CN112707904A

CN112707904A - Naphthalene bisindole derivative and application thereof

Info

Publication number: CN112707904A
Application number: CN202011582571.2A
Authority: CN
Inventors: 曹建华; 朱波; 侯斌; 李程辉; 王学涛; 吕永清; 赵佳
Original assignee: Beijing Bayi Space LCD Technology Co Ltd
Current assignee: Beijing Bayi Space LCD Technology Co Ltd
Priority date: 2020-12-28
Filing date: 2020-12-28
Publication date: 2021-04-27
Anticipated expiration: 2040-12-28
Also published as: CN112707904B

Abstract

The invention relates to the technical field of materials for organic electroluminescent elements, in particular to a naphthalene bisindole derivative and application thereof; the structure of the naphthalene bisindole derivative is shown as a formula (I); the naphthalene bisindole derivative has the capabilities of transferring electrons and blocking holes, is suitable for being used as a material for an organic electroluminescent element, and has the characteristics of low starting voltage and high luminous efficiency. In addition, the naphthalene bisindoles of the inventionThe derivative has good thermal stability and film-forming property, can be applied to materials for organic electroluminescent elements, display devices and lighting devices, can prolong the service life, and can reduce the manufacturing cost of the materials for the organic electroluminescent elements, the display devices and the lighting devices.

Description

Naphthalene bisindole derivative and application thereof

Technical Field

The invention relates to the technical field of materials for organic electroluminescent elements, in particular to a naphthalene bisindole derivative and application thereof.

Background

In recent years, organic electroluminescent display technologies have become mature, and some products have already entered the market, but in the course of industrialization, many problems still need to be solved, especially for various organic materials used for manufacturing devices, there are many problems that are still unsolved, such as carrier injection and transport properties, electroluminescent properties of materials, service life, color purity, matching between various materials and between various electrodes, and the like. Especially, the light emitting element has not yet achieved practical requirements in terms of luminous efficiency and service life, which greatly limits the development of OLED technology.

The organic electroluminescent element has a structure in which a light-emitting layer containing a light-emitting material is sandwiched between a hole-transporting layer and an electron-transporting layer, and an anode and a cathode are attached to both outer sides of the sandwich structure. Organic electroluminescent devices are devices that emit light when excitons generated by recombination of holes and electrons injected into a light-emitting layer are deactivated, and are used in display devices, lighting devices, and the like.

In order to improve the light emitting efficiency, it is necessary that holes and electrons are smoothly combined in the light emitting layer. However, since the conventional organic material has lower electron mobility than hole mobility, it has a disadvantage of low efficiency of combination between holes and electrons, resulting in a decrease in luminous efficiency. Therefore, new compounds that improve electron injection and mobility from the cathode while preventing hole movement are urgently needed.

In view of the above, there is a strong need for an organic compound having excellent electron injection and mobility as well as high thermal stability to improve efficiency and lifetime characteristics of an organic light emitting diode, and the present invention is particularly proposed.

Disclosure of Invention

In order to solve the above problems of the prior art, an embodiment of the present invention provides a naphthalene bisindole derivative having excellent hole and electron transport ability.

Another embodiment of the present invention provides an organic photoelectric device having a low driving voltage and excellent life-span and efficiency characteristics by including the naphthalene bisindole derivative.

Yet another embodiment of the present invention provides a display or a lighting device including the organic photoelectric device.

The embodiments of the present invention are not limited to the above technical objects, and other technical objects can be understood by those of ordinary skill in the art.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a naphthalene bisindole derivative, which has a structure shown in a formula (I):

wherein X is selected from N or CR¹；

R¹～R¹³Same or different, selected from hydrogen, deuterium, having C₁～C₄₀Straight chain alkyl of (2) having C₁～C₄₀Linear heteroalkyl group of (A) having C₃～C₄₀A branched or cyclic alkyl group having C₃～C₄₀A branched or cyclic heteroalkyl group of (A) having C₂～C₄₀Alkenyl or alkynyl group of (A), an aromatic ring system or a heteroaromatic ring system having 5 to 60 carbon atoms, R¹～R¹³Each of which may be substituted by one or more groups R, and wherein two or more adjacent substituent groups may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;

each occurrence of R is the same or different and is selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, a nitro group, and N (Ar)¹)₂、N(R¹⁴)₂、C(＝O)Ar¹、C(＝O)R¹⁴、P(＝O)(Ar¹)₂Having a structure of C₁～C₄₀Straight chain alkyl of (2) having C₁～C₄₀Linear heteroalkyl group of (A) having C₃～C₄₀A branched or cyclic alkyl group having C₃～C₄₀A branched or cyclic heteroalkyl group of (A) having C₂～C₄₀Alkenyl or alkynyl groups of (A), aromatic or heteroaromatic ring systems having from 5 to 80 carbon atoms, aryloxy or heteroaryloxy groups having from 5 to 60 carbon atoms, each of the R groups being optionally substituted by one or more radicals R¹⁴Substituted, or combinations of these systems, wherein one or more non-adjacent-CH₂The radicals may be substituted by R¹⁴C＝CR¹⁴、C≡C、Si(R¹⁴)₂、Ge(R¹⁴)₂、Sn(R¹⁴)₂、C＝O、C＝S、C＝Se、C＝NR¹⁴、P(＝O)(R¹⁴)、SO、SO₂、NR¹⁴O, S or CONR¹⁴And in which one or more hydrogen atoms are replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, where two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R¹⁴Substitution;

R¹⁴each occurrence of the same or different is selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, a nitro group, and N (Ar)¹)₂、N(R¹⁵)₂、C(＝O)Ar¹、C(＝O)R¹⁵、P(＝O)(Ar¹)₂Having a structure of C₁～C₄₀Straight chain alkyl of (2) having C₁～C₄₀Linear heteroalkyl group of (A) having C₃～C₄₀A branched or cyclic alkyl group having C₃～C₄₀A branched or cyclic heteroalkyl group of (A) having C₂～C₄₀One of alkenyl or alkynyl, aromatic or heteroaromatic ring system having 5 to 60 carbon atoms, aryloxy or heteroaryloxy having 5 to 60 carbon atoms, R¹⁴Each radical in (a) may be substituted by one or more radicals R¹⁵Substituted, or combinations of these systems, wherein one or more non-adjacent-CH₂The radicals may be substituted by R¹⁵C＝CR¹⁵、C≡C、Si(R¹⁵)₂、Ge(R¹⁵)₂、Sn(R¹⁵)₂、C＝O、C＝S、C＝Se、C＝NR¹⁵、P(＝O)(R¹⁵)、SO、SO₂、NR¹⁵O, S or CONR¹⁵And wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, wherein two or more adjacent substituents R¹⁴Aliphatic, aromatic or heteroaromatic ring systems which may optionally be joined or fused to form a single ring or multiple rings and which may be interrupted by one or more radicals R¹⁵Substitution;

Ar¹identical or different at each occurrence and selected from aromatic or heteroaromatic ring systems having from 5 to 30 carbon atoms which may be substituted by one or more nonaromatic radicals R¹⁵Substitution; two groups Ar here bonded to the same nitrogen or phosphorus atom¹Can also be selected from N (R) through a single bond¹⁵)、C(R¹⁵)₂Oxygen or sulfur bridging groups;

R¹⁵selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, having C₁～C₂₀An aliphatic hydrocarbon group, an aromatic ring or a heteroaromatic ring system having 5 to 30 carbon atoms, wherein R¹⁵Wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R¹⁵They can form mono-or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.

Aromatic or heteroaromatic ring systems in the sense of the present invention are intended to be taken to mean systems which do not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be linked by non-aromatic units, for example C, N, O or an S atom. Thus, for example, as with systems in which two or more aryl groups are linked by, for example, a short alkyl group, systems such as fluorene, 9' -spirobifluorene, 9-diarylfluorene, triarylamine, diaryl ether, and the like are also considered to refer to aromatic ring systems in the sense of the present invention.

Aryl in the sense of the present invention contains 5 to 60 carbon atoms and heteroaryl in the sense of the present invention contains 5 to 60 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. Aryl or heteroaryl herein is considered to mean a simple aromatic ring, i.e. benzene, naphthalene, etc., or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatic rings, such as biphenyl, which are connected to one another by single bonds, are, in contrast, not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.

Containing 1 to 40 carbon atoms and in which the individual hydrogen atoms or-CH₂The aliphatic hydrocarbon radicals or alkyl or alkenyl or alkynyl radicals which may also be substituted by the abovementioned radicals are preferably to be understood as meaning the following radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. The alkoxy group, preferably an alkoxy group having 1 to 40 carbon atoms, is considered to mean a methoxy group, a trifluoromethoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, a sec-pentyloxy group, a 2-methylbutyloxy group, a n-hexyloxy group, a cyclohexyloxy group, a n-heptyloxy group, a cycloheptyloxy group, a n-octyloxy group, a cyclooctyloxy group, a 2-ethylhexyloxy group, a pentafluoroethoxy group and a 2,2, 2-. HeteroalkanesThe alkyl group preferably having 1 to 40 carbon atoms means an alkyl group in which a single hydrogen atom or-CH 2-group may be substituted by oxygen, sulfur or halogen atom, and is considered to mean an alkoxy group, alkylthio group, fluorinated alkoxy group or fluorinated alkylthio group, particularly methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2,2, 2-trifluoroethoxy, 2,2, 2-trifluoroethylthio, vinyloxy, vinylthio, propenyloxy, propenylthio, butenylthio, butenyloxy, pentenylthio, cyclopentenyloxy, etc, Cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexenyloxy, cyclohexenylthio, ethynyloxy, ethynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio.

In general, the cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, where one or more-CH may be present₂The radicals may be replaced by the radicals mentioned above; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms, or nitrile groups.

The aromatic or heteroaromatic ring atoms according to the invention may in each case also be substituted by the abovementioned radicals R¹⁵Substituted aromatic or heteroaromatic ring systems, in particular radicals derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,

Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, idobenzene, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-indenocarbazole, cis-or trans-indolocarbazole, triindene, isotridenaphthene, spirotriindene, spiroisotridenaphthene, furan, benzofuran, isobenzofuran, isopenzofuran, perylene, terphenyl,Dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo [5,6 ] thiophene]Quinoline, benzo [6,7 ]]Quinoline, benzo [7,8 ]]Quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxaloimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroixazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diaza-thracene, 2, 7-diaza, 2, 3-diaza-pyrene, 1, 6-diaza-pyrene, 1, 8-diaza-pyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescent red ring, naphthyridine, azacarbazole, benzocarbazine, carboline, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, tetrazole, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole, or a group derived from a combination of these systems.

Preferably, R¹～R¹³The same or different, selected from one of hydrogen, deuterium, aromatic ring system or heteroaromatic ring system with 5-60 carbon atoms, wherein R is¹～R¹³Each of which may be substituted by one or more groups R, and wherein two or more adjacent substituent groups may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system.

Preferably, the naphthalene-bis-indole derivatives mainly include the following structures CJHK 861-CJHK 999 and CJHL 000-CJHL 016:

and represents a bond.

Preferably, R¹～R¹³The same or different, selected from hydrogen, deuterium, and one of aromatic ring system or heteroaromatic ring system having 5 to 60 carbon atoms.

The invention also provides application of the naphthalene bisindole derivative in materials for organic elements.

The invention also provides the application of the naphthalene bisindole derivative in organic elements as a luminescent layer material, an electron transport material, a hole barrier layer material or an encapsulation layer material.

Preferably, the organic device is an organic electroluminescent device, an organic field effect transistor, or an organic thin film solar cell.

According to another embodiment of the present invention, there is provided an organic electroluminescent element including a first electrode, a second electrode, and a plurality of organic layers between the first electrode and the second electrode, at least one of the organic layers including the naphthalenediindole derivative.

The organic electroluminescent element includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent device described herein may include one light emitting layer, or it may include a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, wherein the three layers can exhibit blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises, according to the invention, a naphthalene bisindole derivative according to the invention.

In the other layers of the organic electroluminescent element according to the invention, in particular in the electron transport layer and in the hole blocking layer and the light-emitting layer, all materials can be used in the manner conventionally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.

Preference is furthermore given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process in which the temperature in a vacuum sublimation apparatus is below 10^-5Pa, preferably less than 10^-6Initial pressing down of PaThe material is applied by vapor deposition. However, the initial pressure may also be even lower, e.g. below 10^-7Pa。

Preference is likewise given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10^-5The material is applied under a pressure between Pa and 1 Pa. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.

Preference is furthermore given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

Further, the organic layer may further include one or more selected from an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer, a light emitting layer, and a light refraction layer.

The organic electroluminescent element of the present invention may be either a top emission light element or a bottom emission light element. The structure and the production method of the organic electroluminescent element of the present invention are not limited. The organic electroluminescent element prepared by the compound can reduce the starting voltage and improve the luminous efficiency and brightness.

According to still another embodiment of the present invention, there is provided a display device including the organic electroluminescent element.

According to still another embodiment of the present invention, there is provided a lighting device including the organic electroluminescent element.

The material for organic devices of the present invention contains the naphthalenediindole derivative of the present invention. The material for organic devices may be composed of the compound of the present invention alone or may contain other compounds.

The naphthalene bisindole derivative of the present invention contained in the material for an organic electroluminescent element of the present invention can be used as a host material. In this case, the material for an organic electroluminescent element of the present invention may contain another compound as a dopant.

The naphthalene bisindole derivative has improved hole and electron transport capacity by adjusting the energy level of the naphthalene bisindole derivative through substituent adjustment. Specifically, the naphthalene bisindole derivative has a structure in which an aryl group and a heterocyclic group are sequentially repeated, which reduces an energy level, thereby allowing an improvement in electron transport ability. Thus, the naphthalene bisindole derivative according to an embodiment may be an organic thin layer in a hole transport layer, a hole injection layer, an enhancement layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, a photorefractive layer, or a combination thereof, and provides an organic photoelectric device having excellent electrochemical and thermal stability and lifespan, and high luminous efficiency at a low driving voltage.

Compared with the prior art, the invention has the beneficial effects that: the naphthalene bisindole derivative has the capabilities of transferring electrons and blocking holes, is suitable for being used as a material for an organic electroluminescent element, and has the characteristics of low starting voltage and high luminous efficiency. In addition, the naphthalene bisindole derivative of the present invention has excellent thermal stability and film-forming properties, and can be used in a material for an organic electroluminescent element, a display device, and a lighting device, and can prolong the service life thereof, thereby reducing the manufacturing cost of the material for an organic electroluminescent element, the display device, and the lighting device.

Drawings

Fig. 1 is a schematic view of a bottom emission example of an organic electroluminescent element of the present invention;

FIG. 2 is a schematic view of a top emission example of the organic electroluminescent element of the present invention;

in the figure: 1. a substrate; 2. an anode; 3. a hole injection layer; 4. a hole transporting/electron blocking layer; 5. a light emitting layer; 6. a hole blocking/electron transporting layer; 7. an electron injection layer; 8. and a cathode.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.

The following examples illustrate the performance of OLED materials and devices as follows:

OLED element performance detection conditions:

luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;

current density and lighting voltage: testing using a digital source table Keithley 2420;

power efficiency: tested using NEWPORT 1931-C;

and (3) life test: an LTS-1004AC life test apparatus was used.

Example 1

The preparation method of the compound CJHK861 comprises the following steps:

the first step is as follows: preparation of Compound Int-1

0.1mol of 1-bromocarbazole, 0.12mol of 1-iodo-4-bromonaphthalene and 200mL of xylene are mixed, 4.0mmol of tetramethylethylenediamine and 1.0mmol of cuprous iodide are added, the mixture is heated, refluxed and stirred for reaction for 8 hours under the protection of nitrogen, cooled to room temperature, filtered, the filtrate is concentrated under reduced pressure to dryness, and is separated and purified by a silica gel column to obtain a compound Int-1, a yellow solid, and the yield is 92%.

The second step is that: preparation of Compound Int-2

0.1mol of the intermediate Int-1 prepared in the first step is dispersed in 150mL of toluene, 1.0mmol of palladium acetate, 0.2mL of a 10% tri-tert-butylphosphine toluene solution and 0.15mol of sodium tert-butoxide are added under the protection of nitrogen, the temperature is raised to 90 ℃, the mixture is stirred and reacted for 16 hours, the mixture is cooled to room temperature, 50mL of water is added, ethyl acetate is used for extraction, an organic phase is collected, the organic phase is dried and filtered, the filtrate is concentrated to dryness, and then the mixture is separated and purified by a silica gel column to obtain the intermediate Int-2, wherein the yield is 74%.

The third step: preparation of Compound CJHK861

10.0mmol of intermediate Int-2 prepared in the above step was dissolved in 60mL of THF, 12.0mmol of (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid and 20.0mg of Pd (PPh)₃)₄Adding 25.0mmol of anhydrous sodium carbonate and 20mL of water into the catalyst, stirring and refluxing for reaction for 12 hours, adding 50mL of water for dilution, extracting with dichloromethane, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain CJHK861 which is a yellow solid and has the yield of 78%.

MS and of compound CJHK861¹The HNMR test results are as follows:

MS(MALDI-TOF)：m/z 599.2253[M+H]⁺；¹HNMR(δ、CDCl3)：8.34～8.31(4H,m)；8.27～8.24(2H,m)；8.15～8.08(4H,m)；8.01～7.94(5H,m)；7.89～7.87(2H,m)；7.55～7.51(4H,m)；7.45～7.38(4H,m)；7.33～7.29(1H,m)。

example 2

The preparation method of the compound CJHK868 comprises the following steps:

the first step is as follows: preparation of Compound Int-3

47.6mmol tryptamine, 150mL dichloroethane, 57.0mmol 1-bromo-8-naphthaldehyde and several drops of acetic acid, heating up, refluxing, stirring, reacting for 10 hours, cooling to room temperature, stirring, reacting for 1 hour, concentrating under reduced pressure, drying, adding petroleum ether, filtering, washing with petroleum ether to obtain yellow solid, and separating and purifying with silica gel column to obtain white solid. Yield: 75 percent.

The second step is that: preparation of Compound Int-4

Mixing 37.2mmol of intermediate Int-3 with 250mL of xylene, adding 0.18mol of manganese dioxide, heating, refluxing, stirring, reacting for 48 hours, cooling to room temperature, filtering, washing a filter cake with ethyl acetate, concentrating under reduced pressure to dryness, adding petroleum ether, heating to boil, cooling to room temperature, filtering, and washing with petroleum ether to obtain a white solid. Yield: 94 percent.

The third step: preparation of Compound Int-5

35.0mmol of the intermediate Int-4 prepared in the second step is dispersed in 250mL of xylene, under the protection of nitrogen, 0.4mmol of palladium acetate, 0.8mmol of X-Phos and 52.5mmol of sodium tert-butoxide are added, the temperature is raised to 110 ℃, the mixture is stirred and reacted for 14 hours, the mixture is cooled to room temperature, 50mL of water is added, ethyl acetate is used for extraction, an organic phase is collected, dried and filtered, filtrate is concentrated to dryness, and then silica gel column separation and purification are carried out to obtain the intermediate Int-5 with the yield of 76%.

The fourth step: preparation of Compound Int-6

15.0mmol of the intermediate Int-5 prepared in the previous step is dispersed in 80mL of N, N-dimethylformamide, heated to 40 ℃ under the protection of nitrogen, added with 16.5mmol of NBS in portions, stirred for reaction for 2 hours, cooled to room temperature, poured into 200mL of water, filtered, the filter cake is washed with water, and then separated and purified by a silica gel column to obtain the intermediate Int-6 with a yield of 84%.

The fifth step: preparation of Compound CJHK868

10.0mmol of intermediate Int-6 prepared in the previous step was dissolved in 60mL of toluene, and 12.0mmol of (4- (triphenylen-2-yl) phenyl) boronic acid, 20.0mmol of anhydrous sodium carbonate and 0.01mmol of Pd (PPh) were added under nitrogen protection₃)₄Adding 30mL of ethanol and 30mL of water into the catalyst, heating, refluxing, stirring and reacting for 8 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with dichloromethane, collecting a lower organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying the solid by using a silica gel column to obtain a compound CJHK868 which is yellow solid and has the yield of 82%.

MS and of Compound CJHK868¹The HNMR test results are as follows:

MS(MALDI-TOF)：m/z 595.2192[M+H]⁺；¹HNMR(δ、CDCl3)：8.63～8.61(1H,d)；8.31～8.23(5H,m)；8.15～8.13(1H,m)；8.09(1H,s)；7.82～7.73(4H,m)；7.72～7.70(1H,d)；7.61～7.59(1H,d)；7.56～7.45(5H,m)；7.43～7.34(3H,m)；7.28～7.23(4H,m)。

example 3

Preparation of the compounds CJHK 861-CJHK 898, CJHK900, CJHK901, CJHK 937-CJHK 980, CJHL 001-CJHL 016 referring to the preparation methods of example 1 and example 2, the compounds HKCJ 861-CJHK 898, CJHK900, CJHK 937-CJHK 980, CJHL 001-CJHL 016 were prepared by replacing only the (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid of the third step in example 1 with a different boronic acid compound or replacing the (4- (triphenylen-2-yl) phenyl) boronic acid of the fifth step in example 2 with a different boronic acid compound, and other experimental parameters were routinely adjusted.

Example 4

Preparation method of compound CJHK967 as compound T₁＝C(CH₃)₂For example, the method comprises the following steps:

the first step is as follows: preparation of Compound Int-7

15.0mmol of intermediate Int-2 is dissolved in 110mL of dry THF, the temperature is reduced to-78 ℃ by liquid nitrogen under the protection of nitrogen, 16.5mmol of 2.5M N-butyllithium N-hexane solution is added dropwise, the mixture is stirred and reacted for half an hour, 18.0mmol of trimethyl borate is added dropwise, the mixture is stirred and reacted for 1 hour, the mixture is heated to room temperature, 20mL of 2N dilute hydrochloric acid aqueous solution is added, the extraction is carried out by ethyl acetate, an organic phase is collected, the drying and the filtration are carried out, the filtrate is concentrated under reduced pressure and dried, petroleum ether is added for dispersion and the filtration are carried out, and the intermediate Int-7 is obtained, wherein the yield is.

The second step is that: preparation of Compound Int-8

11.0mmol of intermediate Int-7 was dissolved in 60mL of toluene, and under nitrogen protection, 10.0mmol of p-bromoiodobenzene, 20.0mmol of anhydrous sodium carbonate, 0.01mmol of Pd (PPh)₄And heating the catalyst, 30mL of ethanol and 20mL of water, refluxing, stirring and reacting for 4 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain an intermediate Int-8 with the yield of 87%.

The third step: compound CJHK967 (T)₁＝C(CH₃)₂) Preparation of

11.0mmol of intermediate Int-8 is dissolved in 80mL of toluene, and 10.0mmol of N- ([1,1' -biphenyl) is added under the protection of nitrogen]-4-yl) -9, 9-dimethyl-9H-fluoren-2-amine, 15.0mmol of sodium tert-butoxide, 0.01mmol of Pd₂(dba)₃The catalyst and 0.03mmol of Xanphos ligand are heated to 90 ℃ and stirred to react for 14 hours, the reaction mixture is cooled to room temperature, 50mL of water is added to dilute the reaction mixture, ethyl acetate is used for extraction, an organic phase is collected, the drying and the filtration are carried out, the filtrate is concentrated under reduced pressure to be dry, and the separation and purification are carried out by a silica gel column to obtain a compound CJHK967 with the yield of 87%.

Compound CJHK967 (T)₁＝C(CH₃)₂) MS and¹the HNMR test results are as follows:

MS(MALDI-TOF)：m/z 727.3129[M+H]⁺；¹HNMR(δ、CDCl₃)：8.27～8.24(2H,m)；8.19～8.12(6H,m)；7.90～7.85(2H,m)；7.62～7.59(3H,m)；7.52～7.43(3H,m)；7.40～7.26(13H,m)；7.23(1H,s)；7.17～7.12(2H,m)；1.66(6H,m)。

example 5

Preparation of compounds CJHK899, CJHK 902-CJHK 990 referring to the preparation method of example 4, compounds CJHK899, CJHK 902-CJHK 990 were prepared by replacing only the p-bromoiodobenzene of the second step in example 4 with different halides or replacing N- ([1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine of the third step in example 4 with different amines, with other experimental parameters being routinely adjusted.

Example 6

Preparation method of compound CJHK997, using T₁As an example, N-phenyl:

6.0mmol of intermediate Int-6 is dissolved in 50mL of dry toluene, and 5.0mmol of 9-phenyl-9H, 9'H-3,3' -bicarbazole, 7.5mmol of sodium tert-butoxide and 0.01mmol of Pd are added under the protection of nitrogen₂(dba)₃Heating the catalyst and 0.05mL of 10% tri-tert-butylphosphonium toluene solution to 100 ℃, stirring and reacting for 14 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain the compound CJHK997 with the yield of 85%.

Compound CJHK997 (T)₁N-phenyl) and¹the HNMR test results are as follows:

MS(MALDI-TOF)：m/z 699.2566[M+H]⁺；¹HNMR(δ、CDCl₃)：8.96～8.94(1H,d)；8.54～8.52(1H,d)；8.44～8.39(2H,m)；8.33～8.32(2H,d)；8.27～8.21(5H,m)；7.88～7.85(3H,m)；7.76～7.73(1H,d)；7.65～7.62(1H,d)；7.52～7.44(6H,m)；7.39～7.28(7H,m)；7.14～7.12(1H,m)。

example 7

The preparation method of the compound CJHK997, the preparation of the compounds CJHK 991-CJHK 999 and CJHL000, with reference to the preparation method of example 6, the 9-phenyl-9H, 9'H-3,3' -dicarbazole in example 6 was replaced with a different carbazole derivative or aryl-cumylamine, and the other experimental parameters were routinely adjusted to prepare the compounds CJHK 991-CJHK 999 and CJHL 000.

Comparative example 1

The following compound a was used as a green host material, the following compound B was used as a green dopant material, the compound C was used as a hole injection material, the compound D was used as a hole transport material, the compound G was used as an electron transport dopant material, and LiQ was used as an electron transport host material.

Compound C

/D

/A+B(5％)

/LiQ+G(50％)

/LiF

Al (2nm) was sequentially deposited on ITO glass by an EL deposition machine manufactured by SNU to produce a green light element, and an organic electroluminescent element as a green light was produced.

Comparative example 2

The following compound E was used as a red host material, the following compound F was used as a red dopant material, the compound C was used as a hole injection material, the compound H was used as a hole transport material, the compound G was used as an electron transport dopant material, and LiQ was used as an electron transport host material.

Compound C

/H

/E+F(3％)

/LiQ+G(50％)

/LiF

Al (2nm) was sequentially deposited on ITO glass by an EL deposition machine manufactured by SNU to produce a red light element, and an organic electroluminescent element was produced as red light.

Test example 1

The organic electroluminescent element was prepared according to the method of comparative example 1 by replacing compound A in comparative example 1 with the compounds CJHK861 to CJHK999 or CJHL000 to CJHL016 of the present invention.

The results of measuring the properties of the obtained organic electroluminescent element are shown in Table 1, wherein the driving voltage (V), the current efficiency (LE), the color Coordinate (CIE), and the full width at half maximum (FWHM) were measured at a current density of 10mA/cm²Conditions were obtained and the voltage, LE, FWHM and LT 90% were normalized to the reference.

TABLE 1 test results of device Properties

As can be seen from table 1, the driving voltage of the device prepared from the compound of the present invention is substantially equal to that of the device prepared from comparative example 1, but the current efficiency and LT 90% lifetime performance of the device are improved significantly, especially the green device efficiency of CJHK997 as the host material is 1.18 times higher than that of the comparative device.

The properties of only some of the compounds of CJHK 861-CJHK 999 or CJHL 000-CJHL 016 are listed in Table 1, and the properties of other compounds are substantially identical to the structures of the compounds listed in the Table, and are not listed due to space limitation.

Test example 2

The organic electroluminescent element was prepared according to the method of comparative example 2 by replacing compound E in comparative example 2 with the compounds CJHK861 to CJHK999 or CJHL000 to CJHL016 of the present invention.

The results of measuring the properties of the obtained element are shown in Table 2, in which the driving voltage (V), the current efficiency (LE), the color Coordinate (CIE), and the full width at half maximum (FWHM) were measured at a current density of 10mA/cm²Conditions were obtained and the voltage, LE, FWHM and LT 90% were normalized to the reference.

TABLE 2 test results of device Properties

As can be seen from the results of the device performance test of Table 2, the devices prepared from the compounds of the present invention showed significantly lower driving voltage and improved current efficiency compared to the devices prepared from comparative example 2, especially CJHK868 and CJHK997, at an initial luminance of 2000cd/cm²The LT 90% lifetime in the initial condition was 1.8 and 1.3 times that of the comparative element.

In Table 2, the properties of only some of the compounds CJHK 861-CJHK 999 or CJHL 000-CJHL 016 are listed, and the properties of other compounds are substantially identical to the structures of the compounds listed in the table, and are not listed any more due to space limitation.

Test example 3

The organic electroluminescent element was prepared according to the method of comparative example 2 by replacing compound G in comparative example 2 with the compounds CJHK861 to CJHK999 or CJHL000 to CJHL016 of the present invention.

The results of measuring the properties of the obtained element are shown in Table 3, in which the driving voltage (V), the current efficiency (LE), the color Coordinate (CIE), and the full width at half maximum (FWHM) were measured at a current density of 10mA/cm²Conditions were obtained and the voltage, LE, FWHM and LT 90% were normalized to the reference.

TABLE 3 test results of device Properties

As can be seen from the results of the device performance test in Table 3, the device fabricated by the compound of the present invention has significantly reduced driving voltage and improved current efficiency compared to the device fabricated by the comparative example 2 except CJHK967, and the initial luminance of the device is 2000cd/cm²The LT 90% lifetime in the initial condition was up to 2.5 times higher than the control element.

In Table 3, the properties of only some of the compounds CJHK 861-CJHK 999 or CJHL 000-CJHL 016 are listed, and the properties of other compounds are substantially identical to the structures of the compounds listed in the table, and are not listed any more due to space limitation.

As shown in fig. 1 and fig. 2, which are a schematic view of a bottom emission example of the organic electroluminescent device of the present invention and a schematic view of a top emission example of the organic electroluminescent device, respectively, the naphthalene bisindole derivative of the present invention is contained in the light-emitting layer 5 or the electron transport layer 6.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. A naphthalene bis-indole derivative is characterized in that the structure of the naphthalene bis-indole derivative is shown as formula (I):

wherein X is selected from N or CR¹；

2. The naphthalene bisindole derivative according to claim 1, wherein R is¹～R¹³The same or different, selected from one of hydrogen, deuterium, aromatic ring system or heteroaromatic ring system with 5-60 carbon atoms, wherein R is¹～R¹³Each of which may be substituted by one or more groups R, and wherein two or more adjacent substituent groups may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;

said R is the same or different at each occurrence,selected from hydrogen atom, deuterium atom, halogen atom, nitrile group, nitro group, N (Ar)¹)₂、N(R¹⁴)₂、C(＝O)Ar¹、C(＝O)R¹⁴、P(＝O)(Ar¹)₂Having a structure of C₁～C₄₀Straight chain alkyl of (2) having C₁～C₄₀Linear heteroalkyl group of (A) having C₃～C₄₀A branched or cyclic alkyl group having C₃～C₄₀A branched or cyclic heteroalkyl group of (A) having C₂～C₄₀Alkenyl or alkynyl groups of (A), aromatic or heteroaromatic ring systems having from 5 to 80 carbon atoms, aryloxy or heteroaryloxy groups having from 5 to 60 carbon atoms, each of the R groups being optionally substituted by one or more radicals R¹⁴Substituted, or combinations of these systems, wherein one or more non-adjacent-CH₂The radicals may be substituted by R¹⁴C＝CR¹⁴、C≡C、Si(R¹⁴)₂、Ge(R¹⁴)₂、Sn(R¹⁴)₂、C＝O、C＝S、C＝Se、C＝NR¹⁴、P(＝O)(R¹⁴)、SO、SO₂、NR¹⁴O, S or CONR¹⁴And in which one or more hydrogen atoms are replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, where two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R¹⁴Substitution;

R¹⁴each occurrence of the same or different is selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, a nitro group, and N (Ar)¹)₂、N(R¹⁵)₂、C(＝O)Ar¹、C(＝O)R¹⁵、P(＝O)(Ar¹)₂Having a structure of C₁～C₄₀Straight chain alkyl of (2) having C₁～C₄₀Linear heteroalkyl group of (A) having C₃～C₄₀A branched or cyclic alkyl group having C₃～C₄₀A branched or cyclic heteroalkyl group of (A) having C₂～C₄₀Alkenyl or alkynyl groups, aromatic or heteroaromatic ring systems having 5 to 60 carbon atoms, having 5 to 60One of aryloxy or heteroaryloxy of carbon atoms, R¹⁴Each radical in (a) may be substituted by one or more radicals R¹⁵Substituted, or combinations of these systems, wherein one or more non-adjacent-CH₂The radicals may be substituted by R¹⁵C＝CR¹⁵、C≡C、Si(R¹⁵)₂、Ge(R¹⁵)₂、Sn(R¹⁵)₂、C＝O、C＝S、C＝Se、C＝NR¹⁵、P(＝O)(R¹⁵)、SO、SO₂、NR¹⁵O, S or CONR¹⁵And wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, wherein two or more adjacent substituents R¹⁴Aliphatic, aromatic or heteroaromatic ring systems which may optionally be joined or fused to form a single ring or multiple rings and which may be interrupted by one or more radicals R¹⁵Substitution;

3. The naphthalene-bis-indole derivative according to claim 1 or 2, characterized in that it mainly comprises the following structures CJHK 861-CJHK 999 and CJHL 000-CJHL 016:

wherein, T is₁Selected from-O-, -S-, or any of the following structures:

and represents a bond.

4. The naphthalene bisindole derivative according to claim 1, wherein R is¹～R¹³The same or different, selected from hydrogen, deuterium, and one of aromatic ring system or heteroaromatic ring system having 5 to 60 carbon atoms.

5. Use of the naphthalene bisindole derivative according to any one of claims 1 to 4 as a material for organic elements.

6. Use of the naphthalene bisindole derivative according to any of claims 1 to 4 as a light-emitting layer material, electron transport material, hole blocking layer material or encapsulation layer material in an organic component.

7. Use according to claim 5 or 6, wherein the organic element is an organic electroluminescent element, an organic field effect transistor or an organic thin film solar cell.

8. An organic electroluminescent element comprising a first electrode, a second electrode, and a plurality of organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers comprises the naphthalenediindole derivative according to any one of claims 1 to 4.

9. A display device comprising the organic electroluminescent element according to claim 8.

10. A lighting device comprising the organic electroluminescent element according to claim 8.