WO2021036851A1 - Nitrogen-containing compound, organic electroluminescent device and photoelectric conversion device - Google Patents

Abstract

The present disclosure relates to the technical field of electronic components, and provided therein are a nitrogen-containing compound represented by formula (I), an organic electroluminescent device and a photoelectric conversion device. The nitrogen-containing compound may prolong the service life of an electronic device.

Description

Nitrogen-containing compounds, organic electroluminescence devices, and photoelectric conversion devices

Cross-references to related applications

This disclosure claims the priority of the Chinese patent application filed on August 27, 2019 with the application number CN201910797929.4, and the full content of the above-mentioned Chinese patent application is cited here as a part of this disclosure.

Technical field

The present disclosure relates to the technical field of photoelectric technology conversion, in particular to a nitrogen-containing compound, an organic electroluminescence device, and a photoelectric conversion device.

Background technique

With the development of electronic technology, electronic components used to realize electroluminescence or photoelectric conversion have attracted more and more attention.

Taking an organic electroluminescent device as an example, it includes an anode, a hole transport layer, an electroluminescent layer, an electron transport layer, and a cathode stacked in sequence. When voltage is applied to the cathode and anode, the two electrodes generate an electric field. Under the action of the electric field, the electrons on the cathode side move to the electroluminescent layer, the holes on the anode side also move to the light emitting layer, and the electrons and holes are combined in the electroluminescent layer. Excitons are formed, and the excitons are in an excited state and release energy outwards, which in turn makes the electroluminescent layer emit light to the outside.

In the prior art, KR1020170184785, CN201680003736.1, etc. disclose materials that can prepare hole transport layers in organic electroluminescent devices. However, it is still necessary to continue to develop new materials to further improve the performance of electronic components.

It should be noted that the information disclosed in the background art section above is only used to enhance the understanding of the background of the present disclosure, and therefore may include information that does not constitute the prior art known to those of ordinary skill in the art.

Summary of the invention

The purpose of the present disclosure is to provide a nitrogen-containing compound, an organic electroluminescence device, and a photoelectric conversion device, which can improve the life of the device.

According to one aspect of the present disclosure, a nitrogen-containing compound is provided, and the structure of the nitrogen-containing compound is shown in Formula I:

Wherein, X is selected from C(CH ₃ ) ₂ , O, S, Si(CH ₃ ) ₂ ;

R _{1 is} selected from substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms, substituted or unsubstituted alkynes having 2-24 carbon atoms Groups, substituted or unsubstituted cycloalkyl groups with 3-20 carbon atoms, substituted or unsubstituted heterocycloalkyl groups with 2-20 carbon atoms, substituted or unsubstituted carbon atoms with 7-30 Aralkyl, substituted or unsubstituted heteroaralkyl with 2-30 carbon atoms, substituted or unsubstituted aryl with 6-30 carbon atoms, substituted or unsubstituted 2-30 carbon atoms的heteroaryl;

L ₁ and L _{2 are the} same or different, and are independently selected from substituted or unsubstituted arylene groups with 6-30 carbon atoms, substituted or unsubstituted heteroarylene groups with 6-30 carbon atoms, and substituted Or unsubstituted aralkylene groups with 7-30 carbon atoms, substituted or unsubstituted heteroaralkylene groups with 7-30 carbon atoms;

The substituent of R ₁ is selected from deuterium, halogen, cyano, nitro, alkyl with 1-29 carbon atoms, alkenyl with 2-29 carbon atoms, alkynyl with 2-29 carbon atoms, Aryl groups with 6-29 carbon atoms, heteroaryl groups with 6-29 carbon atoms, aryloxy groups with 6-29 carbon atoms, alkoxy groups with 1-29 carbon atoms, and carbon atoms It is an arylamino group with 6-29, a cycloalkyl group with 3-29 carbon atoms, a heterocycloalkyl group with 2-29 carbon atoms, an alkylsilyl group with 1-29 carbon atoms, and a carbon atom Alkyl boron group with 1-29, aryl boron with 6-29 carbon atoms, arylphosphino with 6-29 carbon atoms, or arylsilyl group with 6-29 carbon atoms Constituted group

The substituents of L ₁ and L ₂ are independently selected from deuterium, halogen, cyano, nitro, alkyl with 1-29 carbon atoms, alkenyl with 2-29 carbon atoms, and 2 carbon atoms. -29 alkynyl, carbon 6-29 aryl, carbon 5-29 heteroaryl, carbon 6-29 aryloxy, carbon 1-29 alkane An oxy group, an arylamino group with 6-29 carbon atoms, a cycloalkyl group with 3-29 carbon atoms, a heterocycloalkyl group with 3-29 carbon atoms, and an alkyl group with 1-29 carbon atoms Silyl group, alkyl boron group with 1-29 carbon atoms, aryl boron group with 6-29 carbon atoms, arylphosphino group with 6-29 carbon atoms or 6-29 carbon atoms The group consisting of arylsilyl groups;

According to another aspect of the present disclosure, an organic electroluminescence device is provided. The organic electroluminescence device includes an anode and a cathode arranged oppositely, and a functional layer arranged between the anode and the cathode. The functional layer contains the aforementioned nitrogen-containing compound.

According to another aspect of the present disclosure, a photoelectric conversion device is provided. The photoelectric conversion device includes an anode and a cathode arranged oppositely, and a functional layer arranged between the anode and the cathode. The functional layer contains the aforementioned nitrogen-containing compound.

The nitrogen-containing compound, organic electroluminescence device and photoelectric conversion device of the present disclosure, on the one hand, because the material contains an adamantyl group, the glass transition temperature is increased, the material crystallization is effectively avoided, and the life of the device is increased. On the other hand, the introduction of nitrogen-containing heterocyclic aromatic hydrocarbons can well adjust the hole injection and transport properties of the material. Combined with the structure of the triphenylamine derivative at the other end, it can ensure that the material has good hole injection and transport properties. , Which shows that the device efficiency and life are better.

It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and cannot limit the present disclosure.

Description of the drawings

By describing its exemplary embodiments in detail with reference to the accompanying drawings, the above and other features and advantages of the present disclosure will become more apparent. Obviously, the drawings in the following description are only some embodiments of the present disclosure. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work.

FIG. 1 is a schematic diagram of the structure of an organic electroluminescent device according to an embodiment of the present disclosure;

FIG. 2 is a schematic diagram of the structure of a photoelectric conversion device according to an embodiment of the present disclosure.

In the figure: 100, anode; 200, cathode; 300, functional layer; 310, hole injection layer; 320, hole transport layer; 330, electron blocking layer; 340, light-emitting layer; 350, electron transport layer; 360, electrons Injection layer; 370, photoelectric conversion layer.

detailed description

Example embodiments will now be described more fully with reference to the accompanying drawings. However, the example embodiments can be implemented in various forms, and should not be construed as being limited to the examples set forth herein; on the contrary, these embodiments are provided so that the present disclosure will be comprehensive and complete, and fully convey the concept of the example embodiments to Those skilled in the art. The described features, structures or characteristics can be combined in one or more embodiments in any suitable way. In the following description, many specific details are provided to give a sufficient understanding of the embodiments of the present disclosure. However, those skilled in the art will realize that the technical solutions of the present disclosure can be practiced without one or more of the specific details, or other methods, materials, devices, etc. can be used. In other cases, well-known technical solutions are not shown or described in detail to avoid obscuring various aspects of the present disclosure. The same reference numerals in the figures indicate the same or similar structures, and thus their detailed descriptions will be omitted.

In addition, the drawings are only schematic illustrations of the present disclosure, and are not necessarily drawn to scale. The same reference numerals in the figures denote the same or similar parts, and thus their repeated description will be omitted. The terms "a" and "the" are used to indicate the presence of one or more elements/components/etc.; the terms "including" and "have" are used to indicate open-ended inclusion and mean in addition to the listed elements There may be other elements/components/etc. besides /components/etc.

Embodiments of the present disclosure provide a nitrogen-containing compound. The structure of the nitrogen-containing compound is shown in formula I:

Wherein, X is selected from C(CH ₃ ) ₂ , O, S, Si(CH ₃ ) ₂ ;

R _{1 is} selected from substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms, substituted or unsubstituted alkynes having 2-24 carbon atoms Groups, substituted or unsubstituted cycloalkyl groups with 3-20 carbon atoms, substituted or unsubstituted heterocycloalkyl groups with 2-20 carbon atoms, substituted or unsubstituted carbon atoms with 7-30 Aralkyl, substituted or unsubstituted heteroaralkyl with 2-30 carbon atoms, substituted or unsubstituted aryl with 6-30 carbon atoms, substituted or unsubstituted 2-30 carbon atoms的heteroaryl;

L ₁ and L _{2 are the} same or different, and are independently selected from substituted or unsubstituted arylene groups with 6-30 carbon atoms, substituted or unsubstituted heteroarylene groups with 6-30 carbon atoms, and substituted Or unsubstituted aralkylene groups with 7-30 carbon atoms, substituted or unsubstituted heteroaralkylene groups with 7-30 carbon atoms;

The substituent of R ₁ is selected from deuterium, halogen, cyano, nitro, alkyl with 1-29 carbon atoms, alkenyl with 2-29 carbon atoms, alkynyl with 2-29 carbon atoms, Aryl groups with 6-29 carbon atoms, heteroaryl groups with 6-29 carbon atoms, aryloxy groups with 6-29 carbon atoms, alkoxy groups with 1-29 carbon atoms, and carbon atoms It is an arylamino group with 6-29, a cycloalkyl group with 3-29 carbon atoms, a heterocycloalkyl group with 2-29 carbon atoms, an alkylsilyl group with 1-29 carbon atoms, and a carbon atom Alkyl boron group with 1-29, aryl boron with 6-29 carbon atoms, arylphosphino with 6-29 carbon atoms, or arylsilyl group with 6-29 carbon atoms Constituted group

The substituents of L ₁ and L ₂ are independently selected from deuterium, halogen, cyano, nitro, alkyl with 1-29 carbon atoms, alkenyl with 2-29 carbon atoms, and 2 carbon atoms. -29 alkynyl, carbon 6-29 aryl, carbon 5-29 heteroaryl, carbon 6-29 aryloxy, carbon 1-29 alkane An oxy group, an arylamino group with 6-29 carbon atoms, a cycloalkyl group with 3-29 carbon atoms, a heterocycloalkyl group with 3-29 carbon atoms, and an alkyl group with 1-29 carbon atoms Silyl group, alkyl boron group with 1-29 carbon atoms, aryl boron group with 6-29 carbon atoms, arylphosphino group with 6-29 carbon atoms or 6-29 carbon atoms The group consisting of arylsilyl groups.

In this application, if there is no specific indication that the group is substituted, it means that the group is unsubstituted.

The nitrogen-containing compound of the embodiment of the present disclosure, on the one hand, because it contains an adamantyl group, it increases the glass transition temperature and effectively avoids crystallization of the material, thereby increasing the life of the device. On the other hand, the inclusion of nitrogen-containing heterocyclic aromatic hydrocarbons can well adjust the hole injection and transport properties of the material. Combined with the structure of the triphenylamine derivative at the other end, it can ensure that the material has good hole injection and transport properties. The device performance is that the device efficiency and life are better.

In this application, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have a substituent (hereinafter, for ease of description, the substituents are collectively referred to as Rc). For example, the "substituted or unsubstituted aryl group" refers to an aryl group having a substituent Rc or an unsubstituted aryl group. The above-mentioned substituents, namely Rc, can be, for example, deuterium, halogen groups, cyano groups, heteroaryl groups with 3-20 carbon atoms, aryl groups with 6-20 carbon atoms, and those with 3-12 carbon atoms. Trialkylsilyl group, triarylsilyl group with 18-30 carbon atoms, alkyl group with 1-10 carbon atoms, haloalkyl group with 1-10 carbon atoms, alkene with 2-6 carbon atoms Group, alkynyl with 2-6 carbon atoms, cycloalkyl with 3-10 carbon atoms, heterocycloalkyl with 2-10 carbon atoms, cycloalkenyl with 5-10 carbon atoms, Heterocycloalkenyl with 4-10 carbon atoms, alkoxy with 1-10 carbon atoms, alkylamino with 1-10 carbon atoms, alkylthio with 1-10 carbon atoms, carbon An aryloxy group with 6-18 atoms, an arylthio group with 6-18 carbon atoms, an alkylsulfonyl group with 6-18 carbon atoms, a trialkylphosphino group with 3-18 carbon atoms, A trialkylboron group having 3-18 carbon atoms.

In this specification, "the number of carbon atoms forming a ring" means a group whose atoms are bonded to form a cyclic structure (for example, a monocyclic group, a condensed ring group, a bridging group, a carbocyclic group, a heterocyclic group) The number of carbon atoms among the atoms constituting the ring itself. When the ring is substituted by a substituent, the carbon atoms contained in the substituent are not included in the number of ring carbon atoms. The "number of ring-forming carbon atoms" mentioned below has the same meaning unless otherwise specified. For example, the benzene ring has 6 carbon atoms, the naphthalene ring has 10 carbon atoms, the phenanthrene ring has 14 carbon atoms, the anthracene ring has 14 carbon atoms, and the furan ring has 4 carbon atoms. . In addition, when an alkyl group is substituted as a substituent on the benzene ring or the naphthalene ring, the carbon number of the alkyl group is not included in the number of ring carbon numbers. In addition, when a fluorene ring is bonded as a substituent to the fluorene ring (including a spirofluorene ring), the carbon number of the fluorene ring as the substituent is included in the number of ring-forming carbons.

In this application, the number of carbon atoms of a substituted or unsubstituted functional group refers to the number of all carbon atoms. For example, if L is a substituted arylene group having 12 carbon atoms, all the carbon atoms of the arylene group and the substituents thereon are 12.

In the present application, "alkyl" may include linear or branched alkyl. Alkyl groups can have 1 to 20 carbon atoms. In this application, a numerical range such as "1 to 20" refers to each integer in the given range; for example, "1 to 20 carbon atoms" means that it can contain 1 Carbon atoms, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 Carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, or 20 carbon atoms base. The alkyl group may also be a medium-sized alkyl group having 1 to 10 carbon atoms. The alkyl group may also be a lower alkyl group having 1 to 6 carbon atoms. In addition, the alkyl group may be substituted or unsubstituted. Specific examples of alkyl groups having 1-20 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isoamyl Base, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, n-dodecyl, n-tetradecyl , N-hexadecyl and so on.

In this application, cycloalkyl refers to a saturated hydrocarbon containing an alicyclic structure, including monocyclic and condensed ring structures. Cycloalkyl groups can have 3-10 carbon atoms, and a numerical range such as "3 to 10" refers to each integer in the given range; for example, "3 to 10 carbon atoms" means that it can contain 3 carbon atoms, Cycloalkyl groups of 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, or 10 carbon atoms. The cycloalkyl group may be a small ring, an ordinary ring, or a large ring having 3 to 10 carbon atoms. Cycloalkyl groups can also be classified as monocyclic-only one ring, bicyclic-two rings-or polycyclic-three or more rings. Cycloalkyl groups can also be divided into two rings sharing one carbon atom-a spiro ring, two rings sharing two carbon atoms-a fused ring, and two rings sharing two or more carbon atoms-a bridged ring. In addition, cycloalkyl groups may be substituted or unsubstituted.

In this application, an aryl group refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aryl group can be a monocyclic aryl group (such as a phenyl group) or a polycyclic aryl group. In other words, the aryl group can be a monocyclic aryl group, a condensed ring aryl group, or two or more monocyclic aryl groups conjugated by a carbon-carbon bond. Cyclic aryl groups, monocyclic aryl groups and fused ring aryl groups conjugated through carbon-carbon bonds, and two or more fused ring aryl groups conjugated through carbon-carbon bonds. That is, unless otherwise specified, two or more aromatic groups conjugated through carbon-carbon bonds may also be regarded as aryl groups in the present application. Among them, the fused ring aryl group may include, for example, a bicyclic fused aryl group (for example, a naphthyl group), a tricyclic fused aryl group (for example, a phenanthryl group, a fluorenyl group, an anthryl group), and the like. The aryl group does not contain heteroatoms such as B, N, O, S, P, Se and Si. For example, in this application, biphenyl, terphenyl, etc. are aryl groups. Examples of aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, benzo[9,10] Phenanthryl, pyrenyl, benzofluoranthene,

Base and so on. In this application, the arylene group referred to refers to a divalent group formed by the further loss of one hydrogen atom of an aryl group.

In this application, the substituted aryl group may be one or more of two hydrogen atoms in the aryl group, such as deuterium atom, halogen group, cyano group, aryl group, heteroaryl group, trialkylsilyl group, alkyl group, Cycloalkyl, alkoxy, alkylthio and other groups are substituted. Specific examples of heteroaryl-substituted aryl groups include, but are not limited to, dibenzofuranyl-substituted phenyl groups, dibenzothiophene-substituted phenyl groups, pyridine-substituted phenyl groups, and the like. Specific examples of aryl-substituted aryl groups include, but are not limited to, phenyl-substituted naphthyl, phenyl-substituted phenanthryl, naphthyl-substituted phenyl, phenyl-substituted anthryl, and the like. It should be 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 substituents on the aryl group. For example, a substituted aryl group with 18 carbon atoms refers to an aryl group and a substituted group. The total number of carbon atoms of the group is 18.

In this application, the fluorenyl group as an aryl group can be substituted, and two substituent groups can be combined with each other to form a spiro structure. Specific examples include but are not limited to the following structures:

In the present application, a heteroaryl group refers to a monovalent aromatic ring containing at least one heteroatom in the ring or a derivative thereof. The heteroatom may be at least one of B, O, N, P, Si, Se, and S. The heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. In other words, the heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems conjugated through carbon-carbon bonds, and any aromatic The ring system is an aromatic monocyclic ring or an aromatic fused ring. Exemplarily, heteroaryl groups may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, Acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazine Azinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thiophene Thienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silylfluorenyl, dibenzofuranyl and N-arylcarbazole Group (such as N-phenylcarbazolyl), N-heteroarylcarbazolyl (such as N-pyridylcarbazolyl), N-alkylcarbazolyl (such as N-methylcarbazolyl), etc., Not limited to this. Among them, thienyl, furanyl, phenanthrolinyl, etc. are heteroaryl groups of a single aromatic ring system type, and N-arylcarbazolyl and N-heteroarylcarbazolyl are multiple groups conjugated through carbon-carbon bonds. Heteroaryl group of ring system type. In this application, the involved heteroarylene group refers to a divalent group formed by the heteroaryl group further losing one hydrogen atom.

In this application, the substituted heteroaryl group may be one or more hydrogen atoms in the heteroaryl group, such as deuterium atom, halogen group, cyano group, aryl group, heteroaryl group, trialkylsilyl group, alkane Group, cycloalkyl, alkoxy, alkylthio and other groups are substituted. Specific examples of aryl-substituted heteroaryl groups include, but are not limited to, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothienyl, phenyl-substituted pyridyl, and the like. It should be understood that the number of carbon atoms of the substituted heteroaryl group refers to the total number of carbon atoms of the heteroaryl group and the substituents on the heteroaryl group.

The nitrogen-containing compounds of the embodiments of the present disclosure will be described in detail below:

In one embodiment of the present application, _{the substituent of R 1} is selected from deuterium, fluorine, cyano, alkyl with 1-5 carbon atoms, aryl with 6-15 carbon atoms, and 6 carbon atoms. The group consisting of -20 heteroaryl, carbon 3-10 cycloalkyl, carbon 3-12 alkylsilyl, or carbon 18-29 arylsilyl group .

In one embodiment of the present application, R _{1 is} selected from substituted or unsubstituted alkyl groups with 1-5 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3-10 carbon atoms, substituted or unsubstituted The aryl group with 6-30 carbon atoms, and the substituted or unsubstituted heteroaryl group with 5-25 carbon atoms.

In one embodiment of the present disclosure, R _{1 is} selected from a substituted or unsubstituted aryl group or heteroaryl group having 10-25 ring carbon atoms.

In one embodiment of the present disclosure, R _{1 is} selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl.

In one embodiment of the present disclosure, R _{1 is} selected from substituted or unsubstituted phenanthrenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl , Substituted or unsubstituted carbazolyl.

In one embodiment of the present disclosure, _{the substituent of R 1} is selected from deuterium, fluorine, cyano, alkyl with 1-5 carbon atoms, aryl with 6-15 carbon atoms, and 3 carbon atoms. -20 heteroaryl, 3-10 cycloalkyl, trimethylsilyl, and triphenylsilyl.

In an embodiment of the present disclosure, _{the substituent of R 1} may be selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, phenanthryl, anthracenyl, Pyridyl, dibenzofuranyl, dibenzothienyl, carbazolyl, phenylcarbazolyl, trimethylsilyl, triphenylsilyl, cyclohexane, phenylcarbazolyl.

In one embodiment of the present disclosure, R ₁ is substituted or unsubstituted T ₁ , and unsubstituted T _{1 is} selected from the group consisting of the following groups:

among them,

Represents a chemical bond;

The substituted T ₁ has one or more than two substituents, and the substituents of T ₁ are independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclohexane, tri Methylsilyl, triphenylsilyl, phenyl, biphenyl, phenanthryl, naphthyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, 9,9- Dimethyl fluorenyl.

In one embodiment of the present application, R _{1 is} selected from:

among them,

Represents a chemical bond.

In one embodiment of the present application, R _{1 is} selected from:

R ₁ may be a substituted or unsubstituted aryl group having 6-30 carbon atoms. Take R ₁ as

As an example, it is an aryl group substituted by a cycloalkyl group with 12 carbon atoms and between 6-30.

In addition, R _{1 is} selected from a substituted or unsubstituted aryl group or heteroaryl group having 10 to 25 ring carbon atoms. The number of ring-forming carbon atoms can be 10, 13, 17, 21, 22, 25, and so on.

In one embodiment of the present application, L ₁ and L _{2 are the} same or different, and are independently selected from substituted or unsubstituted arylene groups with 6-20 carbon atoms, and substituted or unsubstituted carbon atoms with 6. -20 heteroarylene.

In one embodiment of the present application, _{the substituents of L 1} and L ₂ are each independently selected from deuterium, fluorine, cyano, alkyl with 1-5 carbon atoms, and aryl with 6-20 carbon atoms. , A group consisting of a heteroaryl group having 5-20 carbon atoms, an alkylsilyl group having 3-12 carbon atoms, or an arylsilyl group having 18-29 carbon atoms.

In one embodiment of the present application, L ₁ and L _{2 are} selected from substituted or unsubstituted arylene groups having 6-12 ring carbon atoms.

In one embodiment of the present application, L ₁ and L ₂ are each independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene.

In one embodiment of the present application, L ₁ and L ₂ are each independently selected from substituted or unsubstituted naphthylene, substituted or unsubstituted terphenylene.

In one embodiment of the present application, L ₁ and L ₂ are each independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene. Further, L ₁ and L ₂ are each independently selected from:

among them,

Represents a chemical bond.

In addition, L ₁ or L _{2 is} selected from substituted or unsubstituted arylene groups having 6-12 ring carbon atoms. The number of ring-forming carbon atoms can be 6, 8, 9, 12, and so on.

The nitrogen-containing compound may be selected from the following compounds:

The embodiments of the present disclosure also provide an organic electroluminescent device. As shown in FIG. 1, the organic electroluminescent device may include an anode 100, a cathode 200, and a functional layer 300, wherein:

The anode 100 and the cathode 200 are arranged opposite to each other. The functional layer 300 is provided between the anode 100 and the cathode 200. The functional layer 300 includes the nitrogen-containing compound described in any of the above embodiments.

In the organic electroluminescent device of the present disclosure, since the material contains an adamantyl group, the glass transition temperature is increased, and the crystallization of the material is effectively avoided. On the other hand, the introduction of nitrogen-containing heterocyclic aromatic hydrocarbons can well adjust the hole injection and transport properties of the material. Combined with the structure of the triphenylamine derivative at the other end, it can ensure that the material has good hole injection and transport properties. , Which shows that the device efficiency and life are better. Hereinafter, each part of the organic electroluminescent device of the embodiment of the present disclosure will be described in detail:

As shown in FIG. 1, the functional layer 300 may include a hole transport layer 320, and the hole transport layer 320 includes the nitrogen-containing compound.

As shown in FIG. 1, the functional layer 300 may further include a light-emitting layer 340 and an electron transport layer 350. Wherein, the light-emitting layer 340 is disposed on the side of the hole transport layer 320 away from the anode 100. The electron transport layer 350 is disposed on the side of the light-emitting layer 340 close to the cathode 200.

As shown in FIG. 1, the functional layer 300 may further include a hole injection layer 310. The hole injection layer 310 may be provided between the hole transport layer 320 and the light emitting layer 340.

As shown in FIG. 1, the functional layer 300 may further include an electron blocking layer 330, and the electron blocking layer 330 includes the nitrogen-containing compound. The electron blocking layer 330 may be provided between the hole injection layer 310 and the light emitting layer 340. Further, the electron blocking layer 330 and the hole transport layer 320 cannot contain the nitrogen-containing compound at the same time.

As shown in FIG. 1, the functional layer 300 may further include an electron injection layer 360. The electron injection layer 360 may be provided between the electron transport layer 350 and the cathode 200.

The embodiments of the present disclosure also provide a photoelectric conversion device. As shown in FIG. 2, the organic electroluminescent device may include an anode 100, a cathode 200 and a functional layer 300, wherein:

The anode 100 and the cathode 200 are arranged opposite to each other. The functional layer 300 is provided between the anode 100 and the cathode 200. The functional layer 300 includes the nitrogen-containing compound described in any of the above embodiments.

The photoelectric conversion device of the present disclosure, due to the adamantyl group contained in the material, increases the glass transition temperature and effectively avoids crystallization of the material, thereby increasing the life of the device and at the same time improving the photoelectric conversion efficiency of the photoelectric conversion device.

Hereinafter, each part of the photoelectric conversion device of the embodiment of the present disclosure will be described in detail:

As shown in FIG. 2, the functional layer 300 may include a hole transport layer 320, and the hole transport layer 320 includes the nitrogen-containing compound.

As shown in FIG. 2, the functional layer 300 may further include a photoelectric conversion layer 370 and an electron transport layer 350. Wherein, the photoelectric conversion layer 370 is disposed on the side of the hole transport layer 320 away from the anode 100. The electron transport layer 350 is provided on the side of the photoelectric conversion layer 370 close to the cathode 200.

As shown in FIG. 2, the functional layer 300 may further include an electron blocking layer 330, and the electron blocking layer 330 includes the nitrogen-containing compound. The electron blocking layer 330 may be provided between the hole transport layer 320 and the photoelectric conversion layer 370. Further, the electron blocking layer 330 and the hole transport layer 320 cannot contain the nitrogen-containing compound at the same time.

In addition, the photoelectric conversion device may be a solar cell, especially an organic thin film solar cell.

Hereinafter, the present invention will be described in further detail through examples. However, the following examples are merely illustrative of the present invention, and do not limit the present invention.

Synthesis Example

Synthesis of compound 117:

Under the protection of nitrogen, add 50mmol 9,9-dimethylacridine, 50mmol p-bromoiodobenzene, 105mL toluene and 100mmol sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then quickly add three Toluene solution of tert-butyl phosphine 5mmol and Pd ₂ (dba) ₃ 10mmol, after the addition, continue to heat up to 100-105°C and reflux for 12h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, and filter ,concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallize to LC>99.5%, and dry to obtain 35mmol of compound 10-(4-bromophenyl)-9,9-dimethyl-9,10-dihydro Acridine, intermediate 1 (yield 70%).

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 3,5-diphenylaniline, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to warm up to 70-80℃, then slowly add _{0.218mmol of Pd 2} (dba) ₃ and 0.436mmol of x-PHOS. After the addition, continue to heat up to 100-105℃ and reflux for 4 hours. After the reaction is complete, cool down and extract with dichloromethane. The organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallize to LC>99.5%. Drying to obtain 35 mmol of intermediate 2 (yield 80%).

Under the protection of nitrogen, add 35mmol Intermediate 1, 35mmol Intermediate 2, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS. After the addition, continue to heat up to 100-105°C and reflux for 6h. After the reaction is completed, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 21 mmol of compound 117 (yield 60%).

¹ HNMR (CDCl ₂ , 400MHz): 7.52 (m, 4H), 7.49 (s, 1H), 7.41-7.33 (m, 8H), 7.19-7.03 (m, 12H), 6.75 (d, 2H), 6.35 ( t,2H),2.12(s,3H),1.95(s,6H),1.82-1.76(m,6H),1.62(m,6H).

Synthesis of compound 119:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 4-(1-naphthyl)aniline, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to increase the temperature. To 70-80℃, then slowly add _{0.218mmol of Pd 2} dba ₃ and 0.436mmol of x-PHOS. After the addition, continue to heat up to 100-105℃ and reflux for 3 hours. After the reaction is complete, cool down and extract with dichloromethane. The phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 32.81 mmol of intermediate 3 (yield 75%).

Under the protection of nitrogen, add 35mmol Intermediate 1, 35mmol Intermediate 3, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS, after the addition, continue to heat up to 100-105°C and reflux for 10h. After the reaction is completed, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 22.75 mmol of compound 119 (yield 65%).

Synthesis of compound 111:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 4-benzidine, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃ , Then slowly add Pd ₂ (dba) ₃ 0.218mmol and x-PHOS 0.436mmol, after the addition, continue to heat up to 100-105°C and reflux for 3h. After the reaction is complete, cool down, extract with dichloromethane, and wash the organic phase with water. Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 37.19 mmol of Intermediate 4 (yield 85%).

Under the protection of nitrogen, add 35mmol Intermediate 1, 35mmol Intermediate 4, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS. After the addition, continue to heat up to 100-105°C and reflux for 5h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 23.8 mmol of compound 111 (yield 68%).

Synthesis of compound 137:

Under the protection of nitrogen, add 50mmol of 9,9-dimethylacridine, 50mmol of 4-bromo-4'-iodobiphenyl, 105mL of toluene and 100mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80 ℃, then quickly add the toluene solution of tri-tert-butyl phosphine 5mmol and Pd ₂ (dba) ₃ 10mmol, after the addition, continue to heat up to 100-105 ℃ reflux reaction for 15h, after the reaction is complete, cool down, extract with dichloromethane, organic The phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of toluene and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 37.5 mmol of intermediate 5 (yield 75%).

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 4-benzidine, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃ , Then slowly add Pd ₂ (dba) ₃ 0.218mmol and x-PHOS 0.436mmol, after the addition, continue to heat up to 100-105°C and reflux for 3h. After the reaction is complete, cool down, extract with dichloromethane, and wash the organic phase with water. Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 37.19 mmol of Intermediate 6 (yield 85%).

Under the protection of nitrogen, add 35mmol Intermediate 5, 35mmol Intermediate 6, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS. After the addition, continue to heat up to 100-105°C and reflux for 5h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 24.5 mmol of compound 137 (yield 70%).

Synthesis of compound 128:

Under the protection of nitrogen, add 1-(4'-bromo-biphenyl-4-yl)adamantane 43.75mmol, 4-benzidine 43.75mmol, toluene 128mL and sodium tert-butoxide 65.625mmol into the reaction flask, stir and Heat to 70-80°C, then slowly add Pd ₂ (dba) ₃ 0.218mmol and x-PHOS 0.436mmol, after the addition, continue to heat up to 100-105°C and reflux for 3h. After the reaction is complete, cool down and use dichloride Methane extraction, organic phase washing, drying, filtering, and concentration. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallize to LC>99.5%, and dry to obtain 36.31mmol of compound N-(4-(adamantan-1-yl)biphenyl)-[1,1' -Biphenyl]-4-amine, intermediate 7 (yield 83%).

Under the protection of nitrogen, add 35mmol Intermediate 5, 35mmol Intermediate 7, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS, after the addition, continue to heat up to 100-105°C and reflux for 3h. After the reaction is completed, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with toluene, recrystallize to LC>99.95%. After drying, 26.25 mmol of compound 128 was obtained (yield 75%).

Synthesis of compound 90:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 1-naphthylamine, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃ , Then slowly add _{0.218mmol of Pd 2} (dba) ₃ and 0.436mmol of x-PHOS. After the addition, continue to heat up to 100-105°C and reflux for 3 hours. After the reaction is completed, cool down, extract with dichloromethane, and wash the organic phase with water. Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 28.44 mmol of Intermediate 8 (yield 65%).

Under the protection of nitrogen, add 35mmol of 10-(4-bromophenyl)-10H-phenoxazine, 35mmol of Intermediate 8, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat up to 70-80 ℃, then slowly add _{0.35mmol of Pd 2} (dba) ₃ and 0.70mmol of s-PHOS. After the addition, continue to heat up to 100-105℃ and reflux for 4 hours. After the reaction is complete, cool down, extract with dichloromethane, and wash the organic phase with water , Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 21 mmol of compound 90 (yield 60%).

Synthesis of compound 153:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 2-amino-9,9-dimethylfluorene, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, and stir. And heating to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.218mmol, x-PHOS 0.436mmol, after the addition, continue to heat up to 100-105℃ reflux reaction for 2h, after the reaction is complete, cool down, use two Extract with methyl chloride, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 30.625 mmol of intermediate 9 (yield 70%).

Under the protection of nitrogen, add 35mmol of 10-(4-bromophenyl)-10H-phenoxazine, 35mmol of Intermediate 9, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80 ℃, then slowly add _{0.35mmol of Pd 2} (dba) ₃ and 0.70mmol of s-PHOS. After the addition, continue to heat up to 100-105℃ and reflux for 14h. After the reaction is complete, cool down, extract with dichloromethane, and wash the organic phase with water , Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 20.3 mmol of compound 153 (yield 58%).

Synthesis of compound 155:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 2-amino-9,9-diphenylfluorene, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, and stir. And heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.218mmol and x-PHOS 0.436mmol, after the addition, continue to heat up to 100-105℃ and reflux for 2h. After the reaction is complete, cool down and use two Extract with methyl chloride, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 30.625 mmol of intermediate 10 (yield 70%).

Under the protection of nitrogen, add 35mmol of 10-(4-bromophenyl)-10H-phenoxazine, 35mmol of Intermediate 10, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80 ℃, slowly add Pd ₂ (dba) ₃ 0.35mmol and s-PHOS 0.70mmol, after the addition, continue to heat up to 100-105℃ and reflux for 14h. After the reaction is complete, cool down, extract with dichloromethane, and wash the organic phase with water. Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 22.75 mmol of compound 155 (yield 65%).

Synthesis of compound 162:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 3-aminodibenzofuran, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70. -80℃, then slowly add _{0.218mmol of Pd 2} (dba) ₃ and 0.436mmol of x-PHOS. After the addition, continue to heat up to 100-105℃ and reflux for 2h. After the reaction is complete, cool down and extract with dichloromethane. The phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 28.44 mmol of Intermediate 11 (yield 65%).

Under the protection of nitrogen, add 35mmol of 10-(4-bromophenyl)-10H-phenoxazine, 35mmol of Intermediate 11, 160mL of toluene and 52.5mmol of sodium tert-butoxide to the reaction flask, stir and heat up to 70-80 ℃, slowly add _{0.35mmol of Pd 2} (dba) ₃ and 0.70mmol of s-PHOS, after the addition, continue to heat up to 100-105℃ and reflux for 6 hours. After the reaction is complete, cool down, extract with dichloromethane, and wash the organic phase with water. Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 21 mmol of compound 162 (yield 60%).

Synthesis of compound 163:

Under the protection of nitrogen, add 50mmol of phenoxazine, 50mmol of 4-bromo-4'-iodobiphenyl, 105mL of toluene and 100mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, and then quickly add three Toluene solution of tert-butyl phosphine 5mmol and Pd ₂ (dba) ₃ 10mmol, after the addition, continue to heat up to 100-105°C and reflux for 15h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, and filter ,concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 39 mmol of intermediate 12 (yield 78%).

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 3-aminodibenzothiophene, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70. -80℃, then slowly add _{0.218mmol of Pd 2} (dba) ₃ and 0.436mmol of x-PHOS. After the addition, continue to heat up to 100-105℃ and reflux for 2h. After the reaction is complete, cool down and extract with dichloromethane. The phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 29.75 mmol of intermediate 13 (yield 68%).

Under the protection of nitrogen, add 35mmol of Intermediate 12, 35mmol of Intermediate 13, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, slowly add Pd ₂ (dba) ₃ 0.35 mmol and 0.70 mmol of s-PHOS, after the addition, continue to heat up to 100-105°C and reflux for 8 hours. After the reaction is completed, the temperature is lowered, extracted with dichloromethane, the organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. After drying, 22.05 mmol of compound 163 was obtained (yield: 63%).

¹ HNMR(CDCl ₂ ,400MHz): 7.92(d,2H),7.74-7.72(d,2H),7.55-7.42(m,5H),7.41-7.33(m,6H),7.19-7.03(m,6H) ), 6.80 (m, 6H), 2.12 (s, 3H), 1.95 (s, 6H), 1.82-1.76 (m, 6H).

Synthesis of compound 9:

Under the protection of nitrogen, add 50mmol of phenothiazine, 50mmol of p-bromoiodobenzene, 105mL of toluene and 100mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, and quickly add the toluene solution of tri-tert-butyl phosphine 5mmol and Pd ₂ (dba) ₃ 10mmol, after the addition, continue to heat up to 100-105°C and reflux for 10 hours. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 35 mmol of Intermediate 14 (yield 70%).

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 2-amino-9,9-dimethylfluorene, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, and stir. And heat to 70-80℃, slowly add Pd ₂ (dba) ₃ 0.218mmol and x-PHOS 0.436mmol, after the addition, continue to heat up to 100-105℃ and reflux for 2h. After the reaction is complete, cool down and use dichloride Methane extraction, the organic phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 30.625 mmol of Intermediate 15 (yield: 70%).

Under the protection of nitrogen, add 35mmol Intermediate 14, 35mmol Intermediate 15, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS, after the addition, continue to heat up to 100-105°C and reflux for 15h. After the reaction is completed, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 19.25 mmol of compound 9 (yield 55%).

Synthesis of compound 3:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 2-aminobiphenyl, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80 ℃, then slowly add _{0.218mmol of Pd 2} (dba) ₃ and 0.436mmol of x-PHOS. After the addition, continue to heat up to 100-105℃ and reflux for 5 hours. After the reaction is complete, cool down, extract with dichloromethane, and wash the organic phase with water , Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 26.25 mmol of Intermediate 16 (yield 60%).

Under the protection of nitrogen, add 35mmol of Intermediate 14, 35mmol of Intermediate 16, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS, after the addition, continue to heat up to 100-105°C and reflux for 15h. After the reaction is completed, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallize to LC>99.95%. After drying, 18.55 mmol of compound 3 was obtained (yield 53%).

Synthesis of compound 10:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 1-naphthylamine, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃ , Then slowly add _{0.218mmol of Pd 2} (dba) ₃ and 0.436mmol of x-PHOS. After the addition, continue to heat up to 100-105°C and reflux for 3 hours. After the reaction is completed, cool down, extract with dichloromethane, and wash the organic phase with water. Dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 28.44 mmol of Intermediate 17 (yield 65%).

Under the protection of nitrogen, add 35mmol of Intermediate 14, 35mmol of Intermediate 17, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS, after the addition, continue to heat up to 100-105°C and reflux for 15h. After the reaction is completed, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 22.75 mmol of compound 10 (yield 65%).

Synthesis of compound 164:

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 4-(1-naphthyl)aniline, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to increase the temperature. To 70-80℃, then slowly add _{0.218mmol of Pd 2} (dba) ₃ and 0.436mmol of x-PHOS, after the addition, continue to heat up to 100-105℃ and reflux for 3h. After the reaction is complete, cool down and extract with dichloromethane , The organic phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 32.81 mmol of Intermediate 18 (yield 75%).

Under the protection of nitrogen, add 35mmol Intermediate 12, 35mmol Intermediate 18, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS, after the addition, continue to heat up to 100-105°C and reflux for 10h. After the reaction is completed, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.95%, and dried to obtain 23.8 mmol of compound 164 (yield 68%).

Synthesis of compound 165:

Under the protection of nitrogen, add 50mmol of phenothiazine, 50mmol of 4-bromo-4'-iodobiphenyl, 105mL of toluene and 100mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then quickly add three Toluene solution of tert-butyl phosphine 5mmol and Pd ₂ (dba) ₃ 10mmol, after the addition, continue to heat up to 100-105°C and reflux for 15h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, and filter ,concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 36.5 mmol of Intermediate 19 (yield 73%).

Under the protection of nitrogen, add 43.75mmol of 1-(4-bromophenyl)adamantane, 43.75mmol of 3-aminodibenzofuran, 128mL of toluene and 65.625mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70. -80℃, then slowly add _{0.218mmol of Pd 2} (dba) ₃ and 0.436mmol of x-PHOS. After the addition, continue to heat up to 100-105℃ and reflux for 4 hours. After the reaction is complete, cool down and extract with dichloromethane. The phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC>99.5%, and dried to obtain 28.44 mmol of intermediate 20 (yield 65%).

Under the protection of nitrogen, add 35mmol Intermediate 19, 35mmol Intermediate 20, 160mL of toluene and 52.5mmol of sodium tert-butoxide into the reaction flask, stir and heat to 70-80℃, then slowly add Pd ₂ (dba) ₃ 0.35mmol and 0.70mmol of s-PHOS. After the addition, continue to heat up to 100-105°C and reflux for 8h. After the reaction is completed, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallize to LC>99.95%. After drying, 23.1 mmol of compound 165 was obtained (yield 66%).

¹ HNMR(CDCl ₂ ,400MHz): 8.03(s,1H),7.98(d,1H),7.55-7.42(m,6H),7.41-7.25(m,10H),7.15-7.03(m,4H), 6.95-6.85 (m, 5H), 2.12 (s, 3H), 1.95 (s, 6H), 1.82-1.76 (m, 6H).

The HRMS values of the compounds synthesized above are shown in Table 1:

Table 1 HRMS value

Compound number	HRMS	Compound number	HRMS	Compound number	HRMS
117	[M+1] + =739.405	90	[M+1] + =611.306	9	[M+1] + =693.330
119	[M+1] + = 713.389	153	[M+1] + =677.353	3	[M+1] + =653.298
111	[M+1] + = 663.373	155	[M+1] + = 801.384	10	[M+1] + =627.283
137	[M+1] + =739.405	162	[M+1] + =651.301	164	[M+1] + =779.345
128	[M+1] + =815.436	163	[M+1] + =743.309	165	[M+1] + =743.309

Example of production and evaluation of organic electroluminescent device

Fabrication of red organic electroluminescent device

Example 1

The anode is prepared by the following process: the thickness is

The ITO substrate (manufactured by Corning) was cut into a size of 40mm×40mm×0.7mm, and a photolithography process was used to prepare it into an experimental substrate with a pattern of cathode, anode and insulating layer, using ultraviolet ozone and O ₂ :N ₂ plasma. Surface treatment to increase the work function of the anode (experimental substrate) and remove scum.

Vacuum evaporate HAT-CN on the experimental substrate (anode) to form a thickness of

The hole injection layer (HIL), and the synthesized compound 117 is vacuum-evaporated on the hole injection layer to form a thickness of

The hole transport layer (HTL). The HAT-CN is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene.

The compound TCTA is vapor-deposited on the HTL as the electron blocking layer (EBL), the thickness is

According to the weight ratio of 100:5, doping 4,4'-N,N'-dicarbazole-biphenyl (referred to as "CBP") as the host and Ir(acac)(piq) ₂ as the guest to form a thickness of

The light-emitting layer (EML).

The weight doped TPO and LiQ with a ratio of 1:1 are evaporated on the EML as the electron transport layer (ETL), and the thickness is

The weight-doped silver (Ag) and magnesium (Mg) are vapor-deposited on the ETL with a ratio of 10:1 as the cathode, and the thickness is

The compound N-(4-(9H-carbazol-9-yl)phenyl)-4'-(9H-carbazol-9-yl)-N-phenyl-[1,1'- was vapor-deposited on the cathode Biphenyl]-4-amine, as the light extraction layer (CPL), the thickness is

The device performance is shown in Table 2.

Example 2-10

The organic electroluminescent device was fabricated in the same manner as in Example 1, except that the compounds shown in Table 2 were each used when forming the hole transport layer (HTL).

That is, Example 2 uses compound 119 to make organic electroluminescent devices, Example 3 uses compound 111 to make organic electroluminescent devices, Example 137 uses compound 4 to make organic electroluminescent devices, and Example 5 uses compound 128 to make organic electroluminescent devices. Light-emitting devices, Example 6 uses compound 90 to make organic electroluminescent devices, Example 7 uses compound 153 to make organic electroluminescent devices, Example 8 uses compound 155 to make organic electroluminescent devices, and Example 9 uses compound 162 to make organic electroluminescent devices. The electroluminescent device, in Example 10, compound 163 was used to make an organic electroluminescent device. The performance of the device is shown in Table 2.

Comparative example 1

In addition to replacing the compound 117 of the hole transport layer with the compound N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine ( Except for NPB), the same method as in Example 1 was used to fabricate an organic electroluminescence device. The device performance is shown in Table 2.

Comparative example 2

Except that the compound 117 of the hole transport layer was replaced with the compound 9,9'-(1,3-phenyl)bis-9H-carbazole (MCP), the organic electroluminescence was produced by the same method as in Example 1. Device. The device performance is shown in Table 2.

Comparative example 3

Except that the compound 117 of the hole transport layer was replaced with the compound 1,3,5-tris(9-carbazolyl)benzene (TCP), the others were the same as in Example 1, and the same preparation process was used for organic electroluminescence. Device preparation.

Comparative example 7

Except that the compound 117 of the hole transport layer is replaced with the compound P1, the other is the same as in Example 1, and the same preparation process is used to prepare the organic electroluminescent device.

Comparative example 8

Except that the compound 117 of the hole transport layer is replaced with the compound P3, the others are the same as in Example 1, and the organic electroluminescent device is prepared by the same preparation process.

Table 2 Device performance

The above data voltage, luminous efficiency, color coordinates, and T95 lifetime are tested ^{at a constant current density of 10mA/cm 2.}

It can be seen from Table 2 that the luminous efficiency (Cd/A) is increased by at least 21.48%, the external quantum efficiency is increased by at least 9.41%, and the lifetime is increased by at least 57.26% when the CIEx is not much different. The organic electroluminescent device made by using the compound of the present invention has higher luminous efficiency and longer life.

Fabrication of blue organic electroluminescent device

Example 11

The anode is prepared by the following process: the thickness is

The ITO substrate (manufactured by Corning) was cut into a size of 40mm×40mm×0.7mm, and a photolithography process was used to prepare it into an experimental substrate with a pattern of cathode, anode and insulating layer, using ultraviolet ozone and O ₂ :N ₂ plasma. Surface treatment to increase the work function of the anode (experimental substrate) and remove scum.

Vacuum evaporate HAT-CN on the experimental substrate (anode) to form a thickness of

The hole injection layer (HIL), the compound NPB is vapor-deposited on the HIL as the hole transport layer (HTL), and the thickness is

The compound 9 of the present invention was vapor-deposited on the HTL as an electron blocking layer (EBL) with a thickness of

According to the weight ratio of 200:2, α, β-ADN is used as the host, 4,4'-(3,8-diphenylpyrene-1,6-diyl) bis(N,N-diphenylaniline) is used as the guest Doping to form a thickness of

The light-emitting layer (EML) is vapor-deposited on the electron blocking layer.

The weight doped TPO and LiQ with a ratio of 1:1 are evaporated on the EML as the electron transport layer (ETL), and the thickness is

The weight-doped silver (Ag) and magnesium (Mg) are vapor-deposited on the ETL with a ratio of 10:1 as the cathode (cathode), and the thickness is

The compound N-(4-(9H-carbazol-9-yl)phenyl)-4'-(9H-carbazol-9-yl)-N-phenyl-[1,1'- was vapor-deposited on the cathode Biphenyl]-4-amine, as the light extraction layer (CPL), the thickness is

The device performance is shown in Table 1.

Examples 12-15

An organic electroluminescence device was produced in the same manner as in Example 11, except that the compounds shown in Table 3 were each used when forming the electron blocking layer.

That is, Example 12 uses compound 3 to make organic electroluminescent devices, Example 13 uses compound 10 to make organic electroluminescent devices, Example 14 uses compound 164 to make organic electroluminescent devices, and Example 15 uses compound 165 to make organic electroluminescent devices Light emitting device. The device performance is shown in Table 3.

Comparative example 4

Except that the compound 9 of the electron blocking layer was replaced with the compound DMFL-NPB, the organic electroluminescence device was fabricated by the same method as in Example 11. The device performance is shown in Table 3. The CAS number of the DMFL-NPB is 357645-40-0, named N,N'-bis(naphthalene-1-yl)-N,N'-diphenyl-2,7-diamino-9,9- Dimethyl fluorene, the structural formula is:

Comparative example 5

Except that the compound 9 of the electron blocking layer was replaced with the compound TQTPA, the organic electroluminescence device was fabricated by the same method as in Example 11. The device performance is shown in Table 3. The CAS number of the TQTPA is 1142945-07-0, named tris(4-(quinolin-8-yl)phenyl)amine, and the structural formula is:

Comparative example 6

Except for the fact that the electron transport layer was not formed, an organic electroluminescence device was fabricated in the same manner as in Example 11. The device performance is shown in Table 3.

Comparative example 9

Except that the compound 9 of the electron blocking layer is replaced with the compound P1, the other is the same as in Example 11, and the same preparation process is used to prepare the organic electroluminescent device.

Comparative example 10

Except that the compound 9 of the electron blocking layer was replaced with the compound P3, the others were the same as in Example 11, and the same preparation process was used to prepare the organic electroluminescent device.

Table 3 Device performance

The above data voltage, efficiency, color coordinate was tested at a constant current density of 10mA / cm ^2, T95 device life test at a constant current density of 10mA / cm ^2.

It can be seen from Table 3 that when the CIEy is not much different, the working voltage is reduced by 0.22V at the maximum; the luminous efficiency (Cd/A) is increased by at least 3.45%, the external quantum efficiency is increased by at least 23.3%, and the lifetime is increased by at least 37.8%.

It can be seen from Table 2 and Table 3 that when the compound of the present disclosure is used as a hole transport layer and an electron blocking layer, the efficiency and lifetime of the organic electroluminescent device can be improved, and the voltage is also slightly reduced. Therefore, the compound of the present disclosure has characteristics of improving efficiency and life.

Those skilled in the art will easily think of other embodiments of the present disclosure after considering the description and practice. This application is intended to cover any variations, uses, or adaptive changes of the present disclosure, and these variations, uses, or adaptive changes follow the general principles of the present disclosure and include common knowledge or conventional technical means in the technical field. The description and the embodiments are only regarded as exemplary, and the true scope and spirit of the present disclosure are pointed out by the appended claims.

Claims (23)

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

   

   Wherein, X is selected from C(CH ₃ ) ₂ , O, S, Si(CH ₃ ) ₂ ;

   R _{1 is} selected from substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms, substituted or unsubstituted alkynes having 2-24 carbon atoms Groups, substituted or unsubstituted cycloalkyl groups with 3-20 carbon atoms, substituted or unsubstituted heterocycloalkyl groups with 2-20 carbon atoms, substituted or unsubstituted carbon atoms with 7-30 Aralkyl, substituted or unsubstituted heteroaralkyl with 2-30 carbon atoms, substituted or unsubstituted aryl with 6-30 carbon atoms, substituted or unsubstituted 2-30 carbon atoms的heteroaryl;

   L ₁ and L _{2 are the} same or different, and are independently selected from substituted or unsubstituted arylene groups with 6-30 carbon atoms, substituted or unsubstituted heteroarylene groups with 6-30 carbon atoms, and substituted Or unsubstituted aralkylene groups with 7-30 carbon atoms, substituted or unsubstituted heteroaralkylene groups with 7-30 carbon atoms;

   The substituent of R ₁ is selected from deuterium, halogen, cyano, nitro, alkyl with 1-29 carbon atoms, alkenyl with 2-29 carbon atoms, alkynyl with 2-29 carbon atoms, Aryl groups with 6-29 carbon atoms, heteroaryl groups with 6-29 carbon atoms, aryloxy groups with 6-29 carbon atoms, alkoxy groups with 1-29 carbon atoms, and carbon atoms It is an arylamino group with 6-29, a cycloalkyl group with 3-29 carbon atoms, a heterocycloalkyl group with 2-29 carbon atoms, an alkylsilyl group with 1-29 carbon atoms, and a carbon atom Alkyl boron group with 1-29, aryl boron with 6-29 carbon atoms, arylphosphino with 6-29 carbon atoms, or arylsilyl group with 6-29 carbon atoms Constituted group

   The substituents of L ₁ and L ₂ are independently selected from deuterium, halogen, cyano, nitro, alkyl with 1-29 carbon atoms, alkenyl with 2-29 carbon atoms, and 2 carbon atoms. -29 alkynyl, carbon 6-29 aryl, carbon 5-29 heteroaryl, carbon 6-29 aryloxy, carbon 1-29 alkane An oxy group, an arylamino group with 6-29 carbon atoms, a cycloalkyl group with 3-29 carbon atoms, a heterocycloalkyl group with 3-29 carbon atoms, and an alkyl group with 1-29 carbon atoms Silyl group, alkyl boron group with 1-29 carbon atoms, aryl boron group with 6-29 carbon atoms, arylphosphino group with 6-29 carbon atoms or 6-29 carbon atoms The group consisting of arylsilyl groups.
2. The nitrogen-containing compound according to claim 1, wherein _{the substituent of R 1} is selected from the group consisting of deuterium, fluorine, cyano, alkyl with 1-5 carbon atoms, and aryl with 6-15 carbon atoms , Heteroaryl groups with 6-20 carbon atoms, cycloalkyl groups with 3-10 carbon atoms, alkylsilyl groups with 3-12 carbon atoms, or aryl groups with 18-29 carbon atoms The group consisting of silyl groups.
3. The nitrogen-containing compound according to claim 1 or 2, wherein R _{1 is} selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms, and substituted or unsubstituted alkyl groups having 3 to 10 carbon atoms. Cycloalkyl groups, substituted or unsubstituted aryl groups with 6-30 carbon atoms, and substituted or unsubstituted heteroaryl groups with 5-25 carbon atoms.
4. The nitrogen-containing compound according to any one of claims 1 to 3, wherein R _{1 is} selected from a substituted or unsubstituted aryl group or heteroaryl group having 10-25 ring carbon atoms.
5. The nitrogen-containing compound according to any one of claims 1 to 4, wherein R _{1 is} selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, Substituted or unsubstituted terphenyl.
6. The nitrogen-containing compound according to any one of claims 1 to 5, wherein R _{1 is} selected from substituted or unsubstituted phenanthryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzofuran Benzothienyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl.
7. The nitrogen-containing compound according to any one of claims 1 to 6, wherein R ₁ is substituted or unsubstituted T ₁ , and unsubstituted T _{1 is} selected from the group consisting of the following groups:

   

   among them,

   

   Represents a chemical bond;

   The substituted T ₁ has one or more than two substituents, and the substituents of T ₁ are independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclohexane, tri Methylsilyl, triphenylsilyl, phenyl, biphenyl, phenanthryl, naphthyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, 9,9- Dimethyl fluorenyl.
8. The nitrogen-containing compound according to any one of claims 1 to 7, wherein R _{1 is} selected from:

   
9. The nitrogen-containing compound according to any one of claims 1 to 8, wherein R _{1 is} selected from:

   

   among them,

   

   Represents a chemical bond.
10. The nitrogen-containing compound according to any one of claims 1 to 9, wherein L ₁ and L _{2 are the} same or different, and are independently selected from substituted or unsubstituted arylenes having 6-20 carbon atoms. The number of the group, substituted or unsubstituted carbon atoms is 6-20 heteroarylene.
11. The nitrogen-containing compound according to any one of claims 1 to 10, wherein the _{substituents of L 1} and L ₂ are independently selected from the group consisting of deuterium, fluorine, cyano, and alkane having 1 to 5 carbon atoms. Group, aryl group with 6-20 carbon atoms, heteroaryl group with 5-20 carbon atoms, alkylsilyl group with 3-12 carbon atoms, or aryl group with 18-29 carbon atoms The group consisting of silyl groups.
12. The nitrogen-containing compound according to any one of claims 1 to 11, wherein L ₁ and L ₂ are each independently selected from substituted or unsubstituted arylenes having 6-12 ring carbon atoms. base.
13. The nitrogen-containing compound according to any one of claims 1 to 12, wherein L ₁ and L ₂ are each independently selected from a substituted or unsubstituted phenylene group, and a substituted or unsubstituted biphenylene group.
14. The nitrogen-containing compound according to any one of claims 1 to 13, wherein L ₁ and L ₂ are each independently selected from a substituted or unsubstituted naphthylene group, and a substituted or unsubstituted terphenylene group.
15. The nitrogen-containing compound according to any one of claims 1 to 14, wherein L ₁ and L ₂ are each independently selected from:

    

    among them,

    

    Represents a chemical bond.
16. The nitrogen-containing compound according to any one of claims 1 to 15, wherein the nitrogen-containing compound is selected from the following compounds:

    

    

    

    

    

    

    
17. An organic electroluminescence device, characterized in that it comprises an anode and a cathode arranged oppositely, and a functional layer arranged between the anode and the cathode;

    The functional layer comprises the nitrogen-containing compound according to any one of claims 1-16.
18. The organic electroluminescent device according to claim 17, wherein the functional layer comprises a hole transport layer, and the hole transport layer contains the nitrogen-containing compound.
19. The organic electroluminescent device according to claim 17 or 18, wherein the functional layer includes an electron blocking layer, and the electron blocking layer includes the nitrogen-containing compound.
20. A photoelectric conversion device, characterized in that it comprises an anode and a cathode arranged oppositely, and a functional layer arranged between the anode and the cathode;

    The functional layer comprises the nitrogen-containing compound according to any one of claims 1-16.
21. The photoelectric conversion device according to claim 20, wherein the functional layer includes a hole transport layer, and the hole transport layer contains the nitrogen-containing compound.
22. The organic electroluminescent device according to claim 20 or 21, wherein the functional layer includes an electron blocking layer, and the electron blocking layer includes the nitrogen-containing compound.
23. The photoelectric conversion device according to any one of claims 20 to 22, wherein the photoelectric conversion device is a solar cell.

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