CN112110928A

CN112110928A - Organic electroluminescent compounds and multi-component host materials and organic electroluminescent devices comprising the same

Info

Publication number: CN112110928A
Application number: CN202011041359.5A
Authority: CN
Inventors: M-J·李; D-H·文; H-R·康; H-J·康; C-S·金; N-K·金; Y－J·曹; H-J·权; K-J·李; B·金; Y-J·都; S-H·李
Original assignee: Rohm and Haas Electronic Materials Korea Ltd
Current assignee: Rohm and Haas Electronic Materials Korea Ltd
Priority date: 2013-12-18
Filing date: 2014-12-18
Publication date: 2020-12-22
Anticipated expiration: 2034-12-18
Also published as: TW201533038A; CN112110928B; KR20150071624A; JP6683609B2; CN105794010A; JP2017503338A; KR20150071685A; KR101712808B1; CN105794010B

Abstract

The present disclosure relates to organic electroluminescent compounds and multi-component host materials and organic electroluminescent devices comprising the same. By using the organic electroluminescent compounds according to the present disclosure, the organic electroluminescent device may have a significantly improved lifetime together with a low driving voltage and excellent current and power efficiency.

Description

Organic electroluminescent compounds and multi-component host materials and organic electroluminescent devices comprising the same

The patent application of the invention is a divisional application of an invention patent application with the international application number of PCT/KR2014/012547, the international application date of 2014, 12 and 18, and the application number of 201480065903.6 entering the Chinese national stage, namely an organic electroluminescent compound, a multi-component host material and an organic electroluminescent device containing the organic electroluminescent compound.

Technical Field

The present disclosure relates to organic electroluminescent compounds and multi-component host materials and organic electroluminescent devices comprising the same.

Background

An Electroluminescent (EL) device is a self-luminous device, which is advantageous in that it provides a wide viewing angle, a large contrast ratio, and a fast response time. Organic EL devices were originally developed by Eastman Kodak for the first time by using small aromatic diamine molecules and aluminum complexes as materials for forming a light emitting layer [ application physics promulgation (appl. phys. lett.)51,913,1987 ].

The most important factor determining the light emitting efficiency in the organic EL device is a light emitting material. Heretofore, fluorescent materials have been widely used as light emitting materials. However, in view of the mechanism of electroluminescence, since phosphorescent materials theoretically enhance the luminous efficiency four (4) times as compared with fluorescent materials, phosphorescent light-emitting materials have been widely studied. Iridium (III) complexes have been widely known as phosphorescent materials, including bis (2- (2' -benzo)Thienyl) -pyridinato-N, C-3') (Acetylacetonate) iridium ((acac) Ir (btp)₂) Tris (2-phenylpyridine) iridium (Ir (ppy)₃) And iridium bis (4, 6-difluorophenylpyridinato-N, C2) picolinate (Firpic) as red, green and blue light-emitting materials, respectively.

Currently, 4,4'-N, N' -dicarbazole-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Recently, Pioneer (japan) et al developed a high-performance organic EL device using Bathocuproine (BCP) and bis (2-methyl-8-quinoline) (4-phenylphenol) aluminum (III) (BAlq) or the like as host materials, which are called hole blocking materials.

Although conventional materials provide good luminescent characteristics, they have the following disadvantages: (1) due to its low glass transition temperature and poor thermal stability, its degradation may occur in vacuum during high temperature deposition processes. (2) The power efficiency of an organic EL device is given by [ (pi/voltage) × current efficiency ], and is inversely proportional to the voltage. Although organic EL devices containing phosphorescent host materials provide higher current efficiencies (cd/a) than organic EL devices containing fluorescent materials, significantly higher drive voltages are necessary. Therefore, there is no advantage in terms of power efficiency (lm/W). (3) Further, the organic EL device has a short lifetime, and improvement in luminous efficiency is still required.

Korean patent application laid-open No. 10-2010-0105501 discloses a compound for an organic electroluminescent device in which one of nitrogen atoms of a biscarbazole is substituted with a quinoline via a phenylene group. However, it does not disclose a compound in which one of the nitrogen atoms of the biscarbazole is substituted with a naphthyridine directly or via a linker, or a compound in which one of the nitrogen atoms of the biscarbazole is substituted with a quinolyl directly or via a heteroarylene group.

Disclosure of Invention

Technical problem

An object of the present disclosure is to provide an organic electroluminescent compound that can provide an organic electroluminescent device showing a long lifetime, a low driving voltage, and excellent current and power efficiency, and a multi-component host material and an organic electroluminescent device comprising the same.

Solution to the problem

The present inventors found that the above object can be achieved by an organic electroluminescent compound represented by the following formula 1.

Wherein L is₁Represents a single bond, a substituted or unsubstituted (3-to 30-membered) heteroarylene group, or a substituted or unsubstituted (C6-C30) arylene group;

X₁represents-NR₁-、-CR₂R₃-, -O-or-S-;

X₂to X₆Each independently represents-CR₄-or-N-;

Ar₁represents hydrogen, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (3-to 30-membered) heteroaryl;

with the proviso that when X₂is-N-or L₁Is not a substituted or unsubstituted (C6-C30) arylene and Ar₁Is not hydrogen;

Y₁to Y₄And Y₁₃To Y₁₆Each independently represents-N-or-CR₅-；

Y₅To Y₁₂Each independently represent

-N-or-CR₆-；

R₁To R₃Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 30-membered) heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, or substituted or unsubstituted (3-to 7-membered) heterocycloalkyl;

R₄to R₆Each independently represents hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-to 7-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 30-membered) heteroaryl, or substituted or unsubstituted di (C6-C30) arylamino; or may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (3-to 30-membered) mono-or polycyclic alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;

each of the heteroaryl (ene) and heterocycloalkyl independently contains at least one heteroatom selected from B, N, O, S, P (═ O), Si, and P; and

a and b each independently represent 0 or 1.

The invention has the advantages of

The organic electroluminescent compounds and multi-component host materials of the present disclosure can provide organic electroluminescent devices having low driving voltages, excellent current and power efficiencies, and significantly improved lifetimes.

Detailed Description

Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the invention and is not intended to limit the scope of the invention in any way.

The present disclosure provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the same.

The details of the organic electroluminescent compounds of formula 1 are as follows.

As used herein, "alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. "alkenyl" includes ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, and the like. "alkynyl" includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl and the like. "cycloalkyl" includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. "(3-to 7-membered) heterocycloalkyl" means a cycloalkyl group having 3 to 7 ring backbone atoms including at least one heteroatom selected from B, N, O, S, P (═ O), Si and P, preferably O, S and N, and includes tetrahydrofuran, pyrrolidine, thiacyclopentane, tetrahydropyran, and the like. Further, "(arylene) group" means a single ring or a condensed ring derived from an aromatic hydrocarbon; can be a spiro compound in which two rings are connected via one atom; and include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, fused tetraphenyl, fluoranthenyl, spirobifluorene, and the like. "(3-to 30-membered) (arylene) heteroaryl" denotes an aryl group having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, P (═ O), Si and P; may be a single ring or a condensed ring condensed with at least one benzene ring; may be partially saturated; may be one formed by bonding at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and include monocyclic type heteroaryl groups such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like, and fused ring type heteroaryl groups such as benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, naphthofuranyl, benzothienyl, benzonaphthofuranyl, benzonaphthothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, orinyl, quinazolinyl, carbazolyl, phenazinyl, oxazinyl, benzoxazolyl, oxadiazolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, quinazolinyl, tetrazolyl, pyrazinyl, and the, Phenanthridinyl, benzodioxolyl, dihydroacridinyl and the like. Further, "halogen" includes F, Cl, Br and I.

In the present context, "substituted" in the expression "substituted or unsubstituted" meansA hydrogen atom in a functional group is replaced with another atom or group (i.e., substituent). At L₁、Ar₁、R₁To R₆、R₂₁To R₂₇、R₃₁To R₃₃、R₁₀₀To R₁₀₉、R₁₁₁To R₁₂₇、L₄And the substituted alkyl, substituted cycloalkyl, substituted cycloalkenyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted diarylamino, substituted alkoxy, and substituted monocyclic or polycyclic alicyclic or aromatic ring substituents of M are each independently selected from the group consisting of deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, (C1-C30) alkyl, halo (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C3-C30) cycloalkyl, (C3-C30) cycloalkenyl, (3-to 7-membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, and (3-to 30-membered) heteroaryl unsubstituted or substituted with (C6-C30) aryl, (C6-C30) aryl which is unsubstituted or substituted by (3-to 30-membered) heteroaryl, tri (C1-C30) alkylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30) alkyldi (C30-C30) arylsilyl, amino, mono-or di- (C30-C30) alkylamino, mono-or di- (C30-C30) arylamino, (C30-C30) alkyl (C30-C30) arylamino, (C30-C30) alkylcarbonyl, (C30-C30) alkoxycarbonyl, (C30-C30) arylcarbonyl, di (C30-C30) arylboronyl, di (C30-C30) alkylboronyl, (C30-C30) boronyl, (C30-C30) arylboronic, or (C30-C30) arylboronic acid group consisting of (C30-C30) arylboronic acid groups, and (C30) aryl groups One kind of the compound is used; and preferably, each is independently at least one selected from the group consisting of cyano, halogen, (C1-C10) alkyl, (C3-C12) cycloalkyl, (C5-C18) aryl, (5-to 18-membered) heteroaryl, di (C6-C12) arylamino, and (C1-C10) alkyl (C5-C18) aryl.

L₁Represents a single bond, a substituted or unsubstituted (3-to 30-membered) heteroarylene group, or a substituted or unsubstituted (C6-C30) arylene group. Preferably, L₁May represent a single bond, a substituted or unsubstituted (5-to 21-membered) heteroarylene group, or a substituted or unsubstituted(C6-C21) arylene. Specifically, L₁May represent a single bond.

X₁represents-NR₁-、-CR₂R₃-, -O-or-S-. Specifically, X₁Can represent-NR₁-。

X₂To X₆Each independently represents-CR₄-or-N-. Preferably, X₂To X₆All of (A) may represent-CR₄-; or X₂To X₆May represent-N-, and X₂To X₆The remainder of (a) may represent-CR₄-. When X is present₂represents-N-is, L₁Is not a substituted or unsubstituted (C6-C30) arylene group, and Ar₁Is not hydrogen. Specifically, when X is₂represents-N-is, L₁May represent a single bond.

Ar₁Represents hydrogen, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (3-to 30-membered) heteroaryl. Ar (Ar)₁May preferably represent hydrogen or a substituted or unsubstituted (C6-C21) aryl group; and more preferably represents hydrogen or (C6-C18) aryl which is unsubstituted or substituted by (C1-C10) alkyl, cyano, (C6-C13) aryl or (5-to 13-membered) heteroaryl. Specifically, Ar₁May represent hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted phenylnaphthyl, or substituted or unsubstituted naphthylphenyl. More specifically, Ar₁May represent hydrogen; or phenyl, biphenyl, naphthyl, terphenyl, anthracenyl, phenanthrenyl, phenylnaphthyl or naphthylphenyl which is unsubstituted or substituted by (C1-C4) alkyl, cyano or pyridyl. Preferably, when Ar is₁When represents hydrogen, X₂To X₆At least one of which may represent-CR₄-, wherein R₄Represents a substituted or unsubstituted (C6-C30) aryl group or a substituted or unsubstituted (3-to 30-membered) heteroaryl group. More preferably, when Ar is₁When represents hydrogen, X₂To X₆ToOne less may represent-CR₄-, wherein R₄Represents a substituted or unsubstituted (C6-C21) aryl or a substituted or unsubstituted (5-to 21-membered) heteroaryl; and even more preferably X₂To X₆One of them may represent-CR₄-, wherein R₄Represents a substituted or unsubstituted (C6-C18) aryl group.

Radical Y₁To Y₄And Y₁₃To Y₁₆Each independently represents-N-or-CR₅-; and preferably represents-CR₅-. Specifically, Y₁To Y₄May represent-CH-; or Y₁To Y₄One of them may represent-CR₅- (wherein R)₅Other than hydrogen), Y₁To Y₄The remainder of (a) may represent-CH-; or Y₁To Y₄Two of them may represent-CH-, Y₁To Y₄The remainder of (a) may represent-CR₅- (wherein R)₅Not hydrogen). Specifically, Y₁₃To Y₁₆May represent-CH-; or Y₁₃To Y₁₆One of them may represent-CR₅- (wherein R)₅Other than hydrogen), Y₁₃To Y₁₆The remainder of (a) may represent-CH-; or Y₁₃To Y₁₆Two of them may represent-CH-, Y₁₃To Y₁₆The remainder of (a) may represent-CR₅- (wherein R)₅Not hydrogen).

Y₅To Y₁₂Each independently represent

-N-or-CR₆-. Preferably, Y₅To Y₁₂Each independently represent

or-CR₆-. Specifically, Y₅To Y₈Can represent

Y₅To Y₈The remainder of (a) may represent-CH-. Specifically, Y₉To Y₁₂Can represent

Y₉To Y₁₂The remainder of (a) may represent-CH-; or Y₉To Y₁₂Can represent

Y₉To Y₁₂Two of (a) may represent-CR₆- (wherein R)₆Not hydrogen) and the remainder may represent-CH-.

R₁To R₃Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 30-membered) heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, or substituted or unsubstituted (3-to 7-membered) heterocycloalkyl. R₁To R₃Each independently may preferably represent a substituted or unsubstituted (C1-C20) alkyl group, a substituted or unsubstituted (C6-C21) aryl group, a substituted or unsubstituted (5-to 21-membered) heteroaryl group, a substituted or unsubstituted (C5-C21) cycloalkyl group, or a substituted or unsubstituted (5-to 7-membered) heterocycloalkyl group; more preferably represents a substituted or unsubstituted (C1-C10) alkyl group or a substituted or unsubstituted (C6-C18) aryl group; and even more preferably represents an unsubstituted (C1-C10) alkyl group or an unsubstituted (C6-C18) aryl group. Preferably, R₂And R₃The same is true. In particular, R₁May represent phenyl, biphenyl or naphthyl; r₂May represent (C1-C4) alkyl or phenyl; and R is₃May represent a (C1-C4) alkyl group or a phenyl group.

R₄To R₆Each independently represents hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-to 7-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 30-membered) heteroaryl, or substituted or unsubstituted di (C893-to 7-membered) heteroarylC6-C30) arylamino; or may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (3-to 30-membered) monocyclic or polycyclic alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur. R₄To R₆Each independently preferably represents hydrogen, halogen, cyano, substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C5-C21) cycloalkyl, substituted or unsubstituted (C6-C21) aryl, substituted or unsubstituted (5-to 21-membered) heteroaryl, or substituted or unsubstituted di (C6-C21) arylamino; or may be fused to an adjacent substituent(s) to form a substituted or unsubstituted (5-to 21-membered) monocyclic or polycyclic aromatic ring, whose carbon atom(s) may be replaced by one or two heteroatoms selected from nitrogen, oxygen and sulfur. More preferably, R₄Represents hydrogen or a substituted or unsubstituted (C6-C18) aryl group. In particular, R₄May represent hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted phenylnaphthyl, or substituted or unsubstituted naphthylphenyl. More preferably, R₅And R₆Represents hydrogen, cyano, substituted or unsubstituted (C1-C10) alkyl, substituted or unsubstituted (C5-C18) cycloalkyl, substituted or unsubstituted (C6-C18) aryl or substituted or unsubstituted di (C6-C18) arylamino; or may be fused to an adjacent substituent(s) to form a substituted or unsubstituted (5-to 18-membered) monocyclic or polycyclic aromatic ring, whose carbon atom(s) may be replaced by heteroatom(s) selected from nitrogen, oxygen and sulfur. In particular, R₅And R₆Each independently may represent hydrogen, cyano, (C1-C4) alkyl, phenyl, cyclohexyl or di (phenyl) amino or may be fused with an adjacent substituent(s) to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted furan ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted indene ring, or aA substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, or a substituted or unsubstituted benzindole ring.

According to one embodiment of the present disclosure, L₁Represents a single bond, a substituted or unsubstituted (5-to 21-membered) heteroarylene group, or a substituted or unsubstituted (C6-C21) arylene group; x₁represents-NR₁-、-CR₂R₃-, -O-or-S-; x₂To X₆All of (A) represent-CR₄-, or X₂To X₆One of them represents-N-, and X₂To X₆The remainder of (a) represents-CR₄-, wherein when X₂is-N-or L₁Is a single bond; ar (Ar)₁Represents hydrogen or a substituted or unsubstituted (C6-C21) aryl group, wherein when Ar is₁When it is hydrogen, R₄Is a substituted or unsubstituted (C6-C21) aryl or a substituted or unsubstituted (5-to 21-membered) heteroaryl; y is₁To Y₄And Y₁₃To Y₁₆Each independently represents-CR₅-；Y₅To Y₁₂Each independently represent

or-CR₆-；R₁To R₃Each independently represents a substituted or unsubstituted (C1-C20) alkyl group, a substituted or unsubstituted (C6-C21) aryl group, a substituted or unsubstituted (5-to 21-membered) heteroaryl group, a substituted or unsubstituted (C5-C21) cycloalkyl group, or a substituted or unsubstituted (5-to 7-membered) heterocycloalkyl group; r₄To R₆Each independently represents hydrogen, halogen, cyano, substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C5-C21) cycloalkyl, substituted or unsubstituted (C6-C21) aryl, substituted or unsubstituted (5-to 21-membered) heteroaryl, or substituted or unsubstituted di (C6-C21) arylamino, or may be fused to an adjacent substituent(s) to form a substituted or unsubstituted (5-to 21-membered) monocyclic or polycyclic aromatic ring, the carbon atom(s) of which may be substituted by one or more members selected from nitrogen, oxygen and sulfurTwo heteroatom substitutions; heteroaryl (ene) and heterocycloalkyl each independently contain at least one heteroatom selected from N, O and S; and a and b each independently represent 0 or 1.

According to another embodiment of the present disclosure, the compound of formula 1 may be represented by formula 2 below:

wherein X₁、Ar₁、Y₁To Y₁₆、R₄、L₁A and b are as defined in formula 1 above; c represents an integer of 1 to 4; and when c is 2 or more, R₄Each of which may be the same or different. Preferably, in formula 2, L₁Represents a single bond; ar (Ar)₁Represents a substituted or unsubstituted (C6-C21) aryl group or a substituted or unsubstituted (5-to 21-membered) heteroaryl group, and R₄Represents hydrogen.

According to another embodiment of the present disclosure, the compound of formula 1 may be represented by any one of the following formulae 3 to 5:

wherein X₁、Ar₁、Y₁To Y₁₆、R₄、L₁A and b are as defined in formula 1; c represents an integer of 1 to 5; and when c is 2 or more, R₄Are the same or different. In formulae 3 to 5, preferably, when Ar₁When it is hydrogen, R₄At least one of which represents a substituted or unsubstituted (C6-C21) aryl group or a substituted or unsubstituted (5-to 21-membered) heteroaryl group. More preferably, Ar₁Represents hydrogen; r₄Represents a substituted or unsubstituted (C6-C18) aryl group, and R₄The remainder of (a) represents hydrogen.

More specifically, the organic electroluminescent compounds of the present disclosure include, but are not limited to, the following:

the organic electroluminescent compounds of formula 1 of the present disclosure can be prepared by synthetic methods known to those skilled in the art. For example, it may be prepared according to any one of the following reaction schemes 1 to 4.

[ reaction scheme 1]

[ reaction scheme 2]

[ reaction scheme 3]

[ reaction scheme 4]

In addition, the present disclosure provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the same.

The material may comprise one or more compounds selected from the group consisting of organic electroluminescent compounds of formula 1. The material may additionally comprise conventional compound(s) already included for organic electroluminescent materials.

The organic electroluminescent device of the present disclosure may include a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer may include at least one compound of formula 1.

One of the first electrode and the second electrode may be an anode, and the other may be a cathode. The organic layer may include a light emitting layer, and may further include at least one layer selected from a hole injection layer, a hole transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron buffer layer, and an electron blocking layer.

The organic electroluminescent compounds of the present disclosure may be included in the light emitting layer. When used in the light emitting layer, the organic electroluminescent compound of the present disclosure may be contained as a host material. The light emitting layer may further comprise at least one dopant. If necessary, the light emitting layer may include two or more compounds selected from the organic electroluminescent compounds of formula 1 of the present disclosure; or may further comprise a second host material other than the organic electroluminescent compound of formula 1 of the present disclosure.

Phosphorescent host materials known in the art may be used as the second host material. A compound selected from the group consisting of compounds of the following formulas 6 to 11 is preferable as the second host material due to driving voltage, lifetime, and luminous efficiency.

H-(Cz-L₄)_h-M(6)H-(Cz)_i-L₄-M(7)

Wherein Cz represents the following structure:

L₄and L₅Each independently represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5-to 30-membered) heteroarylene;

m represents a substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted (5-to 30-membered) heteroaryl, provided that when h of formula 6 is 1, or i of formula 7 is 1, M is not

And M of formulae 8 and 9 is not

(wherein X₂To X₆And Ar₁As defined in formula 1, and denotes a bonding site. ) (ii) a

Z₁And Z₂Each independently represents-O-, -S-, -N (R)₃₁) -or-C (R)₃₂)(R₃₃) With the proviso that Z₁And Z₂Not exist at the same time;

x' represents-O-or-S-;

ring A represents

Ring B represents

D and E each independently represent-O-, -S-, -N (R)₃₄) -or-C (R)₃₅)(R₃₆)-；

Ar₂Represents a substituted or unsubstituted (3-to 30-membered) heteroaryl group or a substituted or unsubstituted (C6-C30) aryl group, with the proviso that Ar₂Is not provided with

R₂₁To R₂₇Each independently represents hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, or R₂₈R₂₉R₃₀Si-; or may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30) mono-or polycyclic alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; provided that when h of formula 6 or i of formula 7 is 1, R₂₆Or R₂₇Does not form Z containing formula 8, formula 9 and formula 11₁、Z₂Ring of formula 10, R of formula D or E₂₂R is not formed to be bonded to formula 8 and formula 9₂₁And R attached to formula 11₂₃An indole ring of (a);

R₂₈to R₃₀Each independently represents a substituted or unsubstituted (C1-C30) alkyl group or a substituted or unsubstituted (C6-C30) aryl group;

R₃₁to R₃₆Each independently represents hydrogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5-to 30-membered) heteroaryl; r₃₂And R₃₃May be the same or different; r₃₅And R₃₆May be the same or different;

heteroaryl (ene) contains one or more heteroatoms selected from B, N, O, S, P (═ O), Si and P;

h and i each independently represent an integer of 1 to 3; j. k, l and p each independently represent an integer of 0 to 4; r, s and t each independently represent an integer of 1 to 4; and when h, i, j, k, L, p, r, s or t is an integer of 2 or more, (Cz-L)₄) Each of (1), (Cz), R₂₁Each of (1), R₂₂Each of (1), R₂₃Each of (1), R₂₄Each of (1), R₂₅Each of (1), R₂₆Each of (1) or R₂₇Each of which may be the same or different.

Preferably, in formula 6 to formula 10, M may represent a substituted or unsubstituted nitrogen-containing (6-to 20-membered) heteroaryl group. Preferably, the substituent of M may be (C1-C20) alkyl; (C6-C24) aryl unsubstituted or substituted with (C1-C10) alkyl, tri (C6-C13) arylsilyl, or (6-to 13-membered) heteroaryl; (6-to 20-membered) heteroaryl unsubstituted or substituted with (C1-C10) alkyl, tri (C6-C13) arylsilyl, or (C6-C24) aryl; or a tri (C6-C20) arylsilyl group. In particular, M may represent a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted morpholinyl group.

R of formula 6 and formula 7₂₆And R₂₇Or R of formula 8 to formula 10₂₁And R₂₂At least one of which may be a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzocarbazolyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted naphthobenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted naphthobenzofuranyl group, (C6-C18) aryl substituted with a substituted or unsubstituted carbazolyl group, (C6-C18) aryl substituted with a substituted or unsubstituted benzocarbazolyl group, (C6-C18) aryl substituted with a substituted or unsubstituted dibenzothienyl group, (C6-C18) aryl substituted with a substituted or unsubstituted naphthobenzothienyl group, (C6-C18) aryl substituted with a substituted or unsubstituted dibenzofuranyl group, or (C6-C18) aryl substituted with a substituted or unsubstituted naphthobenzofuranyl group. When M is aryl, R₂₆And R₂₇At least one of (1) or R₂₁And R₂₂At least one of which may represent a substituted or unsubstituted nitrogen-containing (6-to 20-membered) heteroaryl group; or may have a substituted or unsubstituted nitrogen-containing (6-to 20-membered) heteroaryl group as a substituent. Specifically, the substituted or unsubstituted nitrogen-containing heteroaryl group may represent a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted triazinyl groupPyrazinyl, substituted or unsubstituted quinazolinyl, or substituted or unsubstituted morpholinyl.

D and E may each independently preferably be selected from the group consisting of-O-, -S-and-N (R)₃₄) With the proviso that X and y are not both simultaneously-N (R)₃₄) -. According to one embodiment of the disclosure, X and Y may each independently be selected from the group consisting of-O-and-S-. According to another embodiment of the disclosure, X and Y may each independently be selected from-O-and-S-; and at least one of X and Y may be-S-. R₃₄May preferably represent a substituted or unsubstituted (C6-C30) aryl group, and in particular a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group or a substituted or unsubstituted biphenyl group.

Ar₂May preferably represent a substituted or unsubstituted (6-to 20-membered) heteroaryl group or a substituted or unsubstituted (C6-C20) aryl group; and more preferably represents a substituted or unsubstituted nitrogen-containing (6-to 20-membered) heteroaryl group. Specifically, Ar₂May represent a substituted or unsubstituted triazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinazolinyl group or a substituted or unsubstituted indolinyl group.

Specifically, preferred examples of the second host material include, but are not limited to, the following:

[ wherein TPS represents a triphenylsilyl group. ]

The dopant is preferably at least one phosphorescent dopant. The phosphorescent dopant material used for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from a metallized complex compound of iridium (Ir), osmium (Os), copper (Cu), or platinum (Pt), more preferably an ortho-metallized complex compound selected from iridium (Ir), osmium (Os), copper (Cu), or platinum (Pt), and even more preferably an ortho-metallized iridium complex compound.

The dopant included in the organic electroluminescent device of the present disclosure may be selected from the group consisting of compounds represented by formulae 12 to 14 below.

Wherein L is selected from the following structures:

R₁₀₀represents hydrogen, substituted or unsubstituted (C1-C30) alkyl or substituted or unsubstituted (C3-C30) cycloalkyl; r₁₀₁To R₁₀₉And R₁₁₁To R₁₂₃Each independently represents hydrogen, deuterium, halogen, (C1-C30) alkyl unsubstituted or substituted by halogen, (C3-C30) cycloalkyl substituted or unsubstituted, cyano, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C1-C30) alkoxy; r₁₀₆To R₁₀₉May be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, such as substituted or unsubstituted fluorene, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted dibenzofuran; r₁₂₀To R₁₂₃May be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted quinoline; r₁₂₄To R₁₂₇Each independently represents hydrogenDeuterium, halogen, substituted or unsubstituted (C1-C30) alkyl or substituted or unsubstituted (C6-C30) aryl; when R is₁₂₄R₁₂₇When any of (a) is aryl, it may be bonded to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example substituted or unsubstituted fluorene, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted dibenzofuran; r₂₀₁To R₂₁₁Each independently represents hydrogen, deuterium, halogen, (C1-C30) alkyl unsubstituted or substituted by halogen, (C3-C30) cycloalkyl substituted or unsubstituted or (C6-30) aryl substituted or unsubstituted, R₂₀₈To R₂₁₁May be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, such as substituted or unsubstituted fluorene, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted dibenzofuran; f and g each independently represent an integer of 1 to 3; when f or g is an integer of 2 or more, R₁₀₀Each of which may be the same or different; and n represents an integer of 1 to 3.

Specifically, the doping materials include the following:

according to another aspect of the present invention, there is provided a material for use in the preparation of an organic electroluminescent device. The material may be a material used for preparing a light emitting layer or an electron transport layer of an organic electroluminescent device. When the compound of the present disclosure is included in a material for preparing a light emitting layer of an organic electroluminescent device, the compound of the present disclosure may be included as a host material. When the compound of the present disclosure is included as a host material, the material may include two or more compounds selected from the organic electroluminescent compounds of formula 1 of the present disclosure; or may include a second host material, for example, a material selected from the group consisting of compounds represented by formulas 6 to 11, in addition to the organic electroluminescent compound of formula 1 (first host material) of the present disclosure. The weight ratio between the first host material and the second host material ranges from 1:99 to 99:1, and is preferably 30:70 to 70:30 due to driving voltage, lifetime, and luminous efficiency. When the compound of the present disclosure is included in a material for preparing an electron transport layer of an organic electroluminescent device, the compound of the present disclosure may be included as an electron transport material. The material may be a composition or a mixture. The material may further comprise conventional compound(s) which have been included for organic electroluminescent materials.

In another aspect according to the present disclosure, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a material of the present disclosure used to prepare the organic electroluminescent device.

According to another aspect of the present disclosure, there is provided an organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises one or more light emitting layers; at least one light-emitting layer contains one or more dopant compounds and two or more host compounds; and at least one of the two or more host compounds is represented by formula 1.

According to one embodiment of the present disclosure, in the organic electroluminescent device, a first host compound of the two or more host compounds may be selected from the compounds represented by formula 2 and formula 5.

According to another embodiment of the present disclosure, in the organic electroluminescent device, at least two of the two or more host compounds may each independently be selected from the compounds represented by formula 1.

According to another embodiment of the present disclosure, in the organic electroluminescent device, a first host compound of the two or more host compounds may be represented by formula 1, and a second host compound may be selected from compounds represented by formulae 6 to 11.

According to another embodiment of the present invention, in the organic electroluminescent device, the one or more dopant compounds may be selected from the compounds represented by formulae 12 to 14.

The organic electroluminescent device of the present disclosure includes the compound of formula 1 in an organic layer. The organic electroluminescent device of the present disclosure may further comprise at least one compound selected from the group consisting of arylamine compounds and styrylarylamine compounds.

In the organic electroluminescent device of the present disclosure, the organic layer may further include at least one metal selected from the group consisting of: organometallic of group 1 metals, group 2 metals, period 4 transition metals, period 5 transition metals, lanthanides and d-transition elements of the periodic table, or at least one complex compound comprising said metals.

In addition, the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light emitting layer comprising a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the art in addition to the compound of the present disclosure. If necessary, it may further comprise an orange light emitting layer or a yellow light emitting layer.

In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, referred to as "surface layer") may be disposed on the inner surface(s) of one or both electrodes selected from the chalcogenide layer, the metal halide layer, and the metal oxide layer. Specifically, a layer of a chalcogenide (including oxide) of silicon or aluminum is preferably located on the anode surface of the electroluminescent interlayer, and a layer of a metal halide or a metal oxide is preferably located on the cathode surface of the electroluminescent interlayer. Watch of this typeThe top layer provides operational stability to the organic electroluminescent device. Preferably, the chalcogenide comprises SiO_X(1≤X≤2)、AlO_X(X is more than or equal to 1 and less than or equal to 1.5), SiON, SiAlON and the like; the metal halide includes LiF, MgF₂、CaF₂Rare earth metal fluorides, etc.; and the metal oxide comprises Cs₂O、Li₂O, MgO, SrO, BaO, CaO, etc.

In the organic electroluminescent device of the present invention, a mixed region of an electron transport compound and a reductive dopant or a mixed region of a hole transport compound and an oxidative dopant may be disposed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region into the electroluminescent medium. In addition, the hole-transporting compound is oxidized to cations, and thus it becomes easier to inject and transport holes from the mixed region into the electroluminescent medium. Preferably, the oxidizing dopant includes various Lewis acids (Lewis acids) and acceptor compounds; and the reducing dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. The reducible dopant layer may be used as a charge generation layer to fabricate an electroluminescent device having two or more light emitting layers and emitting white light.

In order to form each layer of the organic electroluminescent device of the present disclosure, a dry film forming method such as vacuum evaporation, sputtering, plasma, and ion plating methods, or a wet film forming method such as inkjet printing, nozzle printing, slit coating, spin coating, dip coating, and flow coating methods may be used.

When a wet film formation method is used, a thin film can be formed by dissolving or diffusing the material forming each layer into any suitable solvent, such as ethanol, chloroform, tetrahydrofuran, dioxane, or the like. The solvent may be any solvent in which the material forming each layer is soluble or diffusible and which does not present film forming ability problems.

In the organic electroluminescent device of the present disclosure, two or more host compounds for the light emitting layer may be co-evaporated or co-evaporated. Herein, co-evaporation indicates a method for depositing two or more materials in a mixture form by introducing each of the two or more materials into a corresponding crucible unit, and applying a current to the unit so that each of the materials is evaporated. Herein, the mixed evaporation indicates a method for causing two or more materials to be deposited in a mixture form by mixing two or more materials in one crucible unit before deposition and applying a current to the unit so that the mixture is evaporated.

By using the organic electroluminescent device of the present disclosure, a display system or a lighting system can be produced.

Hereinafter, the organic electroluminescent compounds, the preparation methods of the compounds, and the light emitting characteristics of the devices of the present invention will be specifically explained with reference to the following examples.

[ example 1]

Preparation of Compounds 1-2

After the reaction of compound 1-1(20g, 100.5mmol), compound 2-1(19g, 150mmol), palladium (0) tetrakis (triphenylphosphine) [ Pd (PPh)₃)₄](5.7g, 5.0mmol) and Na₂CO₃(31g, 300mmol) was added to 500mL of toluene, 250mL of ethanol, and 250mL of pure water, and the mixture was stirred at 120 ℃ for 15 hours. After completion of the reaction, the mixture was left to stand to remove the aqueous layer, and then the organic layer was concentrated. The mixture was purified by column chromatography to give compound 1-2(20g, 83%).

Preparation of Compound H-1

After dissolving Compound 1-2(20g, 83mmol), Compound 1-3(50g, 99mmol) and NaH (4g, 166mmol) in Dimethylformamide (DMF), the mixture was stirred for 15 hours. After completion of the reaction, the solid was filtered and purified by column chromatography to give compound H-1(50g, 82%).

[ example 2]

Preparation of Compounds 1-4

After dissolving compounds 1-3(30g, 73.44mmol) in 370mL of dimethylformamide, sodium hydride (4.4g, 110.16mmol) was slowly added to the mixture, and then the mixture was stirred for 30 minutes. Compound 1-1(17.5g, 88.13mmol) was added to the mixture, and the mixture was then stirred for 4 hours. After the mixture was slowly added to 500mL of distilled water, the mixture was stirred for 30 minutes. The obtained solid was purified by column chromatography and recrystallization to obtain compounds 1 to 4(30g, 71%).

Preparation of Compound H-5

After reaction of compound 1-4(10g, 17.51mmol), compound 2-2(4.2g, 21.01mmol), palladium (0) tetrakis (triphenylphosphine) [ Pd (PPh)₃)₄](0.6g, 0.53mmol), sodium carbonate (4.6g, 43.78mmol), 90mL of toluene, and 22mL of ethanol were introduced into the reactor, and 22mL of distilled water was added to the mixture. The mixture was stirred at 120 ℃ for 4 hours. After completion of the reaction, it was washed with distilled water and the mixture was extracted with ethyl acetate. The resulting organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The product was purified by column chromatography to give compound H-5(5.5g, 46%).

[ example 3]

Preparation of Compound H-80

After reaction of compounds 1-4(10g, 17.51mmol), compounds 2-3(4.2g, 21.01mmol), palladium (0) tetrakis (triphenylphosphine) [ Pd (PPh)₃)₄]After (0.6g, 0.53mmol), sodium carbonate (4.6g, 43.78mmol), 90mL of toluene and 22mL of ethanol were introduced into the reactor, 22mL of distilled water was added to the mixture, and then the mixture was stirred at 120 ℃ for 4And (4) hours. After completion of the reaction, it was washed with distilled water and the mixture was extracted with ethyl acetate. The resulting organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The product was purified by column chromatography to give compound H-80(7.7g, 64%).

[ example 4]

Preparation of Compound 3-1

In the reaction of the compound 10-bromo-7H-benzo [ c]Carbazole (15.5g, 41.64mmol), Compound A (13.1g, 45.80mmol), Pd (PPh)₃)₄(2.4g, 2.08mmol) and 110mL of 2M Na₂CO₃After dissolution in 220mL of toluene and 110mL of ethanol, the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed therefrom with magnesium sulfate, and then the mixture was dried. The product was purified by column chromatography to give compound 3-1(15.4g, yield: 81%).

Preparation of Compound H-55

After compound 1-2(6.3g, 26.17mmol) and compound 3-1(10g, 21.81mmol) were dissolved in 110mL DMF, NaH (0.5g, 14.54mmol, 60% in mineral oil) was added to the mixture. The mixture was stirred at room temperature for 12 hours, and methanol and distilled water were added thereto. The obtained solid was filtered under reduced pressure, and then purified by column chromatography to obtain compound H-55(2.5g, yield: 18%).

[ example 5]

Preparation of Compound 4-1

Naphthalene-2-yl boronic acid (30g, 174.35mmol), 2-bromonitrobenzene (42g, 209.22mmol), Pd (PPh)₃)₄(10g, 8.71mmol) and 425mL of 2M Na₂CO₃After dissolving in 850mL of toluene and 425mL of ethanol in the flask, the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to obtain compound 4-1(40g, yield: 93%).

Preparation of Compound 4-2

After mixing compound 4-1(40g, 160.34mmol) and PPh₃(105.1g, 400.86mmol) was dissolved in 1000mL of Dichlorobenzene (DCB) and the mixture was refluxed at 150 ℃ for 6 hours. After the reaction was completed, the mixture was distilled and wet-milled with methanol. As a result, Compound 4-2(24g, yield: 50%) was obtained.

Preparation of Compounds 4-3

After compound 1-2(24g, 110.46mmol) was dissolved in 570mL of DMF, N-bromosuccinimide (NBS) (17g, 99.42mmol) was added thereto at 0 ℃. The mixture was stirred for 5 hours, and then distilled water was added thereto. The resulting solid was filtered under reduced pressure, added to methanol, stirred, and then filtered under reduced pressure. After the solid was added to ethyl acetate and methanol, the mixture was stirred and filtered under reduced pressure to obtain compound 4-3(23g, yield: 73%).

Preparation of Compound 4-4

After reaction of compound 4-3(23.4g, 79.01mmol), iodobenzene (18mL, 158.02mmol), CuI (7.5g, 39.50mmol), Ethylenediamine (EDA) (2.6mL, 39.50mmol) and Cs₂CO₃(77g, 237.03mmol) was dissolved in 400mL of toluene and the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound 4-4(21.5g, yield: 74%).

Preparation of Compounds 4-5

After adding compound 4-4(21.5g, 57.75mmol), (9H-carbazolyl-3-yl) boric acid (15g, 69.31mmol),Pd(PPh₃)₄(3.4g, 2.88mmol) and 150mL of 2M Na₂CO₃After dissolving in 300mL of toluene and 150mL of ethanol, the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound 4-5(4.2g, yield: 17%).

Preparation of Compound H-88

After the reaction of compound 1-2(2.6g, 10.99mmol), compound 4-5(4.2g, 9.16mmol), and K₂CO₃After (1.2g, 9.16mmol), 4-Dimethylaminopyridine (DMAP) (0.6g, 4.58mmol) and 50mL of Dimethylacetamide (DMA) were introduced into the reactor, the mixture was stirred at reflux for 4 hours. The reaction mixture was cooled to room temperature, and then distilled water was added thereto. The mixture was extracted with dichloromethane (MC), dried over magnesium sulfate, distilled under reduced pressure, and purified by column chromatography to give compound H-88(1.7g, 28%).

[ example 6]

Preparation of Compound 5-1

2-bromo-carbazole (30g, 121.90mmol), phenylboronic acid (18g, 146.28mmol), Pd (PPh)₃)₄(7g, 6.09mmol) and 250mL of 2M Na₂CO₃After dissolving in 500mL of toluene and 250mL of ethanol in the flask, the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed therefrom with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound 5-1(15g, yield: 52%).

Preparation of Compound 5-2

After compound 5-1(14.4g, 59.19mmol) was dissolved in 200mL DMF in a flask, NBS (11g, 59.19mmol) was added thereto at 0 ℃. The mixture was stirred for 12 hours, and then distilled water was added thereto. The resulting solid was filtered under reduced pressure, added to methanol, stirred, and then filtered under reduced pressure. The solid was added to ethyl acetate and methanol. The mixture was stirred and filtered under reduced pressure. As a result, compound 5-2(15.8g, yield: 83%) was obtained.

Preparation of Compounds 5-3

After reaction of compound 5-2(15.8g, 49.04mmol), compound A (15.5g, 53.94mmol), Pd (PPh)₃)₄(3g, 2.452mmol) and 150mL of 2M Na₂CO₃After dissolving in 300mL of toluene and 150mL of ethanol in the flask, the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound 5-3(4g, yield: 17%).

Preparation of Compound H-7

After reaction of compound 5-3(4g, 8.254mmol), compound B (2.4g, 9.905mmol), and K₂CO₃(1.15g, 8.254mmol) and DMAP (0.5g, 4.127mmol) were dissolved in 40mL of DMF in a flask, and the mixture was refluxed at 220 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound H-7(2.8g, yield: 50%).

[ example 7]

Preparation of Compound 6-3

After reaction, compound 6-1(25.4g, 68.22mmol), compound 6-2(20g, 68.22mmol), Pd (PPh)₃)₄(4g, 3.41mmol) and 100mL of 2M K₂CO₃After dissolving 340mL of toluene and 100mL of ethanol in the flask, the mixture was refluxed at 120 ℃ for 3 hours. After the reaction is completed, mixingThe substance was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to obtain compound 6-3(8g, yield: 25%).

Preparation of Compound H-3

After dissolving compound 6-3(11g, 23.99mmol), compound 6-4(9g, 35.98mmol) and NaH (60% in mineral oil) (2.8g, 71.97mmol) in 230mL DMF in a flask, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound H-3(4g, yield: 25%).

	MW	UV	PL	Melting Point
					H-3	662.78	296nm	517nm	234℃

[ example 8]

Preparation of Compound 7-1

After 7H-benzo [ c ] carbazole (50g, 230.12mmol) and N-bromosuccinimide (41g, 230.12mmol) were dissolved in 500mL of DMF in a flask, the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound 7-1(50g, yield: 73%).

Preparation of Compound 7-2

In the reaction of 10-bromo-7H-benzo [ c]Carbazole (Compound 7-1) (15g, 61.00mmol), iodobenzene (14ml, 123.00mmol), CuI (6.0g, 30.00mmol), EDA (4ml, 61.00mmol) and K₃PO₄(40g, 183.00mmol) was dissolved in 500mL of toluene in a flask, and the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound 7-2(13g, yield: 73%).

Preparation of Compound 7-4

In the reaction of the compound 10-bromo-7-phenyl-7H-benzo [ c]Carbazole (Compound 7-2) (10g, 34.10mmol) and Compound 7-3(10g, 40.92mmol) were dissolved in 100mL of toluene, 50mL of ethanol, and 50mL of H₂After O, the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound 7-4(9g, yield: 57%).

Preparation of Compounds 7-7

After the compound 2, 3-dichloroquinoxaline (compound 7-5) (28g, 140.67mmol) and the compound 7-6(24g, 140.67mmol) were dissolved in 100mL of toluene, 50mL of ethanol, 50mL of H₂After O, the mixture was refluxed at 120 ℃ for 5 hours. After the reaction is finishedAfter completion, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound 7-7(30g, yield: 73%).

Preparation of Compound H-4

In the reaction of a compound 10- (9H-carbazolyl-3-yl) -7-phenyl-7H-benzo [ c]Carbazole (Compound 7-4) (9.1g, 19.80mmol), Compound 7-7(9g, 29.7mmol), and K₂CO₃After (5.5g, 39.6mmol), DMAP (1.2g, 9.9mmol) and 100mL of DMF were introduced into the reactor, the mixture was stirred under reflux for 1 hour, cooled to room temperature, and then distilled water was added thereto. The mixture was extracted with dichloromethane, dried over magnesium sulfate, distilled under reduced pressure and purified by column chromatography to obtain compound H-4(5g, yield: 35%).

	MW	UV	PL	Melting Point
					H-4	712.84	334nm	516nm	298.0℃

[ example 9]

Preparation of Compound 91-1

After 9-phenyl-9H, 9'H-3,3' -dicarbazole (33.8g, 82.7mmol), 2, 4-dichloroquinoxaline (17.2g, 86.9mmol), CuI (31.5g, 165.4mmol) and trans-1, 2-diaminocyclohexane (6mL, 49.63mmol) were dissolved in 550mL of o-DCB in a flask, the mixture was stirred at 200 ℃ under reflux for 6 hours. After completion of the reaction, the mixture was extracted with dichloromethane and MgSO₄Dried, column chromatographed, and then methanol was added to the separated material. The obtained solid was filtered under reduced pressure to obtain compound 91-1(32.5g, yield: 69%).

Preparation of Compound H-91

After the compound 91-1[9- (4-chloroquinoline-2-yl) -9' -phenyl-9H, 9' H-3,3' -dicarbazole](32g, 56.13mmol), phenylboronic acid (13.7g, 112.3mmol), Pd (PPh)₃)₄(6.5g, 5.7mmol) and K₂CO₃(19.4g, 140.33mmol) was dissolved in 560mL of toluene, 35mL of ethanol and 70mL of H₂After O, the mixture was refluxed at 120 ℃ for 12 hours. After completion of the reaction, the mixture was extracted with dichloromethane and MgSO₄Dried, column chromatographed, and then hexane was added to the separated material. The obtained solid was filtered under reduced pressure to obtain compound H-91(23g, yield: 67%).

[ example 10]

Preparation of Compound 97-1

After compound 9-phenyl-9H, 9'H-3,3' -dicarbazole (20.5g, 50.24mmol) and compound a (12g, 60.29mmol) were dissolved in 50mL DMF in a flask, NaH (2.6g, 62.31mmol, 60% in mineral oil) was added thereto. The mixture was stirred at room temperature for 12 hours, and methanol and distilled water were added thereto. The produced solid was filtered under reduced pressure, and purified by column chromatography to give compound 97-1(10g, yield: 35%).

Preparation of Compound H-97

After reaction of compound 97-1(10g, 17.51mmol), compound 2-2(4.5g, 22.76mmol) and Pd₂dba₃(0.96g, 1.05mmol) S-phosphorus (0.6g, 1.40mmol) and K₃PO₄(12g, 52.53mmol) was dissolved in 200mL of toluene in a flask, and the mixture was refluxed at 120 ℃ for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, remaining water was removed from the resulting organic layer with magnesium sulfate, and then the organic layer was dried. The product was purified by column chromatography to give compound H-97(3g, yield: 25%).

[ device example 1]OLEDs using the compounds of the present disclosure

Using the compounds of the present disclosure, OLEDs were fabricated as follows. A transparent electrode Indium Tin Oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an Organic Light Emitting Diode (OLED) device (geomantec) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water in order, and then stored in isopropyl alcohol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor deposition apparatus. Will N¹,N¹'- ([1,1' -Biphenyl)]-4,4' -diyl) bis (N)¹- (Naphthalen-1-yl) -N⁴,N⁴Diphenylbenzene-1, 4-diamine) is introduced into the cells of the vacuum vapor deposition apparatus and the pressure in the chamber of the apparatus is subsequently controlled to 10^-6And (4) supporting. Thereafter, a current was applied to the cell to evaporate the above-introduced material, thereby forming a hole injection layer having a thickness of 60nm on the ITO substrate. Subsequently, N ' -bis (4-biphenyl) -N, N ' -bis (4-biphenyl) -4,4' -diaminobiphenyl was introduced into another cell of the vacuum vapor deposition apparatus and evaporated by applying a current to the cell, thereby forming a hole transport layer having a thickness of 20nm on the hole injection layer. Thereafter, the compound H-1 was introduced into one unit of the vacuum vapor deposition apparatus as a main body, and the compound D-88 was introduced into the other unit as a main bodyA dopant. The two materials were evaporated at different rates so that the dopant was deposited in a doping amount of 4 wt% based on the total amount of the host and the dopant to form a light emitting layer having a thickness of 30nm on the hole transport layer. Then 2- (4- (9, 10-di (naphthalene-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d]Imidazole is incorporated into one unit and lithium quinolinate is incorporated into the other unit. Both materials were evaporated at the same ratio so that they were deposited at doping amounts of 50 wt%, respectively, to form an electron transport layer having a thickness of 30nm on the light emitting layer. After depositing lithium quinolinate as an electron injection layer having a thickness of 2nm on the electron transport layer, an Al cathode having a thickness of 150nm was then deposited on the electron injection layer by another vacuum vapor deposition apparatus. Thus, an OLED is produced. All materials used to fabricate OLEDs are available by way of example at 10^-6Those materials purified by vacuum sublimation. The produced OLED showed 1,050cd/m at 4.1V drive voltage²Brightness of (2) and 11.1mA/cm²Red light emission of current density. The minimum time required to reduce to 90% of the brightness of 5,000 nits is 90 hours.

[ device example 2 to device example 8]OLEDs using the compounds of the present disclosure

An OLED was produced in the same manner as device example 1, except that the host and dopant shown in table 2 below were used as the light emitting material. Driving Voltage (V), Current Density (mA/cm) of the produced OLED²) Luminance (cd/m)²) The minimum time (lifetime) required for the color and to decrease to 90% of the brightness of 5000 nits is shown in table 2 below.

Comparative example 1 and comparative example 2]OLEDs using conventional light emitting materials

An OLED was produced in the same manner as device example 1, except that compound T-1 or T-2 shown in table 1 below was used as a host, and a dopant shown in table 2 below was used. Driving Voltage (V), Current Density (mA/cm) of the produced OLED²) Luminance (cd/m)²) The minimum time (lifetime) required for the color and to decrease to 90% of the brightness of 5000 nits is shown in table 2 below.

[ Table 1]

[ Table 2]

As shown in table 2, organic electroluminescent devices using the organic electroluminescent compounds of the present disclosure showed a more significant improvement in lifetime up to 600% than those using conventional compounds, while maintaining excellent driving voltage and excellent current and power efficiency.

[ device example 9]OLEDs in which the first and second host compounds of the present disclosure are co-evaporated

Using the compounds of the present disclosure, OLEDs were fabricated as follows. A transparent electrode Indium Tin Oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an Organic Light Emitting Diode (OLED) device (geomantec) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water in order, and then stored in isopropyl alcohol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor deposition apparatus. Will N⁴,N⁴' -Diphenyl-N⁴,N⁴-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]-4,4' -diamine (compound HI-1) is introduced into a cell of a vacuum vapor deposition apparatus and subsequently the pressure in the apparatus chamber is controlled to 10^-6And (4) supporting. 1,4,5,8,9, 12-hexaazatriphenylene-hexacyanonitrile (compound HI-2) is introduced into another unit of the vacuum vapor deposition apparatus, and then a current is applied to the unit to evaporate the above-introduced material, thereby forming a second hole injection layer having a thickness of 5nm on the first hole injection layer. Reacting N- ([1,1' -biphenyl)]-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazolyl-3-yl) phenyl) -9H-fluoren-2-amine (compound HT-1) is introduced into a unit of a vacuum vapor deposition apparatusAnd then a current was applied to the cell to evaporate the above-introduced material, thereby forming a first hole injection layer having a thickness of 10nm on the second hole injection layer. Thereafter, N-bis ([1,1' -biphenyl ] yl) is reacted with a catalyst]-4-yl) -4'- (9H-carbazolyl-9-yl) - [1,1' -biphenyl]-4-amine (compound HT-3) is introduced into another cell of the vacuum vapor deposition apparatus, and then a current is applied to the cell to evaporate the above-introduced material, thereby forming a second hole transport layer having a thickness of 60nm on the first hole transport layer. Compound H-1 and compound H2-116 were introduced into two units of a vacuum vapor deposition apparatus as host materials, respectively. Compound D-96 was incorporated into another cell as a dopant. The two host materials evaporated at the same rate, and the dopant evaporated at a different rate from the host materials, so that the dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and the dopant to form a light emitting layer having a thickness of 40nm on the electric hole transporting layer. Then 2, 4-bis (9, 9-dimethyl-9H-fluoren-2-yl) -6- (naphthalen-2-yl) -1,3, 5-triazine (compound ET-1) was introduced into one unit and lithium quinoline (compound EI-1) was introduced into the other unit. The two materials were evaporated at a rate of 1:1 to form an electron transport layer having a thickness of 30nm on the light emitting layer. After quinoline lithium (compound EI-1) was deposited on the electron transport layer as an electron injection layer having a thickness of 2nm, an Al cathode having a thickness of 80nm was then deposited on the electron injection layer by another vacuum vapor deposition apparatus. The time required for the brightness to drop to 80% at 5,000nit was 195 hours.

[ device example 10 to device example 16]OLEDs using the multi-component host materials of the present disclosure

OLEDs were produced in the same manner as in device example 9, except that the compounds shown in table 3 below were used as the first host and the second host for preparing the light emitting layer. The minimum time required for the produced OLED to reduce to 80% of the brightness of 5000 nits is shown in table 3 below.

[ comparative example 3 to comparative example 4]OLEDs using only the first host compound as host

An OLED was manufactured in the same manner as in device example 9, except that only the first host compound shown in table 3 was used as a host for the light emitting layer. The minimum time required for the produced OLED to reduce to 80% of the brightness of 5000 nits is shown in table 3 below.

[ Table 3]

As described above, although the organic electroluminescent device using the organic electroluminescent compound of the present disclosure as the only host shows excellent lifetime, the multi-component host material including the organic electroluminescent compound of the present disclosure may provide an organic electroluminescent device having more improved lifetime.

[ device example 17-1 to device example 17-5, device example 18-1 to device example 18-6]Wherein in accordance with the present disclosure And the second host compound of the OLED are co-evaporated

The OLED was manufactured as follows. A transparent electrode Indium Tin Oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an Organic Light Emitting Diode (OLED) device (geomantec) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water in order, and then stored in isopropyl alcohol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor deposition apparatus. 1,4,5,8,9, 12-hexaazatriphenylene-hexacyano-nitrile (compound HI-1) was introduced into one unit of a vacuum vapor deposition apparatus, and then the pressure in the chamber of the apparatus was controlled to 10^-6And (4) supporting. Thereafter, a current was applied to the cell to evaporate the above-introduced material, thereby forming a thickness of 5nm on the ITO substrateA first hole injection layer. Subsequently, N '-bis (naphthalen-1-yl) -N, N' -bis (phenyl) benzidine (compound HI-2) was introduced into another unit of the vacuum vapor deposition apparatus and evaporated by applying a current to the unit, thereby forming a second hole injection layer having a thickness of 95nm on the first hole injection layer. Reacting N- ([1,1' -biphenyl)]-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazolyl-3-yl) phenyl) -9H-fluoren-2-amine (compound HT-1) was introduced into one cell of a vacuum vapor deposition apparatus and evaporated by applying an electric current to the cell to form a hole transport layer having a thickness of 20nm on the second hole transport layer. Two compounds shown in the following table 4 were introduced into two units of a vacuum vapor deposition apparatus as host materials, respectively. Compound D-122 was incorporated into another cell as a dopant. The two host materials evaporated at the same rate of 1:1, while the dopant evaporated at a different rate from the host materials, so that the dopant was deposited at a doping amount of 12 wt% based on the total amount of the host and the dopant to form a light emitting layer having a thickness of 30nm on the hole transport layer. 2,4, 6-tris (9, 9-dimethyl-9H-fluoren-2-yl) -1,3, 5-triazine (compound ET-1) was then introduced into the other unit and evaporated to deposit an electron transport layer with a thickness of 35nm on the light-emitting layer. After quinoline lithium (compound EI-1) was deposited as an electron injection layer having a thickness of 2nm on the electron transport layer, an Al cathode having a thickness of 80nm was subsequently deposited on the electron injection layer by another vacuum vapor deposition apparatus.

Comparative device example 5-1 to device example 5-3]OLEDs using conventional compounds

OLEDs were manufactured in the same manner as in device example 17-1, except that conventional compounds shown in tables 4 and 5 below were used as the first host compound and the second host compound.

The driving voltage, the light emitting efficiency, the CIE color coordinates, and the minimum time required to reduce the luminance of 10,000 nits from 100% to 95% at a constant current of the OLEDs produced in device example 17-1 to device example 17-5, device example 18-1 to device example 18-6, and comparative device example 5-1 to comparative device example 5-3 are shown in table 4 below.

[ Table 4]

[ Table 5]

Claims

1. An organic electroluminescent compound represented by the following formula 2:

wherein L is₁Represents a single bond;

Ar₁represents an unsubstituted (C6-C30) aryl group;

Y₁to Y₄Each independently represents-CR₅-；

Y₅To Y₈Each independently represents-CR₆-；

R₄Represents hydrogen or deuterium;

R₅and R₆Each independently represents hydrogen or deuterium; or may be fused to an adjacent substituent(s) to form a substituted or unsubstituted benzindole ring; and

a represents a number of 0's in the formula,

b represents a number of 0's in the molecule,

c represents an integer of 1 to 4; and when c is an integer of 2 or more, R₄Are the same or different.

2. The organic electroluminescent compound according to claim 1, wherein R is₅And R₆Is gotEach substituent of the substituted benzindole ring is independently at least one selected from deuterium or (C6-C30) aryl.

3. The organic electroluminescent compound according to claim 1, wherein

L₁Represents a single bond;

X₁represents-NR₁-；

Ar₁Represents an unsubstituted (C6-C21) aryl group;

Y₁to Y₄Each independently represents-CR₅-；

Y₅To Y₈Each independently represents-CR₆-；

R₅And R₆Each independently represents hydrogen, or an unsubstituted (C6-C21) aryl group; or may be fused to an adjacent substituent(s) to form a substituted or unsubstituted benzindole ring; and

a represents a number of 0's in the formula,

b represents a number of 0's in the molecule,

4. The organic electroluminescent compound according to claim 3, wherein Ar is Ar₁Represents an unsubstituted phenyl group, an unsubstituted naphthyl group, an unsubstituted biphenyl group, an unsubstituted terphenyl group, an unsubstituted anthryl group, an unsubstituted phenanthryl group, an unsubstituted phenylnaphthyl group or an unsubstituted naphthylphenyl group.

5. The organic electroluminescent compound according to claim 1, wherein the compound is selected from the group consisting of:

6. an organic electroluminescent device comprising the compound according to claim 1.

7. An organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and cathode, wherein the organic layer comprises one or more light-emitting layers; at least one light-emitting layer contains one or more dopant compounds and two or more host compounds; and at least one of the two or more host compounds is the organic electroluminescent compound represented by formula 2 according to claim 1.

8. The organic electroluminescent device according to claim 7, wherein a first host compound of the two or more host compounds is selected from the organic electroluminescent compounds represented by formula 2 of claim 1.

9. The organic electroluminescent device according to claim 7, wherein at least two of the two or more host compounds are each independently selected from the organic electroluminescent compounds represented by formula 2.

10. The organic electroluminescent compound according to claim 7, wherein

A first host compound of the two or more host compounds is the organic electroluminescent compound represented by formula 2, and a second host compound is selected from the compounds represented by formulae 6 to 11 below,

wherein Cz represents the structure:

m represents a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (5-to 30-membered) heteroaryl group, provided that wherein h in formula 6 is 1, or i in formula 7 is 1, M is not

And M in formula 8 and formula 9 is not

Wherein X₂To X₆Each independently represents-CR₄-or-N-; ar (Ar)₁Represents a substituted or unsubstituted (C6-C30) aryl group; r₄Represents hydrogen or deuterium, and represents a bonding site;

x' represents-O-or-S-;

ring A represents

Ring B represents

Wherein X₂To X₆And Ar₁As defined in formula 2, and denotes a bonding site;

R₂₁to R₂₇Each independently represents hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, or R₂₈R₂₉R₃₀Si-; or may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, one or more carbon atoms of which may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; provided that wherein h in formula 6 or i in formula 7 is 1, R₂₆Or R₂₇Does not form Z having formulae 8,9 and 11₁、Z₂Ring of formula 10, R of formula D or E₂₂Does not form a bond to R in formula 8 and formula 9₂₁And to R in formula 11₂₃An indole ring of (a);

R₃₁to R₃₆Each independently represents hydrogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5-to 30-membered) heteroaryl; r₃₂And R₃₃May be the same or different; r₃₅And R₃₆May be the same or different; the heteroaryl (ene) group contains one or more heteroatoms selected from B, N, O, S, p (═ O), Si and p;

h and i each independently represent an integer of 1 to 3; j. k, l and p each independently represent an integer of 0 to 4; r, s and t each independently represent an integer of 1 to 4; and wherein h, i, j, k, L, p, r, s or t is an integer of 2 or more, (Cz-L)₄) Each of (1), (Cz), R₂₁Each of (1), R₂₂Each of (1), R₂₃Each of (1), R₂₄Each of (1), R₂₅Each of (1), R₂₆Each of (1) or R₂₇Each of which may be the same or different.

11. The organic electroluminescent device according to claim 10, wherein the compound represented by formula 6 to formula 11 is selected from the group consisting of: