阅读说明：本技术 含氮化合物以及使用其的电子元件和电子装置 (Nitrogen-containing compound, and electronic element and electronic device using same ) 是由 陈志伟 薛震 王金平 于 2021-09-10 设计创作，主要内容包括：本申请属于有机材料技术领域,提供一种含氮化合物以及使用其的电子元件和电子装置。所述含氮化合物的结构如式I所示,其中,Ar-(1)、Ar-(2)分别独立地选自碳原子数为6-25的取代或未取代的芳基,L-(1)、L-(2)分别独立地选自单键、碳原子数为6-25的取代或未取代的亚芳基等,本申请的含氮化合物可以有效改善电子元件的性能。(The application belongs to the technical field of organic materials, and provides a nitrogen-containing compound, and an electronic element and an electronic device using the nitrogen-containing compound. The structure of the nitrogen-containing compound is shown as a formula I, wherein Ar is 1 、Ar 2 Each independently selected from substituted or unsubstituted aryl groups having 6 to 25 carbon atoms, L 1 、L 2 Each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and the like, the nitrogen-containing compound of the present invention is effectiveThe performance of the electronic component is improved.)

1. A nitrogen-containing compound, wherein the structure of the nitrogen-containing compound is represented by formula I:

wherein Ar is₁、Ar₂The same or different, and are respectively and independently selected from substituted or unsubstituted aryl with 6-25 carbon atoms;

L₁、L₂the same or different, and are respectively and independently selected from single bond, substituted or unsubstituted arylene with 6-25 carbon atoms, substituted or unsubstituted heteroarylene with 2-25 carbon atoms;

ar is selected from substituted or unsubstituted aryl with 6-40 carbon atoms and substituted or unsubstituted heteroaryl with 3-40 carbon atoms; and is

L₁、L₂And the total number of carbon atoms of Ar is not less than 10;

Ar₁、Ar₂、Ar、L₁and L₂Wherein the substituents are the same or different and are each independently selected from deuterium, a halogen group, cyano, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, trialkylsilyl having 3 to 12 carbon atoms, diphenylphosphono, aryl having 6 to 18 carbon atoms optionally substituted with deuterium, a halogen group, alkyl having 1 to 4 carbon atoms, heteroaryl having 3 to 15 carbon atoms; optionally, in Ar, any two adjacent substituents form a 3-15 membered saturated or unsaturated ring.

2. According to the claimsThe nitrogen-containing compound of claim 1, wherein L₁、L₂The same or different, and are respectively and independently selected from single bond, substituted or unsubstituted arylene with 6-20 carbon atoms, substituted or unsubstituted heteroarylene with 2-18 carbon atoms;

preferably, L₁And L₂Wherein the substituents are the same or different and are each independently selected from deuterium, fluorine, cyano, alkyl of 1 to 4 carbon atoms, fluoroalkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 10 carbon atoms, trialkylsilyl of 3 to 7 carbon atoms, aryl of 6 to 15 carbon atoms optionally substituted with deuterium, fluorine, cyano, methyl, isopropyl, tert-butyl, heteroaryl of 5 to 12 carbon atoms.

3. The nitrogen-containing compound according to claim 1, wherein L₁、L₂The same or different, and each is 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 fluorenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted piperazinylene group, a substituted or unsubstituted triazinylene group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted 1, 3, 4-oxadiazolylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted benzopyrimidinylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranylene group, and a substituted or unsubstituted dibenzothiophenylene group;

preferably, L₁And L₂The substituents in (a) are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopentyl, cyclohexyl, trimethylsilyl, phenyl substituted with fluorine, phenyl substituted with deuterium, phenyl substituted with methyl, phenyl substituted with tert-butyl, naphthyl, biphenyl, 9-dimethylfluorenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl.

4. The nitrogen-containing compound according to claim 1, wherein L₁、L₂The same or different, and each independently 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 substituents thereon, each substituent being independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trimethylsilyl, phenyl optionally substituted with deuterium, fluoro, cyano, methyl, isopropyl, tert-butyl, naphthyl, 9, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, biphenyl; when the number of the substituents is more than 1, the substituents may be the same or different.

5. The nitrogen-containing compound according to claim 1, wherein L₁Selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, and a substituted or unsubstituted carbazolyl group; l is₁Each substituent in (a) is independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl or naphthyl;

L₂selected from the group consisting of a single bond or the following groups:

6. the nitrogen-containing compound according to claim 1, wherein Ar is selected from a substituted or unsubstituted aryl group having 6 to 28 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 25 carbon atoms;

preferably, Ar is selected from substituted or unsubstituted aryl groups having 6 to 25 carbon atoms, substituted or unsubstituted heteroaryl groups having 6 to 17 carbon atoms;

preferably, the substituents in Ar are independently selected from deuterium, fluorine, cyano, alkyl with 1-4 carbon atoms, fluoroalkyl with 1-4 carbon atoms, trialkylsilyl with 3-7 carbon atoms, cycloalkyl with 5-10 carbon atoms, aryl with 6-12 carbon atoms, heteroaryl with 5-12 carbon atoms and diphenylphosphonyl; optionally, in Ar, any two adjacent substituents form a cyclopentane, cyclohexane, or fluorene ring.

7. The nitrogen-containing compound according to claim 1, wherein Ar is selected from a substituted or unsubstituted group V₂Unsubstituted radicals V₂Selected from the group consisting of:

substituted radicals V₂Has one or more substituents thereon, each substituent being independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopentyl, cyclohexyl, trimethylsilyl, phenyl, naphthyl, diphenylphosphonyl; when the number of the substituent groups is more than 1, all the substituent groups are the same or different;

preferably, Ar is selected from the group consisting of:

8. the nitrogen-containing compound according to claim 1,selected from the group consisting ofGroup consisting of:

9. the nitrogen-containing compound according to claim 1, wherein Ar is Ar₁、Ar₂The same or different, and are respectively and independently selected from substituted or unsubstituted aryl with 6-15 carbon atoms;

Ar₁、Ar₂wherein the substituents in (A) are the same or different and each is independently selected from deuterium, fluorine, cyano, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a trialkylsilyl group having 3 to 7 carbon atoms, and a phenyl group.

10. The nitrogen-containing compound according to claim 1, wherein Ar is Ar₁、Ar₂The same or different, and each is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted fluorenyl;

preferably, Ar₁、Ar₂Each substituent in (a) is independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trimethylsilyl.

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

12. an electronic component comprising 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 nitrogen-containing compound according to any one of claims 1 to 11.

13. The electronic component according to claim 12, wherein the functional layer comprises an organic light-emitting layer containing the nitrogen-containing compound; and/or

The functional layer comprises an electron transport layer containing the nitrogen-containing compound;

preferably, the electronic element is an organic electroluminescent device or a photoelectric conversion device.

14. An electronic device, characterized by comprising the electronic component of claim 12 or 13.

Technical Field

The application belongs to the technical field of organic materials, and particularly provides a nitrogen-containing compound, and an electronic element and an electronic device using the nitrogen-containing compound.

Background

An organic light emitting diode (light-emitting diode) is abbreviated as an OLED, and the principle of the light-emitting diode is that when an electric field is applied to a cathode and an anode, a hole on the anode side and an electron on the cathode side move to a light-emitting layer, and combine to form an exciton in the light-emitting layer, the exciton is in an excited state and releases energy outwards, and the process of releasing energy from the excited state to a ground state emits light outwards. Since Kodak corporation reports electroluminescence of organic molecules in 1987 and Cambridge university in England reports electroluminescence of polymers in 1990, various countries in the world have developed research and development. The material has the advantages of simple structure, high yield, low cost, active light emission, high response speed, high fraction and the like, has the performances of low driving voltage, all solid state, non-vacuum, oscillation resistance, low temperature resistance and the like, is considered as a new technology which is most likely to replace a liquid crystal display in the future, and draws great attention.

In the conventional organic electroluminescent device, the most important problems are lifetime and efficiency, and as the display has been increased in area, the driving voltage has been increased, and the luminous efficiency and the power efficiency have been increased, so that it is necessary to continuously develop new materials to further improve the performance of the organic electroluminescent device.

Disclosure of Invention

An object of the present application is to provide a nitrogen-containing compound, and an electronic element and an electronic device using the same. The nitrogen-containing compound of the present application can effectively improve the performance of electronic components.

In order to achieve the above object, a first aspect of the present application provides a nitrogen-containing compound, wherein the structure of the nitrogen-containing compound is represented by formula I:

wherein Ar is₁、Ar₂The same or different, and are respectively and independently selected from substituted or unsubstituted aryl with 6-25 carbon atoms;

L₁、L₂the same or different, and are respectively and independently selected from single bond, carbon atom numberA substituted or unsubstituted arylene group of 6 to 25, a substituted or unsubstituted heteroarylene group having 2 to 25 carbon atoms;

ar is selected from substituted or unsubstituted aryl with 6-40 carbon atoms and substituted or unsubstituted heteroaryl with 3-40 carbon atoms; and is

L₁、L₂And the total number of carbon atoms of Ar is not less than 10;

Ar₁、Ar₂、Ar、L₁and L₂Wherein the substituents are the same or different and are each independently selected from deuterium, a halogen group, cyano, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, trialkylsilyl having 3 to 12 carbon atoms, diphenylphosphono, aryl having 6 to 18 carbon atoms optionally substituted with deuterium, a halogen group, alkyl having 1 to 4 carbon atoms, heteroaryl having 3 to 15 carbon atoms; optionally, in Ar, any two adjacent substituents form a 3-15 membered saturated or unsaturated ring.

A second aspect of the present application provides an electronic component including an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode; the functional layer comprises a nitrogen-containing compound according to the first aspect of the present application.

A third aspect of the present application provides an electronic device comprising the electronic component according to the second aspect of the present application.

To the nitrogen-containing compounds of the present application, pyrido [2, 3-d ] is introduced]Pyrimidine structureThe distribution of N atoms in the structure provides more empty orbitals, and the electron transmission efficiency is higher; meanwhile, aryl substituent groups are introduced into the No. 2 and No. 7 positions of the structure, so that the integral stereospecificity of molecules can be improved, the stacking among the molecules is avoided, and the film-forming property of the compound is improved. Aromatic groups are connected to the 4 th position, the asymmetry of the molecules is further improved, the molecular structure has more proper torque, and the rotation angles among the three groups connected to the 2 nd, 7 th and 4 th positions of the parent nucleus are adjusted, so that the compound has the optimal spatial configurationTherefore, the thermal stability and film forming stability of the compound can be further improved. The nitrogen-containing compound can be used as an electron transport layer material or a luminescent layer main body material of an organic electroluminescent device, and the service life of the device can be obviously prolonged.

Additional features and advantages of the present application will be described in detail in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application and not to limit the application.

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 a first electronic device according to an embodiment of the present application.

Fig. 3 is a schematic structural view of a photoelectric conversion device according to an embodiment of the present application.

Fig. 4 is a schematic structural diagram of a second 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; 360. a photoelectric conversion layer; 400. a first electronic device; 500. a second electronic device.

Detailed Description

The following describes in detail specific embodiments of the present application. It should be understood that the detailed description and specific examples, while indicating the present application, are given by way of illustration and explanation only, and are not intended to limit the present application.

Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of 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 application.

In the drawings, the thickness of regions and layers may be exaggerated for clarity. The same reference numerals denote the same or similar structures in the drawings, and thus detailed descriptions thereof will be omitted.

In the present application, the descriptions "… … is independently" and "… … is independently" and "… … is independently selected from" are interchangeable, and should be understood in a broad sense, which means that the specific items expressed between the same symbols do not affect each other in different groups, or that the specific items expressed between the same symbols do not affect each other in the same groups. For example,wherein each q is independently 0, 1, 2 or 3, each R "is independently selected from hydrogen, deuterium, fluoro, chloro" and has the meaning: the formula Q-1 represents that Q substituent groups R ' are arranged on a benzene ring, each R ' can be the same or different, and the options of each R ' are not influenced mutually; the formula Q-2 represents that each benzene ring of biphenyl has Q substituent groups R ', the number Q of the substituent groups R' on the two benzene rings can be the same or different, each R 'can be the same or different, and the options of each R' are not influenced with each other.

In this application, the terms "optional" 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 need not form a ring, which includes: a case where two adjacent substituents form a ring and a case where two adjacent substituents do not form a ring. As another example, "an aryl group having 6 to 18 carbon atoms optionally substituted with an alkyl group having 1 to 4 carbon atoms" includes the following two cases: an unsubstituted aryl group having 6 to 18 carbon atoms; or an aryl group substituted with an alkyl group having 1 to 4 carbon atoms, and the total number of carbon atoms of the substituted aryl group is 6 to 18.

In the present application, the term "substituted or unsubstituted" means that a functional group described later in the term may or may not have a substituent (hereinafter, for convenience of description, the substituent is collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl group or an unsubstituted aryl group having a substituent Rc. The substituent Rc may be deuterium, a halogen group, a cyano group, a heteroaryl group, an aryl group, an alkyl group, a haloalkyl group, a cycloalkyl group, a trialkylsilyl group, an aryl group substituted with an alkyl group, halogen, deuterium, or the like. Optionally, any two of the substituents are attached to each other to form, together with the atoms to which they are attached, a saturated or unsaturated ring. In the present application, a "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, these two substituents Rc may be independently present or attached to each other to form a ring with the atom; when two adjacent substituents Rc exist on a functional group, the adjacent two substituents Rc may exist independently or may form a ring fused with the functional group to which they are attached.

In the present application, the number of carbon atoms of the substituted or unsubstituted functional group means all the number of carbon atoms. For example, if L₁Is a substituted arylene group having 12 carbon atoms, all of the carbon atoms of the arylene group and the substituents thereon are 12. For another example: ar isThe number of carbon atoms is 10; l is₁Is composed ofThe 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 can be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group, in other words, the aryl group can be a monocyclic aryl group, a fused ring aryl group, or a polycyclic aryl groupTwo or more monocyclic aryl groups linked in a carbon-carbon bond conjugate, monocyclic aryl and fused ring aryl groups linked in a carbon-carbon bond conjugate, two or more fused ring aryl groups linked in a carbon-carbon bond conjugate. That is, unless otherwise specified, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered as aryl groups herein. The fused ring aryl group may include, for example, a bicyclic fused aryl group (e.g., naphthyl group), a tricyclic fused aryl group (e.g., phenanthryl group, fluorenyl group, anthracyl group), and the like. The aryl group does not contain a hetero atom such as B, N, O, S, P, Se or Si. In this specification, both biphenyl and fluorenyl groups are referred to as aryl groups. Examples of aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracyl, phenanthryl, biphenyl, terphenyl, benzo [9, 10 ]]Phenanthryl, pyrenyl, benzofluoranthenyl, phenanthrenyl, pyrenyl,and the like.

In the present application, a substituted aryl group may be one in which one or two or more hydrogen atoms are substituted with groups such as deuterium, a halogen group, a cyano group, an aryl group, an alkyl-substituted aryl group, a heteroaryl group, a trialkylsilyl group, a haloalkyl group, an alkyl group, a cycloalkyl group, and the like. It is understood that the number of carbon atoms in a substituted aryl group refers to the total number of carbon atoms in the aryl group and the substituents on the aryl group, for example, a substituted aryl group having a carbon number of 18, refers to a total number of carbon atoms in the aryl group and its substituents of 18. In addition, in the present application, the fluorenyl group may be substituted, and when having two substituents, the two substituents may be combined with each other to form a spiro structure. Specific examples of substituted fluorenyl groups include, but are not limited to,

in this application, reference to arylene is to a divalent group formed by an aryl group further deprived of a hydrogen atom.

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, 31, 32, 34, 35, 36, 38, and the like.

In the present application, heteroaryl means a monovalent aromatic ring 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, or a derivative thereof. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, the heteroaryl group may be a single aromatic ring system or a plurality of aromatic ring systems connected by carbon-carbon bonds in a conjugated manner, and any one of the aromatic ring systems is an aromatic monocyclic ring or an aromatic fused ring. Illustratively, heteroaryl groups can include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, and N-phenylcarbazolyl, N-pyridylcarbazolyl, N-methylcarbazolyl, and the like, without being limited thereto. Wherein, thienyl, furyl, phenanthroline group and the like are heteroaryl of a single aromatic ring system type, and the N-phenylcarbazolyl is heteroaryl of a polycyclic system type connected by carbon-carbon bond conjugation. In this application, reference to heteroarylene means a divalent or higher valent radical formed from a heteroaryl group further lacking one or more hydrogen atoms.

In the present application, substituted heteroaryl groups may be heteroaryl groups in which one or more hydrogen atoms are substituted with groups such as deuterium, halogen groups, cyano, aryl, alkyl-substituted aryl, heteroaryl, trialkylsilyl, alkyl, cycloalkyl, and the like. It is understood that the number of carbon atoms in the substituted heteroaryl group refers to the total number of carbon atoms in the heteroaryl group and the substituent on the heteroaryl group.

In the present application, the number of carbon atoms of the substituted or unsubstituted heteroaryl group may be 3 to 40. For example, the number of carbon atoms of the substituted or unsubstituted heteroaryl group may be 3, 4, 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, 31, 32, 34, 35, and the like.

As used herein, an delocalized linkage refers to a single bond extending from a ring systemIt means that one end of the linkage may be attached to any position in the ring system through which the linkage extends, and the other end to the rest of the compound molecule. For example, as shown in the following formula (f), naphthyl represented by formula (f) is connected with other positions of the molecule through two non-positioned connecting bonds penetrating through a double ring, and the meaning of the naphthyl represented by the formula (f-1) to the formula (f-10) comprises any possible connecting mode shown in the formula (f-1) to the formula (f-10).

As another example, as shown in the following formula (X '), the dibenzofuranyl group represented by formula (X') is attached to another position of the molecule via an delocalized bond extending from the middle of the benzene ring on one side, and the meaning of the dibenzofuranyl group represented by formula (X '-1) to formula (X' -4) includes any of the possible attachment means shown in formulas (X '-1) to (X' -4).

An delocalized substituent, as used herein, refers to a substituent attached by a single bond extending from the center of the ring system, meaning that the substituent may be attached at any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R' represented by the formula (Y) is bonded to the quinoline ring via an delocalized bond, and the meaning thereof includes any of the possible bonding modes as shown in the formulae (Y-1) to (Y-7).

In the present application, the number of carbon atoms of the alkyl group may be 1 to 10, and specifically may be 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, tert-butyl, n-pentyl, isopentyl, n-hexyl, heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, 3, 7-dimethyloctyl, and the like.

In the present application, the halogen group may include fluorine, iodine, bromine, chlorine.

In the present application, the number of carbon atoms of the aryl group as the substituent may be 6 to 18, and the number of carbon atoms is specifically 6, 10, 12, 13, 14, 15, etc., and specific examples of the aryl group include, but are not limited to, phenyl, naphthyl, biphenyl, phenanthryl, anthracyl, etc.

In the present application, the number of carbon atoms of the heteroaryl group as the substituent may be 3 to 15, specific examples of the number of carbon atoms are 3, 4, 5, 8, 9, 10, 12, 13, 14, 15 and the like, and specific examples of the heteroaryl group include, but are not limited to, a pyridyl group, a quinolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group and the like.

In the present application, the number of carbon atoms of the trialkylsilyl group as the substituent may be 3 to 12, for example, 3, 6, 7, 8, 9, etc., and specific examples thereof 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 the substituent may be 3 to 10, for example, 5, 6, 8 or 10, and specific examples include, but are not limited to, cyclopentyl, cyclohexyl, adamantyl, and the like.

In the present application, specific examples of haloalkyl include, but are not limited to, trifluoromethyl.

In the present application, the diphenylphosphonyl group has the structure

In a first aspect, the present application provides a nitrogen-containing compound having a structure represented by formula I:

wherein Ar is₁、Ar₂The same or different, and are respectively and independently selected from substituted or unsubstituted aryl with 6-25 carbon atoms;

L₁、L₂the same or different, and are respectively and independently selected from single bond, substituted or unsubstituted arylene with 6-25 carbon atoms, substituted or unsubstituted heteroarylene with 2-25 carbon atoms;

ar is selected from substituted or unsubstituted aryl with 6-40 carbon atoms and substituted or unsubstituted heteroaryl with 3-40 carbon atoms;

Ar₁、Ar₂、Ar、L₁and L₂Wherein the substituents are the same or different and are each independently selected from deuterium, a halogen group, cyano, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, trialkylsilyl having 3 to 12 carbon atoms, diphenylphosphono, aryl having 6 to 18 carbon atoms optionally substituted with deuterium, a halogen group, alkyl having 1 to 4 carbon atoms, heteroaryl having 3 to 15 carbon atoms; optionally, in Ar, any two adjacent substituents form a 3-15 membered saturated or unsaturated ring.

In this application, L₁、L₂And the total number of carbon atoms of Ar is not less than 10.

In one embodiment, L₁And L₂Each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 17 carbon atoms, and Ar is selected from a substituted or unsubstituted arylene group having 6 to 28 carbon atoms, and a substituted or unsubstituted heteroaryl group having 6 to 17 carbon atoms.

Alternatively, L₁、L₂The same or different, and each is independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 18 carbon atoms. For example, L₁、L₂May 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 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 carbon atoms.

In one embodiment, L₁Selected from single bond, substituted or unsubstituted arylene with 6-15 carbon atoms, L₂Selected from a single bond, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 15 carbon atoms.

In some embodiments, L₁、L₂The same or different, and each is 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 fluorenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted piperazinylene group, a substituted or unsubstituted triazinylene group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted 1, 3, 4-oxadiazolylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted benzopyrimidinylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranylene group, and a substituted or unsubstituted dibenzothiophenylene group.

Alternatively, L₁And L₂Wherein the substituents are the same or different and are each independently selected from deuterium, fluorine, cyano, alkyl of 1 to 4 carbon atoms, fluoroalkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 10 carbon atoms, trialkylsilyl of 3 to 7 carbon atoms, aryl of 6 to 15 carbon atoms optionally substituted with deuterium, fluorine, cyano, methyl, isopropyl, tert-butyl, heteroaryl of 5 to 12 carbon atoms.

Further optionally, L₁And L₂The substituents in (a) are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopentyl, cyclohexyl, trimethylsilyl, phenyl substituted with fluorine, phenyl substituted with deuterium, phenyl substituted with methyl, phenyl substituted with tert-butyl, naphthyl, biphenyl, 9-dimethylfluorenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl.

In some embodiments, L₁、L₂The same or different, and each independently 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 substituents thereon, each substituent being independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trimethylsilyl, phenyl optionally substituted with deuterium, fluoro, cyano, methyl, isopropyl, tert-butyl, naphthyl, 9, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, biphenyl; when the number of the substituents is more than 1, the substituents may be the same or different.

In one embodiment, L₁Selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, and a substituted or unsubstituted carbazolyl group; l is₁Each substituent in (a) is independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl or naphthyl; and is

L₂Selected from the group consisting of a single bond or the following groups:

alternatively, L₂Selected from single bond or the following groupThe group consisting of:

alternatively, Ar is selected from substituted or unsubstituted aryl groups having 6 to 28 carbon atoms, and substituted or unsubstituted heteroaryl groups having 5 to 25 carbon atoms. For example, Ar may be independently selected from: a substituted or unsubstituted aryl group having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 carbon atoms, a substituted or unsubstituted heteroaryl group having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 carbon atoms.

In one embodiment, Ar is selected from the group consisting of substituted or unsubstituted aryl groups having 6 to 25 carbon atoms, and substituted or unsubstituted heteroaryl groups having 6 to 17 carbon atoms.

Alternatively, Ar is not a substituted or unsubstituted five-ring fused heteroaryl group, L₁And L₂Not a substituted or unsubstituted pentacyclic fused heteroaryl group. For example, Ar is not the following group:

L₁and L₂Is not:

optionally, the substituents in Ar are each independently selected from deuterium, fluorine, cyano, alkyl having 1-4 carbon atoms, fluoroalkyl having 1-4 carbon atoms, trialkylsilyl having 3-7 carbon atoms, cycloalkyl having 5-10 carbon atoms, aryl having 6-12 carbon atoms, heteroaryl having 5-12 carbon atoms, diphenylphosphonyl; optionally, in Ar, any two adjacent substituents form a cyclopentane, cyclohexane, or fluorene ring.

Further alternatively, the substituents in Ar are each independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trimethylsilyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, diphenylphosphonyl; optionally, in Ar, any two adjacent substituents form a cyclopentane, cyclohexane, or fluorene ring.

In some embodiments, Ar is selected from a substituted or unsubstituted group V₂Unsubstituted radicals V₂Selected from the group consisting of:

substituted radicals V₂Has one or more substituents thereon, each substituent being independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopentyl, cyclohexyl, trimethylsilyl, phenyl, naphthyl, diphenylphosphonyl; when the number of the substituents is more than 1, the substituents may be the same or different.

Alternatively, Ar is selected from the group consisting of: :

further optionally, Ar is selected from the group consisting of:

in one embodiment, in formula I,selected from the group consisting ofGroup consisting of:

in a particular embodiment of the method of the present invention,selected from the group consisting of:

in one embodiment, L₁Is a single bond, phenylene, naphthylene or carbazolyl, L₂Is substituted or unsubstituted pyridylene, substituted or unsubstituted piperazinylene, substituted or unsubstituted pyrimidylene or substituted or unsubstituted triazinylene, and Ar is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl.

In another embodiment, L₁Is a single bond or phenylene, L₂Is naphthylene or anthrylene, Ar is substituted or unsubstitutedIn the case of substituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, the nitrogen-containing compound is more suitable for use as an electron transport layer material and provides a higher lifetime of the organic electroluminescent device produced.

In yet another embodiment, L₁Is a single bond, L₂In the case where Ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group, the nitrogen-containing compound is more suitable as a host material for a light-emitting layer.

Alternatively, Ar₁、Ar₂The same or different, and are respectively and independently selected from substituted or unsubstituted aryl groups with 6-15 carbon atoms.

Alternatively, Ar₁、Ar₂The same or different, and each is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted fluorenyl.

Alternatively, Ar₁、Ar₂Wherein the substituents in (A) are the same or different and each is independently selected from deuterium, fluorine, cyano, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a trialkylsilyl group having 3 to 7 carbon atoms, and a phenyl group.

Further optionally, Ar₁、Ar₂Each substituent in (a) is independently selected from deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, trimethylsilyl.

In a specific embodiment, Ar₁、Ar₂Each independently selected from the group consisting of:

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

the synthesis method of the nitrogen-containing compound provided by the present application is not particularly limited, and those skilled in the art can determine an appropriate synthesis method according to the preparation method provided by the synthesis examples section of the present application in combination with the nitrogen-containing compound. In other words, the synthesis examples section of the present invention illustratively provides methods for the preparation of nitrogen-containing compounds, and the starting materials employed may be obtained commercially or by methods well known in the art. All nitrogen-containing compounds provided herein are available to those skilled in the art from these exemplary preparative methods, and all specific preparative methods for preparing the nitrogen-containing compounds will not be described in detail herein, and should not be construed as limiting the present application.

In a second aspect, the present application provides an electronic component comprising an anode, a cathode, and a functional layer disposed between the anode and the cathode, wherein the functional layer comprises 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 characteristics of the electronic element such as service life and the like.

Optionally, the functional layer comprises an organic light emitting layer comprising a nitrogen containing compound of the present application. The organic light-emitting layer may be composed of the nitrogen-containing compound provided herein, or may be composed of the nitrogen-containing compound provided herein and other materials.

Optionally, the functional layer comprises an electron transport layer comprising a nitrogen-containing compound of the present application.

In the present application, the electronic element may be an organic electroluminescent device or a photoelectric conversion device.

According to a particular embodiment, the electronic component is an organic electroluminescent device. As shown in fig. 1, the organic electroluminescent device may include an anode 100, a first hole transport layer 321, a second hole transport layer 322, an organic light emitting layer 330 as an energy conversion layer, an electron transport layer 340, and a cathode 200, which are sequentially stacked.

Optionally, the anode 100 comprises an anode material, preferably a material with a large work function that facilitates hole injection into the functional layer. Specific examples of the anode material include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metals and oxides such as ZnO: al or SnO₂Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3, 4- (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole, and polyaniline, but are not limited thereto. Preferably, a transparent electrode including Indium Tin Oxide (ITO) as an anode is included.

Alternatively, the first hole transport layer 321 and the second hole transport layer 322 (also referred to as "electron blocking layers") may respectively include two different hole transport materials, and the hole transport materials may be selected from carbazole multimers, carbazole-linked triarylamine-based compounds, or other types of compounds, which are not specifically limited in this application. For example, the first hole transport layer 321 may be composed of DMFL-NPB, and the second hole transport layer 322 may be composed of TAPC. Alternatively, the first hole transport layer 321 may be composed of NPB, and the second hole transport layer 322 may be composed of TPD.

Alternatively, the organic light emitting layer 330 may be composed of a single light emitting material, and may also include a host material and a guest material. Alternatively, the organic light emitting layer 330 is composed of a host material and a guest material, and a hole injected into the organic light emitting layer 330 and an electron injected into the organic light emitting layer 330 may be combined in the organic light emitting layer 330 to form an exciton, which transfers energy to the host material, and the host material transfers energy to the guest material, thereby enabling the guest material to emit light.

Alternatively, the host material of the organic light emitting layer 330 may be a metal chelate compound, a bisstyryl derivative, an aromatic amine derivative, a dibenzofuran derivative, or other types of materials, which is not particularly limited in this application. For example, the host material may be α, β -ADN or BCzSCN, among others. According to a specific embodiment, the host material of the organic light emitting layer 330 comprises the nitrogen-containing compound of the present application.

The guest material of the organic light emitting layer 330 may be a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative, or other materials, which is not particularly limited in the present application. For example, the guest material may be PCAN, Ir (piq)₂(acac) or Ir (flq)₂(acac)。

The electron transport layer 340 may have a single-layer structure or a multi-layer structure, and may include one or more electron transport materials selected from, but not limited to, benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials. For example, the electron transport layer 340 may be composed of BTB and LiQ. According to a specific embodiment, the electron transport layer 340 comprises the nitrogen-containing compound of the present application, for example, the electron transport layer 340 may be composed of the nitrogen-containing compound and LiQ.

In the present application, the cathode 200 may include a cathode material, which is a material having a small work function that facilitates electron injection into the functional layer. Specific examples of the cathode material include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or a multilayer material such as LiF/Al, Liq/Al, LiO₂Al, LiF/Ca, LiF/Al and BaF₂and/Ca. Preferably, a metal electrode comprising magnesium and silver is 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 made of benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives, or other materials, which are not limited in this application. For example, the material of the hole injection layer 310 may be selected from at least one of HATNA, NATA, F4-TCNQ, and HAT-CN.

Optionally, as shown in fig. 1, an electron injection layer 350 may be further disposed 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 or an alkali metal halide, or may include a complex of an alkali metal and an organic material. For example, the electron injection layer 350 may include LiQ or Yb.

In the present application, the organic electroluminescent device may be a blue device, a red device, or a green device.

In another embodiment, the electronic component is a photoelectric conversion device. The photoelectric conversion device may include 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 nitrogen-containing compound provided by the application.

Optionally, the functional layer comprises an electron transport layer comprising a nitrogen-containing compound of the present application.

According to a specific embodiment, as shown in fig. 3, the photoelectric conversion device may include an anode 100, a hole transport layer 320, a photoelectric conversion layer 360, an electron transport layer 340, and a cathode 200, which are sequentially stacked.

Alternatively, the photoelectric conversion device may be a solar cell, and particularly may be an organic thin film solar cell. For example, in one embodiment of the present application, a solar cell may include an anode, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode, which are sequentially stacked, wherein the electron transport layer includes the nitrogen-containing compound of the present application.

A third aspect of the present application provides an electronic device comprising the electronic component according to the second aspect of the present application.

According to one embodiment, as shown in fig. 2, the electronic device is a first electronic device 400, and the first electronic device 400 includes the organic electroluminescent device. The first electronic device 400 may be, for example, a display device, a lighting device, an optical communication device, or other types of electronic devices, which may include, but are not limited to, a computer screen, a mobile phone screen, a television, electronic paper, an emergency light, an optical module, and the like.

In another embodiment, as shown in fig. 4, the electronic device is a second electronic device 500, and the second electronic device 500 includes the above-mentioned photoelectric conversion device. The second electronic device 500 may be, for example, a solar power generation apparatus, a light detector, a fingerprint recognition apparatus, a light module, a CCD camera, or other types of electronic devices.

The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.

The method for synthesizing the nitrogen-containing compound of the present application will be specifically described below with reference to synthesis examples. Compounds for which no synthetic process is mentioned in this application are all commercially available starting products.

1. Synthesis of intermediate IMX (X represents a variable)

The synthesis of intermediate IMX is illustrated below as the synthesis of intermediate 1:

introducing nitrogen (0.100L/min) into a three-neck flask provided with a mechanical stirrer, a thermometer and a spherical condenser for replacement for 15min, and sequentially adding raw materials of Sub 1-a (23.4g, 100mmol), Sub 1-b (16.4g, 105mmol), potassium carbonate (27.6g, 200mmol), 18 crown 6 ether (5.28g, 20mmol), 1, 10-phenanthroline (3.64g, 20mmol), cuprous bromide (5.82g, 40mmol) and 500mL of xylene. Stirring is started, the temperature is increased to 130-135 ℃, reaction is carried out for 7h, then 500mL of toluene and 500mL of water are added into the reaction solution under stirring, liquid separation is carried out, and the water phase is extracted for 1 time by 200mL of toluene. The combined organic phases were washed 2 times with water, dried over 5g of anhydrous sodium sulfate, filtered, concentrated (50-60 ℃ C., -0.09-0.08 MPa) until no droplets flowed out, 100mL of ethanol was added with stirring to precipitate a solid, filtered, and the filter cake was collected to give intermediate IM 1(18.7g, yield 68.5%).

The intermediate IM X in Table 1 was synthesized by referring to the procedure for intermediate IM 1 except that the starting material Sub 1-a was replaced with the starting material Sub X-a and the starting material Sub 1-b was replaced with the starting material Sub X-b, and the synthesized intermediates and the yields thereof were as shown in Table 1.

TABLE 1

2. Synthesis of intermediate IM I-X

The synthesis of IM I-X is illustrated below by the synthesis of intermediate IM I-1:

under the protection of nitrogen, raw materials of sub I-1(15.4g, 105mmol), sub II-1(23.5g, 100mmol), potassium carbonate (27.6g, 200mmol), tetrabutylammonium bromide (6.45g, 20mmol), 240mL of toluene, 40mL of ethanol and 40mL of water are added into a three-neck flask provided with a mechanical stirrer, a thermometer and a condenser, stirring is started, the temperature is raised to 40-45 ℃, palladium (2.3g, 2mmol) is added, the temperature is raised to 60-65 ℃ for reaction for 8 hours, the reaction liquid is cooled to 25 ℃, then filtration is carried out, and the solid is leached by ethanol to obtain IM I-1(19.6g, the yield is 76.1%).

IM I-X in Table 2 is synthesized by referring to the method of IM I-1, except that sub I-1 is replaced by sub I-X, sub II-1 is replaced by sub II-X, the adopted main raw materials, the synthesized intermediate structure and the yield thereof are shown in Table 2.

TABLE 2

Synthesis example 1: synthesis of Compound 23

A three-necked flask equipped with a mechanical stirrer, a thermometer and a bulb-shaped condenser was purged with nitrogen (0.100L/min) for 15min, and then intermediate IM 1(16.4g, 60mmol), IM I-13(19.7g, 66mmol), cesium carbonate (39.1g, 120mmol) and 200mL of ethanol were added in this order. Starting stirring, and heating to 70-75 ℃ for reaction for 10 h. Then, DDQ (2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, 27.3g, 120mmoL) was slowly added in portions, after the addition, the reaction was continued for 3 hours, the temperature was reduced, the filtration was performed, the filter cake was stirred with 100mL of water for 2 times, the filtration was performed, 100mL of ethanol was stirred for 2 times, the filtration and the drying were performed, and a compound 23(18.5g, yield 56%) was obtained: 552.2[ M + H ] M/z]⁺. Nuclear magnetic data for compound 23:¹H-NMR(CDCl₃，400MHz)δ(ppm)：8.41-8.36(dd，2H)，8.26-8.21(dd，2H)，8.14-8.09(d，2H)，7.95(s，1H)，7.89(s，1H)，7.84-7.78(m，3H)，7.73-7.69(m，2H)，7.63-7.51(m，6H)，7.47-7.41(m，4H)，1.76(s，6H).

synthesis examples 2 to 22

The compounds of table 3 were synthesized with reference to the procedure for compound 23, except that the starting material Y was used instead of IM I-13 and each intermediate IM X was used instead of IM 1, the main starting materials used, the synthesized compounds and their yields, mass spectrometry results are shown in table 3.

TABLE 3

3. Synthesis of intermediate IM II-X

The synthesis of IM II-X is illustrated by the method of IM II-1:

under the protection of nitrogen, raw materials of subA-1(19.5g, 100mmol), sub B-1(24.5g, 105mmol), potassium carbonate (27.6g, 200mmol), 18 crown 6 ether (5.3g, 20mmol), 1, 10 phenanthroline (3.7g, 20mmol), cuprous iodide (7.6g, 40mmol) and 200mL of xylene are sequentially added into a three-neck flask provided with a mechanical stirrer, a thermometer and a spherical condenser. Starting stirring, and heating to 130-135 ℃ for reaction for 7 h. Then, 200mL of toluene and 200mL of water were added to the reaction mixture under stirring, followed by liquid separation, and the aqueous phase was extracted with 100mL of toluene again. The combined organic phases were washed 2 times with water, dried over anhydrous sodium sulfate, filtered, concentrated (50-60 ℃ C., -0.09-0.08 MPa) until no droplets flowed out, 100mL petroleum ether was added with stirring, and filtered to give IM II-1(25.1g, yield 72.2%).

IM II-X listed in Table 4 was synthesized by referring to the synthesis method of IM II-1, except that the raw material sub A-1 was replaced by the raw material sub A-X, the raw material sub B-1 was replaced by the raw material sub B-X, and the main raw materials, the synthesized intermediates and the yields used were as shown in Table 4.

TABLE 4

4. Synthesis of intermediate IM III-X

The synthesis of each IM III-X is illustrated by the method of IM III-1

Under the protection of nitrogen, adding raw material sub C-1(29.4g, 110mmol) and 313mL of tetrahydrofuran into a three-necked flask provided with a mechanical stirring, a thermometer and a constant-pressure dropping funnel, starting stirring, cooling liquid nitrogen to-80-90 ℃, dropping n-hexane solution of n-butyllithium (71.5mL, 143mmol), preserving heat for 1h after dropping, dropping DMF (10.5g, 143mmol), adding 400mL of water and 100mL of petroleum ether into the reaction solution after preserving heat for 1h, fully stirring, separating, washing the organic phase for 4 times with water, and filtering to obtain IM III-1(20.1g, yield 69.9%).

The intermediates IM III-X listed in Table 5 were synthesized by referring to the synthesis method of IM III-1, except that the raw material sub C-1 was replaced with the raw material sub C-X, and the main raw materials, the synthesized intermediates and the yields thereof used were as shown in Table 5.

TABLE 5

Synthesis example 23: synthesis of Compound 65

A three-necked flask equipped with a mechanical stirrer, a thermometer and a bulb-shaped condenser was purged with nitrogen (0.100L/min) for 15min, and IM 1(16.4g, 60mmol), IMI-1(18.5g, 72mmol), cesium carbonate (39.1g, 120mmol) and 200mL of ethanol were sequentially added thereto. Starting stirring, heating toReacting for 10 hours at 70-75 ℃. DDQ (24.5g, 108mmol) is slowly added in batches, reaction is continued for 5H after the addition is finished, the mixture is filtered after temperature reduction, a filter cake is stirred for 2 times by 100mL of water, filtered, stirred for 2 times by 110mL of ethanol, filtered and dried to obtain a compound 65(19.3g, yield 63.1 percent), and M/z is 511.2[ M + H ] (]⁺。

Synthesis examples 24 to 52

The compounds of table 6 were synthesized by the method of reference to compound 65, except that intermediate IM X was used instead of IM 1 and starting material Z was used instead of IM I-1, and the synthesized compounds and their yields, mass spectrometry results are shown in table 6.

TABLE 6

Preparation and evaluation of an organic electroluminescent device:

example 1: preparation of blue organic electroluminescent device

The anode was prepared by the following procedure: the thickness of ITO is set asThe ITO substrate of (1) was cut into a size of 40mm (length) × 40mm (width) × 0.7mm (thickness), and prepared to have a cathode, an anode and an insulating layer pattern by a photolithography processAn experimental substrate, and ultraviolet ozone and O can be used₂∶N₂The plasma performs a surface treatment to increase the work function of the anode.

HATNA was vacuum-deposited on an experimental substrate (anode) to a thickness ofAnd DMFL-NPB is vacuum-evaporated on the hole injection layer to form a layer having a thickness ofThe first hole transport layer of (1).

Depositing TAPC on the first hole transport layer to a thickness ofThe second hole transport layer of (1).

On the second hole transport layer, BCzSCN was used as a main body, PCAN was simultaneously doped at a film thickness ratio of 97: 3, and vapor deposition was performed to form a film having a thickness ofThe light emitting layer of (1).

Mixing the compound 23 and LiQ at a weight ratio of 1: 1, and vapor-depositing the mixture on the light-emitting layer to formA thick electron transport layer.

Subsequently, LiQ was evaporated on the electron transport layer to form a thickness ofThe electron injection layer of (3);

then, magnesium (Mg) and silver (Ag) were mixed at a rate of 1: 9, and vacuum-evaporated on the electron injection layer to form a layer having a thickness ofThe cathode of (1).

Furthermore, the cathode is vapor-deposited thickDegree ofForming a capping layer (CPL), thereby completing the fabrication of the organic light emitting device.

Examples 2 to 22

An organic electroluminescent device was fabricated according to the method of example 1, except that, in forming the electron transport layer, the compounds shown in table 7 were respectively substituted for the compound 23, thereby fabricating an organic electroluminescent device.

Comparative examples 1 to 3

An organic electroluminescent device was fabricated in accordance with the method of example 1, except that compound a, compound B, and compound C were used in place of compound 23 in forming the electron transport layer, respectively, to thereby fabricate an organic electroluminescent device.

In the above examples and comparative examples, the main material structures used are as follows:

the organic electroluminescent device prepared as above was subjected to a performance test at 20mA/cm²The lifetime of the T95 device was tested under the conditions that the IVL performance was 15mA/cm at constant current density²The following tests were carried out and the results are shown in Table 7.

TABLE 7

It can be seen from Table 7 that the organic electroluminescent devices prepared in examples 1 to 22 using the compounds of the present application as electron transport layer materials have higher luminous efficiency and lifespan than those of comparative examples 1 to 3. Specifically, the organic electroluminescent devices prepared in examples 1 to 22 showed current efficiencies of at least 8.0% and lifetimes of at least 11.9% as compared to comparative examples 1 to 3, and the devices of the examples also exhibited lower driving voltages. Compared with comparative example 1, it can be seen that by introducing the characteristic functional groups to specific positions, the twist degree of the molecules can be further controlled, the stability of the molecular skeleton is increased, and the service life of the device is prolonged; comparing examples 1 to 22 with comparative example 2, it is found that the introduction of an aryl group at the ortho position of the nitrogen atom of the core reduces the activity of the nitrogen atom and improves the stability of the entire molecular structure of the compound; comparing examples 1-22 with comparative example 3, it can be seen that the introduction of pyrido [2, 3-d ] pyrimidine groups substituted with aryl groups at positions 2 and 7 into the structure of the compound of the present application can improve the electron mobility of the compound and ensure that the compound has high stability.

Example 23

Preparation of red organic electroluminescent devices:

the anode was prepared by the following procedure: will have a thickness ofThe ITO substrate (manufactured by Corning) of (1) was cut into a size of 40mm × 40mm × 0.7mm, prepared into an experimental substrate having a cathode, an anode and an insulating layer pattern using a photolithography process, using ultraviolet ozone and O₂∶N₂The plasma was surface treated to increase the work function of the anode (experimental substrate) and to remove scum.

NATA was vacuum-evaporated on an experimental substrate (anode) to a thickness ofAnd NPB is deposited on the hole injection layer to form a layer having a thickness ofThe first hole transport layer of (1).

Vacuum evaporating TPD on the first hole transport layer to form a layer with a thickness ofThe second hole transport layer of (1).

On the second hole transporting layer, compound 92 as a host material was simultaneously doped with Ir (flq)₂(acac) vapor deposition was carried out at a film thickness ratio of 97: 3 to obtain a film having a thickness ofThe organic light emitting layer of (1).

BTB and LiQ are mixed in a weight ratio of 1: 1 and evaporated on the luminescent layer to formA thick electron transport layer;

depositing LiQ on the electron transport layer to a thickness ofThe electron injection layer of (3);

then, magnesium (Mg) and silver (Ag) were mixed at a rate of 1: 9, and vacuum-evaporated on the electron injection layer to form a layer having a thickness ofThe cathode of (1).

The thickness of the vapor deposition on the cathode is set toForming an organic capping layer, thereby completing the fabrication of the organic light emitting device.

Examples 24 to 51

An organic electroluminescent device was fabricated as in example 23, except that in the formation of the organic light-emitting layer, the compounds 92 were replaced with the compounds shown in table 8, respectively, to produce organic electroluminescent devices.

Comparative examples 4 to 6

An organic electroluminescent device was fabricated as in example 23, except that in the formation of the organic light-emitting layer, the compound D, the compound E and the compound F were used, respectively, in place of the compound 92, to thereby produce an organic electroluminescent device.

In examples 23 to 51 and comparative examples 4 to 6, the main material structures used are as follows:

performance test was conducted on the organic electroluminescent devices obtained in examples 23 to 51 and comparative examples 4 to 6, in which the organic electroluminescent device was manufactured at 20mA/cm²The lifetime of the T95 device was tested under the conditions that the IVL performance was 15mA/cm at constant current density²The following tests were carried out and the results are shown in Table 8.

TABLE 8

It can be seen from Table 8 that the organic electroluminescent devices prepared in examples 23 to 51 using the compounds of the present application as host materials for the light-emitting layer had improved service lives by at least 15.0% as compared with those of comparative examples 4 to 6, and the devices of examples 23 to 51 also had both lower driving voltages and higher light-emitting efficiencies. Among them, it is clear from examples 23 to 51 that, compared with comparative examples 4 and 5, the introduction of an aryl group at the ortho position of the nitrogen atom of the mother nucleus can reduce the activity of the nitrogen atom and improve the stability of the whole compound molecular structure; in addition, comparing examples 23-51 with comparative example 6, it can be seen that introducing the characteristic functional group to a specific position can further control the degree of twist of the molecule, increase the stability of the molecular skeleton, and consequently increase the lifetime of the device.

The preferred embodiments of the present disclosure have been described in detail, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protective scope of the present disclosure. It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations are not described separately in this application.

In addition, any combination of the various embodiments of the present application is also possible, and the same should be considered as disclosed in the present application as long as it does not depart from the idea of the present disclosure.