CN113845512B - Compound containing heterocycle and organic electroluminescent device thereof - Google Patents

Compound containing heterocycle and organic electroluminescent device thereof Download PDF

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CN113845512B
CN113845512B CN202111101790.9A CN202111101790A CN113845512B CN 113845512 B CN113845512 B CN 113845512B CN 202111101790 A CN202111101790 A CN 202111101790A CN 113845512 B CN113845512 B CN 113845512B
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CN113845512A (en
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郭建华
陆影
孙月
苗玉鹤
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Changchun Hyperions Technology Co Ltd
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    • C07—ORGANIC CHEMISTRY
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    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract

The invention provides a compound containing heterocycle and an organic electroluminescent device thereof, belonging to the technical field of organic electroluminescent. The heterocyclic compound provided by the invention has higher electron mobility, can effectively balance carrier transmission in the device, has good hole blocking capability, can effectively block holes in the luminescent layer, prevents excessive holes from being transmitted to the cathode side, improves the recombination probability of excitons in the luminescent layer, and is applied to the hole blocking/electron transmission layer of the organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life of the device is prolonged. Meanwhile, the compound containing the heterocycle has good refractive index, and when the compound is used as a coating material, the light-emitting efficiency of the device can be effectively improved, and the light-emitting efficiency of the device is further improved. The heterocyclic compound and the organic electroluminescent device thereof have good application effect and industrialization prospect.

Description

Compound containing heterocycle and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a compound containing heterocycle and an organic electroluminescent device thereof.
Background
The organic electroluminescent display (Organic Light Emitting Diode, OLED) technology is a technology for converting electric energy into light energy by means of organic semiconductor functional materials, and the potential of low operating voltage and high brightness thereof has been attracting attention. It generally comprises a cathode, an organic functional layer and an anode, wherein the organic functional layer mainly comprises: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). In addition, in the top emission device, a high refractive index coating layer is generally disposed on the outer side of the semitransparent electrode to adjust the optical interference distance, reduce the total reflection effect of the device, and improve the light extraction efficiency.
Electron transport materials and hole blocking materials are a critical factor in determining the efficiency and stability of OLED devices. In order to balance carriers and improve device efficiency, it is generally required that the electron transport material and the hole blocking material have the following characteristics: (1) can be prepared in large quantities; (2) has good thermal stability; (3) The light-emitting diode has a lower HOMO energy level, can effectively prevent the transmission of holes, and enables an exciton recombination zone to be formed in a light-emitting layer rather than an electron transport layer; (4) The electron mobility is higher, which is beneficial to the transmission of electrons, blocks holes, reduces electron injection barrier and balances carriers; (5) A good amorphous film can be formed, and the performance degradation caused by crystallization can be avoided. For the covering material, the covering material needs to have higher refractive index in the visible light range, higher glass transition temperature, higher thermal stability and good absorption to ultraviolet band, and adverse effect of harmful light on device materials is avoided; the light is not absorbed in the visible light wave band, and the influence on the light emitting efficiency and the color purity of the device is reduced.
However, the electron mobility of the currently used electron transport materials is low, the energy levels are not matched, the injection of carriers in the device is unbalanced, and excessive holes are transported to the cathode side, so that the luminous efficiency of the device is reduced and the service life of the device is shortened. In addition, research on light extraction materials at home and abroad is less, and most of light extraction materials have poor performance, so that light trapped in a device cannot be effectively coupled out. Therefore, development of an organic electroluminescent material having high electron mobility, capable of effectively blocking holes and improving light extraction efficiency is an urgent problem to be solved.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a heterocyclic compound and an organic electroluminescent device thereof, wherein the heterocyclic compound is applied to the organic electroluminescent device as an electron transport/hole blocking layer, so that the luminous efficiency of the device can be improved, and the service life of the device can be prolonged.
The present invention provides a heterocyclic ring-containing compound having a structure represented by chemical formula 1,
Figure BDA0003271207020000011
/>
in chemical formula 1, the Ar 1 、Ar 2 The same or different structures are selected from the structures represented by chemical formula 2
Figure BDA0003271207020000021
The Y are the same or different and are selected from C (Rx) or N, wherein at least one Y is selected from N; the Rx is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, nitryl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rx are connected to form a substituted or unsubstituted ring;
the X is 1 Any one selected from O, S or N (Ry); the Ry is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
said n is selected from 0, 1, 2 or 3;
the E is 1 、E 2 、E 3 Independently selected from any one of hydrogen, a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, and a substituted or unsubstituted pyridine ring;
z is the same or different and is selected from C or N;
the L is 1 ～L 3 The same or different arylene groups are selected from single bonds, substituted or unsubstituted C6-C30 arylene groups and substituted or unsubstituted C2-C30 heteroarylene groups;
The R is 1 、R 2 The same or different cyclic alkyl radicals selected from hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl radicals, substituted or unsubstituted C3-C12 cyclic alkyl radicalsAny one of a group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted C2 to C30 heteroaryl group; the a 1 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; the a 2 Selected from 0, 1, 2 or 3.
The invention also provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, and is characterized in that the organic layer contains any one or a combination of at least two of the compounds containing heterocycle.
The invention has the beneficial effects that: the heterocyclic compound provided by the invention has higher electron mobility, can effectively balance carrier transmission in the device, has good hole blocking capability, can effectively block holes in the luminescent layer, prevents excessive holes from being transmitted to the cathode side, improves the recombination probability of excitons in the luminescent layer, and is applied to the hole blocking/electron transmission layer of the organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life of the device is prolonged. Meanwhile, the compound containing the heterocycle has good refractive index, and when the compound is used as a coating material, the light-emitting efficiency of the device can be effectively improved, and the light-emitting efficiency of the device is further improved.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the present specification, "-" means a moiety attached to another substituent.
In this specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example, the number of the cells to be processed,
Figure BDA0003271207020000031
meter capable of measuringShow->
Figure BDA0003271207020000032
And so on.
The halogen refers to fluorine, chlorine, bromine and iodine.
The alkyl group according to the present invention means a hydrocarbon group having at least one hydrogen atom in an alkane molecule, and may be a straight chain alkyl group or a branched chain alkyl group, preferably having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl and the like, but are not limited thereto.
Cycloalkyl as used herein refers to a hydrocarbon group having at least one hydrogen atom in the cycloparaffin molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, particularly preferably 3 to 6 carbon atoms, and examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, camphene, etc., but are not limited thereto. The alkyl group is preferably a cyclopentyl group, a cyclohexyl group, an adamantyl group, or a norbornyl group.
The aryl group according to the present invention refers to a generic term for monovalent groups remaining after one hydrogen atom is removed from the aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be a monocyclic aryl group, a polycyclic aryl group or a condensed ring aryl group, preferably having 6 to 60 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, triphenylenyl, perylene, etc., but are not limited thereto.
Heteroaryl as used herein refers to the generic term for a monovalent radical that is formed by removing a hydrogen atom from the core atom of an aromatic heterocycle comprising carbon and a heteroatom. The heteroatom may be one or more of N, O, S, si, P, and may be a monocyclic heteroaryl group or a condensed ring heteroaryl group, preferably having 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, most preferably 3 to 8 carbon atoms, and examples may include pyrrolyl, pyridyl, pyrimidinyl, triazinyl, thienyl, furyl, indolyl, quinolinyl, isoquinolinyl, oxazolyl, thiazolyl, imidazolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, pyridooxazolyl, pyridothiazolyl, pyridoimidazolyl, pyrimidothiazolyl, pyrimidyl, dibenzofuranyl, dibenzothienyl, phenazinyl, quinoxalinyl, quinazolinyl, quinoxazolyl, quinolatazolyl, quinoimidazoimidazolyl, purinyl, 2-purinyl, N-imidazolyl, and the like, but are not limited thereto.
The arylene group according to the present invention means that a divalent group is left after two hydrogen atoms are removed from the aromatic nucleus of an aromatic hydrocarbon molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, preferably having 6 to 60 carbon atoms, more preferably 6 to 25 carbon atoms, still more preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include phenylene group, biphenylene group, terphenylene group, naphthylene group, anthrylene group, phenanthrylene group, pyreylene group, triphenylene group, perylene group, etc., but are not limited thereto.
The heteroarylene group according to the present invention means that two hydrogen atoms are removed from the nuclear carbon of an aromatic heterocycle consisting of carbon and hetero atoms, which may be one or more of N, O, S, si, P, a monocyclic heteroarylene group or a condensed ring heteroarylene group, preferably having 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, most preferably 3 to 8 carbon atoms, examples may include, but are not limited to, pyrrolylene, pyridylene, pyrimidinylene, triazinylene, thiophenylene, furanylene, indolylene, quinolinylene, isoquinolylene, oxazolylene, thiazolylene, imidazolylene, benzothiophenylene, benzofuranylene, benzoxazolylene, benzothiazolylene, benzimidazolylene, pyridooxazolylene, pyridothiazolylene, pyridoimidazolylene, pyrimidooxazolylene, pyrimidothiazolyl, pyrimidoimidazolyl, dibenzofuranylene, dibenzothiophenylene, carbazolylene, phenazinylene, quinoxalinylene, quinazolinylene, quinolinooxazolylene, quinolinoimidazolyl, purinylene, and the like.
"substituted" as used herein means that a hydrogen atom in a compound group is replaced with another atom or group, and the position of substitution is not limited.
"substituted or unsubstituted" as used herein means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium, halogen atom, amino group, cyano group, nitro group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C6-C60 aryl group, substituted or unsubstituted C2-C60 heteroaryl group, substituted or unsubstituted C6-C60 arylamine group, substituted or unsubstituted C6-C60 aryloxy group, preferably deuterium, halogen atom, cyano group, C1-C12 alkyl group, C6-C30 aryl group, C2-C30 heteroaryl group, specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano group, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclohexyl, adamantyl, norbornyl, phenyl, tolyl, mesityl, pentadeuterophenyl, biphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, pyrenyl, triphenylenyl, mesityl,
Figure BDA0003271207020000043
A group, perylene group, fluoranthenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, carbazolyl group, 9-phenylcarbazolyl group, spirobifluorenyl group, carbazoloindolyl group, pyrrolyl group, furanyl group, thienyl group, indolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, oxazolyl group, thiazolyl group, imidazolyl group, benzoxazolyl group, benzothiazolyl group, benzotriazolyl group, benzimidazolyl group, pyridooxazolyl group, pyridothiazolyl group, pyridoimidazolyl group, pyrimidothiazyl group, pyrimidoimidazolyl group, quinolino oxazolyl group, quinophthiazolyl group, phenothiazinyl group, phenoxazinyl group, acridinyl group and the like But is not limited thereto. Or when the substituents are plural, adjacent substituents may be bonded to form a ring; when the substituent is plural, plural substituents are the same or different from each other.
The linkage described herein to form a substituted or unsubstituted ring means that the two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:
Figure BDA0003271207020000041
in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed ring, and examples may include benzene, pyridine, pyrimidine, naphthalene, cyclopentene, cyclopentane, cyclohexane acene, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but are not limited thereto.
The present invention provides a heterocyclic ring-containing compound having a structure represented by chemical formula 1,
Figure BDA0003271207020000042
in chemical formula 1, the Ar 1 、Ar 2 The same or different structures are selected from the structures represented by chemical formula 2
Figure BDA0003271207020000051
The Y are the same or different and are selected from C (Rx) or N, wherein at least one Y is selected from N; the Rx is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, nitryl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rx are connected to form a substituted or unsubstituted ring;
The X is 1 Any one selected from O, S or N (Ry); the Ry is selected fromHydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
said n is selected from 0, 1, 2 or 3;
the E is 1 、E 2 、E 3 Independently selected from any one of hydrogen, a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, and a substituted or unsubstituted pyridine ring;
z is the same or different and is selected from C or N;
the L is 1 ～L 3 The same or different arylene groups are selected from single bonds, substituted or unsubstituted C6-C30 arylene groups and substituted or unsubstituted C2-C30 heteroarylene groups;
the R is 1 、R 2 The same or different one is selected from any one of hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; the a 1 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; the a 2 Selected from 0, 1, 2 or 3.
Preferably, the heterocyclic ring-containing compound is selected from any one of the structures shown below,
Figure BDA0003271207020000052
Preferably, the heterocyclic ring-containing compound is selected from any one of structures represented by chemical formulas 1-1 to 1-6,
Figure BDA0003271207020000053
Figure BDA0003271207020000061
the R is 1 One selected from hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene; the a 1 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.
Preferably, the method comprises the steps of,
Figure BDA0003271207020000062
at least one Y is selected from N. />
Preferably, the method comprises the steps of,
Figure BDA0003271207020000063
at least two Y are selected from N, or at least three Y are selected from N, or four Y are selected from N.
Preferably, the method comprises the steps of,
Figure BDA0003271207020000064
at least one Y is selected from N.
Preferably, the method comprises the steps of,
Figure BDA0003271207020000065
at least two Y is selected from N, or at least three Y is selected from N, or at least four Y is selected from N.
Preferably, when n is selected from 0,
Figure BDA0003271207020000066
at least one Y is selected from N.
Preferably, when n is selected from 1, 2 or 3,
Figure BDA0003271207020000067
at least one Y is selected from N.
Preferably, the said
Figure BDA0003271207020000068
Selected from any one of the following groups,
Figure BDA0003271207020000069
wherein the R is 3 The same or different one is selected from any one of hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
m 1 selected from 0, 1, 2 or 3, m 2 Independently selected from 0, 1 or 2, m 3 Independently selected from 0 or 1, m 4 Independently selected from 0, 1, 2, 3, 4 or 5, m 5 Independently selected from 0, 1, 2, 3 or 4, when m 1 、m 2 、m 4 、m 5 Above 1, two or more R 3 The same as or different from each other.
Preferably, the said
Figure BDA0003271207020000071
A/D is selected from any one of the following groups>
Figure BDA0003271207020000072
Preferably, the said
Figure BDA0003271207020000073
Selected from any one of the following groups:
Figure BDA0003271207020000074
/>
Figure BDA0003271207020000081
preferably, when n is 0, the above
Figure BDA0003271207020000082
Selected from those structures containing an N atom on a six-membered ring fused to a five-membered ring in the structure.
Preferably, the L 1 ～L 3 The same or different is selected from single bond or any one of the following groups:
Figure BDA0003271207020000083
wherein the R is 4 Independently selected from any one of hydrogen, deuterium, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl and substituted or unsubstituted C2-C12 heteroaryl;
said b 1 Independently selected from 0, 1, 2, 3 or 4, b 2 Independently selected from 0, 1, 2, 3, 4, 5 or 6, b 3 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, b 4 Independently selected from 0, 1, 2 or 3, b 5 Independently selected from 0, 1 or 2, b 6 Independently selected from 0, 1, 2, 3, 4 or 5, when b 1 、b 2 、b 3 、b 4 、b 5 、b 6 Above 1, two or more R 4 The same as or different from each other.
Preferably, the heterocyclic compound is selected from any one of the following structures:
Figure BDA0003271207020000091
/>
Figure BDA0003271207020000101
/>
Figure BDA0003271207020000111
/>
Figure BDA0003271207020000121
/>
Figure BDA0003271207020000131
/>
Figure BDA0003271207020000141
/>
Figure BDA0003271207020000151
/>
Figure BDA0003271207020000161
/>
Figure BDA0003271207020000171
/>
Figure BDA0003271207020000181
/>
Figure BDA0003271207020000191
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Figure BDA0003271207020000201
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Figure BDA0003271207020000211
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Figure BDA0003271207020000221
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Figure BDA0003271207020000231
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Figure BDA0003271207020000241
the invention also provides a preparation method of the compound containing the heterocycle,
Figure BDA0003271207020000242
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Figure BDA0003271207020000251
E 1 ～E 3 、L 1 ～L 3 、R 0 、R 1 、R 2 、X 1 、Y、Z、n、a 1 、a 2 the definitions are the same as those described above;
the heterocyclic compound of the present invention is involved in the Suzuki reaction.
The present invention may bond the above substituents by a method known in the art, and the kind and position of substituents or the number of substituents may be changed according to a technique known in the art.
The invention also provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises the heterocyclic compound.
The organic layer comprises at least one layer of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a covering layer. However, the structure of the organic electroluminescent device of the present invention is not limited to the above-described structure, and if necessary, a plurality of organic layers may be omitted or simultaneously provided. For example, an electron blocking layer may be further provided between the hole transport layer and the light emitting layer, and a hole blocking layer may be further provided between the electron transport layer and the light emitting layer; the organic layers having the same function may be formed into a laminated structure of two or more layers.
The light-emitting layer according to the present invention may include a host material, a dopant material, or the like, and may be formed of a single-layer structure or a multilayer structure in which the above layers are stacked.
The organic electroluminescent device of the invention has the structure that:
a substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;
A substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer;
a substrate/anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
a substrate/anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;
a substrate/anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
a substrate/anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;
a substrate/anode/hole injection layer/hole transport layer/light emitting auxiliary layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
a substrate/anode/hole injection layer/hole transport layer/light emitting auxiliary layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer;
however, the structure of the organic electroluminescent device is not limited thereto. The organic electroluminescent device can be selected and combined according to the device parameter requirement and the material characteristics, partial organic layers can be added or omitted, and the organic layers with the same function can be made into a laminated structure with more than two layers.
The organic electroluminescent device of the present invention is generally formed on a substrate. The substrate may be a substrate made of glass, plastic, polymer film, silicon, or the like, as long as it is not changed when an electrode is formed or an organic layer is formed.
In the organic electroluminescent device according to the present invention, the anode material preferably uses a high work function material capable of promoting injection of holes into the organic layer. Specific examples of the anode material that can be used in the present invention may include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO); combinations of metals and oxides, such as ITO-Ag-ITO; conductive polymers such as poly (3-methylthiophene), polypyrrole, polyaniline, poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDT), and the like, but are not limited thereto. Preferably, the anode material of the present invention is selected from ITO, ITO-Ag-ITO, and the like.
In the organic electroluminescent device of the present invention, the hole injection material is preferably a material having a good hole accepting ability. Specific examples of the hole injecting material that can be used in the present invention may include: silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, other metal oxides, phthalocyanine compounds, biphenylamine compounds, phenazine compounds, other materials, such as copper phthalocyanine (CuPc), titanyl phthalocyanine, N ' -diphenyl-N, N ' -di- [4- (N, N-diphenylamine) phenyl ] benzidine (NPNPB), N ' -tetra (4-methoxyphenyl) benzidine (MeO-TPD), and bisquinoxalino [2,3-a:2',3' -c ] phenazine (HATNA), 4',4 "-tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN), 4',4" -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like, but are not limited thereto. Preferably, the hole injection material of the present invention is selected from copper phthalocyanine (CuPc), 4',4 "-tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 4',4" -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like.
In the organic electroluminescent device according to the present invention, the hole transporting material is preferably a material having excellent hole transporting property and HOMO level matching with the corresponding anode material. Specific examples of the hole transporting material that can be used in the present invention may include materials such as diphenylamines, triphenylamines, fluorenes, and carbazoles, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -di (naphthalen-1-yl) -N, N ' -di (phenyl) -2,2' -dimethylbenzidine (α -NPD), N ' -diphenyl-N, N ' -di (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4- [1- [4- [ di (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), and the like, but are not limited thereto. Preferably, the hole transport material according to the present invention is selected from the group consisting of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N '-bis (naphthalen-1-yl) -N, N' -bis (phenyl) -2,2 '-dimethylbenzidine (α -NPD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), and the like.
In the organic electroluminescent device of the present invention, the luminescent layer material comprises a luminescent layer host material and a luminescent layer doping material, and the luminescent layer host material may be selected from 4,4 '-bis (9-Carbazolyl) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -ADN), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4', 1':4', 1' -tetrabiphenyl ]-4, 4' -diamine (4 PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), etc., but is not limited thereto. Preferably, the host material of the light emitting layer of the present invention is selected from 9, 10-bis (2-naphthyl) Anthracene (ADN), 9'- (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), AND the like. The light-emitting layer doping material can be selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA), 2,5,8, 11-tetra-tert-butyl perylene (TB)Pe), 4' -bis [4- (diphenylamino) styryl group]Biphenyl (BDAVBi), 4' -di [4- (di-p-tolylamino) styryl]Diphenyl (DPAVBi), bis (2-hydroxyphenylpyridine) beryllium (Bepp 2), bis (4, 6-difluorophenylpyridine-C2, N) iridium picolinate (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy) 3 ) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy) 2 (acac)), 9, 10-bis [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq) 3 ) Ir (piq) iridium bis (1-phenylisoquinoline) (acetylacetonate) 2 (acac)) and the like, but is not limited thereto. Preferably, the light-emitting layer guest according to the present invention is selected from the group consisting of 4,4' -bis [4- (di-p-tolylamino) styryl ]Biphenyl (DPAVBi), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 9, 10-di [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), and the like.
The doping ratio of the host material for the light-emitting layer and the doping material for the light-emitting layer may be varied depending on the materials used, and is usually 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.
In the organic electroluminescent device according to the present invention, the hole blocking material has a strong hole blocking ability and suitable HOMO and LUMO energy levels, and specific examples of the hole blocking material that can be used in the present invention may include, but are not limited to, imidazoles, triazoles, phenanthroline derivatives, quinolines, etc., such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), etc., in addition to the heterocyclic compound according to the present invention. Preferably, the hole blocking material according to the present invention is selected from the heterocyclic ring-containing compounds according to the present invention.
In the organic electroluminescent device according to the present invention, the electron transporting material preferably has a strong electron withdrawing ability and low HOMO and LUMO energy levels, and other heterocyclic ring-containing compounds than those described in the present invention may be used in the present invention Specific examples of the electron transporting material of (B) may include imidazoles, triazoles, phenanthroline derivatives, quinolines and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ]]Benzene (TmPyPB), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 2- (naphthalen-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (hnephen), 8-hydroxyquinoline-lithium, and the Like (LiQ), and the like, but are not limited thereto. Preferably, the electron transport material of the present invention is selected from 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), tris (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), etc., but is not limited thereto, and preferably, the electron transport material of the present invention is selected from the heterocyclic ring-containing compounds of the present invention.
In the organic electroluminescent device according to the present invention, the electron injection material preferably has a small potential barrier difference from an adjacent organic transport material, host material, or the like, and at the same time has an effect of injecting electrons from the cathode. Examples of electron injection materials that can be used in the present invention include: alkali metal salts (e.g., liF, csF), alkaline earth metal salts (e.g., mgF) 2 ) Metal oxides (such as Al 2 O 3 、MoO 3 ) But is not limited thereto. Preferably, the electron injection material of the present invention is selected from lithium fluoride (LiF), 8-hydroxyquinoline-lithium (Liq), and the like.
In the organic electroluminescent device according to the present invention, the cathode material preferably uses a low work function material capable of promoting electron injection into the organic layer. Specific examples of the cathode material that can be used in the present invention may include: metals such as aluminum, magnesium, silver, indium, tin, titanium, and the like, and alloys thereof; multilayer metallic materials, e.g. LiF/Al, mg/Ag, li/Al, liO 2 /Al、BaF 2 Al, etc., but is not limited thereto. Preferably, the cathode of the present invention is selected from Ag, mg-Ag alloy or thin Al.
In the organic electroluminescent device according to the present invention, the material for the cover layer is preferably a material for improving optical coupling. Specific examples of the capping material that can be used in the present invention may include, but are not limited to, arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, and the like, in addition to the heterocyclic ring-containing compound of the present invention, and preferably, the capping material of the present invention is selected from the heterocyclic ring-containing compounds of the present invention. The coating layer may be formed at the same time on the outer side of the anode and the outer side of the cathode, or may be disposed on the outer side of the anode or the outer side of the cathode, and preferably, the coating layer according to the present invention is disposed on the outer side of the cathode.
The thickness of each organic layer of the organic electroluminescent device is not particularly limited, and may be any thickness commonly used in the art.
The organic electroluminescent device of the present invention may be any one of a vacuum evaporation method, a spin coating method, a vapor deposition method, a blade coating method, a laser thermal transfer method, an electrospray coating method, a slit coating method, and a dip coating method, and in the present invention, a vacuum evaporation method is preferably used.
The organic electroluminescent device can be widely applied to the fields of panel display, illumination light sources, flexible OLED, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, indication boards, signal lamps and the like.
The present invention is explained more fully by the following examples, but is not intended to be limited thereby. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue burden.
Preparation and characterization of the Compounds
Description of the starting materials, reagents and characterization equipment:
the raw materials and reagent sources used in the following examples are not particularly limited, and may be commercially available products or prepared by methods well known to those skilled in the art.
The mass spectrum uses a Wotes G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer in UK, chloroform as a solvent;
the elemental analysis uses a Vario EL cube type organic elemental analyzer of Elementar, germany, and the mass of the sample is 5-10 mg;
synthesis example 1 Synthesis of intermediate d-1
Figure BDA0003271207020000291
Preparation of intermediate b-1
Under nitrogen, starting material a-1 (124.80 mmol,24.02 g), B 2 Pin 2 (137.28mmol，34.86g)，K 2 CO 3 (374.40mmol，51.75g)，Pd(PPh 3 ) 4 (2.50 mmol,2.89 g) was added to DMF (600 mL), stirred and heated to reflux temperature and reacted for 4h. After the reaction was completed, cooled to room temperature and 900mL of water was added, extracted with dichloromethane, and the organic layer was dried over anhydrous MgSO 4 Drying, concentration and recrystallization from ethyl acetate gave intermediate b-1 (26.00 g, 87% yield); HPLC purity is not less than 98.78%. Mass spectrum m/z:239.0896 (theory: 239.0884).
Preparation of intermediate d-1
In a nitrogen atmosphere, the reaction flask was charged with intermediate b-1 (99.05 mmol,23.72 g), starting material c-1 (97.11 mmol,19.23 g), pd (PPh) 3 ) 4 (1.94mmol，2.24g)、K 2 CO 3 (194.22 mmol,26.84 g) and 300mL toluene, 150mL ethanol, 150mL water, and the mixture was stirred and reacted under reflux for 3h; after the reaction was completed, cooled to room temperature, suction filtered to obtain a cake, and the cake was purified with toluene/ethanol=5: 1 recrystallisation to give intermediate d-1 (18.59 g, 83% yield); HPLC purity is not less than 98.97%. Mass spectrum m/z:230.0258 (theory: 230.0247). Theoretical element content (%) C 12 H 7 ClN 2 O: c,62.49; h,3.06; n,12.15. Measured element content (%): c,62.44; h,3.05; n,12.17.
The intermediates d-15 to d-542 were prepared by the preparation method of synthetic example 1 by substituting the raw materials correspondingly, and the raw materials are shown in the following table:
Figure BDA0003271207020000292
Figure BDA0003271207020000301
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synthesis example 2 Synthesis of intermediate h-1
Figure BDA0003271207020000302
Preparation of intermediate g-1
A reaction flask was charged with raw material e-1 (104.24 mmol,25.86 g), raw material f-1 (102.20 mmol,23.09 g), pd (PPh) under nitrogen atmosphere 3 ) 4 (2.04mmol，2.36g)，K 2 CO 3 (204.40 mmol,28.25 g) and 300mL toluene, 150mL ethanol, 150mL water, and the mixture was stirred and reacted under reflux for 3h; after the reaction was completed, cooling to room temperature, suction filtration to obtain a cake, flushing the cake with ethanol, and finally subjecting the cake to toluene/ethanol=4: 1 recrystallisation to give intermediate g-1 (31.41 g, 88% yield); HPLC purity is not less than 98.86%. Mass spectrum m/z:348.0481 (theory: 348.0473).
Preparation of intermediate h-1
Intermediate g-1 (82.00 mmol,28.64 g), B under nitrogen atmosphere 2 Pin 2 (180.4mmol，45.81g)，KOAc(246mmol，24.14g)，Pd(dppf)Cl 2 (2.46 mmol,1.80 g) was added to DMF (400 mL), stirred and heated to reflux temperature and reacted for 4h. After the reaction was completed, cooled to room temperature and 900mL of water was added, extracted with dichloromethane, and the organic layer was dried over anhydrous MgSO 4 Drying, concentration and recrystallization from ethyl acetate gave intermediate h-1 (34.05 g, 78% yield); HPLC purity is more than or equal to 99.04%. Mass spectrum m/z:532.2948 (theory: 532.2956). Theoretical element content (%) C 34 H 38 B 2 O4: c,76.72; h,7.20. Measured element content (%): c,76.67; h,7.23.
The intermediates h-15 to h-526 were prepared by the preparation method of synthetic example 2 by replacing the starting materials correspondingly, as shown in the following table:
Figure BDA0003271207020000311
synthesis example 3 Synthesis of intermediate h' -1
Figure BDA0003271207020000312
Preparation of intermediate k-1
The reaction flask was charged with raw material i-1 (92.20 mmol,19.74 g), raw material j-1 (94.04 mmol,14.71 g), pd (PPh) under nitrogen atmosphere 3 )4(1.84mmol，2.13g)，K 2 CO 3 (184.40 mmol,25.49 g) and 300mL toluene, 150mL ethanol, 150mL water, and the mixture was stirred and reacted under reflux for 3h; after the reaction, cooling to room temperature, suction filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene/ethanol=5:1 to obtain an intermediate k-1 (19.94 g, yield 88%); HPLC purity is not less than 98.89%. Mass spectrum m/z:245.0997 (theory: 245.0989).
Preparation of intermediate e' -1
Intermediate k-1 (75 mmol,18.43 g), B 2 Pin 2 (82.50 mmol,20.95 g), KOAc (225 mmol,22.08 g) was dissolved in anhydrous dioxane (840 mL), and after nitrogen substitution, pd (dppf) Cl was added 2 (1.80 mmol,1.32 g) was heated under reflux for 3 hours. After the reaction was completed, cooled to room temperature and 900mL of water was added, extracted with dichloromethane, and the organic layer was dried over anhydrous MgSO 4 Drying, concentration and recrystallization from ethyl acetate gave intermediate e' -1 (21.50 g, 85% yield); HPLC purity is more than or equal to 99.11%. Mass spectrum m/z:337.2220 (theory: 337.2230).
Preparation of intermediate g' -1:
a reaction flask was charged with raw material e' -1 (60 mmol,20.24 g), raw material f-1 (58.82 mmol,13.29 g), pd (dppf) Cl under nitrogen atmosphere 2 (1.18 mmol,0.86 g), KOAc (117.64 mmol,11.55 g), 180mL toluene, 90mL ethanol, 90mL water, and stirring and mixingReacting for 4 hours under reflux; after the reaction was completed, cooling to room temperature, suction filtration to obtain a cake, flushing the cake with ethanol, and finally subjecting the cake to toluene/ethanol=20: 3 to obtain intermediate g' -1 (16.98 g, yield 81%); HPLC purity is more than or equal to 99.24%. Mass spectrum m/z:355.0923 (theory: 355.0912).
Preparation of intermediate h' -1
Intermediate g' -1 (45 mmol,16.03 g), B under nitrogen atmosphere 2 Pin 2 (99mmol，25.14g)，KOAc(135mmol，13.25g)，Pd(dppf)Cl 2 (1.35 mmol,0.99 g) was added to DMF (220 mL), stirred and heated to reflux temperature and reacted for 5h. After the reaction was completed, cooled to room temperature and 900mL of water was added, extracted with dichloromethane, and the organic layer was dried over anhydrous MgSO 4 Drying, concentration and recrystallization from ethyl acetate gave intermediate h' -1 (18.93 g, 78% yield); HPLC purity is more than or equal to 99.48%. Mass spectrum m/z:539.3385 (theory: 539.3396). Theoretical element content (%) C 34 H 31 D 7 B 2 O 4 : c,75.72; h,8.41. Measured element content (%): c,75.76; h,8.42.
The intermediates h '-23 to h' -542 were prepared by the preparation method of synthetic example 3 by replacing the starting materials accordingly, as shown in the following table:
Figure BDA0003271207020000321
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Figure BDA0003271207020000331
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Figure BDA0003271207020000341
synthesis example 4 Synthesis of Compound 1
Figure BDA0003271207020000342
Preparation of Compound 1
To the reaction flask was added intermediate h-1 (30 mmol,15.97 g), intermediate d-1 (61.20 mmol,14.12 g), pd under nitrogen 2 (dba) 3 (0.30mmol，0.27g)，P(t-Bu) 3 (2.40 mmol,2.4mL of 1.0mol/L toluene solution), K 2 CO 3 (60 mmol,8.29 g), THF (300 mL), the mixture was stirred and reacted under reflux for 4.5 hours; after the reaction was completed, cooling to room temperature, suction filtration to obtain a cake, flushing the cake with ethanol, and finally subjecting the cake to toluene/ethanol=10: 1 recrystallisation to give compound 1 (13.84 g, 69% yield); HPLC purity is more than or equal to 99.77%. Mass spectrum m/z:668.2223 (theory: 668.2212). Theoretical element content (%) C 46 H 28 N 4 O 2 : c,82.62; h,4.22; n,8.38. Measured element content (%): c,82.57; h,4.24; n,8.39.
The preparation of compounds 10 to 542 was carried out by the preparation method of synthetic example 4 with corresponding substitutions of intermediates, as shown in the following table:
Figure BDA0003271207020000351
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Figure BDA0003271207020000361
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Figure BDA0003271207020000371
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Figure BDA0003271207020000381
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Figure BDA0003271207020000391
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Figure BDA0003271207020000401
device examples 1 to 20
The ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. Vacuum evaporating HI-1 on an ITO glass substrate to serve as a hole injection layer, wherein the evaporating thickness is 10nm; vacuum evaporating HT-1 on the hole injection layer as a hole transport layer, wherein the evaporating thickness is 40nm; vacuum evaporation RH is carried out on the hole transport layer, RD=97:3 is used as a light-emitting layer, and the evaporation thickness is 25nm; vacuum evaporating the compound 15 as electron transport layer on the light emitting layer, wherein the evaporating thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 0.5nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 70nm.
Figure BDA0003271207020000402
Device examples 2 to 16: an organic electroluminescent device was produced by the same procedure as in device example 1, except that the compound 15 of the present invention in device example 1 was replaced with the compounds 73, 74, 107, 140, 184, 213, 233, 260, 392, 418, 446, 481, 504, 515, 542, respectively, as electron transporting materials.
Comparative examples 1 to 5: an organic electroluminescent device was produced by the same procedure as in device example 1, except that the compound 15 of the present invention in device example 1 was replaced with the comparative compound 1, comparative compound 2, comparative compound 3, comparative compound 4, and comparative compound 5, respectively, as electron transport layers.
Test software, a computer, a K2400 digital source list manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research, U.S. are combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature. The results of the luminescence characteristic test of the obtained organic electroluminescent device are shown in table 1. Table 1 shows the results of the luminescence characteristics test of the organic electroluminescent devices prepared from the compounds prepared in the inventive examples and the comparative substances.
TABLE 1 test of luminescence characteristics of organic electroluminescent devices
Figure BDA0003271207020000411
T97 represents the time required for the brightness of the device to drop to 97% of the initial brightness at a constant current density.
As can be seen from the results of table 1, the organic electroluminescent device of the present invention exhibits advantages of high luminous efficiency and long life compared to comparative examples 1 to 5.
Device examples 17 to 39
The ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. Vacuum evaporating HI-1 on an ITO glass substrate to serve as a hole injection layer, wherein the evaporating thickness is 10nm; vacuum evaporating HT-1 on the hole injection layer as a hole transport layer, wherein the evaporating thickness is 40nm; vacuum evaporation RH is carried out on the hole transport layer, RD=97:3 is used as a light-emitting layer, and the evaporation thickness is 25nm; vacuum evaporating the compound 10 as a hole blocking layer on the light-emitting layer, wherein the evaporation thickness is 12nm; vacuum evaporating ET-1 on the hole blocking layer as an electron transport layer, wherein the evaporating thickness is 20nm, vacuum evaporating LiF on the electron transport layer as an electron injection layer, and the evaporating thickness is 0.5nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 70nm.
Device examples 2 to 39: an organic electroluminescent device was manufactured by the same procedure as in device example 17, except that the compound 10 of the present invention in device example 17 was used as a hole blocking material in place of the compound 10 of the present invention in device example 17, respectively, 23, 64, 66, 128, 210, 246, 342, 354, 423, 426, 461, 488, 504, 511, 515.
Comparative examples 6 to 10: an organic electroluminescent device was produced by the same procedure as in device example 17, except that the compound 10 of the present invention in device example 17 was replaced with the comparative compound 1, comparative compound 2, comparative compound 3, comparative compound 4, and comparative compound 5, respectively, as a hole blocking material.
Test software, a computer, a K2400 digital source list manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research, U.S. are combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature. The results of the luminescence characteristic test of the obtained organic electroluminescent device are shown in table 2. Table 2 shows the results of the test of the luminescence characteristics of the organic electroluminescent devices prepared from the compounds prepared in the inventive examples and the comparative substances.
TABLE 2 test of luminescence characteristics of organic electroluminescent devices
Figure BDA0003271207020000421
Figure BDA0003271207020000431
As can be seen from the results of table 2, the organic electroluminescent devices of the present invention exhibited advantages of high luminous efficiency and long life compared to comparative examples 6 to 10.
Device examples 33 to 41
The glass substrate was ultrasonically cleaned with 5% glass cleaning solution for 2 times, 20 minutes each time, and then with deionized water for 2 times, 10 minutes each time. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. ITO/Ag/ITO is used as an anode on a glass substrate; vacuum evaporating HI-1 on the anode to form a hole injection layer, wherein the evaporating thickness is 10nm; vacuum evaporating HT-1 on the hole injection layer as a hole transport layer, wherein the evaporating thickness is 40nm; vacuum evaporation RH is carried out on the hole transport layer, RD=97:3 is used as a light-emitting layer, and the evaporation thickness is 25nm; vacuum evaporating ET-1 on the luminous layer as an electron transport layer, wherein the evaporating thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 0.5nm; vacuum evaporating Mg on the electron injection layer: ag=1:9 as cathode, the evaporation thickness was 20nm. The compound 1 of the present invention was vacuum-deposited as a coating material on the cathode with a deposition thickness of 70nm.
Device examples 34 to 41: an organic electroluminescent device was manufactured by the same procedure as in device example 33, except that the compound 1 according to the invention in device example 33 was replaced with the compounds 21, 23, 66, 140, 210, 334, 511, 526, respectively, as the capping layer material.
Comparative examples 11 to 12: an organic electroluminescent device was produced by the same procedure as in device example 33, except that the compound 1 of the present invention in device example 33 was replaced with the comparative compound 4 and the comparative compound 5 as the capping layer material.
Test software, a computer, a K2400 digital source list manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research, U.S. are combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. The environment tested was atmospheric and the temperature was room temperature. The results of the luminescence characteristic test of the obtained organic electroluminescent device are shown in table 3. Table 3 shows the results of the test of the luminescence characteristics of the organic electroluminescent devices prepared from the compounds prepared in the inventive examples and the comparative substances.
TABLE 3 test of luminescence characteristics of organic electroluminescent devices
Figure BDA0003271207020000441
As can be seen from the results of table 3, the organic electroluminescent devices of the present invention exhibited the advantage of high luminous efficiency as compared with comparative examples 11 to 12.
It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.

Claims (6)

1. A compound containing a heterocyclic ring, characterized in that the compound containing a heterocyclic ring is selected from any one of structures represented by chemical formulas 1-1 to 1-4 and chemical formulas 1 to 6,
Figure FDA0004062651510000011
the R is 1 One selected from hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl; the a 1 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; the a 1-1 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; the a 1-2 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; the term "substituted or unsubstituted" means that it is not substituted or substituted with one or more substituents selected from the group consisting of: deuterium; when R is 1 When one of methyl, ethyl, isopropyl, tertiary butyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl is selected, the a 1 Selected from 0, 1 or 2; the a 1-1 Selected from 0, 1 or 2; the a 1-2 Selected from 0, 1 or 2;
the Ar is as follows 1 、Ar 2 The same or different structures are selected from the structures represented by chemical formula 2
Figure FDA0004062651510000012
The said
Figure FDA0004062651510000013
Selected from any one of the following groups,
Figure FDA0004062651510000014
the said
Figure FDA0004062651510000015
Selected from any one of the following groups:
Figure FDA0004062651510000016
the X is 1 Any one selected from O or S;
said n is selected from 1;
the L is 1 ～L 2 Selected from single bonds;
the L is 3 Selected from any one of the following groups:
Figure FDA0004062651510000021
wherein the R is 4 Independently selected from any one of hydrogen and deuterium;
said b 1 Independently selected from 0, 1, 2, 3 or 4, when b 1 Above 1, two or more R 4 The same or different from each other;
the R is 2 Selected from hydrogen, deuterium; the a 2 Selected from 0, 1, 2 or 3.
2. A compound comprising a heterocyclic ring as described in claim 1, wherein the
Figure FDA0004062651510000022
Selected from any one of the following groups:
Figure FDA0004062651510000023
3. a compound comprising a heterocyclic ring according to claim 1, wherein the heterocyclic compound is selected from any one of the following structures:
Figure FDA0004062651510000024
4. an organic electroluminescent device comprising an anode, a cathode, and an organic layer, wherein the organic layer comprises at least one of the heterocyclic ring-containing compounds according to any one of claims 1 to 3.
5. An organic electroluminescent device according to claim 4, wherein the organic layer is located between the anode and cathode, wherein the organic layer comprises at least one of an electron transport layer or a hole blocking layer comprising at least one of the heterocyclic ring-containing compounds according to claims 1 to 3.
6. An organic electroluminescent device as claimed in claim 4, wherein the organic layer is located outside the cathode, characterized in that the organic layer comprises a cover layer comprising at least one of the heterocyclic ring-containing compounds according to any one of claims 1 to 3.
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