CN112724073A - Organic compound, application thereof, organic electroluminescent device using organic compound and electronic device - Google Patents

Organic compound, application thereof, organic electroluminescent device using organic compound and electronic device Download PDF

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CN112724073A
CN112724073A CN202110042643.2A CN202110042643A CN112724073A CN 112724073 A CN112724073 A CN 112724073A CN 202110042643 A CN202110042643 A CN 202110042643A CN 112724073 A CN112724073 A CN 112724073A
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岳富民
曹佳梅
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Abstract

The application provides an organic compound with a structure shown in a formula 1, application thereof, an organic electroluminescent device using the organic compound and an electronic device, and belongs to the technical field of organic materials. The organic compound is applied to OLED devices as an electron transport material, can reduce the driving voltage of the devices, improve the luminous efficiency and greatly prolong the service life of the devices,
Figure DDA0002896497600000011
wherein X is selected from O, S, Se, SO2、C(R1R2)、N(R3)、Ge(R4R5) Or Si (R)6R7) (ii) a L is independently selected from: a substituted or unsubstituted aryl group having 6 to 15 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 15 carbon atoms; ar (Ar)1And Ar2Are the same or different from each other and are each independently selected from: a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

Description

Organic compound, application thereof, organic electroluminescent device using organic compound and electronic device
Technical Field
The application belongs to the technical field of organic materials, and particularly provides an organic compound, application thereof, and an organic electroluminescent device and an electronic device using the organic compound.
Background
Organic electroluminescent devices (OLEDs) are devices prepared by depositing a layer of Organic material between two metal electrodes by spin coating or vacuum evaporation, and a classic three-layer Organic electroluminescent device comprises a hole transport layer, a light emitting layer and an electron transport layer. Holes generated by the anode are combined with electrons generated by the cathode through the hole transport layer and the electron transport layer to form excitons in the light emitting layer, and then the excitons emit light. The organic electroluminescent device can be adjusted to emit various desired lights by changing the material of the light emitting layer as desired.
The organic charge transport material is a material which can realize the controllable directional order of current carriers (electrons or holes) under the action of an electric field when the current carriers are injectedAn organic semiconductor material that migrates to effect charge transport. Compared with inorganic materials, organic charge transport materials have the advantages of low cost, low toxicity, easy processing and forming, chemical modification to meet different requirements, capability of manufacturing fully flexible devices and the like, are widely applied to the fields of xerography, sensors, electroluminescence, field effect transistors, solar cells and the like at present, and become one of the hot spots of domestic and foreign research. The organic charge transport material may be divided into an organic hole transport (p-type) material and an organic electron transport (n-type) material. The development of n-type materials is slower compared to organic p-type materials, such as aluminum 8-hydroxyquinoline (Aq)3) And oxadiazole derivative PBD is an n-type material that was studied earlier.
The hole mobility of the hole transporting material in the device is generally much greater than the electron mobility of the electron transporting material, which can cause significant degradation in device performance. Conventional electron transport materials, e.g. aluminum 8-hydroxyquinoline (Aq)3) The degradation is slow, the preparation energy consumption is high, the environmental protection is not facilitated, and the light can be absorbed to influence the efficiency of the device. Aq of3When the traditional electron transport material is applied to an OLED device, the device driving voltage is higher due to the defects of the material, and the service life of the device is also greatly influenced.
Disclosure of Invention
The purpose of the present invention is to provide an organic electroluminescent material having excellent properties, which can be used as an electron transport layer, a hole blocking layer, or the like in an organic electroluminescent device.
In order to achieve the above object, the present application provides an organic compound having a structure as shown in formula 1 below:
Figure BDA0002896497580000011
wherein R is1And R2The same or different from each other, and are independently selected from deuterium, cyano group, halogen group, trialkylsilyl group having 3-12 carbon atoms, triarylsilyl group having 18-24 carbon atoms, alkyl group having 1-10 carbon atoms, substituted or unsubstituted alkyl group having 6-30 carbon atomsAryl, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, or any two adjacent R1Are linked to each other to form a ring, or any two adjacent R2Are connected with each other to form a ring; n is1Is R1Number of (2), n2Is R2The number of (2);
n1selected from 0, 1,2, 3 or 4, when n is1When greater than 1, any two R1The same or different;
n2selected from 0, 1,2, 3 or 4, when n is2When greater than 1, any two R2The same or different;
x is selected from O, S, Se, SO2、C(R3R4)、N(R5)、Ge(R6R7) Or Si (R)8R9)；
R3～R9Are the same or different from each other and are each independently selected from: alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, heterocycloalkyl having 2 to 10 carbon atoms, or R3And R4Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or R6And R7Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or R8And R9Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring;
l is independently selected from: a substituted or unsubstituted arylene group having 6 to 15 carbon atoms or a substituted or unsubstituted heteroarylene group having 4 to 15 carbon atoms;
Ar1and Ar2Are the same or different from each other and are each independently selected from: a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms;
Ar1、Ar2、R1、R2and the substituents of L are the same or different from each other and are each independently selected from: deuterium, fluorine, chlorine, bromine, cyano, having 3-20 carbon atomsThe heteroaryl group, the aryl group with 6-20 carbon atoms, the trialkylsilyl group with 3-12 carbon atoms, the triarylsilyl group with 18-24 carbon atoms, the alkyl group with 1-10 carbon atoms, the halogenated alkyl group with 1-10 carbon atoms, the naphthenic group with 3-10 carbon atoms, the heterocyclic alkyl group with 2-10 carbon atoms and the alkoxyl group with 1-10 carbon atoms.
A second aspect of the present application provides the use of an organic compound as described in the first aspect of the present application in an organic electroluminescent device.
In a third aspect, there is provided an organic electroluminescent device having an electron transport layer and/or a hole blocking layer comprising an organic compound as described in the first aspect of the present application.
A fourth aspect of the present application provides an electronic device comprising an organic electroluminescent device as described in the third aspect of the present application.
The organic compounds of the present application have an adamantane spiro-heterocyclic structure as a core and contain multiple heteroaryl groups. On one hand, the heteroaryl, especially the nitrogen-containing heteroaryl is taken as a typical strong electron-withdrawing group, and a compound taking the heteroaryl as a substituent has high electron mobility and lower energy level, and the electron mobility of the compound is obviously improved as a plurality of groups are connected. On one hand, the spiro ring formed by the spiro ring and the adamantane is a three-dimensional spatial structure, so that the aggregation among molecules can be effectively prevented, and the spiro ring is not easy to crystallize; the strong rigidity of the spiro ring ensures that the compound has stable structure. On the other hand, the compound structure has an extensible three-dimensional structure, and the continuous pi-conjugate is used for bringing better electron mobility, so that the compound has high electron mobility; and, the combination of the three makes the carrier transport balanced. The organic light-emitting diode is applied to an electron transport layer and/or a hole blocking layer of an organic light-emitting device, so that the device has the advantages of low driving voltage and high light-emitting efficiency.
Additional features and advantages of the present application will be described in detail in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application and not to limit the application. In the drawings:
fig. 1 is a schematic structural diagram of an embodiment of the organic electroluminescent device of the present application.
Fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
Description of the 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 electroluminescent layer; 340. a hole blocking layer; 350. an electron transport layer; 360. an electron injection layer; 370. an electron blocking layer; 400. an electronic device.
Detailed Description
The following detailed description of embodiments of the present application will be made with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present application, are given by way of illustration and explanation only, and are not intended to limit the present application.
The present application provides an organic compound having a structure represented by the following formula 1:
Figure BDA0002896497580000031
wherein R is1And R2The same or different from each other, and are independently selected from deuterium, cyano group, halogen group, trialkylsilyl group having 3-12 carbon atoms, triarylsilyl group having 18-24 carbon atoms, alkyl group having 1-10 carbon atoms, substituted or unsubstituted aryl group having 6-30 carbon atoms, substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3-20 carbon atoms, or any two adjacent R1Are linked to each other to form a ring, or any two adjacent R2Are connected with each other to form a ring; n is1Is R1Number of (2), n2Is R2The number of (2);
n1is selected from0.1, 2, 3 or 4, when n is1When greater than 1, any two R1The same or different;
n2selected from 0, 1,2, 3 or 4, when n is2When greater than 1, any two R2The same or different;
x is selected from O, S, Se, SO2、C(R3R4)、N(R5)、Ge(R6R7) Or Si (R)8R9)；
R3～R9Are the same or different from each other and are each independently selected from: alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, heterocycloalkyl having 2 to 10 carbon atoms, or R3And R4Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or R6And R7Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or R8And R9Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring;
l is independently selected from: a substituted or unsubstituted arylene group having 6 to 15 carbon atoms or a substituted or unsubstituted heteroarylene group having 4 to 15 carbon atoms;
Ar1and Ar2Are the same or different from each other and are each independently selected from: a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms;
Ar1、Ar2、R1、R2and the substituents of L are the same or different from each other and are each independently selected from: deuterium, fluorine, chlorine, bromine, cyano, heteroaryl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, trialkylsilyl having 3 to 12 carbon atoms, triarylsilyl having 18 to 24 carbon atoms, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, heterocycloalkyl having 2 to 10 carbon atoms, and alkoxy having 1 to 10 carbon atoms.
In the formula 1, the middle bracket 2]Radicals indicated in parenthesesAny atom in the group may be bonded to
Figure BDA0002896497580000032
Is connected when X is
Figure BDA0002896497580000033
When attached, X is selected from
Figure BDA0002896497580000034
Wherein R is5Is' as a quilt
Figure BDA0002896497580000041
Substituted R5，R3Is' as a quilt
Figure BDA0002896497580000042
Substituted R3，R6Is' as a quilt
Figure BDA0002896497580000043
Substituted R6，R8Is' as a quilt
Figure BDA0002896497580000044
Substituted R8。
The organic compounds of the present application have an adamantane spiro-heterocyclic structure as a core and contain multiple heteroaryl groups. The heteroaryl, especially the nitrogen-containing heteroaryl is taken as a typical strong electron-withdrawing group, and a compound taking the heteroaryl as a substituent has high electron mobility, and the electron mobility of the compound is obviously improved by connecting a plurality of groups. On one hand, the spiro ring formed by the compound and the adamantane is a three-dimensional spatial structure, so that the aggregation among molecules can be effectively prevented, the material is not easy to crystallize, and the film-forming property of the material is improved; and the strong rigidity of the spiro ring ensures that the compound structure is stable. On the other hand, the compound structure has an extendable three-dimensional structure, and the continuous pi-conjugate is attached to better electron mobility, thereby having high electron mobility.
The material can be used independently, can also be used for compounding with LiQ or metal lithium, is applied to an organic light-emitting device, is used as an electron transport layer and/or a hole blocking layer, is favorable for improving the electron transport and injection capability of the material, and improves the electron affinity of the material so as to improve the electron transport rate, thereby enabling the device to show the advantages of low driving voltage and high luminous efficiency.
Further preferably, when Ar is1And Ar2When the compounds are nitrogen-containing heteroaryl, the compounds can form stable complexes with metals such as Li and the like due to the continuous arrangement of the N-containing heteroaryl, thereby having better electron transport characteristics.
In the present application, since adamantane is a three-dimensional structure, in the structure diagram of the compound, since drawing angles are different, planar shapes are different, and the cyclic structures formed on 9, 9-dimethylfluorene are all adamantane, and the connecting positions are also the same. For example:
Figure BDA0002896497580000045
all have the same structure.
In the present application, the descriptions "… … is independently" and "… … is independently" and "… … is independently selected from" are interchangeable, and should be understood in a broad sense, which means that the specific items expressed between the same symbols do not affect each other in different groups, or that the specific items expressed between the same symbols do not affect each other in the same groups. For example,') "
Figure BDA0002896497580000046
Wherein each q is independently 0, 1,2 or 3, each R "is independently selected from hydrogen, deuterium, fluoro, chloro" and has the meaning: the formula Q-1 represents that Q substituent groups R ' are arranged on a benzene ring, each R ' can be the same or different, and the options of each R ' are not influenced mutually; the formula Q-2 represents that each benzene ring of biphenyl has Q substituent groups R ', the number Q of the substituent groups R' on the 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 with each other.
In the present application, an delocalized bond is defined as a bond derived fromSingle bonds extending in ring systems
Figure BDA0002896497580000047
It means that one end of the linkage may be attached to any position in the ring system through which the linkage extends, and the other end to the rest of the compound molecule.
For example, as shown in the following formula (f), naphthyl represented by formula (f) is connected with other positions of the molecule through two non-positioned connecting bonds penetrating through a double ring, and the meaning of the naphthyl represented by the formula (f-1) to the formula (f-10) comprises any possible connecting mode shown in the formula (f-1) to the formula (f-10).
Figure BDA0002896497580000048
As another example, as shown in the following formula (X '), the phenanthryl group represented by formula (X') is bonded to other positions of the molecule via an delocalized bond extending from the middle of the benzene ring on one side, and the meaning of the phenanthryl group includes any of the possible bonding modes as shown in formulas (X '-1) to (X' -4).
Figure BDA0002896497580000051
An delocalized substituent, as used herein, refers to a substituent attached by a single bond extending from the center of the ring system, meaning that the substituent may be attached at any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R' represented by the formula (Y) is bonded to the quinoline ring via an delocalized bond, and the meaning thereof includes any of the possible bonding modes as shown in the formulae (Y-1) to (Y-7).
Figure BDA0002896497580000052
In this application L, Ar1、Ar2、R1、R2The number of carbon atoms of (b) means all the number of carbon atoms. For example,if L is selected from the group consisting of substituted arylene groups having 12 carbon atoms, then all of the carbon atoms of the arylene group and substituents thereon are 12.
In the present application, the alkyl group having 1 to 10 carbon atoms may be a straight chain alkyl group or a branched alkyl group. Specifically, the alkyl group having 1 to 10 carbon atoms may be a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms; further, the alkyl group may be a straight-chain alkyl group having 1 to 10 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms. More specifically, the alkyl group having 1 to 10 carbon atoms may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, or the like, but is not limited thereto.
In the present application, when a specific definition is not otherwise provided, "hetero" means that at least 1 hetero atom of B, N, O, S or P or the like is included in one functional group and the remaining atoms are carbon and hydrogen. An unsubstituted alkyl group can be a "saturated alkyl group" without any double or triple bonds.
In the present application, "alkyl" may include straight chain alkyl or branched alkyl. Alkyl groups may have 1 to 10 carbon atoms, and numerical ranges such as "1 to 10" refer herein to each integer in the given range; for example, "1 to 10 carbon atoms" refers to an alkyl group that may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms. The alkyl group may also be a lower alkyl group having 1 to 6 carbon atoms. Further, the alkyl group may be substituted or unsubstituted.
Alternatively, the alkyl group is selected from alkyl groups having 1 to 5 carbon atoms, and specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl.
In the present application, aryl refers to an optional functional group or substituent derived from an aromatic hydrocarbon 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 fused ring aryl group, conjugated by a carbon-carbon bondTwo or more monocyclic aryl groups linked by a carbon-carbon bond, monocyclic aryl groups and fused ring aryl groups linked by a carbon-carbon bond, two or more fused ring aryl groups linked by a carbon-carbon bond. That is, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered as an aryl group in the present application. Wherein the aryl group does not contain a heteroatom such as B, N, O, S or P. For example, in the present application, phenyl, biphenyl, terphenyl, and the like are aryl groups. Examples of the aryl group may include phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, hexabiphenyl, benzo [9,10 ]]Phenanthryl, pyrenyl, benzofluoranthenyl, phenanthrenyl, pyrenyl, phenanthrenyl, pyrenyl,
Figure BDA0002896497580000061
a phenyl group, a fluorenyl group, and the like, without being limited thereto. An "aryl" group herein may contain from 6 to 30 carbon atoms, in some embodiments the number of carbon atoms in the aryl group may be from 6 to 25, in other embodiments the number of carbon atoms in the aryl group may be from 6 to 18, and in other embodiments the number of carbon atoms in the aryl group may be from 6 to 13. For example, the number of carbon atoms may be 6, 12, 13, 18, 20, 25 or 30, and of course, other numbers may be used, which are not listed here.
In this application, substituted aryl refers to an aryl group in which one or more hydrogen atoms are replaced with another group. For example, at least one hydrogen atom is substituted with deuterium atoms, F, Cl, Br, I, CN, hydroxyl, amino, branched alkyl, linear alkyl, cycloalkyl, alkoxy, alkylamino, aryl, heteroaryl, or other groups. It is understood that a substituted aryl group having 18 carbon atoms refers to an aryl group and the total number of carbon atoms in the substituents on the aryl group being 18. For example, the number of carbon atoms of the 9, 9-dimethylfluorenyl group is 15.
In the present application, the aryl group as a substituent is exemplified by, but not limited to, phenyl, biphenyl, naphthyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, anthracenyl, phenanthrenyl,
Figure BDA0002896497580000062
and (4) a base.
In particular embodiments herein, the aryl group having 6 to 30 carbon atoms may be selected from phenyl, naphthyl, pyrenyl, fluorenyl, dimethylfluorenyl, benzofluorenyl, spirobifluorenyl, anthracenyl, benzanthracenyl, fluoranthenyl, phenanthrenyl, fluorenyl, pyrenyl,
Figure BDA0002896497580000063
one or more of phenyl, acenaphthenyl, biphenyl, terphenyl, quaterphenyl, 1,3, 5-triphenylphenyl, perylene, triphenylene, pyrenyl, indenyl, phenanthrenyl, phenylphenanthryl, phenylnaphthyl, naphthylphenyl, phenylanthryl, anthrylphenyl, phenylfluorenyl, phenylpyryl and pyrenylphenyl.
In the present application, the heteroaryl group may be a heteroaryl group including at least one of B, O, N, P, Si and S as a heteroatom. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, the heteroaryl group may be a single aromatic ring system or a plurality of aromatic ring systems connected by carbon-carbon bonds in a conjugated manner, and any one of the aromatic ring systems is an aromatic monocyclic ring or an aromatic fused ring. Exemplary heteroaryl groups can include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, N-arylcarbazolyl, N-heteroarylcarbazolyl, N-alkylcarbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuryl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzosilyl, dibenzofuryl, phenyl-substituted dibenzofuryl, Dibenzofuranyl-substituted phenyl groups, and the like, without being limited thereto. Wherein, thienyl, furyl, phenanthroline group and the like are heteroaryl of a single aromatic ring system, and N-aryl carbazolyl, N-heteroaryl carbazolyl, phenyl-substituted dibenzofuryl group and the like are heteroaryl of a plurality of aromatic ring systems connected by carbon-carbon bond conjugation.
In this application, substituted heteroaryl refers to heteroaryl wherein one or more hydrogen atoms are replaced by a group thereof, for example at least one hydrogen atom is replaced by a deuterium atom, a halogen group, a cyano group, an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a silyl group, a triarylsilyl group, a phosphonooxy group, or other groups.
In the present application, heteroaryl as a substituent is exemplified by, but not limited to, pyridyl, pyrimidinyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl.
In this application, the explanation for aryl applies to arylene and the explanation for heteroaryl applies equally to heteroarylene.
In the present application, the halogen group may be fluorine, chlorine, bromine, iodine.
In the present application, specific examples of the trialkylsilyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, and the like.
In the present application, specific examples of triarylsilyl groups include, but are not limited to, triphenylsilyl groups, and the like.
In the present application, specific examples of haloalkyl include, but are not limited to, trifluoromethyl.
The meaning of the connection or substitution is the same as that of the connection or substitution, and will not be described further.
In a specific embodiment of the present application, the heteroaryl group having 2 to 30 carbon atoms may be one or more selected from dibenzofuranyl, dibenzothienyl, carbazolyl, pyridyl, quinolyl, dibenzofuranylphenyl, dibenzothienyl phenyl, carbazolyl phenyl, pyridylphenyl, triazinyl, triazinylphenyl.
In one embodiment of the present application, formula 1 is selected from any one of formulae 1-1, formulae 1-2, formulae 1-3, formulae 1-4, formulae 1-5, or formulae 1-6:
Figure BDA0002896497580000071
wherein R is5Is' as a quilt
Figure BDA0002896497580000072
Substituted R5。
In one embodiment of the present application, the Ar1And Ar2Are the same or different and are each independently selected from the group consisting of: deuterium, cyano, fluorine, trimethylsilyl, triphenylsilyl, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms.
In one embodiment of the present application, the Ar1And Ar2Each independently selected from the group consisting of:
Figure BDA0002896497580000073
wherein the content of the first and second substances,
Figure BDA0002896497580000074
represents a chemical bond; m1Selected from a single bond or
Figure BDA0002896497580000075
Z1～Z5And Z'1～Z’10Each independently selected from N or C (F)1) And Z is1～Z5Is selected from N, Z'1～Z’4Is selected from N, Z'6～Z’8Is selected from N, Z'9And Z'10At least one is selected from N; when Z is1～Z5Two or more of C (F)1) When, two arbitrary F1The same or different; z'1～Z’4Two or more of C (F)1) When, two arbitrary F1The same or different; z'6～Z’8Two or more of C (F)1) When, two arbitrary F1The same or different; z'9And Z'10Are all selected from C (F)1) When two are F1The same or different;
Z’11selected from O or S;
Z6～Z15each independently selected from N or C (F)2) And Z is6～Z10At least one is selected from N, Z11～Z15At least one is selected from N; when Z is6～Z10Two or more of C (F)2) When, two arbitrary F2The same or different; when Z is11～Z15Two or more of C (F)2) When, two arbitrary F2The same or different;
Z16～Z30each independently selected from N or C (F)3) And Z is16～Z20At least one is selected from N, Z21～Z25At least one is selected from N, Z26～Z30At least one is selected from N; when Z is16～Z20Two or more of C (F)3) When, two arbitrary F3The same or different; when Z is21～Z25Two or more of C (F)3) When, two arbitrary F3The same or different; when Z is26～Z30Two or more of C (F)3) When, two arbitrary F3The same or different;
Z31～Z45each independently selected from N or C (F)4) And Z is31～Z35At least one is selected from N, Z36～Z40At least one is selected from N, Z41～Z45At least one is selected from N; when Z is31～Z35Two or more of C (F)4) When, two arbitrary F4The same or different; when Z is36～Z40Two or more of C (F)4) When, two arbitrary F4The same or different; when Z is41～Z45Two or more of C (F)4) When, two arbitrary F4The same or different;
each G1～G4、F1～F4Each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, aryl with 6 to 20 carbon atoms, trialkylsilyl with 3 to 12 carbon atoms, triarylsilyl with 8 to 12 carbon atoms, alkyl with 1 to 5 carbon atoms, haloalkyl with 1 to 10 carbon atoms, cycloalkyl with 3 to 10 carbon atoms, heterocycloalkyl with 2 to 10 carbon atoms, alkoxy with 1 to 10 carbon atoms;
g1～g4in gkIs represented by G1～G4With GkK is a variable and represents an arbitrary integer of 1 to 4, gkRepresents a substituent GkThe number of (2); wherein, when k is 1, gkSelected from 1,2, 3,4, 5 or 6; when k is 2, 3 or 4, gkSelected from 1,2, 3 or 4; when g iskWhen greater than 1, any two GkThe same or different;
K1selected from O, S, Se, N (G)5)、C(G6G7)、Si(G8G9) (ii) a Wherein G is5～G9Are the same or different from each other and are each independently selected from: aryl group having 6 to 12 carbon atoms, heteroaryl group having 3 to 10 carbon atoms, alkyl group having 1 to 5 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, heterocycloalkyl group having 2 to 10 carbon atoms, or G6And G7Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or G8And G9Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring; for example, in the chemical formula i-5
Figure BDA0002896497580000081
In, when K2Is a single bond, G1Is hydrogen, K2Is a single bond, K1Is C (G)6G7) When is optional G6And G7Are linked to form a 5-13 membered saturated or unsaturated ring with the atoms to which they are commonly attached, i.e.: g6And G7Can be connected with each other to form a ring, and can also exist independently; when G is6And G7When the ring is formed, the number of carbon atoms of the ring may be 5-membered, for example
Figure BDA0002896497580000082
Or may be a 6-membered ring, e.g.
Figure BDA0002896497580000083
And may also be a 13-membered ring, e.g.
Figure BDA0002896497580000084
Of course, G6And G7The number of carbon atoms forming the ring can also be other values, which are not listed one by one, and the number of carbon atoms forming the ring is not particularly limited in the present application;
K2selected from single bond, O, S, Se, N (G)10)、C(G11G12)、Si(G13G14) (ii) a Wherein G is10～G14Are the same or different from each other and are each independently selected from: aryl group having 6 to 12 carbon atoms, heteroaryl group having 3 to 10 carbon atoms, alkyl group having 1 to 5 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, heterocycloalkyl group having 2 to 10 carbon atoms, or G11And G12Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or G13And G14Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-to 13-membered saturated or unsaturated ring, not G11And G12Number of carbon atoms in Ring formation, G13And G14The number of carbon atoms forming the ring is specifically limited. G11And G12Cyclization G13And G14Number of carbon atoms in ring formation and G6And G7The same ring formation process is not repeated here.
In one embodiment of the present application, Ar1And Ar2Each independently selected from substituted or unsubstituted heteroaryl groups having 3 to 18 carbon atoms. Wherein said heteroaryl means comprising at least one N atom as a heteroatomThe number of N atoms in the heteroaryl group may be 1 to 10, and for example, 1N atom, 2N atoms, 3N atoms, 4N atoms or 5N atoms may be included, and in one embodiment, the heteroaryl group may further include at least one of B, O, P, Si and S as a heteroatom.
In one embodiment of the present application, the Ar1And Ar2Each independently selected from substituted or unsubstituted W selected from the group consisting of:
Figure BDA0002896497580000091
wherein the content of the first and second substances,
Figure BDA0002896497580000092
represents a chemical bond of a compound represented by the formula,
when W is substituted, the substituent of W is selected from deuterium, fluorine, chlorine, cyano, trimethylsilyl, triphenylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, pyridyl, pyrimidyl; when there are a plurality of substituents for W, the substituents may be the same or different.
In one embodiment of the present application, the Ar1And Ar2Each independently selected from the group consisting of:
Figure BDA0002896497580000093
Figure BDA0002896497580000101
in one embodiment of the present application, the Ar1And Ar2The substituents of (a) are the same or different and are each independently selected from deuterium, cyano, fluoro, trimethylsilyl, triphenylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, pyridyl, pyrimidinyl, benzoxazole, carbazolyl, dibenzofuranPhenyl, dibenzothienyl.
In one embodiment of the present application, L is selected from the group consisting of:
Figure BDA0002896497580000102
wherein the content of the first and second substances,
Figure BDA0002896497580000103
represents a group L with Ar1Or Ar2A chemical bond to which any one of them is attached;
Figure BDA0002896497580000104
represents a chemical bond on the L group to the atom in parenthesis;
M2selected from the group consisting of single bonds,
Figure BDA0002896497580000105
Q1～Q5Each independently selected from N or C (F)5) And Q is1～Q5At least one is selected from N; when Q is1～Q5Two or more of C (F)5) When, two arbitrary F5The same or different;
Q6～Q13each independently selected from N or C (F)6) And Q is6～Q13At least one is selected from N; when Q is6～Q13Two or more of C (F)6) When, two arbitrary F6The same or different;
E1～E3、F5～F6each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, heteroaryl having 3 to 10 carbon atoms, aryl having 6 to 12 carbon atoms, trialkylsilyl having 3 to 12 carbon atoms, triarylsilyl having 8 to 12 carbon atoms, alkyl having 1 to 5 carbon atoms, haloalkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, heterocycloalkyl having 2 to 10 carbon atoms, and heteroaryl having 1 to 10 carbon atomsAn alkoxy group;
e1～e3with erIs represented by1～E3With ErR is a variable and is an arbitrary integer of 1 to 3, erRepresents a substituent ErThe number of (2); when r is selected from 1, erSelected from 1,2 or 3; when r is selected from 2, erSelected from 1,2, 3,4, 5 or 6; when r is 3, erSelected from 1,2, 3 or 4; when e isrWhen greater than 1, any two of ErThe same or different;
K3selected from the group consisting of a single bond, O, S, Se, N (E)4)、C(E5E6)、Si(E7E8) (ii) a Wherein E is4To E8Each independently selected from: aryl group having 6 to 12 carbon atoms, heteroaryl group having 3 to 10 carbon atoms, and alkyl group having 1 to 5 carbon atoms.
In one embodiment of the present application, L is selected from substituted or unsubstituted Z; wherein unsubstituted Z is selected from the group consisting of:
Figure BDA0002896497580000111
wherein the content of the first and second substances,
Figure BDA0002896497580000112
represents a group L with Ar1Or Ar2A chemical bond to which any one of them is attached;
Figure BDA0002896497580000113
represents a chemical bond on the L group to the atom in parenthesis;
the substituents in said substituted Z are selected from deuterium, fluoro, chloro, cyano, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, pyridyl, pyrimidinyl; when there are a plurality of substituents for Z, the substituents may be the same or different.
In one embodiment of the present application, L is selected from the group consisting of:
Figure BDA0002896497580000114
wherein the content of the first and second substances,
Figure BDA0002896497580000115
represents a group L with Ar1Or Ar2A chemical bond to which any one of them is attached;
Figure BDA0002896497580000116
represents a chemical bond on the L group to the atom in parenthesis.
In one embodiment of the present application, L is selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted pyrimidylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted biphenylene, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted quinazolinylene, substituted or unsubstituted 1, 5-naphthyridinylene, substituted or unsubstituted pyridinylene, substituted or unsubstituted carbazolyl; or a group formed by connecting two or three of the above groups by a single bond, wherein the substituents of the above groups are the same or different from each other and are independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, pyridyl, naphthyl and trimethylsilyl.
In one embodiment of the present application, L is selected from the group consisting of substituted or unsubstituted arylene groups having 6 to 12 carbon atoms, and substituted or unsubstituted heteroarylene groups having 4 to 10 carbon atoms.
In one embodiment of the present application, the substituent of L is selected from deuterium, cyano, fluoro, trimethylsilyl, phenyl, pyridyl, pyrimidinyl, naphthyl, cyclohexyl.
In one embodiment of the present application, the R is1And R2The same or different from each other, and each is independently selected from deuterium, cyano, fluorine, trimethylsilyl, an alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 10 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms.
In one embodiment of the present application, the R is1And R2Identical or different from each other and are each independently selected from deuterium, cyano, fluoro, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, pyrimidinyl, pyridyl, cyclohexyl.
In one embodiment of the present application, the organic compound is selected from the group consisting of:
Figure BDA0002896497580000121
Figure BDA0002896497580000131
Figure BDA0002896497580000141
Figure BDA0002896497580000151
Figure BDA0002896497580000161
Figure BDA0002896497580000171
Figure BDA0002896497580000181
Figure BDA0002896497580000191
Figure BDA0002896497580000201
a second aspect of the present application provides the use of an organic compound as described in the first aspect of the present application in the preparation of an organic electroluminescent device.
According to the application, the organic compound has better electron transport performance and stability, and can be used as an electron transport material and/or a hole blocking material of the organic electroluminescent device.
More preferably, the electron transport layer further comprises LiQ.
A third aspect of the present application provides an organic electroluminescent device comprising an anode, a cathode, and at least one functional layer interposed between the anode and the cathode. The functional layer may comprise an organic compound as described in the first aspect of the present application.
Optionally, the functional layer 300 comprises an electron transport layer 350, the electron transport layer 350 comprising a luminescent material as provided herein. In one embodiment, the electron transport layer 350 can be composed of an organic compound as provided herein; in another embodiment, the electron transport layer 350 may be composed of the compounds provided herein in combination with other materials.
A fourth aspect of the present application provides an electronic device comprising the organic electroluminescent device according to the third aspect of the present application.
In one embodiment of the present invention, as shown in fig. 1, the organic electroluminescent device of the present invention includes an anode 100, a cathode 200, and at least one functional layer 300 interposed between the anode layer and the cathode layer, where the functional layer 300 includes a hole injection layer 310, a hole transport layer 320, an organic electroluminescent layer 330, an electron transport layer 350, and an electron injection layer 360, the hole injection layer 310, the hole transport layer 320, the organic electroluminescent layer 330, the electron transport layer 350, and the electron injection layer 360 may be sequentially formed on the anode 100, and the electron transport layer 350 may include the organic compound of the first aspect of the present invention, and preferably includes at least one of the compounds 1 to 232.
In one embodiment of the present application, as shown in fig. 1, the functional layer 320 of the organic electroluminescent device includes a first hole transport layer 321 and a second hole transport layer 322.
Optionally, the anode 100 comprises an anode material, 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 metals and oxides, e.g. ZnO: Al or SnO2Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole, and polyaniline, but are not limited thereto. Preferably, a transparent electrode including Indium Tin Oxide (ITO) as an anode is included.
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 tri-nitrogen-containing compounds, or other types of compounds, which are not specifically limited herein. For example, in one embodiment of the present application, the first hole transport layer 321 is composed of the compound NPB.
Alternatively, the organic light emitting layer 330 may be composed of a single light emitting material, and may also 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 a hole injected into the organic light emitting layer 330 and an electron injected into the organic light emitting layer 330 may be combined in the organic light emitting layer 330 to form an exciton, which transfers energy to the host material, and the host material transfers energy to the guest material, thereby enabling the guest material to emit light.
The host material of the organic light-emitting layer 330 may be a metal-chelated octylene compoundA bisstyryl derivative, an aromatic amine derivative, a dibenzofuran derivative, or other types of materials, which are not particularly limited in this application. In one embodiment of the present application, the host material of the organic light emitting layer 330 may be Ir (piq)2(acac) or TCP.
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 application. In one embodiment of the present application, the guest material of the organic light emitting layer 330 may be CBP or TPA.
The electron transport layer 350 may have a single-layer structure or a multi-layer structure, and may include one or more electron transport materials, and the electron transport materials may be selected from benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials, which is not particularly limited in this application. For example, in one embodiment of the present application, the electron transport layer 340 may be composed of ET-06 and LiQ.
Optionally, the cathode 200 comprises a cathode material, which is a material with 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 multilayer material such as LiF/Al, Liq/Al, LiO2Al, LiF/Ca, LiF/Al and BaF2But not limited thereto,/Ca. It is preferable to include a metal electrode including magnesium (Mg) and silver (Ag) as a cathode.
In a further embodiment, the functional layer 300 of the organic electroluminescent device may further include a hole blocking layer 340 and an electron blocking layer 370, the hole blocking layer 340 may be disposed between the organic electroluminescent layer 330 and the electron transport layer 350, and the electron blocking layer 370 may be disposed between the hole transport layer 320 and the organic electroluminescent layer 330.
Based on the excellent performance of the luminescent material, the organic electroluminescent device obtained by using the compound as a hole transport layer material can reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency and prolong the service life of the device.
In one embodiment, the first hole transport layer contains the light emitting material; the organic electroluminescent device is a red light device.
In one embodiment, the second hole transport layer contains the light emitting material; the organic electroluminescent device is a green light or blue light device.
A fourth aspect of the present application provides an electronic device comprising the organic electroluminescent device according to the third aspect of the present application.
Compounds of synthetic methods not mentioned in this application are all commercially available starting products.
Analytical detection of intermediates and compounds in this application uses an ICP-7700 mass spectrometer and an M5000 element analyzer.
The following will specifically explain the method for synthesizing the organic compound of the present application with reference to the synthesis examples.
Synthetic examples
A preparation method of an organic light-emitting material comprises the following steps:
step 1: synthesis of intermediates
The organic luminescent material related to the invention, the needed intermediate in the preparation process of the compound can be represented by formula I-1:
Figure BDA0002896497580000221
wherein X is O, S, SO2、C(R1R2) Or N (R)3) (ii) a The structures and numbers of the intermediates are listed in table 1:
TABLE 1
Figure BDA0002896497580000222
Figure BDA0002896497580000231
Step 2: synthesis of Compounds
Figure BDA0002896497580000232
Synthesis example 1: synthesis of intermediate I-A
Figure BDA0002896497580000233
(1) Adding 0.5mol of raw material C and 900mL of dried tetrahydrofuran into a 2L three-neck flask, cooling to below 0 ℃ by using a low-temperature constant-temperature cold bath under stirring, slowly dropwise adding 0.55mol (550mL) of 1mol/L phenylmagnesium bromide tetrahydrofuran solution under the protection of nitrogen, preserving heat for 4 hours after dropwise adding is finished, naturally heating to room temperature, continuing stirring for 2 hours, dropwise adding water to quench and react, extracting the reaction solution by using ethyl acetate, drying an organic phase by using magnesium sulfate, then distilling under reduced pressure, recrystallizing the obtained solid by using a mixed solvent of dichloromethane and n-heptane (the volume ratio is 1:4) to obtain a compound I-A-a, wherein the HPLC purity is more than 99%, and the single-step yield: 57-69%.
(2) Adding 0.45mol of compound I-A-a and 1L of dichloromethane into a 2L three-neck flask, cooling to below 0 ℃ by using a low-temperature constant-temperature cold bath, then slowly dropwise adding 0.65mol of trifluoromethanesulfonic acid, keeping the temperature at 0 ℃ for reaction for 30min after the dropwise addition is finished, and naturally heating to room temperature. Adding sodium bicarbonate solution into the reaction liquid, washing the reaction liquid to be neutral by water, extracting the water phase with dichloromethane after liquid separation, combining organic phases, drying the organic phases for 2 hours by anhydrous magnesium sulfate, filtering the mixture to remove the anhydrous magnesium sulfate, then distilling the mixture under reduced pressure to obtain a light yellow solid crude product, and recrystallizing the light yellow solid crude product twice by using a mixed solvent of dichloromethane and n-heptane (the volume ratio is 1:3) to obtain a white solid compound I-A-b, wherein the HPLC purity is more than 99 percent, and the single-step yield is as follows: 54-66 percent.
(3) Adding 0.3mol of compound I-A-b and 300mL of dried tetrahydrofuran into a 1L three-neck flask, cooling to below-80 ℃ under stirring, slowly dropwise adding 165mL (0.33mol) of n-butyllithium n-hexane solution with the concentration of 2mol/L under the protection of nitrogen, preserving heat for 30min after dropwise adding, then adding a mixed solution of 0.33mol of adamantanone and 300mL of tetrahydrofuran, preserving heat for 30min, naturally raising the temperature to room temperature, continuing stirring for 2 hours, dropwise adding water to quench the reaction solution, extracting the reaction solution with ethyl acetate, drying an organic phase with magnesium sulfate, then distilling under reduced pressure, recrystallizing the obtained solid with a mixed solution of dichloromethane and n-heptane (volume ratio of 1:4) to obtain compound I-A-c, wherein the HPLC purity is more than 99%, and the single-step yield is as follows: 68-74 percent.
(4) Adding 0.2mol of compound I-A-c and 500mL of glacial acetic acid into a 1L three-neck flask, slowly dropwise adding 5mL of concentrated sulfuric acid under stirring, heating to 80 ℃ for reacting for 8 hours, adding water into reaction liquid, separating out white solid, filtering, washing a filter cake with water to be neutral, then leaching with ethanol, recrystallizing the obtained solid with ethyl acetate to obtain an intermediate I-A-d, wherein the HPLC purity is more than 99%, and the single-step yield is as follows: 63-68 percent.
(5) Adding 0.15mol of compound I-A-d (42.0g, 125.41mmol), 0.225mol of sodium tert-butoxide (18.06g, 188.12mmol) and 350mL of dimethyl sulfoxide (DMSO) into a 500mL three-neck flask, stirring and cooling to 0-10 ℃ in a low-temperature constant-temperature cold bath under the protection of nitrogen, then slowly dropwise adding 0.45mol of raw material R-I (iodohydrocarbon), keeping the temperature for 30min, and slowly heating to 70 ℃ for reaction for 2h to finish the reaction; cooling to room temperature, washing the reaction solution to neutrality with deionized water, adding dichloromethane (100mL) into the water phase for extraction, combining the organic phases, drying with anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by silica gel chromatography using n-heptane as the eluting solvent to give intermediate I-a as a white solid with HPLC purity > 99% single step yield: 78-85%.
When the method of synthesis example 1 is used to synthesize each intermediate I-a in table 1, the required raw materials and the total yield are shown in table 2:
TABLE 2
Figure BDA0002896497580000241
Synthesis example 2: preparation of intermediates I-B and I-C
Figure BDA0002896497580000242
(1) Adding 0.5mol of raw material F, 0.5mol of raw material XH and N-methyl-2-pyrrolidone (800mL) into a 2L three-neck flask, stirring and heating to 150 ℃ under the protection of nitrogen, continuously stirring for 15 hours, stopping the reaction, distilling the reaction liquid under reduced pressure to remove the solvent, dissolving the obtained solid crude product by using dichloromethane, washing the solid crude product to be neutral by using water, separating the liquid, drying an organic phase by using magnesium sulfate, distilling the liquid under reduced pressure, recrystallizing the obtained solid by using a mixed solvent of dichloromethane and N-heptane (the volume ratio is 1:5), and obtaining a compound I-B-a (or I-C-a), wherein the HPLC purity is more than 99%, and the single-step yield: 68-80%.
(2) 0.35mol of compound I-B-a (or I-C-a) and 750mL of dry tetrahydrofuran are added into a 2L three-neck flask, the temperature is reduced to below minus 80 ℃ under stirring, under the protection of nitrogen, 147.6mL (349.145mmol) of n-butyllithium n-hexane solution with the concentration of 2mol/L is slowly dripped, heat preservation is carried out for 30min after dripping is finished, then 52.45g (349.145mmol) of adamantanone and 400mL of tetrahydrofuran mixed solution are added, the temperature is kept for 30min, the mixture is naturally raised to the room temperature and then stirred for 2 hours, dropping water to quench the reaction, extracting the reaction solution with ethyl acetate, drying the organic phase with magnesium sulfate, then distilling under reduced pressure, recrystallizing the obtained solid with a mixed solvent of dichloromethane and n-heptane (1: 4) to obtain a compound I-B-B (or I-C-B), wherein the HPLC purity is more than 99%, and the single-step yield is as follows: 55-67%.
(3) Adding 0.2mol of compound I-B-B (or I-C-B) and 500mL of glacial acetic acid into a 1L three-neck flask, slowly dropwise adding 5mL of concentrated sulfuric acid under stirring, heating to 80 ℃ to react for 8 hours, adding water into reaction liquid to separate out white solid, filtering, washing a filter cake to be neutral by using water, then leaching by using ethanol, recrystallizing the obtained solid twice by using ethyl acetate to obtain an intermediate I-B (I-C), wherein the HPLC purity is more than 99%, and the single-step yield is as follows: 49-67%.
Synthetic example 3: synthesis of intermediates I-D
Figure BDA0002896497580000251
Adding 0.1mol of intermediate I-C and 200mL of glacial acetic acid into a 500mL three-neck flask, slowly dropping 34.5% hydrogen peroxide into 26mL (0.3mol) under stirring, starting heating after dropping, and heating to 80 ℃ for reacting for 4 hours to finish the reaction. Cooling to room temperature, adding equal volume of water, precipitating a white solid, filtering, washing a filter cake to be neutral by using water, then leaching by using ethanol, recrystallizing the obtained solid twice by using ethyl acetate and cyclohexane (the volume ratio is 1:3) to obtain an intermediate I-D, wherein the HPLC purity is more than 99%, and the single-step yield is as follows: 75-82%.
When the intermediate I-B, I-C was synthesized by the method of synthesis example 2 and each of the intermediates I-D in table 3 was synthesized by the method of synthesis example 3, the required starting materials and overall yields are shown in table 3:
TABLE 3
Figure BDA0002896497580000252
Synthetic example 4: synthesis of intermediates I-E
Figure BDA0002896497580000261
Wherein: the dotted line indicates that the starting material N may or may not contain Cl, and when the starting material N does not contain Cl, the Cl of the intermediates I to E is replaced by Ar3And (4) introducing.
(1) In a 1L three-necked flask, 0.4mol of raw material N, 0.45mol of iodobenzene and 0.8mol of sodium tert-butoxide are added in sequence at room temperature, 150mL of toluene is added, and N is introduced2After 20 minutes, 1.2mmol of o-bis (2-phenyl) bis (diphenylphosphine) and 1.2mmol of palladium (II) chloride were added and the reaction was continued with N2For 20 minutes, heat to reflux and stir for 12 hours. Cooling to room temperature, vacuum filtering to remove sodium tert-butoxide, vacuum distilling to remove solvent, separating and purifying with silica gel chromatographic column to obtain compound I-E-a with HPLC purity>99%, yield: 82-89%.
(2) In a 1L one-necked flask, 0.4mol of di-tert-butyl dicarbonate (BOC) was added to 600mL of tetrahydrofuran at room temperature, and then 0.2mol of the compound I-E-a was added thereto, purged with nitrogen for 20 minutes and heated to reflux and stirred for 24 hours. The mixture was then poured into 1L of water and the product was extracted with dichloromethane. Drying the organic phase by anhydrous magnesium sulfate, removing the solvent after separation, and separating and purifying by using a silica gel chromatographic column to obtain the compound I-E-b, wherein the HPLC purity is more than 99 percent, and the yield is as follows: 88 to 95 percent.
(3) In a 1L three-necked flask, 0.15mol of the compound I-E-b was added to 500mL of dry tetrahydrofuran, and then the temperature was lowered to-80 ℃ and a 2.5M n-butyllithium-n-hexane solution (0.16mol, 64mL) was slowly added dropwise. Stirring was continued for 2 hours under an argon atmosphere. A solution of 0.16mol adamantane and 250mL tetrahydrofuran was added, stirring was continued for 2 hours and then slowly warmed to room temperature. The solvent was distilled off under reduced pressure, 600mL of glacial acetic acid were added, nitrogen was purged for 20 minutes, 30mL of concentrated hydrochloric acid was added, and the mixture was heated to reflux, stirred for 24 hours to terminate the reaction, poured into 1.5L of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, separated, the solvent was distilled off under reduced pressure, and the white solid compound I-E-c was isolated and purified by silica gel chromatography using dichloromethane/petroleum ether (volume ratio 1:5) with HPLC purity > 99%, yield: 61-70%.
(4) 0.1mol of compound I-E-c and 10mmol of raw material Br-Ar3 are added into a 1L three-neck flask under argon atmosphere, 600mL of toluene is used as a solvent, and after the raw materials are dissolved, 0.3mol of sodium tert-butoxide, 5mmol of tri-tert-butylphosphine and 2mmol of palladium acetate are sequentially added. Heating, refluxing, stirring and reacting for 24 hours, cooling to room temperature, pouring 200mL of water into reaction liquid, quenching and reacting, extracting a product by using dichloromethane, washing an organic phase to be neutral, drying the organic phase by using anhydrous magnesium sulfate, removing a solvent by reduced pressure distillation after separation, and separating and purifying by using a silica gel chromatographic column to obtain a light yellow solid intermediate I-E, wherein the HPLC purity is more than 99%, and the yield is as follows: 59-68 percent.
When the intermediates I to E in table 4 were synthesized using the method of synthesis example 4, the required starting materials and overall yields are shown in table 4:
TABLE 4
Figure BDA0002896497580000262
Figure BDA0002896497580000271
Synthesis example 5: preparation of Compound 1
Figure BDA0002896497580000272
Adding intermediate I-A1(37.1g, 102.21mmol), pinacol diboron (31.16g, 122.68mmol), 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl (0.96g, 2.044mmol), potassium acetate (20.05g, 204.44mmol) and 1, 4-dioxane (300mL) into a 500mL three-neck flask, adding tris (dibenzylideneacetone) dipalladium (0.93g, 1.022mmol), heating to 80 ℃ under nitrogen protection, and stirring for 3 h; then cooling to room temperature, washing the reaction solution to be neutral, combining organic phases, adding 50g of anhydrous magnesium sulfate, drying overnight, filtering, and removing the solvent from the filtrate under reduced pressure; the crude product was purified by recrystallization from toluene to give compound I-A1-1 as a white solid (35.99g, yield 77.41%).
Figure BDA0002896497580000273
Under the protection of nitrogen, adding compound I-A1-1(35.5g, 77.564mmol), 3, 5-dichloro-1-bromobenzene (17.52g, 77.564mmol), toluene (280mL), ethanol (140mL), water (70mL), potassium carbonate (23.58g, 170.86mmol) into a 1000mL three-neck flask, stirring, heating to 50-60 ℃, rapidly adding tetrakis (triphenylphosphine) palladium (1.79g, 1.55mmol), tetrabutylammonium bromide TBAB (5.0g, 15.51mmol), after adding, continuing heating to 70-75 ℃, refluxing for reaction overnight, after reaction, cooling, adding water to quench the reaction, separating, washing the organic phase to neutrality with water, extracting the aqueous phase with toluene once, combining the organic phases, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent. Recrystallization from a mixed solvent of ethyl acetate and n-heptane gave compound I-A1-2(26.2g, yield 71.4%) as a white solid.
Figure BDA0002896497580000281
Adding intermediate I-A1-2(22g, 50.07mmol), pinacol diboron (33.13g, 132.16mmol), tris (dibenzylideneacetone) dipalladium (2.02g, 2.20mmol), 2-dicyclohexylphosphonium-2 ',4',6' -triisopropylbiphenyl (0.52g, 1.10mmol) and potassium acetate (21.62g, 220.26mmol) to 1, 4-dioxane (210mL), heating to 80 ℃ under nitrogen protection, stirring for 3 h; cooling to room temperature, washing the reaction solution to be neutral, combining organic phases, adding anhydrous magnesium sulfate, drying overnight, filtering, and removing the solvent from the filtrate under reduced pressure; the crude product was purified by recrystallization from toluene to give compound I-A1-3 as a white solid (25.03g, yield 69.2%).
Figure BDA0002896497580000282
Under the protection of nitrogen, adding compound I-A1-3(11.4g, 17.364mmol), 2-bromopyridine (6.04g, 38.2mmol), toluene (90mL), ethanol (45mL), water (25mL), tetrabutylammonium bromide TBAB (2.37g, 7.342mmol) and potassium carbonate (9.6g, 69.46mmol) into a 250mL three-neck flask, stirring, heating to 50-60 ℃, rapidly adding tetrakis (triphenylphosphine) palladium (0.803g, 0.695mmol), after adding, continuing heating to 70-75 ℃, refluxing and reacting overnight, after finishing the reaction, cooling, adding water to quench the reaction, separating the organic phase, washing to neutrality with water, extracting the aqueous phase once with toluene, combining the organic phases, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent. Recrystallizing with mixed solvent of dichloromethane and n-heptane (volume ratio 1:4) to obtain white solid compound 1, vacuum drying at 80 deg.C for 12 hr, sublimating under high vacuum to obtain high purity product (4.52g, yield 46.5%), (M/z ═ 558.3[ M + H ], (M + H))]+)。
Synthetic example 6: synthesis of Compound 8
Figure BDA0002896497580000283
Under the protection of nitrogen, compound I-A1-3(13.2g, 20.106mmol), 2-bromo-4, 6-diphenyl- [1,3,5] triazine (6.09g, 19.501mmol), toluene (100mL), ethanol (50mL), water (25mL), tetrabutylammonium bromide (TBAB) (1.29g, 4.02mmol) and potassium carbonate (6.11g, 44.23mmol) are added into a 250mL three-neck flask, stirred, heated to 50-60 ℃, tetrakis (triphenylphosphine) palladium (0.46g, 0.402mmol) is rapidly added, after the addition, the temperature is raised to 70-75 ℃ for reflux reaction overnight, the reaction is finished, the temperature is reduced, water is added for quenching reaction, the organic phase is washed to neutrality after liquid separation, the aqueous phase is extracted once with toluene, the combined organic phases are dried with anhydrous magnesium sulfate, filtered, and the solvent is removed by reduced pressure distillation. Recrystallization from a mixed solvent of ethyl acetate and n-heptane (volume ratio 1:3) gave compound I-A1-4 as a white solid (9.4g, yield 61.4%).
Figure BDA0002896497580000291
Under the protection of nitrogen, adding compound I-A1-4(9.03g, 11.85mmol), 6-bromo-2, 2' -bipyridine (2.78g, 11.85mmol), toluene (60mL), ethanol (30mL), water (15mL), tetrabutylammonium bromide (TBAB) (0.76g, 2.37mmol) and potassium carbonate (3.6g, 26.07mmol) into a 250mL three-neck flask, stirring, heating to 50-60 ℃, rapidly adding tetrakis (triphenylphosphine) palladium (0.27g, 0.237mmol), after adding, continuing to increase the temperature to 70-75 ℃ for reflux reaction overnight, after the reaction is finished, reducing the temperature, adding water for quenching reaction, washing an organic phase to neutrality after liquid separation, extracting the aqueous phase with toluene once, combining the organic phases, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to remove the solvent. Recrystallizing with mixed solvent of dichloromethane and n-heptane (volume ratio 1:4) to obtain white solid compound 8, vacuum drying at 80 deg.C for 12 hr, sublimating under high vacuum to obtain high purity product (6.1g, yield 38.6%), (M/z ═ 791.39[ M + H ], (M + H))]+)。
Synthetic example 7: preparation of compounds 22, 26, 36, 48, 61, 70, 88, 102, 116
Compounds 22, 26, 36, 48, respectively, were synthesized in the same manner as in the preparation of Compound 1 and Compound 8,61. 70, 88, 102, 116, except that: respectively, intermediates of Table 1 were used instead of intermediate I-A1, raw material 3 of Table 5 was used instead of 3, 5-dichloro-1-bromobenzene, and Ar of Table 5 was used1-Br instead of 2-bromopyridine, Ar in Table 52-Br instead of 6-bromo-2, 2' -bipyridine; when Ar is1And Ar2When the same, the same synthesis as that of Compound 1 in Synthesis example 5 was carried out, and 2.2eq equivalent of Ar was added1Br, Ar is omitted2Br charge and indicated by "/".
TABLE 5
Figure BDA0002896497580000292
Figure BDA0002896497580000301
Figure BDA0002896497580000311
Figure BDA0002896497580000321
TABLE 6 partial compound nuclear magnetic data sheet
Figure BDA0002896497580000331
Device embodiments
Embodiments of the present invention also provide an organic electroluminescent device including an anode, a cathode, and an organic layer interposed between the anode and the cathode, the organic layer including the above organic compound of the present invention.
The anode includes an anode material, which is preferably a material having a large work function (work function) that facilitates hole injection into the organic layer. Specific examples of the anode material include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or the likeAlloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metals and oxides, e.g. ZnO: Al or SnO2Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole, and polyaniline, but are not limited thereto. A transparent electrode including Indium Tin Oxide (ITO) as an anode is preferable.
The cathode includes a cathode material, which is a material having a small work function that facilitates electron injection into the organic 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 multi-layer materials, e.g. LiF/Al, Liq/Al, LiO2Al, LiF/Ca, LiF/Al and BaF2But not limited thereto,/Ca. A metal electrode containing aluminum is preferred as the cathode.
Specifically, the organic layer at least comprises a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer and an electron injection layer; the organic compound of the present invention is located in the electron transport layer. The organic layer may further include a hole blocking layer, an electron blocking layer, an organic capping layer, and the like, which are not described in detail herein.
Specific organic electroluminescent device examples are given below.
Example 1: fabrication of blue organic electroluminescent device
The anode was prepared by the following procedure: will have a thickness of
Figure BDA0002896497580000332
The ITO substrate of (1) was cut into a size of 40mm × 40mm × 0.7mm, and prepared into a top emission experimental substrate having a cathode lap joint region, an anode, and an insulating layer pattern by using a photolithography process using ultraviolet ozone and O2:N2The plasma performs surface treatment to increase the work function of the anode (test substrate) and clean the test substrate.
NPNPB (N, N '-Diphenyl-N, N' -di- [4- (N, N-Diphenyl-amino) phenyl) is vacuum evaporated on an experimental substrate (anode)]benzadine) to form a thickness of
Figure BDA0002896497580000333
And NPB is vacuum-evaporated on the hole injection layer to form a layer having a thickness of
Figure BDA0002896497580000334
A Hole Transport Layer (HTL).
Then vacuum evaporating a layer of TAPC on the hole transport layer to form a layer with a thickness of
Figure BDA0002896497580000335
Electron Blocking Layer (EBL).
BD-1 was doped simultaneously with α, β -ADN as a host, and the host and the dopant were formed to have a thickness of 30:3
Figure BDA0002896497580000336
The organic electroluminescent layer (EML).
Then, the compound 1 of the present invention and LiQ were co-deposited on the light-emitting layer at a film thickness ratio of 1:1 to form a layer having a thickness of
Figure BDA0002896497580000337
The mixed film layer of (2) serves as an Electron Transport Layer (ETL) of the organic electroluminescent device. Depositing Yb on the electron transport layer to a thickness of
Figure BDA0002896497580000338
Then magnesium (Mg) and silver (Ag) were mixed at a rate of 1:9, and vacuum-evaporated on the electron injection layer to form an Electron Injection Layer (EIL) having a thickness of
Figure BDA0002896497580000341
The cathode of (1).
Further, the cathode is deposited with a thickness of
Figure BDA0002896497580000342
N- (4- (9H-carbazol-9-yl) phenyl) -4'- (9H-carbazol-9-yl) -N-phenyl- [1,1' -biphenyl]-4-amine, forming a capping layer (CPL), fromThereby completing the fabrication of the organic light emitting device.
Wherein the structural formulas of NPNPB, NPB, TAPC, alpha, beta-ADN, BD-1, LiQ and CP-1 are as follows:
Figure BDA0002896497580000343
examples 2 to 33
Organic electroluminescent devices were produced in the same manner as in example 1, except that the compounds shown in table 6 were each used in forming the Electron Transport Layer (ETL).
Example 34
An organic electroluminescent device was fabricated in the same manner as in example 1, except that the functional layer was formed on the light-emitting layer using only the compound 116 by vacuum evaporation when the Electron Transport Layer (ETL) was formed.
Examples 35 to 37
An organic electroluminescent device was fabricated in the same manner as in example 34, except that the electron transport layers in example 35, example 36 and example 37 were each formed using the compound 160, the compound 163 and the compound 170 for the formation of the Electron Transport Layer (ETL).
Comparative examples 1 to 4
In comparative examples 1 to 4, organic electroluminescent devices were fabricated by the same fabrication method as in example 1, except that LiQ, compound a, compound B, and compound C were used as electron transport layers instead of compound 1.
Wherein the structural formulas of the compound A, the compound B and the compound C are as follows:
Figure BDA0002896497580000344
Figure BDA0002896497580000351
the organic electroluminescent device prepared above was operated at 10mA/cm2Test the IVL performance under the condition of T95% device life of 20mA/cm at constant current density2The test was performed.
TABLE 6
Figure BDA0002896497580000352
Figure BDA0002896497580000361
As can be seen from table 6, in examples 1 to 33 of the present invention, the Electron Transport Layer (ETL) of the organic electroluminescent device is a mixed film layer formed by co-evaporating the compound of the present invention and LiQ. Compared with the device performance of comparative examples 1-4, the device performance is improved, wherein the voltage is reduced by at least 0.18V, the luminous efficiency (Cd/A) is improved by at least 7.14%, and the service life (T95) is improved by at least 12%. In addition, compared with the device performances of the embodiments 34 to 37, the device performances of the embodiments 11 and 16 to 18 of the invention are improved to a certain extent, so that the voltage, the efficiency and the service life of the devices of the embodiments 11 and 16 to 18 are improved to a certain extent. However, the most significant performance improvement is shown in the device lifetime, i.e., the device lifetime of examples 11 and 16-18 is improved by at least 6.1% compared with the device lifetime of examples 34-37. Therefore, the compound provided by the invention is used for an electron transport layer of an organic electroluminescent device, so that the working voltage of the organic electroluminescent device can be remarkably reduced, and the luminous efficiency of the organic electroluminescent device can be improved.
The reason for this is that the compound of the present invention is formed by combining a large plane condensed ring structure formed by screwing adamantane and a plurality of heteroaryl groups, wherein the spiro structure containing the adamantane rich electron group provides a core group with rigidity and high electron mobility for molecules, and the compound and a plurality of electron-withdrawing heteroaryl structures can further increase the electron transfer capability of the material, so that the compound is suitable for the material of an electron transport layer of an organic electroluminescent device, and the prepared organic electroluminescent device has the characteristics of low voltage and high efficiency.
In addition, the present inventionThe provided compound has a structure of a plurality of N atom-containing heteroaryl groups, so that the molecule can also form stable metal complexes with a plurality of metal (such as Li) atoms. Therefore, the mixed film layer formed by co-evaporation of LiQ and the LiQ is used as an electron transport layer material, and compared with the single use of LiQ as the electron transport layer material, the service life of the device is greatly prolonged, mainly because Li is formed after the mixed film layer is formed+The compound can form weak complex bonds with the compound, greatly improves the electron mobility, and simultaneously can improve the stability of a film layer, thereby being beneficial to prolonging the service life of a device.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (16)

1. An organic compound having a structure represented by the following formula 1:
Figure FDA0002896497570000011
wherein R is1And R2The same or different from each other, and are independently selected from deuterium, cyano, halogen group, trialkylsilyl group having 3-12 carbon atoms, triarylsilyl group having 18-24 carbon atoms, alkyl group having 1-10 carbon atomsA substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or any two adjacent R1Are linked to each other to form a ring, or any two adjacent R2Are connected with each other to form a ring; n is1Is R1Number of (2), n2Is R2The number of (2);
n1selected from 0, 1,2, 3 or 4, when n is1When greater than 1, any two R1The same or different;
n2selected from 0, 1,2, 3 or 4, when n is2When greater than 1, any two R2The same or different;
x is selected from O, S, Se, SO2、C(R3R4)、N(R5)、Ge(R6R7) Or Si (R)8R9)；
R3～R9Are the same or different from each other and are each independently selected from: alkyl having 1 to 10 carbon atoms, aryl having 6 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, heterocycloalkyl having 2 to 10 carbon atoms, or R3And R4Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or R6And R7Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or R8And R9Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring;
l is independently selected from: a substituted or unsubstituted arylene group having 6 to 15 carbon atoms or a substituted or unsubstituted heteroarylene group having 4 to 15 carbon atoms;
Ar1and Ar2Are the same or different from each other and are each independently selected from: a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms;
Ar1、Ar2、R1、R2and the substituents of L are the same or different from each other and are each independently selected from: deuterium, fluorine, chlorine, bromineCyano, heteroaryl with 3-20 carbon atoms, aryl with 6-20 carbon atoms, trialkylsilyl with 3-12 carbon atoms, triarylsilyl with 18-24 carbon atoms, alkyl with 1-10 carbon atoms, haloalkyl with 1-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, heterocycloalkyl with 2-10 carbon atoms, and alkoxy with 1-10 carbon atoms.
2. The organic compound according to claim 1, wherein the organic compound has a structure represented by any one of formula 1-1, formula 1-2, formula 1-3, formula 1-4, formula 1-5, or formula 1-6:
Figure FDA0002896497570000012
Figure FDA0002896497570000021
wherein R is5Is' as a quilt
Figure FDA0002896497570000022
Substituted R5。
3. The organic compound of claim 1, wherein the Ar is1And Ar2Are the same or different and are each independently selected from the group consisting of: deuterium, cyano, fluorine, trimethylsilyl, triphenylsilyl, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms.
4. The organic compound of claim 1, wherein the Ar is1And Ar2Each independently selected from the group consisting of:
Figure FDA0002896497570000023
wherein the content of the first and second substances,
Figure FDA0002896497570000024
represents a chemical bond; m1Selected from a single bond or
Figure FDA0002896497570000025
Z1～Z5And Z'1～Z’10Each independently selected from N or C (F)1) And Z is1～Z5Is selected from N, Z'1～Z’4Is selected from N, Z'6～Z’8Is selected from N, Z'9And Z'10At least one is selected from N; when Z is1～Z5Two or more of C (F)1) When, two arbitrary F1The same or different; z'1～Z’4Two or more of C (F)1) When, two arbitrary F1The same or different; z'6～Z’8Two or more of C (F)1) When, two arbitrary F1The same or different; z'9And Z'10Are all selected from C (F)1) When two are F1The same or different;
Z’11selected from O or S;
Z6～Z15each independently selected from N or C (F)2) And Z is6～Z10At least one is selected from N, Z11～Z15At least one is selected from N; when Z is6～Z10Two or more of C (F)2) When, two arbitrary F2The same or different; when Z is11～Z15Two or more of C (F)2) When, two arbitrary F2The same or different;
Z16～Z30each independently selected from N or C (F)3) And Z is16～Z20At least one selected fromN，Z21～Z25At least one is selected from N, Z26～Z30At least one is selected from N; when Z is16～Z20Two or more of C (F)3) When, two arbitrary F3The same or different; when Z is21～Z25Two or more of C (F)3) When, two arbitrary F3The same or different; when Z is26～Z30Two or more of C (F)3) When, two arbitrary F3The same or different;
Z31～Z45each independently selected from N or C (F)4) And Z is31～Z35At least one is selected from N, Z36～Z40At least one is selected from N, Z41～Z45At least one is selected from N; when Z is31～Z35Two or more of C (F)4) When, two arbitrary F4The same or different; when Z is36～Z40Two or more of C (F)4) When, two arbitrary F4The same or different; when Z is41～Z45Two or more of C (F)4) When, two arbitrary F4The same or different;
each G1～G4、F1～F4Each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, aryl with 6 to 20 carbon atoms, trialkylsilyl with 3 to 12 carbon atoms, alkyl with 1 to 5 carbon atoms, haloalkyl with 1 to 10 carbon atoms, cycloalkyl with 3 to 10 carbon atoms, heterocycloalkyl with 2 to 10 carbon atoms and alkoxy with 1 to 10 carbon atoms;
g1～g4in gkIs represented by G1～G4With GkK is a variable and represents an arbitrary integer of 1 to 4, gkRepresents a substituent GkThe number of (2); wherein, when k is 1, gkSelected from 1,2, 3,4, 5 or 6; when k is 2, 3 or 4, gkSelected from 1,2, 3 or 4; when g iskWhen greater than 1, any two GkThe same or different;
K1selected from O, S, Se, N (G)5)、C(G6G7)、Si(G8G9) (ii) a Wherein G is5～G9Are the same or different from each other and are each independently selected from: aryl group having 6 to 12 carbon atoms, heteroaryl group having 3 to 10 carbon atoms, alkyl group having 1 to 5 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, heterocycloalkyl group having 2 to 10 carbon atoms, or G6And G7Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or G8And G9Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring;
K2selected from single bond, O, S, Se, N (G)10)、C(G11G12)、Si(G13G14) (ii) a Wherein G is10～G14Are the same or different from each other and are each independently selected from: aryl group having 6 to 12 carbon atoms, heteroaryl group having 3 to 10 carbon atoms, alkyl group having 1 to 5 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, heterocycloalkyl group having 2 to 10 carbon atoms, or G11And G12Are linked to each other to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring, or G13And G14Are linked to form, together with the atoms to which they are commonly attached, a 5-13 membered saturated or unsaturated ring.
5. The organic compound of claim 1, wherein the Ar is1And Ar2Each independently selected from substituted or unsubstituted heteroaryl groups having 3 to 18 carbon atoms.
6. The organic compound of claim 1, wherein the Ar is1And Ar2Each independently selected from substituted or unsubstituted W selected from the group consisting of:
Figure FDA0002896497570000031
wherein the content of the first and second substances,
Figure FDA0002896497570000041
represents a chemical bond of a compound represented by the formula,
when W is substituted, the substituent of W is selected from deuterium, fluorine, chlorine, cyano, trimethylsilyl, triphenylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, pyridyl, pyrimidyl; when there are a plurality of substituents for W, the substituents may be the same or different.
7. The organic compound of claim 1, wherein the Ar is1And Ar2Each independently selected from the group consisting of:
Figure FDA0002896497570000042
8. the organic compound of claim 1, wherein L is selected from the group consisting of:
Figure FDA0002896497570000043
Figure FDA0002896497570000051
wherein the content of the first and second substances,
Figure FDA0002896497570000052
represents a group L with Ar1Or Ar2A chemical bond to which any one of them is attached;
Figure FDA0002896497570000058
represents a chemical bond on the L group to the atom in parenthesis;
M2selected from the group consisting of single bonds,
Figure FDA0002896497570000053
Q1～Q5Each independently selected from N or C (F)5) And Q is1～Q5At least one is selected from N; when Q is1～Q5Two or more of C (F)5) When, two arbitrary F5The same or different;
Q6～Q13each independently selected from N or C (F)6) And Q is6～Q13At least one is selected from N; when Q is6～Q13Two or more of C (F)6) When, two arbitrary F6The same or different;
E1～E3、F5～F6each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, heteroaryl having 3 to 10 carbon atoms, aryl having 6 to 12 carbon atoms, trialkylsilyl having 3 to 12 carbon atoms, alkyl having 1 to 5 carbon atoms, haloalkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, heterocycloalkyl having 2 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms;
e1～e3with erIs represented by1～E3With ErR is a variable and is an arbitrary integer of 1 to 3, erRepresents a substituent ErThe number of (2); when r is selected from 1, erSelected from 1,2 or 3; when r is selected from 2, erSelected from 1,2, 3,4, 5 or 6; when r is 3, erSelected from 1,2, 3 or 4; when e isrWhen greater than 1, any two of ErThe same or different;
K3selected from the group consisting of a single bond, O, S, Se, N (E)4)、C(E5E6)、Si(E7E8) (ii) a Wherein E is4To E8Each independently selected from: aryl group having 6 to 12 carbon atoms, heteroaryl group having 3 to 10 carbon atoms, and alkyl group having 1 to 5 carbon atoms.
9. The organic compound of claim 1, wherein L is selected from substituted or unsubstituted Z; wherein unsubstituted Z is selected from the group consisting of:
Figure FDA0002896497570000054
wherein the content of the first and second substances,
Figure FDA0002896497570000055
represents a group L with Ar1Or Ar2A chemical bond to which any one of them is attached;
Figure FDA0002896497570000056
represents a chemical bond on the L group to the atom in parenthesis;
the substituents in said substituted Z are selected from deuterium, fluoro, chloro, cyano, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, pyridyl, pyrimidinyl; when there are a plurality of substituents for Z, the substituents may be the same or different.
10. The organic compound of claim 1, wherein L is selected from the group consisting of:
Figure FDA0002896497570000057
Figure FDA0002896497570000061
wherein the content of the first and second substances,
Figure FDA0002896497570000062
represents a group L with Ar1Or Ar2A chemical bond to which any one of them is attached;
Figure FDA0002896497570000063
represents a chemical bond on the L group to the atom in parenthesis.
11. The organic compound according to claim 1, wherein L is selected from a substituted or unsubstituted arylene group having 6 to 12 carbon atoms or a substituted or unsubstituted heteroarylene group having 4 to 10 carbon atoms.
12. The organic compound of claim 1, wherein R is1And R2The same or different from each other, and each is independently selected from deuterium, cyano, fluorine, trimethylsilyl, an alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 10 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms.
13. The organic compound of claim 1, wherein the organic compound is selected from the group consisting of:
Figure FDA0002896497570000064
Figure FDA0002896497570000071
Figure FDA0002896497570000081
Figure FDA0002896497570000091
Figure FDA0002896497570000101
Figure FDA0002896497570000111
Figure FDA0002896497570000121
Figure FDA0002896497570000131
Figure FDA0002896497570000141
14. use of an organic compound according to any one of claims 1 to 13 in an organic electroluminescent device.
15. An organic electroluminescent device, wherein an electron transport layer and/or a hole blocking layer of the organic electroluminescent device comprises the organic compound according to any one of claims 1 to 13;
optionally, the electron transport layer further comprises LiQ.
16. An electronic device comprising the organic electroluminescent element according to claim 15.
CN202110042643.2A 2020-09-28 2021-01-13 Organic compound, application thereof, organic electroluminescent device using organic compound and electronic device Withdrawn CN112724073A (en)

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