CN115322162B - Organic compound, organic electroluminescent device and electronic apparatus - Google Patents

Organic compound, organic electroluminescent device and electronic apparatus Download PDF

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CN115322162B
CN115322162B CN202211000585.8A CN202211000585A CN115322162B CN 115322162 B CN115322162 B CN 115322162B CN 202211000585 A CN202211000585 A CN 202211000585A CN 115322162 B CN115322162 B CN 115322162B
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CN115322162A (en
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徐先彬
杨雷
金荣国
聂齐齐
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Shaanxi Lighte Optoelectronics Material Co Ltd
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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Abstract

The application belongs to the field of organic luminescent materials, and particularly relates to an organic compound, an organic electroluminescent device and an electronic device. The structure of the organic compound is shown as a formula I, and the nitrogen-containing compound is used in an organic electroluminescent device, so that the performance of the device can be improved.

Description

Organic compound, organic electroluminescent device and electronic apparatus
Technical Field
The application belongs to the technical field of organic luminescent materials, and particularly provides an organic compound, an organic electroluminescent device comprising the organic compound and an electronic device.
Background
Along with the development of electronic technology and the progress of material science, the application range of electronic components for realizing electroluminescence or photoelectric conversion is becoming wider and wider. In recent years, organic electroluminescent devices (OLEDs) are increasingly coming into the field of view as a new generation of display technology. Such electronic components typically include oppositely disposed cathodes and anodes, and a functional layer disposed between the cathodes and anodes. The functional layer is composed of a plurality of organic or inorganic film layers and generally includes an energy conversion layer, a hole transport layer between the energy conversion layer and the anode, and an electron transport layer between the energy conversion layer and the cathode. When voltage is applied to the cathode and the anode, the two electrodes generate electric fields, electrons on the cathode side move to the light-emitting layer under the action of the electric fields, electrons on the anode side also move to the light-emitting layer, the two electrodes 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 emits light outwards.
At present, the organic electroluminescent device still has the problem of poor performance, and particularly how to improve the service life of the device under the condition of ensuring that the device has lower driving voltage and higher luminous efficiency is still a problem to be solved.
Disclosure of Invention
In view of the foregoing problems of the prior art, it is an object of the present application to provide an organic compound, and an organic electroluminescent device and an electronic apparatus including the same. The organic compound is used in organic electroluminescent device and can raise the performance of the device.
In order to achieve the above object, a first aspect of the present application provides an organic compound having a structure as shown in formula I:
in the formula I, R 1 And R is 2 The same or different and are each independently selected from hydrogen or methyl; n is selected from 1 or 2;
x is selected from C (R) 5 R 6 ) O or S; r is R 5 And R is 6 Identical or different and each is independentIs selected from alkyl with 1-10 carbon atoms and aryl with 6-20 carbon atoms, optionally R 5 And R is 6 Are mutually connected to form a saturated or unsaturated 5-15 membered ring;
R 0 represents hydrogen orR represents hydrogen or->
L、L 1 、L 2 、L a The same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 25 carbon atoms;
Ar 1 、Ar 2 、Ar a The same or different and are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
L、L 1 、L 2 、L a 、Ar 1 、Ar 2 and Ar is a group a Substituent of (2) and R 3 And R is 4 The two groups are identical or different and are each independently selected from deuterium, cyano, halogen groups, alkyl groups with 1 to 10 carbon atoms, halogenated alkyl groups with 1 to 10 carbon atoms, deuterated alkyl groups with 1 to 10 carbon atoms, trialkyl silicon groups with 3 to 12 carbon atoms, triphenyl silicon groups, aryl groups with 6 to 18 carbon atoms, heteroaryl groups with 3 to 15 carbon atoms and cycloalkyl groups with 3 to 10 carbon atoms; optionally, any two adjacent substituents form a saturated or unsaturated 3-to 15-membered ring;
n 3 r represents 3 Is selected from 0, 1 or 2, when n 3 When the number is 2, each R 3 The same or different; n is n 4 R represents 4 Is selected from 0, 1, 2 or 3, when n 2 When the number is greater than 1, each R 4 The same or different;
het represents a nitrogen-containing heteroarylene group having 2 to 15 carbon atoms.
A second aspect of the present application provides an organic electroluminescent device, including an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode; wherein the functional layer comprises the organic compound according to the first aspect of the present application.
A third aspect of the present application provides an electronic device comprising an organic electroluminescent device as described in the second aspect of the present application.
The organic compounds of the present application can significantly enhance the electron transport properties of the organic compounds of the present application. When the compound is used as a main material, the carrier balance in the light-emitting layer can be improved, the carrier recombination region can be widened, the exciton generation and utilization efficiency can be improved, and the light-emitting efficiency and the service life of the device can be improved.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment 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 light emitting layer; 340. an electron transport layer; 350. an electron injection layer; 400. an electronic device.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Example embodiments will now be described more fully with reference to the accompanying drawings. However, the exemplary embodiments may be embodied in many 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 present application.
In this application, the descriptions used herein of the manner in which each … … is independently "and" … … is independently "and" … … is 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, "Wherein each q is independently 0, 1, 2 or 3, and each R "is independently selected from hydrogen, deuterium, fluorine, chlorine", 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 this application, the terms "optional," "optionally," and "optionally" mean that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where the event or circumstance occurs or does not. For example, "optionally, any two adjacent substituents form a ring" means that any two substituents may form a ring but do not necessarily form a ring, including: a scenario in which two adjacent substituents form a ring and a scenario in which two adjacent substituents do not form a ring.
In the present application, such terms as "substituted or unsubstituted" mean that the functional group described later in the term may or may not have a substituent (hereinafter, for convenience of description, substituents are collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl or unsubstituted aryl having a substituent Rc. Wherein the substituent Rc may be, for example, deuterium, a halogen group, cyano, heteroaryl, aryl, alkyl, haloalkyl, cycloalkyl, trialkylsilyl, etc. In the present application, the "substituted" functional group may be substituted with 1 or 2 or more of the above Rc; when two substituents Rc are attached to the same atom, the two substituents Rc may be present independently or attached to each other to form a ring with the atom; when two adjacent substituents Rc are present on a functional group, the adjacent two substituents Rc may be present independently or fused to the functional group to which they are attached to form a ring.
In the present application, "any two adjacent substituents form a saturated or unsaturated ring having 3 to 15 carbon atoms", the saturated ring formed may be cyclopentane, for exampleCyclohexane->The unsaturated ring formed may be, for example, a benzene ring, naphthalene ring or fluorene ring +.>
In the present application, the number of carbon atoms of a substituted or unsubstituted functional group refers to all the numbers of carbon atoms. For example, if L 1 Is a substituted arylene group having 12 carbon atoms, then the arylene group and all of the substituents thereon have 12 carbon atoms. For another example: ar (Ar) 1 Is thatThe number of carbon atoms is 10; l is->The number of carbon atoms is 12.
In this application, aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aryl group may be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group, in other words, the aryl group may be a monocyclic aryl group, a condensed ring 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 conjugateA group, two or more fused ring aryl groups conjugated through carbon-carbon bonds. That is, two or more aromatic groups conjugated through carbon-carbon bonds may also be considered aryl groups herein unless otherwise indicated. Among them, the condensed ring aryl group may include, for example, a bicyclic condensed aryl group (e.g., naphthyl group), a tricyclic condensed aryl group (e.g., phenanthryl group, fluorenyl group, anthracenyl group), and the like. The aryl group does not contain hetero atoms such as B, N, O, S, P, se, si and the like. In the present application, biphenyl and fluorenyl are both regarded as aryl groups. Examples of aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, biphenyl, terphenyl, benzo [9,10 ] ]Phenanthryl, pyrenyl, benzofluoranthenyl,A base, etc.
In the present application, a 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, a halogen group, cyano, aryl, heteroaryl, trialkylsilyl, haloalkyl, alkyl, cycloalkyl, and 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 its substituents being 18. In addition, in this application, the fluorenyl group may be substituted, and when two substituents are present, the two substituents may combine with each other to form a spiro structure. Specific examples of substituted fluorenyl groups include but are not limited to,
in the present application, reference to arylene means a divalent or trivalent or higher valent group formed by further loss of one hydrogen atom from the aryl group.
In the present application, the number of carbon atoms of the substituted or unsubstituted aryl group may be 6 to 30. Specifically, the number of carbon atoms of the substituted or unsubstituted aryl group may be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30.
In the present application heteroaryl means a monovalent aromatic ring or derivative thereof containing 1, 2, 3, 4, 5 or more heteroatoms in the ring, which may be one or more of B, O, N, P, si, se and S. 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, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, thiophenyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, and N-phenylcarbazolyl, N-pyridylcarbazolyl, N-methylcarbazolyl, and the like, without limitation thereto. Wherein thienyl, furyl, phenanthroline and the like are heteroaryl groups of a single aromatic ring system type, and N-phenylcarbazolyl is heteroaryl groups of a polycyclic ring system type which are connected in a conjugated manner through carbon-carbon bonds. In the present application, reference to heteroarylene refers to a divalent or higher radical formed by further loss of one or more hydrogen atoms from the heteroaryl group.
In this application, nitrogen-containing heteroaryl refers to heteroaryl groups that include an N atom in the ring.
In the present application, a substituted heteroaryl group may be one in which one or more hydrogen atoms in the heteroaryl group are substituted with groups such as deuterium, a halogen group, cyano, aryl, heteroaryl, trialkylsilyl, alkyl, cycloalkyl, 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.
In the present application, the number of carbon atoms of the substituted or unsubstituted heteroaryl group may be 3 to 30. For example, the number of carbon atoms of the substituted or unsubstituted heteroaryl group can be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and the like.
In the present application, non-positional connection means a single bond extending from a ring systemIt 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, as shown in formula (f), 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):
As another example, as shown in the following formula (X '), the dibenzofuranyl group represented by the formula (X') is linked to the other position of the molecule through an unoositioned linkage extending from the middle of one benzene ring, and the meaning represented by this linkage includes any possible linkage as shown in the formulas (X '-1) to (X' -4).
An delocalized substituent in this application refers to a substituent attached by a single bond extending from the center of the ring system, which means that the substituent may be attached at any possible position in the ring system. For example, as shown in formula (Y) below, the substituent R' represented by formula (Y) is attached to the quinoline ring via an unoositioned bond, which means that it includes any of the possible linkages shown in formulas (Y-1) to (Y-7):
in the present application, the number of carbon atoms of the alkyl group may be 1 to 10, specifically 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and the alkyl group may include a straight chain alkyl group and a branched chain alkyl group. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, 3, 7-dimethyloctyl, and the like.
In the present application, halogen groups may include fluorine, iodine, bromine, chlorine.
In the present application, the number of carbon atoms of the aryl group as a substituent may be 6 to 18, and the number of carbon atoms is specifically, for example, 6, 10, 12, 13, 14, 15, 16, 18, etc., and specific examples of the aryl group as a substituent include, but are not limited to, phenyl, naphthyl, biphenyl, phenanthryl, anthracenyl, fluorenyl, etc.
In the present application, the heteroaryl group as a substituent may have a carbon number of 3 to 15, and the carbon number is specifically, for example, 5, 8, 9, 10, 12, 13, 14, 15, etc., and specific examples of the heteroaryl group as a substituent include, but are not limited to, pyridyl, quinolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc.
In the present application, the number of carbon atoms of the trialkylsilyl group as a substituent may be 3 to 12, for example, 3, 6, 7, 8, 9, etc., and specific examples of the trialkylsilyl group include, but are not limited to, trimethylsilyl group, ethyldimethylsilyl group, triethylsilyl group, etc.
In the present application, the number of carbon atoms of the cycloalkyl group as a substituent may be 3 to 10, for example, 5, 6, 8 or 10, and specific examples of the cycloalkyl group include, but are not limited to, cyclopentyl, cyclohexyl, adamantyl, and the like.
In the present application, the number of carbon atoms of the haloalkyl group as a substituent may be 1 to 10. For example, the haloalkyl group may be a fluoroalkyl group having 1 to 4 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms. Specific examples of haloalkyl groups include, but are not limited to, trifluoromethyl.
In the present application, the deuterated alkyl group as a substituent may have 1 to 10 carbon atoms. For example, the deuterated alkyl group may be a deuterated alkyl group having 1 to 4 carbon atoms or a deuterated alkyl group having 1 to 5 carbon atoms. Specific examples of deuterated alkyl groups include, but are not limited to, tridentate methyl.
In a first aspect, the present application provides an organic compound having a structure according to formula I:
in the formula I, R 1 And R is 2 The same or different and are each independently selected from hydrogen or methyl; n is selected from 1 or 2;
x is selected from C (R) 5 R 6 ) O or S; r is R 5 And R is 6 Identical or different and are each independently selected from alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, optionally R 5 And R is 6 Are mutually connected to form a saturated or unsaturated 5-15 membered ring;
R 0 represents hydrogen orR represents hydrogen or->
L、L 1 、L 2 、L a The same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 25 carbon atoms;
Ar 1 、Ar 2 、Ar a Identical or different and are each independently selected from substituted or unsubstituted C6-C30 membersSubstituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;
L、L 1 、L 2 、L a 、Ar 1 、Ar 2 and Ar is a group a Substituent of (2) and R 3 And R is 4 The two groups are identical or different and are each independently selected from deuterium, cyano, halogen groups, alkyl groups with 1 to 10 carbon atoms, halogenated alkyl groups with 1 to 10 carbon atoms, deuterated alkyl groups with 1 to 10 carbon atoms, trialkyl silicon groups with 3 to 12 carbon atoms, triphenyl silicon groups, aryl groups with 6 to 18 carbon atoms, heteroaryl groups with 3 to 15 carbon atoms and cycloalkyl groups with 3 to 10 carbon atoms; optionally, any two adjacent substituents form a saturated or unsaturated 3-to 15-membered ring;
n 3 r represents 3 Is selected from 0, 1 or 2, when n 3 When the number is 2, each R 3 The same or different; n is n 4 R represents 4 Is selected from 0, 1, 2 or 3, when n 2 When the number is greater than 1, each R 4 The same or different;
het represents a nitrogen-containing heteroarylene group having 2 to 15 carbon atoms.
In the present application, when n is 1, the structure of formula I is specifically as follows:
when n is 2, the structure of formula I is specifically as follows:
in this structure, two R 1 And may be the same or different, two R' s 2 May be the same or different.
In a preferred embodiment, R 1 And R is 2 Are all hydrogen. Namely, the structure of the formula I is shown as a formula A or a formula B:
preferably, the structure of the organic compound is shown as a formula B, and X is O or S, so that the service life of the organic electroluminescent device can be further prolonged.
In the present application, the nitrogen-containing heteroarylene group represented by Het is an electron-deficient heteroaryl group. Optionally, the nitrogen-containing heteroarylene is a 6-14 membered nitrogen-containing heteroarylene. In one embodiment, the nitrogen-containing heteroarylene group includes at least two N atoms, for example, two N atoms or three N atoms.
Alternatively, het is selected from the group consisting of triazinylene, pyrimidinylene, quinolinylene, quinoxalinylene, isoquinolylene, quinazolinylene, and:
the triazinylene, pyrimidinylene, quinolinylene, quinoxalinylene, isoquinolinyl and quinazolinylene each have three connecting bonds, and the three connecting bonds are respectively connected to L, L 1 And R is 0 . For example, the triazinylene group has the structureThree connecting bonds in this structure +.>Respectively connected to L, L 1 And R is 0 。
Alternatively, the process may be carried out in a single-stage,selected from the group consisting of:
wherein->Represents a bond to L, absentWhen R is represented by 0 H.
In some embodiments, the structure of the organic compound is selected from the group consisting of:
in the present application, when R is H, R 4 R may be substituted or unsubstituted. For example, when the organic compound has a structure represented by the following formulas 1 to 6 (R is H), and n 3 Is 0, R 4 Deuterium, n 4 At 3, in formulae 1 to 6Is that
Alternatively, R 3 And R is 4 And are the same or different and are each independently selected from deuterium, fluorine, cyano, alkyl having 1 to 5 carbon atoms, fluoroalkyl having 1 to 5 carbon atoms, trialkylsilyl having 3 to 7 carbon atoms, aryl having 6 to 12 carbon atoms, and heteroaryl having 5 to 12 carbon atoms. R is R 3 And R is 4 Specific examples of (c) include, but are not limited to, deuterium, fluorine, cyano, methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, tridentate methyl, trimethylsilyl, phenyl or naphthyl.
Alternatively, R 5 And R is 6 And are identical or different and are each independently selected from alkyl groups having 1 to 4 carbon atoms (for example methyl) or phenyl groups, optionally,R 5 and R is 6 Are linked to each other to form a cyclopentane, cyclohexane or fluorene ring.
Optionally L, L 1 、L 2 And L a And are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 15 carbon atoms. For example L, L 1 、L 2 And L a And may each be independently selected from a single bond, a substituted or unsubstituted arylene group having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms.
Optionally L, L 1 、L 2 And L a And are each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, and a substituted or unsubstituted carbazole group.
Further optionally, L, L 1 、L 2 And L a And are the same or different and are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group.
Optionally L, L 1 、L 2 And L a The substituents in (a) are each independently selected from deuterium, fluorine, cyano, alkyl having 1 to 4 carbon atoms, fluoroalkyl having 1 to 4 carbon atoms, deuteroalkyl having 1 to 4 carbon atoms, trialkylsilyl having 3 to 7 carbon atoms, and aryl having 6 to 12 carbon atoms.
Optionally L, L 1 、L 2 And L a Each substituent of (a) is independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, tridentate methyl, trimethylsilyl, phenyl or naphthyl.
In a specific embodiment, L, L 1 、L 2 And L a Identical or different and are each independently selected from the group consisting of single bonds and:
alternatively, ar 1 、Ar 2 And Ar is a group a And are the same or different and are each independently selected from a substituted or unsubstituted aryl group having 6 to 25 carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 25 carbon atoms. For example, ar 1 、Ar 2 And Ar is a group a May each be independently selected from: substituted or unsubstituted aryl groups having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 carbon atoms, and substituted or unsubstituted heteroaryl groups having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
Alternatively, ar 1 、Ar 2 And Ar is a group a And are each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, and substituted or unsubstituted benzoxazolyl.
Alternatively, ar 1 、Ar 2 And Ar is a group a Each substituent of (a) is independently selected from deuterium, fluorine, cyano, alkyl having 1 to 5 carbon atoms, fluoroalkyl having 1 to 5 carbon atoms, deuteroalkyl having 1 to 5 carbon atoms, trialkylsilyl having 3 to 7 carbon atoms, aryl having 6 to 12 carbon atoms, and heteroaryl having 5 to 12 carbon atoms; ar (Ar) 1 、Ar 2 And Ar is a group a Optionally, any two adjacent substituents form a 5-15 membered saturated or unsaturated ring.
Alternatively, ar 1 、Ar 2 And Ar is a group a Each independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, tridentate methyl, trimethylsilyl, phenyl, naphthyl, pyridinyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl; ar (Ar) 1 、Ar 2 And Ar is a group a Optionally, any two adjacent substituents form a benzene ring, naphthalene ring, cyclopentane, cyclohexane or fluorene ring.
In one embodiment, ar 1 And Ar is a group 2 And are each independently selected from the group consisting of substituted or unsubstituted groups Z, wherein unsubstituted groups Z are selected from the group consisting of:
the substituted group Z has one or more than two substituents, and each substituent is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tertiary butyl, phenyl, trifluoromethyl, tridentate methyl, trimethylsilyl, phenyl or naphthyl; when the number of substituents is greater than 1, each substituent may be the same or different.
Alternatively, ar 1 And Ar is a group 2 Each independently selected from the group consisting of:
alternatively, ar 1 And Ar is a group 2 Each independently selected from the group consisting of:
in one embodiment of the present invention, in one embodiment,identical or different and are each independently selected from the group consisting of:
in one embodiment, ar a Selected from the group consisting of substituted or unsubstituted groups V, wherein unsubstituted groups V are selected from the group consisting of:
the substituted group V has one or more than two substituents, and each substituent is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tertiary butyl, phenyl, trifluoromethyl, tridentate methyl, trimethylsilyl or phenyl; when the number of substituents is greater than 1, each substituent may be the same or different.
Alternatively, the process may be carried out in a single-stage,selected from the group consisting of:
alternatively, the process may be carried out in a single-stage,selected from the group consisting of:
in one embodiment of the present invention, in one embodiment,selected from the group consisting of:
optionally, the organic compound is selected from the group consisting of:
the synthetic method of the organic compound provided in the present application is not particularly limited, and a person skilled in the art can determine a suitable synthetic method from the preparation method provided in the organic compound of the present application in combination with the synthesis example section. In other words, the synthesis examples section of the present invention illustratively provides a process for the preparation of organic compounds using starting materials which are commercially available or which are well known in the art. All organic compounds provided herein can be obtained by one skilled in the art from these exemplary preparation methods, and all specific preparation methods for preparing the organic compounds are not described in detail herein, and should not be construed as limiting the present application.
A second aspect of the present application provides an organic electroluminescent device comprising an anode, a cathode, and a functional layer disposed between the anode and the cathode, wherein the functional layer may contain the organic compound of the first aspect of the present application.
The organic compound provided by the application can be used for forming at least one organic film layer in the functional layers so as to improve the service life and other characteristics of the organic electroluminescent device.
Optionally, the functional layer comprises an organic light emitting layer comprising an organic compound provided herein.
Alternatively, the organic electroluminescent device may be a green device, a red device, or a blue device.
Preferably, the organic electroluminescent device is a red organic electroluminescent device or a green organic electroluminescent device.
According to one embodiment, the organic electroluminescent device includes an anode 100, a hole transport layer 320, an organic light emitting layer 330 as an energy conversion layer, an electron transport layer 340, and a cathode 200, which are sequentially stacked. The organic compound provided by the application can be applied to the organic light-emitting layer 330 of the organic electroluminescent device to effectively improve the performance of the organic electroluminescent device.
Alternatively, the organic light emitting layer 330 includes a host material and a guest material, and the hole injected into the organic light emitting layer 330 and the electron injected into the organic light emitting layer 330 may be recombined in the organic light emitting layer 330 to form an exciton, which transfers energy to the host material, which transfers energy to the guest material, thereby enabling the guest material to emit light. The host material may comprise an organic compound of the present application.
The guest material of the organic light emitting layer 330 may be selected with reference to the related art, and may be selected from iridium (III) organometallic complexes, platinum (II) organometallic complexes, ruthenium (II) complexes, for example. Specifically, the guest material may be selected from at least one of the following compounds:
in a specific embodiment, the guest material is D-6, i.e., ir (piq) 2 (dpm). In another specific embodiment, the guest material is D-7, ir (3 mppy) 3 。
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, e.g. such as ZnO, al or SnO 2 Sb; or conductive polymers, such as poly (3-methylthiophene), 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.
In this application, the material of the hole transport layer 320 may be selected from phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, benzidine type triarylamines, styrene amine type triarylamines, diamine type triarylamines, or other types of materials, and those skilled in the art can select them with reference to the prior art. For example, the hole transport layer material is selected from the group consisting of:
in this application, the hole transport layer 320 may have a one-layer or two-layer structure. Alternatively, as shown in fig. 1, the hole transport layer 320 includes a first hole transport layer 321 and a second hole transport layer 322 that are stacked, wherein the first hole transport layer 321 is closer to the anode 100 than the second hole transport layer 322. In a specific embodiment, the first hole transport layer 321 is comprised of HT-5 (i.e., α -NPD) and the second hole transport layer 322 is comprised of HT-6.
In the present application, 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, which may generally include a metal complex and/or a nitrogen-containing heterocyclic derivative, where the metal complex material may be selected from LiQ, alq, for example 3 、Bepq 2 Etc.; the nitrogen-containing heterocyclic derivative may be an aromatic ring having a nitrogen-containing six-membered ring or five-membered ring skeleton, a condensed aromatic ring having a nitrogen-containing six-membered ring or five-membered ring skeleton, or the like, and specific examples include, but are not limited to, 1, 10-phenanthroline-based compounds such as BCP, bphen, NBphen, DBimiBphen, bimiBphen, or compounds having the structures shown below. In a specific embodiment, the electron transport layer 340 comprises LiQ and ET-1.
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 magnesium and silver is preferably included as a cathode.
Optionally, as shown in fig. 1, a hole injection layer 310 is further disposed between the anode 100 and the first hole transport layer 321 to enhance the ability to inject holes into the first hole transport layer 321. The hole injection layer 310 may be a benzidine derivative, a starburst arylamine compound, a phthalocyanine derivative, or other materials, which are not particularly limited in this application. For example, hole injection layer 310 is selected from the group consisting of:
in a specific embodiment, the material of hole injection layer 310 is HAT-CN.
Optionally, as shown in fig. 1, an electron injection layer 350 is further provided between the cathode 200 and the electron transport layer 340 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. For example, the material of the electron injection layer 350 may be selected from LiF, naCl, csF, li 2 O、BaO、LiQ、NaCl、CsF、Cs 2 CO 3 One or more of Na, li, ca, al, yb. In a specific embodiment, the material of the electron injection layer 350 may include LiQ or Yb.
In a third aspect, the present application provides an electronic device comprising the organic electroluminescent device described above.
As shown in fig. 2, the electronic device is an electronic device 400, and the electronic device 400 may be a display device, a lighting device, an optical communication device, or other types of electronic devices, including, but not limited to, a computer screen, a mobile phone screen, a television, an electronic paper, an emergency lighting device, an optical module, etc.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way. Compounds for the synthesis are not mentioned as commercially available starting products.
1. Synthesis of Sub-aX
The synthesis of each Sub-aX is illustrated with Sub-a 1.
3-bromo-5, 8-tetramethyl-5, 6,7, 8-tetrahydronaphthalen-2-ol (14.16 g,50 mmol), 4-chloro-2-fluorophenylboronic acid (9.59 g,55 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 0.58g,0.5 mmol), anhydrous potassium carbonate (13.82 g,100 mmol), toluene (140 mL), anhydrous ethanol (35 mL) and deionized water (35 mL), stirring and heating were turned on, and the temperature was raised to reflux for 16h. After the system was cooled to room temperature, it was extracted with methylene chloride (100 mL. Times.3 times), and the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to give a crude product. Purification by silica gel column chromatography using n-heptane as the mobile phase afforded Sub-a1 (7.16 g, 43% yield) as a white solid.
The other Sub-aX listed in Table 1 was synthesized with reference to the synthesis method of Sub-a1, except that reactant A was used in place of 3-bromo-5, 8-tetramethyl-5, 6,7, 8-tetrahydronaphthalene-2-ol and reactant B was used in place of 4-chloro-2-fluorobenzeneboronic acid.
TABLE 1
2. Synthesis of Sub-bX
The synthesis of each Sub-bX is illustrated by Sub-b 1.
To a 250mL three-necked flask, sub-a1 (16.64 g,50 mmol), cesium carbonate (32.58 g,100 mmol) and dimethyl sulfoxide (DMSO, 160 mL) were added under nitrogen atmosphere, stirring and heating were turned on, and the temperature was raised to 80℃for reaction for 4 hours. After the system was cooled to room temperature, it was extracted with methylene chloride (100 mL. Times.3 times), and the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to give a crude product. Purification by silica gel column chromatography using n-heptane as a mobile phase afforded Sub-b1 (13.92 g, 89% yield) as a white solid.
The other Sub-bX listed in Table 2 was synthesized with reference to the synthesis method of Sub-b1, except that reactant C was substituted for Sub-a1.
TABLE 2
3. Synthesis of Sub-cX
The synthesis of each Sub-cX is illustrated with Sub-c1 as an example.
Sub-a9 (15 g,43.6 mmol) is added into a 10L three-mouth bottle under nitrogen atmosphere, heating is started to melt, sublimed sulfur (25.8 g,100.5 mmol) is added, at the moment, the system is yellow, heating is continued to 115-120 ℃, aluminum trichloride (0.35 g,2.6 mmol) is added in batches, in the process of adding aluminum trichloride, the system gradually turns black, a large amount of hydrogen sulfide gas is discharged, after the aluminum trichloride is added, the temperature is kept for 4 hours, the reaction starts to slowly heat up to 200-210 ℃, after the reaction is carried out for 4 hours, the reaction solution is poured into a 250mL single-mouth bottle while the reaction solution is still hot, the vacuum degree of an oil pump is reduced to about 40Pa, 8.2g white crystals are obtained, the solid is dissolved by absolute ethyl alcohol, and crystallized at-20 ℃ for two times, and Sub-c1 (7.3 g, yield 45%) is obtained).
The other Sub-cX listed in Table 3 were synthesized with reference to the synthesis of Sub-c1, except that reactant D was substituted for Sub-a9.
TABLE 3 Table 3
4. Synthesis of Sub-d1
In a 250mL three-necked flask, sub-a11 (20.78 g,55 mmol) was dissolved in 50mL THF, cooled to-78deg.C, then n-BuLi (22 mL,2.5M,55 mmol) was added dropwise, after 4h of reaction, benzophenone (10 g,55 mmol) was added, after 30min of incubation, the reaction was warmed to room temperature for 30min, quenched with methanol, and the solvent was removed under reduced pressure. Glacial acetic acid (100 mL) and hydrochloric acid (25 mL) were then added, the mixture was refluxed for 24h, cooled to room temperature, the reaction solution was washed with water to neutrality, and the precipitate was filtered and dried to give Sub-d1 (15.87 g, yield 62.3%).
5. Synthesis of Sub-e 1:
in a 250mL three-necked flask, 2, 5-dichloro-2, 5-dimethylhexane (10 g,54.6 mmol) was dissolved in 50mL Dichloroethane (DCE), and then the reaction solution was cooled to 0deg.C and AlCl was added 3 (7.3 g,54.6 mmol) and 2-bromo-9, 9-dimethyl-9H-fluorene (14.9 g,54.6 mmol) were added dropwise to a solution of DCE (50 mL) under nitrogen atmosphere, and after 30min of reaction, the temperature of the reaction solution was raised to 80℃for 12H. Thereafter, the mixture was cooled to room temperature, and ice (100 g) and concentrated hydrochloric acid (20 mL) were added thereto and stirred for 20 minutes. The reaction solution was extracted three times with methylene chloride, dried over anhydrous magnesium sulfate, and then passed through a silica gel column to give a crude product, which was finally recrystallized using methylene chloride/methanol to give Sub-e1 (16.5 g, yield 78.6%).
6. Synthesis of Sub-fX
The synthesis of each Sub-fX is illustrated with Sub-f 1.
Sub-b1 (15.64 g,50 mmol), bisboronic acid pinacol ester (15.24 g,60 mmol), potassium acetate (10.8 g,110 mmol) and 1, 4-dioxane (160 mL) are added into a 500mL three-necked flask in sequence under nitrogen atmosphere, stirring and heating are started, and the system is heated to 40 ℃ and is quickly heatedAdding tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 0.46g,0.5 mmol) and 2-dicyclohexylphosphine-2 ',4',6' triisopropylbiphenyl (XPhos, 0.48g,1 mmol), the reaction was continued to warm to reflux and stirred overnight. After the system is cooled to room temperature, 200mL of water is added into the system, the mixture is stirred for 30min, the pressure is reduced, the filtration is carried out, the filter cake is washed to be neutral by deionized water, and then 100mL of absolute ethyl alcohol is used for leaching, so that gray solid is obtained; the crude product was slurried once with n-heptane, purified by 200mL of toluene, passed through a silica gel column, the catalyst removed, and concentrated to give Sub-f1 (15.36 g, 76% yield) as a white solid.
The other Sub-fX listed in Table 4 were synthesized with reference to the synthesis method of Sub-f1, except that reactant E was substituted for Sub-b1.
TABLE 4 Table 4
7. Synthesis of Sub-gX
The synthesis of each Sub-gX is illustrated with Sub-g 1.
2, 4-dichloro-6-phenyl-1, 3, 5-triazine (16.95 g,75 mmol), dibenzothiophene-1-boronic acid (11.40 g,50 mmol), tetrakis (triphenylphosphine) palladium (0.58 g,0.5 mmol), tetrabutylammonium bromide (1.61 g,5 mmol), anhydrous potassium carbonate (13.82 g,100 mmol), toluene (170 mL) and deionized water (45 mL) were sequentially added to a 500mL three-necked flask under nitrogen atmosphere, and the mixture was stirred and heated to 65-70℃for 16h. After the system was cooled to room temperature, it was extracted with methylene chloride (100 mL. Times.3 times), and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to give a crude product. The crude product was recrystallized from toluene to give Sub-g1 (12.15 g, yield 65%) as a white solid.
The other Sub-gX listed in Table 5 was synthesized with reference to the synthesis of Sub-G1, except that reactant F was used instead of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine and reactant G was used instead of dibenzothiophene-1 boronic acid.
TABLE 5
8. Synthesis of Sub-hX
The synthesis of each Sub-hX is illustrated by Sub-h 1:
to a 500mL three-necked flask, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (13.38 g,50 mmol), dibenzothiophene-1-boronic acid (11.35 g,55 mmol), tetrakis (triphenylphosphine) palladium (0.58 g,0.5 mmol), tetrabutylammonium bromide (1.61 g,5 mmol), anhydrous potassium carbonate (13.82 g,100 mmol), toluene (140 mL), tetrahydrofuran (35 mL) and deionized water (35 mL) were sequentially added under nitrogen atmosphere, stirring and heating were turned on, and the temperature was raised to reflux reaction for 16h. After the system was cooled to room temperature, it was extracted with methylene chloride (100 mL. Times.3 times), and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to give a crude product. The crude product was recrystallized from toluene to give Sub-h1 (16.15 g, yield 82%) as a white solid.
The other Sub-hX listed in Table 6 were synthesized with reference to the synthesis of Sub-H1, except that reactant H was substituted for 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and reactant J was substituted for dibenzothiophene-1 boronic acid.
TABLE 6
9. Synthesis of Sub-jX
The synthesis of each Sub-hX is illustrated with Sub-j 1:
to a 500mL three-necked flask, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (13.38 g,50 mmol), sub-f12 (24.13 g,55 mmol), tetrakis (triphenylphosphine) palladium 0.58g,0.5 mmol), tetrabutylammonium bromide (1.61 g,5 mmol), anhydrous potassium carbonate (13.82 g,100 mmol), toluene (240 mL), anhydrous ethanol (60 mL) and deionized water (60 mL) were sequentially added under nitrogen atmosphere, and stirring and heating were turned on, and the temperature was raised to reflux reaction for 16h. After the system was cooled to room temperature, it was extracted with methylene chloride (100 mL. Times.3 times), and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to give a crude product. The crude product was recrystallized from toluene to give Sub-j1 as a white solid (20.95 g, yield 77%).
The other Sub-jX listed in Table 7 was synthesized with reference to the synthesis of Sub-j1, except that reactant K was used in place of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine and reactant L was used in place of Sub-f12.
TABLE 7
10. Synthesis of Sub-kX
The synthesis of each Sub-kX is illustrated with Sub-k 1:
sub-b8 (21.55 g,55 mmol), 9H-carbazole (8.36 g,50 mmol), pd were added sequentially to a 500mL three-necked flask under nitrogen atmosphere 2 (dba) 3 (0.916 g,1 mmol), XPhos (0.95 g,2 mmol), sodium t-butoxide (9.61 g,100 mmol) and xylene (220 mL), warmed to reflux and stirred overnight; after the system is cooled to room temperature, pouring the reaction solution into 500mL of deionized water, fully stirring for 30min, carrying out suction filtration, leaching a filter cake to be neutral by using deionized water, and leaching by using absolute ethyl alcohol (200 mL) to remove water; after recrystallisation of the filter cake with toluene, sub-k1 (16.73 g, 70% yield) was finally obtained as a grey solid.
The other Sub-kX listed in Table 8 were synthesized with reference to the synthesis of Sub-k1, except that Sub-b8 was replaced with reactant M and 9H-carbazole was replaced with reactant N.
TABLE 8
11. Synthesis of Sub-mX
The synthesis of each Sub-mX is illustrated with Sub-m 1:
sub-j3 (23.95 g,50 mmol), bisboronic acid pinacol ester (15.24 g,60 mmol), potassium acetate (10.8 g,110 mmol) and 1, 4-dioxane (240 mL) are added into a 500mL three-necked flask in sequence under nitrogen atmosphere, stirring and heating are started, pd is added when the temperature of the system is raised to 40 DEG C 2 (dba) 3 (0.46 g,0.5 mmol) and XPhos (0.48 g,1 mmol) were continued to warm to reflux and the reaction was stirred overnight. After the system is cooled to room temperature, 500mL of water is added into the system, the mixture is fully stirred for 30min, the pressure is reduced, the filtration cake is washed to be neutral by deionized water, and then 100mL of absolute ethyl alcohol is used for leaching, so that gray solid is obtained; the crude product was slurried once with n-heptane, purified by 200mL of toluene, passed through a silica gel column, the catalyst removed, and concentrated to give Sub-m1 (19.11 g, 67% yield) as a white solid.
The other Sub-mX listed in Table 9 was synthesized with reference to the synthesis method of Sub-m1, except that reactant O was used instead of Sub-j3.
TABLE 9
Synthesis example 1
Synthesis of Compound 1:
sub-f4 (22.24 g,55 mmol), 2-chloro-4, 6-propertyish are added sequentially to a 500mL three-necked flask under nitrogen atmosphere Diphenyl-1, 3, 5-triazine (13.38 g,50 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 0.58g,0.5 mmol), tetrabutylammonium bromide (TBAB, 1.61g,5 mmol), anhydrous potassium carbonate (13.82 g,100 mmol), toluene (220 mL), tetrahydrofuran (55 mL) and deionized water (55 mL), stirring and heating were turned on, and the temperature was raised to reflux for 16h. After the system was cooled to room temperature, it was extracted with methylene chloride (100 mL. Times.3 times), and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to give a crude product. The crude product was recrystallized from toluene to give compound 1 (21.15 g, yield 83%) as a white solid, mass spectrum: m/z=510.3 [ m+h ]] + 。
Synthesis examples 2 to 71
The compounds listed in Table 10 were synthesized with reference to the synthesis method of compound 1, except that reactant P was substituted for Sub-f4, reactant Q was substituted for 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, and the main raw materials employed, the corresponding synthesized compounds, and the yields and mass spectrum characterization results thereof were shown in Table 10.
Table 10
Synthesis example 72
Synthesis of compound 676:
sub-j7 (32.21 g,50 mmol), 9H-carbazole (9.20 g,55 mmol), tris (dibenzylideneacetone) dipalladium (Pd) were added sequentially to a 500mL three-necked flask under nitrogen atmosphere 2 (dba) 3 0.916g,1 mmol), XPhos (0.95 g,2 mmol), sodium t-butoxide (9.61 g,100 mmol) and xylene (220 mL), warmed to reflux and stirred overnight; after the system is cooled to room temperature, pouring the reaction solution into 500mL of deionized water, fully stirring for 30min, carrying out suction filtration, leaching a filter cake to be neutral by using deionized water, and leaching by using absolute ethyl alcohol (200 mL) to remove water; after recrystallisation of the filter cake with toluene, a white solid is finally obtained, compound 676 (24.0 g, 62% yield); mass spectrometry: m/z=775.3 [ m+h ] ] + 。
Synthesis examples 73 to 75
The compounds listed in Table 11 were synthesized with reference to the synthesis of compound 676, except that reactant R was used in place of Sub-j7 and reactant S was used in place of Sub-j7, and the main starting materials employed, the corresponding synthesized compounds, and the yields and mass spectrum characterization results thereof were shown in Table 11.
TABLE 11
The nuclear magnetic data of some compounds are shown in table 12:
table 12
Example 1: red organic electroluminescent device
The anode pretreatment is carried out by the following steps: in the thickness of in turnThe ITO/Ag/ITO substrate is subjected to surface treatment by utilizing ultraviolet ozone and O2: N2 plasma to increase the work function of an anode, and the surface of the ITO substrate is cleaned by adopting an organic solvent to remove impurities and greasy dirt on the surface of the ITO substrate.
Vacuum vapor deposition of HAT-CN on a test substrate (anode) to form a film of thicknessIs then vacuum evaporated on the hole injection layer to form a-NPD with a thickness +.>Is provided.
Vacuum evaporation on first hole transport layerCompound HT-6 formed to a thickness ofIs provided.
Next, on the second hole transport layer, RH-P: compound 6:ir (piq) 2 (dpm) was mixed at 49%:49% to 2% of film thickness ratio, and forming a film of thickness Is provided.
On the organic light-emitting layer, mixing and evaporating the compounds ET-1 and LiQ in a weight ratio of 1:1 to formA thick Electron Transport Layer (ETL) on which Yb is vapor deposited to form a thickness +.>Then magnesium (Mg) and silver (Ag) are mixed at a vapor deposition rate of 1:9, and vacuum vapor deposited on the electron injection layer to form a film having a thickness +.>Is provided.
In addition, the thickness of the vacuum evaporation on the cathode isTo complete the manufacture of the red organic electroluminescent device.
Examples 2 to 60
An organic electroluminescent device was prepared by the same method as in example 1, except that the compound in table 13 (collectively referred to as "compound X") was used instead of the compound 6 in example 1, respectively, in the production of an organic light-emitting layer.
Comparative examples 1 to 5
An organic electroluminescent device was prepared by the same method as in example 1, except that compound a, compound B, compound C, compound D and compound E were used in place of compound 1 in example 1, respectively, in the fabrication of an organic light-emitting layer.
In the above examples and comparative examples, the main material structures employed were as follows:
performance test was performed on the red organic electroluminescent devices prepared in examples 1 to 60 and comparative examples 1 to 5, specifically at 10mA/cm 2 IVL performance of the device was tested under the conditions of T95 device lifetime at 20mA/cm 2 The test was conducted under the conditions of (2) and the test results are shown in Table 13.
TABLE 13
Example 61: preparation of green light organic electroluminescent device
The anode pretreatment is carried out by the following steps: in the thickness of in turnThe ITO/Ag/ITO substrate is subjected to surface treatment by utilizing ultraviolet ozone and O2: N2 plasma to increase the work function of an anode, and the surface of the ITO substrate is cleaned by adopting an organic solvent to remove impurities and greasy dirt on the surface of the ITO substrate.
Vacuum vapor deposition of HAT-CN on a test substrate (anode) to form a film of thicknessIs then vacuum evaporated on the hole injection layer to form a-NPD with a thickness +.>Is provided.
Vacuum evaporating compound HT-6 on the first hole transport layer to form a film having a thickness ofIs provided.
On the second hole transport layer, compound 1: GH-P: ir (3 mppy) 3 45%:45%: co-evaporation was performed at a film thickness ratio of 10% to give a film thickness ofGreen light organic light emitting layer of (a).
On the organic light-emitting layer, mixing and evaporating the compounds ET-1 and LiQ in a weight ratio of 1:1 to formA thick Electron Transport Layer (ETL) on which Yb is vapor deposited to form a thickness +. >Then magnesium (Mg) and silver (Ag) are mixed at a vapor deposition rate of 1:9, and vacuum vapor deposited on the electron injection layer to form a film having a thickness +.>Is provided.
In addition, the thickness of the vacuum evaporation on the cathode isCP-1 of (c), thus completingAnd (5) manufacturing the green organic electroluminescent device.
Examples 62 to 75
An organic electroluminescent device was produced by the same method as in example 61, except that the compound in table 14 below (collectively referred to as "compound X") was used instead of the compound 1 in example 61 when the light-emitting layer was produced.
Comparative examples 6 to 7
An organic electroluminescent device was manufactured by the same method as in example 61, except that compound F and compound G were used in place of compound 1 in example 61, respectively, when the light-emitting layer was manufactured.
The green organic electroluminescent devices prepared in examples 61 to 75 and comparative examples 6 to 7 were subjected to performance test, particularly at 10mA/cm 2 IVL performance of the device was tested under the conditions of T95 device lifetime at 20mA/cm 2 The test was conducted under the conditions of (2) and the test results are shown in Table 14.
TABLE 14
Referring to tables 13 and 14 above, it is understood that when the organic compound of the present application is used as a host material for an organic electroluminescent device, the efficiency is improved by at least 13.6% and the lifetime is improved by at least 16% when the organic compound is used as a red light host material; as green light main material, the efficiency is improved by at least 15.6%, and the service life is improved by at least 17.1%. The preferred embodiments of the present application have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.

Claims (10)

1. The organic compound is characterized in that the structure of the organic compound is shown as a formula I:
in the formula I, R 1 And R is 2 The same or different and are each independently selected from hydrogen or methyl; n is selected from 1 or 2;
x is selected from C (R) 5 R 6 ) O or S; r is R 5 And R is 6 The same or different and are each independently selected from alkyl groups having 1 to 4 carbon atoms or phenyl groups;
r represents hydrogen or
Selected from the group consisting of:
L、L 1 、L 2 and L a The same or different and are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group;
L、L 1 、L 2 and L a Each substituent of (a) is independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, tridentate methyl, trimethylsilyl, phenyl or naphthyl;
Ar 1 、Ar 2 and Ar is a group a Identical or different and are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstitutedSubstituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl;
Ar 1 、Ar 2 And Ar is a group a Each independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, tridentate methyl, trimethylsilyl, phenyl, naphthyl, pyridinyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl; ar (Ar) 1 、Ar 2 And Ar is a group a Optionally, any two adjacent substituents form a benzene ring, naphthalene ring, cyclopentane, cyclohexane or fluorene ring;
R 3 and R is 4 Identical or different and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, tridentate methyl, trimethylsilyl, phenyl or naphthyl;
n 3 r represents 3 Is selected from 0, 1 or 2, when n 3 When the number is 2, each R 3 The same or different; n is n 4 R represents 4 Is selected from 0, 1, 2 or 3, when n 4 When the number is greater than 1, each R 4 The same or different.
2. The organic compound according to claim 1, wherein the structure of the organic compound is selected from the group consisting of:
3. the organic compound according to claim 1, wherein Ar 1 And Ar is a group 2 Identical or different and each independentlySelected from the group consisting of substituted or unsubstituted groups Z, unsubstituted groups Z being selected from the group consisting of:
the substituted group Z has one or more than two substituents, and each substituent is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tertiary butyl, trifluoromethyl, trideuteromethyl, trimethylsilyl, phenyl or naphthyl; when the number of substituents is greater than 1, each substituent may be the same or different.
4. The organic compound according to claim 1, wherein Ar a Selected from the group consisting of substituted or unsubstituted groups V, unsubstituted groups V being selected from the group consisting of:
the substituted group V has one or more than two substituents, and each substituent is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tertiary butyl, trifluoromethyl, trideuteromethyl, trimethylsilyl or phenyl; when the number of substituents is greater than 1, each substituent may be the same or different.
5. The organic compound according to claim 1, wherein,identical or different and are each independently selected from the group consisting of:
6. the organic compound according to claim 5, wherein,selected from the group consisting of:
7. the organic compound according to claim 1, wherein the organic compound is selected from the group consisting of:
8. the organic electroluminescent device is 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 contains the organic compound according to any one of claims 1 to 7.
9. The organic electroluminescent device of claim 8, wherein the functional layer comprises an organic light-emitting layer comprising the organic compound.
10. An electronic device comprising the organic electroluminescent device as claimed in claim 8 or 9.
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CN113348171A (en) * 2019-11-29 2021-09-03 株式会社Lg化学 Compound and organic light-emitting element comprising same
CN113348172A (en) * 2019-11-29 2021-09-03 株式会社Lg化学 Compound and organic light emitting device including the same
KR20220109864A (en) * 2021-01-29 2022-08-05 주식회사 엘지화학 Compound, and organic light emitting device comprising same

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