electrons due to the vibrational energy of molecules and intermolecular interactions. Therefore, it can be seen that the compound of Comparative Example 2 (Ref. 2), in which the deuterium substitution range is less than that of the compound of the present invention and deuterium is substituted in the trizaine region, which is the electron transfer unit, shows lower characteristics in devices than the compound of the present invention.

[0432] In addition, the expansion of the linker between dibenzofuran / dibenzothiophene and carbazole delocalizes the HOMO electron cloud, thereby stabilizing the HOMO region and facilitating charge transfer. Therefore, the compounds of the present invention exhibited superior device performance compared to compounds without a linker between dibenzofuran / dibenzothiophene and carbazole. Specifically, Ref. 7 used in Comparative Example 7 did not contain a linker compared to Compound 10 used in Example 1, and it was confirmed that the driving voltage increased, the luminous efficiency decreased, and the lifespan was reduced by about 50% compared to Example 1.

[0433] In addition, Ref. 1 used in Comparative Example 1 does not include deuterium in the linker and carbazole structure, and Ref. 2 used in Comparative Example 2 not only does not include deuterium in the carbazole structure, but also includes deuterium in the azine group. In addition, Ref. 3 of Comparative Example 3 does not include deuterium in the linker, and Ref. 4 and Ref. 5 used in Comparative Examples 4 and 5 do not satisfy the deuterium feature of the present invention as well as the linker configuration between the core structure and the carbazole group. Finally, Ref. 6 of Comparative Example 6 differs from the present invention in that it includes a linker between the azine group and the core structure as well as the deuterium feature of the present invention.

[0434] That is, when an organic light-emitting device is manufactured using a compound that does not satisfy all the configurations of the present invention, it cannot provide excellent performance in terms of driving voltage, luminous efficiency, and lifespan, whereas it was confirmed that an organic light-emitting device manufactured using the heterocyclic compound of the present invention obtains significantly improved performance.

[0435]

[0436] Experimental Example 2

[0437] 1) Fabrication of organic light-emitting devices

[0438] A glass substrate coated with a 1,500 Å thick ITO film was ultrasonically cleaned in distilled water. After the distilled water cleaning, it was ultrasonically cleaned with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UVO for 5 minutes in a UV cleaner. Afterwards, the substrate was transferred to a plasma cleaner (PT), where it was 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.

[0439] A common layer, a hole injection layer 2-TNATA (4,4′,4′′-Tris[2-naphthyl (phenyl)amino]triphenylamine) and a hole transport layer NPB (N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine), were formed on the ITO transparent electrode (anode).

[0440] On top of that, a light-emitting layer was thermally vacuum deposited as follows. The light-emitting layer was pre-mixed with one heterocyclic compound of Chemical Formula 1 and one compound of Chemical Formula 2, as shown in Table 10 below, as a host, and then deposited at 360Å in one hole, and the green phosphorescent dopant was doped with Ir(mppy)3 at 7% of the thickness of the light-emitting layer deposition and deposited. After that, 60Å of BCP was deposited as a hole-blocking layer, and 200Å of Alq3 was deposited as an electron-transporting layer thereon. Finally, lithium fluoride (LiF) was deposited with a thickness of 10Å on the electron-transporting layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited with a thickness of 1,200Å on the electron injection layer to form a cathode, thereby manufacturing an organic electroluminescent device.

[0441] Meanwhile, all organic compounds required for OLED device production are 10 for each material. -8 ~10 -6 It was purified by vacuum sublimation under 10 torr and used in OLED production.

[0442] 2) Driving voltage and luminous efficiency of organic field effect devices

[0443] The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured using M7000 from Max Science, and the standard luminance was determined to be 6,000 cd / m using the life measurement equipment (M6000) manufactured by Max Science based on the measurement results. 2 At that time, T90 was measured.

[0444] The results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifespan of the organic light-emitting device manufactured according to the present invention were as shown in Table 10 below.

[0445] Compound ratio (weight ratio) Driving voltage (V) Luminous efficacy (cd / A) Color coordinate Lifespan (T90) Example 32892-21:13.5860.8Green200 Example 331:23.6163.5Green208 Example 341:33.8365.8Green225 Example 35282-41:13.6060.1Green181 Example 361:23.6362.2Green192 Example 371:33.7963.5Green225 Example 382372-151:13.7562.1Green275 Example 391:23.8063.3Green299 Example 4 01:33.8664.8Green311Example415302-311:14.0549.2Green105Example421:24.1650.5Green135Example431:34.2952.2Green160Example441272-511:13.8065.1Green278Example451:23.8666.8Green295Example461:33.9167.0Green333Example471792-551:13.6865.2Green258Example481:23.7766.3Green282Example491:33.9068.1G reen326Example 50212-861:13.4769.6Green185Example 511:23.5070.1Green204Example 521:33.5271.8Green220Example 53692-1171:13.7060.1Green169Example 541:23.7662.8Green185Example 551:33.8165.0Green201Example 565212-681:14.1550.5Green150Example 571:24.2852.3Green155Example 581:34.3055.5Green170Example 5916 32-1231:14.0563.8Green151Example601:24.2565.2Green161Example611:34.3066.1Green179Example62942-1331:13.5670.8Green308Example631:23.6075.2Green316Example641:33.6978.7Green333Example654622-1351:13.6662.9Green322Example661:23.8263.6Green360Example671:33.9969.0Green388Example681872-1441:13.6859.7Green318Example 691:23.6960.3Green359Example 701:33.7662.2Green397.

[0446] Comparing the results of Tables 9 and 10 above, it was confirmed that when the heterocyclic compound of the present invention was used alone, the driving voltage, luminous efficiency, and lifespan were all significantly improved when the compound of Chemical Formula 2 was used in combination.

[0447] From the above results, it can be expected that an exciplex phenomenon will occur when the heterocyclic compound of chemical formula 1 and the compound of chemical formula 2 are simultaneously included.

[0448] The exciplex phenomenon is a phenomenon in which energy is released in the size of the HOMO energy level of the donor (p-host) and the LUMO energy level of the acceptor (n-host) due to the exchange of electrons between two molecules. When the exciplex phenomenon occurs between two molecules, reverse intersystem crossing (RISC) occurs, and this can increase the internal quantum efficiency of fluorescence emission to 100%.

[0449] When a donor (p-host) with good hole transport capability and an acceptor (n-host) with good electron transport capability are used as hosts for the light-emitting layer, holes are injected into the p-host and electrons are injected into the n-host. At this time, excitons are not quenched due to intermolecular electron exchange, and the lifetime of excitons that can have energy increases. As a result, the overall current efficiency is improved and the lifespan of the device can be improved. In the present invention, it was confirmed that when the compound of the above chemical formula 1 acts as an acceptor and the compound of the above chemical formula 2 acts as a donor and they are used together as a host for the light-emitting layer, excellent device characteristics are exhibited.

Claims

1. A heterocyclic compound of the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, Y is O or S, X1 to X3 are each independently N or CH, and at least one is N, Ar1 and Ar2 are each independently an aryl group having C6 to C60; or a heteroaryl group having C2 to C60; L is an arylene group of C10 to C30 substituted with deuterium, m is an integer of 1 to 3, and when it is 2 or more, L is the same or different, R1 to R8 are each independently hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group, or adjacent groups are bonded to each other to form a ring. At least one of R1 to R8 is deuterium, D is deuterium, and n is an integer from 0 to 6.

2. In claim 1, the chemical formula 1 includes structures of the following chemical formulas A to C, wherein the deuterium substitution rate of the chemical formula A is 0% to 100%, the deuterium substitution rate of the chemical formula B is 0%, and the deuterium substitution rate of the chemical formula C is more than 0% and less than or equal to 100%, a heterocyclic compound: [Chemical Formula A] [Chemical Formula B] [Chemical formula C] In the above chemical formulas A to C, The definitions of Y, X1 to X3, Ar1, Ar2, L, m and R1 to R8 are the same as those in the chemical formula 1 above, One of D1 to D8 is a group represented by the chemical formula B, the other is a group represented by the chemical formula C, and the remainder is hydrogen; or deuterium, is the position where the above chemical formulas B and C are bonded to the above chemical formula A.

3. In claim 1, the chemical formula 1 is a heterocyclic compound represented by the following chemical formula 1-1 or 1-2: [Chemical Formula 1-1] [Chemical Formula 1-2] In the above chemical formulas 1-1 and 1-2, The definition of each substituent is the same as that in the chemical formula 1 above.

4. In claim 1, L is a heterocyclic compound represented by any one of the following structural formulas: In the above structural formula, is the position that binds to the chemical formula 1 above, D is deuterium, a1, a2, a3, b1, b3, b6 and c3 are integers from 0 to 4, respectively. a4, a6 and b2 are integers from 0 to 3, b4, b5, c2, c5 and c6 are integers from 0 to 5, respectively. a5 is an integer from 0 to 2, a1+b1, a2+b2+c2, a3+b3+c3, a4+b4, a5+b5+c5, and a6+b6+c6 are each integers greater than or equal to 1.

5. A heterocyclic compound according to claim 1, wherein Ar1 is a C6 to C20 aryl group, and Ar2 is a C6 to C20 aryl group; or a C2 to C20 heteroaryl group.

6. A heterocyclic compound according to claim 1, wherein the deuterium substitution rate of the chemical formula 1 is 10% to 90%.

7. In claim 1, the chemical formula 1 is a heterocyclic compound represented by any one of the following compounds:

8. An organic light-emitting device comprising a first electrode; a second electrode; and at least one organic layer provided between the first electrode and the second electrode, An organic light-emitting device, wherein at least one of the organic layers comprises at least one heterocyclic compound according to any one of claims 1 to 7.

9. An organic light-emitting device according to claim 8, wherein the organic layer includes a light-emitting layer, and the light-emitting layer includes at least one heterocyclic compound.

10. An organic light-emitting device according to claim 9, wherein the light-emitting layer comprises a host, and the host comprises at least one heterocyclic compound.

11. In claim 8, an organic light-emitting device wherein the organic layer including the heterocyclic compound further includes a compound of the following chemical formula 2: [Chemical formula 2] In the above chemical formula 2, At least one of R11 to R18 is a substituted or unsubstituted carbazole group, or adjacent groups of R11 to R18 combine to form a substituted or unsubstituted heterocycle, The remainder of R11 to R18 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted phosphine oxide group; or a substituted or unsubstituted amine group, L11 is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group, l11 is an integer from 1 to 3, and if it is 2 or more, the substituents in the parentheses are the same or different, Ar11 is a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

12. In claim 11, the chemical formula 2 is an organic light-emitting device represented by the following chemical formula 2-1 or 2-2: [Chemical Formula 2-1] [Chemical Formula 2-2] In the above chemical formulas 2-1 and 2-2, The definitions of L11, l11 and Ar11 are the same as those in the chemical formula 2 above, R21 and R22 are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted phosphine oxide group; or a substituted or unsubstituted amine group, L12 and L13 are each independently a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group, Ar12 and Ar13 are each independently a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group, r21 and r22 are integers from 1 to 7, respectively. r23 is an integer from 1 to 6, r24 is an integer from 1 to 4, l12 and l13 are integers from 1 to 3, respectively. When r21, r22, r23, r24, l12, and l13 are each 2 or more, the substituents in parentheses are the same or different.

13. In claim 11, an organic light-emitting device wherein the chemical formula 2 is selected from the following compounds:

14. A heterocyclic compound according to any one of claims 1 to 7; and A composition for an organic layer of an organic light-emitting device comprising a compound of the following chemical formula 2: [Chemical formula 2] In the above chemical formula 2, At least one of R11 to R18 is a substituted or unsubstituted carbazole group, or adjacent groups of R11 to R18 combine to form a substituted or unsubstituted heterocycle, The remainder of R11 to R18 is hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted phosphine oxide group; or a substituted or unsubstituted amine group, L11 is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group, l11 is an integer from 1 to 3, and if it is 2 or more, the substituents in the parentheses are the same or different, Ar11 is a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

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