KR102422466B1 - Nitrogen-containing compounds, organic electroluminescent devices and photoelectric conversion devices - Google Patents

Abstract

The present invention provides a nitrogen-containing compound represented by the following formula (I), an organic electroluminescent device and a photoelectric conversion device, and relates to the field of electronic device technology. The nitrogen-containing compound may improve the lifespan of an electronic device.

Description

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

The present invention relates to the field of photoelectric conversion technology, and more particularly to nitrogen-containing compounds, organic electroluminescent devices and photoelectric conversion devices.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority of the Chinese patent application filed on August 27, 2019 with the application number CN201910797929.4, and the entire contents of the application are incorporated herein by reference.

With the development of electronic technology, electronic devices for realizing electroluminescence or photoelectric conversion are attracting more attention.

In the case of an organic electroluminescent device, it includes an anode, a hole transporting layer, an electroluminescent layer, an electron transporting layer and a cathode that are sequentially stacked. When a voltage is applied to the cathode and anode, the two electrodes generate an electric field, and by the action of the electric field, electrons on the cathode side move to the electroluminescent layer, and holes on the anode side also move to the light emitting layer, and electrons and holes are combined in the electroluminescent layer. to form excitons, the excitons emit energy to the outside in an excited state, and accordingly, the electroluminescent layer emits light to the outside.

In the prior art, patents such as KR1020170184785, CN201680003736.1, etc. disclosed a material capable of manufacturing a hole transport layer inside an organic electroluminescent device. However, in order to further improve the performance of electronic devices, it is necessary to continuously develop new materials.

The information disclosed in the background section is used only to enhance the understanding of the background of the present invention, and may include information that does not constitute the prior art known to those skilled in the art.

An object of the present invention is to provide a nitrogen-containing compound, an organic electroluminescent device, and a photoelectric conversion device capable of improving the lifetime of the device.

A first aspect of the present invention provides a nitrogen-containing compound, wherein the structure of the compound is represented by the following formula (I):

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

R ₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, 3 to 20 A substituted or unsubstituted cycloalkyl group having 2 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, 2 to 30 carbon atoms a substituted or unsubstituted heteroaralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms;

L ₁ and L ₂ are the same or different and are each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 6 to 30 carbon atoms, and 7 to 30 carbon atoms a substituted or unsubstituted aralkylene group having a group, a substituted or unsubstituted heteroaralkylene group having 7 to 30 carbon atoms;

The substituent of R ₁ is deuterium, halogen, cyano group, nitro group, an alkyl group having 1 to 29 carbon atoms, an alkenyl group having 2 to 29 carbon atoms, an alkynyl group having 2 to 29 carbon atoms, 6 to 29 carbon atoms an aryl group having 6 to 29 carbon atoms, a heteroaryl group having 6 to 29 carbon atoms, an aryloxy group having 6 to 29 carbon atoms, an alkoxy group having 1 to 29 carbon atoms, an arylamino group having 6 to 29 carbon atoms, 3 to 29 carbon atoms A cycloalkyl group having carbon atoms, a heterocycloalkyl group having 2 to 29 carbon atoms, an alkylsilyl group having 1 to 29 carbon atoms, an alkylboron group having 1 to 29 carbon atoms, an arylboron group having 6 to 29 carbon atoms, selected from the group consisting of an arylphosphine group having 6 to 29 carbon atoms or an arylsilyl group having 6 to 29 carbon atoms;

The substituents of L ₁ and L ₂ are each independently deuterium, halogen, cyano group, nitro group, an alkyl group having 1 to 29 carbon atoms, an alkenyl group having 2 to 29 carbon atoms, an alkynyl group having 2 to 29 carbon atoms, An aryl group having 6 to 29 carbon atoms, a heteroaryl group having 5 to 29 carbon atoms, an aryloxy group having 6 to 29 carbon atoms, an alkoxy group having 1 to 29 carbon atoms, aryl having 6 to 29 carbon atoms An amino group, a cycloalkyl group having 3 to 29 carbon atoms, a heterocycloalkyl group having 3 to 29 carbon atoms, an alkylsilyl group having 1 to 29 carbon atoms, an alkylboron group having 1 to 29 carbon atoms, 6 to 29 carbon atoms It is selected from the group consisting of an arylboron group having a valence atom, an arylphosphine group having 6 to 29 carbon atoms, or an arylsilyl group having 6 to 29 carbon atoms.

Another aspect of the present invention provides an organic electroluminescent device. The organic electroluminescent device includes an anode, a cathode, and a functional layer provided between the anode and the cathode. The functional layer includes the nitrogen-containing compound.

Another aspect of the present invention provides a photoelectric conversion device. The photoelectric conversion device includes an anode, a cathode, and a functional layer provided between the anode and the cathode. The functional layer includes the nitrogen-containing compound.

The nitrogen-containing compound, organic electroluminescent device and photoelectric conversion device of the present invention, on the one hand, because the material contains an adamantyl group, improves the glass transition temperature and effectively prevents crystallization of the material, thereby improving the lifetime of the device. . On the other hand, by introducing a nitrogen-containing heterocyclic aromatic hydrocarbon, the hole injection and transport properties of the material can be well controlled, and it is combined with the structure of the triphenylamine derivative at the opposite end so that the material has excellent hole injection and transport performance. guarantee, and the efficiency and lifetime of the device are both improved.

The foregoing general description and the following detailed description are illustrative and explanatory, and should not be construed as limiting the invention.

The above and other features and advantages of the present invention will become more apparent by describing the embodiments of the present invention in detail in conjunction with the accompanying drawings. The accompanying drawings described below show some embodiments of the present invention, and a person of ordinary skill in the art can obtain other accompanying drawings based on these accompanying drawings without creative labor.
1 is a structural diagram of an organic electroluminescent device according to an embodiment of the present invention.
2 is a structural diagram of a photoelectric conversion device according to an embodiment of the present invention.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. However, exemplary embodiments may be implemented in various forms and should not be construed as being limited to the examples described herein; On the other hand, these embodiments are provided so that the present invention will be more comprehensive and complete, and will fully convey the principles of the exemplary embodiments to those skilled in the art. A feature, structure, or characteristic described herein may be combined in one or more embodiments in any suitable manner. In the following description, numerous specific details are provided in order to provide a thorough understanding of the embodiments of the present invention. However, one of ordinary skill in the art may recognize that the technical solutions of the present invention may be practiced without one or more of the specific details or using other methods, materials, apparatus, and the like. In other instances, well-known technical solutions have not been shown or described in detail in order to avoid obscuring various aspects of the present invention. Since the same reference numerals in the drawings indicate the same or similar structures, detailed descriptions thereof will be omitted.

In addition, the accompanying drawings are only schematic illustrations of the present invention, and are not necessarily drawn to scale. In the drawings, the same reference numerals denote the same or similar parts, and thus detailed description thereof will be omitted. The terms "a" and "the" indicate that there is one or more elements/components and the like; The terms “comprising” and “having” mean an open-ended inclusion, meaning that there may be other elements/components/etc in addition to the listed elements/components/etc.

Embodiments of the present invention provide nitrogen containing compounds. The structure of the nitrogen-containing compound is represented by the following formula (I),

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

R ₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, 3 to 20 A substituted or unsubstituted cycloalkyl group having 2 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, 2 to 30 carbon atoms a substituted or unsubstituted heteroaralkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms;

L ₁ and L ₂ are the same or different and are each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 6 to 30 carbon atoms, and 7 to 30 carbon atoms a substituted or unsubstituted aralkylene group having a group, a substituted or unsubstituted hetero aralkylene group having 7 to 30 carbon atoms;

The substituent of R ₁ is deuterium, halogen, cyano group, nitro group, an alkyl group having 1 to 29 carbon atoms, an alkenyl group having 2 to 29 carbon atoms, an alkynyl group having 2 to 29 carbon atoms, 6 to 29 carbon atoms an aryl group having 6 to 29 carbon atoms, a heteroaryl group having 6 to 29 carbon atoms, an aryloxy group having 6 to 29 carbon atoms, an alkoxy group having 1 to 29 carbon atoms, an arylamino group having 6 to 29 carbon atoms, 3 to 29 carbon atoms A cycloalkyl group having carbon atoms, a heterocycloalkyl group having 2 to 29 carbon atoms, an alkylsilyl group having 1 to 29 carbon atoms, an alkylboron group having 1 to 29 carbon atoms, an arylboron group having 6 to 29 carbon atoms, selected from the group consisting of an arylphosphine group having 6 to 29 carbon atoms or an arylsilyl group having 6 to 29 carbon atoms;

The substituents of L ₁ and L ₂ are each independently deuterium, halogen, cyano group, nitro group, an alkyl group having 1 to 29 carbon atoms, an alkenyl group having 2 to 29 carbon atoms, an alkynyl group having 2 to 29 carbon atoms, An aryl group having 6 to 29 carbon atoms, a heteroaryl group having 5 to 29 carbon atoms, an aryloxy group having 6 to 29 carbon atoms, an alkoxy group having 1 to 29 carbon atoms, aryl having 6 to 29 carbon atoms An amino group, a cycloalkyl group having 3 to 29 carbon atoms, a heterocycloalkyl group having 3 to 29 carbon atoms, an alkylsilyl group having 1 to 29 carbon atoms, an alkylboron group having 1 to 29 carbon atoms, 6 to 29 carbon atoms It is selected from the group consisting of an arylboron group having a valence atom, an arylphosphine group having 6 to 29 carbon atoms, or an arylsilyl group having 6 to 29 carbon atoms.

In the present invention, unless otherwise specified, a group refers to an unsubstituted group.

Since the nitrogen-containing compound according to an embodiment of the present invention contains an adamantyl group on the one hand, the glass transition temperature is improved to effectively prevent crystallization of the material, thereby improving the lifetime of the device. On the other hand, by including the nitrogen-containing heterocyclic aromatic hydrocarbon, the hole injection and transport properties of the material can be well controlled, and the material has excellent hole injection and transport performance by combining with the structure of the triphenylamine derivative at the opposite end. This ensures that both the efficiency and lifespan of the device are improved.

In the present invention, the term “substituted or unsubstituted” means that the functional group described after the term may or may not have a substituent (hereinafter, for convenience of description, the substituent is collectively referred to as Rc). For example, "a substituted or unsubstituted aryl group" means an aryl group having a substituent (Rc) or an unsubstituted aryl group. The substituent (Rc) is, for example, deuterium, a halogen group, a cyano group, a heteroaryl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, 18 to triarylsilyl group having 30 carbon atoms, alkyl group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, alkynyl group having 2 to 6 carbon atoms, 3 A cycloalkyl group having to 10 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 5 to 10 carbon atoms, a heterocycloalkenyl group having 4 to 10 carbon atoms, a heterocycloalkenyl group having 1 to 10 carbon atoms An alkoxy group, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, 6 to 18 carbon atoms alkylsulfonyl having carbon atoms, trialkylphosphine having 3 to 18 carbon atoms, trialkylboron having 3 to 18 carbon atoms.

As used herein, the term “ring carbon atoms” refers to carbon atoms in the atoms constituting the ring itself in a group in which atoms are bonded in a cyclic structure (eg, monocyclic group, condensed cyclic group, bridging group, carbocyclic group, heterocyclic group). means the number of When the ring is substituted with a substituent, the carbon atoms included in the substituent are not included in the number of carbon atoms forming the ring. Unless otherwise specified, "the number of ring carbon atoms" has the same meaning. For example, the benzene ring has 6 ring carbon atoms, the naphthalene ring has 10 ring carbon atoms, the phenanthrene ring has 14 ring carbon atoms, the anthracene ring has 14 ring carbon atoms, and furan The number of ring carbon atoms in the ring is four. In addition, when the alkyl group is substituted with a substituent in the benzene ring or the naphthalene ring, the number of carbon atoms in the alkyl group is not included in the number of carbon atoms in the ring. In the case where a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the number of carbon atoms in the fluorene ring as a substituent is included in the number of ring carbon atoms.

In the present invention, the number of carbon atoms in the substituted or unsubstituted functional group means the total number of carbon atoms. For example, when L is a substituted arylene group having 12 carbon atoms, the number of all carbon atoms in the arylene group and its substituents is 12.

In the present invention, the “alkyl group” may include a straight-chain or branched-chain alkyl group. An alkyl group may have 1 to 20 carbon atoms, and in the present invention, a numerical range such as “1 to 20” represents each integer in the given range, for example, “1 to 20 carbon atoms” means 1 carbon atom, 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 carbons which may contain 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 is an alkyl group. The alkyl group may also be an intermediate 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 a substituted or unsubstituted alkyl group. Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n- heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and the like.

In the present application, cycloalkyl refers to a saturated hydrocarbon containing alicyclic structures including monocyclic and condensed ring structures. A cycloalkyl group can have 3 to 10 carbon atoms, eg, a numerical range such as “3 to 10” means each integer in the given range, eg, “3 to 10 carbon atoms” means 3 may refer to a cycloalkyl group containing 4 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms or 10 carbon atoms. A cycloalkyl group may have a small ring, a normal ring or a large ring having 3 to 10 carbon atoms. Cycloalkyl groups may also be divided into monocyclic-only one ring, bicyclic-2 rings or polycyclic-3 or more rings. Cycloalkyl groups can also be divided into spiro rings in which two rings share one carbon atom, fused rings in which two rings share two carbon atoms, and bridged rings in which two rings share two or more carbon atoms. . In addition, the cycloalkyl group may be substituted or unsubstituted.

In the present invention, the aryl group means any functional group or substituent derived from an aromatic carbocyclic ring. The aryl group may be a monocyclic aryl group (eg, a phenyl group) or a polycyclic aryl group, that is, the aryl group is a monocyclic aryl group, a condensed cyclic aryl group, two or more monocyclic aryl groups conjugated through a carbon-carbon bond; It may be a monocyclic aryl group and a condensed cyclic aryl group conjugated by a carbon-carbon bond, or two or more condensed cyclic aryl groups conjugated by a carbon-carbon bond. That is, unless otherwise specified, two or more aromatic groups conjugated through a carbon-carbon bond may be considered as an aryl group in the present invention. The condensed cyclic aryl group may be, for example, a bicyclic condensed aryl group (eg, a naphthyl group), a tricyclic condensed aryl group (eg, a phenanthryl group, a fluorenyl group, an anthryl group), and the like. The aryl group does not include hetero atoms such as B, N, O, S, P, Se and Si. For example, in the present invention, biphenyl, terphenyl, and the like are aryl groups. Examples of the aryl group include a phenyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a tetraphenyl group, a pentaphenyl group, a benzo[9,10]phenanthryl group, pyrene, benzofluoran ten, chrysene groups, and the like, but are not limited thereto. In the present invention, the arylene group means a divalent group formed by further losing one hydrogen atom of the aryl group.

In the present invention, the substituted aryl group is one or more hydrogen atoms in the aryl group by a deuterium atom, a halogen group, a cyano group, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, etc. It may be a substituted aryl group. Specific examples of the heteroaryl group substituted aryl group may include, but are not limited to, a dibenzofuran substituted phenyl group, a dibenzothiophene substituted phenyl group, a pyridyl substituted phenyl group, 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. The number of carbon atoms in the substituted aryl group indicates the total number of carbon atoms in the aryl group and the substituents of the aryl group, for example, a substituted aryl group having 18 carbon atoms indicates that the total number of carbon atoms in the aryl group and the substituents is 18 .

In the present invention, the fluorenyl group that is an aryl group may be substituted, and two substituents may be bonded to each other to form a spiro structure, and specific examples may include the following structure, but are not limited thereto.

.

.

In the present invention, the heteroaryl group refers to a monovalent aromatic ring or a derivative thereof including one or more heteroatoms in the ring, and the heteroatom may be one or more of B, O, N, P, Si , Se and S. The heteroaryl group may be a single ring heteroaryl group or a multiple ring heteroaryl group, that is, the heteroaryl group may be a single aromatic ring system or a multiple aromatic ring system conjugated via a carbon-carbon bond, any aromatic ring system comprising one aromatic single ring or one aromatic fused ring. Illustratively, the heteroaryl group is a thiophene group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridyl group, a bipyridyl group, a pyrimidinyl group, Triazinyl group, acridinyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phenoxazinyl group, phthalazinyl group, pyridinopyrimidinyl, pyridopyrazinyl, Pyrazinopyrazinyl, isoquinolinyl group, indolyl group, carbazolyl group, benzooxazolyl, benzoimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophene group, dibenzothiophene, thienothiophene group , benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group, benzothiazolyl, phenothiazinyl group, silafluorenyl, dibenzofuran and N-aryl group carbazolyl group (for example, N-phenylcarbazolyl group), N-heteroaryl group carbazolyl group (eg, N-pyridyl group carbazolyl group), N-alkylcarbazolyl group (eg, N-methylcarba sleepy group) and the like, but is not limited thereto. The thiophene group, furanyl group, phenanthroline group, etc. are heteroaryl groups of a single aromatic ring type, and the N-aryl group carbazolyl group and the N-heteroaryl group carbazolyl group are conjugated through a carbon-carbon bond. It is a polycyclic type heteroaryl group. In the present invention, the heteroarylene group means a divalent group formed by further losing one hydrogen atom of the aryl group.

In the present invention, the substituted heteroaryl group is one or more hydrogen atoms in the heteroaryl group is a deuterium atom, a halogen group, a cyano group, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, etc. It may be a heteroaryl group substituted by a group. Specific examples of the aryl substituted heteroaryl group may include, but are not limited to, a phenyl substituted dibenzofuran, a phenyl substituted dibenzothiophene, a phenyl substituted pyridyl group, and the like. The number of carbon atoms in the substituted heteroaryl group refers to the total number of carbon atoms in the heteroaryl group and the substituents of the heteroaryl group.

Hereinafter, the nitrogen-containing compound according to an embodiment of the present invention will be described in detail.

In one embodiment of the present invention, the substituent of R ₁ is deuterium, fluorine, cyano, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkylsilyl group having 3 to 12 carbon atoms or an arylsilyl group having 18 to 29 carbon atoms.

In one embodiment of the present invention, R ₁ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 30 carbon atoms a cyclic aryl group, a substituted or unsubstituted heteroaryl group having 5 to 25 carbon atoms.

In one embodiment of the present invention, R ₁ is selected from a substituted or unsubstituted aryl group or heteroaryl group having 10 to 25 ring-forming carbon atoms.

In one embodiment of the present invention, R ₁ is selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl, and a substituted or unsubstituted terphenyl.

In one embodiment of the present invention, R ₁ is a substituted or unsubstituted phenanthrenyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophene group, a substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl.

In one embodiment of the present invention, the substituent of R ₁ is deuterium, fluorine, cyano group, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, It is selected from a cycloalkyl group having 3 to 10 carbon atoms, a trimethylsilyl group, and a triphenylsilyl group.

In one embodiment of the present invention, the substituent of R ₁ is deuterium, fluorine, cyano group, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, phenanthryl, anthracenyl, pyridyl, dibenzofuranyl, It may be selected from a dibenzothiophene group, carbazolyl, phenylcarbazolyl, trimethylsilyl, triphenylsilyl, cyclohexane, and phenylcarbazolyl.

In an embodiment of the present invention, R ₁ is substituted or unsubstituted T ₁ , and unsubstituted T ₁ is selected from the group consisting of the following groups.

.

.

는 화학결합을 나타내며;remind

represents a chemical bond;

Substituted T ₁ has 1 or 2 or more substituents, and the substituents of T ₁ are independently deuterium, fluorine, cyano group, methyl, ethyl, isopropyl, tert-butyl, cyclohexane, trimethylsilyl, triphenylsilyl, phenyl, biphenyl, phenanthryl, naphthyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothiophene group, 9,9-dimethylfluorenyl.

In one embodiment of the present invention, R ₁ is selected from the following compounds,

는 화학결합을 나타낸다.remind

represents a chemical bond.

In one embodiment of the present invention, R ₁ is selected from the following compounds.

.

.

을 예를 들면, 사이클로알킬기로 치환된 아릴기이고, 12개의 탄소원자를 가지며, 탄소원자수는 6 내지 30개 사이에 속한다.R ₁ may be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. R ₁

For example, it is an aryl group substituted with a cycloalkyl group, has 12 carbon atoms, and the number of carbon atoms is between 6 and 30.

Further, R ₁ is selected from a substituted or unsubstituted aryl group or heteroaryl group having 10 to 25 ring-forming carbon atoms. The number of ring-forming carbon atoms may be 10, 13, 17, 21, 22, 25, or the like.

In an embodiment of the present invention, L ₁ and L ₂ are the same or different, and each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted hetero group having 6 to 20 carbon atoms arylene groups.

In one embodiment of the present invention, the substituents of L ₁ and L ₂ are each independently deuterium, fluorine, cyano group, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, 5 to 20 carbon atoms. is selected from the group consisting of a heteroaryl group having a single atom, an alkylsilyl group having 3 to 12 carbon atoms, or an arylsilyl group having 18 to 29 carbon atoms.

In one embodiment of the present invention, L ₁ and L ₂ are selected from a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.

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

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

In an embodiment of the present invention, L ₁ and L ₂ are each independently selected from substituted or unsubstituted phenylene and substituted or unsubstituted biphenylene. In addition, L ₁ and L ₂ are each independently selected from the following compounds,

;

;

는 화학결합을 나타낸다.remind

represents a chemical bond.

Further, L ₁ or L ₂ is selected from a substituted or unsubstituted arylene group having 6 to 12 carbon atoms. The number of ring-forming carbon atoms may be 6, 8, 9, 12, or the like.

The nitrogen-containing compound is selected from the following compounds.

.

.

An embodiment of the present invention also provides 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 ,

The anode 100 and the cathode 200 are installed to face 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 according to any of the above embodiments.

Since the organic electroluminescent device of the present invention contains an adamantyl group in the material, the glass transition temperature is improved, and crystallization of the material is effectively prevented. On the other hand, by introducing a nitrogen-containing heterocyclic aromatic hydrocarbon, the hole injection and transport properties of the material can be well controlled, and it is combined with the structure of the triphenylamine derivative at the opposite end so that the material has excellent hole injection and transport performance. guarantee, and the efficiency and lifetime of the device are both improved. Hereinafter, each part of the organic electroluminescent device according to an embodiment of the present invention will be described in detail.

1 , the functional layer 300 may include a hole transport layer 320 including the nitrogen-containing compound.

1 , the functional layer 300 may further include an emission layer 340 and an electron transport layer 350 . The light emitting layer 340 is provided on one side of the hole transport layer 320 far away from the anode 100 . The electron transport layer 350 is provided on one side of the emission layer 340 adjacent to the cathode 200 .

1 , the functional layer 300 may also include a hole injection layer 310 . The hole injection layer 310 may be provided between the hole transport layer 320 and the emission layer 340 .

1 , the functional layer 300 may further include an electron blocking layer 330 including the nitrogen-containing compound. The electron blocking layer 330 may be provided between the hole injection layer 310 and the emission layer 340 . Also, the electron blocking layer 330 and the hole transporting layer 320 cannot contain the nitrogen-containing compound at the same time.

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 .

An embodiment of the present invention also provides 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 ,

The anode 100 and the cathode 200 are installed to face 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 according to any of the above embodiments.

Since the photoelectric conversion device of the present invention contains an adamantyl group in the material, the glass transition temperature is improved to effectively prevent crystallization of the material, thereby improving the lifetime of the device and improving the photoelectric conversion efficiency of the photoelectric conversion device.

Hereinafter, each part of the photoelectric conversion device according to an embodiment of the present invention will be described in detail.

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

2 , the functional layer 300 may further include a photoelectric conversion layer 370 and an electron transport layer 350 . The photoelectric conversion layer 370 is provided on one side far away from the anode 100 of the hole transport layer 320 . The electron transport layer 350 is provided on one side of the photoelectric conversion layer 370 adjacent to the cathode 200 .

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

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

Hereinafter, the present invention will be described in detail through examples. However, the following examples illustrate the present invention, and do not limit the present invention.

Synthesis Example

Synthesis of compound 117:

In a reaction flask under nitrogen protection, 50 mmol of 9,9-dimethylacridine, 50 mmol of bromoiodobenzene, 105 mL of toluene and 100 mmol of sodium tert-butoxide were added, stirred and heated to 70-80°C, followed by tri-tert- 5 mmol of a toluene solution of butylphosphine and 10 mmol of Pd ₂ (dba) ₃ were rapidly added, followed by heating to 100-105° C. and refluxing for 12 hours, after completion of the reaction, cooling and extraction with dichloromethane, organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization to LC>99.5%, and drying to compound 10-(4-bromophenyl)-9,9-dimethyl-9,10-dihydroacry 35 mmol of Dean, i.e. Intermediate 1 (yield 70%) is obtained.

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 3,5-diphenylaniline, 128 mL of toluene, and 65.625 mmol of sodium tert-butoxide were added and stirred at 70-80°C. After heating to a furnace, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, followed by heating at 100-105° C. to reflux for 4 hours, and after completion of the reaction, cooling and dichloromethane extracted, the organic phase washed with water, dried, filtered and concentrated. It is passed through a column with a mixed solvent of dichloromethane and n-heptane and recrystallized to LC>99.5%. Drying gives intermediate 2 (35 mmol, yield 80%).

Intermediate 1 (35mmol), Intermediate 2 (35mmol), 160mL of toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was added slowly, continuously heated to 100-105 ° C., and refluxed for 6 hours. After the reaction was completed, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 117 (21 mmol, yield 60%).

¹ HNMR (CDCl ₂ , 400 MHz): 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:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 4-(1-naphthyl)aniline, 128 mL of toluene, and 65.625 mmol of sodium tert-butoxide were added and stirred to 70- After heating to 80° C., 0.218 mmol of Pd ₂ (dba ₃ ) and 0.436 mmol of x-PHOS were slowly added, followed by heating to 100-105° C. to reflux for 3 hours, and after completion of the reaction, cooled and dichloromethane Extraction with methane, the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 3 (32.81 mmol, yield 75%).

Intermediate 1 (35mmol), Intermediate 3 (35mmol), 160mL toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection and heated to 70-80°C with stirring, followed by Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was slowly added, continuously heated to 100-105 ° C., and refluxed for 10 hours. After completion of the reaction, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 119 (22.75 mmol, yield 65%).

Synthesis of compound 111:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 4-biphenylamine, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added, stirred and heated to 70-80°C. After that, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, heated to 100-105 ° C., and refluxed for 3 hours. After the reaction was completed, cooled and 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, recrystallization was performed at LC>99.5% and dried to obtain Intermediate 4 (37.19 mmol, yield 85%).

Intermediate 1 (35mmol), Intermediate 4 (35mmol), 160mL toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was slowly added, continuously heated to 100-105 ° C., and refluxed for 5 hours. After completion of the reaction, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 111 (23.8 mmol, yield 68%).

Synthesis of compound 137:

In a reaction flask under nitrogen protection, 50 mmol of 9,9-dimethylacridine, 50 mmol of 4-bromo-4'-iodobiphenyl, 105 mL of toluene, and 100 mmol of sodium tert-butoxide were added, stirred and heated to 70-80 ° C. After that, 5 mmol of a toluene solution of tri-tert-butylphosphine and 10 mmol of Pd ₂ (dba) ₃ were rapidly added, and then heated to 100-105° C. and refluxed for 15 hours. After the reaction was completed, cooled and dichloromethane Extraction with methane, the organic phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of toluene and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 5 (37.5 mmol, yield 75%).

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 4-biphenylamine, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added, stirred and heated to 70-80°C. After that, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, heated to 100-105 ° C., and refluxed for 3 hours. After the reaction was completed, cooled and 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>99.5% and dried to obtain Intermediate 6 (37.19 mmol, yield 85%).

Intermediate 5 (35mmol), Intermediate 6 (35mmol), 160mL of toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was slowly added, continuously heated to 100-105 ° C., and refluxed for 5 hours. After completion of the reaction, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 137 (24.5 mmol, yield 70%).

Synthesis of compound 128:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4'-bromo-biphenyl-4-yl)adamantane, 43.75 mmol of 4-biphenylamine, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added and stirred After heating to 70-80 ℃, Pd ₂ (dba) ₃ 0.218 mmol and x-PHOS 0.436 mmol were slowly added, and then heated to 100-105 ℃ to reflux for 3 hours, and after the reaction was completed, Cool and extract with dichloromethane, the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization to LC>99.5% and drying to compound N-(4-(adamantan-1-yl)biphenyl)-[1,1' -Biphenyl]-4-amine 36.31 mmol, that is, intermediate 7 (yield 83%) is obtained.

Intermediate 5 (35mmol), Intermediate 7 (35mmol), 160mL toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was added slowly, continuously heated to 100-105 ° C., and refluxed for 3 hours. After completion of the reaction, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. Pass the column through toluene and recrystallize to LC>99.95%. Drying to give compound 128 (26.25 mmol, yield 75%).

Synthesis of compound 90:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 1-naphthylamine, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added, stirred and heated to 70-80°C. After that, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, heated to 100-105 ° C., and refluxed for 3 hours. After the reaction was completed, cooled and extracted with dichloromethane. , the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 8 (28.44 mmol, yield 65%).

To a reaction flask under nitrogen protection, 35 mmol of 10-(4-bromophenyl) -10H -phenoxazine, Intermediate 8 (35 mmol), 160 mL of toluene and 52.5 mmol of sodium tert-butoxide were added, stirred and heated to 70-80°C After that, 0.35 mmol of Pd ₂ (dba) ₃ and 0.70 mmol of s-PHOS were slowly added, continuously heated to 100-105 ° C., and refluxed for 4 hours. After the reaction was completed, cooled and extracted with dichloromethane. , the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 90 (21 mmol, yield 60%).

Synthesis of compound 153:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 2-amino-9,9-dimethylfluorene, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added and stirred. After heating to 70-80 ° C, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, followed by heating to 100-105 ° C, reflux reaction for 2 hours, and after completion of the reaction, cooling and extracted with dichloromethane, the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 9 (30.625 mmol, yield 70%).

35mmol of 10-(4-bromophenyl)-10H-phenoxazine, Intermediate 9 ( 35mmol ), 160mL of toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80°C After that, 0.35 mmol of Pd ₂ (dba) ₃ and 0.70 mmol of s-PHOS were slowly added, continuously heated to 100-105 ° C., and refluxed for 14 hours. After the reaction was completed, cooled and extracted with dichloromethane. , the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 153 (20.3 mmol, yield 58%).

Synthesis of compound 155:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 2-amino-9,9-diphenylfluorene, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added and stirred. After heating to 70-80 ° C, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, followed by heating to 100-105 ° C. and reflux reaction for 2 hours, after the reaction was completed, Cool 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 is recrystallized to LC>99.5% and dried to obtain Intermediate 10 (30.625 mmol, yield 70%).

35mmol of 10-(4-bromophenyl)-10H-phenoxazine, intermediate 10 ( 35mmol ), 160mL of toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80°C After that, 0.35 mmol of Pd ₂ (dba) ₃ and 0.70 mmol of s-PHOS were slowly added, continuously heated to 100-105 ° C., and refluxed for 14 hours. After the reaction was completed, cooled and extracted with dichloromethane. , the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 155 (22.75 mmol, yield 65%).

Synthesis of compound 162:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 3-aminodibenzofuran, 128 mL of toluene, and 65.625 mmol of sodium tert-butoxide were added and stirred to 70-80°C. After heating, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, followed by heating to 100-105° C. and refluxing for 2 hours, after completion of the reaction, cooling and extraction with dichloromethane and the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 11 (28.44 mmol, yield 65%).

35mmol of 10-(4-bromophenyl)-10H-phenoxazine, intermediate 11 ( 35mmol ), 160mL of toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80°C After that, 0.35 mmol of Pd ₂ (dba) ₃ and 0.70 mmol of s-PHOS were slowly added, continuously heated to 100-105 ° C., and refluxed for 6 hours. After the reaction was completed, cooled and extracted with dichloromethane. , the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 162 (21 mmol, yield 60%).

Synthesis of compound 163:

50 mmol of phenoxazine, 50 mmol of 4-bromo-4'-iodobiphenyl, 105 mL of toluene, and 100 mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80° C., followed by tri-tert- 5 mmol of a toluene solution of butylphosphine and 10 mmol of Pd ₂ (dba) ₃ were rapidly added, followed by heating to 100-105° C. and refluxing for 15 hours, after completion of the reaction, cooling and extraction with dichloromethane, organic phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.5% and dried to obtain Intermediate 12 (39 mmol, yield 78%).

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 3-aminodibenzothiophene, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added and stirred at 70-80°C. After heating to a furnace, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, followed by heating at 100-105° C. to reflux for 2 hours, and after completion of the reaction, cooling and dichloromethane extracted, the organic phase washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 13 (29.75 mmol, yield 68%).

Intermediate 12 (35mmol), Intermediate 13 (35mmol), 160mL toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was slowly added, continuously heated to 100-105 ° C., and refluxed for 8 hours. After the reaction was completed, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. It is passed through a column with a mixed solvent of dichloromethane and n-heptane and recrystallized to LC>99.95%. Drying to obtain compound 163 (22.05 mmol, yield 63%).

¹ HNMR (CDCl ₂ , 400 MHz): 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:

In a reaction flask under nitrogen protection, 50 mmol of phenothiazine, 50 mmol of bromoiodobenzene, 105 mL of toluene and 100 mmol of sodium tert-butoxide were added, stirred and heated to 70-80° C., followed by toluene of tri-tert-butylphosphine. 5 mmol of the solution and 10 mmol of Pd ₂ (dba) ₃ were rapidly added, followed by heating to 100-105° C. and refluxing for 10 hours, after completion of the reaction, cooling and extraction with dichloromethane, washing the organic phase with water, Dry, filter and concentrate. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 14 (35 mmol, yield 70%).

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 2-amino-9,9-dimethylfluorene, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added and stirred. After heating to 70-80°C, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, followed by heating to 100-105° C. to reflux for 2 hours, and after completion of the reaction, cooling and extracted with dichloromethane, the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.5% and dried to obtain Intermediate 15 (30.625 mmol, yield 70%).

Intermediate 14 (35mmol), Intermediate 15 (35mmol), 160mL of toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was slowly added, continuously heated to 100-105 ° C., and refluxed for 15 hours. After the reaction was completed, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 9 (19.25 mmol, yield 55%).

Synthesis of compound 3:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 2-aminobiphenyl, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added, stirred and heated to 70-80°C After that, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, heated to 100-105 ° C., and refluxed for 5 hours. After the reaction was completed, cooled and extracted with dichloromethane. , the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 16 (26.25 mmol, yield 60%).

Intermediate 14 (35mmol), Intermediate 16 (35mmol), 160mL toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was slowly added, continuously heated to 100-105 ° C., and refluxed for 15 hours. After the reaction was completed, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. It is passed through a column with a mixed solvent of dichloromethane and n-heptane and recrystallized to LC>99.95%. Drying to obtain compound 3 (18.55 mmol, yield 53%).

Synthesis of compound 10:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 1-naphthylamine, 128 mL of toluene and 65.625 mmol of sodium tert-butoxide were added, stirred and heated to 70-80°C. After that, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, heated to 100-105 ° C., and refluxed for 3 hours. After the reaction was completed, cooled and 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>99.5% and dried to obtain intermediate 17 (28.44 mmol, yield 65%).

Intermediate 14 (35mmol), Intermediate 17 (35mmol), 160mL toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was slowly added, continuously heated to 100-105 ° C., and refluxed for 15 hours. After the reaction was completed, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. After passing through a column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 10 (22.75 mmol, yield 65%).

Synthesis of compound 164:

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 4-(1-naphthyl)aniline, 128 mL of toluene, and 65.625 mmol of sodium tert-butoxide were added and stirred to 70- After heating to 80 °C, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added thereto, followed by heating to 100-105 °C, refluxing for 3 hours, and after completion of the reaction, cooled and dichloromethane Extraction with methane, 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>99.5% and dried to obtain Intermediate 18 (32.81 mmol, yield 75%).

Intermediate 12 (35mmol), Intermediate 18 (35mmol), 160mL of toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was slowly added, continuously heated to 100-105 ° C., and refluxed for 10 hours. After completion of the reaction, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallization was performed at LC>99.95% and dried to obtain compound 164 (23.8 mmol, yield 68%).

Synthesis of compound 165:

In a reaction flask under nitrogen protection, 50 mmol of phenothiazine, 50 mmol of 4-bromo-4'-iodobiphenyl, 105 mL of toluene, and 100 mmol of sodium tert-butoxide were added, stirred and heated to 70-80° C., followed by tri-tert - 5 mmol of a toluene solution of butylphosphine and 10 mmol of Pd ₂ (dba) ₃ are rapidly added, and then heated to 100-105° C. and refluxed for 15 hours. After completion of the reaction, cooled and extracted with dichloromethane, The organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 19 (36.5 mmol, yield 73%).

To a reaction flask under nitrogen protection, 43.75 mmol of 1-(4-bromophenyl)adamantane, 43.75 mmol of 3-aminodibenzofuran, 128 mL of toluene, and 65.625 mmol of sodium tert-butoxide were added and stirred to 70-80°C. After heating, 0.218 mmol of Pd ₂ (dba) ₃ and 0.436 mmol of x-PHOS were slowly added, followed by heating at 100-105° C. to reflux for 4 hours, and after completion of the reaction, cooling and extraction with dichloromethane and the organic phase is washed with water, dried, filtered and concentrated. After passing through a column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.5% and dried to obtain Intermediate 20 (28.44 mmol, yield 65%).

Intermediate 19 (35mmol), Intermediate 20 (35mmol), 160mL toluene and 52.5mmol of sodium tert-butoxide were added to a reaction flask under nitrogen protection, stirred and heated to 70-80℃, Pd ₂ (dba) ₃ 0.35mmol And 0.70 mmol of s-PHOS was added slowly, continuously heated to 100-105 ° C., and refluxed for 8 hours. After completion of the reaction, cooled and extracted with dichloromethane, the organic phase was washed with water, dried, filtered and Concentrate. It is passed through a column with a mixed solvent of dichloromethane and n-heptane and recrystallized to LC>99.95%. Drying gives compound 165 (23.1 mmol, yield 66%).

¹ HNMR (CDCl ₂ , 400 MHz): 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).

HRMS values of the synthesized compounds are shown in Table 1.

Table 1 HRMS values

Examples of manufacturing and evaluation of organic electroluminescent devices

Preparation of red organic electroluminescent device

Example 1

The anode is manufactured through the following process. That is: an ITO substrate (Corning Corporation) having an ITO thickness of 1500 Å is cut to a size of 40 mm × 40 mm × 0.7 mm, and is manufactured as an experimental substrate having a cathode, anode and insulating layer pattern through a photolithography process, UV, ozone and O ₂ Surface treatment is performed using :N ₂ plasma to increase the work function of the anode (experimental substrate) and remove scum.

HAT-CN was vacuum deposited on the test substrate (anode) to form a hole injection layer (HIL) with a thickness of 100 Å, and the synthesized compound 117 was vacuum deposited on the hole injection layer (HIL) to form a hole transport layer (HTL) with a thickness of 850 Å. to form The HAT-CN is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrine.

The compound TCTA was deposited to a thickness of 100 Å as an electron blocking layer (EBL) on the HTL.

4,4'-N,N'-dicarbazole-biphenyl (abbreviated as “CBP”) as a host material and Ir(acac)(piq) ₂ as a guest material in a weight ratio of 100:5 to a light emitting layer with a thickness of 330 Å (EML) is formed.

TPO and LiQ are mixed in a weight ratio of 1:1, and deposited to a thickness of 350 Å on EML as an electron transport layer (ETL).

Silver (Ag) and magnesium (Mg) are mixed in a weight ratio of 10:1 and deposited to a thickness of 150 Å on the ETL as a cathode.

Compound N-(4-( 9H -carbazol-9-yl)phenyl)-4'-( 9H -carbazol-9-yl)-N-phenyl- on the cathode as a light extraction layer (CPL) [1,1'-biphenyl]-4-amine is deposited to a thickness of 650 Å. The device performance can be referred to Table 2.

Examples 2 to 10

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compounds shown in Table 2 were respectively used when the hole transport layer (HTL) was formed.

That is, in Example 2, an organic electroluminescent device was prepared using compound 119, in Example 3 an organic electroluminescent device was manufactured using compound 111, and in Example 4, an organic electroluminescent device was prepared using compound 137. In Example 5, an organic electroluminescent device was prepared using compound 128, in Example 6 an organic electroluminescent device was prepared using compound 90, and in Example 7, an organic electroluminescent device was prepared using compound 153. In Example 8, an organic electroluminescent device was prepared using compound 155, in Example 9 an organic electroluminescent device was prepared using compound 162, and in Example 10, an organic electroluminescent device was prepared using compound 163. The device is manufactured, and the device performance is shown in Table 2.

Comparative Example 1

Except for replacing compound 117 of the hole transport layer with compound N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) to manufacture an organic electroluminescent device in the same manner as in Example 1. The device performance can be referred to Table 2.

Comparative Example 2

An organic electroluminescent device was prepared in the same manner as in Example 1, except that compound 117 of the hole transport layer was replaced with compound 9,9'-(1,3-phenyl)di- 9H -carbazole (MCP). do. The device performance can be referred to Table 2.

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that compound 117 of the hole transport layer was replaced with compound 1,3,5-tris(9-carbazolyl)benzene (TCP).

Comparative Example 7

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that compound 117 of the hole transport layer was replaced with compound P1.

Comparative Example 8

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that compound 117 of the hole transport layer was replaced with compound P3.

Table 2 Device Performance

Data such as voltage, luminous efficiency, color coordinates and T95 lifetime were tested at a constant current density of 10 mA/cm ² .

As can be seen from Table 2, under the condition that the difference in CIEx is not large, the luminous efficiency (Cd/A) is improved by 21.48%, the external quantum efficiency by 9.41%, and the lifetime by 57.26% or more. Organic electroluminescent devices manufactured using the compounds of the present invention have higher luminous efficiency and longer lifetime.

Fabrication of blue organic electroluminescent device

Example 11

The anode is manufactured through the following process. That is: an ITO substrate (Corning Corporation) having an ITO thickness of 1500 Å is cut to a size of 40 mm × 40 mm × 0.7 mm, and is manufactured as an experimental substrate having a cathode, anode and insulating layer pattern through a photolithography process, UV, ozone and O ₂ Surface treatment is performed using :N ₂ plasma to increase the work function of the anode (experimental substrate) and remove scum.

HAT-CN is vacuum deposited on the test substrate (anode) to form a hole injection layer (HIL) with a thickness of 100 Å, and a compound NPB is vacuum deposited on the hole injection layer (HIL) to form a hole transport layer (HTL) with a thickness of 850 Å .

On the HTL, the compound 9 of the present invention as an electron blocking layer (EBL) is deposited to a thickness of 100 Å.

α,β-ADN as host material and 4,4′-(3,8-diphenylpyrene-1,6-diyl)bis(N,N-diphenylaniline) as guest material in a weight ratio of 200:2 The mixture is deposited on the electron blocking layer to form an emission layer (EML) having a thickness of 220 Å.

TPO and LiQ are mixed in a weight ratio of 1:1, and deposited to a thickness of 350 Å on EML as an electron transport layer (ETL).

Silver (Ag) and magnesium (Mg) are mixed in a weight ratio of 10:1 and deposited to a thickness of 150 Å on the ETL as a cathode.

Compound N-(4-( 9H -carbazol-9-yl)phenyl)-4'-( 9H -carbazol-9-yl)-N-phenyl- on the cathode as a light extraction layer (CPL) [1,1'-biphenyl]-4-amine is deposited to a thickness of 650 Å. The device performance can be referred to Table 3.

Examples 12 to 15

An organic electroluminescent device was manufactured in the same manner as in Example 11, except that the compounds shown in Table 3 were used in forming the electron blocking layer, respectively.

That is, in Example 12, an organic electroluminescent device was prepared using Compound 3, in Example 13 an organic electroluminescent device was manufactured using Compound 10, and in Example 14, an organic electroluminescent device was prepared using Compound 164. prepared, and in Example 15, an organic electroluminescent device was prepared using compound 165. The device performance can be referred to Table 3.

Comparative Example 4

An organic electroluminescent device was prepared in the same manner as in Example 11, except that compound 9 of the electron blocking layer was replaced with compound DPFL-NPB. The device performance can be referred to Table 3. The CAS number of the DPFL-NPB is 357645-40-0, N,N'-bis(naphthalen-1-yl)-N,N'-diphenyl-2,7-diamino-9,9-dimethylflu It is named oren, and the structural formula is as follows.

.

.

Comparative Example 5

An organic electroluminescent device was manufactured in the same manner as in Example 11, except that compound 9 of the electron blocking layer was replaced with compound TQTPA. The device performance can be referred to Table 3. The CAS number of the TQTPA is 1142945-07-0, and is named tris(4-(quinolin-8-yl)phenyl)amine, and the structural formula is as follows.

.

.

Comparative Example 6

An organic electroluminescent device was manufactured in the same manner as in Example 11, except that the electron transport layer was not formed. The device performance can be referred to Table 3.

Comparative Example 9

An organic electroluminescent device was manufactured in the same manner as in Example 11, except that compound 9 of the electron blocking layer was replaced with compound P1.

Comparative Example 10

An organic electroluminescent device was manufactured in the same manner as in Example 11, except that compound 9 of the electron blocking layer was replaced with compound P3.

Table 3 Device Performance

Data such as voltage, efficiency, color coordinates, and lifetime of the T95 device were tested at a constant current density of 10 mA/cm ² .

As can be seen from Table 3, under the condition that the difference in CIEy is not large, the operating voltage is reduced by 0.22V to the maximum, the luminous efficiency (Cd/A) is 3.45% or more, the external quantum efficiency is 23.3% or more, and the lifetime is 37.8% more improved

As can be seen from Tables 2 and 3, when the compound of the present invention is used as a hole transport layer and an electron blocking layer, the efficiency and lifespan of the organic electroluminescent device can be improved, and the voltage is also reduced to some extent. Accordingly, the compounds of the present invention have properties to improve efficiency and lifetime.

Those of ordinary skill in the art of the present invention can easily derive other embodiments of the present invention by referring to and practicing the specification. The present invention is intended to cover any modifications, uses or adaptive modifications to the present invention, such modifications, uses or adaptive modifications being based on the general principles of the present invention, common knowledge or common sense in the art of the present invention. including technical means. The specification and examples are to be regarded as illustrative only, the true scope and spirit of the invention being defined by the following claims.

100, anode; 200, cathode;
300, functional layer; 310, hole injection layer;
320, hole transport layer; 330, an electron blocking layer;
340, a light emitting layer; 350, an electron transport layer;
360, electron injection layer; 370, a photoelectric conversion layer.

Claims (23)

In the nitrogen-containing compound wherein the structure of the compound is represented by the following formula (I),

wherein X is selected from C(CH ₃ ) ₂ , O, S;
R ₁ is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms; The substituted or unsubstituted aryl group having 6 to 30 carbon atoms is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, 13 ring formation selected from substituted or unsubstituted aryl groups having carbon atoms; The substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms is

,

,

,

wherein the substituents of the aryl group and the heteroaryl group are selected from an alkyl group having 1 carbon atom, an aryl group having 6 carbon atoms; or R ₁ is

,

is selected from;
L ₁ and L ₂ are the same or different and are each independently selected from an unsubstituted arylene group having 6 to 12 ring-forming carbon atoms. According to claim 1,
R ₁ is selected from the following compounds,

remind

represents a chemical bond. According to claim 1,
L ₁ and L ₂ are each independently selected from unsubstituted phenylene and unsubstituted biphenylene. According to claim 1,
L ₁ and L ₂ are each independently selected from the following compounds,

;
remind

is a nitrogen-containing compound, characterized in that it represents a chemical bond. According to claim 1,
A nitrogen-containing compound, characterized in that the nitrogen-containing compound is selected from the following compounds.

An organic electroluminescent device comprising:
an anode, a cathode, and a functional layer provided between the anode and the cathode;
The functional layer is an organic electroluminescent device comprising the nitrogen-containing compound of any one of claims 1 to 5. A photoelectric conversion device comprising:
an anode, a cathode, and a functional layer provided between the anode and the cathode;
The said functional layer contains the nitrogen-containing compound of any one of Claims 1-5, The photoelectric conversion device characterized by the above-mentioned. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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