CN113816935A

CN113816935A - Nitrogen-containing compound, electronic component, and electronic device

Info

Publication number: CN113816935A
Application number: CN202110961441.8A
Authority: CN
Inventors: 张林伟; 许佳聪
Original assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Current assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Priority date: 2021-08-20
Filing date: 2021-08-20
Publication date: 2021-12-21
Anticipated expiration: 2041-08-20
Also published as: CN113816935B

Abstract

The present disclosure provides a nitrogen-containing compound having a core group formed of a substituted oxadihydrophenanthrene group and a triarylamine group. The fused aromatic rings on the benzene rings on the two sides of the oxadihydrophenanthrene can further improve the electron density of a core structure and improve the hole transmission efficiency of the compound. The nitrogen-containing compound can be used for a hole transport layer of an organic electroluminescent device or a photoelectric conversion device to improve the luminescent performance and the service life of the organic electroluminescent device or the photoelectric conversion device.

Description

Nitrogen-containing compound, electronic component, and electronic device

Technical Field

The present disclosure relates to the field of organic materials, and in particular, to a nitrogen-containing compound, an electronic component, and an electronic device.

Background

With the development of electronic technology and the advancement of material science, the application range of electronic elements for realizing electroluminescence or photoelectric conversion is becoming wider and wider. Such electronic components, such as organic electroluminescent devices or photoelectric conversion devices, generally include a cathode and an anode that are oppositely disposed, and a functional layer disposed between the cathode and the anode. The functional layer is composed of multiple 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.

For example, when the electronic element is an organic electroluminescent device, it generally includes an anode, a hole transport layer, an organic light emitting layer as an energy conversion layer, an electron transport layer, and a cathode, which are sequentially stacked. When voltage is applied to the anode and the cathode, the two electrodes generate an electric field, electrons on the cathode side move to the organic light emitting layer under the action of the electric field, holes on the anode side also move to the light emitting layer, the electrons and the holes are combined in the organic light emitting layer to form excitons, and the excitons are in an excited state and release energy outwards, so that the organic light emitting layer emits light outwards.

The above information disclosed in this background section is only for enhancement of understanding of the background of the application and therefore it may contain information that does not constitute prior art that is known to a person of ordinary skill in the art.

Disclosure of Invention

An object of the present disclosure is to provide a nitrogen-containing compound that can improve the performance of an electronic component, and an electronic device.

In order to achieve the purpose, the technical scheme adopted by the disclosure is as follows:

according to a first aspect of the present disclosure, there is provided a nitrogen-containing compound having a structural formula shown in chemical formula 1:

wherein one of the ring A and the ring B is selected from a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring, and the other is a naphthalene ring or a phenanthrene ring;

R₁and R₂Are the same or different from each other and are each independently selected from a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, or R₁And R₂Are connected with each other to form a cycloalkyl group with 5-10 carbon atoms; the R is₁And R₂The substituents on the substituent groups are the same or different and are respectively and independently selected from deuterium, cyano, halogen groups or alkyl groups with 1-4 carbon atoms;

L₁、L₂and L are the same or different from each other 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 5 to 30 carbon atoms;

Ar₁and Ar₂The same or different from each other, and each is independently selected from substituted or unsubstituted aryl group having 6 to 33 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, triarylsilyl group having 18 to 24 carbon atoms;

n₃represents R₃The number of (2); n is₃Is 0, 1,2, 3,4, 5, 6, 7, 8 or 9; when n is₃When greater than 1, any two R₃The same or different;

each R₃Independently selected from deuterium, a halogen group, a cyano group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a deuterated alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 6 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, optionally, any two adjacent R₃Are connected with each other to form an aromatic ring with 6 or 10 carbon atoms;

L₁、L₂、L、Ar₁、Ar₂wherein each substituent is the same or different and is independently selected from deuterium, a halogen group, a cyano group, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms; optionally, at L₁、L₂、L、Ar₁And Ar₂Wherein any two adjacent substituents form a substituted or unsubstituted 5-to 14-membered ring, and the substituent on the 14-membered ring is an alkyl group having 1 to 6 carbon atoms.

According to a second aspect of the present disclosure, there is provided 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 contains the above-mentioned nitrogen-containing compound.

According to a third aspect of the present disclosure, an electronic device is provided, which includes the above electronic element.

Drawings

The above and other features and advantages of the present application will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached 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.

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.

The reference numerals of the main elements in the figures are explained as follows:

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; 323. an electron blocking 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

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.

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. One skilled in the relevant art will recognize, however, that the subject matter of the present application can be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring major technical ideas of the application.

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 having a substituent Rc or an unsubstituted aryl group. Wherein Rc as the substituent may be, for example, deuterium, a halogen group, a cyano group, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. In the present application, a "substituted" functional group may be substituted with 1 or 2 or more substituents Rc as described above.

In the present application, "any two adjacent substituents form a ring," any two adjacent "may include two substituents on the same atom, and may also include one substituent on each of two adjacent atoms; wherein, when two substituents are present on the same atom, both substituents may form a saturated or unsaturated ring with the atom to which they are both attached; when two adjacent atoms have a substituent on each, the two substituents may be fused to form a ring.

In the present application, the number of carbon atoms of a substituted or unsubstituted group refers to all the number of carbon atoms. For example, if Ar₁Is a substituted aryl group having 12 carbon atoms, all of the carbon atoms of the aryl group and the substituents thereon are 12.

The descriptions used in this application that "… … independently" and "… … independently" and "… … independently selected from" are interchangeable and should be understood in a broad sense to mean that the particular items expressed between the same symbols do not interfere with each other in different groups or that the particular items expressed between the same symbols do not interfere with each other in the same groups. For example: in "

Wherein each q is independently 0, 1,2 or 3, and each R "is independently selected from the group consisting of hydrogen, 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 may or may not occur. For example, "optionally, any two adjacent substituents x form a ring" means that the two substituents may form a ring but do not necessarily form a ring, including: a case where two adjacent substituents form a ring and a case where two adjacent substituents do not form a ring.

In the present application, "alkyl" may include straight chain alkyl groups, branched chain alkyl groups. The alkyl group may have a specified number of carbon atoms, for example, an alkyl group having 1 to 12 carbon atoms. In the present application, numerical ranges such as "1 to 10" when used to define the number of carbon atoms refer to the individual integers in the given ranges; for example, "an alkyl group having 1 to 5 carbon atoms" means an alkyl group that may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)₃) Ethyl group (Et, -CH)₂CH₃) N-propyl (n-Pr, -CH)₂CH₂CH₃) Isopropyl group (i-Pr, -CH (CH)₃)₂) N-butyl (n-Bu, -CH)₂CH₂CH₂CH₃) Isobutyl (i-Bu, -CH)₂CH(CH₃)₂) Sec-butyl (s-Bu, -CH (CH)₃)CH₂CH₃) Tert-butyl (t-Bu, -C (CH)₃)₃) And the like.

In the present application, the halogen group as a substituent includes fluorine, chlorine, bromine or iodine.

In the present application, "haloalkyl" means an alkyl group substituted with one or more halogen atoms, wherein the alkyl group has the meaning as described herein, and examples of haloalkyl include, but are not limited to, trifluoromethyl and the like.

In the present application, aryl refers to an optional functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group, in other words, the aryl group may be a monocyclic aryl group, a fused ring aryl group, two or more monocyclic aryl groups linked by a carbon-carbon bond conjugate, a carbon-carbon bond conjugate linkageA monocyclic aryl group and a fused ring aryl group, two or more fused ring aryl groups linked by carbon-carbon bonds. That is, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered as an aryl group in the present application. 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, Se, Si or P. Examples of the aryl group may include phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, quaterphenyl, benzo [9,10 ]]Phenanthryl, pyrenyl, benzofluoranthenyl, phenanthrenyl, pyrenyl,

an indenyl group, etc., without being limited thereto.

In the present application, substituted aryl groups may be aryl groups in which one or two or more hydrogen atoms are substituted with groups such as deuterium atoms, halogen groups, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, cycloalkyl, alkoxy, alkylthio, and the like. It is understood that the number of carbon atoms of a substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituent on the aryl group, for example, a substituted aryl group having a carbon number of 18 refers to the total number of carbon atoms of the aryl group and the substituent being 18.

In the present application, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure, and specific examples include, but are not limited to, the following structures:

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 is-6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 25, 30 or 33. In some embodiments, a substituted or unsubstituted aryl group is an aryl group having from 6 to 33 carbon atoms, in other embodiments a substituted or unsubstituted aryl group is an aryl group having from 6 to 25 carbon atoms, in other embodiments a substituted or unsubstituted aryl group is an aryl group having from 6 to 18 carbon atoms, and in other embodiments an aryl group has from 6 to 15 carbon atoms.

In this application, as L₁、L₂、L、Ar₁、Ar₂Examples of aryl groups as substituents of (a) are, but not limited to, phenyl, naphthyl, anthryl, phenanthryl, biphenyl, fluorenyl, dimethylfluorenyl.

In the present application, heteroaryl refers to a monovalent aromatic ring containing 1,2, 3,4, 5, or 6 heteroatoms in the ring, which may be at least one of B, O, N, P, Si, Se, and S, or derivatives 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.

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 atoms, halogen groups, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, cycloalkyl, alkoxy, alkylthio, 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 is selected from 3,4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some embodiments, a substituted or unsubstituted heteroaryl group is a heteroaryl group having 5 to 30 carbon atoms, in other embodiments a substituted or unsubstituted heteroaryl group is a heteroaryl group having 5 to 18 carbon atoms, and in other embodiments a substituted or unsubstituted heteroaryl group is a heteroaryl group having 5 to 12 carbon atoms.

In this application, as L₁、L₂、L、Ar₁、Ar₂Such as, but not limited to, pyridyl, pyrimidinyl, quinolinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, benzopyrimidinyl, isoquinolinyl.

The "ring" in the present application includes saturated rings, unsaturated rings; saturated rings, i.e., cycloalkyl, heterocycloalkyl, unsaturated rings, i.e., cycloalkenyl, heterocycloalkenyl, aryl, and heteroaryl. In this application, the ring system formed by n atoms is an n-membered ring. For example, phenyl is a 6-membered aryl. The 5-14 membered ring in this application is exemplified by, but not limited to: cyclopentane, cyclohexane, benzene ring, indene ring, fluorene ring, 9H-xanthene ring, naphthalene ring, etc. The 5-14 membered ring means a ring system formed by 5-14 ring atoms, for example, the fluorene ring belongs to the 13 membered ring.

In the present application, specific examples of the trialkylsilyl group having 3 to 12 carbon atoms include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, and the like.

In the present application, specific examples of the cycloalkyl group having 3 to 12 carbon atoms include, but are not limited to, cyclopentyl, cyclohexyl, adamantyl, and the like.

An delocalized bond refers to a single bond extending from a ring system

It means that one end of the linkage may be attached to any position in the ring system through which the linkage extends, and the other end to the rest of the compound molecule.

For example, as shown in the following formula (f), naphthyl represented by formula (f) is connected with other positions of the molecule through two non-positioned connecting bonds penetrating through a double ring, and the meaning of the naphthyl represented by the formula (f-1) to the formula (f-10) comprises any possible connecting mode shown in the formula (f-1) to the formula (f-10).

As another example, as shown in the following formula (X '), the phenanthryl group represented by formula (X') is bonded to other positions of the molecule via an delocalized bond extending from the middle of the benzene ring on one side, and the meaning of the phenanthryl group includes any of the possible bonding modes as shown in formulas (X '-1) to (X' -4).

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' group 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).

The present disclosure provides a nitrogen-containing compound, wherein the structural formula of the nitrogen-containing compound is shown in chemical formula 1:

R₁and R₂Are the same or different from each other and are each independently selected from the group consisting of a C1-6 substituent orUnsubstituted alkyl, substituted or unsubstituted aryl having 6 to 14 carbon atoms, or R₁And R₂Are connected with each other to form a cycloalkyl group with 5-10 carbon atoms; the R is₁And R₂The substituents on the substituent groups are the same or different and are respectively and independently selected from deuterium, cyano, halogen groups or alkyl groups with 1-4 carbon atoms;

L₁、L₂、L、Ar₁、Ar₂wherein each substituent is the same or different and is independently selected from deuterium, a halogen group, a cyano group, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atomsAryloxy group of 6-20, arylthio group of 6-20 carbon atoms, trialkylsilyl group of 3-12 carbon atoms and cycloalkyl group of 3-12 carbon atoms; optionally, at L₁、L₂、L、Ar₁And Ar₂Wherein any two adjacent substituents form a substituted or unsubstituted 5-to 14-membered ring, and the substituent on the 14-membered ring is an alkyl group having 1 to 6 carbon atoms.

The nitrogen-containing compounds provided herein have a core group formed from a substituted oxadihydrophenanthrene group and a triarylamine group. In the substituted oxadihydrophenanthrene radicals, the substituents R₁And R₂Can provide electrons to the oxadihydrophenanthrene group through a conjugation/super-conjugation effect, so that the oxadihydrophenanthrene group has a high conjugated electron cloud density. The fused aromatic rings on the benzene rings on the two sides of the oxadihydrophenanthrene can further improve the electron density of a core structure and improve the hole transmission efficiency of the compound. When the substituted oxadihydrophenanthrene group is combined with an arylamine group to form a triarylamine group, the nitrogen-containing compound can have a shallow LUMO energy level, a proper HOMO energy level and a high triplet state energy level, so that the compound has high hole mobility, and the nitrogen-containing compound can be used for a hole transport layer of an organic electroluminescent device or a photoelectric conversion device, so that the luminescent performance and the service life of the organic electroluminescent device or the photoelectric conversion device are improved.

In some embodiments, one of ring a and ring B is selected from a benzene ring or a naphthalene ring and the other is a naphthalene ring or a phenanthrene ring.

In some embodiments, the nitrogen-containing compounds of the present application have a structure represented by the following formula (1-1) -formula (1-18):

in the above-mentioned formulae (1-1), (1-3), (1-4), (1-5), (1-6),(1-8), (1-11), (1-13), (1-14), (1-15), (1-16) and (1-18), the position marked with "H" on the mother nucleus indicates that the position does not carry a substituent nor is connected

For example,

in (1),

the connection is at bit number 8 or 9.

In some embodiments, R₁And R₂Each independently selected from methyl, phenyl or naphthyl, or R₁And R₂Linked to each other to form cyclopentane, cyclohexane or adamantane. Thus, R₁And R₂Can provide electrons to the oxadihydrophenanthrene group to increase the electron cloud density of the oxadihydrophenanthrene group.

In some embodiments, the Ar is₁And Ar₂The same or different from each other, and are respectively and independently selected from substituted or unsubstituted aryl with 6-33 carbon atoms, substituted or unsubstituted heteroaryl with 5-25 carbon atoms, and triphenylsilicon group; wherein Ar is₁、Ar₂Wherein each substituent is the same or different and is independently selected from deuterium, a halogen group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 14 carbon atoms, a heteroaryl group having 5 to 12 carbon atoms, a trimethylsilyl group, a cycloalkyl group having 5 to 10 carbon atoms; at Ar₁And Ar₂When two substituents are present on the same atom, optionally, two of said substituents are linked to each other to form a cyclopentane together with the atom to which they are commonly linked

Cyclohexane

Adamantane

9H-xanthene ring

Or a substituted or unsubstituted fluorene ring

And the substituent on the fluorene ring is alkyl with 1-4 carbon atoms.

In some embodiments, the substituted or unsubstituted aryl group having 6 to 33 carbon atoms includes, but is not limited to: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted fluorenyl, and substituted or unsubstituted spirobifluorenyl.

In some embodiments, the substituted or unsubstituted heteroaryl group having 5 to 25 carbon atoms includes, but is not limited to, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phenanthrolinyl, substituted or unsubstituted benzimidazolyl, and substituted or unsubstituted fluorenylspiroxanthene ring.

In some embodiments, Ar₁、Ar₂Each substituent in (a) is the same or different from each other, and each is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, cyclohexyl, cyclopentyl, adamantyl, phenyl, naphthyl, pyridyl, quinolyl; optionally, Ar₁、Ar₂Any two adjacent substituents in the group form a cyclopentane, cyclohexane, adamantane, fluorene ring, tert-butyl substituted fluorene ring.

Further, said Ar₁And Ar₂Are identical to or different from each other and are each independently selected from the group consisting ofOr unsubstituted radicals Y₁The unsubstituted radical Y₁Selected from the group consisting of:

said Y is₁When the radical is substituted by one or more substituents, Y₁Each substituent of (a) is independently selected from the group consisting of deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, cyclohexyl, cyclopentyl, adamantyl, phenyl, naphthyl, pyridyl, quinolinyl; said Y is₁When more than 1 substituent is present, each substituent may be the same or different.

In some specific embodiments, the Ar is₁And Ar₂Are identical or different from each other and are each independently selected from the following groups:

in some embodiments, L₁、L₂And L are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 18 carbon atoms; l is₁、L₂And each substituent in L is independently selected from deuterium, fluorine, cyano, alkyl with 1-4 carbon atoms, halogenated alkyl with 1-4 carbon atoms, aryl with 6-12 carbon atoms, heteroaryl with 5-12 carbon atoms or trimethylsilyl.

Optionally, in some embodiments, L₁、L₂And L are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 12 carbon atoms.

Alternatively, L₁、L₂And each substituent in L is independently selected from deuterium, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, tert-butyl or trimethylsilyl.

In some embodiments, L₁、L₂And L are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, or a new subunit group formed by connecting two or three of the above subunits through a single bond;

L₁、L₂and each substituent in L is independently selected from deuterium, fluoro, chloro, cyano, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or pyridyl.

In some embodiments, L₁、L₂Each independently selected from a single bond, substituted or unsubstituted group W₁The unsubstituted group W₁Selected from the group consisting of:

the W is₁When a group is substituted by one or more substituents, W₁Each substituent of (a) is independently selected from the group consisting of deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, cyclohexyl, cyclopentyl, phenyl, naphthyl, pyridyl, quinolinyl; the W is₁When the number of the substituents is more than 1, the substituents may be the same or different.

In some more specific embodiments, L₁、L₂Selected from a single bond, orAny one of:

in some embodiments, L is selected from a single bond, a substituted or unsubstituted group W₂The unsubstituted group W₂Selected from the group consisting of:

the W is₂When a group is substituted by one or more substituents, W₂Each substituent of (a) is independently selected from the group consisting of deuterium, fluoro, cyano, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, cyclohexyl, cyclopentyl, phenyl, naphthyl, pyridyl; the W is₂When the number of the substituents is more than 1, the substituents may be the same or different.

In some more specific embodiments, L is selected from a single bond, or any one of the following groups:

in some embodiments of the present application, L₁And L₂Is a single bond or a substituted or unsubstituted phenylene group, L₁、L₂Each substituent in (a) is independently selected from deuterium, fluoro, chloro, cyano, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl or phenyl.

In some embodiments of the present application, L is a single bond, phenylene, naphthylene, or biphenylene.

In some embodiments of the present application, R₃Selected from fluoro, cyano, deuterium, phenyl, tert-butyl, methyl, isopropyl, trimethylsilyl.

In some embodiments of the present application, in formula 1

Selected from the following structures:

in some more specific embodiments of the present application, the nitrogen-containing compound is selected from the group consisting of:

the application also provides an electronic element, which comprises an anode and a cathode which are oppositely arranged, and a functional layer arranged between the anode and the cathode; the functional layer contains the above-mentioned nitrogen-containing compound.

The nitrogen-containing compounds provided herein can be used to form at least one organic film layer in a functional layer to improve voltage characteristics, efficiency characteristics, or lifetime characteristics of an electronic component.

Optionally, the functional layer comprises an energy conversion layer and a hole transport layer between the energy conversion layer and the anode, the hole transport layer comprising the nitrogen-containing compound to improve the transport of holes between the anode and the energy conversion layer.

In one embodiment of the present disclosure, the hole transport layer includes a first hole transport layer and a second hole transport layer (also referred to as a hole adjustment layer) which are sequentially stacked, wherein the first hole transport layer is close to the anode relative to the second hole transport layer; the second hole transport layer comprises the nitrogen-containing compound of the present application. Optionally, the second hole transport layer is composed of the nitrogen-containing compound of the present application

The electronic element of the present application may be an organic electroluminescent device or a photoelectric conversion device. For an organic electroluminescent device, its functional layers may include an organic light-emitting layer as an energy conversion layer; for a photoelectric conversion device, the functional layer may include a photoelectric conversion layer as an energy conversion layer.

According to one embodiment, the electronic component is an organic electroluminescent device. The organic electroluminescent device may be, for example, a red organic electroluminescent device, a blue organic electroluminescent device, a green organic electroluminescent device, a yellow organic electroluminescent device, a white organic electroluminescent device, or an organic electroluminescent device of other colors.

As shown in fig. 1, the organic electroluminescent device includes an anode 100 and a cathode 200 oppositely disposed, and a functional layer 300 disposed between the anode 100 and the cathode 200; the functional layer 300 comprises a nitrogen-containing compound as provided herein.

Alternatively, the functional layer 300 includes a hole transport layer 320, and the hole transport layer 320 is disposed between the organic light emitting layer 330 and the anode 100. The hole transport layer 320 may include the nitrogen-containing compound of the present application.

In a specific embodiment, the hole transport layer 320 includes a first hole transport layer 321 and a second hole transport layer 322 (also referred to as a hole adjusting layer) stacked in sequence, wherein the first hole transport layer 321 is located on a side of the second hole transport layer 322 close to the anode 100. Wherein the second hole transport layer 322 is comprised of a nitrogen containing compound as provided herein. On one hand, the nitrogen-containing compound provided by the application has high hole transport efficiency, and can improve the hole transport efficiency of the hole transport layer 320; on the other hand, the nitrogen-containing compound provided by the application avoids forming a plurality of triarylamine structures, and further avoids the situation that the LUMO energy level of the nitrogen-containing compound is too shallow, which can improve the energy level difference between the second hole transport layer 322 and the organic light-emitting layer 330, so that the second hole transport layer 322 can realize a certain electron blocking effect, and the service life of the organic electroluminescent device is prolonged. On the other hand, the nitrogen-containing compound provided by the present application can have a suitable HOMO level, so that the HOMO levels between the second hole transport layer 322 and the first hole transport layer 321 are both small, and thus the injection efficiency of the first hole transport layer 321 can be improved, and the driving voltage of the organic electroluminescent device can be reduced.

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. Optionally, 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, and the exciton transfers energy to the host material, and the host material transfers energy to the guest material, so that the guest material can emit light. For example, the guest material can be Ir (piq)₂(acac)。

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. 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 host material may be RH-1.

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

Optionally, the cathode 200 comprises a cathode material, which is a material with a small work function that facilitates electron injection into the functional layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or a multilayer material such as LiF/Al, Liq/Al, LiO₂Al, LiF/Ca, LiF/Al and BaF₂But not limited thereto,/Ca. Preferably, a metal electrode comprising an Mg-Ag alloy is included as a cathode.

Optionally, the functional layer 300 may further include a hole injection layer 310, and the hole injection layer 310 is disposed on a surface of the anode 100 near the organic light emitting layer 330. When the functional layer 300 includes the hole transport layer 320 and the hole injection layer 310, the hole injection layer 310 is interposed between the hole transport layer 320 and the anode 100. 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 hole injection layer 310 may include F4-TCNQ and NPB.

Alternatively, as shown in fig. 1, an electron transport layer 340 may be further disposed between the cathode 200 and the organic light emitting layer 330. 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, and the electron transport material may be selected from benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials, which is not particularly limited in this application. For example, the material of the electron transport layer may include ET-06 and LiQ.

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 material for electron injection is Yb.

According to another embodiment, the electronic component may be a photoelectric conversion device, which may include an anode 100 and a cathode 200 oppositely disposed, and a functional layer 300 disposed between the anode 100 and the cathode 200, as shown in fig. 3; the functional layer 300 comprises a nitrogen-containing compound as provided herein. Among them, the functional layer includes a photoelectric conversion layer 360 as an energy conversion layer.

Alternatively, the nitrogen-containing compound provided herein may be used to form at least one organic thin layer in the functional layer 300 to improve the photoelectric conversion device performance, in particular, to increase the open circuit voltage of the photoelectric conversion device or to increase the photoelectric conversion efficiency of the photoelectric conversion device.

According to a specific embodiment, 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. Wherein the hole transport layer contains the nitrogen-containing compound of the present application.

Alternatively, the photoelectric conversion device may be a solar cell, and particularly may be an organic thin film solar cell. .

According to one embodiment, as shown in fig. 2, the electronic device provided by the present application is a first electronic device 400, and the first electronic device 400 includes the organic electroluminescent device. The electronic device 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. Since the electronic device has the organic electroluminescent device, the electronic device has the same beneficial effects, and the details are not repeated.

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.

Hereinafter, the present application will be described in further detail with reference to examples. However, the following examples are merely illustrative of the present application and do not limit the present application.

In the synthesis examples described below, all temperatures are in degrees celsius unless otherwise stated. Some of the reagents were purchased from commercial suppliers such as Aldrich Chemical Company, Arco Chemical Company and Alfa Chemical Company, and some of the intermediates that could not be purchased directly were prepared by simple reaction of commercially available starting materials and were used without further purification unless otherwise stated. The rest of conventional reagents are purchased from Nanjing Congralin chemical industry and industry Co., Ltd, Qingdao Tenglong chemical reagent Co., Ltd, Qingdao ocean chemical plant, etc.

In purification, the column was silica gel column, silica gel (80-120 mesh) was purchased from Qingdao oceanic plant.

In each synthesis example, the conditions for measuring low resolution Mass Spectrometry (MS) data were: agilent 6120 four-stage rod HPLC-M (column model: Zorbax SB-C18, 2.1X 30mm,3.5 μ M, 6min, flow rate 0.6 mL/min. mobile phase: ratio of 5% -95% (acetonitrile containing 0.1% formic acid) in (water containing 0.1% formic acid)), using electrospray ionization (ESI), at 210nm/254nm, with UV detection.

Hydrogen nuclear magnetic resonance spectroscopy: bruker 400MHz NMR instrument in CDCl at room temperature₃Or CD₂Cl₂TMS (0ppm) was used as a reference standard for the solvent (in ppm).

When describing the concentration, M means mol/L. For example, a THF solution of 3M phenylmagnesium bromide means that the concentration of phenylmagnesium bromide in the THF solution is 3 mol/L.

Synthesis of Compounds

1. Synthesis of intermediate I

a. Synthesis of intermediate I-A1

Step (1): synthesis of intermediate I-A-1

Adding 2-iodine-1-methoxynaphthalene (60.00g, 211.19mmol), 3-chloro-2-fluorophenylboronic acid (40.51g, 232.31mmol), potassium carbonate (58.29g, 422.39mmol), tetrabutylammonium bromide (7.02g, 21.12mmol), toluene (300mL), ethanol (180mL) and deionized water (120mL) into a three-neck flask, stirring for 15min under nitrogen protection, adding tetrakis (triphenylphosphine) palladium (2.44g, 2.11mmol), heating to 75 ℃ -80 ℃, and stirring for 6 hours; the reaction solution was cooled to room temperature, washed with water for a plurality of times, dried over anhydrous magnesium sulfate, the organic phase was decompressed to remove the solvent, and recrystallized from dichloroethane/n-heptane to give intermediate I-a-1(31.5g, yield 52.2%) as a white solid.

Step (2): synthesis of intermediate I-A-2

Adding the intermediate I-A-1(29g, 101.14mmol) and dichloromethane (230mL) into a three-neck flask, stirring, slowly dropwise adding boron tribromide (50.68g, 202.28mmol) at the temperature of-5 ℃ under the protection of nitrogen, strictly controlling the temperature of-5 ℃ in the dropwise adding process, controlling the temperature of-5 ℃ after dropwise adding for 2 hours to complete the reaction, slowly dropwise adding the reaction liquid into ice water for quenching, extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, filtering, removing the solvent from the filtrate under reduced pressure to obtain a yellow solid crude product, and boiling, washing and purifying the crude product with petroleum ether to obtain a light yellow solid intermediate I-A-2(16.95g, yield 61.4%).

And (3): synthesis of intermediate I-A1

Intermediate I-A-2(16.8g, 61.6mmol) and DMF (168mL) were added to a three-necked flask, stirred to dissolve under nitrogen and Cs was added₂CO₃(30.11g, 61.6mmol), then heating to 70-80 ℃ for reaction for 4 h; the reaction was cooled to room temperature, deionized water (170mL) was added with stirring, a large amount of solid precipitated with stirring, filtered after 1 hour, and the filtered solid was purified by washing with petroleum ether to give intermediate I-A1(13.1g, 84.1% yield) as a gray solid.

In the following intermediate I-A, intermediates I-A2 to intermediate I-A12 including but not limited to the following Table 1 were prepared in the same synthetic manner as intermediate I-A1 except that starting material 1 was used in place of 2-iodo-1-methoxynaphthalene in the above step (1) and starting material 2 was used in place of 3-chloro-2-fluorophenylboronic acid in step (1):

table 1:

b. synthesis of intermediates I-B:

(1) synthesis of intermediate I-B1:

intermediate I-A1(13g,51.45mmol), lithium (0.79g,113.12mmol), tetramethylethylenediamine (10.2mL,113.12mmol) and 130mL of dried diethyl ether were heated to reflux for 24 h; adding acetone (2.34mL,51.45mmol) at-78 ℃, naturally raising the reaction system to room temperature after the addition, stirring for 12 hours, then slowly adding 3N diluted hydrochloric acid for hydrolysis, separating liquid, adding 130mL concentrated hydrochloric acid into the organic phase under stirring, separating liquid after stirring for 2 hours at room temperature, extracting the aqueous phase with dichloromethane (50mL x 3), combining the organic phases, washing with water to neutrality, adding anhydrous magnesium sulfate for drying, filtering, and removing the solvent from the filtrate under reduced pressure; using a dichloromethane/n-heptane column, off-white solid intermediate I-B1(3.75g, yield 24.7%) and off-white solid intermediate I-B2 were obtained, respectively

(3.3g, yield 21.7%).

Intermediates I-B in the following table were synthesized with reference to the synthesis procedures of intermediates I-B1, I-B2, except that in intermediates I-B below, intermediates I-B including but not limited to intermediates I-B in table 2 below were prepared using the same synthetic route as intermediates I-B1, I-B2, except that intermediate I-a (I-a selected from a group consisting of part or all of I-a2 through I-a 15) was used in place of intermediate I-a1, and starting material 3 was used in place of acetone:

table 2:

synthesis of intermediate I-B38 and intermediate I-B39

Synthesis of intermediates I-B38 and I-B39 with reference to intermediates I-B1 and I-B2, intermediates I-B38 (yield 21%) and I-B39 (yield 14.7%) were prepared using the same synthetic route as intermediates I-B1 and I-B2, except that M-Br (CAS:2111850-52-1) was used instead of intermediate I-A1.

c. Synthesis of intermediates I-C:

(1) synthesis of intermediates I-C1:

step (1):

adding the intermediate I-B1(1.7g,5.76mmol), pinacol diboron (1.91g,5.76mmol), tris (dibenzylideneacetone) dipalladium (0.053g,0.058mmol), 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (0.075g,0.16mmol), potassium acetate (1.41g,14.14mmol) and 1, 4-dioxane (20mL) into a three-necked round bottom flask, heating to 80 ℃ under nitrogen protection, and stirring for 4 h; then cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate for drying, filtering, and removing the solvent from the filtrate under reduced pressure; the crude product was purified by recrystallization from toluene to give intermediate I-C-1 as a solid (1.65g, yield 74.1%).

Step (2):

adding intermediate I-C1-1(1.6g,4.14mmol), 4-chloro-bromobenzene (0.78g,4.14mmol), palladium acetate (0.0093g,0.0.041mmol), 2-dicyclohexyl phosphorus-2 ', 4 ', 6 ' -triisopropyl-biphenyl (0.04g,0.083mmol), potassium carbonate (1.14g,8.28mmol), toluene (15mL), absolute ethanol (10mL) and deionized water (5mL) into a round-bottomed flask, heating to 78 ℃ under nitrogen protection, and stirring for 5 h; then cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate for drying, filtering, and removing the solvent from the filtrate under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to afford intermediate I-C1 as a solid (0.98g, yield 63.5%).

Referring to the procedure for the synthesis of intermediates I-C1 intermediates I-C in the following table were synthesized using the same synthetic route as intermediate I-C1, including but not limited to the intermediates I-C in table 3 below, except that each intermediate I-B was used in place of intermediate I-B1 in step (1) and starting material 4 was used in place of 4-chloro-bromobenzene in step (2):

table 3:

2. preparation of intermediate II:

synthesis example of intermediate II-1

Adding 4-bromobiphenyl (4.50g, 19.3mmol), 4-aminobiphenyl (3.27g, 19.3mmol), tris (dibenzylideneacetone) dipalladium (0.18g,0.19mmol), 2-dicyclohexylphosphorus-2 ', 4 ', 6 ' -triisopropylbiphenyl (0.18g, 0.39mmol) and sodium tert-butoxide (2.78g, 28.96mmol) into toluene (80mL), heating to 108 ℃ under nitrogen protection, stirring for 2h, cooling to room temperature, washing the reaction solution with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, and removing the solvent from the filtrate under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield intermediate II-1 as a white-like solid (4.8g, 77.4% yield).

The following intermediate II was synthesized by reference to the synthesis of intermediate II-1, using the same synthetic route as intermediate II-1 except that starting material 5 was used instead of 4-bromobiphenyl and starting material 6 was used instead of 4-aminobiphenyl, to prepare intermediate II including, but not limited to, the following table 4:

table 4:

secondly, synthesis of the compound:

synthesis example 1 synthesis of compound 1:

adding the intermediate I-B2(2g, 6.78mmol), the intermediate II-1 (2.18g, 6.78mmol), the tris (dibenzylideneacetone) dipalladium (0.06g, 0.068mmol), the 2-dicyclohexyl phosphorus-2 ', 6' -dimethoxy biphenyl (0.056g, 0.14mmol) and the sodium tert-butoxide (0.98g, 10.18mmol) into toluene (30mL), heating to 108 ℃ under the protection of nitrogen, stirring for 3h, cooling to room temperature, washing the reaction liquid with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, and decompressing the filtrate to remove the solvent; the crude product was purified by recrystallization from toluene to give compound 1 as a white solid (2.65g, 67.4% yield).

Mass spectrum LC-MS (ESI, pos.ion): 580.3[ M + H ] M/z]⁺

¹HNMR(400MHz,CDCl₃,):8.53(d,1H),8.41(d,1H),7.95(d,1H),7.89(d,1H),7.84(d,1H),7.65-7.55(m,14H),7.52-7.48(m,2H),7.17-7.07(m,1H),6.99(d,4H),6.94(d,1H),1.67(s,6H).

Synthesis example 2 synthesis of compound 338:

adding the intermediate I-C6(5g, 13.48mmol), the intermediate II-2 (3.31g, 13.4mmol), the tris (dibenzylideneacetone) dipalladium (0.12g, 0.13mmol), the 2-dicyclohexyl phosphorus-2 ', 6' -dimethoxy biphenyl (0.11g, 0.27mmol) and the sodium tert-butoxide (1.94g, 20.22mmol) into toluene (50mL), heating to 108 ℃ under the protection of nitrogen, stirring for 3h, cooling to room temperature, washing the reaction liquid with water, separating, drying the organic phase with anhydrous magnesium sulfate, filtering, and removing the solvent from the filtrate under reduced pressure; the crude product was purified by recrystallization from toluene to give compound 338(5.32g, 68.06%) as a white solid.

Mass spectrum LC-MS (ESI, pos.ion): 580.3[ M + H ] M/z]⁺

¹HNMR(400MHz,CDCl₃,):8.56(d,1H),8.33-8.29(m,3H),8.27(s,1H),8.06-7.99(m,6H),7.93-7.89(m,3H),7.81(d,1H),7.77-7.72(m,4H),7.63(s,1H),7.16-7.13(m,1H),7.10(d,2H),6.98(d,2H),6.95(d,2H),1.69(s,6H).

Referring to the synthesis of compound 338, the following compounds can be prepared using intermediates in the list of intermediates II in Table 5 in place of intermediates II-1 or II-2 in the above reaction and intermediates in the list of intermediates I in place of intermediates I-B2 or I-C6:

table 5:

preparation examples of organic electroluminescent device

Device example 1: red organic electroluminescent device

The anode was prepared by the following procedure: will have a thickness of

The 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 subjected to a surface treatment to increase the work function of the anode (experimental substrate) and remove scum.

Compound F4-TCNQ: NPB at 3%: evaporation rate ratio of 97%Vapor deposition to a thickness of

A Hole Injection Layer (HIL);

depositing NPB on the surface of the hole injection layer to a thickness of

The first hole transport layer (HTL-1).

Vacuum evaporating compound 1 on the first hole transport layer to a thickness of

The hole adjusting layer (HTL-2, i.e., the second hole transport layer).

On the second hole transport layer, a compound RH-1: ir (piq)₂(acac) at 95%: 5% of evaporation rate ratio, and forming a thickness of

Red emitting layer (EML).

On the red light-emitting layer, compounds ET-06 and LiQ were co-evaporated at a weight ratio of 1:1 to form

A thick Electron Transport Layer (ETL).

Vapor plating ytterbium (Yb) on the electron transport layer to a thickness of

Electron Injection Layer (EIL).

On the electron injection layer, magnesium (Mg) and silver (Ag) were mixed in a ratio of 1: 10 by weight ratio to form a film having a thickness of

The cathode of (1).

Finally, CP-05 is evaporated on the cathode to form a film with a thickness of

And (4) an organic capping layer (CPL), thereby completing the fabrication of the organic light emitting device.

Examples 2 to 44

An organic electroluminescent device was fabricated by the same method as example 1, except that the compounds shown in table 7 were used instead of compound 1 in forming the second hole transport layer.

Comparative example 1

An organic electroluminescent device was fabricated by the same method as example 1, except that compound a was used instead of compound 1 in forming the second hole transport layer.

Comparative example 2

An organic electroluminescent device was fabricated in the same manner as in example 1, except that compound b was used instead of compound 1 in forming the second hole transport layer.

Comparative example 3

An organic electroluminescent device was fabricated in the same manner as in example 1, except that the compound c was used instead of the compound 1 in forming the second hole transport layer.

Comparative example 4

An organic electroluminescent device was fabricated by the same method as example 1, except that compound d was used instead of compound 1 in forming the second hole transport layer.

Comparative example 5

An organic electroluminescent device was fabricated by the same method as in example 1, except that compound e was used instead of compound 1 in forming the second hole transport layer.

The material structures used in the above examples and comparative examples are shown in table 6:

TABLE 6

For the organic electroluminescent device prepared as above, at 15mA/cm²Under the condition of (1), the performance of the device, such as driving voltage, efficiency and the like, is analyzed and is at 20mA/cm²The T95 performance of the devices was analyzed under the conditions shown in table 7:

TABLE 7

According to the test results, the current efficiency of the device is improved by at least 13.5% and the light-emitting life of the device is improved by at least 16.5% in examples 1 to 44 in which the compound of the present invention is used as the second hole transport layer in the organic electroluminescent device, compared with comparative examples 1 to 5.

Therefore, when the novel compound disclosed by the invention is used as a second hole transport layer for preparing a red organic electroluminescent device, the efficiency and the service life of the organic electroluminescent device can be effectively improved.

From the test results in the above table, it can be seen that when the compound c of comparative example 3 has two strongly-powered arylamine groups, compared with the compounds of comparative examples 1 to 5, the HOMO level of the compound c of comparative example 3 is too shallow, which results in a larger HOMO level difference ratio with the first hole transport layer, and the efficiency of hole transport to the electron blocking layer and the organic light emitting layer is reduced, and further the light emitting efficiency is reduced, which results in poor current efficiency and poor lifetime of T95 of the device. Compared with the compound a in the comparative example 1, the compound a in the comparative example has a spiro ring ortho-position to the oxygen atom, the space conformation is basically fixed, the carrier transmission efficiency is insufficient, more joule heat is generated between organic layers of the light-emitting device or between the organic layers and the metal electrode, and the service life of the device is reduced to a certain extent. The small parent nucleus of compounds b and c, without the condensed conjugated aromatic group, makes the region slightly lower in electron density and transport properties, and also reduces the lifetime of the device, compared to comparative examples 2 and 3.

Claims

1. A nitrogen-containing compound, wherein the nitrogen-containing compound has a structural formula shown in chemical formula 1:

each R₃Independently selected from deuterium, halogen groups, cyano groups, carbon atomsHaloalkyl with 1-12 carbon atoms, alkyl with 1-12 carbon atoms, deuterated alkyl with 1-12 carbon atoms, alkoxy with 1-12 carbon atoms, cycloalkyl with 3-12 carbon atoms, alkylthio with 1-12 carbon atoms, trialkylsilyl with 3-12 carbon atoms, arylsilyl with 6-18 carbon atoms, aryl with 6-20 carbon atoms, heteroaryl with 3-20 carbon atoms, aryloxy with 6-20 carbon atoms, arylthio with 6-20 carbon atoms, and optionally, any two adjacent R₃Are connected with each other to form an aromatic ring with 6 or 10 carbon atoms;

2. The nitrogen-containing compound according to claim 1, wherein R₁And R₂Are identical or different from one another and are each independently selected from methyl, phenyl or naphthyl, or R₁And R₂Linked to each other to form cyclopentane, cyclohexane or adamantane.

3. The nitrogen-containing compound according to claim 1, wherein the Ar is₁And Ar₂The same or different from each other, and are respectively and independently selected from substituted or unsubstituted aryl with 6-33 carbon atoms, substituted or unsubstituted heteroaryl with 5-25 carbon atoms, and triphenylsilicon group; wherein Ar is₁、Ar₂Wherein each substituent is the same or different from each other and is independently selectedFrom deuterium, a halogen group, a cyano group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 14 carbon atoms, a heteroaryl group having 5 to 12 carbon atoms, a trimethylsilyl group, a cycloalkyl group having 5 to 10 carbon atoms; at Ar₁And Ar₂When two substituents are present on the same atom, optionally, two of the substituents are bonded to each other to form a cyclopentane, cyclohexane, adamantane, 9H-xanthene ring or a substituted or unsubstituted fluorene ring together with the atom to which they are bonded, and the substituent on the fluorene ring is an alkyl group having 1 to 4 carbon atoms.

4. The nitrogen-containing compound according to claim 1, wherein the Ar is₁And Ar₂Are identical or different from one another and are each independently selected from substituted or unsubstituted radicals Y₁The unsubstituted radical Y₁Selected from the group consisting of:

5. The nitrogen-containing compound according to claim 1, wherein L₁、L₂And L are each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a,A substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted anthracylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, or a new subunit group formed by connecting two or three of the above subunits through a single bond;

6. The nitrogen-containing compound according to claim 1, wherein L₁、L₂Each independently selected from a single bond, substituted or unsubstituted group W₁The unsubstituted group W₁Selected from the group consisting of:

7. The nitrogen-containing compound according to claim 1, wherein L is selected from the group consisting of a single bond, a substituted or unsubstituted group W₂The unsubstituted group W₂Selected from the group consisting of:

8. The nitrogen-containing compound according to claim 1, wherein L is selected from a single bond, or any one of the following groups:

9. the nitrogen-containing compound according to claim 1, wherein L₁、L₂Each independently selected from a single bond, or any one of the following groups:

10. the nitrogen-containing compound according to claim 1, wherein L is a single bond.

11. The nitrogen-containing compound according to claim 1, wherein R₃Each independently selected from fluoro, cyano, deuterium, phenyl, tert-butyl, methyl, isopropyl, trimethylsilyl.

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

13. 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; the functional layer comprises the nitrogen-containing compound according to any one of claims 1 to 12.

14. The electronic component according to claim 13, wherein the functional layer comprises an energy conversion layer and a hole transport layer between the energy conversion layer and the anode, the hole transport layer containing the nitrogen-containing compound;

optionally, the hole transport layer includes a first hole transport layer and a second hole transport layer stacked in sequence, and the first hole transport layer is closer to the anode than the second hole transport layer; the second hole transport layer contains the nitrogen-containing compound.

15. An electronic device comprising the electronic component of claim 13 or 14.