CN114292278B

CN114292278B - Nitrogen-containing compound, organic electroluminescent device and electronic device

Info

Publication number: CN114292278B
Application number: CN202111385330.3A
Authority: CN
Inventors: 陈志伟; 王金平; 薛震
Original assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Current assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Priority date: 2021-09-24
Filing date: 2021-11-22
Publication date: 2023-05-23
Anticipated expiration: 2041-11-22
Also published as: CN114292278A

Abstract

The application belongs to the field of organic luminescent materials, and particularly relates to a nitrogen-containing compound, an organic electroluminescent device and an electronic device. The structure of the nitrogen-containing compound is shown as formula 1, and the nitrogen-containing compound is used in an organic electroluminescent device, so that the performance of the device can be improved.

Description

Nitrogen-containing compound, organic electroluminescent device and electronic device

Technical Field

The application belongs to the technical field of organic luminescent materials, and particularly provides a nitrogen-containing compound, an organic electroluminescent device comprising the same 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 a nitrogen-containing compound, and an organic electroluminescent device and an electronic apparatus including the same. The nitrogen-containing compound is used in an organic electroluminescent device, and can improve the performance of the device.

In order to achieve the above object, a first aspect of the present application provides a nitrogen-containing compound having a structure as shown in formula 1:

in formula 1, X ₁ ～X ₃ Identical or different and are each independently selected from C (H) or N, and at least one is N;

L、L ₁ and L ₂ The same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms;

Ar ₁ and Ar is a group ₂ The same or different and are each independently selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms and substituted or unsubstituted heteroaryl groups having 5 to 40 carbon atoms;

Ar ₁ 、Ar ₂ 、L、L ₁ and L ₂ The substituents in (a) are the same or different and are each independently selected from deuterium, halogen group, cyano, alkyl with 1-10 carbon atoms, haloalkyl with 1-10 carbon atoms, trialkylsilyl with 3-12 carbon atoms, aryl with 6-18 carbon atoms, heteroaryl with 5-18 carbon atoms and cycloalkyl with 3-10 carbon atoms; optionally in Ar ₁ 、Ar ₂ Any two adjacent substituents form a saturated or unsaturated ring having 3 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 a nitrogen-containing compound as described in 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.

In the nitrogen-containing compounds of the present application, 7-oxa-7H-benzo [ DE]Anthracene (A)

The structure formed by fusing indole at a specific position on the No. 5 and the No. 6 is taken as a mother nucleus, the mother nucleus structure has stronger conjugation effect, the bond energy between atoms is higher by combining O and N atoms contained in the mother nucleus, the whole mother nucleus has better hole transmission capability, and the electron infusion groups such as triazines and the like which lack electrons are further introduced into the N atoms in the mother nucleus, so that the compound has higher T ₁ The energy level can reduce charge accumulation caused by interface effect between the hole transport layer and the luminescent layer, and triazine groups and the parent nucleus have proper rotation angles in space, so that the stability of the compound can be improved. Therefore, the nitrogen-containing compound is used as a main material in the organic electroluminescent device, and can further improve the luminous efficiency and the service life of the device.

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, for example, cyclopentane

Cyclohexane->

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 that

The 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 conjugate, two or more condensed ring aryl groups connected by a carbon-carbon bond conjugate. 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, the arylene group refers to a divalent group formed by further losing one hydrogen atom of the aryl group.

In the present application, the number of carbon atoms of the substituted or unsubstituted aryl group may be 6 to 40. For example, 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, or the like.

In the present application, heteroaryl refers to a monovalent aromatic ring or derivative thereof containing 1,2, 3,4, 5 or more heteroatoms in the ring, which may be at least one 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, but are not limited to, 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, benzofuranyl, phenanthroline, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, and N-phenylcarbazolyl, N-pyridylcarbazolyl, N-methylcarbazolyl, and the like. 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 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 5 to 40. 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 system

It means that one end of the bond can be attached to any position in the ring system through which the bond extends, and the other end is attached to the remainder of the compound molecule. For example, as shown in the following formula (f), the naphthyl group represented by the formula (f) is linked to other positions of the molecule through two non-positional linkages penetrating through the bicyclic ring, and the meaning of the linkage includes any one of the possible linkages shown in the formulas (f-1) to (f-10).

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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 the following formula (Y), the substituent R' represented by the formula (Y) is linked to the quinoline ring through an unoositioned linkage, and the meaning represented by the same includes any one of possible linkages as shown in the formulae (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 such as 6, 10, 12, 13, 14, 15, 16, 18, etc., and specific examples of the aryl group include, but are not limited to, phenyl, naphthyl, biphenyl, phenanthryl, anthracenyl, fluorenyl, etc.

In the present application, the carbon number of the heteroaryl group as a substituent may be 5 to 18, and the carbon number is specifically, for example, 5, 8, 9,10, 12, 13, 14, 15, 18, etc., and specific examples of the heteroaryl group 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 5 carbon atoms. Specific examples of haloalkyl groups include, but are not limited to, trifluoromethyl.

In a first aspect, the present application provides a nitrogen-containing compound having a structure according to formula 1:

in formula 1, X ₁ ～X ₃ Identical or different and are each independently selected from C (H) or N, and X ₁ ～X ₃ At least one of which is N;

In the present application, X ₁ ～X ₃ One, two or three of which may be N atoms. In one embodiment, X ₁ ～X ₃ Two of which are N atoms and the remaining one is C (H), e.g. X ₁ And X ₃ Is N, X ₂ C (H); or X ₁ And X ₂ Is N, X ₃ C (H); or X ₂ And X ₃ Is N, X ₁ C (H). In another embodiment, X ₁ ～X ₃ Are all N atoms.

Alternatively, ar ₁ And Ar is a group ₂ And are the same or different and are each independently selected from a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms. For example, ar ₁ And Ar is a group ₂ 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, 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, 20 carbon atoms.

In a specific embodiment, ar ₁ Selected from substituted or unsubstituted aryl groups with 10-25 carbon atoms, substituted or unsubstituted heteroaryl groups with 12-20 carbon atoms, ar ₂ Selected from substituted or unsubstituted aryl groups having 6 to 20 carbon atoms and substituted or unsubstituted heteroaryl groups having 5 to 18 carbon atoms.

Alternatively, ar ₁ And Ar is a group ₂ 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, trialkylsilyl having 3 to 7 carbon atoms, aryl having 6 to 12 carbon atoms, heteroaryl having 5 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms; optionally in Ar ₁ 、Ar ₂ Any two adjacent substituents form a saturated or unsaturated ring with 5-15 carbon atoms. For example, ar ₁ And Ar is a group ₂ Specific examples of substituents in (a) include, but are not limited to, deuterium, fluoro, cyano, methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, trimethylsilyl, phenyl, naphthyl, biphenyl, pyridyl, quinolinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, cyclopentyl, cyclohexyl.

In some embodiments, ar ₁ And Ar is a group ₂ Identical or different and are each independently selected from substituted or unsubstituted phenyl groups, takenSubstituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthracenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, and substituted or unsubstituted carbazolyl.

Alternatively, ar ₁ 、Ar ₂ Each of the substituents is independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, trimethylsilyl, phenyl, naphthyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothienyl, carbazolyl, cyclopentyl, cyclohexyl; optionally Ar ₁ 、Ar ₂ Any two adjacent substituents form a benzene ring, cyclopentane, cyclohexane or fluorene ring.

In one embodiment, ar ₁ And Ar is a group ₂ Identical or different and are each independently selected from the group consisting of substituted or unsubstituted groups Z selected from the group consisting of:

the substituted group Z has one or more than two substituents, each substituent is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tertiary butyl, trifluoromethyl, trimethylsilyl, phenyl, naphthyl, biphenyl and pyridyl, and when the number of the substituents is more than 1, each substituent is the same or different.

Alternatively, ar ₁ Selected from the group consisting of:

in a specific embodiment, ar ₁ Selected from the group consisting of:

alternatively, ar ₂ Selected from the group consisting of:

in a specific embodiment, ar ₂ Selected from the group consisting of:

optionally L, L ₁ And L ₂ And are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 12 to 18 carbon atoms.

Also optionally, L, L ₁ And L ₂ 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, 18, 19, 20 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18 carbon atoms.

Optionally L, L ₁ And L ₂ The substituents in (a) 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. For example L, L ₁ And L ₂ The substituents of (a) may each be independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trimethylsilyl, phenyl, naphthyl, biphenyl, pyridinyl, quinolinyl, dibenzofuranyl, dibenzothiophenyl.

In some embodiments, L, L ₁ And L ₂ 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 phenanthrylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothienyl group, and a substituted or unsubstituted carbazolylene group.

Optionally L, L ₁ And L ₂ Each of the substituents is independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, trimethylsilyl, phenyl, naphthyl, biphenyl, pyridinyl, dibenzofuranyl, dibenzothiophenyl.

In one embodiment, L is selected from a single bond, a substituted or unsubstituted group V, the unsubstituted group 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, trimethylsilyl, phenyl and naphthyl; when the number of substituents is greater than 1, each substituent may be the same or different.

Optionally, L is selected from a single bond or the group consisting of:

further alternatively, L is selected from the group consisting of a single bond or:

in one embodiment, L ₁ And L ₂ Identical or different 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, L ₁ And L ₂ Each of the substituents in (a) is independently selected from deuterium, fluoro, cyano, methyl, isopropyl, t-butyl, trifluoromethyl or phenyl.

Alternatively, L ₁ And L ₂ Identical or different and are each independently selected from the group consisting of single bonds or:

in one embodiment, L is a single bond,

ar in (1) ₁ And L ₁ The total number of carbon atoms of not less than 10, preferably 10 to 30, for example, ar ₁ And L ₁ Is 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30.

In a preferred embodiment, ar ₁ Is a substituted or unsubstituted group Q, wherein the structure of the unsubstituted group Q is as follows:

y is selected from O, S, C (R) _a R _b ) N (Ar) or N, R _a And R is _b Each independently selected from hydrogen, methyl or phenyl; optionally R _a And R is _b Forming a cyclopentane, cyclohexane or fluorene ring with the commonly attached C atom; ar is an aryl group having 6 to 12 carbon atoms, such as phenyl, naphthyl, biphenyl;

the substituted group Q comprises one or more than two substituents, each substituent is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tertiary butyl, phenyl and naphthyl, and when the number of the substituents is more than 1, each substituent is the same or different.

Alternatively, L ₁ Is a single bond or phenylene.

Alternatively, ar ₁ Selected from the group consisting of:

in a preferred embodiment of the present invention,

selected from the group consisting of:

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in a further specific embodiment of the present invention,

selected from the group consisting of:

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optionally, the nitrogen-containing compound is selected from the group consisting of:

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the synthesis method of the provided nitrogen-containing compound is not particularly limited in this application, and a person skilled in the art can determine a suitable synthesis method from the preparation method provided in the synthesis example section in combination with the nitrogen-containing compound of this application. In other words, the synthesis examples section of the present invention illustratively provides a process for the preparation of nitrogen-containing compounds, using starting materials which are commercially available or are well known in the art. All of the nitrogen-containing compounds provided herein may be obtained by one skilled in the art from these exemplary methods of preparation, and all specific methods of preparation for such nitrogen-containing 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 nitrogen-containing compound of the first aspect of the present application.

The nitrogen-containing compound provided by the application can be used for forming at least one organic film layer in the functional layer 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 a nitrogen-containing compound provided herein.

Alternatively, the organic electroluminescent device may be a green device, a red device, or a blue device.

In a preferred embodiment, the organic electroluminescent device is a red light device.

According to one embodiment, the organic electroluminescent device may include 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 nitrogen-containing 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 a nitrogen-containing 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 RD-1, i.e., ir (piq) ₂ (acac)。

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:

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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-8 and the second hole transport layer 322 is comprised of HT-14.

Alternatively, the electron transport layer 340 may be a single layer structure or a multi-layer structure, and may include one or more electron transport materials, which may generally include metal complexes and/or nitrogen-containing heterocyclic derivatives, wherein the metal complex materials may be selected from, for example, liQ, alq 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 compounds such as BCP, bphen, NBphen, DBimiBphen, bimiBphen, or heteroaryl-containing anthracene compounds, triazines, or pyrimidines having the structures shown below. In a specific embodiment, the electron transport layer 340 comprises LiQ and BimiBphen.

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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 asMagnesium, 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 may be 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 may be selected from the group consisting of:

in a specific embodiment, the material of hole injection layer 310 is PPDN.

Optionally, as shown in fig. 1, an electron injection layer 350 may also be 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, etc. 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, for example, may include, but is not limited to, a computer screen, a mobile phone screen, a television, an electronic paper, an emergency lighting device, an optical module, and the like.

The invention is further illustrated by the following examples, which are not intended to be limiting in any way.

The compounds of the synthetic method are not mentioned in this application as commercially available starting products.

1. Synthesis of intermediate IM I

(1) After nitrogen was introduced into a three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser for 10 minutes (2L/min), raw material sub a-1 (105 mmol,14.69 g), raw material sub-1 (100 mmol,23.71 g), potassium carbonate (200 mmol,27.60 g), toluene (200 mL), ethanol (50 mL) and water (50 mL) were added, and stirring was started; the temperature is raised to 40 to 45 ℃, dichlorodi-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (0.1 mmol,0.07 g) is added, the temperature is continuously raised to 60 to 65 ℃ and the reaction is carried out for 2 hours. After the reaction solution was cooled to 25 ℃, the solution was separated, toluene (50 mL) was added to the aqueous phase for extraction, the organic phases were combined, washed with water for 2 times, the obtained organic phase was dried over anhydrous sodium sulfate, filtered, the organic phase was concentrated to dryness under negative pressure, ethanol (50 mL) was added, filtered, and dried to obtain intermediate IM I-1 (23.21 g, yield 92.0%).

(2) After nitrogen was introduced into a three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser for 10min (2L/min), intermediate IM I-1 (90 mmol,22.7 g) and THF (160 mL) were added, stirring was turned on, the temperature was lowered to-25 to-20℃and an n-hexane solution of n-butyllithium (108 mmol,54 mL) was added dropwise, the temperature was kept for 2h after the dropwise addition was completed, and 1, 2-dibromoethane (108 mmol,20.29 g) was added dropwise and the temperature was kept for 2h after the dropwise addition was completed. Water (100 mL) and methylene chloride (100 mL) were added, the solution was separated, the aqueous phase was extracted with 50mL of methylene chloride, the organic phases were combined, washed with water 2 times, dried over anhydrous sodium sulfate, filtered, the organic phase was concentrated to dryness, recrystallized from ethanol (100 mL), and dried to give intermediate IM I-2 (23.18 g, yield 77.8%).

(3) After introducing nitrogen gas into a three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser for 10 minutes (2L/min), IM I-2 (60 mmol,19.87 g) and methylene chloride (100 mL) were sequentially added, and stirring was started. Cooling to-5-0 ℃, dropwise adding boron tribromide (90 mmol,22.55 g), keeping the temperature for 3h after dropwise adding, adding water (100 mL), separating liquid, sequentially washing the organic phase with water for 2 times, adding anhydrous sodium sulfate into the organic phase for drying, filtering, concentrating the organic phase to dryness to obtain an intermediate IM I-3 (18.39 g, yield 96.6%).

(4) After nitrogen was introduced into a three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser for 10 minutes (2L/min), IM I-3 (50 mmol,15.86 g), DMF (90 mL) and cesium carbonate (100 mmol,32.58 g) were added in this order, and stirring was started. Heating to 90-100 ℃, preserving heat for 5h, adding water (100 mL) and dichloromethane (100 mL), separating liquid, extracting water phase with dichloromethane (50 mL), merging organic phases, washing for 2 times successively, drying the organic phases with anhydrous sodium sulfate, filtering, concentrating the organic phases to dryness, adding petroleum ether (100 mL) for recrystallization, and drying to obtain an intermediate IM I-4 (13.37 g, yield 90%).

(5) After nitrogen is introduced into a three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser for 10min (2L/min), IM I-4 (40 mmol,11.88 g), raw material sub c-1 (42 mmol,5.36 g), sodium tert-butoxide (80 mmol,7.68 g) and Pd are added in sequence ₂ (dba) ₃ (0.4 mmol,0.37 g), x-phos (1 mmol,0.48 g) and toluene (80 mL), stirring was turned on. Continuously replacing with nitrogen for 2 times, heating to 90-100 ℃ and preserving heat for 2 hours, adding water (50 mL), separating liquid, extracting the water phase with toluene (50 mL), combining organic phases, and continuously washing with water for 2 timesThe organic phase was added with anhydrous sodium sulfate, filtered, the organic phase concentrated to a residual 30mL, cooled to room temperature, filtered, and dried to give intermediate IM I-5 (11.00 g, 80% yield).

(6) After introducing nitrogen into a three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser for 10 minutes (2L/min), IM I-5 (30 mmol,10.31 g), cesium carbonate (60 mmol,19.55 g), tricyclohexylphosphine tetrafluoroborate (3 mmol,1.11 g), palladium acetate (1.5 mmol,0.34 g) and N, N-dimethylacetamide (80 mL) were sequentially added, and stirring was started. Heating to 130-140 ℃ and preserving heat for 10h, adding water (400 mL), filtering, passing the solid through a heat preservation column at 80-90 ℃ by using n-heptane, concentrating the column passing liquid until the residual liquid is 50mL, cooling to room temperature, filtering, drying to obtain an intermediate IM I (5.07 g, yield 55%).

2. Synthesis of Compounds

Synthesis example 1: synthesis of Compound 4

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Nitrogen (0.100L/min) is introduced into a three-necked flask equipped with a mechanical stirrer, a thermometer and a spherical condenser for 15min replacement, raw materials sub d-1 (11 mmol,3.78 g), intermediate IM I (10 mmol,3.07 g) and DMF (30 mL) are sequentially added, stirring is started, naH (12 mmol,2.88 g) is added in portions at room temperature, and the reaction is continued for 4h after the addition is completed. Water (20 mL) and dichloromethane (30 mL) were added, the solution was separated, and the aqueous phase was extracted 1 more times with dichloromethane (20 mL). The combined organic phases were washed with water 2 times, dried over anhydrous sodium sulfate, filtered, the organic phases concentrated to dryness, recrystallized by the addition of toluene (10 mL), filtered and dried to give compound 4 (5.23 g, yield 85%), ms m/z=615.2 [ m+h ]] ⁺ The method comprises the steps of carrying out a first treatment on the surface of the Nuclear magnetic data: ¹ H NMR(CDCl ₃ ,400MHz):δppm 8.55(d,1H),8.43-8.39(m,3H),8.26(d,1H),8.17(d,1H),8.01(d,1H),7.92(s,1H),7.83-7.78(m,4H),7.62-7.58(m,3H),7.53-7.47(m,7H),7.36(s,1H),7.28-7.24(m,3H)。

synthesis examples 2 to 20

The compounds listed in Table 1 were synthesized by the reference compound 4 method except that raw material A shown in Table 1 was used in place of sub d-1, and the synthesized compounds, their yields and mass spectrum characterization results are shown in Table 1.

TABLE 1

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3. Synthesis of intermediate IM-AX

Taking intermediate IM-A1 as an example, the synthesis of intermediate IM-AX is described:

after nitrogen is introduced into a three-neck flask equipped with a mechanical stirrer, a thermometer and a condenser tube for 10min (2L/min), raw materials of sub-e-1 (20 mmol,6.88 g), raw materials of sub-f-1 (21 mmol,3.29 g), potassium carbonate (60 mmol,8.28 g), toluene (60 mL), ethanol (20 mL) and water (20 mL) are added, stirring is started, the temperature is raised to 40-45 ℃, tetrakis (triphenylphosphine) palladium (0.2 mmol,0.23 g) is added, and the temperature is continuously raised to 60-65 ℃ for reaction for 8h. The reaction solution was cooled to 25 ℃, filtered and dried to give intermediate IM-A1 (7.14 g, yield 85.2%).

Other IM-AX were synthesized by the method described with reference to IM-A1, except that raw material B was used in place of sub-e-1, raw material C was used in place of sub-f-1, and the main raw materials used, the synthesized intermediates and their yields are shown in Table 2.

TABLE 2

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4. Synthesis of Compounds

Synthesis example 21: synthesis of Compound 133

A three-necked flask equipped with a mechanical stirrer, a thermometer and a spherical condenser was purged with nitrogen (0.100L/min) for 15min, and then IM-A1 (11 mmol,4.62 g), IM I (10 mmol,3.07 g), potassium carbonate (20 mmol,2.76 g), cuprous chloride (5 mmol,0.5 g) and DMF (40 mL) were added in this order, followed by stirring, heating to 130-135℃and reaction at a constant temperature for 12h. Water (20 mL) and dichloromethane (30 mL) were added, the solution was separated, and the aqueous phase was extracted 1 more times with dichloromethane (20 mL). The organic phases were combined and washed 2 times with water, dried over anhydrous sodium sulfate, passed through a silica gel column, the organic phases concentrated to dryness, recrystallized by adding toluene (15 mL), filtered and dried to give compound 133 (5.45 g, yield 79%), mass spectrum: m/z=691.2 [ m+h ]] ⁺ 。

Synthesis examples 22 to 40

The compounds listed in Table 3 were synthesized by the method described with reference to Compound 133 except that starting material D shown in Table 3 was used in place of IM-A1, and the synthesized compounds, their yields and mass spectrum characterization structures were as shown in Table 3.

TABLE 3 Table 3

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In addition, the nuclear magnetic data of compound 166 are: ¹ H NMR(CDCl ₃ ,400MHz):δppm 8.53(d,1H),8.27(s,1H),8.23(dd,2H),8.12(d,1H),8.03-7.99(m,4H),7.87-7.81(m,6H),7.78-7.73(m,5H),7.68-7.59(m,5H),7.38(s,1H),7.27-7.19(m,6H)。

organic electroluminescent device preparation and evaluation examples

Preparation of red organic electroluminescent device

Example 1

An organic electroluminescent device was prepared by the following procedure: the ITO thickness is equal to

Is cut into a size of 40mm (length) ×40mm (width) ×0.7mm (thickness), and a test substrate having a cathode, an anode and an insulating layer pattern is prepared by a photolithography process using ultraviolet ozone and O ₂ :N ₂ The plasma is used for surface treatment to increase the work function of the anode, and an organic solvent is used for cleaning the surface of the ITO substrate to remove impurities and greasy dirt on the surface of the ITO substrate.

Vacuum evaporating PPDN on experimental substrate (anode) to form thickness

Is formed by vacuum evaporation of HT-8 on the Hole Injection Layer (HIL) to form a layer having a thickness +.>

Is a first hole transport layer (HTL 1).

Evaporating HT-14 on the first hole transport layer (HTL 1) to form a layer having a thickness of

Is a second hole transport layer (HTL 2).

On the second hole transport layer, ir (piq) was doped simultaneously with Compound 4 as host material at a film thickness ratio of 100:3 ₂ (acac) formed to a thickness of

An organic light emitting layer (EML).

Mixing BimiBphen and LiQ at a weight ratio of 1:1, and evaporating on an organic light emitting layer (EML) to form

A thick Electron Transport Layer (ETL). Evaporating LiQ on the electron transport layer to form a film having a thickness +.>

Electron Injection Layer (EIL).

Mixing magnesium (Mg) and silver (Ag) at a vapor deposition rate of 1:9, vacuum evaporating on the electron injection layer to obtain a film with a thickness of

Is provided. In addition, a thickness of +.>

And forming a capping layer (CPL), thereby completing the manufacture of the organic light emitting device.

Example 2-example 40

An organic electroluminescent device was fabricated by the same method as in example 1, except that the compounds shown in table 4 were used as host materials instead of the compounds 4, respectively, when forming the organic light-emitting layers.

Comparative example 1-comparative example 4

An organic electroluminescent device was manufactured by the same method as in example 1, except that compound a, compound B, compound C, and compound D were used as host materials instead of compound 4, respectively, when forming an organic light-emitting layer.

In examples and comparative examples, the structural formulas of the main materials for preparing the organic electroluminescent device are as follows:

the organic electroluminescent devices prepared in examples and comparative examples were subjected to performance test in which the test was conducted at 10mA/cm ² The IVL performance of the device was analyzed under the conditions of 15mA/cm ² The T95 lifetime of the device was analyzed under the conditions and the test results are shown in table 4.

TABLE 4 Table 4

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As can be seen from the results of table 4, in the case where the color coordinates are equivalent, the organic electroluminescent devices prepared in examples 1 to 40 using the nitrogen-containing compounds of the present application as the light-emitting host materials have a further improved lifetime and light-emitting efficiency, particularly, the devices prepared in examples 1 to 40 have an improved lifetime by at least 11.1% and a current efficiency by at least 13.2% as compared with the devices prepared in comparative examples 1 to 4 using the compounds a to D as the light-emitting host materials, respectively, while maintaining the device driving voltage low. In addition, as is clear from examples 1 to 40, when the substituent on the triazine group in the compound structure of the present application includes a dibenzofive-membered ring structure, the prepared organic electroluminescent device has a longer service life.

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. In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further. Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the disclosure, which should also be considered as the disclosure of the invention.

Claims

1. A nitrogen-containing compound, characterized in that the structure of the nitrogen-containing compound is shown in formula 1:

l is selected from a single bond, a substituted or unsubstituted group V 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, cyano, fluorine, methyl, ethyl, isopropyl, tert-butyl and phenyl; when the number of the substituents is more than 1, each substituent is the same or different;

L ₁ and L ₂ Identical or different, andeach independently selected from a single bond, a substituted or unsubstituted phenylene group, L ₁ And L ₂ Each substituent of (a) is independently selected from deuterium, cyano, fluoro or phenyl;

Ar ₁ and Ar is a group ₂ Identical or different and are each independently selected from the group consisting of substituted or unsubstituted groups Z 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, tert-butyl and phenyl; when the number of substituents is greater than 1, each substituent may be the same or different.

2. The nitrogen-containing compound according to claim 1, wherein Ar ₁ Selected from the group consisting of:

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3. the nitrogen-containing compound according to claim 1, wherein Ar ₂ Selected from the group consisting of:

4. the nitrogen-containing compound of claim 1, wherein the nitrogen-containing compound is selected from the group consisting of:

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5. an organic electroluminescent device, comprising an anode and a cathode which are arranged oppositely, and a functional layer arranged between the anode and the cathode; the functional layer contains the nitrogen-containing compound according to any one of claims 1 to 4.

6. The organic electroluminescent device of claim 5, wherein the functional layer comprises an organic light-emitting layer comprising the nitrogen-containing compound.

7. An electronic device comprising the organic electroluminescent device as claimed in claim 5 or 6.