CN111892531B - Organic compound and organic electroluminescent device thereof - Google Patents

Organic compound and organic electroluminescent device thereof Download PDF

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CN111892531B
CN111892531B CN202010936642.8A CN202010936642A CN111892531B CN 111892531 B CN111892531 B CN 111892531B CN 202010936642 A CN202010936642 A CN 202010936642A CN 111892531 B CN111892531 B CN 111892531B
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CN111892531A (en
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刘喜庆
韩春雪
苗玉鹤
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Changchun Hyperions Technology Co Ltd
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Abstract

The invention provides an organic compound and an organic electroluminescent device thereof, and relates to the technical field of organic photoelectric materials. The organic compound with the tetramethyl spiro indane structure has higher glass transition temperature and molecular thermal stability, is not easy to crystallize in a thin film state, and meanwhile, the electron-withdrawing groups such as pyridine, pyrimidine, triazine, imidazole, quinoline and the like are introduced into the structure, so that the electron mobility of the material is effectively improved.

Description

Organic compound and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organic compound and an organic electroluminescent device thereof.
Background
As a new generation of display technology, organic electroluminescent (OLED) devices have the advantages of self-luminescence, wide viewing angle, low power consumption, high reaction rate, full color and the like, and have extremely high research and development values and wide application prospects.
A typical organic light emitting device is composed of a cathode, an anode, and an organic functional layer between the cathode and the anode. The composition of the device includes a transparent ITO anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Emission Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), a cathode, and the like. The light emitting principle of the organic electroluminescent device is that holes and electrons are injected from an anode and a cathode respectively under the action of a direct current electric field by applying voltage, carriers are transmitted through a hole transmission layer and an electron transmission layer respectively and meet and combine in a light emitting layer to form excitons, and the excitons are changed into a ground state under an excitation state to generate light.
Organic electroluminescent devices are mainly used in the fields of panels and lighting, and these devices are required to have high luminous efficiency, low driving voltage, long service life and the like. Therefore, the main content of OLED research is to improve the efficiency of the device, reduce the driving voltage, prolong the service life and the like, on one hand, the manufacturing process of the device is optimized, and the efficiency of the device is improved by adding multiple functional auxiliary layers and adopting a doping mode; on the other hand, an organic electroluminescent material with excellent performance is searched, and the performance of the material directly influences the efficiency, the service life and the stability in the period.
Although the development of OLED display technology has been a series of breakthroughs and successes, there are still many obstacles in the development process, and among them, the development of OLED organic materials faces great difficulties and challenges. Although most organic materials have been developed and are well known, there is a large imbalance in the development of various types of organic materials. For example, the lag in the development of electron transport materials relative to hole transport materials has resulted in limitations in the selection of electron transport materials during the fabrication of devices and has limited the improvement of device performance and efficiency. Since the electron mobility of the electron transport material is much lower than the hole mobility of the hole transport material, the mobility of the carriers cannot reach a balance, which results in low light emitting efficiency of the device and further affects the service life of the device. In order to solve the restriction of the OLED device on organic materials at present, the development of efficient electron transport materials is of great importance for improving the performance of the OLED device.
Disclosure of Invention
Technical problem
The invention provides an organic compound and an organic electroluminescent device thereof, aiming at solving the problem of low efficiency of the organic electroluminescent device caused by low electron mobility of an electron transport material in the prior art. The organic compound provided by the invention has good electron transport capacity, good stability and high glass transition temperature, and meanwhile, the structure has deep HOMO energy level, can be used as an electron transport layer material of an organic electroluminescent device, and can effectively improve the recombination efficiency of electrons and holes in a light-emitting layer, thereby improving the light-emitting efficiency of the device and prolonging the service life of the device.
Technical solution
The invention provides an organic compound, which has a structural general formula shown in chemical formula 1:
Figure BDA0002672163520000021
wherein R is1、R2The aryl group is any one of hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C2-C30 heteroaryl group;
L1、L2the aryl group is any one of single bond, substituted or unsubstituted arylene group with C6-C30 and substituted or unsubstituted heteroarylene group with C2-C30;
Ar1、Ar2the same or different from each other, wherein at least one is selected from any one of the groups shown in chemical formula 2 to chemical formula 5, and the rest is independently selected from any one of substituted or unsubstituted aryl of C6 to C30 and heteroaryl of C2 to C30:
Figure BDA0002672163520000022
X1～X5independently selected from CR3N atom, X1～X5At least one of them is selected from N atoms;
Z1～Z8independently selected from CR4N atom, Z1、Z2At least one of them is selected from N atoms;
Q1selected from O, S, NR5Any one of, Q2～Q5Independently selected from CR6And N atom;
A1selected from the group consisting of CR7And N atom;
R3～R8independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
when there are two or more R3、R4、R6When present, two or more R3、R4、R6Identical or different from each other, or two adjacent R6Are connected into a ring;
R9、R10any one of which is and L1、L2A bonding position, and the other is any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;
the substituted group in the substituted or unsubstituted is any one of deuterium, halogen atom, cyano, nitro, C1-C12 alkyl, C6-C30 aryl and C2-C30 heteroaryl.
The invention also provides an organic electroluminescent device which comprises a first electrode, a second electrode and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises the organic compound.
Preferably, the organic layer comprises an electron transport layer comprising the organic compound of the present invention.
Advantageous effects
The organic compound provided by the invention contains a tetramethyl spiroindane group, and molecules are not completely coplanar in a spatial structure, so that the crystallization of the material can be effectively avoided.
Meanwhile, electron-withdrawing groups such as pyridine, pyrimidine, triazine, imidazole, quinoline and the like are introduced into the structure, so that the material has high electron mobility, and meanwhile, the introduced groups have good rigidity, so that the stability of the whole structure can be improved; meanwhile, due to the existence of rigid groups, the material has higher glass transition temperature, and is ensured not to crystallize in a thin film state.
When the organic compound provided by the invention is used for an electron transport layer of an organic electroluminescent device, the compound has high electron mobility, and the electron transport capacity is greatly improved, so that the transport of electrons and holes is balanced, the recombination efficiency of the electrons and the holes in a light emitting layer can be effectively improved, the light emitting efficiency of the device is improved, and the service life of the device is prolonged.
Drawings
FIG. 1 is a drawing showing a scheme for preparing a compound 51 of the present invention1H NMR chart;
FIG. 2 shows Compound 73 of the present invention1H NMR chart;
FIG. 3 is a drawing of Compound 91 of the present invention1H NMR chart;
FIG. 4 is a drawing showing a scheme of preparing a compound 131 of the present invention1H NMR chart;
FIG. 5 is a drawing of compound 136 of the present invention1H NMR chart;
FIG. 6 shows a scheme for preparing a compound 149 of the present invention1H NMR chart;
FIG. 7 is a drawing of a compound 190 of the present invention1H NMR chart.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the present invention are described below with reference to the following examples. However, these embodiments are exemplary and do not limit the present invention.
Definition of
In the context of the present specification,
Figure BDA0002672163520000031
means a moiety attached to another substituent.
Examples of halogen atoms described herein may include fluorine, chlorine, bromine, and iodine.
The alkyl group in the present invention refers to a hydrocarbon group formed by dropping one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group, a branched-chain alkyl group, or a cyclic alkyl group, and preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms, and examples may include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, a n-hexyl group, a cyclohexyl group, and the like, but are not limited thereto.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, preferably having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms, and the aryl group may be substituted or unsubstituted, and examples thereof may include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylenyl group, pyrenyl group, fluorenyl group, spirofluorenyl group, and the like,
Figure BDA0002672163520000041
Perylene, fluoranthene, but not limited thereto.
Heteroaryl as used herein refers to a general term in which one hydrogen atom is removed from the core carbon of an aromatic heterocyclic ring composed of carbon and heteroatoms, including but not limited to oxygen, sulfur, nitrogen atoms, which may be monocyclic heteroaryl, polycyclic heteroaryl or fused ring heteroaryl, preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 12 carbon atoms, and most preferably 3 to 8 carbon atoms, and which may be substituted or unsubstituted, and examples may include thienyl, pyrrolyl, furyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, phenothiazinyl, phenoxazinyl, indolyl, benzothienyl, benzofuranyl, benzimidazolyl, and the like, Isobenzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, carbazolyl, and the like, but are not limited thereto.
The arylene group in the present invention means an aromatic hydrocarbonAfter removal of two hydrogen atoms from the aromatic nucleus carbon of the molecule, a generic term for divalent groups remains, which may be monocyclic arylene, polycyclic arylene or fused ring arylene, preferably having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 14 carbon atoms, most preferably 6 to 12 carbon atoms, the arylene group may be substituted or unsubstituted, and examples may include phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, triphenylene, pyrenylene, fluorenylene, spirofluorenylene, and fluorenylene
Figure BDA0002672163520000042
Perylene, fluoranthene, etc., but not limited thereto.
Heteroarylene groups according to the present invention are aromatic heterocycles consisting of carbon and heteroatoms including, but not limited to, oxygen, sulfur, nitrogen atoms, which may be monocyclic, polycyclic or fused ring heteroarylene groups, preferably having from 2 to 30 carbon atoms, more preferably from 2 to 20 carbon atoms, especially from 3 to 12 carbon atoms, and most preferably from 3 to 8 carbon atoms, with the proviso that two hydrogen atoms are removed from the core carbon leaving a generic term for divalent radicals, and may be substituted or unsubstituted, examples of which may include thienyl, pyrrolylene, furanylene, imidazolyl, thiazolyl, oxazolylene, oxadiazolylene, thiadiazolylene, triazolylene, pyridinylene, pyrazinylene, pyridazinylene, pyrimidinylene, isoquinolinylene, quinoxalylene, quinazolinylene, phenothiazinylene, phenazinylene, and, Indolylene, benzothiophene, benzofuranylene, benzimidazolene, isobenzothiophenene, isobenzofuranylene, dibenzofuranylene, dibenzothiophenene, carbazolyl, and the like, but is not limited thereto.
The term "substituted or unsubstituted" as used herein means unsubstituted or substituted with one or more of the following groups: deuterium, halogen atom, amino group, cyano group, nitro group or C1-C30 alkyl group, C2-C30 alkenyl group, C1-C30 alkoxy group, C3-C20 cycloalkyl group, C3-C20 heterocycloalkyl group, C6-C30 aryl group and C2-C30 heteroaryl group are preferable, and deuterium, halogen atom, cyano groupNitro, C1-C12 alkyl, C6-C30 aryl, and C2-C30 heteroaryl. Specific examples may include deuterium, fluorine, chlorine, bromine, iodine, amino, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, pyrenyl, and the like,
Figure BDA0002672163520000043
A perylene group, a fluoranthenyl group, a benzyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, a dimethylamino group, a diphenylamine group, a carbazolyl group, a 9-phenylcarbazolyl group, a pyrrolyl group, a furyl group, a thienyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an isobenzothienyl group, a deuterium group, a phenothiazinyl group, a phenoxazinyl group, an acridinyl group, a biphenyl group, a terphenyl group and the like, but not limited thereto.
The term "integer selected from 0 to M" as used herein means any one of the integers having a value selected from 0 to M, including 0, 1,2 … M-2, M-1, M. For example, "a1An integer selected from 0 to 4 "means a1Selected from 0, 1,2, 3, 4; "a" is2An integer selected from 0 to 3 "means a2Selected from 0, 1,2, 3; "a" is3An integer selected from 0 to 2 "means a3Selected from 0, 1, 2; "c1An integer selected from 0 to 6 "means c1Selected from 0, 1,2, 3,4, 5, 6; "c2An integer selected from 0 to 5 "means c2Selected from 0, 1,2, 3,4, 5; "c3An integer selected from 0 to 4 "means c3Selected from 0, 1,2, 3, 4; "p" is1An integer selected from 0 to 4 "means p1Selected from 0, 1,2, 3, 4; "p" is2An integer selected from 0 to 3 "means p2Selected from 0, 1,2, 3.
The linking to form a ring as described herein means that two groups are linked to each other by a chemical bond. As exemplified below:
Figure BDA0002672163520000051
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, such as phenyl, naphthyl, cyclopentenyl, cyclopentylalkyl, cyclohexanophenyl, quinolyl, isoquinolyl, dibenzothienyl, phenanthryl or pyrenyl, but is not limited thereto.
The invention provides an organic compound, which has a structural general formula shown in chemical formula 1:
Figure BDA0002672163520000052
wherein R is1、R2The aryl group is any one of hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C2-C30 heteroaryl group;
L1、L2the aryl group is any one of single bond, substituted or unsubstituted arylene group with C6-C30 and substituted or unsubstituted heteroarylene group with C2-C30;
Ar1、Ar2the same or different from each other, wherein at least one is selected from any one of the groups shown in chemical formula 2 to chemical formula 5, and the rest is independently selected from any one of substituted or unsubstituted aryl of C6 to C30 and heteroaryl of C2 to C30:
Figure BDA0002672163520000053
X1～X5independently selected from CR3N atom, X1～X5At least one of them is selected from N atoms;
Z1～Z8independently selected from CR4N atom, Z1、Z2At least one of them is selected from N atoms;
Q1selected from O, S, NR5Any one of, Q2～Q5Independently selected from CR6And N atom;
A1selected from the group consisting of CR7And N atom;
R3～R8independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
when there are two or more R3、R4、R6When present, two or more R3、R4、R6Identical or different from each other, or two adjacent R6Are connected into a ring;
R9、R10any one of which is and L1、L2A bonding position, and the other is any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;
the substituted group in the substituted or unsubstituted is any one of deuterium, halogen atom, cyano, nitro, C1-C12 alkyl, C6-C30 aryl and C2-C30 heteroaryl.
Preferably, the compound represented by chemical formula 1 is selected from any one of chemical formula 6 or chemical formula 7:
Figure BDA0002672163520000061
R1、R2、L1、L2、Ar1、Ar2the definitions are the same as above.
Preferably, R1、R2The alkyl group is any one selected from hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, furyl, thienyl, benzofuryl and benzothienyl.
Preferably, R1、R2The same as each other, and is selected from any one of hydrogen, deuterium, methyl, ethyl and phenyl.
Preferably, Ar is1、Ar2The same or different from each other, wherein at least one is selected from any one of substituted or unsubstituted pyridyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridophenazinyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted imidazopyridinyl, and substituted or unsubstituted triazolyl.
More preferably, Ar1、Ar2At least one of them is selected from any one of the following groups:
Figure BDA0002672163520000062
Figure BDA0002672163520000071
R3～R10the definitions are the same as the above definitions;
a1an integer selected from 0 to 4, a2An integer selected from 0 to 3, a3An integer selected from 0 to 2; c. C1An integer selected from 0 to 6, c2An integer selected from 0 to 5, c3An integer selected from 0 to 4; p is a radical of1An integer selected from 0 to 4, p2An integer selected from 0 to 3.
Preferably, R3、R4、R6、R7、R9、R10Independently selected from hydrogen, deuterium, methyl, ethyl, tertiary butyl and any one of the following groups:
Figure BDA0002672163520000072
when there are two or more R3、R4、R6When present, two or more R3、R4、R6Are the same or different from each other; or two adjacent R6Are connected into a ring;
the R is5、R8Independently selected from any one of hydrogen, deuterium, methyl, ethyl, phenyl, biphenyl and naphthyl.
More preferably, Ar1、Ar2At least one of them is selected from any one of the following groups:
Figure BDA0002672163520000073
Figure BDA0002672163520000081
more preferably, Ar1And Ar2Are identical to each other.
Preferably, L1、L2Independently selected from single bond, any one of the following groups:
Figure BDA0002672163520000082
further preferably, L1、L2Independently selected from single bond, any one of the following groups:
Figure BDA0002672163520000083
most preferably, the compound of chemical formula 1 is selected from any one of the following chemical structures:
Figure BDA0002672163520000091
Figure BDA0002672163520000101
Figure BDA0002672163520000111
Figure BDA0002672163520000121
Figure BDA0002672163520000131
Figure BDA0002672163520000141
Figure BDA0002672163520000151
Figure BDA0002672163520000161
Figure BDA0002672163520000171
Figure BDA0002672163520000181
some specific structural forms of the organic compound of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all the substituents based on the structure shown in chemical formula 1 are included as the above-defined groups.
The preparation method of the organic compound of the present invention can be prepared by the following synthetic route, but the present invention is not limited thereto:
Figure BDA0002672163520000182
wherein, R is1、R2、L1、L2、Ar1、Ar2The definition of (b) is the same as that in chemical formula 1.
The invention also provides an organic electroluminescent device, which comprises a first electrode, a second electrode and an organic layer between the first electrode and the second electrode; the organic layer contains the organic compound described in the present invention.
The organic layer of the organic electroluminescent device of the present invention may include a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer, an electron blocking layer, a light emitting layer, and the like.
Preferably, the electron transport layer comprises the organic compound of the present invention.
In addition to the organic layers enumerated above, the organic electroluminescent device may further include a capping layer on the outer surface of the electrode, and accordingly, the organic electroluminescent device structure of the present invention is preferably configured in several cases:
(1) anode/hole transport layer/light-emitting layer/electron transport layer (comprising the compound of the present invention)/cathode
(2) Anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer (comprising the compound of the present invention)/electron injection layer/cathode
(3) Anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer (comprising the compound of the present invention)/electron injection layer/cathode/capping layer
(4) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer (comprising the compound of the present invention)/electron injection layer/cathode/capping layer
(5) Anode/hole injection layer/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer (comprising the compound of the present invention)/electron injection layer/cathode
(6) Anode/hole injection layer/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer (comprising the compound of the present invention)/electron injection layer/cathode/capping layer
However, the structure of the organic electroluminescent device of the present invention is not limited to the above structure, and multiple organic layers may be omitted or simultaneously provided as necessary.
The anode material is preferably a material having a high work function in order to easily inject holes into the organic layer. Specific examples of the anode material that can be used in the present invention include: metals, such as vanadium, chromium, copper, zinc or gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), or Indium Zinc Oxide (IZO); metal/oxide compositions, e.g. ZnO: Al or SNO2Sb; and conductive polymers, such as poly (3-methylthiophene) poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polyaniline, but not limited thereto.
The hole injection material is a material that easily receives holes from the anode at a low voltage, and the HOMO of the hole injection material is preferably located between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material that can be used in the present invention include: carbazole compounds, triarylamine compounds, biphenyldiamine compounds, fluorene compounds, phthalocyanine compounds, hexacyanohexatriphenylene, F4-TCNQ, polythiophene, polyvinylcarbazole, and the like, but are not limited thereto.
The hole transport material is preferably a material having high hole mobility, which is capable of transferring holes from the anode or the hole injection layer to the light-emitting layer. Specific examples of the hole transport material that can be used in the present invention include: carbazole compounds, triarylamine compounds, biphenyldiamine compounds, fluorene compounds, phthalocyanine compounds, hexacyanohexanotribenzene, F4-TCNQ, polythiophene, polyvinylcarbazole, polyethylene, and the like, but are not limited thereto.
The light-emitting material is capable of receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes and the electrons to emit light in the visible light regionA material, and preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples of the luminescent material that can be used in the present invention include: 8-hydroxy-quinoline aluminum complex (Alq)3) Carbazole-based compounds, dimeric styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole-, benzothiazole-and benzimidazole-based compounds, spiro compounds, polyfluorenes, but are not limited thereto.
The light-emitting layer may include a host material and a dopant material, and specific examples of the host material include fused aromatic ring derivatives, heterocyclic compounds, or the like, and specifically, examples of the fused aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, or the like, but are not limited thereto.
Specific examples of the doping material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like, and specifically, aromatic amine derivatives include pyrene, anthracene, having an arylamine group,
Figure BDA0002672163520000201
Diindenopyrene, and the like; the styrylamine compounds include styrylamine, styrenediamine, and the like; the metal complex includes iridium complex, platinum complex, etc., but is not limited thereto.
The electron transport material is a material capable of easily receiving electrons from the cathode and transferring the received electrons to the light emitting layer. In addition to the compounds provided by the present invention being useful for organic electroluminescent devices, specific examples of electron transport materials commonly used in the art include: oxazazoles, thiazoles, triazoles, triazines, triazobenzenes, oxines, diazoanthracenes, silaheterocycles, quinolines, phenanthrolines, Alq3, benzimidazoles, and the like, but are not limited thereto.
The electron injection material preferably has an ability to transport electrons, has an effect of injecting electrons from the cathode, and has an excellent thin film forming ability. Specific examples of the electron injecting material that can be used in the present invention include: lithium, lithium fluoride, lithium oxide, lithium nitride, 8-hydroxyquinoline lithium, cesium carbonate, 8-hydroxyquinoline cesium, calcium fluoride, calcium oxide, magnesium fluoride, magnesium oxide, fluorenone, a nitrogen-containing five-membered ring derivative, and the like, but these compounds may be used alone or in combination with other materials.
The cathode material is preferably a material having a low work function in order to easily inject electrons into the organic layer. Specific examples of cathode materials that can be used in the present invention include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, aluminum, silver, tin, lead, or alloys thereof; and multilayer materials, e.g. LiF/Al or LiO2and/Al, but not limited thereto.
According to the present invention, when an organic light emitting element is produced, the following production method can be selected: the organic el device is manufactured by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (Physical Vapor Deposition) method such as a sputtering method or an electron beam evaporation method (e-beam evaporation) to form an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer on the anode, and then depositing a substance that can be used as a cathode on the organic layer. In addition to this method, a cathode material, an organic layer, and an anode material may be sequentially deposited on a substrate to manufacture an organic light-emitting device. The host and the dopant of the light-emitting layer can be formed by a solution coating method as well as a vacuum deposition method. Here, the solution coating method refers to spin coating, knife coating, dip coating, spraying, inkjet printing, screen printing, and the like, but is not limited thereto.
On the other hand, the organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a bi-directional emission type, depending on the material used.
The organic electroluminescent device can be applied to the application fields of flat panel displays, lighting sources, signboards, signal lamps and the like.
The present invention will be explained in more detail by the following examples, but the present invention is not limited thereto. 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 inventive effort.
Preparation and characterization of the Compounds
Description of raw materials, reagents and characterization equipment:
the raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.
The mass spectrum was analyzed by matrix-assisted laser desorption ionization (AXIMA-CFR plus) from Kratos Analytical, Inc. of Shimadzu corporation, U.K., using chloroform as a solvent;
the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;
nuclear magnetic resonance (1H NMR Spectroscopy) A nuclear magnetic resonance spectrometer model Bruker-510 (Bruker, Germany), 500MHz, CDCl3As solvent, TMS as internal standard.
EXAMPLE 1 Synthesis of intermediate B
Figure BDA0002672163520000211
Bisphenol A (100g, 438mmol) and methanesulfonic acid (500mL) were added to a reaction flask, dissolved with stirring, stirred at room temperature for 4 days, and after the reaction was terminated, 600g of crushed ice was added to the reaction mixture, stirred to room temperature and filtered, and the resulting solid was washed with water. Dissolving the solid with ethanol under reflux, adding 50 deg.C hot water until no solid is separated out, filtering while hot, washing filter cake with hot water, and oven drying to obtain white flocculent solid, i.e. intermediate A (40.49g, 90%), and solid purity greater than or equal to 99.9% by HPLC detection.
Dissolving the intermediate A (20g, 64.9mmol) in 600mL of dichloromethane, cooling in ice bath with stirring at 0 ℃, dropwise adding trifluoromethanesulfonic anhydride (15.4mL), slowly heating the system to room temperature, stirring for reacting for 1h, diluting the reaction solution with diethyl ether, washing the organic phase with 10% hydrochloric acid solution, saturated sodium bicarbonate solution and saturated sodium chloride solution in turn, and drying the organic layer with anhydrous sodium sulfate. After that, the organic layer was distilled under reduced pressure. And then recrystallized from ethanol. The resulting solid was filtered and dried to afford intermediate B (34.16g, 92%) which was > 99.8% pure by HPLC.
Mass spectrum m/z: 572.14 (theoretical value: 572.53). Theoretical element content (%) C23H22F6O6S2: c, 48.25; h, 3.87; f, 19.91; o, 16.77; and S, 11.20. Measured elemental content (%): c, 48.27; h, 3.87; f, 19.94; o, 16.74; s, 11.18. The above results confirmed that the obtained product was the objective product.
EXAMPLE 2 Synthesis of Compound 7
Figure BDA0002672163520000212
To a reaction flask were added intermediate B (17.16g, 30mmol), intermediate 7-1(12.02g, 60.4mmol), and a toluene solvent (300mL), to the system was added a potassium carbonate solution (12.44g, 90mmol), and then palladium tetratriphenylphosphine [ Pd (PPh) was further added thereto3)4](0.35g, 0.3mmol), vacuumizing for three times to replace nitrogen, heating and stirring, performing reflux reaction for 8 hours, cooling the system to room temperature after the reaction is stopped, filtering, concentrating the filtrate, combining filter cakes after filtering, washing the filter cakes for three times by using distilled water, adding a toluene solvent into the obtained solid for recrystallization to finally obtain a compound 7(13.1g, 75 percent), wherein the purity of the solid is more than or equal to 99.9 percent by HPLC detection.
Mass spectrum m/z: 582.28 (theoretical value: 582.79). Theoretical element content (%) C43H38N2: c, 88.62; h, 6.57; and N, 4.81. Measured elemental content (%): c, 88.58; h, 6.57; and N, 4.85. The above results confirmed that the obtained product was the objective product. [ example 3]Synthesis of Compound 24
Figure BDA0002672163520000221
Compound 24(12.09, 69%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 24-1, and had a solid purity of 99.2% or more as determined by HPLC.
Mass spectrum m/z: 584.81 (theoretical value: 584.77). Theoretical element content (%) C41H36N4: c, 84.21; h, 6.21; and N, 9.58. Measured elemental content (%): c, 84.20; h, 6.21; and N, 9.59. The above results confirmed that the obtained product was the objective product. [ example 4]]Synthesis of Compound 51
Figure BDA0002672163520000222
Compound 51(15.73g, 71%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 51-1, and had a solid purity of 99.3% or more as determined by HPLC.
Mass spectrum m/z: 738.35 (theoretical value: 738.94). Theoretical element content (%) C51H42N6: c, 82.90; h, 5.73; n, 11.37. Measured elemental content (%): c, 82.87; h, 5.75; n, 11.38.1H NMR(500MHz,CDCl3)(δ,ppm):8.64(dd,4H),8.44(dd,4H),8.17(s,4H),7.77–7.74(m,4H),7.69(dd,2H),7.31(d,2H),7.28–7.25(m,4H),7.18(d,2H),2.26(t,2H),2.07(t,2H),1.33(s,6H),1.28(s,6H)。1The H NMR is shown in FIG. 1. The above results confirmed that the obtained product was the objective product.
EXAMPLE 5 Synthesis of Compound 73
Figure BDA0002672163520000223
Compound 73(15.02g, 68%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 73-1, and had a solid purity of 99.4% or more as determined by HPLC.
Mass spectrum m/z: 736.35 (theoretical value: 736.96). Theoretical element content (%) C53H44N4：C,86.38; h, 6.02; and N, 7.60. Measured elemental content (%): c, 86.35; h, 6.06; and N, 7.59.1H NMR(500MHz,CDCl3)(δ,ppm):8.26–8.22(m,8H),8.03(s,2H),7.66(dd,2H),7.59(d,2H),7.54–7.49(m,8H),7.46–7.41(m,4H),7.27(d,2H),2.26(t,2H),2.07(t,2H),1.33(s,6H),1.28(s,6H)。1The H NMR is shown in FIG. 2. The above results confirmed that the obtained product was the objective product.
EXAMPLE 6 Synthesis of Compound 74
Figure BDA0002672163520000231
Compound 74(14.8g, 67%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 74-1, and had a solid purity of 99.6% or more as determined by HPLC.
Mass spectrum m/z: 736.39 (theoretical value: 736.96). Theoretical element content (%) C53H44N4: c, 86.38; h, 6.02; and N, 7.60. Measured elemental content (%): c, 86.35; h, 6.05; and N, 7.60. The above results confirmed that the obtained product was the objective product. [ example 7]Synthesis of Compound 91
Figure BDA0002672163520000232
Compound 91(15.95g, 72%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 91-1, and had a solid purity of 99.8% or more as determined by HPLC.
Mass spectrum m/z: 739.43 (theoretical value: 739.94). Theoretical element content (%) C51H42N6: c, 82.90; h, 5.73; n, 11.37. Measured elemental content (%): c, 82.87; h, 5.75; n, 11.38.1H NMR(500MHz,CDCl3)(δ,ppm):8.33–8.29(m,8H),7.66(d,2H),7.62(dd,2H),7.52–7.47(m,12H),7.27(d,2H),2.26(t,2H),2.07(t,2H),1.33(s,6H),1.28(s,6H)。1The H NMR is shown in FIG. 3. The above results confirmed that the obtained product was the objective product.
EXAMPLE 8 Synthesis of Compound 92
Figure BDA0002672163520000233
Compound 92(18.70g, 70%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 92-1, and had a solid purity of 99.7% or more as determined by HPLC.
Mass spectrum m/z: 891.48 (theoretical value: 891.14). Theoretical element content (%) C63H50N6: c, 84.91; h, 5.66; n, 9.43. Measured elemental content (%): c, 84.88; h, 5.67; and N, 9.42. The above results confirmed that the obtained product was the objective product. [ example 9]Synthesis of Compound 95
(1) Preparation of intermediate 95-1
Slowly dripping isopropyl magnesium chloride (22.1g, 150mmol) into a methyl tert-butyl ether (100mL) solution of 2, 4-bis ([1,1' -biphenyl ] -4-yl) -6-chloro-1, 3, 5-triazine (41.91g, 100mmol) at 0-10 ℃ under the protection of argon, keeping the temperature for reaction for 1h after dripping, slowly dripping triisopropyl borate (37.6g, 200mmol) into the reaction solution, keeping the temperature in the range of-10 ℃ to 0 ℃, keeping the temperature for reaction for 1h after dripping, slowly heating to room temperature, stirring for 10h, adding a 2N hydrochloric acid aqueous solution (350mL) into the reaction solution at 10 ℃, stirring for 3h after dripping, layering, extracting an aqueous layer with ethyl acetate (50mL), combining the aqueous layer with a plurality of layers, washing with water, dried over anhydrous sodium sulfate, concentrated and recrystallized with a dichloromethane-n-butane mixed solvent to obtain intermediate 95-1(31.55g, 73.5%) with a solid purity of greater than or equal to 98.9% by HPLC.
Mass spectrum m/z: 429.14 (theoretical value: 429.29). Theoretical element content (%) C27H20BN3O2: c, 75.54; h, 4.70; b, 2.52; n, 9.79; and O, 7.45. Measured elemental content (%): c, 75.48; h, 4.76; b, 2.48; n, 9.80; and O, 7.48. The above results confirmed that the obtained product was the objective product.
(2) Preparation of Compound 95
Figure BDA0002672163520000241
Compound 95(20.64g, 66%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 95-1, and had a solid purity of 99.5% or more as determined by HPLC.
Mass spectrum m/z: 1042.45 (theoretical value: 1042.33). Theoretical element content (%) C75H58N6: c, 86.34; h, 5.60; and N, 8.06. Measured elemental content (%): c, 86.39; h, 5.56; and N, 8.05. The above results confirmed that the obtained product was the objective product.
EXAMPLE 10 Synthesis of Compound 98
(1) Preparation of intermediate 98-1
Slowly dripping isopropyl magnesium chloride (22.1g, 150mmol) into a methyl tert-butyl ether (100mL) solution of 2-chloro-4- (1-naphthyl) -6-phenyl-1, 3, 5-triazine (31.78g, 100mmol) under the protection of argon at the temperature of 0-10 ℃, keeping the temperature for reaction for 1h after dripping is finished, slowly dripping triisopropyl borate (37.6g, 200mmol) into the reaction solution, controlling the temperature to be in the range of-10 ℃ to 0 ℃, keeping the temperature for reaction for 1h after dripping is finished, slowly heating to room temperature, stirring for 10h, adding a 2N hydrochloric acid aqueous solution (350mL) into the reaction solution at the temperature of 10 ℃, stirring for 3h after dripping is finished, layering, extracting an aqueous layer with ethyl acetate (50mL), combining the aqueous layer with a plurality of layers, washing with water, drying with anhydrous sodium sulfate, after concentration, the mixture is recrystallized by a dichloromethane-n-butane mixed solvent to obtain an intermediate 98-1(23.55g, 72.0 percent) with the solid purity of more than or equal to 99.2 percent by HPLC detection.
Mass spectrum m/z: 326.89 (theoretical value: 327.15). Theoretical element content (%) C19H14BN3O2: c, 69.76; h, 4.31; b, 3.30; n, 12.84; and O, 9.78. Measured elemental content (%): c, 69.69; h, 4.34; b, 3.36; n, 12.78; and O, 9.83. The above results confirmed that the obtained product was the objective product.
(2) Preparation of Compound 98
Figure BDA0002672163520000251
Compound 98(16.35g, 65%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 98-1, and had a solid purity of 99.3% or more as determined by HPLC.
Mass spectrum m/z: 838.73 (theoretical value: 839.06). Theoretical element content (%) C59H46N6: c, 84.46; h, 5.53; and N, 10.02. Measured elemental content (%): c, 84.45; h, 5.55; and N, 10.01. The above results confirmed that the obtained product was the objective product. [ example 11]Synthesis of Compound 100
Figure BDA0002672163520000252
Compound 100(19.14g, 68%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 100-1, and had a solid purity of 99.0% or more as determined by HPLC.
Mass spectrum m/z: 938.80 (theoretical value: 939.18). Theoretical element content (%) C67H50N6: c, 85.69; h, 5.37; and N, 8.95. Measured elemental content (%): c, 85.67; h, 5.37; and N, 8.98. The above results confirmed that the obtained product was the objective product. [ example 12]Synthesis of Compound 93
(1) Preparation of intermediate 93-1
Under the protection of argon, slowly dropwise adding isopropyl magnesium chloride (22.1g, 150mmol) into a methyl tert-butyl ether (100mL) solution of 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (34.38g, 100mmol) at 0-10 ℃, keeping the temperature for reaction for 1h after dropwise adding, slowly dropwise adding triisopropyl borate (37.6g, 200mmol) into the reaction solution, controlling the temperature to be in the range of-10 ℃ to 0 ℃, keeping the temperature for reaction for 1h after dropwise adding, slowly heating to room temperature, stirring for 10h, adding a 2N hydrochloric acid aqueous solution (350mL) into the reaction solution at 10 ℃, stirring for 3h after dropwise adding, layering, extracting an aqueous layer with ethyl acetate (50mL), and combining several layers, washed by water, dried by anhydrous sodium sulfate, concentrated and recrystallized by a dichloromethane-n-butane mixed solvent to obtain an intermediate 93-1(26.16g, 74.1 percent) with the solid purity of more than or equal to 99.5 percent by HPLC detection.
Mass spectrum m/z: 354.41 (theoretical value: 353.19). Theoretical element content (%) C21H16BN3O2: c, 71.42; h, 4.57; b, 3.06; n, 11.90; and O, 9.06. Measured elemental content (%): c, 71.37; h, 4.55; b, 3.12; n, 11.91; and O, 9.05. The above results confirmed that the obtained product was the objective product.
(2) Preparation of Compound 93
Figure BDA0002672163520000261
Compound 93(19.49g, 73%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 93-1, and had a solid purity of 99.4% or more as determined by HPLC.
Mass spectrum m/z: 891.38 (theoretical value: 891.14). Theoretical element content (%) C63H50N6: c, 84.91; h, 5.66; n, 9.43. Measured elemental content (%): c, 84.87; h, 5.68; and N, 9.45. The above results confirmed that the obtained product was the objective product. [ example 13]Synthesis of Compound 96
Figure BDA0002672163520000262
Compound 96(19.50g, 73%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 96-1, and had a solid purity of 99.0% or more as determined by HPLC.
Mass spectrum m/z: 891.37 (theoretical value: 891.14). Theoretical element content (%) C63H50N6: c, 84.91; h, 5.66; n, 9.43. Measured elemental content (%): c, 84.99; h, 5.61; and N, 9.40. The above results confirmed that the obtained product was the objective product. [ example 14]Synthesis of Compound 116
(1) Preparation of intermediate 116-1
Slowly dripping isopropyl magnesium chloride (22.1g, 150mol) into a methyl tert-butyl ether (100mL) solution of 2-chloro-1, 4, 5-triphenyl-1H-imidazole (33.01g, 100mmol) at 0-10 ℃ under the protection of argon, keeping the temperature for reaction for 1H after dripping is finished, slowly dripping triisopropyl borate (37.6g, 200mol) into the reaction solution, controlling the temperature to be in a range of-10 ℃ to 0 ℃, keeping the temperature for reaction for 1H after dripping is finished, slowly heating to room temperature, stirring for 10H, adding a 2N hydrochloric acid aqueous solution (350mL) into the reaction solution at 10 ℃, stirring for 3H after dripping is finished, demixing, extracting an aqueous layer with ethyl acetate (50mL), then combining with a plurality of layers, washing with water, drying with anhydrous sodium sulfate, concentrating, recrystallizing with a dichloromethane-N-butane mixed solvent, the intermediate 116-1(24.45g, 71.9%) was obtained with a solid purity of 99.6% or more by HPLC.
Mass spectrum m/z: 339.76 (theoretical value: 340.14). Theoretical element content (%) C21H17BN2O2: c, 74.14; h, 5.04; b, 3.18; n, 8.23; and O, 9.41. Measured elemental content (%): c, 74.06; h, 5.00; b, 3.24; n, 8.26; and O, 9.44. The above results confirmed that the obtained product was the objective product.
(2) Preparation of Compound 116
Figure BDA0002672163520000271
Compound 116(18.15g, 70%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 116-1, and had a solid purity of 99.1% or more as determined by HPLC.
Mass spectrum m/z: 864.98 (theoretical value: 865.14). Theoretical element content (%) C63H52N4: c, 87.47; h, 6.06; and N, 6.48. Measured elemental content (%): c, 87.44; h, 5.99; and N, 6.57. The above results confirmed that the obtained product was the objective product. [ example 15]Synthesis of Compound 131
Figure BDA0002672163520000272
Compound 131(14.07g, 71%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 131-1, and was found to have a solid purity of 99.3% or more by HPLC.
Mass spectrum m/z: 660.31 (theoretical value: 660.87). Theoretical element content (%) C47H40N4: c, 85.42; h, 6.10; and N, 8.48. Measured elemental content (%): c, 85.44; h, 6.11; and N, 8.46.1H NMR(500MHz,CDCl3)(δ,ppm):7.89(dd,2H),7.70(dd,2H),7.57(dd,2H),7.50–7.47(m,4H),7.47–7.43(m,2H),7.42–7.39(m,2H),7.38(d,2H),7.34–7.31(m,2H),7.31–7.28(m,4H),7.26(d,2H),2.26(t,2H),2.07(t,2H),1.33(s,6H),1.28(s,6H)。1The H NMR is shown in FIG. 4. The above results confirmed that the obtained product was the objective product. [ example 16]Synthesis of Compound 134
Figure BDA0002672163520000273
Compound 134(11.71g, 72%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 134-1, and had a solid purity of 99.7% or more as determined by HPLC.
Mass spectrum m/z: 542.23 (theoretical value: 542.76). Theoretical element content (%) C35H30N2S2: c, 77.45; h, 5.57; n, 5.16; s, 11.81. Measured elemental content (%): c, 77.50; h, 5.57; n, 5.13; s, 11.80. The above results confirmed that the obtained product was the objective product.
EXAMPLE 17 Synthesis of Compound 136
Figure BDA0002672163520000274
Compound 136(14.50g, 73%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 136-1, and had a solid purity of 99.3% or more as determined by HPLC.
Mass spectrum m/z: 662.26 (theoretical value: 662.83). Theoretical element content (%) C47H38N2O2: c, 85.17; h, 5.78; n, 4.23; and O, 4.83. Measured elemental content (%): c, 85.14; h, 5.60; n, 4.20; and O, 4.86.1H NMR(500MHz,CDCl3)(δ,ppm):8.13–8.10(m,4H),7.72–7.70(m,2H),7.69–7.66(m,4H),7.62–7.60(m,2H),7.43(dd,2H),7.38–7.31(m,4H),7.20(d,2H),7.15(d,2H),2.26(t,2H),2.07(t,2H),1.33(s,6H),1.28(s,6H)。1The H NMR is shown in FIG. 5. The above results confirmed that the obtained product was the objective product.
EXAMPLE 18 Synthesis of Compound 149
Figure BDA0002672163520000281
Compound 149(11.29g, 71%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 149-1, and had a solid purity of 99.8% or more as determined by HPLC.
Mass spectrum m/z: 530.94 (theoretical value: 530.72). Theoretical element content (%) C39H34N2: c, 88.26; h, 6.46; and N, 5.28. Measured elemental content (%): c, 88.24; h, 6.45; n, 5.31.1H NMR(500MHz,CDCl3)(δ,ppm):8.82–8.79(m,2H),8.27–8.23(m,4H),8.01(d,2H),7.81(dd,2H),7.52–7.49(m,2H),7.48(dd,2H),7.21(d,2H),7.16(d,2H),2.26(t,2H),2.07(t,2H),1.33(s,6H),1.28(s,6H)。1The H NMR is shown in FIG. 6. The above results confirmed that the obtained product was the objective product.
EXAMPLE 19 Synthesis of Compound 156
Figure BDA0002672163520000282
Compound 156(11.14g, 70%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 156-1, and had a solid purity of 99.9% or more as determined by HPLC.
Mass spectrum m/z: 530.27 (theoretical value: 530.72). Theoretical element content (%) C39H34N2: c, 88.26; h, 6.46; and N, 5.28. Measured elemental content (%): c, 88.29; h, 6.44; and N, 5.27. The above results confirmed that the obtained product was the objective product. Example 20]Synthesis of Compound 190
Figure BDA0002672163520000283
Compound 190(14.99g, 73%) was prepared according to the synthetic method of example 2 by replacing intermediate 7-1 in example 2 with an equimolar amount of intermediate 190-1, and had a solid purity of 99.6% or more as determined by HPLC.
Mass spectrum m/z: 685.21 (theoretical value: 684.89). Theoretical element content (%) C49H40N4: c, 85.93; h, 5.89; and N, 8.18. Measured elemental content (%): c, 85.94; h, 5.86; and N, 8.20.1H NMR(500MHz,CDCl3)(δ,ppm):8.17(dd,2H),7.98–7.95(m,2H),7.75–7.70(m,6H),7.66(dd,2H),7.59(d,2H),7.52–7.47(m,6H),7.45–7.41(m,2H),7.27(d,2H),2.26(t,2H),2.07(t,2H),1.33(s,6H),1.28(s,6H)。1The H NMR is shown in FIG. 7. The above results confirmed that the obtained product was the objective product.
Device example 1
Firstly, the thickness is
Figure BDA0002672163520000294
The ITO glass substrate is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, then the ITO glass substrate is repeatedly cleaned for 2 times, the ultrasonic cleaning is carried out for 10 minutes, after the cleaning of the distilled water is finished, solvents of isopropanol, acetone and methanol are adopted for carrying out ultrasonic cleaning in sequence and then drying, the dried substrate is transferred into a plasma cleaning machine, and after the cleaning is carried out for 5 minutes, the substrate is transferred into an evaporation machine.
Then HAT is evaporated on the cleaned ITO substrate to be used as a hole injection layer, and the evaporation thickness is
Figure BDA0002672163520000295
NPB is vacuum evaporated on the hole injection layer to form a hole transport layer with a thickness of
Figure BDA0002672163520000296
H1 as a host material and a D1 compound as a doping material are vacuum-evaporated on the hole transport layer to form a light-emitting layer, and the evaporation thickness is
Figure BDA0002672163520000297
On the light-emitting layer, the compound 7 prepared in the above synthetic example 2 was vacuum-evaporated to form an electron transporting layer with a thickness of
Figure BDA00026721635200002911
Vacuum evaporating LiQ to form an electron injection layer on the electron transport layer, wherein the evaporation thickness is
Figure BDA0002672163520000298
Sequentially vacuum-evaporating the electron injection layer to a thickness of
Figure BDA00026721635200002910
With a thickness of lithium fluoride (LiF) of
Figure BDA0002672163520000299
The aluminum of (a) forms a cathode, thereby preparing an organic electroluminescent device.
Figure BDA0002672163520000291
In the above process, the evaporation rate of the organic substance is maintained at
Figure BDA0002672163520000292
The evaporation rate of the electrode metal is in
Figure BDA0002672163520000293
The vacuum degree of the system should be maintained at 5 × 10 during vapor deposition-5Pa or less。
Device example 2
An organic electroluminescent device was obtained by the same production method as in device example 1 except that compound 24 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 3
An organic electroluminescent device was obtained by the same production method as in device example 1 except that compound 51 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 4
An organic electroluminescent device was obtained by the same production method as device example 1, except that compound 73 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 5
An organic electroluminescent device was obtained by the same production method as in device example 1, except that compound 91 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 6
An organic electroluminescent device was obtained by the same production method as in device example 1, except that compound 92 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 7
An organic electroluminescent device was obtained by the same production method as in device example 1, except that compound 95 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 8
An organic electroluminescent device was obtained by the same production method as in device example 1 except that compound 93 was used instead of compound 7 in device example 1 as an electron transport layer.
Device example 9
An organic electroluminescent device was obtained by the same production method as in device example 1, except that compound 96 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 10
An organic electroluminescent device was obtained by the same production method as in device example 1, except that compound 116 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 11
An organic electroluminescent device was obtained by the same production method as device example 1, except that compound 131 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 12
An organic electroluminescent device was obtained by the same production method as in device example 1, except that compound 149 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 13
An organic electroluminescent device was obtained by the same production method as in device example 1, except that compound 156 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 14
An organic electroluminescent device was obtained by the same production method as in device example 1, except that compound 100 was used as an electron transport layer instead of compound 7 in device example 1.
Device example 15
An organic electroluminescent device was obtained by the same preparation method as device example 1, except that compound 190 was used as an electron transport layer instead of compound 7 in device example 1.
[ comparative example 1]
An organic electroluminescent device was obtained by the same production method as device example 1, except that compound ET1 was used as the electron transport layer instead of compound 7 in device example 1.
[ comparative example 2]
An organic electroluminescent device was obtained by the same production method as device example 1, except that compound ET2 was used as the electron transport layer instead of compound 7 in device example 1.
[ comparative example 3]
An organic electroluminescent device was obtained by the same production method as device example 1, except that compound ET3 was used as the electron transport layer instead of compound 7 in device example 1.
Figure BDA0002672163520000311
For the organic electroluminescent devices prepared using the compounds as electron transport layers as shown in the above device examples 1 to 15 and comparative examples 1 to 3, the concentration was 10mA/cm2The driving voltage and the luminous efficiency were measured at a current density of 20mA/cm2The time (LT) until 95% of the initial brightness is reached is measured at the current density of (1)95)。
The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency and CIE color coordinates of the organic light emitting device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 1.
[ Table 1]
Figure BDA0002672163520000312
Figure BDA0002672163520000321
As shown in table 1, the examples of the present invention showed lower driving voltage, higher luminous efficiency, and much improved lifetime than those of comparative examples 1 to 3.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims (5)

1. An organic compound, wherein the structural formula of the organic compound is shown in chemical formula 6:
Figure FDA0003211702280000011
wherein R is1、R2The same as each other, is selected from any one of methyl and ethyl;
L1、L2the groups are the same or different from each other and are independently selected from a single bond and any one of the following groups;
Figure FDA0003211702280000012
Ar1、Ar2the same or different from each other, and is selected from any one of the following groups:
Figure FDA0003211702280000013
a1an integer selected from 0 to 4, a2An integer selected from 0 to 3, a3An integer selected from 0 to 2; c. C1An integer selected from 0 to 6, c2An integer selected from 0 to 5, c3An integer selected from 0 to 4; p is a radical of1An integer selected from 0 to 4, p2An integer selected from 0 to 3;
R3independently selected from hydrogen, deuterium, any one of the following groups:
Figure FDA0003211702280000014
R4、R6independently selected from hydrogen, deuterium, any one of the following groups:
Figure FDA0003211702280000015
R7、R9、R10independently selected from any one of the following groups:
Figure FDA0003211702280000016
R5、R8independently selected from any one of phenyl and biphenyl.
2. An organic compound according to claim 1, wherein Ar is Ar1、Ar2Any one selected from the following groups:
Figure FDA0003211702280000021
3. an organic compound, wherein the compound is selected from any one of the following chemical structures:
Figure FDA0003211702280000031
Figure FDA0003211702280000041
Figure FDA0003211702280000051
Figure FDA0003211702280000061
Figure FDA0003211702280000071
Figure FDA0003211702280000081
Figure FDA0003211702280000091
4. an organic electroluminescent device comprising:
a first electrode and a second electrode;
an organic layer interposed between the first electrode and the second electrode;
characterized in that the organic layer comprises the organic compound according to any one of claims 1 to 3.
5. An organic electroluminescent device according to claim 4, wherein the organic layer comprises an electron transport layer comprising the organic compound according to any one of claims 1 to 3.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1397148A (en) * 2000-11-24 2003-02-12 东丽株式会社 Luminescent element material and luminescent element comprising the same
EP1424381A2 (en) * 2002-11-26 2004-06-02 Konica Minolta Holdings, Inc. Organic electroluminescent element, and display and illuminator
JP2006080272A (en) * 2004-09-09 2006-03-23 Konica Minolta Holdings Inc Organic electroluminescence element, lighting system and display device
JP4305046B2 (en) * 2003-05-14 2009-07-29 コニカミノルタホールディングス株式会社 Organic electroluminescence element, lighting device and display device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1397148A (en) * 2000-11-24 2003-02-12 东丽株式会社 Luminescent element material and luminescent element comprising the same
EP1424381A2 (en) * 2002-11-26 2004-06-02 Konica Minolta Holdings, Inc. Organic electroluminescent element, and display and illuminator
JP4305046B2 (en) * 2003-05-14 2009-07-29 コニカミノルタホールディングス株式会社 Organic electroluminescence element, lighting device and display device
JP2006080272A (en) * 2004-09-09 2006-03-23 Konica Minolta Holdings Inc Organic electroluminescence element, lighting system and display device

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