Diamine derivative and organic electroluminescent device thereof

文档序号：1915928 发布日期：2021-12-03 浏览：18次中文

阅读说明：本技术 一种二胺衍生物及其有机电致发光器件 (Diamine derivative and organic electroluminescent device thereof ) 是由李梦茹杜明珠孙敬于 2021-09-26 设计创作，主要内容包括：本发明提供了一种二胺衍生物及其有机电致发光器件,涉及有机电致发光材料技术领域。本发明式1所示的二胺衍生物含有9-芴取代的咔唑官能团,本发明的有机电致发光器件的空穴传输区域或覆盖层中含有式1的咔唑衍生物。本发明式1所示的二胺衍生物具有较好的空穴传输性能以及较好的稳定性,所制备的空穴传输区域中含有式1的二胺衍生物的有机电致发光器件,表现出较高的发光效率、较长的使用寿命以及较低的驱动电压。另外,本发明式1的二胺衍生物还是较好的覆盖层材料,所制备的覆盖层中含有式1的二胺衍生物的有机电致发光器件,表现出较高的发光效率、较长的使用寿命。(The invention provides a diamine derivative and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescent materials. The diamine derivative shown in formula 1 of the invention contains 9-fluorene substituted carbazole functional group, and the hole transport region or the covering layer of the organic electroluminescent device contains the carbazole derivative shown in formula 1. The diamine derivative shown in the formula 1 has good hole transport performance and good stability, and the prepared organic electroluminescent device containing the diamine derivative shown in the formula 1 in a hole transport region shows high luminous efficiency, long service life and low driving voltage. In addition, the diamine derivative of formula 1 of the present invention is also a good covering layer material, and the organic electroluminescent device prepared by using the covering layer containing the diamine derivative of formula 1 shows high luminous efficiency and long service life.)

1. A diamine derivative is characterized by having a general structural formula shown as a formula 1:

ar is₁、Ar₂、Ar₃Independently selected from one of the groups shown in the following,

the R is₀The same or different one selected from hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and substituted or unsubstituted C12-C30 arylamine, or two adjacent groups can be connected to form a ring,

x is selected from O, S, C (R)_x)₂、N(R_x) Said R is_xThe same or different hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3EOne of C20 naphthenic base, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, or two adjacent groups can be connected to form a ring;

the L is selected from one of the groups shown as follows,

said L₀The same or different one selected from single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted tetrahydronaphthylene, substituted or unsubstituted indanylene,

the R is₃The same or different one selected from hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups can be connected to form a ring,

y is selected from O, S, C (R)_y)₂、N(R_y) Said R is_yThe same or different one selected from hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups can be connected to form a ring;

said L₁、L₂、L₃、L₄Independently selected from single bond, substituted or unsubstituted arylene of C6-C30, and substituted or unsubstituted heteroarylene of C3-C30;

the R is₁、R₂Independently one selected from hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups can be connected to form a ring;

ar is selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;

m is selected from 0,1, 2,3 or 4, n is selected from 0,1, 2 or 3, e is selected from 0,1, 2,3, 4 or 5, and f is selected from 0,1, 2.

2. Diamine derivative according to claim 1, characterized in that said groupIs selected from one of the groups shown below,

the R is one selected from hydrogen, deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted tetrahydronaphthyl group, a substituted or unsubstituted indanyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group and a substituted or unsubstituted carbazolyl group.

3. Diamine derivative according to claim 1, characterized in that said groupIs selected from one of the groups shown below,

ar is selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted indanyl and substituted or unsubstituted tetrahydronaphthyl.

4. Diamine derivative according to claim 1, characterized in that L is₁、L₂、L₃、L₄Independently selected from a single bond or one of the groups shown below,

the Lx are the same or different and are selected from one of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted tetrahydronaphthyl and substituted or unsubstituted indanyl,

the R is₄The same or different one selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted bornyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted phenyl group, or two adjacent groups may be linked to form a ring,

and m is selected from 0,1, 2,3 or 4.

5. A diamine derivative as defined in claim 1 wherein Ar is₁、Ar₂、Ar₃Independently selected from one of the groups shown in the following,

the R is_nOne selected from deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloheptyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted camphyl group, a substituted or unsubstituted norbornanyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, and a substituted or unsubstituted naphthyl group.

6. A diamine derivative as defined in claim 1 wherein L is selected from the group consisting of,

7. diamine derivative according to claim 1, characterized in that L is₁、L₂、L₃、L₄Independently selected from a single bond or one of the groups shown below,

8. a diamine derivative according to claim 1, wherein the diamine derivative is selected from the group consisting of those represented by the following structures,

9. an organic electroluminescent element comprising an anode, an organic layer, and a cathode in this order, wherein the organic layer comprises a hole transport layer comprising the diamine derivative according to any one of claims 1 to 8.

10. An organic electroluminescent element comprising an anode, an organic material layer, a cathode, and a cover layer in this order, wherein the cover layer contains the diamine derivative according to any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of organic electroluminescent materials, in particular to a diamine derivative and an organic electroluminescent device thereof.

Background

With the progress of modern science and technology and the development of society, display technology becomes an indispensable link in daily life of people, the OLED technology is a new generation of display technology in various flat panel display technologies, and compared with the traditional cathode ray tube display and other flat panel display devices represented by liquid crystal, the OLED display has many advantages: (1) the method has the characteristics of low cost, relatively simple process and less used raw materials; (2) the self-luminous LED lamp has self-luminous property, and does not need a backlight source; (3) the direct current driving circuit has the characteristics of low voltage driving and low power consumption, the direct current driving voltage is below 10 volts, and the direct current driving circuit is easy to use on a portable mobile display terminal; (4) the display panel has the characteristics of all solid state, no vacuum cavity, no liquid component, strong shock resistance and capability of realizing flexible display; (5) the LED has high-efficiency light-emitting characteristics and can be used as a novel environment-friendly light source; (6) the display has high brightness and bright and fine display effect; (7) has wide temperature range characteristic and can normally work within the range of minus 40 ℃ to plus 80 ℃. The characteristics of the OLED technology attract a plurality of scientific research units and panel display enterprises, and a great deal of manpower and financial resources are invested, so that the OLED device has a wide application prospect.

The organic electroluminescent device comprises an anode, a cathode, and organic functional layers between and outside the two electrodes, wherein each organic functional layer comprises: hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer, capping layer, and the like. Organic electroluminescent devices can be classified into: bottom emitting devices, top emitting devices.

With the social demands and the requirements of industrial production, the development direction of organic electroluminescent devices in the future is high-efficiency, long-life and low-cost white light devices and full-color display devices, wherein the light-emitting efficiency of bottom-emitting organic electroluminescent devices is only 20%, and the improvement of the light-emitting performance mainly focuses on developing hole transport layer materials with appropriate HOMO energy levels, higher hole mobility and good thermal stability, so that the injection balance of carriers is promoted, the light-emitting efficiency of the devices is improved, and the service life of the devices is prolonged. The light-emitting efficiency of the top-emission organic electroluminescent device is 100% in theory, but the light-emitting efficiency is greatly reduced due to the plasma element effect, the waveguide effect and the like of the cathode and the covering layer at the outermost side, the improvement of the light-emitting performance is mainly focused on developing the covering layer material with high refractive index, no absorption of visible light wave band and good film stability, the design of the thickness and the structure of the covering layer and the like, the light-emitting efficiency of the device is improved, and the light-emitting efficiency and the service life of the device are further improved,

therefore, in order to improve the luminous efficiency of the device and prolong the service life of the device, the development of a hole transport material with a proper HOMO energy level, higher hole mobility and good thermal stability and a covering layer material with high refractive index, no absorption to visible light wave band and good film stability become problems to be solved in the field of organic electroluminescent devices.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a diamine derivative and an organic electroluminescent device thereof.

The diamine derivative provided by the invention has a structural general formula shown in a formula 1:

ar is₁、Ar₂、Ar₃Independent of each otherIs selected from one of the groups shown below,

x is selected from O, S, C (R)_x)₂、N(R_x) Said R is_xThe same or different one selected from hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups can be connected to form a ring;

the L is selected from one of the groups shown as follows,

y is selected from O, S, C (R)_y)₂、N(R_y) Said R is_yThe same or different hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl,One of substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups can be connected to form a ring;

said L₁、L₂、L₃、L₄Independently selected from single bond, substituted or unsubstituted arylene of C6-C30, and substituted or unsubstituted heteroarylene of C3-C30;

m is selected from 0,1, 2,3 or 4, n is selected from 0,1, 2 or 3, e is selected from 0,1, 2,3, 4 or 5, and f is selected from 0,1, 2.

In addition, the invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer and a cathode, wherein the organic layer contains a hole transport layer, and the hole transport layer contains the diamine derivative.

The invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer, a cathode and a covering layer, wherein the covering layer contains the diamine derivative.

Has the advantages that:

according to the device embodiment, the diamine derivative shown in formula 1 of the present invention has good hole transport performance and good stability, and the organic electroluminescent device prepared by using the diamine derivative shown in formula 1 in the hole transport region shows high luminous efficiency, long service life and low driving voltage.

In addition, as can be seen from the device examples, the diamine derivative of formula 1 of the present invention is also a better covering layer material, and the organic electroluminescent device prepared by using the covering layer containing the diamine derivative of formula 1 shows higher luminous efficiency and longer service life.

Detailed Description

The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will fall within the scope of the claims of this application after reading the present invention.

In the present invention, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example,can representAnd so on.

The term "unsubstituted" in "substituted or unsubstituted" as used herein means that a hydrogen atom on the group is not replaced with any substituent.

The term "substituted" in the "substituted or unsubstituted" as used herein means that at least one hydrogen atom on the group is replaced by a substituent. When a plurality of hydrogens is replaced with a plurality of substituents, the plurality of substituents may be the same or different. The position of the hydrogen substituted by the substituent may be any position.

The substituent group represented by the "substituted" in the "substituted or unsubstituted" in the present invention is selected from deuterium, a substituted or unsubstituted alkyl group having C1 to C20, a substituted or unsubstituted cycloalkyl group having C3 to C20, a substituted or unsubstituted aliphatic cyclic group having C3 to C20, a substituted or unsubstituted aliphatic cyclic group having C3 to C20, a substituted or unsubstituted aryl group having C6 to C30, a substituted or unsubstituted heteroaryl group having C3 to C30, a substituted or unsubstituted arylamine group having C12 to C30, and the like, and specifically may be selected from deuterium, methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, bornane, norbornane, tetrahydropyrrole, piperidyl, azepane, azacycloheptyl, azacyclooctyl, tetrahydroquinolyl, tetrahydroisoquinolinyl, indolinyl, isoindolyl, phenyl, biphenyl, and the like, Naphthyl, tetrahydronaphthyl, indanyl, indenyl, dihydronaphthyl, phenanthryl, triphenylene, fluorenyl, benzofluorenyl, spirobifluorenyl, benzospirobifluorenyl, carbazolyl, benzocarbazolyl, dibenzofuranyl, dibenzothiophenyl, diphenylamine-yl, and the like.

The "C1 to C20" in the "substituted or unsubstituted C1 to C20 alkyl group" in the present invention means the number of carbon atoms in the unsubstituted "alkyl group" and does not include the number of carbon atoms in the substituent. The "C3 to C20" in the "substituted or unsubstituted C3 to C20 cycloalkyl group" means the number of carbon atoms in the unsubstituted "cycloalkyl group" and does not include the number of carbon atoms in the substituent. The "C6 to C30" in the "substituted or unsubstituted aryl group having C6 to C30" means the number of carbon atoms in the unsubstituted "aryl group" and does not include the number of carbon atoms in the substituent. The "C3 to C30" in the "substituted or unsubstituted C3 to C30 heteroaryl group" means the number of carbon atoms in the unsubstituted "heteroaryl group" and does not include the number of carbon atoms in the substituent. And so on.

In the present invention, "two adjacent groups are linked to form a ring" means that the adjacent groups are bonded to each other and optionally aromatized to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring. The hydrocarbon ring may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. The heterocyclic ring may include an aliphatic heterocyclic ring or an aromatic heterocyclic ring. The aliphatic cyclic hydrocarbon may be a saturated aliphatic hydrocarbon ring or an unsaturated aliphatic hydrocarbon ring, and the aliphatic heterocyclic ring may be a saturated aliphatic heterocyclic ring or an unsaturated aliphatic heterocyclic ring. The hydrocarbon rings and heterocycles may be monocyclic or polycyclic groups. In addition, a ring formed by the combination of adjacent groups may be connected to another ring to form a spiro structure. As exemplified below:

in the present invention, the ring to be connected may be an aromatic ring system, an aliphatic ring system, or a ring system formed by a fusion of the two, and the ring to be connected may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, or a fused ring, such as benzene, naphthalene, cyclopentene, cyclopentane, cyclopentanobenzene, cyclohexane, cyclohexanobenzene, quinoline, isoquinoline, dibenzothiophene, phenanthrene, or pyrene, but not limited thereto.

The chain alkyl group having more than three carbon atoms in the present invention includes isomers thereof, for example, propyl includes n-propyl and isopropyl, and butyl includes n-butyl, sec-butyl, isobutyl and tert-butyl. And so on.

The alkyl refers to a univalent group formed by subtracting one hydrogen atom from alkane molecules. The alkyl group has a carbon number of from C1 to C20, preferably from C1 to C15, more preferably from C1 to C10, and still more preferably from C1 to C6. Examples of the alkyl group include, but are not limited to, the groups described below, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like.

The cycloalkyl refers to a monovalent group formed by omitting one hydrogen atom from a cycloalkane molecule. The cycloalkyl group has carbon atoms of C3 to C20, preferably C3 to C15, more preferably C3 to C10, and still more preferably C3 to C6. Examples of such cycloalkyl groups include, but are not limited to, the groups described below, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, bornyl, and the like.

The aryl refers to a univalent group formed by subtracting one hydrogen atom from an aromatic nucleus carbon of an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl group, polycyclic aryl group, and condensed ring aryl group. The aryl group has a carbon number of C6 to C30, preferably C6 to C20, more preferably C6 to C15, and still more preferably C6 to C12. Examples of the aryl group include, but are not limited to, phenyl, biphenyl, fluorenyl, spirobifluorenyl, spiroanthracenyl, benzofluorenyl, benzospirobifluorenyl, naphthyl, phenanthrenyl, triphenylenyl, and the like, as described below.

The heteroaryl group in the present invention refers to a monovalent group in which at least one of the aromatic nuclear carbon atoms in the aryl group is substituted with a heteroatom. The heteroaryl includes monocyclic heteroaryl and fused ring heteroaryl. Such heteroatoms include, but are not limited to, the atoms described below, N, O, S, Si, B, P, and the like. The heteroaryl group has a carbon number of from C3 to C30, preferably from C3 to C20, more preferably from C3 to C15, and still more preferably from C3 to C12. Examples of such heteroaryl groups include, but are not limited to, carbazolyl, benzocarbazolyl, furanyl, dibenzofuranyl, thienyl, dibenzothienyl, spirofluorene xanthenyl, spirofluorene thianthrenyl, spirofluorene azaanthracenyl, and the like, as described below.

The arylamine group in the present invention refers to a group shown below,and Ax and Ay are independently substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. The arylamine group has carbon atoms of C12-C30, preferably C12-C20. Examples of the arylamine group include, but are not limited to, groups described below, a diphenylamino group, an N-phenyl-4-benzidine, a bisbiphenyl-4-ylamine, and the like.

The arylene group in the invention is a divalent group formed by omitting two hydrogen atoms from an aromatic nucleus carbon in an aromatic hydrocarbon molecule. The arylene group includes monocyclic arylene, polycyclic arylene, fused ring arylene, or combinations thereof. The arylene group has carbon atoms of C6 to C30, preferably C6 to C20, more preferably C6 to C15, and further preferably C6 to C12. Examples of the arylene group include, but are not limited to, a phenylene group, a biphenylene group, a terphenylene group, a fluorenylene group, a spirobifluorenylene group, a benzofluorenylene group, a benzospirobifluorenylene group, a naphthylene group, a phenanthrylene group, a triphenylene group and the like.

The heteroarylene group means a divalent group in which at least one carbon atom in the arylene group is substituted with a heteroatom. The heteroarylene group includes a monocyclic heteroarylene group, a polycyclic heteroarylene group, a fused ring heteroarylene group, or a combination thereof. The heteroatoms include, but are not limited to, the atoms shown below, N, O, S, Si, B, P, and the like. The heteroarylene group has carbon atoms of C3 to C30, preferably C3 to C20, and more preferably C3 to C15. Examples of the heteroarylene group include, but are not limited to, carbazolyl, benzocarbazolyl, furanylene, dibenzofuranylene, thienylene, dibenzothiophenylene, and the like as described below.

The invention provides a diamine derivative, which has a structural general formula shown in a formula 1:

ar is₁、Ar₂、Ar₃Independently selected from one of the groups shown in the following,

the L is selected from one of the groups shown as follows,

said L₀The same or different is selected from single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted tetrahydrochyseneNaphthyl, substituted or unsubstituted indanylene,

said L₁、L₂、L₃、L₄Independently selected from single bond, substituted or unsubstituted arylene of C6-C30, and substituted or unsubstituted heteroarylene of C3-C30;

m is selected from 0,1, 2,3 or 4, n is selected from 0,1, 2 or 3, e is selected from 0,1, 2,3, 4 or 5, and f is selected from 0,1, 2.

Preferably, the groupIs selected from one of the groups shown below,

Preferably, said L₁、L₂、L₃、L₄Independently selected from a single bond or one of the groups shown below,

the R is₄Identical or different from hydrogen, deuterium,One of substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted adamantyl, substituted or unsubstituted bornyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, or two adjacent groups may be linked to form a ring,

and m is selected from 0,1, 2,3 or 4.

Preferably, Ar is₁、Ar₂、Ar₃Independently selected from one of the groups shown in the following,

Preferably, the L is selected from one of the groups shown as follows,

preferably, said L₁、L₂、L₃、L₄Independently selected from a single bond or one of the groups shown below,

preferably, the diamine derivative is selected from one of the structures shown below,

some specific chemical structures of the diamine derivatives of formula 1 of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and any diamine derivatives of formula 1 as a basis should be included, wherein the substituents are as defined above.

Furthermore, the invention also provides an organic electroluminescent device, which sequentially comprises an anode, an organic layer and a cathode, wherein the organic layer contains a hole transport layer, and the hole transport layer contains the diamine derivative.

Furthermore, the invention also provides an organic electroluminescent device, which sequentially comprises an anode, an organic layer, a cathode and a covering layer, wherein the covering layer contains the diamine derivative.

The functional layer of the organic electroluminescent device of the present invention may further include one or more of a hole injection layer, an electron transport layer, an electron blocking layer, a hole blocking layer, a light emitting layer, etc., in addition to the hole transport layer and/or the capping layer, but is not limited thereto, and any functional layer having a hole injection and/or transport property and a functional layer having an electron injection and/or transport property should be included. Each functional layer may be formed of a single layer film or a multilayer film, and each layer film may contain one material or a plurality of materials. The thickness of each functional layer can be adjusted as necessary, and is generally 0.01nm to 2 μm.

The method for preparing each layer of the thin film in the organic electroluminescent device of the present invention is not particularly limited, and vacuum evaporation, sputtering, spin coating, spray coating, screen printing, laser transfer printing, and the like can be used, but is not limited thereto.

The material of each layer of the thin film in the organic electroluminescent device of the present invention is not particularly limited, and those known in the art can be used. The following description is made of the electrodes on both sides of the organic electroluminescent device and the organic functional layers of the above-mentioned organic electroluminescent device, respectively:

the anode of the present invention has a function of injecting holes into the hole transport layer. The anode material includes, but is not limited to, materials such as aluminum (Al), silver (Ag), platinum (Pt), gold (Au), indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO), silver/indium tin oxide/silver (Ag/ITO/Ag), Aluminum Zinc Oxide (AZO), Indium Tin Oxide (ITO), poly (3-methylthiophene) poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDOT), and the like, metals or alloys thereof, laminates, metal oxides, polymers, and the like.

The cathode of the present invention has a function of injecting electrons into the electron transport layer. The cathode material includes, but is not limited to, materials, metals or alloys thereof, etc., such as aluminum (Al), ytterbium (Yb), silver (Ag), lead (Pb), indium (In), lithium aluminum (Li: Al), ytterbium silver (Yb: Ag), magnesium silver (Mg: Ag), etc.

The hole injection layer has the characteristic of increasing hole injection between the anode and the hole transport layer, and is used as a buffer layer between the anode and the hole transport layer, so that the hole injection efficiency is improved. The hole injection material includes, but is not limited to, aromatic amine-based compounds, metal phthalocyanine-based compounds, cyano group-containing compounds, and the like, such as 4,4',4 ″ -tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), 4', 4' -tris [ 2-naphthyl (phenyl) amino ] triphenylamine (2-TNATA), N ' -bis [ 4-di (m-tolyl) aminophenyl ] -N, N ' -diphenylbenzidine (DNTPD), oxytitanium phthalocyanine (TiOPC), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoxydimethyl-p-benzoquinone (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN), and the like.

The electron injection layer has the characteristic of increasing the electron injection between the cathode and the electron transport layer, and is used as a buffer layer between the cathode and the electron transport layer, so that the electron injection efficiency is improved. The electron injection material includes, but is not limited to, materials described below, metal organic compounds, metal inorganic compounds, and the like, such as lithium quinolate (LiQ), lithium fluoride (LiF), cesium carbonate (Cs)₂CO₃) And the like.

The hole transport layer can increase the injection efficiency of holes, and can reduce the potential barrier of hole injection, thereby improving the luminous performance of the device. The diamine derivative represented by formula 1 of the present invention is preferable.

The electron transport layer can increase the injection efficiency of electrons, reduce the potential barrier of electron injection and further improve the luminous performance of the device. The electron transporting material includes, but is not limited to, materials such as zinc complexes, beryllium complexes, aluminum complexes, imidazole derivatives, high molecular compounds, and the like, for example, bis (8-hydroxyquinoline) zinc (II) (Znq), bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (Bepq)₂) Tris (8-hydroxyquinoline) aluminum (III) (Alq)₃) 1- (4- (9, 10-bis (naphthalen-2-yl) anthracen-2-yl) phenyl) -2-phenyl-1H-benzo [ d]Imidazole, poly [ (9, 9-dihexylfluorene-2, 7-diyl) -co- (pyridine-3, 5-diyl)](PF-Py), etc.

The hole blocking layer has a function of preventing holes from leaking from the light emitting layer to the electron transport layer. The hole blocking material includes, but is not limited to, the following: metal complexes, imidazole derivatives, phenanthroline derivatives, triazole derivatives, triazine derivatives, and the like, for example, bis (8-hydroxy-2-methylquinoline) - (4-phenylphenoxy) aluminum (BAlq), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (BCP), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like.

The cladding layer of the present invention has the effect of coupling out light trapped within the device. The diamine derivative represented by formula 1 of the present invention is preferable.

The light-emitting layer of the present invention may contain both a host material and a dopant material, or may contain no host material.

As the light emitting layer host material of the present invention, a condensed aromatic ring derivative, a heterocyclic compound, or the like may be included, for example, 9-bis [4- (pyrenyl) phenyl ] -9 hfluorene (BPPF), 2-tert-butyl-9, 10-di (naphthalen-2-yl) anthracene (TBADN), 10' -bis (biphenyl-4-yl) -9,9' -Bianthracene (BANE), 1,3, 5-tris (carbazol-9-yl) benzene (TCP), 3- (4- (9H-carbazol-9-yl) phenyl) -9- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -9H carbazole (CPCBPTz), 2' -bis (4-carbazolylphenyl) biphenyl (BCBP), 2, 7-bis (carbazol-9-yl) -9, 9-dioctylfluorene (DOFL-CBP), 9- (5- (3- (9H-carbazol-9-yl) phenyl) pyridin-3-yl) -9H-carbazole (CPPyC). But is not limited thereto.

Doping as the light emitting layer of the present inventionThe reagent material may include a condensed aromatic compound, a styrylamine compound, an aromatic amine derivative, a metal complex, etc., such as 2,5,8, 11-tetra-t-butylperylene (TBPe), 4' -bis [4- (diphenylamino) styryl]Biphenyl (BDAVBi), N '-bis (naphthalen-2-yl) -N, N' -bis (phenyl) -tris- (9, 9-dimethylfluorene) (BNP3FL), 9, 10-bis [ N, N-di- (p-tolyl) -amino]Anthracene (TTPA), tris (2-phenylpyridine) iridium (Ir (ppy)₃) Tris [2- (4-n-hexylphenyl) quinoline)]Iridium (III) (Hex-Ir (phq)₃) And the like. But is not limited thereto.

The organic electroluminescent device is mainly applied to the technical field of information display, and is widely applied to various information displays in the aspect of information display, such as mobile phones, intelligent watches, tablet computers, flat televisions, wearable equipment, digital cameras, VR (virtual reality), vehicle-mounted systems and the like.

Synthetic examples

Raw materials and reagents: the starting materials and reagents used in the following synthetic examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art. The raw materials and reagents used in the invention are all pure reagents.

The instrument comprises the following steps: G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer (waters, uk); a Vario EL cube type organic element analyzer (Elementar Co., Germany).

The method for preparing the diamine derivative of formula 1 of the present invention is not particularly limited, and conventional methods well known to those skilled in the art may be used. For example, carbon-nitrogen coupling reaction, carbon-carbon coupling reaction, etc., the diamine derivative of formula 1 of the present invention can be prepared, for example, by the following synthetic route.

Said X_n、X_n1、X_n2Are halogen atoms, which may be identical or different, selected, for example, from the halogen atoms I, Br, Cl described below.

Synthetic examples

Synthesis example 1 Synthesis of Compound 1

Preparation of intermediate 1-1:

intermediate a-1(50.00mmol, 17.83g), tetrahydrofuran (250mL) and n-butyllithium (30mL of 1.6M in hexanes) were added to a reaction flask under nitrogen and the reaction stirred at-78 deg.C for 50 minutes. A tetrahydrofuran solution (275mL) containing b-1(55.00mmol, 14.21g) was added dropwise to the flask, and the reaction was stirred at-78 ℃ for 50 minutes and at room temperature for 3 hours. After the reaction, a saturated ammonium chloride solution was added to separate the organic layer, and the organic layer was concentrated.

The concentrated organic solid, acetic anhydride (450mL) and hydrochloric acid (18mL) were put into a reaction flask, and stirred at 100 ℃ for reaction for 3 hours, after the reaction was completed, cold water (180mL) was added to precipitate a solid product, which was filtered, and purified by a silica gel column (petroleum ether/dichloromethane 10: 1) to obtain intermediate 1-1(22.28g, yield 86%) having an HPLC purity of 98.63% or more. Mass spectrum m/z: 517.1584 (theoretical value: 517.1597).

Preparation of intermediates 1-2:

under the protection of nitrogen, intermediate 1-1(42.00mmol, 21.76g), raw material c-1(44.10mmol, 4.11g), Pd (OAc)₂(0.84mmol，0.19g)、P(t-Bu)₃(3.36mmol, 0.68g), NaOt-Bu (84.00mmol, 8.07g) and 150mL of toluene were placed in a reaction flask and reacted at reflux for 4 hours. After completion of the reaction, cooled to room temperature, filtered through celite, the filtrate was concentrated, and the residue was extracted with toluene/ethanol ═ 10: 1, recrystallizing the concentrated solution to obtain an intermediate 1-2(19.55g, yield 81%); HPLC purity is more than or equal to 98.89%. Mass spectrum m/z: 574.2419 (theoretical value: 574.2409).

Preparation of intermediates 1 to 3:

under the protection of nitrogen, raw material c-1(137.00mmol, 12.76g), raw material e-1(130.48mmol, 20.49g), Pd (OAc)₂(2.61mmol，0.59g)、P(t-Bu)₃(10.44mmol, 2.11g), NaOt-Bu (260.96mmol, 25.08g) and 500mPlacing L toluene in a reaction bottle, stirring, heating and refluxing for 1.5 hours under the protection of nitrogen; after the reaction was complete, the reaction mixture was cooled to room temperature, filtered through celite, the filtrate was concentrated, and the concentrate was purified by distillation with toluene/ethanol 4: 1, recrystallizing, filtering, leaching and leaching with toluene to obtain a recrystallized solid to obtain an intermediate 1-3(17.44g, yield 79%); the HPLC purity is more than or equal to 99.15 percent. Mass spectrum m/z: 169.0899 (theoretical value: 169.0891).

Preparation of intermediates 1 to 4:

under the protection of nitrogen, intermediate 1-3(96.50mmol, 16.33g), raw material f-1(91.90mmol, 24.59g), Pd (dppf) Cl₂(1.84mmol，1.34g)、P(t-Bu)₃(7.36mmol, 1.49g), t-BuOK (183.80mmol, 20.62g) and 350mL of toluene were placed in a reaction flask and reacted at reflux for 3.5 hours. After completion of the reaction, cooled to room temperature, filtered through celite, the filtrate was concentrated, and the residue was extracted with toluene/ethanol ═ 5: 1, recrystallizing the concentrated solution to obtain an intermediate 1-4(25.18g, yield 77%); the HPLC purity is more than or equal to 99.43 percent. Mass spectrum m/z: 355.1117 (theoretical value: 355.1128).

Preparation of compound 1:

under the protection of nitrogen, intermediate 1-4(32.00mmol, 11.39g), intermediate 1-2(33.60mmol, 19.31g), Pd₂(dba)₃(0.32mmol，0.29g)、P(t-Bu)₃(2.56mmol, 0.52g), t-BuOK (64.00mmol, 7.18g) and 120mL of toluene were placed in a reaction flask, stirred and heated under reflux for 4.5 hours; after full reaction, cooling to room temperature, filtering with diatomite, concentrating the filtrate, recrystallizing the concentrated solution with toluene, filtering, leaching and leaching with toluene to obtain a recrystallized solid, and obtaining the compound 1(20.03g, yield 70%) with an HPLC purity of not less than 99.81%. Mass spectrum m/z: 893.3782 (theoretical value: 893.3770). Theoretical element content (%) C₆₇H₄₇N₃: c, 90.00; h, 5.30; and N, 4.70. Measured elemental content (%): c, 90.08; h, 5.27; and N, 4.66.

Synthesis example 2 Synthesis of Compound 17

Compound 17(18.59g) was obtained by substituting f-1 for the equimolar f-17 according to the same preparation method as in Synthesis example 1, and had a solid purity of 99.75% by HPLC. Mass spectrum m/z: 817.3471 (theoretical value: 817.3457). Theoretical element content (%) C₆₁H₄₃N₃: c, 89.56; h, 5.30; and N, 5.14. Measured elemental content (%): c, 89.63; h, 5.27; n, 5.11.

Synthesis example 3 Synthesis of Compound 42

c-42 preparation:

under the protection of nitrogen, raw material g-42(94.86mmol, 23.16g), raw material h-42(93.00mmol, 16.00g), Pd (PPh) were added to the reaction flask in sequence₃)₄(1.86mmol, 2.15g), KOAc (186.00mmol, 18.25g), 300mL of toluene, 100mL of ethanol, and 100mL of water, stirring the mixture, and refluxing the reaction for 2.5 hours; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (5: 1 recrystallization to give c-42(15.57g, 80% yield); the HPLC purity is more than or equal to 99.38 percent. Mass spectrum m/z: 209.1215 (theoretical value: 209.1204).

Preparation of compound 42:

according to the same preparation method as that of synthetic example 1, compound 42(20.93g) was obtained by replacing c-1 with an equal mole of c-42, intermediates 1 and 4 with an equal mole of intermediate 17-4, and intermediates 1 and 2 with an equal mole of intermediate 42-2, and the purity of the solid was 99.78% or more by HPLC. Mass spectrum m/z: 933.4102 (theoretical value: 933.4083). Theoretical element content (%) C₇₀H₅₁N₃: c, 90.00; h, 5.50; and N, 4.50. Measured elemental content (%): c, 90.04; h, 5.55; n, 4.42.

Synthesis example 4 Synthesis of Compound 52

According to the combinationBy following the same preparation method as in example 1, substituting c-1 for equimolar c-52, intermediates 1-4 for equimolar intermediate 17-4, and intermediates 1-2 for equimolar intermediate 52-2, compound 52(21.75g) was obtained, and the purity by HPLC was ≧ 99.77%. Mass spectrum m/z: 984.4206 (theoretical value: 984.4192). Theoretical element content (%) C₇₃H₅₂N₄: c, 88.99; h, 5.32; and N, 5.69. Measured elemental content (%): c, 88.93; h, 5.36; and N, 5.72.

Synthesis example 5 Synthesis of Compound 60

According to the same preparation method as that of synthetic example 1, a-1 was replaced with an equimolar a-60, c-1 was replaced with an equimolar d-60, e-1 was replaced with an equimolar e-60, f-1 was replaced with an equimolar f-17, and intermediate 1-2 was replaced with an equimolar intermediate 60-2 to obtain compound 60(21.63g) with a solid purity of 99.80% by HPLC. Mass spectrum m/z: 993.4069 (theoretical value: 993.4083). Theoretical element content (%) C₇₅H₅₁N₃: c, 90.60; h, 5.17; and N, 4.23. Measured elemental content (%): c, 90.58; h, 5.23; and N, 4.20.

Synthesis example 6 Synthesis of Compound 65

Compound 65(21.51g) was obtained by substituting e-1 for equimolar e-65 and f-1 for equimolar f-65 according to the same preparation method as in Synthesis example 1, and had a purity of 99.72% by HPLC. Mass spectrum m/z: 973.4415 (theoretical value: 973.4396). Theoretical element content (%) C₇₃H₅₅N₃: c, 90.00; h, 5.69; and N, 4.31. Measured elemental content (%): c, 89.91; h, 5.72; and N, 4.38.

Synthesis example 7 Synthesis of Compound 69

According to the same preparation method as that of synthetic example 1, a-1 was replaced with an equimolar a-69, e-1 was replaced with an equimolar e-69, f-1 was replaced with an equimolar f-17, and intermediate 1-2 was replaced with an equimolar intermediate 69-2, to obtain compound 69(21.66g) with a solid purity of 99.71% by HPLC. Mass spectrum m/z: 1009.4411 (theoretical value: 1009.4396). Theoretical element content (%) C₇₆H₅₅N₃: c, 90.35; h, 5.49; and N, 4.16. Measured elemental content (%): c, 90.37; h, 5.52; and N, 4.10.

Synthesis example 8 Synthesis of Compound 75

According to the same preparation method as that of synthetic example 1, e-1 was replaced with equimolar e-75, f-1 was replaced with equimolar f-17, and intermediate 1-2 was replaced with equimolar intermediate 69-2, to obtain compound 75(22.00g) with a purity of 99.74% by HPLC. Mass spectrum m/z: 1025.4693 (theoretical value: 1025.4709). Theoretical element content (%) C₇₇H₅₉N₃: c, 90.11; h, 5.79; and N, 4.09. Measured elemental content (%): c, 90.04; h, 5.82; n, 4.11.

Synthesis example 9 Synthesis of Compound 87

According to the same preparation method as that of synthetic example 1, e-1 was replaced with equimolar e-87, f-1 was replaced with equimolar f-87, and intermediate 1-2 was replaced with equimolar intermediate 69-2, so as to obtain compound 87(21.71g) with a solid purity of 99.70% or more by HPLC. Mass spectrum m/z: 982.4017 (theoretical value: 982.4035). Theoretical element content (%) C₇₃H₅₀N₄: c, 89.18; h, 5.13; and N, 5.70. Measured elemental content (%): c, 89.23; h, 5.16; and N, 5.63.

Synthesis example 10 Synthesis of Compound 96

b-96 preparation:

under the protection of nitrogen, raw materials g-96(90.78mmol, 11.07g), raw material h-96(89.00mmol, 28.05g) and Pd (PPh) are sequentially added into a reaction bottle₃)₄(1.78mmol, 2.06g), KOAc (178.00mmol, 17.47g) and 300mL of toluene, 100mL of ethanol, 100mL of water, stirring the mixture, and refluxing the reaction for 2.5 hours; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (5: 1 recrystallization to give b-96(22.52g, 81% yield); the HPLC purity is more than or equal to 99.30 percent. Mass spectrum m/z: 312.1526 (theoretical value: 312.1514).

Preparation of compound 96:

according to the same preparation method as that of synthetic example 1, substitution of a-1 for equimolar a-69, substitution of b-1 for equimolar b-96, substitution of c-1 for equimolar c-96, substitution of intermediate 1-4 for equimolar intermediate 17-4, and substitution of intermediate 1-2 for equimolar intermediate 96-2 gave compound 96(21.24g) having a solid purity of not less than 99.72% by HPLC. Mass spectrum m/z: 947.4223 (theoretical value: 947.4239). Theoretical element content (%) C₇₁H₅₃N₃: c, 89.93; h, 5.63; n, 4.43. Measured elemental content (%): c, 89.84; h, 5.66; and N, 4.50.

Synthesis example 11 Synthesis of Compound 108

According to the same preparation method as that of synthetic example 1, b-1 was replaced with equimolar b-108, c-1 was replaced with equimolar c-108, e-1 was replaced with equimolar e-108, f-1 was replaced with equimolar f-17, and intermediate 1-2 was replaced with equimolar intermediate 108-2, to obtain compound 108(22.58g) with a solid purity of 99.68% by HPLC. Quality of foodSpectrum m/z: 1052.4799 (theoretical value: 1052.4818). Theoretical element content (%) C₇₈H₆₀N₄: c, 88.94; h, 5.74; n, 5.32. Measured elemental content (%): c, 88.96; h, 5.77; and N, 5.26.

Synthesis example 12 Synthesis of Compound 127

According to the same preparation method as that of synthetic example 1, c-1 was replaced with an equimolar amount of c-127, e-1 was replaced with an equimolar amount of e-127, f-1 was replaced with an equimolar amount of f-127, and intermediate 1-2 was replaced with an equimolar amount of intermediate 127-2, to obtain compound 127(22.13g) having a solid purity of 99.67% or more by HPLC. Mass spectrum m/z: 1031.5098 (theoretical value: 1031.5117). Theoretical element content (%) C₇₇H₅₇D₄N₃: c, 89.58; h, 6.35; and N, 4.07. Measured elemental content (%): c, 89.55; h, 6.32; n, 4.14.

Synthesis example 13 Synthesis of Compound 147

According to the same preparation method as that of synthetic example 1, b-1 was replaced with equimolar b-147, c-1 was replaced with equimolar c-127, c-1 was replaced with equimolar d-147, e-1 was replaced with equimolar e-65, f-1 was replaced with equimolar f-17, and intermediate 1-2 was replaced with equimolar intermediate 147-2 to obtain compound 147(22.48g) having a solid purity of 99.76% by HPLC. Mass spectrum m/z: 1063.4876 (theoretical value: 1063.4865). Theoretical element content (%) C₈₀H₆₁N₃: c, 90.28; h, 5.78; and N, 3.95. Measured elemental content (%): c, 90.31; h, 5.81; and N, 3.88.

Synthesis example 14 Synthesis of Compound 151

According to the same preparation method as that of synthetic example 1, c-1 was replaced with equimolar c-127, c-1 was replaced with equimolar d-147, e-1 was replaced with equimolar e-151, f-1 was replaced with equimolar f-17, and intermediate 1-2 was replaced with equimolar intermediate 127-2 to obtain compound 151(22.89g) with a solid purity of 99.79% by HPLC. Mass spectrum m/z: 1099.4491 (theoretical value: 1099.4502). Theoretical element content (%) C₈₂H₅₇N₃O: c, 89.51; h, 5.22; and N, 3.82. Measured elemental content (%): c, 89.45; h, 5.27; and N, 3.86.

Synthesis example 15 Synthesis of Compound 169

According to the same preparation method as that of synthetic example 1, c-1 was replaced with equimolar c-169, e-1 was replaced with equimolar e-169, f-1 was replaced with equimolar f-87, and intermediate 1-2 was replaced with equimolar intermediate 169-2 to obtain compound 169(19.56g) with a solid purity of 99.75% by HPLC. Mass spectrum m/z: 872.3944 (theoretical value: 872.3927). Theoretical element content (%) C₆₅H₄₀D₅N₃: c, 89.42; h, 5.77; and N, 4.81. Measured elemental content (%): c, 89.35; h, 5.75; and N, 4.89.

Synthesis example 16 Synthesis of Compound 185

Preparation of a-185:

under the protection of nitrogen, raw materials g-185(89.76mmol, 32.85g), raw materials h-185(88.00mmol, 20.98g) and Pd (PPh) are added into a reaction bottle in sequence₃)₄(1.76mmol, 2.03g), KOAc (176.00mmol, 17.27g), 300mL of toluene, 100mL of ethanol, and 100mL of water, stirring the mixture, and refluxing the reaction for 3 hours; after the reaction is finished, cooling to room temperature, filtering to obtain a filter cake, washing the filter cake with ethanol, and finally, washing the filter cake with toluene/ethyl acetateAlcohol 20: 3 recrystallization to give a-185(31.61g, 83% yield); HPLC purity is more than or equal to 99.32 percent. Mass spectrum m/z: 431.0086 (theoretical value: 431.0076).

Preparation of compound 185:

according to the same preparation method as that of synthetic example 1, compound 185(22.39g) was obtained by replacing a-1 with an equimolar amount of a-185, b-1 with an equimolar amount of b-185, c-1 with an equimolar amount of c-185, intermediate 1-4 with an equimolar amount of intermediate 17-4, and intermediate 1-2 with an equimolar amount of intermediate 185-2, and the purity of the solid was 99.64% or more by HPLC. Mass spectrum m/z: 1059.4568 (theoretical value: 1059.4552). Theoretical element content (%) C₈₀H₅₇N₃: c, 90.62; h, 5.42; and N, 3.96. Measured elemental content (%): c, 90.57; h, 5.51; and N, 3.93.

Synthesis example 17 Synthesis of Compound 189

According to the same preparation method as that of synthetic example 1, a-1 was replaced with an equimolar a-69, b-1 was replaced with an equimolar b-189, c-1 was replaced with an equimolar c-189, e-1 was replaced with an equimolar e-189, f-1 was replaced with an equimolar f-87, and intermediate 1-2 was replaced with an equimolar intermediate 189-2, to obtain compound 189(22.26g) having a solid purity of 99.66% by HPLC. Mass spectrum m/z: 1037.4690 (theoretical value: 1037.4709). Theoretical element content (%) C₇₈H₅₉N₃: c, 90.23; h, 5.73; and N, 4.05. Measured elemental content (%): c, 90.19; h, 5.69; and N, 4.12.

Synthesis example 18 Synthesis of Compound 201

a-201 preparation:

under the protection of nitrogen, raw material g-185(81.60mmol, 29.87g), raw material h-201(80.00mmol, 25.16g), Pd (PPh) were added into a reaction flask in sequence₃)₄(1.60mmol, 1.85g), KOAc (160.00mmol, 15.70g), 300mL of toluene, 100mL of ethanol, and 100mL of water, stirring the mixture, and refluxing the reaction for 3.5 hours; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol: 1 recrystallization to give a-201(33.38g, 82% yield); the HPLC purity is more than or equal to 99.44 percent. Mass spectrum m/z: 507.0398 (theoretical value: 507.0389).

Preparation of compound 201:

according to the same preparation method as that of synthetic example 1, a-1 was replaced with an equimolar amount of a-201, c-1 was replaced with an equimolar amount of d-147, e-1 was replaced with an equimolar amount of e-201, f-1 was replaced with an equimolar amount of the starting material f-17, and the intermediate 1-2 was replaced with an equimolar amount of the intermediate 201-2, to obtain a compound 201(23.72g) having a solid purity of 99.73% or more by HPLC. Mass spectrum m/z: 1139.5166 (theoretical value: 1139.5178). Theoretical element content (%) C₈₆H₆₅N₃: c, 90.57; h, 5.74; and N, 3.68. Measured elemental content (%): c, 90.65; h, 5.70; and N, 3.63.

Synthesis example 19 Synthesis of Compound 246

According to the same preparation method as that of synthetic example 1, c-1 was replaced with equimolar c-246, e-1 was replaced with equimolar e-60, f-1 was replaced with equimolar f-17, and intermediate 1-2 was replaced with equimolar intermediate 246-2 to obtain compound 246(22.94g) with a solid purity of 99.77% by HPLC. Mass spectrum m/z: 1085.4699 (theoretical value: 1085.4709). Theoretical element content (%) C₈₂H₅₉N₃: c, 90.66; h, 5.47; and N, 3.87. Measured elemental content (%): c, 90.57; h, 5.52; n, 3.92.

[ Synthesis example 20] Synthesis of Compound 279

According to the combinationFollowing the same procedure as in example 1, intermediate 1-1 was replaced with equimolar intermediate 69-1, c-1 was replaced with equimolar c-279, c-1 was replaced with equimolar c-127, e-1 was replaced with equimolar e-151, f-1 was replaced with equimolar f-17, and intermediate 1-2 was replaced with equimolar intermediate 279-2 to give compound 279(23.24g) with a purity of 99.65% by HPLC. Mass spectrum m/z: 1099.4521 (theoretical value: 1099.4502). Theoretical element content (%) C₈₂H₅₇N₃O: c, 89.51; h, 5.22; and N, 3.82. Measured elemental content (%): c, 89.45; h, 5.26; and N, 3.88.

Synthesis example 21 Synthesis of Compound 327

Compound 327(20.03g) was obtained by substituting f-1 for f-327 in an equimolar amount according to the same production method as in Synthesis example 1, and had a solid purity of > 99.72% by HPLC. Mass spectrum m/z: 893.3785 (theoretical value: 893.3770). Theoretical element content (%) C₆₇H₄₇N₃: c, 90.00; h, 5.30; and N, 4.70. Measured elemental content (%): c, 89.95; h, 5.32; n, 4.74.

Synthesis example 22 Synthesis of Compound 331

Compound 331(21.42g) was obtained by substituting intermediate 1-3 with an equal mole of intermediate 246-3 and f-1 with an equal mole of f-331 according to the same preparation method as in Synthesis example 1, and had a solid purity of not less than 99.69% by HPLC. Mass spectrum m/z: 969.4071 (theoretical value: 969.4083). Theoretical element content (%) C₇₃H₅₁N₃: c, 90.37; h, 5.30; n, 4.33. Measured elemental content (%): c, 90.42; h, 5.33; and N, 4.24.

Synthesis example 23 Synthesis of Compound 339

According to the same preparation method as that of Synthesis example 1, compound 339(22.61g) was obtained by substituting c-1 with equimolar c-96, e-1 with equimolar e-339 and f-1 with equimolar f-339, and the purity of the solid was ≧ 99.78% by HPLC. Mass spectrum m/z: 1069.4408 (theoretical value: 1069.4396). Theoretical element content (%) C₈₁H₅₅N₃: c, 90.89; h, 5.18; and N, 3.93. Measured elemental content (%): c, 90.78; h, 5.24; and N, 3.97.

Synthesis example 24 Synthesis of Compound 360

According to the same preparation method as that of synthetic example 1, c-1 was replaced with equimolar c-127, e-1 was replaced with equimolar e-360, f-1 was replaced with equimolar f-331, and intermediate 1-2 was replaced with equimolar intermediate 360-2, so as to obtain compound 360(23.10g) having a solid purity of 99.80% by HPLC. Mass spectrum m/z: 1109.4329 (theoretical value: 1109.4345). Theoretical element content (%) C₈₃H₅₅N₃O: c, 89.78; h, 4.99; n, 3.78. Measured elemental content (%): c, 89.73; h, 4.93; and N, 3.85.

[ Synthesis example 25] Synthesis of Compound 373

According to the same preparation method as that of synthetic example 1, a-1 was replaced with an equimolar amount of a-185, c-1 was replaced with an equimolar amount of d-147, f-1 was replaced with an equimolar amount of f-331, and intermediate 1-2 was replaced with an equimolar amount of intermediate 373-2, to obtain compound 373(23.29g) with a solid purity of 99.70% or more by HPLC. Mass spectrum m/z: 1085.4697 (theoretical value: 1085.4709). Theoretical element content (%) C₈₂H₅₉N₃: c, 90.66; h, 5.47; and N, 3.87. Measured elemental content (%): c, 90.59; h, 5.50;N,3.92。

synthesis example 26 Synthesis of Compound 379

According to the same preparation method as that of synthetic example 1, intermediate 1-1 was replaced with an equimolar amount of intermediate 69-1, c-1 was replaced with an equimolar amount of c-189, e-1 was replaced with an equimolar amount of e-379, f-1 was replaced with an equimolar amount of f-327, and intermediate 1-2 was replaced with an equimolar amount of intermediate 379-2, to obtain compound 379(24.14g) with a purity of 99.68% by HPLC. Mass spectrum m/z: 1159.4881 (theoretical value: 1159.4865). Theoretical element content (%) C₈₈H₆₁N₃: c, 91.08; h, 5.30; and N, 3.62. Measured elemental content (%): c, 91.12; h, 5.36; and N, 3.53.

Synthesis example 27 Synthesis of Compound 386

According to the same preparation method as that of synthetic example 1, intermediate 1-1 was replaced with an equal mole of 69-1, c-1 was replaced with an equal mole of c-386, intermediate 1-4 was replaced with an equal mole of intermediate 373-4, and intermediate 1-2 was replaced with an equal mole of intermediate 386-2 to obtain compound 386(22.73g) with a solid purity of > 99.72% by HPLC. Mass spectrum m/z: 1059.4538 (theoretical value: 1059.4552). Theoretical element content (%) C₈₀H₅₇N₃: c, 90.62; h, 5.42; and N, 3.96. Measured elemental content (%): c, 90.67; h, 5.47; and N, 3.87.

Synthesis example 28 Synthesis of Compound 395

Preparation of a-395:

under the protection of nitrogen, raw material g-395(81.60mmol, 29.87g) and raw material were sequentially added into a reaction flaskh-395(80.00mmol，23.08g)、Pd(PPh₃)₄(1.60mmol, 1.85g), KOAc (160.00mmol, 15.70g), 300mL of toluene, 100mL of ethanol, and 100mL of water, stirring the mixture, and refluxing the reaction for 3 hours; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (20: 3 recrystallization to give a-395(31.29g, 81% yield); the HPLC purity is more than or equal to 99.52 percent. Mass spectrum m/z: 481.0246 (theoretical value: 481.0233).

Preparation of compound 395:

according to the same preparation method as that of synthetic example 1, a-1 was replaced with an equal mole of a-395, c-1 was replaced with an equal mole of c-395, intermediates 1-4 were replaced with an equal mole of intermediate 373-4, and intermediates 1-2 were replaced with an equal mole of intermediate 395-2, so that compound 395(23.43g) was obtained, which was equal to or greater than 99.71% purity by HPLC. Mass spectrum m/z: 1125.4098 (theoretical value: 1125.4117). Theoretical element content (%) C₈₃H₅₅N₃S: c, 88.50; h, 4.92; n, 3.73. Measured elemental content (%): c, 88.61; h, 4.86; and N, 3.65.

Synthesis example 29 Synthesis of Compound 401

According to the same preparation method as that of synthetic example 1, a-1 was replaced with an equimolar of a-401, c-1 was replaced with an equimolar of c-401, f-1 was replaced with an equimolar of f-327, and intermediate 1-2 was replaced with an equimolar of intermediate 401-2, to obtain compound 401(23.08g) with a solid purity of not less than 99.69% by HPLC. Mass spectrum m/z: 1108.4516 (theoretical value: 1108.4505). Theoretical element content (%) C₈₃H₅₆N₄: c, 89.86; h, 5.09; and N, 5.05. Measured elemental content (%): c, 89.76; h, 5.12; and N, 5.13.

Synthesis example 30 Synthesis of Compound 411

According to the same preparation method as that of synthetic example 1, intermediates 1 to 3 were replaced with equimolar intermediates 246 to 3, and f-1 was replaced with equimolar h-395, to give compound 411(21.15g) having a solid purity of 99.70% or more by HPLC. Mass spectrum m/z: 943.3907 (theoretical value: 943.3926). Theoretical element content (%) C₇₁H₄₉N₃: c, 90.32; h, 5.23; and N, 4.45. Measured elemental content (%): c, 90.23; h, 5.28; and N, 4.50.

Synthesis example 31 Synthesis of Compound 416

Compound 416(23.05g) was obtained by the same production method as in Synthesis example 1, except that e-1 was replaced with equimolar e-416 and f-1 was replaced with equimolar h-395, and its purity by HPLC was ≧ 99.81%. Mass spectrum m/z: 1107.4570 (theoretical value: 1107.4552). Theoretical element content (%) C₈₄H₅₇N₃: c, 91.03; h, 5.18; n, 3.79. Measured elemental content (%): c,91.08H, 5.15; n, 3.73.

Synthesis example 32 Synthesis of Compound 420

Compound 420(21.51g) was obtained by substituting e-1 for the equivalent mole of e-420 and f-1 for the equivalent mole of f-420 according to the same preparation method as in Synthesis example 1, and had a purity of 99.68% by HPLC. Mass spectrum m/z: 973.3504 (theoretical value: 973.3491). Theoretical element content (%) C₇₁H₄₇N₃S: c, 87.53; h, 4.86; and N, 4.31. Measured elemental content (%): c, 87.59; h, 4.92; and N, 4.24.

Synthesis example 33 Synthesis of Compound 443

According to the same preparation method as that of synthetic example 1, intermediate 1-1 was replaced with an equal mole of intermediate 69-1, c-1 was replaced with an equal mole of c-443, c-1 was replaced with an equal mole of d-443, e-1 was replaced with an equal mole of e-169, f-1 was replaced with an equal mole of h-395, and intermediate 1-2 was replaced with an equal mole of intermediate 443-2, to obtain compound 443(23.58g) with a solid purity of 99.62% by HPLC. Mass spectrum m/z: 1115.5006 (theoretical value: 1115.5024). Theoretical element content (%) C₈₄H₄₅D₁₀N₃: c, 90.37; h, 5.87; and N, 3.76. Measured elemental content (%): c, 90.31; h, 5.91; n, 3.79.

Synthesis example 34 Synthesis of Compound 447

b-447 preparation:

under the protection of nitrogen, raw materials g-447(69.36mmol, 8.46g), raw material h-447(68.00mmol, 23.88g) and Pd (PPh) are sequentially added into a reaction flask₃)₄(1.36mmol, 1.57g), KOAc (176.00mmol, 17.27g), 300mL of toluene, 100mL of ethanol, and 100mL of water, stirring the mixture, and refluxing the reaction for 2.5 hours; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (5: 1 recrystallization to give b-447(18.95g, 80% yield); the HPLC purity is more than or equal to 99.49 percent. Mass spectrum m/z: 348.1159 (theoretical value: 348.1150).

Preparation of compound 447:

according to the same preparation method as that of synthetic example 1, b-1 was replaced with equimolar b-447, c-1 was replaced with equimolar c-447, f-1 was replaced with equimolar h-395, and intermediate 1-2 was replaced with equimolar intermediate 447-2 to obtain compound 447(22.14g) with a solid purity of 99.82% or more by HPLC. Mass spectrum m/z: 1047.3837 (theoretical value: 1047.3825). Theoretical element content (%) C₇₇H₄₉N₃O₂: c, 88.23; h, 4.71; and N, 4.01. Measured elemental content (%): c, 88.15; h, 4.77; and N, 4.06.

Synthesis example 35 Synthesis of Compound 455

Compound 455(21.98g) was obtained by substituting intermediate 1-3 for an equivalent mole of intermediate 246-3 and f-1 for an equivalent mole of f-455 according to the same preparation method as in Synthesis example 1, and had a solid purity of 99.78% or more by HPLC. Mass spectrum m/z: 1009.4409 (theoretical value: 1009.4396). Theoretical element content (%) C₇₆H₅₅N₃: c, 90.35; h, 5.49; and N, 4.16. Measured elemental content (%): c, 90.28; h, 5.54; n, 4.19.

Synthesis example 36 Synthesis of Compound 475

According to the same preparation method as that of synthetic example 1, f-1 was replaced with an equal mole of f-475, and intermediate 1-2 was replaced with an equal mole of intermediate 69-2, so as to obtain compound 475(22.35g) with a solid purity ≧ 99.79% by HPLC. Mass spectrum m/z: 1057.4413 (theoretical value: 1057.4396). Theoretical element content (%) C₈₀H₅₅N₃: c, 90.79; h, 5.24; and N, 3.97. Measured elemental content (%): c, 90.83; h, 5.30; and N, 3.88.

Synthesis example 37 Synthesis of Compound 499

According to the same preparation method as that of Synthesis example 1, intermediates 1 to 3 were replaced with equimolar amounts of intermediate 246 to 3 and f-1 was replaced with equimolar amounts of f-499 to give compound 499(21.73g) with a solid purity of 99.87% or more by HPLC. Mass spectrum m/z: 983.3892 (theoretical value: 983.3876). Theoretical element content (%) C₇₃H₄₉N₃O: c, 89.09; h, 5.02; and N, 4.27. Measured elemental content (%): c, 89.17; h, 5.07;N,4.18。

synthesis example 38 Synthesis of Compound 514

Compound 514(21.96g) was obtained by substituting e-1 for equimolar e-65 and f-1 for equimolar f-514 according to the same preparation method as in Synthesis example 1, and had a purity of 99.74% by HPLC. Mass spectrum m/z: 1023.4204 (theoretical value: 1023.4189). Theoretical element content (%) C₇₆H₅₃N₃O: c, 89.12; h, 5.22; and N, 4.10. Measured elemental content (%): c, 89.18; h, 5.16; and N, 4.15.

Synthesis example 39 Synthesis of Compound 531

According to the same preparation method as that of synthetic example 1, compound 531(21.90g) was obtained by replacing c-1 with equimolar c-531, f-1 with equimolar f-531 and intermediate 1-2 with equimolar intermediate 531-2, and the solid purity was not less than 99.69% by HPLC. Mass spectrum m/z: 1005.4099 (theoretical value: 1005.4117). Theoretical element content (%) C₇₃H₅₅N₃S: c, 87.13; h, 5.51; and N, 4.18. Measured elemental content (%): c, 87.08; h, 5.44; and N, 4.24.

Synthesis example 40 Synthesis of Compound 539

According to the same preparation method as that of synthetic example 1, f-1 was replaced with equimolar f-539 to give compound 539(21.40g) having a solid purity ≧ 99.67% by HPLC. Mass spectrum m/z: 982.4051 (theoretical value: 982.4035). Theoretical element content (%) C₇₃H₅₀N₄: c, 89.18; h, 5.13; and N, 5.70. Measured elemental content (%): c, 89.21;H,5.06；N,5.73。

device embodiments

In the invention, the ITO/Ag/ITO and ITO glass substrates are ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning liquid, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. The organic materials are sublimated, and the purity of the organic materials is over 99.99 percent.

The driving voltage, the luminous efficiency and the CIE color coordinate of the organic electroluminescent device are tested by combining test software, a computer, a K2400 digital source meter manufactured by Keithley of the United states and a PR788 spectral scanning luminance meter manufactured by Photo Research of the United states into a combined IVL test system. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature.

The device is prepared by adopting a vacuum evaporation system and continuously evaporating under a vacuum uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. The thermal evaporation rate of the organic material or the doped parent organic material is generally set at 0.1nm/s, and the evaporation rate of the doped material is adjusted according to the doping ratio; the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process^-5And (3) evaporating an organic layer and a metal electrode respectively by replacing a mask plate under Pa, detecting the evaporation speed by using an SQM160 quartz crystal film thickness detector of Inficon, and detecting the film thickness by using a quartz crystal oscillator.

Example 1: preparation of organic electroluminescent device 1

ITO is used as an anode on a glass substrate; evaporating HAT-CN with the thickness of 6nm on the anode in vacuum to form a hole injection layer; vacuum evaporating 85nm of TPD10 on the hole injection layer to form a first hole transport layer; vacuum evaporating 10nm of the compound 1 of the invention on the first hole transport layer to form a second hole transport layer; vacuum evaporating 40nm CPCBP Ir (ppy) on the second hole transport layer₃Forming a light emitting layer at 90: 10; vacuum evaporation of 23nm ET onto the light-emitting layer-1 forming an electron transport layer; vacuum evaporating LiF with the thickness of 1nm on the electron transport layer to form an electron injection layer; a cathode was formed by vacuum evaporation of 110nm Al on the electron injection layer.

Examples 2 to 20: preparation of organic electroluminescent device 2-20

The same procedures were carried out except for replacing compound 1 in the second hole transport layer of example 1 with compound 42, compound 65, compound 69, compound 75, compound 87, compound 96, compound 127, compound 147, compound 151, compound 201, compound 327, compound 373, compound 411, compound 447, compound 455, compound 475, compound 499, compound 531, and compound 539, respectively, to obtain organic electroluminescent devices 2 to 20.

Comparative examples 1 to 3: preparation of organic electroluminescent devices 1-3

The compound 1 in the second hole transport layer of example 1 was replaced with R-1, R-2, and R-3, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 1 to 3.

The results of the test of the light emitting characteristics of the organic electroluminescent devices prepared in examples 1 to 20 of the present invention and comparative examples 1 to 3 are shown in table 1.

Table 1 test data of light emitting characteristics of organic electroluminescent device

As can be seen from Table 1, the organic electroluminescent devices 1 to 20 of the present invention have lower driving voltage, higher luminous efficiency and longer service life than the comparative devices 1 to 3, which indicates that the diamine derivative represented by formula 1 of the present invention is a second hole transporting material with good performance.

Example 21: preparation of organic electroluminescent device 21

ITO is used as an anode on a glass substrate; forming a hole injection layer on the anode by vacuum evaporation of HAT-CN with the thickness of 15 nm; vacuum evaporating 86nm of the compound 17 of the present invention on the hole injection layer to form a hole transport layer; vacuum evaporation of 40nm CPCBP Ir (ppy) on the hole transport layer₃Forming a light emitting layer at 90: 10; vacuum evaporating 23nm of ET-1 on the light-emitting layer to form an electron transport layer; vacuum evaporating LiF with the thickness of 1nm on the electron transport layer to form an electron injection layer; a cathode was formed by vacuum evaporation of 110nm Al on the electron injection layer.

Examples 22 to 39: preparation of organic electroluminescent devices 22-39

By replacing the compound 17 in the hole transport layer in example 21 with the compound 60, the compound 108, the compound 169, the compound 185, the compound 189, the compound 246, the compound 279, the compound 331, the compound 339, the compound 360, the compound 379, the compound 386, the compound 395, the compound 401, the compound 416, the compound 420, the compound 443, and the compound 514, the same procedure was carried out, and organic electroluminescent devices 22 to 39 were obtained.

Comparative examples 4 to 6: preparation of organic electroluminescent devices 4-6

The compound 17 in the hole transport layer of example 21 was replaced with R-1, R-2, and R-3, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 4 to 6.

The results of the tests of the light emitting characteristics of the organic electroluminescent devices prepared in examples 21 to 39 of the present invention and comparative examples 4 to 6 are shown in table 2.

Table 2 light emitting characteristic test data of organic electroluminescent device

As can be seen from Table 2, the organic electroluminescent devices 21 to 39 of the present invention have lower driving voltage, higher luminous efficiency and longer service life than the comparative devices 4 to 6, which indicates that the diamine derivatives represented by formula 1 of the present invention are hole transporting materials with good performance.

Example 40: preparation of organic electroluminescent device 40

ITO/Ag/ITO is used as an anode on the glass substrate; vacuum evaporating 56nm 2-TNATA on the anode to form a hole injection layer; forming a hole transport layer by vacuum evaporation of NPD (nitrogen-doped phosphorus) with the thickness of 50nm in the hole injection layer; vacuum evaporating 30nm of TBADN (BDAVBi) 94:6 on the hole transport layer to form a light-emitting layer; vacuum evaporating 10nm of BAlq hole blocking layer on the luminescent layer; vacuum evaporation of 44nm Alq onto the hole-blocking layer₃Forming an electron transport layer; vacuum evaporating LiF with the thickness of 0.1nm on the electron transport layer to form an electron injection layer; forming a cathode by vacuum evaporation of 16nm of Mg and Ag (1: 9) on the electron injection layer; a coating layer was formed on the cathode by vacuum deposition of 50nm of Compound 1 of the present invention.

Examples 41 to 54: preparation of organic electroluminescent devices 41-54

The compound 1 in the cover layer of example 40 was replaced with compound 17, compound 42, compound 52, compound 65, compound 87, compound 96, compound 151, compound 279, compound 327, compound 360, compound 386, compound 416, compound 475, and compound 499, respectively, and the same procedure was followed to obtain organic electroluminescent devices 41 to 54.

Comparative example 7: preparation of organic electroluminescent device 7

A comparative organic electroluminescent device 7 was obtained by replacing the compound 1 in the covering layer of example 40 with R-4 and carrying out the same procedures.

The results of the light emission characteristics test of the organic electroluminescent devices prepared in examples 40 to 54 of the present invention and comparative example 7 are shown in table 3.

Table 3 test data of light emitting characteristics of organic electroluminescent device

As can be seen from Table 3, the organic electroluminescent devices 40 to 54 of the present invention have higher luminous efficiency and longer service life than the comparative device 7, which indicates that the diamine derivatives represented by formula 1 of the present invention are a covering layer material with good performance.

It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

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Diamine derivative and organic electroluminescent device thereof

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