CN113490730A - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Organic electroluminescent compounds and organic electroluminescent device comprising the same Download PDF

Info

Publication number
CN113490730A
CN113490730A CN202080015226.2A CN202080015226A CN113490730A CN 113490730 A CN113490730 A CN 113490730A CN 202080015226 A CN202080015226 A CN 202080015226A CN 113490730 A CN113490730 A CN 113490730A
Authority
CN
China
Prior art keywords
substituted
unsubstituted
group
alkyl
organic electroluminescent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202080015226.2A
Other languages
Chinese (zh)
Inventor
金荣光
尹承贤
吴洪世
李东炯
李泰珍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Electronic Materials Korea Ltd
Original Assignee
Rohm and Haas Electronic Materials Korea Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Electronic Materials Korea Ltd filed Critical Rohm and Haas Electronic Materials Korea Ltd
Priority claimed from PCT/KR2020/002389 external-priority patent/WO2020171587A1/en
Publication of CN113490730A publication Critical patent/CN113490730A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C09K2211/1062—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. By including the organic electroluminescent compound, an organic electroluminescent device having high luminous efficiency and/or high power efficiency can be provided.

Description

Organic electroluminescent compounds and organic electroluminescent device comprising the same
Technical Field
The present disclosure relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same.
Background
An electroluminescent device (EL device) is a self-luminous display device, which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. The first organic EL device was developed by Eastman Kodak in 1987 by using small aromatic diamine molecules and aluminum complexes as materials for forming a light emitting layer [ appl. phys. lett. [ appucation letters ]51,913,1987 ].
An organic electroluminescent device (OLED) converts electrical energy into light by applying power to an organic electroluminescent material, and generally includes an anode, a cathode, and an organic layer formed between the two electrodes. The organic layers of the organic EL device may include a hole injection layer, a hole transport layer, a hole assist layer, a light emission assist layer, an electron blocking layer, a light emitting layer (containing a host and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. Materials used in the organic layer may be classified into a hole injection material, a hole transport material, a hole assist material, a light emission assist material, an electron blocking material, a light emitting material, an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, and the like according to their functions. In such an organic EL device, holes from an anode and electrons from a cathode are injected into a light emitting layer by applying a voltage, and excitons having high energy are generated by recombination of the holes and the electrons. The organic light emitting compound moves to an excited state by energy and emits light by the energy when the organic light emitting compound returns to a ground state from the excited state.
The most important factor determining the luminous efficiency in an organic EL device is a light emitting material. The luminescent material is required to have the following characteristics: high quantum efficiency, high electron and hole mobility, and uniformity and stability of the formed light emitting material layer. The light emitting materials are classified into blue, green and red light emitting materials according to emission colors, and further include yellow or orange light emitting materials. In addition, in terms of functions, the light emitting material is classified into a host material and a dopant material. Recently, development of an organic EL device having high efficiency and long life is an urgent task. In particular, in view of EL characteristics required for medium-and large-sized OLED panels, development of highly excellent light emitting materials superior to conventional materials is urgently required. For this reason, preferably, as the solvent and the energy emitter in a solid state, the preferred characteristics of the host material should have high purity and suitable molecular weight for deposition under vacuum. In addition, the host material is required to have a high glass transition temperature and pyrolysis temperature to achieve thermal stability, high electrochemical stability to achieve a long life, easy formability of an amorphous thin film, good adhesion to an adjacent layer, and no mobility between layers.
In addition, there is a need to develop materials that have good thermal stability in hole transport layers, buffer layers, electron transport layers, etc., and that can improve the performance of EI devices, such as driving voltage, light emission efficiency, and lifetime characteristics.
KR 2016-0076881A discloses examples which are fused phenanthryl compounds for electron transport auxiliary layers and as host compounds.
Disclosure of Invention
Technical problem
The object of the present disclosure is, first, to provide an organic electroluminescent compound capable of producing an organic electroluminescent device having high luminous efficiency and/or high power efficiency; and secondly to provide an organic electroluminescent device comprising the organic electroluminescent compound.
Solution to the problem
As a result of intensive studies to solve the above technical problems, the present inventors found that the aforementioned object can be achieved by an organic electroluminescent compound represented by the following formula 1, and then completed the present invention.
Figure BDA0003217736670000021
In the formula 1, the first and second groups,
Y1and Y2Each independently represents O or S;
L1each independently represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (3-to 30-membered) heteroarylene;
Ar1each independently represents hydrogen, deuterium, halogen, cyano, 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, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyl di (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, (C3-C30) aliphatic ring and (C6-C30) fused ring, substituted or unsubstituted aromatic or-N (Ar 6382) fused ring 4)(Ar5) (ii) a Or may be linked to an adjacent substituent to form a ring;
Ar4and Ar5Each independently represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C2-C30) alkenyl group, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (3-to 30-membered) heteroaryl group;
R1and R2Each independently represents hydrogen, deuterium, halogen, cyano, 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, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyl di (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino; or may be linked to an adjacent substituent to form a ring; and is
a represents an integer of 0 to 4, and when a is 2 or more, each-L1-Ar1May be the same or different.
The invention has the advantages of
By including the organic electroluminescent compounds according to the present disclosure, an organic electroluminescent device having high luminous efficiency and/or high power efficiency can be prepared.
Detailed Description
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the invention and is not meant to limit the scope of the invention in any way.
The present disclosure relates to an organic electroluminescent compound represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the organic electroluminescent material.
The term "organic electroluminescent compound" in the present disclosure means a compound that can be used for an organic electroluminescent device and can be contained in any material layer constituting the organic electroluminescent device if necessary.
Herein, the "organic electroluminescent material" means a material that may be used in an organic electroluminescent device and may include at least one compound. The organic electroluminescent material may be contained in any layer constituting the organic electroluminescent device, if necessary. For example, the organic electroluminescent material may be a hole injection material, a hole transport material, a hole assist material, a light emission assist material, an electron blocking material, a light emitting material (containing a host material and a dopant material), an electron buffering material, a hole blocking material, an electron transport material, an electron injection material, or the like.
Herein, "(C1-C30) alkyl" means a straight or branched chain alkyl group having 1 to 30 carbon atoms constituting a chain, wherein the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10. The above alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. "(C3-C30) cycloalkyl" is a monocyclic or polycyclic hydrocarbon having 3 to 30 ring backbone carbon atoms, wherein the number of carbon atoms is preferably 3 to 20, and more preferably 3 to 7. The cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentylAlkyl, cyclohexyl, and the like. "(C6-C30) (arylene) is a monocyclic or fused ring group derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, wherein the number of ring backbone carbon atoms is preferably 6 to 20, more preferably 6 to 15, which may be partially saturated, and may comprise a spiro structure. Examples of the aryl group specifically include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, dimethylfluorenyl, diphenylfluorenyl, benzofluorenyl, diphenylbenzofluorenyl, dibenzofluorenyl, phenanthryl, benzophenanthryl, phenylphenanthryl, anthryl, benzanthryl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, binaphthyl, and the like,
Figure BDA0003217736670000041
Radical, benzo
Figure BDA0003217736670000042
Mesityl, naphthonaphthyl, fluoranthenyl, benzofluoranthenyl, tolyl, xylyl, mesityl, cumenyl, spiro [ fluorene-fluorene ]]Spiro [ fluorene-benzofluorene ] s]Mesityl, azulene and the like. More specifically, the aryl group may be o-tolyl, m-tolyl, p-tolyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesitylene, o-cumenyl, m-cumenyl, p-tert-butylphenyl, p- (2-phenylpropyl) phenyl, 4' -methylbiphenyl, 4 "-tert-butyl-p-terphenyl-4-yl, o-biphenyl, m-biphenyl, p-terphenyl, o-terphenyl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-quaterphenyl, 1-naphthyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-quaterphenyl, m-terphenyl, p-terphenyl-3-1-naphthyl, p-terphenyl-3-l, p-terphenyl-4-biphenyl, p-l, p-terphenyl-l, p-biphenyl, p-l, p-terphenyl-l, p-terphenyl-p-terphenyl, p-l, p-terphenyl, p-n-p-n-p-n-p-n-p-n-p-n-p-n-p-n-p-n-p-, 2-naphthyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 9-dimethyl-1-fluorenyl, 9-dimethyl-2-fluorenyl, 9-dimethyl-3-fluorenyl, 9-dimethyl-4-fluorenyl, 9-diphenyl-1-fluorenyl, 9-diphenyl-2-fluorenyl, 9-diphenyl-3-fluorenyl, 9-diphenyl-4-fluorenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-
Figure BDA0003217736670000043
Base 2-
Figure BDA0003217736670000044
Base 3-
Figure BDA0003217736670000045
Base, 4-
Figure BDA0003217736670000046
Base 5-
Figure BDA0003217736670000047
Base 6-
Figure BDA0003217736670000048
Radical, benzo [ c]Phenanthryl, benzo [ g ]]
Figure BDA0003217736670000049
A group such as a 1-triphenylene group, a 2-triphenylene group, a 3-triphenylene group, a 4-triphenylene group, a 3-fluoranthenyl group, a 4-fluoranthenyl group, an 8-fluoranthenyl group, a 9-fluoranthenyl group, or a benzofluoranthenyl group. "(3-to 30-membered) (arylene) heteroaryl" is an aryl group having 3 to 30 ring backbone atoms, wherein the number of ring backbone atoms is preferably 5 to 25, including at least one, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, Si, P and Ge. The above-mentioned heteroaryl group may be a monocyclic ring, or a condensed ring condensed with at least one benzene ring; and may be partially saturated. Further, the above-mentioned heteroaryl group may be a heteroaryl group formed by connecting at least one heteroaryl group or aryl group to a heteroaryl group via one or more single bonds. Examples of heteroaryl groups may specifically include monocyclic heteroaryl groups including furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like, and fused-ring heteroaryl groups including benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, and the like, and fused-ring heteroaryl groups including benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl Oxazolyl, benzoxazolyl, imidazopyridinyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, azacarbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, indolizinyl, acridinyl (arylidinyl), silafluorenyl (silafluoroenyl), germafluoroenyl and the like. More specifically, the heteroaryl group may be a 1-pyrrolyl group, a 2-pyrrolyl group, a 3-pyrrolyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 4-pyrimidyl group, a 5-pyrimidyl group, a 6-pyrimidyl group, a 1,2, 3-triazin-4-yl group, a 1,2, 4-triazin-3-yl group, a 1,3, 5-triazin-2-yl group, a 1-imidazolyl group, a 2-imidazolyl group, a 1-pyrazolyl group, a 1-indolizidinyl group, a 2-indolizidinyl group, a 3-indolizidinyl group, a 5-indolizidinyl group, a 6-indolizidinyl group, a 7-indolizidinyl group, an 8-indolizidinyl group, a 2-imidazopyridinyl group, a, 3-imidazopyridinyl, 5-imidazopyridinyl, 6-imidazopyridinyl, 7-imidazopyridinyl, 8-imidazopyridinyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl, 1-isobenzofuryl, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalyl group, 5-quinoxalyl group, 6-quinoxalyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, azacarbazol-1-yl group, azacarbazol-2-yl group, a, Azacarbazol-3-yl, azacarbazol-4-yl, azacarbazol-5-yl, azacarbazol-6-yl, azacarbazol-7-yl, azacarbazol-8-yl, azacarbazol-9-yl, 1-phenanthridinyl, azacarbazol-3-yl, azacarbazol-4-yl, azacarbazol-5-yl, azacarbazol-6-yl, azacarbazol-7-yl, azacarbazol-9-yl, azaphenanthridinyl, and azacarbazol-1-yl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazanyl, 2-thienyl, 3-thienyl, 2-methylpyrrol-1-yl, 2-methylpyrrol-3-yl, 2-methylpyrrol-4-yl, 2-methylpyrrole-5-yl, 3-methylpyrrole-1-yl, 3-methylpyrrole-2-yl, 3-methylpyrrol-4-yl, 3-methylpyrrol-5-yl, 2-tert-butylpyrrol-4-yl, 3- (2-phenylpropyl) pyrrol-1-yl, 2-methyl-1-indolyl, 4-methyl-1-indolyl, 2-methyl-3-indolyl, 4-methyl-3-indolyl, 2-tert-butyl-1-indolyl, 4-tert-butyl-1-indolyl, 2-tert-butyl-3-indolyl, 4-tert-butyl-3-indolyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl, methyl-1-indolyl, 1-dibenzothienyl, 2-dibenzothienyl, 3-dibenzothienyl, 4-dibenzothienyl, 1-silafluorenyl, 2-silafluorenyl, 3-silafluorenyl, 4-silafluorenyl, 1-germanium fluorenyl, 2-germanium fluorenyl, 3-germanium fluorenyl, 4-germanium fluorenyl, and the like. As used herein, "halogen" includes F, Cl, Br and I.
Further, "o", "m", and "p" mean the substitution positions of all substituents. The ortho positions are compounds having substituents adjacent to each other, for example at the 1 and 2 positions on benzene. The meta position is a substitution position next to the substitution position immediately, and for example, the compound has a substituent at the 1-position and the 3-position on benzene. The para position is the next substitution position of the meta position, and for example, the compound has substituents at the 1-and 4-positions on benzene.
Herein, "ring formed by connecting to adjacent substituents" means a substituted or unsubstituted (3-to 30-membered) monocyclic or polycyclic alicyclic ring, aromatic ring, or a combination thereof formed by connecting or fusing two or more adjacent substituents; preferably, the alicyclic ring, aromatic ring, or a combination thereof, which may be substituted or unsubstituted (3-to 26-membered) monocyclic or polycyclic. Furthermore, the ring formed may comprise at least one heteroatom selected from the group consisting of B, N, O, S, Si and P, preferably N, O and S. According to one embodiment of the present disclosure, the number of atoms in the ring backbone is from 5 to 20; according to another embodiment of the disclosure, the number of atoms in the ring backbone is 5 to 15. In one embodiment, the fused ring may be, for example, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted fluorene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted indene ring, a substituted or unsubstituted benzene ring, or a substituted or unsubstituted carbazole ring, etc.
Further, "substituted" in the expression "substituted or unsubstituted" means that a hydrogen atom in a certain functional group is replaced with another atom or functional group (i.e., substituent). At L1、Ar1、Ar4、Ar5、R1And R2In (1), substituted (C1-C30) alkyl, substituted (C2-C30) alkenyl, substituted (C6-C30) (arylene), substituted (3-to 30-membered) (arylene) heteroaryl, substituted (C3-C30) cycloalkyl, substituted (C1-C30) alkoxy, each of the substituents of the substituted tri (C1-C30) alkylsilyl, the substituted di (C1-C30) alkyl (C6-C30) arylsilyl, the substituted (C1-C30) alkyldi (C6-C30) arylsilyl, the substituted tri (C6-C30) arylsilyl, the fused ring of the substituted (C3-C30) aliphatic ring and the (C6-C30) aromatic ring, and the substituted (C1-C30) alkyl (C6-C30) arylamino is independently at least one 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, (C6-C30) aryl substituted or unsubstituted (5-to 30-membered) heteroaryl, (5-to 30-membered) heteroaryl substituted or unsubstituted (C6-C30) aryl, tri (C1-C7) alkylsilyl, tri (C6-C30) arylsilyl, di (C30-C30) alkyl (C30-C30) arylsilyl, (C30-C36 30 2) arylsilyl, Amino, mono-or di (C1-C30) alkylamino, (C1-C30) ) Alkyl substituted or unsubstituted mono-or di (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, (C1-C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) arylboronocarbonyl, di (C1-C30) alkylboronocarbonyl, (C1-C30) alkyl (C6-C30) arylboronocarbonyl, (C6-C30) aryl (C1-C30) alkyl, and (C1-C30) alkyl (C6-C30) aryl. For example, the substituent may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted m-biphenyl group, a substituted or unsubstituted triazinyl group, or the like.
Hereinafter, an organic electroluminescent compound according to an embodiment will be described.
An organic electroluminescent compound according to one embodiment is represented by the following formula 1.
Figure BDA0003217736670000071
In the formula 1, the first and second groups,
Y1and Y2Each independently represents O or S;
L1each independently represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (3-to 30-membered) heteroarylene;
Ar1each independently represents hydrogen, deuterium, halogen, cyano, 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, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyl di (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted (C3-C30) aliphatic ring and (C6-C30) aromatic ring, or-N (Ar 6382) fused ring 4)(Ar5) (ii) a Or may be linked to an adjacent substituent to form a ring;
Ar4and Ar5Each independently represents hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, or a mixture thereofA substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (3-to 30-membered) heteroaryl;
R1and R2Each independently represents hydrogen, deuterium, halogen, cyano, 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, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyl di (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino; or may be linked to an adjacent substituent to form a ring;
a represents an integer of 0 to 4, and when a is 2 or more, each-L1-Ar1May be the same or different.
In one embodiment, Y1And Y2Can be both O or both S.
In one embodiment, L 1Each independently may be a single bond, a substituted or unsubstituted (C6-C25) arylene, or a substituted or unsubstituted (5-to 25-membered) heteroarylene, preferably a single bond, a substituted or unsubstituted (C6-C18) arylene, or a substituted or unsubstituted (5-to 18-membered) heteroarylene, for example, may be a single bond, phenylene, naphthylene, or pyridylene.
In one embodiment, Ar1Each independently may be hydrogen, substituted or unsubstituted (C6-C25) aryl, substituted or unsubstituted (5-to 25-membered) heteroaryl, -N (Ar)4)(Ar5) (ii) a Or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3-to 30-membered), mono-or polycyclic, alicyclic ring, aromatic ring, or a combination thereof. Preferably, Ar1Each independently may be hydrogen, substituted or unsubstituted (C6-C18) aryl, or substituted or unsubstituted (5-to 18-membered) heteroaryl, -N (Ar)4)(Ar5) (ii) a Or may be linked to an adjacent substituent to form a substituted or unsubstituted (5-membered)To 25-membered) monocyclic or polycyclic aromatic ring, or a combination thereof, for example, can be hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted triazinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, -N (Ar) 4)(Ar5) (ii) a Or may be associated with a plurality of adjacent Ar' s1Joined to form a substituted or unsubstituted fused ring.
In one embodiment, Ar4And Ar5Each independently can be hydrogen, deuterium, a substituted or unsubstituted (C1-C10) alkyl group, a substituted or unsubstituted (C2-C10) alkenyl group, a substituted or unsubstituted (C6-C25) aryl group, a substituted or unsubstituted (5-to 25-membered) heteroaryl group, preferably a substituted or unsubstituted (C6-C18) aryl group or a substituted or unsubstituted (5-to 18-membered) heteroaryl group, for example, can be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted carbazolyl group.
In one embodiment, R1And R2Each independently can be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C10) alkyl, substituted or unsubstituted (C6-C25) aryl, or substituted or unsubstituted (5-to 25-membered) heteroaryl; or may be associated with a plurality of adjacent R1Or a plurality of adjacent R2Or adjacent R1And R2Are linked to form a ring. Preferably R1And R2Each independently represents a substituted or unsubstituted (C6-C18) aryl, or a substituted or unsubstituted (5-to 18-membered) heteroaryl; or may be associated with a plurality of adjacent R 1Or a plurality of adjacent R2Or adjacent R1And R2The linkage forms a ring, and may be, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazolyl group.
In one embodiment, when a plurality of adjacent R' s1Or a plurality of adjacent R2Or adjacent R1And R2When they are linked to each other to form a ring, they may beTo form the following structure so that a screw structure can be formed together with the core having formula 1.
Figure BDA0003217736670000091
In the above structure, is the point of attachment to the core of formula 1.
The organic electroluminescent compound having formula 1 according to one embodiment may be represented by any one of the following formulae 2 to 4.
Figure BDA0003217736670000092
Figure BDA0003217736670000101
In the formulae 2 to 4, the first and second groups,
Y1、Y2、R1、R2、L1、Ar1and a is as defined in formula 1;
Ar2、Ar3and Ar6Is as in Ar1Are defined as such;
Y3representation O, S, -N (L)2-Ar7) or-C (Ar)8)(Ar9)；
L2Is represented by L1Are defined as such;
Ar7is represented by Ar4Are defined as such;
Ar8and Ar9Each independently represents a substituted or unsubstituted (C1-C30) alkyl group or a substituted or unsubstituted (C6-C30) aryl group;
b to d each independently represent an integer of 1 to 4, e represents an integer of 1 or 2; and is
When b to e are 2 or more, each Ar2、Ar3、Ar6and-L1-Ar1May be the same or different.
In one embodiment, Ar2And Ar3Each independently may be hydrogen, substituted or unsubstituted (C6-C25) aryl, substituted or unsubstituted (5-to 25-membered) heteroaryl, -N (Ar) 4)(Ar5) (ii) a Or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3-to 30-membered), mono-or polycyclic, alicyclic ring, aromatic ring, or combination thereof, preferably, may be hydrogen, substituted or unsubstituted (C6-C18) aryl, substituted or unsubstituted (5-to 18-membered) heteroaryl, -N (Ar)4)(Ar5) (ii) a Or an aromatic ring which may be linked to an adjacent substituent to form a substituted or unsubstituted (5-to 25-membered) monocyclic or polycyclic ring, or a combination thereof, and may be, for example, hydrogen, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted triazinyl group, -N (Ar)4)(Ar5) For example, substituted or unsubstituted diarylamines; or may be fused with an adjacent substituent to form a substituted or unsubstituted fluorene ring or a substituted or unsubstituted carbazole ring.
In one embodiment, Ar6Each independently may be hydrogen, substituted or unsubstituted (C6-C25) aryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (3-to 30-membered), mono-or polycyclic, alicyclic ring, aromatic ring, or combination thereof, preferably, may be hydrogen, unsubstituted (C6-C18) aryl; or an aromatic ring which may be linked to an adjacent substituent to form a substituted or unsubstituted (5-to 25-membered) monocyclic or polycyclic ring, or a combination thereof, for example, hydrogen, substituted or unsubstituted phenyl; or may be fused with an adjacent substituent to form a substituted or unsubstituted fluorene ring.
In one embodiment, L2May be a single bond, a substituted or unsubstituted (C6-C25) arylene, or a substituted or unsubstituted (5-to 25-membered) heteroarylene, preferably a single bond, a substituted or unsubstituted (C6-C18) arylene, or a substituted or unsubstituted (5-to 18-membered) heteroarylene. For example, L2May be a single bond, phenylene, or pyridylene.
In one embodiment, Ar7May be a substituted or unsubstituted (C6-C25) aryl or a substituted or unsubstituted (5-to 25-membered) heteroaryl, preferably a substituted or unsubstituted(C6-C18) aryl or substituted or unsubstituted (5-to 18-membered) heteroaryl, for example, may be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triazinyl, substituted or unsubstituted pyridyl, or substituted or unsubstituted pyrimidyl.
According to one embodiment, Ar1、Ar4、Ar5、R1And R2Each independently may be selected from any one of the substituents listed in group 1 below.
[ group 1 ]
Figure BDA0003217736670000111
Figure BDA0003217736670000121
Figure BDA0003217736670000131
According to one embodiment, the organic electroluminescent compound represented by formula 1 may be more specifically illustrated by the following compounds, but is not limited thereto.
Figure BDA0003217736670000141
Figure BDA0003217736670000151
Figure BDA0003217736670000161
Figure BDA0003217736670000171
Figure BDA0003217736670000181
Figure BDA0003217736670000191
Figure BDA0003217736670000201
The compound represented by formula 1 according to the present disclosure may be prepared as represented by the following reaction schemes 1 and 2, but is not limited thereto; the compounds may be further produced by synthetic methods known to those skilled in the art.
[ reaction scheme 1]
Figure BDA0003217736670000211
[ reaction scheme 2]
Figure BDA0003217736670000212
In reaction schemes 1 and 2, the substituents are as defined in formulas 1 to 4.
As described above, exemplary synthesis examples of the compound represented by formula 1 according to one embodiment are described, but they are based on the Buchwald-hartwigh (Buchwald-Hartwig) cross-coupling reaction, Suzuki (Suzuki) cross-coupling reaction, bromination reaction, organolithium reaction, phosphine-mediated reductive cyclization reaction, and the like. It will be understood by those skilled in the art that the above reaction continues even if other substituents defined in formulae 1 to 4 are bonded in addition to the substituents described in the specific synthetic examples.
The present disclosure may provide an organic electroluminescent material including the organic electroluminescent compound having formula 1, and an organic electroluminescent device including the organic electroluminescent material.
The organic electroluminescent material may be composed of only the organic electroluminescent compound of the present disclosure, or may further include conventional materials included in the organic electroluminescent material. When two or more materials are included in one layer, the at least two compounds may be evaporated or co-evaporated as a mixture to form a layer. The organic electroluminescent material according to one embodiment may include at least one compound represented by formula 1. For example, the compound having formula 1 may be included as a Hole Transport Layer (HTL) material of an organic electroluminescent device.
The organic electroluminescent material of the present disclosure may further comprise a host compound other than the organic electroluminescent compound having formula 1. Preferably, the organic electroluminescent material may further comprise at least one dopant.
The dopant included in the organic electroluminescent material of the present disclosure may be at least one phosphorescent dopant or fluorescent dopant, preferably a phosphorescent dopant. The phosphorescent dopant material applied to the organic electroluminescent device of the present disclosure is not particularly limited, but may be preferably one or more metallized complex compounds of one or more metal atoms selected from the group consisting of: iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably one or more ortho-metallated complex compounds of one or more metal atoms selected from: iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably one or more ortho-metallated iridium complex compounds.
The dopant contained may use a compound represented by the following formula 101, but is not limited thereto:
Figure BDA0003217736670000221
in the formula 101, the first and second groups,
wherein L is selected from the following structures 1 or 2:
Figure BDA0003217736670000222
R100to R103Each independently represents hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, cyano, substituted or unsubstituted (3-to 30-membered) heteroaryl, or substituted or unsubstituted (C1-C30) alkoxy; or R 100To R103May be linked to one or more adjacent substituents to form a substituted or unsubstituted fused ring, for example, substituted or unsubstituted quinoline, substituted or unsubstituted benzofuropyridine, substituted or unsubstituted benzothienopyridine, substituted or unsubstituted indenopyridine, substituted or unsubstituted benzofuroquinoline, substituted or unsubstituted benzothienoquinoline, or substituted or unsubstituted indenoquinoline;
R104to R107Each independently represents hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 30-membered) heteroaryl, cyano, or substituted or unsubstituted (C1-C30) alkoxy; or R104To R107May be linked to one or more adjacent substituents to form a substituted or unsubstituted fused ring, for example, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted indenopyridine, substituted or unsubstituted benzofuropyridine, or substituted or unsubstituted benzothienopyridine;
R201to R211Each independently represents hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, or substituted or unsubstituted (C6-C30) aryl; or may be linked to one or more adjacent substituents to form a substituted or unsubstituted fused ring; and is
s represents an integer of 1 to 3.
Specific examples of dopant compounds include, but are not limited to, the following:
Figure BDA0003217736670000231
Figure BDA0003217736670000241
Figure BDA0003217736670000251
Figure BDA0003217736670000261
Figure BDA0003217736670000271
hereinafter, an organic electroluminescent device to which the above organic electroluminescent compound or organic electroluminescent material is applied will be described.
An organic electroluminescent device according to an embodiment may include a first electrode; a second electrode; and at least one organic layer between the first electrode and the second electrode.
The compound represented by formula 1 of the present disclosure may be included in one or more layers constituting an organic electroluminescent device. According to one embodiment, the organic layer includes a light emitting layer, a hole transport layer and/or a hole assist layer including the organic electroluminescent compound according to the present disclosure. In one embodiment, when the compound having formula 1 is included in the light emitting layer, it may be included as a host material. Among them, the host material may be a host material of an organic electroluminescent device for green or red light emission. In addition, when the compound having formula 1 is contained in the hole transport layer and/or the hole assist layer, it may be contained as the hole transport material and/or the hole assist material. For example, the light emitting layer, the hole transport layer, and/or the hole auxiliary layer may include only the organic electroluminescent compound of the present disclosure or at least two of the organic electroluminescent compounds of the present disclosure, and may further include conventional materials included in the organic electroluminescent material.
In addition, the organic layer may include a light emitting layer, a hole transport layer, and a hole assist layer, and may further include at least one layer selected from the group consisting of: a hole injection layer, a light emission auxiliary layer, an electron transport layer, an electron injection layer, an intermediate layer, a hole blocking layer, an electron blocking layer, and an electron buffer layer. Each layer may further consist of several layers. In addition, the organic layer may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds, and further include at least one metal selected from the group consisting of: an organometallic of a metal of group 1, a metal of group 2, a transition metal of period 4, a transition metal of period 5, a lanthanide and a d-transition element of the periodic table, or at least one complex compound comprising such a metal.
According to one embodiment, an organic electroluminescent material may be used as a light emitting material for a white organic light emitting device. According to the arrangement of R (red), G (green), B (blue), or YG (yellow-green) light emitting cells, various structures have been proposed for a white organic light emitting device, such as a parallel side-by-side arrangement method, a stack arrangement method, or a CCM (color conversion material) method, or the like. Further, according to an embodiment, the organic electroluminescent material may also be applied to an organic electroluminescent device including QDs (quantum dots).
One of the first electrode and the second electrode may be an anode, and the other may be a cathode. Wherein the first electrode and the second electrode may be each formed of a transmissive conductive material, a transflective conductive material, or a reflective conductive material. The organic electroluminescent device may be a top emission type, a bottom emission type, or a both-side emission type according to the kind of materials forming the first electrode and the second electrode.
A hole injection layer, a hole transport layer, an electron blocking layer, or a combination thereof may be used between the anode and the light emitting layer. The hole injection layer may be a multilayer to lower a hole injection barrier (or hole injection voltage) from the anode to the hole transport layer or the electron blocking layer, wherein each of the multilayer may use two compounds at the same time. The hole injection layer may be doped with a p-type dopant. In addition, an electron blocking layer may be disposed between the hole transport layer (or the hole injection layer) and the light emitting layer, and excitons may be confined within the light emitting layer by blocking electrons from overflowing from the light emitting layer to prevent light emission leakage. The hole transport layer or the electron blocking layer may be a multilayer, and a plurality of compounds may be used for each layer.
An electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof may be used between the light emitting layer and the cathode. The electron buffer layer may be a multi-layer to control injection of electrons and improve interface characteristics between the light emitting layer and the electron injection layer, wherein each of the multi-layers may use two compounds at the same time. The hole blocking layer or the electron transporting layer may also be a multilayer, in which a plurality of compounds may be used for each layer. In addition, the electron injection layer may be doped with n-type dopants.
The light emission assisting layer may be disposed between the anode and the light emitting layer, or between the cathode and the light emitting layer. When a light-emitting auxiliary layer is placed between the anode and the light-emitting layer, it can be used to facilitate hole injection and/or hole transport, or to prevent electron overflow. When the light-emitting auxiliary layer is placed between the cathode and the light-emitting layer, it may be used to facilitate electron injection and/or electron transport, or to prevent hole overflow. In addition, a hole assist layer may be disposed between the hole transport layer (or the hole injection layer) and the light emitting layer, and the hole transport rate (or the hole injection rate) may be effectively promoted or blocked, thereby enabling control of charge balance. When the organic electroluminescent device includes two or more hole transport layers, the hole transport layers further included may serve as a hole assist layer or an electron blocking layer. The light-emitting auxiliary layer, the hole auxiliary layer, or the electron blocking layer may have an effect of improving the efficiency and/or lifetime of the organic electroluminescent device.
In the organic electroluminescent device of the present disclosure, it may be preferable to select from a chalcogenide layer, a metal halide layer and metal oxideAt least one layer (hereinafter, "surface layer") of the chemical layer is placed on one or more inner surfaces of one or both electrodes. Specifically, a chalcogenide (including oxide) layer of silicon and aluminum is preferably placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on the cathode surface of the electroluminescent medium layer. The operational stability of the organic electroluminescent device can be obtained by the surface layer. Preferably, the chalcogenide comprises SiO X(1≤X≤2)、AlOX(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.
Further, in the organic electroluminescent device of the present disclosure, 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 to the electroluminescent medium. In addition, the hole-transporting compound is oxidized into cations, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidizing dopant includes various 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 reductive dopant layer may be used as a charge generation layer to prepare an organic 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, ion plating method, etc., or a wet film forming method such as inkjet printing, nozzle printing, slot coating, spin coating, dip coating, flow coating method, etc., may be used.
When a wet film formation method is used, a thin film may be formed by dissolving or diffusing a material forming each layer into any suitable solvent (e.g., ethanol, chloroform, tetrahydrofuran, dioxane, or the like). The solvent may be any solvent in which a material forming each layer can be dissolved or diffused and which has no problem in terms of film-forming ability.
In addition, the present disclosure may provide a display device using the compound represented by formula 1. That is, by using the compound of the present disclosure, it can be used for manufacturing a display device or a lighting device. Specifically, the organic electroluminescent device of the present disclosure may be used to manufacture a display device such as a display device of a smart phone, a tablet computer, a notebook computer, a PC, a TV, or a vehicle, or a lighting device such as outdoor or indoor lighting.
Hereinafter, the preparation method of the compound according to the present disclosure will be explained with reference to the synthesis method of a representative compound or an intermediate compound of the present disclosure, in order to understand the present disclosure in detail.
[ example 1] Synthesis of Compound C-3
Figure BDA0003217736670000301
Synthesis of Compound 1-1
Catechol (20g, 181.7mmol), α -dichlorodiphenylmethane (43g, 181.7mmol), and 454mL of toluene were added to a 1L Round Bottom Flask (RBF), and stirred at 100 ℃ for 27 hours. The reaction mixture was then cooled to room temperature and concentrated by distillation. The resulting mixture was purified by column chromatography to obtain compound 1-1(41g, 82%).
Synthesis of Compound 1-2
Compound 1-1(20g, 73.0mmol) and 730mL of Dimethylformamide (DMF) were added to 1L RBF and stirred at room temperature for 10 minutes, and then N-bromosuccinimide (NBS) (13.6g, 76mmol) was added to the mixture, followed by reaction at room temperature for 24 hours. After completion of the reaction, a solid obtained by distilling the reaction mixture was purified by column chromatography to obtain compound 1-2(24.4g, 95%).
Synthesis of Compound C-3
Reacting N- ([1,1' -diphenyl group)]-4-yl) -9, 9-dimethyl-9H-fluoren-2-amine (6.8g, 19.4mmol), tris (dibenzylideneacetone) dipalladium (0) (Pd)2(dba)3) (710mg, 0.776mmol), 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (s-phos) (637mg, 1.55mmol), sodium tert-butoxide (NaOtBu) (2.8g, 29mmol), and 144mL of toluene were added to 500mL of RBF and heated to 100 ℃. Compound 1-2 was dissolved in 50mL of toluene, which was then added dropwise to the reaction mixture, and then reacted for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the organic layer was extracted with dichloromethane. The remaining liquid of the organic layer was MgSO4Removed and dried, and then the reaction mixture was purified by column chromatography to obtain compound C-3(1g, 8%).
[ example 2] Synthesis of Compound C-1
Figure BDA0003217736670000311
Reacting N-phenyl- [1,1' -diphenyl]-4-amine (10g, 19.4mmol), Pd2dba3(1.5g, 1.64mmol), s-phos (1.3g, 3.3mmol), NaOtBu (5.9g, 61mmol), and 310mL of toluene were added to 500mL of RBF and heated to 100 ℃. Compound 1-2 was dissolved in 100mL of toluene, which was then added dropwise to the reaction mixture, and then reacted for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the organic layer was extracted with dichloromethane. The remaining liquid of the organic layer was MgSO4Removed and dried, and then the reaction mixture was purified by column chromatography to obtain compound C-1(7.5g, 35%).
Hereinafter, a method of manufacturing an organic electroluminescent device including the organic electroluminescent compound of the present disclosure and characteristics thereof will be described in order to understand the present disclosure in detail.
Device examples 1 and 2 production of OLED Using organic electroluminescent Compounds according to the present disclosure
An OLED is produced by using the organic electroluminescent compound according to the present disclosure. First, it will be used for OLA transparent electrode Indium Tin Oxide (ITO) thin film (10 Ω/sq) (geomama co., LTD., japan) on a glass substrate of ED was subjected to ultrasonic washing with acetone and isopropyl alcohol in this order, and then stored in isopropyl alcohol. Next, the ITO substrate was mounted on a substrate holder of the vacuum vapor deposition apparatus. Introducing the compound HI-1 into a chamber of a vacuum vapor deposition apparatus, and then controlling the pressure in the chamber of the apparatus to 10 -6And (4) supporting. Thereafter, a current was applied to the cell to evaporate the introduced material, thereby forming a first hole injection layer having a thickness of 80nm on the ITO substrate. Then, the compound HI-2 was introduced into another cell of the vacuum vapor deposition apparatus, and a current was applied to the cell to evaporate the introduced material, thereby forming a second hole injection layer having a thickness of 5nm on the first hole injection layer. Next, the compound HT-1 was introduced into another chamber of the vacuum vapor deposition apparatus. Thereafter, a current was applied to the cell to evaporate the introduced material, thereby forming a first hole transport layer having a thickness of 10nm on the second hole injection layer. Then, the compounds listed in table 1 below were introduced as a second hole transport material into another cell of the vacuum vapor deposition apparatus, and a current was applied to the cell to evaporate the introduced material, thereby forming a second hole transport layer (hole assist layer) having a thickness of 30nm on the first hole transport layer. After forming the hole injection layer and the hole transport layer, a light emitting layer is then deposited thereon as follows: the compound H-1 was introduced as a host into one cell and the compound D-1 was introduced as a dopant into the other cell of the vacuum vapor deposition apparatus. The dopant was doped at a doping amount of 10 wt% with respect to the deposition rate of the light emitting layer to form a light emitting layer having a thickness of 40nm on the hole transport layer. Next, compounds ET-1 and EI-1 were introduced into another cell, evaporated at a rate of 1:1, and deposited to form an electron transport layer having a thickness of 35nm on the light emitting layer. After the 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 800nm was deposited on the electron injection layer by another vacuum vapor deposition apparatus. Thus, an OLED was produced.
Comparative example 1 production of OLEDs not according to the present disclosure
An OLED was produced in the same manner as in device example 1, except that the compound HT-1 was used in the second host transport material (hole auxiliary material).
The results of the driving voltage, the current efficiency, the power efficiency, the external quantum efficiency, and the color coordinates at a luminance of 1,000 nits for the organic electroluminescent devices of device examples 1 and 2 and device comparative example 1 produced as described above are shown in table 1 below.
[ TABLE 1]
Figure BDA0003217736670000321
Referring to table 1 above, when the organic electroluminescent compound according to the present disclosure uses the material of the second hole transport layer of the organic electroluminescent device, it can be confirmed that the organic electroluminescent device according to one embodiment is superior in current efficiency, power efficiency, and external quantum efficiency compared to the device comparative example 1 using the conventional hole transport material. Thus, the organic electroluminescent device according to one embodiment can be expected to have high luminous efficiency.
The compounds used in apparatus examples 1 and 2 and apparatus comparative example 1 are specifically shown in table 2 below.
[ TABLE 2 ]
Figure BDA0003217736670000331

Claims (8)

1. An organic electroluminescent compound represented by the following formula 1:
Figure FDA0003217736660000011
wherein the content of the first and second substances,
Y1And Y2Each independently represents O or S;
L1each independently represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (3-to 30-membered) heteroarylene;
Ar1each independently represents hydrogen, deuterium, halogen, cyano, 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, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyl di (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted (C3-C30) aliphatic ring and (C6-C30) aromatic ring, or-N (Ar 6382) fused ring4)(Ar5) (ii) a Or may be linked to an adjacent substituent to form a ring;
Ar4and Ar5Each independently represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C2-C30) alkenyl group, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (3-to 30-membered) heteroaryl group;
R1and R2Each independently represents hydrogen, deuterium, halogen, cyano, 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, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted (C1-C30) alkyl di (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino; or may be linked to an adjacent substituent to form a ring; and is
a represents an integer of 0 to 4, and when a is 2 or more, each-L1-Ar1May be the same or different.
2. The organic electroluminescent compound according to claim 1, wherein the formula 1 is represented by any one of the following formulae 2 to 4:
Figure FDA0003217736660000021
wherein the content of the first and second substances,
Y1、Y2、R1、R2、L1、Ar1and a is as defined in claim 1;
Ar2、Ar3and Ar6Is as in Ar1Are defined as such;
Y3representation O, S, -N (L)2-Ar7) or-C (Ar)8)(Ar9)；
L2Is as in L1Are defined as such;
Ar7is as in Ar4Are defined as such;
Ar8and Ar9Each independently represents a substituted or unsubstituted (C1-C30) alkyl group or a substituted or unsubstituted (C6-C30) aryl group;
b to d each independently represent an integer of 1 to 4, e represents an integer of 1 or 2; and is
When b to e are 2 or more, each Ar2、Ar3、Ar6and-L1-Ar1May be the same or different.
3. The organic electroluminescent compound according to claim 1, Ar1、Ar4、Ar5、R1And R2Each independently selected from any one of the substituents listed in group 1 below:
[ group 1 ]
Figure FDA0003217736660000022
Figure FDA0003217736660000031
Figure FDA0003217736660000041
Figure FDA0003217736660000051
4. The organic electroluminescent compound according to claim 1, wherein at L1、Ar1、Ar4、Ar5、R1And R2The substituted (C1-C30) alkyl group, the substituted (C2-C30) alkenyl group, the substituted (C6-C30) (arylene group, the substituted (3-to 30-membered) (arylene) heteroaryl group, the substituted (C3-C30) cycloalkyl group, the substituted (C1-C30) alkoxy group, the substituted tri (C1-C30) alkylsilyl, the substituted di (C1-C30) alkyl (C6-C30) arylsilyl, the substituted (C1-C30) alkyldi (C6-C30) arylsilyl, the substituted tri (C6-C30) arylsilyl, the fused ring of the substituted (C3-C30) aliphatic ring and the (C6-C30) aromatic ring, and the substituent of the substituted (C1-C30) alkyl (C6-C30) arylamino each independently represent at least one selected from the group consisting of: deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, (C-C) alkyl, halo (C-C) alkyl, (C-C) alkenyl, (C-C) alkynyl, (C-C) alkoxy, (C-C) alkylthio, (C-C) cycloalkyl, (C-C) cycloalkenyl, (3-to 7-membered) heterocycloalkyl, (C-C) aryloxy, (C-C) arylthio, (C-C) aryl substituted or unsubstituted (5-to 30-membered) heteroaryl, (5-to 30-membered) heteroaryl substituted or unsubstituted (C-C) aryl, tri (C-C) alkylsilyl, tri (C-C) arylsilyl, di (C-C) alkyl (C-C) arylsilyl, (C-C) alkyldi (C-C) arylsilyl, tri (C-C) arylsilyl, di (C-C) arylsilyl, halo (C-C) alkyl, (C-C) cycloalkenyl, halo (C-C) alkenyl, (C-C) alkynyl, (C-C) alkoxy, (C) alkylthio, (C) cycloalkyl, (C-C) cycloalkenyl, (C) 3-C) heterocycloalkyl, (C) heteroaryl substituted or unsubstituted (C) aryl, tri (C) arylsilyl, tri (C-C) arylsilyl, tri (C) arylsilyl, halo, and (C) aryl, halo, or halo, or C, halo, or halo, or C, halo, or C, halo, alkoxy, or halo, or C-C, Amino, mono-or di- (C1-C30) alkylamino, (C1-C30) alkyl substituted or unsubstituted mono -or di- (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, (C1-C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) arylboronocarbonyl, di (C1-C30) alkylboronocarbonyl, (C1-C30) alkyl (C6-C30) arylboronocarbonyl, (C6-C30) aryl (C1-C30) alkyl, and (C1-C30) alkyl (C6-C30).
5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
Figure FDA0003217736660000052
Figure FDA0003217736660000061
Figure FDA0003217736660000071
Figure FDA0003217736660000081
Figure FDA0003217736660000091
Figure FDA0003217736660000101
Figure FDA0003217736660000111
Figure FDA0003217736660000121
6. an organic electroluminescent material comprising the organic electroluminescent compound according to claim 1.
7. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
8. The organic electroluminescent device according to claim 7, wherein the organic electroluminescent compound is contained in at least one of a light-emitting layer, a hole transport layer and a hole assist layer.
CN202080015226.2A 2019-02-20 2020-02-19 Organic electroluminescent compounds and organic electroluminescent device comprising the same Pending CN113490730A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
KR10-2019-0019815 2019-02-20
KR20190019815 2019-02-20
KR1020200010274A KR20200101838A (en) 2019-02-20 2020-01-29 Organic electroluminescent compound and organic electroluminescent device comprising the same
KR10-2020-0010274 2020-01-29
PCT/KR2020/002389 WO2020171587A1 (en) 2019-02-20 2020-02-19 Organic electroluminescent compound and organic electroluminescent device comprising the same

Publications (1)

Publication Number Publication Date
CN113490730A true CN113490730A (en) 2021-10-08

Family

ID=72292015

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080015226.2A Pending CN113490730A (en) 2019-02-20 2020-02-19 Organic electroluminescent compounds and organic electroluminescent device comprising the same

Country Status (2)

Country Link
KR (1) KR20200101838A (en)
CN (1) CN113490730A (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102198515B1 (en) 2014-12-23 2021-01-05 솔루스첨단소재 주식회사 Organic light-emitting compound and organic electroluminescent device comprising the same

Also Published As

Publication number Publication date
KR20200101838A (en) 2020-08-28

Similar Documents

Publication Publication Date Title
CN111868210A (en) Composition material for organic electroluminescent device, various host materials and organic electroluminescent device comprising the same
CN112679310A (en) Multiple light emitting materials and organic electroluminescent device comprising the same
CN113015777A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN111801399A (en) Composition material for organic electroluminescent device, various host materials, and organic electroluminescent device comprising same
CN113950475A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN112209802A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN113454186A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN113072925A (en) Organic electroluminescent materials and organic electroluminescent device comprising the same
CN112955523A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN114835626A (en) Organic electroluminescent compounds, various host materials and organic electroluminescent device comprising the same
CN112689911A (en) Multiple host materials and organic electroluminescent device comprising the same
CN114380804A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN112292437A (en) Organic electroluminescent compound, organic electroluminescent material, and organic electroluminescent device comprising same
CN112400007A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN111511879A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN114573520A (en) Organic electroluminescent compounds, various host materials containing the same, and organic electroluminescent device
CN114141959A (en) Organic electroluminescent device
CN113698304A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN113410415A (en) Multiple host materials and organic electroluminescent device comprising the same
CN113372257A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN112920179A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN113614203A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN112437989A (en) Multiple host materials and organic electroluminescent device comprising the same
CN112119139A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
KR20200122531A (en) Organic electroluminescent compound and organic electroluminescent device comprising the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination