CN114075191B - Organic electroluminescent material, electronic element, and electronic device - Google Patents

Organic electroluminescent material, electronic element, and electronic device Download PDF

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CN114075191B
CN114075191B CN202011497049.4A CN202011497049A CN114075191B CN 114075191 B CN114075191 B CN 114075191B CN 202011497049 A CN202011497049 A CN 202011497049A CN 114075191 B CN114075191 B CN 114075191B
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赵宇
薛震
王金平
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Abstract

The present invention relates to an organic electroluminescent material, an electronic element including the organic electroluminescent material, and an electronic device including the electronic element. The compound structure of the organic electroluminescent material provided by the invention comprises a fused heteroaromatic ring and a pyridopyrimidine mother nucleus structure, so that the whole molecule has a bipolar structure, the polarity and electron density difference at two sides of the molecule are obvious, the dipole moment of the molecule is increased, the triplet energy state of the compound is high, the energy transfer efficiency is improved, the driving voltage of an organic electroluminescent device is reduced, the service life of the device is prolonged, and the performance of the organic electroluminescent device can be obviously improved when the compound is used in a luminescent layer of the organic electroluminescent device.

Description

Organic electroluminescent material, electronic element, and electronic device
Technical Field
The invention belongs to the technical field of organic materials, and particularly relates to an organic electroluminescent material, an electronic element and an electronic device.
Background
As a new generation display technology, the organic electroluminescent material (OLED) has the advantages of ultra-thin, self-luminescence, wide viewing angle, quick response, high luminous efficiency, good temperature adaptability, simple production process, low driving voltage, low energy consumption and the like, and is widely applied to industries of flat panel display, flexible display, solid-state lighting, vehicle-mounted display and the like.
An organic light-emitting diode (OLED) is simply referred to. The principle is that when an electric field is applied to the anode and cathode, holes on the anode side and electrons on the cathode side move to the light-emitting layer, and are combined to form excitons on the light-emitting layer, the excitons are in an excited state to release energy outwards, and the process of releasing energy from the excited state to a ground state releases energy outwards. The material has the advantages of simple structure, high yield, low cost, active luminescence, high response speed, high fraction and the like, has the performances of low driving voltage, full solid state, non-vacuum, anti-oscillation, low temperature resistance (-40 ℃) and the like, is considered to be a new technology most likely to replace a liquid crystal display in the future, and is greatly concerned.
The main problems of the existing organic electroluminescent device are low efficiency and short service life. Accordingly, there is a continuing need to develop new materials to further improve the performance and lifetime of organic electroluminescent devices.
Disclosure of Invention
The invention aims to provide an organic electroluminescent material applied to an Organic Light Emitting Diode (OLED) and application thereof in an electronic element, so that the organic electroluminescent material has the advantages of excellent photoelectric property and long service life, and an electronic device comprising the electronic element.
According to a first aspect of the present invention, there is provided an organic electroluminescent material having a structure represented by formula i:
Figure BDA0002842474540000011
wherein L is 1 、L 2 And L 3 The same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms;
R 1 、R 2 and R is 3 Each independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted monocyclic heteroaryl group having 4 to 12 carbon atoms, a substituted or unsubstituted fused heteroaryl group having 7 to 30 carbon atoms, a group represented by the formula (2-1), a group represented by the formula (2-2), and R 1 、R 2 And R is 3 At least one of the groups is selected from the group consisting of a group represented by formula (2-1) or a group represented by formula (2-2);
Figure BDA0002842474540000012
ring A is a substituted or unsubstituted condensed aromatic ring having 15 to 25 carbon atoms or a substituted or unsubstituted condensed heteroaromatic ring having 12 to 30 carbon atoms;
Ar 1 a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms;
each R is 4 Independently selected from deuterium, halogen group, cyano group, alkyl group having 1-6 carbon atoms, haloalkyl group having 1-6 carbon atoms, alkoxy group having 1-6 carbon atoms, aryloxy group having 6-12 carbon atoms, arylthio group having 6-12 carbon atoms, aryl group having 6-15 carbon atoms, heteroaryl group having 3-18 carbon atoms, trialkylsilyl group having 3-12 carbon atoms and cycloalkyl group having 5-10 carbon atoms;
n 4 Represents a substituent R 4 Number n of (n) 4 Selected from 0, 1, 2, 3, 4, 5 or 6;
ring A, ar 1 、R 1 、R 2 、R 3 、L 1 、L 2 And L 3 The substituents in (a) are the same or different and are each independently selected from: deuterium, fluorine, chlorine, bromine, cyano, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, alkylthio having 1 to 6 carbon atoms, aryl having 6 to 18 carbon atoms, heteroaryl having 3 to 18 carbon atoms, trialkylsilyl having 3 to 12 carbon atoms, arylsilyl having 6 to 18 carbon atoms, aryloxy having 6 to 12 carbon atoms, arylthio having 6 to 12 carbon atoms.
According to a second aspect of the present invention, there is provided an electronic component comprising an anode and a cathode disposed opposite to each other, and a functional layer provided between the anode and the cathode; the functional layer comprises the organic electroluminescent material. According to one embodiment of the invention, the functional layer comprises a light-emitting layer comprising the organic electroluminescent material.
According to a third aspect of the present invention, there is provided an electronic device comprising the electronic element described above.
The compound structure of the organic electroluminescent material provided by the invention comprises a ring A serving as a condensed heteroaromatic ring and a pyridopyrimidine mother nucleus structure, so that the whole molecule has a bipolar structure, the polarity and electron density difference at two sides of the molecule are obvious, the dipole moment of the molecule is increased, the triplet state energy of the compound is high, the carrier mobility is high, the driving voltage of an organic electroluminescent device is reduced, the service life of the device is prolonged, and the performance of the organic electroluminescent device can be obviously improved when the compound is used in a luminescent layer of the organic electroluminescent device.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a first electronic device according to an embodiment of the present invention.
Reference numerals
100. An anode; 200. a cathode; 300. a functional layer; 310. a hole injection layer; 320. a hole transport layer; 321. a first hole transport layer; 322. a second hole transport layer; 330. an organic light emitting layer; 340. an electron transport layer; 350. an electron injection layer; 400. a first electronic device.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. However, the exemplary embodiments may be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the example embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a thorough understanding of embodiments of the invention.
In the present invention,
Figure BDA0002842474540000021
refers to a position that binds to other substituents or binding positions.
In the present invention, the term "substituted" in "substituted or unsubstituted" may mean that a substituent is included on the group, and the substituent may be selected from deuterium, fluorine, chlorine, bromine, cyano, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, carbon atomCycloalkyl group having 5 to 10 carbon atoms, alkylthio group having 1 to 6 carbon atoms, aryl group having 6 to 15 carbon atoms, heteroaryl group having 3 to 18 carbon atoms, trialkylsilyl group having 3 to 12 carbon atoms, arylsilyl group having 6 to 18 carbon atoms, aryloxy group having 6 to 12 carbon atoms, arylthio group having 6 to 12 carbon atoms; ar (Ar) 1 、R 1 、R 2 、R 3 、L 1 、L 2 And L 3 The number of carbon atoms refers to all the numbers of carbon atoms. For example, if R 2 Selected from the group consisting of substituted or unsubstituted aryl groups having 12 carbon atoms, then the aryl group and substituents thereon have 12 carbon atoms. For example, 2, 4-diphenyl-1, 3, 5-triazinyl is a substituted heteroaryl group having 15 carbon atoms.
The descriptions used in this disclosure that "… …" and "… …" are each independently "and" … … "are independently selected from" are interchangeable, and should be understood in a broad sense to mean that the specific options expressed between the same symbols in different groups do not affect each other, or that the specific options expressed between the same symbols in the same groups do not affect each other. For example, the number of the cells to be processed,
Figure BDA0002842474540000031
Wherein each q is independently 0, 1, 2 or 3, and each R "is independently selected from hydrogen, fluoro, chloro", with the meaning: the formula Q-1 represents Q substituent groups R ' on the benzene ring, wherein R ' can be the same or different, and the options of each R ' are not mutually influenced; the formula Q-2 represents that each benzene ring of the biphenyl has Q substituent groups R ', the number Q of the substituent groups R' on two benzene rings can be the same or different, each R 'can be the same or different, and the options of each R' are not influenced each other.
In the present invention, "hetero" means that at least one hetero atom selected from B, N, O, S, se, si and P is included in one functional group.
As used herein, "alkylsilyl" or "trialkylsilyl" refers to
Figure BDA0002842474540000032
Wherein R is G1 、R G2 、R G3 Each independently is an alkyl group, in some embodiments having 3 to 12 carbon atoms, in other embodiments having 3 to 6 carbon atoms, and specific examples of alkyl silicon groups include, but are not limited to, trimethylsilyl, triethylsilicon.
As used herein, "aryl silicon-based" or "triarylsilicon-based" refers to
Figure BDA0002842474540000033
Wherein R is G4 、R G5 、R G6 Each independently an aryl group, in some embodiments, the triarylsilyl group has 6 to 18 carbon atoms, and specific examples of aryl silyl groups include, but are not limited to, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.
In the present invention, as the halogen group as a substituent, there is fluorine, chlorine, bromine or iodine.
In the present invention, "alkyl" may include a straight chain alkyl group or a branched alkyl group. In some embodiments, the alkyl groups contain 1 to 12 carbon atoms, in other embodiments, the alkyl groups contain 1 to 10 carbon atoms, in other embodiments, the alkyl groups contain 1 to 6 carbon atoms, and in other embodiments, the alkyl groups contain 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include, but are not limited to, methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) N-propyl (n-Pr, -CH) 2 CH 2 CH 3 ) Isopropyl (i-Pr, -CH (CH) 3 ) 2 ) N-butyl (n-Bu, -CH) 2 CH 2 CH 2 CH 3 ) 2-methylpropyl or isobutyl (i-Bu, -CH) 2 CH(CH 3 ) 2 ) 1-methylpropyl or sec-butyl (s-Bu, -CH (CH) 3 )CH 2 CH 3 ) Tert-butyl (t-Bu, -C (CH) 3 ) 3 ) Etc.
In the present invention, "alkoxy" means an alkyl group attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy groups contain 1 to 12 carbon atoms. In another embodiment, the alkoxy group contains from 1 to 10 carbon atoms; in another embodiment, the alkoxy group contains 1 to 6 carbon atoms; in yet another embodiment, the alkoxy group contains 1 to 4 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH) 3 ) Ethoxy (EtO, -OCH) 2 CH 3 ) 1-propoxy (n-PrO, n-propoxy, -OCH) 2 CH 2 CH 3 ) 2-propoxy (i-PrO, i-propoxy, -OCH (CH) 3 ) 2 ) 1-butoxy (n-BuO, n-butoxy, -OCH) 2 CH 2 CH 2 CH 3 ) 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH) 2 CH(CH 3 ) 2 ) 2-butoxy (s-BuO, s-butoxy, -OCH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC (CH) 3 ) 3 ) And so on.
In the present invention, "alkylthio" means that an alkyl group is attached to the remainder of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkylthio group contains 1 to 6 carbon atoms. In another embodiment, the alkylthio group contains 1 to 4 carbon atoms. Examples of alkylthio groups include, but are not limited to, methylthio (MeS, -SCH 3 ) Ethylthio (EtS, -SCH) 2 CH 3 ) 1-propylthio (n-PrS, n-propylthio, -SCH) 2 CH 2 CH 3 ) 2-propylthio (i-PrS, i-propylthio, -SCH (CH) 3 ) 2 ) And so on.
In the present invention, "haloalkyl" or "haloalkoxy" means an alkyl or alkoxy group substituted with one or more halogen atoms, wherein the alkyl and alkoxy groups have the meaning as described herein, examples of which include, but are not limited to, trifluoromethyl, trifluoromethoxy, and the like. In one embodiment, the haloalkyl is a haloalkyl having 1 to 6 carbon atoms; in another embodiment Haloalkyl is C 1 -C 4 Haloalkyl, in particular fluoro-substituted C 1 -C 4 An alkyl group; in yet another embodiment, the haloalkyl is trifluoromethyl.
Cycloalkyl in the present invention refers to a radical obtained by removing a hydrogen atom from a monocyclic or polycyclic saturated cyclic hydrocarbon, and the "cycloalkyl" may have one or more points of attachment to the remainder of the molecule. In some embodiments, cycloalkyl is a ring system containing 3 to 10 ring carbon atoms; in other embodiments, cycloalkyl is a ring system containing 5 to 10 ring carbon atoms; in other embodiments, cycloalkyl is a ring system containing 5 to 7 ring carbon atoms; in other embodiments, cycloalkyl is a ring system containing 3 to 6 ring carbon atoms. The cycloalkyl groups may independently be unsubstituted or substituted with one or more substituents described herein. As non-limiting examples thereof, cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl (norbornyl), adamantyl (amantayl), and the like.
In the present invention, "aryl" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group, in other words, the aryl group may be a monocyclic aryl group, a condensed aryl group, two or more monocyclic aryl groups connected by a carbon-carbon bond conjugate, a monocyclic aryl group and a condensed ring aryl group connected by a carbon-carbon bond conjugate, two or more condensed ring aryl groups connected by a carbon-carbon bond conjugate. Examples of aryl groups in the present invention may include, but are not limited to, phenyl, naphthyl, anthryl, phenanthryl, biphenyl, terphenyl, tetrabiphenyl, pentabiphenyl, benzo [9,10 ] ]Phenanthryl, pyrenyl, benzofluoranthenyl,
Figure BDA0002842474540000041
A group, a perylene group, a fluorenyl group, a triphenylene group, a tetracene group, a triphenylene group (triphenylenyl) and the like. />
Fused aryl (fused aromatic ring) refers to a ring system of two or more contiguous rings, wherein each two contiguous rings share two atoms and a bond formed by the shared atoms (i.e., two atoms), wherein at least one of the ring systems is aromatic and the other rings may be cycloalkyl, aryl, heterocyclyl, aryl.
In the present application, the number of atoms of the condensed aryl group may be 10, 12, 13, 14, 15, 16, 17, 18, 20 or 25. Substituted or unsubstituted condensed aromatic rings having 10 to 25 carbon atoms such as, but not limited to, substituted or unsubstituted: naphthyl, anthracenyl, fluorenyl, phenanthrenyl, pyrenyl, perylenyl, wherein the number of carbon atoms is 15-25, substituted fused aromatic rings such as, for example, but not limited to, 9-dimethylfluorene ring and 9, 9-diphenylfluorene ring.
In the present invention, the substituted aryl group may be one in which one or two or more hydrogen atoms in the aryl group are substituted with a group such as deuterium atom, halogen group, cyano group, aryl group, heteroaryl group, alkylsilyl group, arylsilyl group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, alkylthio group, or the like. It is understood that the number of carbon atoms of a substituted aryl refers to the total number of carbon atoms of the aryl and substituents on the aryl, e.g., a substituted aryl having 18 carbon atoms refers to the total number of carbon atoms of the aryl and substituents being 18.
In the present invention, the number of carbon atoms of the substituted or unsubstituted aryl group may be selected from 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 25 or 30. In some embodiments, the aryl group is an aryl group having 6 to 30 carbon atoms, in other embodiments, the aryl group is an aryl group having 6 to 20 carbon atoms, in other embodiments, the aryl group is an aryl group having 6 to 18 carbon atoms, in other embodiments, the aryl group is an aryl group having 6 to 15 carbon atoms. Specific examples of aryl groups as substituents include, but are not limited to: phenyl, naphthyl, anthryl, phenanthryl, biphenyl, fluorenyl, and dimethylfluorenyl.
In the present invention, the arylene group is a 2-valent group, and the above description of the aryl group can be applied in addition thereto.
Aryl groups as substituents in the present application are, for example, but not limited to, phenyl, naphthyl, anthryl, phenanthryl, biphenyl, fluorenyl, dimethylfluorenyl.
In the present invention, heteroaryl refers to a monocyclic or polycyclic ring system having at least one heteroatom independently selected from O, N, P, si, se, B, and S in the ring, and wherein at least one ring system is aromatic. Each ring system in heteroaryl groups contains a ring of 3 to 7 carbon atoms and has one or more attachment points to the remainder of the molecule. Heteroaryl groups may be monocyclic heteroaryl or polycyclic heteroaryl, in other words, heteroaryl groups may be a single aromatic ring system or multiple aromatic ring systems that are conjugated through carbon-carbon bonds, with either aromatic ring system being an aromatic monocyclic ring or an aromatic fused ring. Illustratively, heteroaryl groups may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, isothiazolyl, oxadiazolyl, triazolyl, oxazolyl, furazayl, pyridyl, bipyridyl, phenanthridinyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, benzopyrimidinyl, benzopyridinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, and N-phenylcarbazolyl, N-pyridocarbazolyl, N-alkyl carbazolyl (such as N-methyl carbazolyl), and the like, without limitation thereto.
In the present invention, a substituted heteroaryl group may be one in which one or more hydrogen atoms in the heteroaryl group are substituted with a group such as a deuterium atom, a halogen group, a cyano group, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, or the like. Specific examples of aryl-substituted heteroaryl groups include, but are not limited to, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothiophenyl, phenyl-substituted pyridinyl, phenyl-substituted carbazolyl, and the like. It is understood that the number of carbon atoms of the substituted heteroaryl refers to the total number of carbon atoms of the heteroaryl and substituents on the heteroaryl. For example, a substituted heteroaryl group having 14 carbon atoms refers to a heteroaryl group and a substituent having 14 total carbon atoms.
In the present invention, the number of carbon atoms of the substituted or unsubstituted heteroaryl group may be selected from 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some embodiments, the heteroaryl is a heteroaryl having 3 to 30 carbon atoms, in other embodiments the heteroaryl is a heteroaryl having 3 to 18 carbon atoms. Specific examples are, but are not limited to, pyridyl, bipyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, isoquinolinyl, indolyl, carbazolyl, dibenzothienyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, and N-phenylcarbazolyl.
Heteroaryl groups as substituents in the present application are for example, but not limited to, pyridyl, pyrimidinyl, quinolinyl, dibenzothienyl, dibenzofuranyl, carbazolyl.
Fused heteroaryl (fused heteroaryl ring) refers to a ring system consisting of two or more adjacent rings, wherein any two adjacent rings share two atoms and bonds formed by the shared atoms, and at least one of the rings is a heteroaryl ring, and the other rings may be cycloalkyl, heterocyclyl, cycloalkenyl, aryl. In this application, the number of atoms of the fused heteroaryl group can be 7, 8, 9,10, 12, 13, 14, 15, 16, 17, 18, 20, 24, or 30. Substituted or unsubstituted fused heteroaryl rings having 12 to 30 carbon atoms such as, but not limited to, substituted or unsubstituted: dibenzofuran ring, dibenzothiophene ring, N-phenylcarbazole ring, N-naphthylcarbazole ring, N-biphenylcarbazole ring, N-pyrimidinylcarbazole ring, N-pyridylcarbazole ring, N-benzopyrimidinyl-carbazole ring, 10-phenyl-10H-phenoxazine, 10-phenyl-10H-phenothiazine, phenoxytheophylline, dibenzodioxin ring, thianthrene ring, 9-dimethyl-10-phenyl-9, 10-dihydroacridine ring, 9, 10-tetramethyl-9, 10-dihydroanthracene or 9, 9-dimethyl-9H-xanthene.
"alkyl", "aryl", "heteroaryl", and the like in the present invention also include polyvalent groups such as alkylene, alkylidene, arylene, heteroarylidene, and the like.
The non-positioning connection key in the present invention refers to a single bond extending from the ring system
Figure BDA0002842474540000061
It means that one end of the bond can be attached to any position in the ring system through which the bond extends, and the other end is attached to the remainder of the compound molecule.
For example, the naphthyl group represented by formula (f) is linked to the other positions of the molecule via two non-positional linkages extending through the bicyclic ring, which means includes any of the possible linkages shown in formulas (f-1) to (f-10).
Figure BDA0002842474540000062
As another example, the phenanthryl group represented by the following formula (X ') is linked to the other position of the molecule through an unoriented linkage extending from the middle of one side benzene ring, and the meaning of the linkage includes any one of the possible linkages represented by the formulas (X ' -1) to (X ' -4).
Figure BDA0002842474540000063
The meaning of the non-positioning connection is the same as here, and will not be described in detail later.
The invention provides an organic electroluminescent material, which has a structure shown as a chemical formula I:
Figure BDA0002842474540000064
Wherein L is 1 、L 2 And L 3 The same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms;
R 1 、R 2 and R is 3 Each independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted monocyclic heteroaryl group having 4 to 12 carbon atoms, a substituted or unsubstituted fused heteroaryl group having 7 to 30 carbon atoms, a group represented by the formula (2-1) or a group represented by the formula (2-2), and R 1 、R 2 And R is 3 At least one of the groups is selected from the group consisting of a group represented by formula (2-1) or a group represented by formula (2-2);
Figure BDA0002842474540000071
ring A is a substituted or unsubstituted condensed aromatic ring having 15 to 25 carbon atoms or a substituted or unsubstituted condensed heteroaromatic ring having 12 to 30 carbon atoms;
Ar 1 a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms;
each R is 4 Independently selected from deuterium, halogen group, cyano group, alkyl group having 1-6 carbon atoms, haloalkyl group having 1-6 carbon atoms, alkoxy group having 1-6 carbon atoms, aryloxy group having 6-12 carbon atoms, arylthio group having 6-12 carbon atoms, aryl group having 6-15 carbon atoms, heteroaryl group having 3-18 carbon atoms, silane group having 3-12 carbon atoms and cycloalkyl group having 5-10 carbon atoms;
n 4 Represents a substituent R 4 Number n of (n) 4 Selected from 0, 1, 2, 3, 4, 5 or 6;
ring A, ar 1 、R 1 、R 2 、R 3 、L 1 、L 2 And L 3 The substituents in (a) are the same or different and are each independently selected from: deuterium, fluorine, chlorine, bromine, cyano, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, alkylthio group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms, heteroaryl group having 3 to 18 carbon atoms, trialkylsilyl group having 3 to 12 carbon atoms, arylsilyl group having 6 to 18 carbon atoms, aryloxy group having 6 to 12 carbon atoms, aryl group having 6 to 12 carbon atomsA thio group.
In the group represented by the formula (2-1) or the formula (2-2), the substituent R 4 Replacing a hydrogen at any position in the fused heteroaromatic ring. For example, when ring A is an unsubstituted dibenzothiophene ring, ar 1 Is phenyl, n 4 Is 1, and R 4 For the trimethylsilyl group attached at position 2 in ring A, the group of formula (2-1) may be:
Figure BDA0002842474540000072
in some embodiments, R 1 、R 2 And R is 3 1 or 2 selected from the structures represented by the formula (2-1) or the formula (2-2).
In some embodiments, R 1 、R 2 And R is 3 Neither is hydrogen.
In some embodiments, R 1 Selected from the group represented by the formula (2-1)
Figure BDA0002842474540000073
In some embodiments, R 2 Selected from the group represented by the formula (2-1)
Figure BDA0002842474540000074
In some embodiments, R 2 Selected from the group represented by the formula (2-1) or the group represented by the formula (2-2), L 2 Is a single bond.
In some embodiments, R 1 Selected from the group represented by formula (2-1) or the group represented by formula (2-2), L 1 Is a single bond.
In some embodiments, ring A in formulas (2-1) and (2-2)
Figure BDA0002842474540000081
Each independently selected from the following formula (3-1) or formula (3-2):
Figure BDA0002842474540000082
wherein Y is 1 And Y 2 Each independently selected from single bond, O, S, C (R) 5 R 6 ) Or N (R) 7 ) And Y is 1 And Y 2 At most one of them is a single bond;
each R is 5 、R 6 And R is 7 Are the same or different from each other, and are each independently an alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 18 carbon atoms.
In some embodiments of the present application, each R 7 Are the same or different from each other and are each independently selected from methyl, ethyl, n-propyl, isopropyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, pyridazinyl or pyrazinyl;
Each R is 5 And R is 6 Are the same or different from each other and are each independently methyl, ethyl, n-propyl, isopropyl or phenyl;
the substitution refers to substitution by a substituent selected from deuterium, fluorine, chlorine, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, phenyl, naphthyl and pyridyl.
In some embodiments, the Ar 1 Selected from a substituted or unsubstituted group W, wherein the unsubstituted group W is selected from the following groups:
Figure BDA0002842474540000083
Figure BDA0002842474540000084
wherein the substituted group W is unsubstitutedW is a group formed by substitution of one or more substituents selected from deuterium, fluorine, chlorine, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, t-butyl, methoxy, ethoxy, isopropoxy, phenyl, naphthyl, pyridyl, and when the number of substituents on W is plural, any two substituents may be the same or different.
In some embodiments, the Ar 1 Selected from the following groups:
Figure BDA0002842474540000085
Figure BDA0002842474540000091
in some embodiments, ring A in formula (2-1) or formula (2-2)
Figure BDA0002842474540000092
Each independently is a dibenzofuran ring, a dibenzothiophene ring, an N-phenylcarbazole ring, an N-naphthylcarbazole ring, an N-biphenylcarbazole ring, an N-pyrimidinylcarbazole ring, an N-pyridylcarbazole ring, an N-benzopyrimidinyl-carbazole ring, a 10-phenyl-10H-phenoxazine, a 10-phenyl-10H-phenothiazine, a phenoxytheophylline, a dibenzodioxin ring, a dimethylfluorene ring, a diphenylfluorene ring, a thianthrene ring, a 9, 9-dimethyl-10-phenyl-9, 10-dihydroacridine ring, a 9, 10-tetramethyl-9, 10-dihydroanthracene or a 9, 9-dimethyl-9H-xanthene.
In some embodiments, ring A in formulas (2-1) and (2-2)
Figure BDA0002842474540000093
Each independently selected from the following structures: />
Figure BDA0002842474540000094
Figure BDA0002842474540000101
In some embodiments, wherein the formula (2-1)
Figure BDA0002842474540000102
Selected from the following groups: />
Figure BDA0002842474540000103
Figure BDA0002842474540000111
In some embodiments, wherein the formula (2-1)
Figure BDA0002842474540000112
Selected from the following groups: />
Figure BDA0002842474540000113
Figure BDA0002842474540000121
In some embodiments, wherein the formula (2-2)
Figure BDA0002842474540000122
Selected from the following groups: />
Figure BDA0002842474540000123
In some embodiments, the R 1 、R 2 And R is 3 Each independently selected from hydrogen, a group represented by the formula (2-1), a group represented by the formula (2-2), a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted monocyclic heteroaryl group having 4 to 12 carbon atoms, a substituted or unsubstituted condensed group having 7 to 12 carbon atomsHeteroaryl; and R is 1 、R 2 And R is 3 At least one of the groups is selected from the group represented by formula (2-1) or the group represented by formula (2-2).
In some embodiments of the present application, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is a substituted or unsubstituted following group: phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, anthracenyl, phenanthryl, pyrenyl, perylenyl.
In some embodiments of the present application, a substituted or unsubstituted monocyclic heteroaryl group having 4 to 12 carbon atoms is a substituted or unsubstituted following group: pyrimidinyl, pyridinyl, pyrazinyl, and pyridazinyl.
In some embodiments of the present application, a substituted or unsubstituted fused heteroaryl group having 7-12 carbon atoms is a substituted or unsubstituted group of: quinolinyl, quinazolinyl, isoquinolinyl, benzopyrimidinyl, pyridopyrimidinyl, benzopyridyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzopyrazinyl, benzopyridazinyl.
In some embodiments, optionally, R 1 、R 2 And R is 3 The substituents in (2) are the same or different from each other and are each independently selected from deuterium, fluorine, chlorine, bromine, cyano, methyl, n-propyl, ethyl, isopropyl, tert-butyl, ethoxy, trifluoromethyl, trimethylsilyl, phenyl, pyridyl, triphenylsilyl.
In some embodiments, the R 1 、R 2 And R is 3 Each independently selected from hydrogen, a group represented by formula (2-1), a group represented by formula (2-2), or a substituted or unsubstituted group Z 1 And R is 1 、R 2 And R is 3 At least one selected from the group represented by formula (2-1) or the group represented by formula (2-2); wherein the unsubstituted radical Z 1 Selected from the following groups:
Figure BDA0002842474540000131
/>
wherein Z is substituted 1 Is unsubstituted Z 1 Is one or more ofAnd is selected from deuterium, fluorine, chlorine, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, t-butyl, methoxy, ethoxy, isopropoxy, phenyl, naphthyl, pyridinyl, pyrimidinyl, and when Z 1 When the number of substituents is plural, any two substituents may be the same or different.
In some embodiments, the R 1 、R 2 And R is 3 Each independently selected from hydrogen, a group represented by formula (2-1), a group represented by formula (2-2), or a group selected from the following:
Figure BDA0002842474540000132
in some embodiments, the R in the compound of formula I 1 In the case of hydrogen, L 1 Is a single bond; or said R 2 In the case of hydrogen, L 2 Is a single bond; or said R 3 In the case of hydrogen, L 3 Is a single bond.
In some embodiments, L 1 、L 2 And L 3 All are single bonds.
In some embodiments, the L 1 、L 2 And L 3 And are each independently selected from one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted fluorenylene group, or a subunit group formed by the single bond connection of any two of the above subunits; l (L) 1 、L 2 And L 3 The substituents in (2) are the same or different from each other and are each independently selected from the group consisting of deuterium, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, n-propyl, t-butyl, methoxy, ethoxy, phenyl, trifluoromethyl, trimethylsilyl.
In some embodiments, the L 1 、L 2 And L 3 Identical or different and are each independently selected from single bonds, substituted or unsubstituted:
Figure BDA0002842474540000141
the substituents in the above groups are the same or different from each other and are each independently selected from the group consisting of deuterium, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, n-propyl, t-butyl, methoxy, ethoxy, phenyl, trifluoromethyl, trimethylsilyl.
In some embodiments, the L 1 、L 2 And L 3 Identical or different and are each independently selected from a single bond or from the following groups:
Figure BDA0002842474540000142
in some more specific embodiments, each R 4 Are identical to or different from each other and are each independently selected from deuterium, fluorine, cyano, methyl, n-propyl, ethyl, isopropyl, tert-butyl, ethoxy, trifluoromethyl, trimethylsilyl, phenyl, pyridyl, dimethylfluorenyl, dibenzofuranyl, dibenzothienyl, pyrimidinyl, triazinyl, cyclohexyl, n 4 Selected from 0, 1, 2, 3 or 4.
Alternatively, the organic electroluminescent material is selected from the group consisting of, but not limited to:
Figure BDA0002842474540000143
/>
Figure BDA0002842474540000151
/>
Figure BDA0002842474540000161
/>
Figure BDA0002842474540000171
/>
Figure BDA0002842474540000181
/>
Figure BDA0002842474540000191
/>
Figure BDA0002842474540000201
the invention also provides an electronic element, which comprises an anode and a cathode which are oppositely arranged, and a functional layer arranged between the anode and the cathode; the functional layer comprises the organic electroluminescent material.
The organic electroluminescent material provided by the invention can be used for forming at least one organic film layer in the functional layers so as to improve the voltage characteristic, the efficiency characteristic and the service life characteristic of the electronic element. Optionally, an organic film layer comprising the organic electroluminescent material of the invention is located between the anode and the energy conversion layer of the electronic component, in order to improve the transport of electrons between the anode and the energy conversion layer. Further, the functional layer comprises an organic light-emitting layer, and the organic light-emitting layer comprises a light-emitting main body material and a doping material, wherein the light-emitting main body material comprises the organic electroluminescent material.
For example, the electronic component may be an organic electroluminescent device. As shown in fig. 1, the organic electroluminescent device includes an anode 100 and a cathode 200 disposed opposite to each other, and a functional layer 300 disposed between the anode 100 and the cathode 200; the functional layer 300 comprises the organic electroluminescent material provided by the invention.
Alternatively, the organic electroluminescent material provided by the present invention may be used to form at least one organic thin layer in the functional layer 300 to improve life characteristics, efficiency characteristics, and reduce driving voltage of the organic electroluminescent device; in some embodiments, the electrochemical stability and the thermal stability of the organic electroluminescent device can be improved, and the uniformity of the performance of the mass-produced organic electroluminescent device can be improved.
Alternatively, the anode 100 includes an anode material that is preferably a material with a large work function that facilitates hole injection into the functional layer. Specific examples of the anode material include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metal and oxide such as ZnO, al or SnO 2 Sb; or conductive polymers such as poly (3-methylthiophene) and poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole, and polyaniline, but not limited thereto. Preferably, a transparent electrode including Indium Tin Oxide (ITO) as an anode is included.
Alternatively, the cathode 200 includes a cathode material that is a material having a small work function that facilitates electron injection into the functional layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or a multi-layer material such as LiF/Al, liq/Al, liO 2 Al, liF/Ca, liF/Al and BaF 2 /Ca, but is not limited thereto. A metal electrode containing aluminum is preferably included as a cathode.
As shown in fig. 1, the functional layer 300 of the organic electroluminescent device includes a hole transport layer 320, an organic light emitting layer 330, and an electron transport layer 340. Wherein the light emitting layer 330 is disposed on a side of the hole transporting layer 320 away from the anode 100. The electron transport layer 340 is disposed on a side of the organic light emitting layer 330 near the cathode 200.
Alternatively, the hole transport layer 320 includes a first hole transport layer 321 and a second hole transport layer 322, wherein the first hole transport layer 321 is disposed on a surface of the second hole transport layer 322 near the anode 100.
Alternatively, the first hole transport layer 321 may include one or more hole transport materials, and the hole transport materials may be selected from carbazole multimers, carbazole-linked triarylamine compounds, or other types of compounds, which are not particularly limited in the present invention. For example, the first hole transport layer 321 is composed of the compound NDDP.
Alternatively, the second hole transport layer 322 corresponds to a hole auxiliary layer and includes one or more electron blocking materials, which may be selected from carbazole multimers or other types of compounds, which are not particularly limited in the present invention. For example, the second hole transport layer 322 is composed of the compound TPD.
Alternatively, the organic light emitting layer 330 may be composed of a single light emitting material, and may include a host material and a guest material. Alternatively, the organic light emitting layer 330 is composed of a host material and a guest material, and holes injected into the organic light emitting layer 330 and electrons injected into the organic light emitting layer 330 may be recombined at the organic light emitting layer 330 to form excitons, which transfer energy to the host material, which transfers energy to the guest material, thereby enabling the guest material to emit light.
Alternatively, the host material of the organic light emitting layer 330 may include the organic compound provided by the present invention, and may further include a metal chelating compound, a bisstyryl derivative, an aromatic amine derivative, and a dibenzofuran derivative, which is not particularly limited in the present invention. That is, the host material of the light-emitting layer of the organic electroluminescent device of the present invention may contain only the organic compound provided by the present invention, or may be a mixture comprising the organic compound provided by the present invention and other substances. For example, the host material may comprise the luminescent material compound of the invention.
Alternatively, the guest material of the organic light emitting layer 330 may be a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative, or other materials, which is not particularly limited in the present invention. In one embodiment of the present invention, the guest material of the organic light emitting layer 330 may be DCM2 or Ir (piq) 2 (acac)。
Alternatively, the electron transport layer 340 may have a single layer structure or a multi-layer structure, and may include one or more electron transport materials selected from benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials, which are not particularly limited in the present invention. For example, in one embodiment of the present invention, electron transport layer 340 may be composed of DBimiBphen and LiQ.
Optionally, the functional layer 300 may further include a hole injection layer 310, where the hole injection layer 310 is disposed between the first hole transport layer 321 and the anode 100 to enhance the ability to inject holes into the first hole transport layer 321. The hole injection layer 310 may be selected from benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives, and other materials, which are not particularly limited in the present invention. In one embodiment of the present invention, hole injection layer 310 may be composed of m-MTDATA or HAT-CN.
Optionally, the functional layer 300 may further include an electron injection layer 350, wherein the electron injection layer 350 is disposed between the electron transport layer 340 and the cathode 200 to enhance the ability to inject electrons into the electron transport layer 340. The electron injection layer 350 may include an inorganic material such as an alkali metal sulfide, an alkali metal halide, or may include a complex of an alkali metal and an organic substance. In one embodiment of the present invention, the electron injection layer 350 may include LiQ.
As another example, as shown in fig. 2, the present invention provides an electronic apparatus 400, where the electronic apparatus 400 includes any one of the organic electroluminescent devices described in the above-mentioned embodiments of the organic electroluminescent device. The electronic device 400 may be a display device, a lighting device, an optical communication device, or other type of electronic device, which may include, for example, but not limited to, a computer screen, a cell phone screen, a television, an electronic paper, an emergency light, an optical module, etc. Since the electronic device 400 belongs to any one of the organic electroluminescent devices described in the foregoing embodiments of the organic electroluminescent device, the present invention is not repeated here, and therefore has the same beneficial effects.
The present invention will be described in detail with reference to examples, but the following description is intended to explain the present invention and is not intended to limit the scope of the invention in any way.
Synthetic examples
In the synthesis examples described below, all temperatures are in degrees celsius unless otherwise indicated. Some reagents were purchased from commercial suppliers such as Aldrich Chemical Company, arco Chemical Company and Alfa ChemicalCompany and were used without further purification unless otherwise stated. The rest conventional reagents are purchased from Shanshan chemical plant, guangdong chemical plant, guangzhou chemical plant, tianjin good-apartment chemical limited company, tianjin Fuchen chemical plant, wuhan Xinhua far-tech development limited company, nanjing Kang Manlin chemical plant, qingdao ocean chemical plant and the like.
The reactions in each synthesis example are typically carried out under nitrogen or argon positive pressure, or a dry tube is placed over anhydrous solvent (unless otherwise stated); in the reaction, the reaction flask was capped with a suitable rubber stopper and the substrate was injected into the flask via syringe. The individual glassware used was dried. In purification, the chromatographic column is a silica gel column, and silica gel (100-200 mesh) is purchased from Qingdao ocean chemical plant.
In each synthesis example, the measurement conditions for low resolution Mass Spectrometry (MS) data were: agilent 6120 four-stage HPLC-M (column type: zorbax SB-C18, 2.1X130 mm,3.5 μm, 6min, flow rate 0.6mL/min. Mobile phase: 5% -95% (acetonitrile with 0.1% formic acid) in water with 0.1% formic acid) was detected by electrospray ionization (ESI) at 210nm/254nm with UV.
Nuclear magnetic resonance hydrogen spectrum: bruker (Bruker) 300MHz nuclear magnetic instrument, CD under room temperature condition 3 Cl、CD 2 Cl 2 TMS (0 ppm) was used as a reference standard for solvents (in ppm). When multiple peaks occur, the following abbreviations will be used: s (single, singlet), d (doublet ), t (triplet), m (multiplet ).
The target compound was detected by UV at 210nm/254nm using Agilent 1260pre-HPLC or Calesep pump 250pre-HPLC (column model: NOVASEP50/80 mmDAC).
1. General synthetic routes
Some of the compounds in this application can be prepared according to the following schemes one to two.
The synthesis scheme I is as follows:
Figure BDA0002842474540000231
in the above synthesis scheme one, Y 1 、L 1 、L 2 、L 3 、Ar 1 、R 1 、R 2 、R 3 All have the meanings as described in the specification.
The reaction process comprises the following steps: coupling a raw material compound X-1 and dihaloaniline X-2 to obtain a compound X-3, and carrying out palladium-catalyzed intramolecular arylation reaction to obtain a condensed heteroaryl compound X-4; and introducing an aromatic group on nitrogen through a substitution reaction in the intermediate X-4 to obtain a compound X-5, carrying out boron esterification on the intermediate X-5 to obtain a compound X-6, and coupling the intermediate X-6 with a halogenated pyridopyrimidine compound X-7 to obtain the compound with the structure shown in X-8. Coupling compound X-6 with halogenated pyridopyrimidine compound X-9 to obtain the compound with the structure shown as X-10. Coupling compound X-6 with halogenated pyridopyrimidine compound X-11 to obtain the compound with the structure shown in X-12.
The synthesis scheme II is as follows:
Figure BDA0002842474540000241
in the second synthesis scheme, Y 1 、L 1 、L 3 、R 1 、R 4 、R 3 、n 4 All have the meanings as described in the specification.
The reaction process comprises the following steps: coupling a raw material compound X-13 and halogenated aniline X-14 to obtain a compound X-15, and carrying out palladium-catalyzed intramolecular arylation reaction to obtain a condensed heteroaryl compound X-16; coupling compound X-16 with halogenated pyridopyrimidine compound X-7 gives a compound of the present application having the structure shown as X-17.
The compounds of the present application can be prepared according to the above synthetic schemes, and the specific synthetic procedure will be shown below by way of example only with respect to some of the compounds.
2. Synthesis of example 1 (Compound 3)
Figure BDA0002842474540000242
(1) Sequentially adding raw material 3a (593.45 mmol), raw material 3b (600.00 mmol), sodium tert-butoxide (1186.91 mmol), 500mL toluene under nitrogen protection of a three-port reaction bottle equipped with a mechanical stirring, a thermometer and a condenser, heating to reflux, water diversion for 1h, cooling to 70-80 ℃, adding X-phos (1.2 mmol), pd 2 (dba) 3 (0.6 mmol), the reaction mixture was warmed to reflux and reacted for 1h. The reaction solution is cooled to room temperature, 500.0mL of water is added, water is washed, liquid is separated, the water phase is extracted by 200mL of toluene, liquid is separated, the organic phases are combined, the organic phases are washed for 2 times by 300.0mL of water, 10g of anhydrous sodium sulfate is used for drying, filtration is carried out, the filtrate is subjected to (100-120) mesh silica gel column, the filtrate is subjected to column passing concentration (50-70 ℃ C., -0.09-0.08 MPa) to leave 120.0mL of organic phases, concentration is stopped, 240mL of absolute ethyl alcohol is added, the temperature is reduced to 15-20 ℃ C., a large amount of solids are precipitated, filtration is carried out, and intermediate 3-1 (403.55 mmol) is obtained, and the yield is 68%.
Figure BDA0002842474540000243
(2) To a three-port flask with mechanical stirring, thermometer, condenser under nitrogen protection was added successively 3-1 (403.55 mmol), cesium carbonate (807.10 mmol), tricyclohexylphosphine tetrafluoroborate (26.2 mmol), pd (OAc) 2 (7.24 mmol), 180.0mLN, N-dimethylacetamide, stirring, heating to 130-140 ℃ for reaction for 10h, pouring the reaction solution into 1000mL of water, stirring, adding 1500mL of dichloroethane, standing, separating liquid, extracting the water phase with 900mL of 2 times of dichloroethane, combining organic phases, washing the organic phases with 1000mL of water for 2 times, drying with 100g of anhydrous sodium sulfate, filtering, passing the filtrate through a (80-120) mesh silica gel column, passing the column liquid (50-70 ℃ C., -0.09-0.08 MPa) until no water is discharged, adding 500mL of n-heptane under stirring, filtering, recrystallizing the obtained solid crude product with ethyl acetate (3.2 mL of ethyl acetate per 1g of product) to obtain an intermediate3-2 (242.13 mmol, 60% yield).
Figure BDA0002842474540000251
(3) To a three-port flask equipped with a mechanical stirrer, a thermometer and a condenser under nitrogen protection, intermediate 3-2 (242.13 mmol), raw material 3c (290.56 mmol), cesium carbonate (484.26 mmol), 4-dimethylaminopyridine (19.42 mmol), 500.0mL DMSO were added sequentially, and the temperature was raised to 100-110℃for 2h of reaction. The reaction solution was cooled to room temperature, 600mL of toluene and 600mL of water were added, water was washed, the separated solution was extracted with 300mL of toluene, the organic phases were combined, the organic phases were washed with 500mL of water for 2 times, dried with 20g of anhydrous sodium sulfate, filtered, the filtrate was passed through a (80-120) -mesh silica gel column, the remaining 150.0mL of the organic phases was concentrated by passing through the column solution (50-70 ℃ C., -0.09-0.08 MPa), the concentration was stopped, the temperature was lowered to 15-20 ℃ C., a large amount of solids were precipitated, and the filtration was carried out to obtain intermediate 3-3 (181.60 mmol, yield 75%).
Figure BDA0002842474540000252
(4) After nitrogen substitution in a three-port reaction flask equipped with a mechanical stirrer, a thermometer and a condenser, intermediate 3-3 (181.60 mmol), raw material 3d (218 mmol), potassium acetate (363.32 mmol), 560mL of 1, 4-dioxane, stirring, heating to 45-50℃and adding X-Phos (1.09 mmol), pd 2 (dba) 3 (0.55 mmol) and then the temperature is raised to 90-100 ℃ for 2h. The reaction solution was cooled to room temperature, 300mL of methylene chloride and 300mL of water were added, stirred, left standing, the aqueous phase was extracted with 150mL of methylene chloride for 1 time, the separated liquids were combined, the organic phase was washed with 300mL of water for 2 times, the separated liquids were separated, the organic phase was dried by adding 15g of anhydrous sodium sulfate, filtration was performed, the organic phase was passed through a silica gel column, and eluted with 300mL of methylene chloride, when 80mL of organic phase remained after concentration (-0.08-0.09 MPa, 40-50 ℃ C.) was stopped, concentration was stopped, 160mL of petroleum ether was added, stirring was performed at room temperature for 1.0 hour, filtration was performed, and the cake was eluted with petroleum ether to obtain intermediate 3-4 (145.28 mmol, yield 80%).
Figure BDA0002842474540000253
(5) To a three-port reaction flask equipped with a mechanical stirrer, a thermometer and a condenser tube under the protection of nitrogen, raw material 3e (89.16 mmol), intermediate 3-4 (98.08 mmol), tetrabutylammonium bromide (8.92 mmol), 120mL toluene, 60mL ethanol, 60mL water, potassium carbonate (178.32 mmol) were added sequentially, the temperature was raised to 45-50 ℃, triphenylphosphine palladium (0.45 mmol) was added, the temperature was continuously raised to reflux, and the reaction was continued for 8h under heat preservation. 200mL of water is added, the solution is separated, the aqueous phase is extracted with 100mL of toluene, the organic phases are combined, 150mL of water is added for 2 times, the solution is separated, 10g of anhydrous sodium sulfate is added into the organic phases, the mixture is stirred and dried, the mixture is filtered, when the organic phases are concentrated (-0.08 to-0.09 MPa, 55-65 ℃) and the residual organic phases are 100mL, the mixture stops heating and is cooled to room temperature, a large amount of solids are separated out, the mixture is filtered, and a filter cake is leached by ethanol, so that the compound 3 (53.49 mmol, yield 60%) is obtained.
1 H NMR(CDCl 3 ，300MHz)：δ(ppm)＝7.29(d，1H)，δ(ppm)＝7.41-7.69(m，8H)，δ(ppm)＝7.93-8.05(d，2H)，δ(ppm)＝8.13(s，1H)，δ(ppm)＝8.20(d，1H)，δ(ppm)＝8.45-8.48(m，2H)，δ(ppm)＝8.61-8.68(m，2H)，δ(ppm)＝8.71(d，1H)。
3. Example 2 Synthesis of Compound 27
Figure BDA0002842474540000261
/>
To a three-port reaction flask equipped with a mechanical stirrer, a thermometer and a condenser tube under the protection of nitrogen, raw material 27a (89.16 mmol), intermediate 3-4 (98.08 mmol), tetrabutylammonium bromide (8.92 mmol), 120mL toluene, 60mL ethanol, 60mL water, potassium carbonate (178.32 mmol) were added sequentially, the temperature was raised to 45-50 ℃, triphenylphosphine palladium (0.45 mmol) was added, the temperature was continuously raised to reflux, and the reaction was continued for 8h under heat preservation. Adding 200mL of water, separating, extracting the water phase with 100mL of toluene, mixing the organic phases, adding 150mL of water, washing for 2 times, separating, adding 10g of anhydrous sodium sulfate into the organic phases, stirring and drying, filtering, concentrating the organic phases (-0.08 to-0.09 MPa, 55-65 ℃) until the residual organic phases are 100mL, and stopping heatingCooling to room temperature, precipitating a large amount of solid, filtering, leaching the filter cake with ethanol to obtain compound 27 (57.95 mmol, yield 65%), mass Spectrometry (MS): m/z=605.2 [ m+h] + 。
1 HNMR(CDCl 3 ，300MHz)：δ(ppm)＝9.08-9.05(d，1H)，δ(ppm)＝8.83-8.80(d，1H)，δ(ppm)＝8.52-8.48(m，3H)，δ(ppm)＝8.33-8.29(d，1H)，δ(ppm)＝8.27-8.21(m，6H)，δ(ppm)＝7.81(s，1H)，δ(ppm)＝7.62-7.57(m，10H)，δ(ppm)＝7.42-7.39(m，1H)。
4. Example 3 Synthesis of Compound 51
Figure BDA0002842474540000262
To a three-port reaction flask equipped with a mechanical stirrer, a thermometer and a condenser tube under nitrogen protection, raw material 51a (47.14 mmol), intermediate 3-4 (51.86 mmol), tetrabutylammonium bromide (4.72 mmol), 60mL toluene, 30mL ethanol, 30mL water, potassium carbonate (94.28 mmol) were added sequentially, the temperature was raised to 45-50 ℃, tetraphenylphosphine palladium (0.24 mmol) was added, the temperature was continuously raised to reflux, and the reaction was continued for 8h under heat preservation. Adding 100mL of water, separating liquid, extracting the water phase with 50mL of toluene, combining the organic phases, adding 75mL of water for 2 times, separating liquid, adding 10g of anhydrous sodium sulfate into the organic phases, stirring and drying, filtering, stopping heating when the organic phases are concentrated (-0.08 to-0.09 MPa, 55-65 ℃) and the remaining organic phases are 50mL, cooling to room temperature, separating out solids, filtering, eluting a filter cake with ethanol to obtain a compound 51 (63.52 mmol, yield 63%); mass Spectrometry (MS): m/z=631.2 [ m+h ] +
1 HNMR(CDCl 3 ，300MHz)：δ(ppm)＝8.74-8.72(d，1H)，δ(ppm)＝8.53-8.50(d，1H)，δ(ppm)＝8.47-8.44(m，2H)，δ(ppm)＝8.35-8.32(d，1H)，δ(ppm)＝8.16-8.14(d，1H)，δ(ppm)＝8.08-8.05(d，1H)，δ(ppm)＝8.01-7.96(m，3H)，δ(ppm)＝7.92(s，1H),δ(ppm)＝7.76-7.68(m，6H),δ(ppm)＝7.63-7.58(m，9H)。
5. Synthesis of examples 4 to 24
The compounds of Table 1 were synthesized in the same manner as in example 1, except that starting materials 3a, 3b and 3c in example 1 were replaced with starting materials Ia, ib and Ic in Table 1, respectively, and the starting materials used and the corresponding prepared compounds and mass spectrum data were as shown in Table 1.
TABLE 1
Figure BDA0002842474540000271
/>
Figure BDA0002842474540000281
/>
Figure BDA0002842474540000291
/>
Figure BDA0002842474540000301
6. Synthesis of examples 25 to 28
The compounds in Table 2 were synthesized in the same manner as in example 1, except that the raw materials 3a, 3c and 3e in example 1 were replaced with the raw materials IIa, IIc and IIe in Table 2, respectively, and the raw materials used and the corresponding prepared compounds and mass spectrum data were specifically shown in Table 2.
TABLE 2
Figure BDA0002842474540000302
/>
Figure BDA0002842474540000311
7. Example 30 Synthesis of Compound 138
Referring to the synthesis method of the intermediate 3-2, 2-chloro-5-fluoroaniline is used for replacing 2, 5-dichlorophenylamine to synthesize the intermediate 138-2, and the yield is 65%.
Figure BDA0002842474540000312
Figure BDA0002842474540000313
To a three-port reaction flask equipped with a mechanical stirrer, a thermometer and a condenser under nitrogen protection, intermediate 138-2 (50 mmol), raw material 3e (55 mmol), cesium carbonate (100 mmol), 4-dimethylaminopyridine (5 mmol), 200mL DMSO were added sequentially, and the temperature was raised to 100-110℃for 2h of reaction. The reaction solution was cooled to room temperature, 200mL of toluene and 200mL of water were added, the solution was separated, the aqueous phase was extracted with 100mL of toluene, the organic phases were combined, the organic phase was washed 2 times with 200mL of water, dried over 5g of anhydrous sodium sulfate, filtered, the filtrate was passed through (80-120) mesh silica gel column chromatography, the remaining 30mL of the organic phase was concentrated by column chromatography (50-70 ℃ C., -0.09-0.08 MPa), the concentration was stopped, the temperature was lowered to 15-20 ℃ C., a large amount of solids was precipitated, and filtered to obtain compound 138 (37 mmol, yield 74%).
1 H-NMR(CDCl 3 ，400MHz)：δ(ppm)＝8.63-8.60(m，2H)，δ(ppm)＝8.58-8.56(m，2H)，δ(ppm)＝8.12-8.09(d,1H)，δ(ppm)＝8.01-7.99(d，1H)，δ(ppm)＝7.91-7.88(m，3H)，δ(ppm)＝7.82-7.76(m，5H)，δ(ppm)＝7.73-7.68(m，5H)，δ(ppm)＝7.25(s，1H)，δ(ppm)＝7.05-7.03(d，1H)。
Red light organic electroluminescent device preparation and evaluation
Application example 1:
the anode was prepared by the following procedure: will be of the thickness of
Figure BDA0002842474540000322
The ITO substrate (manufactured by Corning) was cut into a size of 40 mm. Times.40 mm. Times.0.7 mm, and a test substrate having a cathode, an anode and an insulating layer pattern was prepared by a photolithography step, and an ultraviolet ozone and O were used 2 :N 2 The plasma was surface treated to increase the work function of the anode (experimental substrate) and to descum.
In the experimental baseVacuum vapor deposition of HAT-CN on plate (anode) to form a thickness of
Figure BDA0002842474540000323
Is deposited on the Hole Injection Layer (HIL) to form a layer having a thickness of +.>
Figure BDA0002842474540000324
Is provided.
Vacuum evaporating TPD on the hole transport layer to form a layer with a thickness of
Figure BDA0002842474540000325
Is provided.
Evaporating compound 3 as main body on the hole auxiliary layer, doping DCM2, forming a film with a thickness of
Figure BDA0002842474540000326
Is an emission layer (EML).
DBimiBphen and LiQ are mixed in a weight ratio of 1:1 and evaporated to form
Figure BDA0002842474540000327
A thick Electron Transport Layer (ETL), liQ is evaporated on the electron transport layer to form a thickness +.>
Figure BDA0002842474540000328
Electron Injection Layer (EIL) of (a), then magnesium (Mg) and silver (Ag) are mixed at 1:9, and vacuum evaporating on the electron injection layer to form a film with a thickness of +. >
Figure BDA0002842474540000329
Is provided.
In addition, the thickness of the vapor deposited on the cathode is
Figure BDA00028424745400003210
An organic capping layer (CPL) was formed to complete the manufacture of an organic light-emitting device, and the manufactured device was denoted as application example 1.
Application examples 2 to 30
An organic electroluminescent device was produced in the same manner as in application example 1, except that the compounds shown in examples 2 to 30 were used for the light-emitting bodies in the formation of the light-emitting layers, and the produced devices were referred to as application examples 2 to 30.
Comparative examples 1 to 3
In comparative examples 1 to 3, organic electroluminescent devices, which are referred to as comparative examples 1 to 3, were manufactured in the same manner as in example 1, except that compound a, compound B, and compound C were used as light-emitting hosts of light-emitting layers instead of compound 1, respectively.
Wherein, the structural formulas of HAT-CN, NDDP, TPD, DCM2, DBimiBphen, liQ, CP-1, compound A, compound B and compound C are as follows:
Figure BDA0002842474540000321
/>
Figure BDA0002842474540000331
fabrication of organic electroluminescent device
Application examples 1 to 30 and comparative examples 1 to 3 on the organic electroluminescent devices produced at 20mA/cm 2 Under the conditions of testing the life of the T95 device, the data voltage, the efficiency and the color coordinates are that the constant current density is 10mA/cm 2 The test was performed as follows, and the results are shown in table 3.
Table 3 list of electronic luminescence characteristics of organic electroluminescent devices
Figure BDA0002842474540000332
/>
Figure BDA0002842474540000341
From the above results, it is understood that application examples 1 to 30 using the compound of the present invention as a light-emitting host material are compared with comparative examples 1 to 3 using known light-emitting host materials:
the driving voltages of the organic electroluminescent devices prepared in application examples 1 to 30 are between 3.47 and 3.90V, which is lower than that of the organic electroluminescent devices of comparative examples 1 to 3; the drive voltage is reduced by at least 0.32V.
The organic electroluminescent devices prepared in application examples 1 to 30 had a T95 lifetime of at least 388 hours. The device lifetime was increased by at least 74 hours compared to comparative examples 1-3, which is a significant performance improvement in the art compared to comparative example 1, the device T95 lifetime was increased by more than 23%.
As a main luminescent material, the fused heteroaryl and pyridopyrimidine mother nucleus structure in the molecular structure ensures that the whole molecule has a bipolar structure, the triplet energy level is high, the carrier mobility is high, and the organic electroluminescent devices have higher device efficiency. In the compound, when at least one aromatic substituent is connected to the pyridopyrimidine mother nucleus, the molecular stability is further improved, and the service life of the device is prolonged; furthermore, when the fused heteroaryl connected with the pyridopyrimidine parent nucleus in the compound is carbazolo indole, the dipole moment between two partial structures in the molecule is increased, the triplet energy level of the molecule is further improved, the energy transfer and carrier transmission are facilitated, the service life of the device can be further prolonged, and the performance of the organic electroluminescent device can be remarkably improved when the device is used in a luminescent layer of the organic electroluminescent device.

Claims (7)

1. An organic electroluminescent material having a structure represented by formula i:
Figure FDA0004053445000000011
wherein L is 1 、L 2 And L 3 Each independently selected from single bonds;
R 1 、R 2 and R is 3 Each independently of the otherSelected from hydrogen, a group of formula (2-1), a group of formula (2-2) or a substituted or unsubstituted group Z 1 The method comprises the steps of carrying out a first treatment on the surface of the And R is 1 、R 2 And R is 3 At least one of the groups is selected from a group represented by formula (2-1) or a group represented by formula (2-2);
Figure FDA0004053445000000012
wherein the unsubstituted radical Z 1 Selected from the following groups:
Figure FDA0004053445000000013
wherein Z is substituted 1 Is unsubstituted Z 1 A group substituted with one or more substituents selected from deuterium, fluoro, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, t-butyl, and when Z 1 When the number of the substituents is plural, any two substituents are the same or different;
wherein the ring A in the formula (2-1) and the formula (2-2)
Figure FDA0004053445000000014
Each independently selected from formula (3-1) or formula (3-2):
Figure FDA0004053445000000015
wherein Y is 1 And Y 2 Each independently selected from single bond, O, S, C (R) 5 R 6 ) Or N (R) 7 ) And Y is 1 And Y 2 At most one of them is a single bond;
each R is 7 Are identical to or different from each other and are each independently selected from methyl, ethyl, n-propyl, isopropyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triplex Phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl;
each R is 5 And R is 6 Are the same or different from each other and are each independently methyl or phenyl;
said substitution means substitution with a substituent selected from deuterium, fluoro, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, t-butyl and phenyl;
Ar 1 selected from a substituted or unsubstituted group W, wherein the unsubstituted group W is selected from the following groups:
Figure FDA0004053445000000021
wherein the substituted group W is a group formed by substituting one or more substituents selected from deuterium, fluorine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, naphthyl and pyridyl, and when the number of substituents on W is plural, any two substituents are the same or different;
R 4 selected from deuterium and halogen groups;
n 4 represents a substituent R 4 Number n of (n) 4 Selected from 0 or 1.
2. The organic electroluminescent material according to claim 1, wherein Ar is selected from the group consisting of 1 Selected from the following groups:
Figure FDA0004053445000000022
3. the organic electroluminescent material according to claim 1, wherein the ring A in the formula (2-1) or the formula (2-2)
Figure FDA0004053445000000023
Each independently is a dibenzofuran ring, a dibenzothiophene ring, an N-phenylcarbazole ring, an N-naphthylcarbazole ring, an N-biphenylcarbazole ring, an N-pyrimidinylcarbazole ring, an N-pyridylcarbazole ring, an N-benzopyrimidinyl-carbazole ring, a 10-phenyl-10H-phenoxazine, a 10-phenyl-10H-phenothiazine, a phenoxytheophylline, a dibenzodioxin ring, a dimethylfluorene ring, a diphenylfluorene ring, a thianthrene ring, a 9, 9-dimethyl-10-phenyl-9, 10-dihydroacridine ring, a 9, 10-tetramethyl-9, 10-dihydroanthracene or a 9, 9-dimethyl-9H-xanthene.
4. The organic electroluminescent material according to claim 1, wherein the structure of the compound is selected from any one of the following:
Figure FDA0004053445000000031
/>
Figure FDA0004053445000000041
/>
Figure FDA0004053445000000051
/>
Figure FDA0004053445000000061
/>
Figure FDA0004053445000000071
/>
Figure FDA0004053445000000081
5. an electronic component, characterized by comprising an anode and a cathode which are oppositely arranged, and a functional layer arranged between the anode and the cathode;
the functional layer comprising the organic electroluminescent material as claimed in any one of claims 1 to 4.
6. The electronic component of claim 5, wherein the functional layer comprises a light-emitting layer comprising the organic electroluminescent material.
7. An electronic device comprising the electronic component according to any one of claims 5 to 6.
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