CN111377914B - Compound, application thereof and organic electroluminescent device comprising compound - Google Patents

Compound, application thereof and organic electroluminescent device comprising compound Download PDF

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CN111377914B
CN111377914B CN201811621012.0A CN201811621012A CN111377914B CN 111377914 B CN111377914 B CN 111377914B CN 201811621012 A CN201811621012 A CN 201811621012A CN 111377914 B CN111377914 B CN 111377914B
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CN111377914A (en
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魏金贝
高文正
李国孟
王冰
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Beijing Eternal Material Technology Co Ltd
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Abstract

The invention provides a compound, application thereof and an organic electroluminescent device comprising the compound, wherein the compound has a structure shown in a formula (I), E is selected from one of substituted or unsubstituted C3-C30 heteroaryl, D has a structure shown in a formula (II), and L 1 And L 2 Each independently selected from one of a single bond, a substituted or unsubstituted C6-C30 arylene group and a substituted or unsubstituted C3-C30 heteroarylene group, and the compound is used as an electron transport material in an organic electroluminescent device, wherein the electron transport material has stronger electron transport capacity and lower injection energy barrier, and can effectively reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency and reduce the efficiency roll-off.

Description

Compound, application thereof and organic electroluminescent device comprising compound
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a compound, application thereof and an organic electroluminescent device comprising the compound.
Background
The electroluminescent phenomenon based on tris (8-hydroxyquinoline) aluminum (Alq 3) was first reported in 1987 by profound chinese scientists Deng Qingyun, opening the booming trend in organic electroluminescent diode (OLEDs) research. OLEDs have many advantages such as self-luminescence, high contrast, low power consumption, etc., and thus have attracted extensive attention in the chemical and industrial fields.
Common organic electroluminescent devices have a typical sandwich structure and are often composed of a plurality of functional layers such as a hole transport layer, a light emitting layer, an electron transport layer and the like. In the organic electroluminescent device, the higher exciton injection energy barrier tends to result in high voltage, and the injection energy barrier of the current electron transport material is still to be further improved. In addition, the carrier mobility of the existing electron transport materials is often lower than that of hole transport materials, so that the phenomena of unstable electroluminescence spectrum, serious efficiency roll-off and the like caused by deviation of exciton recombination regions are caused.
CN108822114A discloses an OLED electron transport material and application thereof, the material takes 2,7-diphenyl-1,3,6,8-tetraazapyrene with electron deficiency as a core, and a proper substituent group is introduced into the electron deficiency center to form a micromolecule OLED functional layer material with excellent electron transport performance, the molecular weight is 510-820, the material has a closed loop structure and excellent thermal stability, and can be suitable for an evaporation process for manufacturing a micromolecule organic electroluminescent device, but the electron transport performance and the electron injection performance of the material are further optimized.
CN108409730A discloses an organic small molecule electron transport material and a preparation method thereof. The preparation method of the organic micromolecule electron transport material comprises the following steps: (1) Performing coupling reaction on 2-chloro-4,6-diphenyl-1,3,5-triazine and 3-bromo-phenylboronic acid, and performing subsequent treatment to obtain a bromine-containing intermediate; (2) Carrying out Suzuki reaction on the bromine-containing intermediate and diboron pinacol ester, and carrying out subsequent treatment to obtain a borate intermediate; (3) And (3) carrying out coupling reaction on the borate intermediate and 3-bromo-1,10-phenanthroline, and carrying out subsequent treatment to obtain the organic micromolecule electron transport material. The organic micromolecule electron transport material has a simple structure and good thermal stability and morphology stability; an n-doped electron transport layer formed by n-doping is used for an organic electroluminescent device and has high luminous efficiency and high stability, but the electron transport capability and the electron injection capability of the organic electroluminescent device are required to be further optimized.
CN108475735a discloses an organic electron transport material comprising a phosphine oxide derivative substituted with one or both of aryl and heteroaryl groups, and may have an atomic group of one or more phosphine oxide groups, and further substituted with an atom or an atomic group of a group consisting of a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, a formyl group, a carbonyl group, an alkoxycarbonyl group, and a trifluoromethyl group, which is a novel organic electron transport material having excellent stability and durability due to high chemical stability of a C — P bond in an anionic state, but its electron transport ability and electron injection ability are still to be further optimized.
Therefore, there is a need in the art to develop a compound having a strong electron transport capability and a low injection energy barrier, so that when the compound is applied to an electron transport material in an organic electroluminescent device, the compound can further reduce the driving voltage, improve the luminous efficiency, and reduce the efficiency roll-off.
Disclosure of Invention
The invention aims to provide a compound, which has the structure of formula (I),
Figure BDA0001926862330000011
in the formula (I), R is 1 、R 2 、R 3 And R 4 Each independently selected from one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;
in the formula (I), E is selected from one of substituted or unsubstituted C3-C30 heteroaryl;
in the formula (I), D has a structure shown in a formula (II),
Figure BDA0001926862330000021
wherein the dotted line represents an access position connected with other groups, the dotted line or the solid line is led out from the middle of the benzene ring, and represents that a substituent can be substituted at any substitutable position of the benzene ring, and the following relates to similar representation methods and has the same meaning;
in the formula (II), R is 5 Represents a mono-to maximum permissible substituent, said R 5 Each independently of each otherIndependently selected from one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, or R 5 And the aromatic rings connected with the aromatic ring are condensed to form one of substituted or unsubstituted C10-C30 aryl and substituted or unsubstituted C9-C30 heteroaryl;
if condensation is carried out, R 5 One selected from the group consisting of substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;
the maximum permissible substituents mean the maximum number of the substituents as set forth above with respect to the number of the substituents satisfying the chemical bond requirements by the substituents, and illustratively, when the structure of the formula (II) is a phenylene group, R 5 It may be one or more, but up to the maximum permissible substituents (i.e. 4) for the phenylene group. The same meanings apply hereinafter to the same descriptions (monosubstituted to the maximum permissible substituents);
the R is 5 And the aromatic rings to which they are attached are fused to each other means: the R is 5 The group may be one or more, and the one or more R 5 Between radicals, and optionally one or more R 5 Radicals and radicals with said one or more R 5 The aromatic rings connected with the groups can be arbitrarily fused to form a ring, and can be a plurality of adjacent R 5 The radicals being condensed with one another and also being R 5 The group and the connected aromatic ring are fused to form a ring, the specific fusion mode is not limited in the invention, and the group has the same meaning when the same description is related;
in the formula (I), L is 1 And L 2 Each independently selected from one of a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;
the substituted substituent is independently selected from one of halogen, cyano, C1-C10 alkyl, C1-C10 naphthenic base, C2-C6 alkenyl, C2-C6 cycloalkenyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 monocyclic aryl, C6-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl and C3-C30 condensed ring heteroaryl.
The invention aims to provide a compound with electron transport performance, which selects a pyrido triazole group as a parent nucleus of the compound, and the parent nucleus has good electron deficiency and conjugation, so that the mobility of carriers is improved, higher electron transport capacity and lower charge injection energy barrier are obtained, and the aims of effectively reducing driving voltage, improving luminous efficiency and reducing efficiency roll-off when the compound is applied to an organic electroluminescent device are fulfilled.
Preferably, said L 1 And L 2 Each independently selected from a single bond or a structure having formula (L-1),
Figure BDA0001926862330000022
in the formula (L-1), p and q are independently selected from 0 or 1 and are not 0 at the same time, and in the formula (L-1), F and G are independently selected from any one of the following substituted or unsubstituted S1-S7 groups:
Figure BDA0001926862330000031
wherein the dotted line, which crosses two or three rings, represents that a substituent may be substituted at any substitutable position of the two or three rings, and hereinafter the same notations appear to have the same meaning;
the substituted substituent is respectively and independently selected from one of halogen, cyano-group, C1-C10 alkyl, C1-C10 naphthenic base, C2-C6 alkenyl, C2-C6 cycloalkenyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 monocyclic aryl, C6-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl and C3-C30 condensed ring heteroaryl.
Preferably, F and G are each independently selected from one of the following substituted or unsubstituted groups:
Figure BDA0001926862330000032
preferably, said E has the structure of formula (III),
Figure BDA0001926862330000033
said X is 1 、X 2 、X 3 、X 4 、X 5 Each independently selected from nitrogen atom or CR 7 And said X 1 、X 2 、X 3 、X 4 、X 5 At least one of them is a nitrogen atom;
said R is 7 Each independently selected from one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, or the R 7 And the aromatic rings connected with the aromatic ring are condensed with each other to form one of substituted or unsubstituted C9-C30 heteroaryl;
if condensed, the R 7 One selected from the group consisting of substituted or unsubstituted C6 to C30 arylamino, substituted or unsubstituted C3 to C30 heteroarylamino, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C3 to C30 heteroaryl;
the substituted substituent groups are respectively and independently selected from one of halogen, cyano, C1-C10 alkyl, C1-C10 cycloalkyl, C2-C6 alkenyl, C2-C6 cycloalkenyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 monocyclic aryl, C6-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl and C3-C30 condensed ring heteroaryl.
In order to improve the electron transport performance of the compound, an electron-withdrawing substituent E containing a nitrogen atom is introduced into the compound, so that the electron-withdrawing substituent E plays a synergistic role with a pyridine triazole parent nucleus, and the intramolecular and intermolecular forces are enriched, thereby further improving the electron transport performance of the compound, reducing the electron injection energy barrier, improving the luminous efficiency of a device, and reducing the driving voltage and the efficiency roll-off.
Preferably, D has a structure of formula (2-1) or formula (2-2),
Figure BDA0001926862330000034
the R is 5 Represents a mono-to maximum permissible substituent, said R 5 Each independently selected from one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, or R 5 And the aromatic rings connected with the aromatic ring are condensed to form one of substituted or unsubstituted C10-C30 aryl and substituted or unsubstituted C9-C30 heteroaryl;
if condensed, the R 5 One selected from the group consisting of substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl.
Preferably, said R is 5 Each independently selected from one of pyridyl, phenanthryl and triphenylene.
Preferably, D is selected from phenylene or one of the following groups:
Figure BDA0001926862330000041
a, B, C is independently selected from one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, preferably one of substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C3-C12 heteroaryl;
the R is 5 Represents a mono-to maximum permissible substituent, said R 5 Each independently selected from one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, or R 5 And the aromatic rings connected with the aromatic ring are condensed with each other to form one of substituted or unsubstituted C10-C30 aryl and substituted or unsubstituted C9-C30 heteroaryl;
if condensed, the R 5 One selected from the group consisting of substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;
the substituted substituent groups are respectively and independently selected from one of halogen, cyano, C1-C10 alkyl, C1-C10 naphthenic base, C2-C6 alkenyl, C2-C6 cycloalkenyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 monocyclic aryl, C6-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl and C3-C30 condensed ring heteroaryl.
Preferably, D is selected from one of the following substituted or unsubstituted groups:
Figure BDA0001926862330000042
preferably, E is selected from one of the following groups:
Figure BDA0001926862330000051
z is 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 、Z 7 、Z 8 、Z 9 、Z 10 、Z 11 、Z 12 、Z 13 Are independent of each otherIs selected from nitrogen atom or CR 7 ；
The R is 7 Each independently selected from one of hydrogen, C1-C12 alkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, or R 7 And the aromatic rings connected with the aromatic ring are condensed with each other to form one of substituted or unsubstituted C10-C30 aryl and substituted or unsubstituted C9-C30 heteroaryl;
if condensed, the R 7 One selected from the group consisting of substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;
the substituted substituent is respectively and independently selected from one of halogen, cyano, C1-C10 alkyl, C1-C10 naphthenic base, C2-C6 alkenyl, C2-C6 cycloalkenyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 monocyclic aryl, C6-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl and C3-C30 condensed ring heteroaryl;
z is 1 、Z 2 、Z 3 、Z 4 、Z 5 At least one of which is a nitrogen atom;
z is 6 、Z 7 、Z 8 、Z 9 、Z 10 、Z 11 、Z 12 、Z 13 At least one of which is a nitrogen atom.
In order to improve the electron transmission performance of the compound, the groups E have better electron-withdrawing ability of the formulas (3-1) and (3-2), have more obvious synergistic effect with a pyridine triazole parent nucleus, and the prepared organic electroluminescent device has higher luminous efficiency and lower driving voltage and efficiency roll-off.
Preferably, the E is selected from one of substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted quinoline, substituted or unsubstituted triazine, substituted or unsubstituted quinoxaline and substituted or unsubstituted quinazoline;
the substituted substituent groups are respectively and independently selected from one of halogen, cyano-group, C1-C10 alkyl, C1-C10 naphthenic base, C2-C6 alkenyl, C2-C6 cycloalkenyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 monocyclic aryl, C6-C30 condensed ring aryl, C3-C30 monocyclic heteroaryl and C3-C30 condensed ring heteroaryl.
Preferably, the compound is selected from one of the following compounds:
Figure BDA0001926862330000052
Figure BDA0001926862330000061
Figure BDA0001926862330000071
Figure BDA0001926862330000081
Figure BDA0001926862330000091
the second purpose of the invention is to provide the application of the compound in the first purpose, wherein the application is used as an electron transport material in an organic electroluminescent device.
It is a further object of the present invention to provide an organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, said organic layers comprising at least one compound according to one of the objects.
The organic electroluminescent device includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
A substrate may be used under the first electrode or over the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material serving as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO 2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multi-layer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3,4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as the compounds shown below in HT-1 to HT-34, or any combination thereof.
Figure BDA0001926862330000101
Figure BDA0001926862330000111
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI1-HI3 described below; one or more of the compounds HI1 to HI3 described below may also be doped with one or more compounds HT-1 to HT-34.
Figure BDA0001926862330000121
The light emitting layer includes a light emitting dye (i.e., dopant) that can emit different wavelength spectrums, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the material of the light-emitting layer can be different materials such as a fluorescent electroluminescent material, a phosphorescent electroluminescent material, a thermal activation delayed fluorescence luminescent material and the like. In an organic electroluminescent device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
When the luminescent layer adopts the technology of phosphorescence electroluminescence, the host material of the luminescent layer is selected from, but not limited to, one or more of GPH-1 to GPH-80.
Figure BDA0001926862330000122
Figure BDA0001926862330000131
Figure BDA0001926862330000141
When the light-emitting layer adopts the phosphorescent electroluminescence technology, the phosphorescent dopant of the light-emitting layer can be selected from, but is not limited to, one or more combinations of GPD-1 to GPD-47 listed below.
Figure BDA0001926862330000151
Figure BDA0001926862330000161
When the luminescent layer adopts the technology of thermal activation delayed fluorescence luminescence, the fluorescent dopant of the luminescent layer can be selected from, but is not limited to, one or more of TDE-1 to TDE-39 listed below.
Figure BDA0001926862330000162
Figure BDA0001926862330000171
Figure BDA0001926862330000181
The organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
The electron transport layer material may be selected from, but is not limited to, combinations of one or more of ET-1 through ET-57 listed below.
Figure BDA0001926862330000182
Figure BDA0001926862330000191
Figure BDA0001926862330000201
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer materials including, but not limited to, combinations of one or more of the following.
LiQ、LiF、NaCl、CsF、Li 2 O、Cs 2 CO 3 、BaO、Na、Li、Ca。
The electron transport functional layer of the present invention should also comprise the following compounds:
Figure BDA0001926862330000202
compared with the prior art, the invention has the following beneficial effects:
(1) The invention selects the pyrido triazole group as the parent nucleus of the compound, and the parent nucleus has good conjugation and high carrier mobility, thereby obtaining higher electron transport capacity and lower charge injection energy barrier, and being applied to organic compoundsWhen the electroluminescent device is used, the driving voltage can be effectively reduced, the luminous efficiency can be improved, the efficiency roll-off can be reduced, and the maximum brightness is 46000cd/m 2 The starting voltage is 3.1V or below, and the maximum external quantum efficiency is more than 18%.
(2) In the preferred technical scheme, an electron-deficient substituent E containing nitrogen atoms is introduced to have a synergistic effect with a pyridine triazole parent nucleus, so that intramolecular and intermolecular acting force can be enriched, the electron transport capacity of the compound can be further improved, the electron injection energy barrier can be reduced, and when the compound is used for an organic electroluminescent device, the device has higher luminous efficiency, lower driving voltage and efficiency roll-off.
(3) In a further preferred scheme, substituents with stronger electron-withdrawing ability of pyridine, pyrimidine, triazine and quinoline are selected to act with a pyridyltriazole parent nucleus synergistically, so that intramolecular and intermolecular acting force can be further enriched, the electron transport capacity of the compound can be further improved, the electron injection energy barrier can be further reduced, and when the compound is used for an organic electroluminescent device, the organic electroluminescent device with higher luminous efficiency, lower driving voltage and efficiency roll-off can be obtained.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
A representative synthetic route for compounds of general formula (la) is as follows:
Figure BDA0001926862330000211
preparation example 1
The synthesis steps of M1 are as follows:
Figure BDA0001926862330000212
(1) Synthesis of intermediate M1-2
10.9g (100 mmol) of 2-hydrazinopyridine is added into 100mL of absolute ethyl alcohol, after heating and refluxing, 100mL of absolute ethyl alcohol solution dissolved with 19.4g (105 mmol) of p-bromobenzaldehyde is added dropwise, after about 20min, the dropwise addition is finished, and then the stirring and the refluxing are continued for 1h. After the reaction is finished, the temperature is reduced to room temperature, the mixture is stirred for 30min in an ice-water bath, and then the mixture is filtered and drained. The resulting solid sample (M73-1) was dissolved in 100mL of dichloromethane, and 43.0g of [ bis (trifluoroacetoxy) iodo ] benzene (BTA, 100 mmol) was added and stirred at room temperature for 1h. After 150mL of methylene chloride was added to the reaction system, the reaction system was washed with a 10% sodium hydrogen sulfite solution (400 mL), a 10% sodium carbonate solution (400 mL) and a large amount of water in this order. The organic phase was concentrated and recrystallized from absolute ethanol to yield a large amount of off-white solid, 21.9g, 80.1% yield.
The mass of the molecular ions determined by mass spectrometry was: 273.01 (calculated: 272.99); theoretical element content (%) C 12 H 8 BrN 3 : c,52.58; h,2.94; br,29.15; n,15.33. Measured elemental content (%): c,52.53; h,2.95; n,15.31.
The above analysis results show that the obtained product is the expected product.
(2) Synthesis of intermediate M1-3
A dry 1000mL three-necked flask is taken, 3.5g (10 mmol) of the M1-2 intermediate obtained in the first step, 5.1g (20 mmol) of pinacol diboron diboride and 1.46g (2 mmol) of 1,1' -bis-diphenylphosphine ferrocene palladium dichloride are sequentially added under the nitrogen condition, and finally 500mL of dry 1,4-dioxane is added, and heating reflux reaction is carried out for 15h. After the completion of the reaction, the solvent in the reaction system was removed by distillation under reduced pressure. Extraction with dichloromethane, washing with a large amount of water, combining organic phases and performing column chromatography. Column chromatography with petroleum ether =1:2 as eluent gave large amounts of white solid, 4.5g, 86.5% yield.
The mass of the molecular ions determined by mass spectrometry was: 396.21 (calculated: 396.20); theoretical element content (%) C 18 H 20 BN 3 O 2 : c,67.31; h,6.28; b,3.37; n,13.08; and O,9.96. Measured elemental content (%): c,67.29; h,6.36; and N,13.06.
The above analysis results showed that the obtained product was the intended product.
(3) Synthesis of Compound M1
A dry 500mL two-necked bottle was charged with 2.6g (8.1 mmol) of M1-3, 2.67g (10 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.38g (10 mmol) of anhydrous potassium carbonate, and 230mg (2 mmol) of palladium tetratriphenylphosphine in that order. After nitrogen substitution was carried out three times, 5mL of water, 5mL of ethanol and 300mL of toluene were added, and the mixture was refluxed for 12 hours. The solvent of the reaction system was distilled under reduced pressure, extracted with methylene chloride, and washed with a large amount of water. The combined organic phases were concentrated and column chromatographed using dichloromethane to petroleum ether =4:1 as eluent to give a white solid, 3.2g, 88.9% yield.
The mass of the molecular ions determined by mass spectrometry was: 426.19 (calculated: 426.16); theoretical element content (%) C 27 H 18 N 6 : c,76.04; h,4.25; n,19.71. Measured elemental content (%): c,76.05; h,4.22; n,19.69.
The above analysis results showed that the obtained product was the intended product.
Preparation example 2
The difference from preparation example 1 was that M-bromobenzaldehyde was replaced with p-bromobenzaldehyde in an equivalent amount to obtain compound M2 as a white solid (3.4 g, yield 94.5%)
The mass of the molecular ions determined by mass spectrometry was: 426.17 (calculated: 426.16); theoretical element content (%) C 27 H 18 N 6 : c,76.04; h,4.25; n,19.71. Measured elemental content (%): c,76.03; h,4.26; n,19.68.
Preparation example 3
The difference from preparation example 1 is that 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced with an equivalent amount of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine to give compound M4 as a white solid, 3.6g, yield 71.7%.
The mass of the molecular ions determined by mass spectrometry was: 502.16 (calculated: 502.19); theoretical element content (%) C 33 H 22 N 6 : c,78.87; h,4.41; n,16.72. Measured elemental content (%): c,73.85; h,4.42; n is added to the reaction solution to form a reaction solution,16.73。
the above analysis results show that the obtained product is the expected product.
Example 1
The preparation process of the organic electroluminescent device comprises the following steps:
glass plates coated with indium tin oxide (ITO, thickness 150 nm) transparent conductive layers were sonicated in commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10 -5 ～1×10 -4 Pa, performing vacuum evaporation on the anode layer film to obtain HI-2 and HT-2 which are respectively used as a hole injection layer and a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10nm and 40nm respectively;
vacuum evaporation of "GPH-77: TDE-7 (30nm, 5% by weight) "as a light-emitting layer of the organic electroluminescent device, the evaporation rate was 0.1nm/s, and the total film thickness was 30nm; wherein "5wt%" refers to the doping ratio of the dye, i.e. the weight ratio of the host material to the TDE-7 is 95.
A compound M1 is evaporated on the luminescent layer in vacuum to be used as an electron transport layer of the organic electroluminescent device, the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 25nm;
and (3) evaporating LiF with the thickness of 0.5nm as an electron injection layer and Al with the thickness of 150nm as a cathode on the electron transport layer in vacuum.
The device structure is as follows:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/GPH-77：TDE-7(30nm,5％wt)/M1(25nm)/LiF(0.5nm)/Al(150nm)。
example 2
The difference from example 1 is that compound M1 is replaced by compound M2.
Example 3
The difference from example 1 is that compound M1 is replaced by compound M5.
Example 4
The difference from example 1 is that compound M1 is replaced by compound M10.
Example 5
The difference from example 1 is that compound M1 is replaced by compound M80.
Example 6
The difference from example 1 is that compound M1 was replaced with compound M89.
Example 7
The difference from embodiment 1 is that, by replacing TDE-7 with GPD-1, the device structure is as follows:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/GPH-77：GPD-1(30nm,5wt％)/M1(25nm)/LiF(0.5nm)/Al(150nm)。
example 8
The difference from example 7 is that compound M1 is replaced by compound M22.
Example 9
The difference from example 7 is that compound M1 is replaced by compound M65.
Example 10
The difference from example 7 is that compound M1 is replaced by compound M70.
Example 11
The difference from example 7 is that compound M1 is replaced by compound M84.
Example 12
The difference from example 7 is that compound M1 is replaced by compound M91.
Example 13
The difference from example 7 is that compound M1 is replaced by compound M44.
Example 14
The difference from example 7 is that compound M1 is replaced by compound M100.
Example 15
The difference from example 7 is that compound M1 is replaced by compound M33.
Comparative example 1
Differs from example 1 in that Compound M1 is replaced by Compound R-1
Figure BDA0001926862330000241
Comparative example 2
The difference from example 7 is that Compound M1 is replaced by Compound R-1
Figure BDA0001926862330000242
And (3) performance testing:
the organic electroluminescent devices prepared in examples and comparative examples were measured for turn-on voltage, maximum luminance and maximum external quantum efficiency using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1cd/m 2 The voltage is the starting voltage, the current density at the moment is measured, and the maximum external quantum efficiency is calculated according to data such as spectrum and the like.
The results of the performance tests are shown in tables 1 and 2.
TABLE 1
Maximum luminance/cd/m 2 Turn-on voltage/V Maximum external quantum efficiency/%)
Example 1 53562 2.9 21.2
Example 2 50608 3.0 20.4
Example 3 49694 2.9 19.7
Example 4 46397 3.0 18.9
Example 5 47734 3.1 18.6
Example 6 49519 3.0 19.2
Comparative example 1 40295 3.6 14.4
TABLE 2
Maximum luminance/cd/m 2 Turn-on voltage/V Maximum external quantum efficiency/%)
Example 7 51482 3.0 20.3
Example 8 51020 3.0 19.6
Example 9 53500 3.1 21.2
Example 10 52212 2.9 20.1
Example 11 52297 3.0 18.4
Example 12 52194 3.1 19.4
Example 13 52500 3.0 20.5
Example 14 51056 2.9 21.6
Example 15 52205 3.0 20.6
Comparative example 2 42648 3.7 13.1
As can be seen from tables 1 and 2, when the compound of the present invention is used as an electron transport material for Thermally Activated Delayed Fluorescence (TADF) and phosphorescent dye, the turn-on voltage, the maximum luminance and the maximum external quantum efficiency are all improved compared to the comparative examples, and excellent device performance is shown, wherein, as can be seen from comparative examples 1 to 6, comparative example 1, examples 7 to 15 and comparative example 2, the introduction of the pyrido-triazole group plays a crucial role in improving the performance of the device, because the pyrido-triazole group is used as the parent nucleus of the electron transport material, the parent nucleus has good conjugation property and high current carrying capacity, so as to obtain higher electron transport capacity and lower charge injection energy barrier, and when the compound is applied to an organic electroluminescent device, the drive voltage can be effectively reduced, the light emitting efficiency can be improved, the efficiency can be reduced, and the device mobility can be shown. And the conjugation degree of R-1 is larger, the triplet state energy level of the whole molecule is obviously reduced, and the diffusion energy of excitons in the blocking light-emitting layer is deteriorated, so that the turn-on voltage is increased, and the efficiency is reduced.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (5)

1. A compound having the structure of formula (I),
Figure FDA0004101277750000011
in the formula (I), R is 1 、R 2 、R 3 And R 4 Each independently selected from one of hydrogen, C1-C12 alkyl and C6-C30 aryl;
in the formula (I), E is selected from one of substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted quinolyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinoxalinyl and substituted or unsubstituted quinazolinyl;
in the formula (I), D has a structure of a formula (2-1) or a formula (2-2),
Figure FDA0004101277750000012
said R is 5 Represents a mono-to maximum permissible substituent, said R 5 Each independently selected from one of hydrogen, C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;
in the formula (I), L is 1 And L 2 Each independently selected from a single bond or a structure having formula (L-1),
Figure FDA0004101277750000013
in the formula (L-1), p and q are independently selected from 0 or 1 and are not simultaneously 0, and F and G are independently selected from any one of the following S1-S3 groups:
Figure FDA0004101277750000014
the substituted substituent is independently selected from one of halogen, cyano, C1-C10 alkyl, C6 monocyclic aryl and C3 monocyclic heteroaryl.
2. The compound of claim 1, wherein F and G are each independently selected from one of the following groups:
Figure FDA0004101277750000015
3. a compound selected from one of the following compounds:
Figure FDA0004101277750000016
Figure FDA0004101277750000021
Figure FDA0004101277750000031
Figure FDA0004101277750000041
Figure FDA0004101277750000051
4. use of a compound according to any of claims 1 to 3 as an electron transport material in an organic electroluminescent device.
5. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layers comprise at least one compound according to any one of claims 1 to 3.
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