CN116986997A - Deuterated composition, organic electroluminescent device and display device - Google Patents

Deuterated composition, organic electroluminescent device and display device Download PDF

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Publication number
CN116986997A
CN116986997A CN202210420136.2A CN202210420136A CN116986997A CN 116986997 A CN116986997 A CN 116986997A CN 202210420136 A CN202210420136 A CN 202210420136A CN 116986997 A CN116986997 A CN 116986997A
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deuterated
deuteration
nicl
pdcl
compound
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齐建宝
王雪岚
李志强
王占奇
金振禹
陆金波
黄常刚
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Fuyang Sineva Material Technology Co Ltd
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Fuyang Sineva Material Technology Co Ltd
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Priority to CN202210420136.2A priority Critical patent/CN116986997A/en
Priority to PCT/CN2023/086303 priority patent/WO2023202377A1/en
Publication of CN116986997A publication Critical patent/CN116986997A/en
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Abstract

The invention provides a deuterated composition, an organic electroluminescent device and a display device. The deuterated composition comprises a deuterated mixture prepared by deuteration reaction of the compound A; the compound A has a structure shown in a formula I. The prepared OLED device has lower driving voltage, higher current efficiency and longer service life by taking the deuterated composition as the hole layer material.

Description

Deuterated composition, organic electroluminescent device and display device
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to a deuterated composition, an organic electroluminescent device and a display device.
Background
Displays integrate electronic, communication and information processing technologies and are considered to be a further significant development opportunity behind electronics and computers. Display technology and displays have taken a very important role in the development of information technology. Displays on televisions, computers, telephones and various instruments provide a great deal of information for people's daily life and work. In recent years, a novel display technology is an important research point of people, wherein a flat panel display has the advantages of small weight, low power consumption, easiness in carrying and the like, and becomes a research hot spot.
Among the various flat panel displays available today, liquid Crystal Displays (LCDs) are important, however, they have many disadvantages: the light source is required to be used for emitting no light, or the ambient light is required to be used for the light source, the problem of visual angle exists, the response speed is low, the resolution ratio is not high, and the like. Accordingly, new flat panel display technologies have been sought. The organic electroluminescence phenomenon has been found as early as 1963, but has not been paid attention to at the time; until the U.S. Kodak company Tang research group in 1987 published the preparation of high-brightness, high-efficiency thin film organic electroluminescent devices (OLEDs) driven by low DC voltages from organic fluorescent materials and hole materials, the technology was not focused again and a new research area was created.
The OLED has the outstanding advantages of low power consumption, high response speed, flexibility, wide viewing angle, large-area display, full luminescent color and the like, can be compatible with various existing standards and technologies to be manufactured into a low-cost luminescent device, and has wide application prospect in the aspect of realizing color flat panel display. Over the last decades, OLEDs have evolved as a new display technology, with wide spread use in the fields of flat panel displays, flexible displays, solid state lighting and in-vehicle displays.
Currently, organic electroluminescence has become a mainstream display technology, and accordingly, various novel OLED materials have been developed. As the hole layer material, hole injection materials, hole transport materials, and electron blocking materials are mainly triarylamine compounds containing one or more N atoms. However, various performances thereof have yet to be improved, especially in terms of efficiency, lifetime, voltage, etc.
Therefore, development of more kinds of hole materials with more perfect performance to meet the use requirements of the hole materials in high-performance OLED devices is a research focus in the field.
Disclosure of Invention
In view of the shortcomings of the prior art, it is an object of the present invention to provide a deuterated composition, an organic electroluminescent device, and a display device. According to the invention, the triarylamine compound is subjected to deuteration reaction to obtain the deuterated mixture, and the obtained deuterated mixture is used as a hole layer material, so that the prepared OLED device has lower driving voltage, higher current efficiency and longer service life.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a deuterated composition comprising a deuterated mixture prepared from compound a via a deuteration reaction;
The compound A has a structure shown in a formula I:
wherein Ar is 11 、Ar 12 、Ar 21 、Ar 22 Ar is independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C12-C20 heteroaryl;
Ar 11 、Ar 12 can be connected by single bond, ar 21 、Ar 22 The two can be connected through a single bond; ar, ar 12 Can be connected by single bond, ar 11 Can be connected by single bond, ar 21 Can be connected by single bond, ar 22 The two can be connected through a single bond;
n is selected from 0 or 1;
Ar 11 、Ar 12 、Ar 21 、Ar 22 the substituent groups of Ar are respectively and independently selected from at least one of C1-C12 alkyl, C1-C12 alkoxy and C6-C12 aryl.
According to the invention, the triarylamine compound is subjected to deuteration reaction to obtain the deuterated mixture, and the obtained deuterated mixture is used as a hole layer material, so that the prepared OLED device has lower driving voltage, higher current efficiency and longer service life.
In the technical field of display, triarylamine compounds are often used as hole layer materials for preparing organic electroluminescent devices, but various performances of the organic electroluminescent devices prepared from the triarylamine compounds are still to be improved, in particular in the aspects of efficiency, service life, voltage and the like. Therefore, in the prior art, deuterated triarylamine compounds can be used as hole layer materials to improve various performances of the organic electroluminescent device, but the process for preparing the deuterated triarylamine compounds in the prior art is complicated and has high cost. For example, in the synthesis of deuterated triarylamine compound D8-HTSP2, the preparation process is as follows:
In the preparation process, 2-bromodeuterated biphenyl is required, and complicated reaction and purification processes are required to obtain 2-bromodeuterated biphenyl with higher purity, so that the preparation of deuterated triarylamine compound D8-HTSP2 is complicated, the cost is high, and when D8-HTSP2 is used as a hole layer material, the comprehensive performance of the prepared OLED device is poor.
In the invention, the compound (compound A) with a specific structure is subjected to deuteration reaction, and the deuterated mixture is obtained through simple post-treatment, so that the OLED light-emitting device prepared from the deuterated mixture has good comprehensive performance, low driving voltage, high current effect and long service life.
The preparation of the deuterated mixture avoids complicated purification work, and has the advantages of simple preparation method, mild reaction conditions and simple post-treatment.
In the organic reaction, when the reactive sites on the reactive molecule are not significantly different, it is difficult to perform substitution reaction at the characteristic reactive sites, and thus, in the present invention, a mixture (deuterated mixture) is obtained by deuterating the compound a.
In the present invention, ar 11 、Ar 12 、Ar 21 、Ar 22 Ar is independently selected from substituted or unsubstituted C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, substituted or unsubstituted C12-C20 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) heteroaryl.
Ar 11 、Ar 12 、Ar 21 、Ar 22 The substituents substituted in Ar are each independently selected from C1-C12 (e.g., C1, C2, C5, C6, C8, C10, C12, etc.) alkyl, C1-C12 (exampleFor example, at least one of C1, C2, C5, C6, C8, C10, or C12) alkoxy and C6 to C12 (for example, C6, C7, C8, C9, C10, C11, or C12) aryl may be used.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
As a preferable embodiment of the invention, the Ar 11 、Ar 12 、Ar 21 、Ar 22 Ar is independently selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylenyl, fluoranthracenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl, hydrogenated benzanthrenyl, dibenzofuran, dibenzothiophene, naphthobenzofuran, naphthobenzothiophene, dinaphthiophene, dinaphthofuran, dibenzofuran;
the substituted substituents are each independently selected from at least one of C1-C12 (e.g., C1, C2, C5, C6, C8, C10, or C12, etc.) alkyl, C1-C12 (e.g., C1, C2, C5, C6, C8, C10, or C12, etc.) alkoxy, C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12) aryl.
Preferably, the Ar 11 、Ar 12 、Ar 21 、Ar 22 The substituents substituted in Ar are each independently selected from at least one of methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl or naphthyl.
As a preferred embodiment of the present invention, ar is selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, triphenylene, fluorenyl, benzofluorenyl;
the substituent of the substituent is selected from at least one of methyl, ethyl, tertiary butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothienyl or naphthyl.
In the invention, ar is selected from any one of the following groups:
preferably, the Ar 11 、Ar 12 、Ar 21 、Ar 22 Each independently selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, triphenylene, fluoranthenyl, 9-dimethylfluorenyl, 9-dibenzofluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, dibenzobenzofuranyl, dibenzothiophenyl;
The substituted substituents are each independently selected from at least one of methyl, ethyl, t-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, or naphthyl.
In the invention, ar is as follows 11 、Ar 12 、Ar 21 、Ar 22 Each independently selected from any one of the following groups:
as a preferred embodiment of the present invention, the compound a is selected from any one of the following compounds:
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as a preferred embodiment of the present invention, the deuteration reaction includes the following steps:
in the presence of a catalyst, placing a compound A in D 2 O and solvent, carrying out deuteration reaction to obtain the deuteration mixture.
As a preferred embodiment of the present invention, the catalyst is selected from PdCl 2 、NiCl 2 Any one or a combination of at least two of triphenylphosphine or tri-o-tolylphosphine; further preferred is PdCl 2 And NiCl 2 Is a combination of PdCl 2 、NiCl 2 And triphenylphosphine, pdCl 2 、NiCl 2 And a combination of any one or at least two of tri-o-tolylphosphine.
Preferably, the PdCl 2 And NiCl 2 PdCl in combination of (a) 2 And NiCl 2 The ratio of the amounts of the substances (1-2) to (1): 1 (for example, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1 or 2:1, etc.), and more preferably 1:1.
Preferably, the PdCl 2 、NiCl 2 And triphenylphosphine, the amount of triphenylphosphine material and PdCl 2 And NiCl 2 The ratio of the sum of the amounts of the substances is (1 to 3) 1 (for example, 1:1, 1.5:1, 2:1, 2.2:1, 2.5:1 or 3:1, etc.), and more preferably (2 to 2.5) 1.
Preferably, the PdCl 2 、NiCl 2 And tri-o-tolylphosphine in combination with PdCl 2 And NiCl 2 The ratio of the sum of the amounts of the substances is (1 to 3) 1 (for example, 1:1, 1.5:1, 2:1, 2.2:1, 2.5:1 or 3:1, etc.), and more preferably (2 to 2.2) 1.
In the invention, deuteration reaction is carried out in the presence of active carbon, so that the catalyst is adsorbed on the surface of the active carbon, the contact area between the catalyst and reactants can be increased, and the reaction is promoted.
As a preferred embodiment of the present invention, the solvent is selected from benzene, toluene, ethyl acetate or C 6 D 6 Any one or a combination of at least two, further preferably C 6 D 6 。
C is the same as 6 D 6 Is a product obtained by replacing all hydrogen atoms on benzene with deuterium atoms.
Preferably, the deuteration reaction is performed at a temperature of 60 to 200℃and may be performed at 60℃70℃80℃90℃100℃110℃120℃130℃140℃150℃160℃170℃180℃190℃200℃or the like.
Preferably, the deuteration reaction is performed in a hydrogen atmosphere.
Preferably, the pressure of the deuteration reaction is 0.01-2 MPa, and for example, 0.01MPa, 0.05MPa, 0.1MPa, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa or 2MPa, etc. can be used.
Preferably, the deuteration ratio of the deuterated mixture is 15% to 99% (e.g., 15%, 20%, 28%, 38%, 50%, 53%, 60%, 69%, 70%, 80%, 90%, 99%, etc.), and more preferably 28% to 90%.
In the present invention, the deuteration rate refers to the number percentage of deuterium atoms (D) in the total of the number of deuterium atoms and the number of hydrogen atoms (H) in the composition or the compound, that is, deuteration rate=y/(x+y) ×100%, where y is the number of deuterium atoms in the composition or the compound, x is the number of hydrogen atoms in the composition or the compound, and assuming that all of the composition or the compound is H, the deuteration rate is 0% and if all of the H in the composition or the compound is replaced by D, the deuteration rate is 100%.
It should be noted that the deuteration reaction of the present invention is performed in the presence of activated carbon, and the method of post-treatment is further included after the deuteration reaction of the present invention is completed, and the post-treatment method includes cooling, filtering, separating liquid, and drying.
As a preferred embodiment of the present invention, the deuterated composition further comprises a compound B;
the compound B is selected from any one of the following HI-1 to HI-9 compounds:
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preferably, the volume percentage of compound B in the deuterated composition is 3-5%, for example, it may be 3%, 3.3%, 3.6%, 4%, 4.2%, 4.6%, or 5%, etc.
In a second aspect, the present invention provides an organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;
the material of the organic thin film layer comprises the deuterated composition according to the first aspect.
Preferably, the organic thin film layer includes a hole layer including a hole injection layer, a hole transport layer, and an electron blocking layer;
the material of the hole layer comprises a deuterated composition according to the first aspect.
In a third aspect, the present invention provides a display device comprising an organic electroluminescent device as described in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the compound A is subjected to deuteration reaction to obtain a deuterated mixture, and the obtained deuterated mixture is used as a hole layer material, so that the prepared OLED device has lower driving voltage, higher current efficiency and longer service life; meanwhile, the deuteration reaction process for preparing the deuteration mixture is simple, the reaction conditions are mild, a complicated purification process is not needed, the post-treatment is simple, and the method is suitable for preparing the organic electroluminescent device.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
This example provides a HTSP1-D series deuterated mixture having the following reaction equation:
wherein a1, b1 and c1 are integers from 0 to 4; d1 is an integer from 0 to 3; e1 and h1 are integers from 0 to 5; f1 and g1 are integers from 0 to 4; and a1+b1+c1+d1+e1+g1+h1 is not less than 1.
The preparation method of the HTSP1-D series deuterated mixture comprises the following steps:
HTSP1 (6.36 g,0.01 mol), palladium chloride (0.0177 g,0.0001 mol), activated carbon (0.2 g), D were charged into a 500mL autoclave at room temperature 2 O (30 mL) and C 6 D 6 (100 mL), introducing hydrogen to the pressure of 0.02MPa, heating to 90 ℃ for reaction for a certain time, cooling to room temperature, filtering, separating liquid, drying the separated organic layer by magnesium sulfate, decolorizing by a short silica gel column, concentrating to dryness, vacuum drying for 24 hours, and weighing to obtain HTSP1-D series deuterated mixture;
the products obtained by different reaction times are weighed and sublimated, and then deuterated rate detection is carried out (deuteration rate test adopts an internal standard method, for example, reference is made to the literature Wu Yurong, chen Min, the content [ J ] of deuterated bromobenzene is measured by a 1HNMR method, the university of Sichuan university journal of Nature science edition 1997,34 (6): 2', and the values of the reaction time and the deuteration rate of the products are shown in the following table 1:
TABLE 1
Sequence number Deuterated mixture Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP1-D01 1 6.28 12.3％
2 HTSP1-D02 2 6.31 22.1％
3 HTSP1-D03 4 6.32 31.2％
4 HTSP1-D04 10 6.38 55.6％
5 HTSP1-D05 30 6.45 75.1％
6 HTSP1-D06 60 6.55 88.6％
7 HTSP1-D07 120 6.56 98.1％
Example 2
This example provides a HTSP2-D series deuterated mixture having the following reaction equation:
wherein a1, b1 and c1 are integers from 0 to 4; d1 and g2 are integers from 0 to 3; e1 is selected from integers from 0 to 5; f1 and h2 are integers from 0 to 4; m is an integer of 0 to 3, n is an integer of 0 to 3, and a1+b1+c1+d1+e1+g2+h2+3-m+3-n is not less than 1.
The preparation method of the HTSP2-D series deuterated mixture refers to the preparation method of the HTSP1-D series deuterated mixture, and the difference is only that HTSP1 is replaced by HTSP2 with equal amount of substances, and other conditions are the same.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 2:
TABLE 2
Sequence number Deuterated mixture Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP2-D01 1 6.55 8.9％
2 HTSP2-D02 2 6.57 16.2％
3 HTSP2-D03 4 6.59 23.8％
4 HTSP2-D04 10 6.71 45.1％
5 HTSP2-D05 30 6.66 60.1％
6 HTSP2-D06 55 6.77 77.3％
7 HTSP2-D07 120 6.88 82.2％
8 HTSP2-D08 180 6.79 81.9％
By carrying out hydrogen spectrum nuclear magnetic analysis on HTSP2-D07, 1 H-NMR (Bruker, switzerland, avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl) 3 ) There is only a single peak at δ1.70, with no other peaks. It was confirmed that the hydrogen atom on the methyl group in the HTSP2 molecule could not be replaced with a deuterium atom.
Example 2-1
This example provides a HTSP2-D series deuterated mixture having the following reaction equation:
wherein a1, b1 and c1 are integers from 0 to 4; d1 and g2 are integers from 0 to 3; e1 is selected from integers from 0 to 5; f1 and h2 are integers from 0 to 4; m is an integer of 0 to 3, n is an integer of 0 to 3, and a1+b1+c1+d1+e1+g2+h2+3-m+3-n is not less than 1.
The preparation method of the HTSP2-D series deuterated mixture comprises the following steps:
HTSP2 (6.76 g,0.01 mol), palladium chloride (0.0177 g,0.0001 mol), anhydrous nickel chloride (0.013 g,0.0001 mol), activated carbon (0.2 g), D were charged into a 500mL autoclave at room temperature 2 O (30 mL) and C 6 D 6 (100 mL), introducing hydrogen to the pressure of 0.02MPa, heating to 90 ℃ for reaction for a certain time, cooling to room temperature, filtering, separating liquid, drying the separated organic layer by magnesium sulfate, decolorizing by a short silica gel column, concentrating to dryness, vacuum drying for 24h, and weighing to obtain HTSP2-D series deuterated mixture.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 2-1:
TABLE 2-1
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP2-D21 1 6.66 15.6％
2 HTSP2-D22 2 6.70 28.8％
3 HTSP2-D23 4 6.70 55.7％
4 HTSP2-D24 10 6.81 71.8％
5 HTSP2-D25 30 6.83 88.9％
6 HTSP2-D26 70 6.90 98.2％
7 HTSP2-D27 100 6.91 98.7％
As can be seen from a comparison of the data in Table 2 and Table 2-1, if a mixture of palladium chloride and nickel chloride is used as the catalyst, the deuteration reaction is substantially complete after 70 hours, and the deuteration rate is greater than 98%.
Example 2-2
This example provides a HTSP2-D series deuterated mixture differing from example 2-1 only in that anhydrous nickel chloride was added in an amount of 0.0002mol (in this case, the ratio of the amounts of palladium chloride and nickel chloride species was 1:2), with the other conditions being the same as example 2-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following tables 2-2:
TABLE 2-2
Example 3
This example provides a HTSP3-D series deuterated mixture having the following reaction equation:
wherein a1, b1 and c1 are integers from 0 to 4; d1 and g2 are integers from 0 to 3; e1 is selected from integers from 0 to 5; f1 and h2 are integers from 0 to 4; m is an integer of 0 to 3, n is an integer of 0 to 3, and a1+b1+c1+d1+e1+g2+h2+3-m+3-n is not less than 1.
The preparation method of the HTSP2-D series deuterated mixture described above refers to the preparation method of the HTSP2-D series deuterated mixture described above in example 2-1, except that HTSP2 is replaced with HTSP3 in the same amount of the same substance, and the other conditions are the same as in example 2-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 3:
TABLE 3 Table 3
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP3-D01 4 6.68 50.1％
2 HTSP3-D02 10 6.72 68.8％
3 HTSP3-D03 30 6.81 89.1％
4 HTSP3-D04 80 6.83 98.6％
As can be seen from the contents of Table 3, the deuteration reaction was substantially complete after 80 hours by using a mixture of palladium chloride and nickel chloride as the catalyst, and the deuteration rate was more than 98%.
Example 4-1
This example provides a HTSP4-D series deuterated mixture having the following reaction equation:
wherein b1 is an integer from 0 to 4; c1, a1, d1 and g2 are integers from 0 to 3; e1 is selected from integers from 0 to 5; f1 and h2 are integers from 0 to 4; m, n, p, q, r, s, t, u is an integer from 0 to 3, and a1+b1+c1+d1+e1+f1+g2+h2+3-m+3-n+p+q+r+s+t+u is not less than 1.
The preparation method of the HTSP4-D series deuterated mixture described above refers to the preparation method of the HTSP2-D series deuterated mixture provided in example 2-1, except that HTSP2 is replaced with HTSP4 in the same amount of substance as in example 2-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 4-1:
TABLE 4-1
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP4-D01 4 7.65 21.1％
2 HTSP4-D02 30 7.69 46.8％
3 HTSP4-D03 80 7.78 58.6％
4 HTSP4-D04 120 7.61 64.1％
As can be seen from the comparison of the data in Table 2-1 and Table 4-1, if a mixture of palladium chloride and nickel chloride is used as the catalyst, the catalytic efficiency of HTSP4 compounds is low, and the deuteration rate of the product is still less than 65% after 120 hours of reaction.
The HTSP4-D04 was subjected to nuclear magnetic analysis, 1 H-NMR (Bruker, switzerland, avance II 400MHz Nuclear magnetic resonance spectrometer, CDCl) 3 ) There is only a single peak at δ1.31, with no other detailed peaks of H atoms. It was confirmed that the hydrogen atom on the tert-butyl group in the HTSP4 molecule could not be replaced with a deuterium atom.
Example 4-2
This example provides a HTSP4-D series deuterated mixture having the following reaction equation:
wherein b1 is an integer from 0 to 4; c1, a1, d1 and g2 are integers from 0 to 3; e1 is selected from integers from 0 to 5; f1 and h2 are integers from 0 to 4; m, n, p, q, r, s, t, u is an integer from 0 to 3, and a1+b1+c1+d1+e1+f1+g2+h2+3-m+3-n+p+q+r+s+t+u is not less than 1.
The preparation method of the HTSP4-D series deuterated mixture in this example was compared with the preparation method of the deuterated mixture in example 4-1, except that the catalyst in this example was palladium chloride (0.0177 g,0.0001 mol), anhydrous nickel chloride (0.013 g,0.0001 mol) and triphenylphosphine (0.1 g,0.0004 mol), and the other conditions were the same as in example 4-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 4-2:
TABLE 4-2
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP4-D21 4 7.58 38.8％
2 HTSP4-D22 30 7.61 66.9％
3 HTSP4-D23 60 7.90 96..9％
4 HTSP4-D24 80 8.17 98.9％
As can be seen from the contents of Table 4-2, if the mixture of palladium chloride, nickel chloride and triphenylphosphine is used as the catalyst, the catalyst efficiency of HTSP4 compounds is higher, the deuteration reaction is basically complete after 60-80 hours of reaction, and the deuteration rate of the product is more than 95%.
Examples 4 to 3
The reaction equation for the HTSP4-D series deuterated mixture of this example is as follows:
wherein b1 is an integer from 0 to 4; c1, a1, d1 and g2 are integers from 0 to 3; e1 is selected from integers from 0 to 5; f1 and h2 are integers from 0 to 4; m, n, p, q, r, s, t, u is an integer from 0 to 3, and a1+b1+c1+d1+e1+f1+g2+h2+3-m+3-n+p+q+r+s+t+u is not less than 1;
P(o-Tol) 3 is tri-o-tolylphosphine with the structural formula:
the preparation method of the deuterated mixture of HTSP4-D series in this example was referred to the preparation method of deuterated mixture in example 4-2, except that triphenylphosphine was replaced with an equal amount of tri-o-tolylphosphine, and the other conditions were the same as in example 4-2.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following tables 4-3:
TABLE 4-3
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP4-D31 4 7.62 58.18％
2 HTSP4-D32 20 7.86 89.2％
3 HTSP4-D33 30 8.11 98..8％
As can be seen from the contents of tables 4 to 3, when the mixture of palladium chloride, nickel chloride and tri-o-tolylphosphine is used as the catalyst, the deuteration reaction is basically complete after 30 hours of reaction, and the deuteration rate of the product is more than 95%.
As can be seen from the contents of tables 4-1, 4-2 and 4-3, the catalyst is a mixture of palladium chloride, nickel chloride and tri-o-tolylphosphine, the catalytic efficiency to HTSP4 is good, and after 30 hours of deuteration reaction, the reaction is basically complete, and the deuteration rate is more than 98%.
Examples 4 to 4
This example HTSP4-D series deuterated mixture differs from examples 4-3 only in that 0.0004mol of tri-o-tolylphosphine was replaced with equal 0.0002mol of tri-o-tolylphosphine, with the other conditions being the same as in examples 4-3.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following tables 4-4:
Tables 4 to 4
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP4-D41 4 7.33 28.6％
2 HTSP4-D42 50 7.62 35.7％
3 HTSP4-D43 80 7.77 41.2％
4 HTSP4-D44 120 7.82 46.1％
Examples 4 to 5
This example HTSP4-D series deuterated mixture differs from examples 4-3 only in that 0.0004mol of tri-o-tolylphosphine was replaced with equal 0.0006mol of tri-o-tolylphosphine, with the other conditions being the same as in examples 4-3.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following tables 4-5:
tables 4 to 5
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTSP4-D51 4 7.51 59.1％
2 HTSP4-D52 20 7.98 89.2％
3 HTSP4-D53 30 7.60 78..2％
4 HTSP4-D54 50 7.87 76.1％
As can be seen from the contents of tables 4-3, 4-4 and 4-5, if the mixture of palladium chloride, nickel chloride and tri-o-tolylphosphine is used as the catalyst, the deuteration reaction proceeds more slowly and the deuteration rate of the product is still lower after a long period of time if the amount of tri-o-tolylphosphine used is smaller (example 4-4); if the amount of tri-o-tolylphosphine used is large (examples 4 to 5), the deuteration reaction proceeds faster, but the side reaction increases, and after 30 hours of reaction, the deuteration rate of the product decreases instead.
Example 5
This example provides an HTCZ1-D series deuterated mixture having the following reaction equation:
Wherein a3 and f3 are selected from integers of 0-5, b3, d3, e3 and h3 are selected from integers of 0-4, c3, g3, p and q are selected from integers of 0-3, and a3+b3+c3+d3+e3+f3+g3+h3+p+q is more than or equal to 1.
The above preparation method of the HTCZ1-D series deuterated mixture refers to the preparation method of the deuterated mixture provided in example 2-1, except that HTSP2 is replaced with HTCZ1 in the same amount of the same substance, and other conditions are the same as in example 2-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 5:
TABLE 5
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTCZ1-D01 4 6.81 50.3％
2 HTCZ1-D02 10 6.91 77.8％
3 HTCZ1-D03 30 7.00 92.6％
4 HTCZ1-D04 80 7.02 99.1％
Example 6
This example provides HTCZ2-D series deuterated mixtures having the following reaction equations:
wherein a4 and b4 are selected from integers of 0-5, c4, f4, e4 and d4 are selected from integers of 0-4, h4 and g4 are selected from integers of 0-3, and a4+b4+c4+d4+e4+f4+g4+h4 is more than or equal to 1.
The above preparation method of the HTCZ2-D series deuterated mixture refers to the preparation method of the deuterated mixture provided in example 2-1, except that HTSP2 is replaced with HTCZ2 in the same amount of the same substance, and other conditions are the same as in example 2-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 6:
TABLE 6
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTCZ2-D01 4 6.19 58.1％
2 HTCZ2-D02 10 6.33 80.3％
3 HTCZ2-D03 30 6.35 95.8％
4 HTCZ2-D04 80 6.48 98.5％
Example 7
This example provides an HTBP1-D series deuterated mixture having the following reaction equation:
wherein at least one H atom in HTBP1-D is replaced by D.
The preparation method of the above-described HTBP1-D series deuterated mixture refers to the preparation method of the deuterated mixture provided in example 2-1, except that HTSP2 is replaced with HTBP1 in the same amount of the same substance, and the other conditions are the same as in example 2-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 7:
TABLE 7
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTBP1-D01 4 7.91 55.8％
2 HTBP1-D02 10 8.03 71.3％
3 HTBP1-D03 30 8.11 85.8％
4 HTBP1-D04 60 8.13 98.1％
Example 8
This example provides an HTBP2-D series deuterated mixture having the following reaction equation:
wherein at least one H atom in HTBP2-D is replaced by D.
The preparation method of the above-described HTBP2-D series deuterated mixture refers to the preparation method of the deuterated mixture provided in example 2-1, except that HTSP2 is replaced with HTBP2 in the same amount of the same substance, and the other conditions are the same as in example 2-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 8:
TABLE 8
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTBP2-D01 4 4.69 39.9％
2 HTBP2-D02 10 4.78 62.3％
3 HTBP2-D03 30 4.82 79.8％
4 HTBP2-D04 60 4.89 97.9％
Example 9
This example provides HTTPA1-D series deuterated mixtures having the following reaction equations:
wherein at least one H atom in HTTPA1-D is replaced by D.
The preparation method of the above-described HTBP2-D series deuterated mixture refers to the preparation method of deuterated mixture provided in examples 4-3, except that HTSP4 is replaced with HTTPA1 in the same amount of the same substance, and the other conditions are the same as in examples 4-3.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as that above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 9:
TABLE 9
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTTPA1-D01 4 7.71 59.2％
2 HTTPA1-D02 20 7.83 81.3％
3 HTTPA1-D03 30 7.89 98.8％
Example 10
This example provides HTTPA2-D series deuterated mixtures having the following reaction equations:
wherein at least one H atom in HTTPA2-D is replaced by D.
The above preparation method of the HTTPA2-D series deuterated mixture refers to the preparation method of the deuterated mixture provided in example 2-1, except that HTSP2 is replaced with HTTPA2 in the same amount as that of the same substance, and the other conditions are the same as in example 2-1.
The products prepared in different reaction times are weighed, sublimated, and then subjected to deuteration rate detection (the test method is the same as the above), and the values of the reaction time and the deuteration rate of the products are shown in the following table 10:
table 10
Sequence number Deuterated composition Reaction time/(h) Product weight/(g) Deuteration rate
1 HTBPA2-D01 4 5.11 39.9％
2 HTBPA2-D02 10 5.32 68.1％
3 HTBPA2-D03 30 5.33 95.1％
4 HTBPA2-D04 60 5.34 98.9％
In the process of preparing an OLED device, the deuterated composition provided by the invention needs to be evaporated in an evaporation manner, so that the components of evaporation are required to be kept relatively stable, and the following evaporation experiment is carried out: 2g of HTSP2-D05, HTSP4-D21, HTCZ1-D02 and HTSP2-D01 were placed in a crucible of a deposition machine at 1X 10 -6 Pa～9×10 -5 Heating to 300 ℃ under Pa pressure, sequentially evaporating materials in the crucible onto the glass substrates with the serial numbers of 1-9 until the materials in the crucible remain about 10%, and obtaining 9 glass substrates according to the evaporation sequence. The deuteration rates of the materials on the 9 glass substrates were analyzed separately as shown in table 11 below:
TABLE 11
From the above table, it can be seen that the deuteration rates of the materials deposited on the glass substrate at different time periods are substantially the same, indicating that the components of the deuterated composition provided by the invention can remain relatively stable during the deposition process.
The specific structures of the compounds used in the following application examples are shown below:
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The synthesis method of the D8-HTSP2, the D8-HTSP3, the D8-HTSP4, the D8-HTCZ1 and the D18-HTCZ2 comprises the following steps:
(I) Synthesis of D8-HTSP 2:
into a 500mL three-necked flask under nitrogen atmosphere, 200mL of dry toluene, 5.0g (0.0095 mol) of the compound represented by MA, 2.4g (0.0099 mol) of 2-bromodeuterated biphenyl, 0.0575g (0.0001 mol) of Pd (dba) were added 2 (bis (dibenzylideneacetone palladium)), 0.4g (0.0002 mol) of a toluene solution containing 10% by mass of tri-tert-butylphosphine and 1.44g (0.015 mol) of sodium tert-butoxide, heating to reflux, reacting for 12 hours, cooling to room temperature, adding water, and then subjecting the organic layer to a reactionWashing with water to neutrality, drying over magnesium sulfate, filtering to remove magnesium sulfate, concentrating to dryness, separating by silica gel column chromatography, eluting with petroleum ether to obtain 5.1g of compound D8-HTSP2.
Mass spectrometry detection of compound D8-HTSP 2: the mass to charge ratio (m/z) was measured to be 684.35.
(II) Synthesis of D8-HTSP 3:
referring to the synthesis method of D8-HTSP2, the compound shown in MA is replaced with other substancesD8-HTSP3 was obtained.
Mass spectrometry detection of compound D8-HTSP 3: the mass to charge ratio (m/z) was measured to be 684.35.
(III) Synthesis of D8-HTSP 4:
(1) Synthesis of intermediate M-1
To a 500mL three-necked flask under nitrogen, 200mL of dry toluene, 10g (0.048 mol) of 2-amino-9, 9-dimethylfluorene, 11.6g (0.048 mol) of 2-bromodeuterated biphenyl, 0.1725g (0.0003 mol) of Pd (dba) were added 2 (bis-dibenzylideneacetone palladium), 1.2g (0.0006 mol) of a toluene solution containing 10% by mass of tri-t-butylphosphine and 5.76g (0.06 mol) of sodium t-butoxide, heating to reflux, cooling to room temperature after reaction for 12 hours, adding water to the aqueous solution, washing the organic layer to neutrality, drying over magnesium sulfate, filtering to remove magnesium sulfate, concentrating to dryness, separating by silica gel column chromatography, separating by petroleum ether: ethyl acetate = 20:1 (volume ratio) to give 6.9g of intermediate M-1.
Mass spectrometry detection was performed on intermediate M-1: the mass-to-charge ratio (m/z) was 370.24, and the molecular formula of the product was C 27 H 14 D 9 N。
(2) Synthesis of D8-HTSP 4:
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referring to the method for synthesizing D8-HTSP2, the compound shown in MA is replaced by the compound shown in M-1 in the amount of the equivalent substance, and 2-bromodeuterated biphenyl is replaced by the compound shown in M-1 in the amount of the equivalent substanceD8-HTSP4 was obtained.
Mass spectrometry detection was performed on compound D8-HTSP 4: the mass to charge ratio (m/z) was measured to be 796.47.
(IV) synthesis of D8-HTCZ 1:
referring to the synthesis method of D8-HTSP2, the compound shown in MA is replaced by the equivalent amount of the substance2-bromodeuterated biphenyl is changed into 4-bromodeuterated biphenyl with the same amount of substances to obtain D8-HTCZ1.
Mass spectrometry detection was performed on compound D8-HTCZ 1: mass to charge ratio (m/z) of 687.36
(V) synthesis of D18-HTCZ 2:
referring to the synthesis method of D8-HTSP2, the compound shown in MA is replaced by the equivalent amount of the substanceSubstitution of 2-bromodeuterated biphenyl with 4-bromodeuterated biphenyl and the amount of 4-bromodeuterated biphenyl substance is +.>2 times the amount of the substance of sodium tert-butoxide>2.2 times the amount of the catalyst, the reaction time was 36 hours, and D18-HTCZ2 was obtained.
Mass spectrometry detection was performed on compound D18-HTCZ 2: the mass to charge ratio (m/z) was measured to be 654.37.
Application example 1
The application example provides an organic electroluminescent device, which has the structure that: ITO/HTL: HI-2 (5%) (20 nm)/HTL (50 nm)/HTSP 3 (20 nm)/BH 257: BD-2 (5%) (20 nm)/ETL-1 (30 nm)/EIL-1 (1 nm)/Al (150 nm);
the preparation process comprises the following steps: placing the materials into a vacuum chamber, and vacuumizing to 1×10 -5 ～1×10 -6 Pa, sequentially vacuum evaporating on the cleaned ITO substrate. For example, HTL: HI-2 (5%) (20 nm) means that in the device, HTL and HI-2 co-evaporate in a volume ratio of 95:5 to form a hole injection layer, the hole injection layer having a thickness of 20nm.
In this application example, the HTL material was deuterated mixture HTSP1-D01 provided in example 1.
In the device, HTL is HI-2 (5%) (20 nm) is a hole injection layer, HTL (50 nm) is a hole transport layer, HTSP3 (20 nm) is an electron blocking layer. HTSP1-D01 is used as both a hole injection material and a hole transport material in the present device.
It is also understood that BH257: BD-2 (5%) (20 nm) means that in the device BH257 and BD-2 co-evaporate in a volume ratio of 95:5 to form a light-emitting layer, the thickness of which is 20nm.
Application examples 2 to 11
Application examples 2 to 11 each provided an organic electroluminescent device differing from application example 1 only in HTL materials (specific composition and volume ratio are described in table 12 below), and other preparation steps were the same as application example 1.
Comparative application examples 1 to 7
Comparative examples 1 to 7 each provided an organic electroluminescent device differing from example 1 only in HTL materials (specific composition and volume ratio are described in table 12 below), and other preparation steps were the same as example 1.
Performance testing
The testing method comprises the following steps: testing by using an OLED-1000 multichannel accelerated aging life and photochromic performance analysis system produced by Hangzhou remote production, wherein the test items comprise brightness, driving voltage, current efficiency and LT80 of the organic electroluminescent device; wherein LT80 means maintaining the initial luminance of the device at 1000cd/m 2 The current density of the device is unchanged, and the device efficiency is reduced to 1000cd/m of initial brightness 2 The time required for 80% of the corresponding efficiency.
The specific test results are shown in table 12 below:
table 12
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As can be seen from application examples 1 to 4 and comparative application examples 1 to 3, as the deuteration rate increases, the voltage decreases first and then increases, the current efficiency gradually increases, and the lifetime increases first and then decreases. However, the organic electroluminescent device prepared by using the deuterated mixture provided by the present invention as a hole layer material has good overall performance, corresponding to approximately the same deuteration ratio (e.g., comparative application example 2 compared to application example 1, comparative application example 3 compared to application example 2, and application comparative example 5 compared to application example 6). The reason is that even though the deuteration rates are about the same, e.g., D8-HTSP1 and HTSP1-D03, HTSP1-D03 is a mixture of multiple components, and D8-HTSP1 is a single component, HTSP1-D03 has poorer crystallization properties, better film forming properties of the material, and higher hole mobility, thus improving the device performance.
Meanwhile, as can be seen from the data of application examples 5 to 8 and comparative application examples 4 to 5 and the data of application examples 9 to 11 and comparative application examples 6 to 7, the organic electroluminescent device prepared by using the deuterated mixture provided by the invention as a hole layer material has good comprehensive performance.
Application example 12
The application example provides an organic electroluminescent device, which has the structure that: ITO/HTL: HI-3 (5%) (20 nm)/HTL (50 nm)/HTSP 3 (20 nm)/BH 21: BD-2 (5%) (20 nm)/ETL-1 (30 nm)/EIL-1 (1 nm)/Al (150 nm);
the preparation process comprises the following steps: placing the materials into a vacuum chamber, and vacuumizing to 1×10 -5 ～1×10 -6 Pa, sequentially vacuum evaporating on the cleaned ITO substrate. Wherein, HTL: HI-3 (5%) (20 nm) means that HTL and HI-3 co-evaporate in a volume ratio of 95:5 to form a hole injection layer in the device, and the thickness of the hole injection layer is 20nm.
In this application example, the HTL material was deuterated mixture HTCZ1-D01 provided in example 5.
In the device, HTL is HI-2 (5%) (20 nm) is a hole injection layer, HTL (50 nm) is a hole transport layer, HTSP3 (20 nm) is an electron blocking layer. HTCZ1-D01 is used in the present device as both a hole injecting material and a hole transporting material.
As is also understood, BH21: BD-2 (5%) (20 nm) refers to the co-evaporation of BH21 and BD-2 in a volume ratio of 95:5 to form a light-emitting layer in the device, the thickness of the light-emitting layer being 20nm.
Application example 13
Application example 13 provides an organic electroluminescent device differing from application example 1 only in HTL materials (specific composition and volume ratio are as described in table 13 below), and other preparation steps are the same as application example 12.
Comparative application examples 8 to 11
Comparative examples 8 to 11 each provided an organic electroluminescent device differing from example 1 only in HTL materials (specific composition and volume ratio are shown in table 13 below), and other preparation steps were the same as example 12.
Performance testing
The testing method comprises the following steps: testing by using an OLED-1000 multichannel accelerated aging life and photochromic performance analysis system produced by Hangzhou remote production, wherein the test items comprise brightness, driving voltage, current efficiency and LT80 of the organic electroluminescent device; wherein LT80 means that the initial brightness of the device is maintained at 1000cd/m 2 The current density of the device is unchanged, and the device efficiency is reduced to 1000cd/m of initial brightness 2 The time required for 80% of the corresponding efficiency.
The specific test results are shown in table 13 below:
TABLE 13
As can be seen from the contents of table 13, when the deuteration rates of HTL materials are substantially the same (for example, comparative application example 11 is compared with application example 13), the organic electroluminescent device prepared by using the deuterated mixture provided by the present invention as the hole layer material has better overall performance. The reason is that even though the deuteration rates are about the same, e.g., D18-HTCZ2 and HTCZ2-D01, HTCZ2-D01 is a mixture of multiple components, and D18-HTCZ2 is a single component, HTCZ2-D01 has poorer crystallization properties, better film forming properties of the material, and higher hole mobility, thus improving the performance of the device.
Meanwhile, as can be seen from the data of application examples 12-13 and comparative application examples 8-11, the prepared organic electroluminescent device has good comprehensive performance by using the deuterated mixture provided by the invention as a hole layer material.
Application example 14
The application example provides an organic electroluminescent device, which has the structure that: ITO/HIL02 (100 nm)/HTSP 2 (30 nm)/EBL (20 nm)/BH 21: BD-2 (5%) (20 nm)/ETL-1 (30 nm)/EIL-1 (1 nm)/Al (150 nm);
the preparation process comprises the following steps: placing the materials into a vacuum chamber, and vacuumizing to 1×10 -5 ～1×10 -6 Pa, sequentially vacuum evaporating on the cleaned ITO substrate.
In this application example, the HTL (hole transport layer) material is compound HTSP2; the EBL material is deuterated mixture HTTPA1-D01 provided in example 9.
BH21: BD-2 (5%) (20 nm) means that in the device BH21 and BD-2 are co-evaporated in a volume ratio of 95:5 to form a light-emitting layer, the thickness of which is 20nm.
Application examples 15 to 17
Application examples 15 to 17 provide an organic electroluminescent device differing from application example 14 only in the EBL material (specific composition and volume ratio are as described in table 14 below), and other production steps are the same as application example 14.
Comparative application examples 12 to 13
Comparative examples 12 to 13 provided an organic electroluminescent device differing from example 14 only in the EBL materials (specific composition and volume ratio are as described in table 14 below), and other preparation steps were the same as example 14.
Performance testing
The testing method comprises the following steps: testing by using an OLED-1000 multichannel accelerated aging life and photochromic performance analysis system produced by Hangzhou remote production, wherein the test items comprise brightness, driving voltage, current efficiency and LT80 of the organic electroluminescent device; wherein LT80 means maintaining the initial luminance of the device at 1000cd/m 2 The current density of the device is unchanged, and the device efficiency is reduced to 1000cd/m of initial brightness 2 The time required for 80% of the corresponding efficiency.
The specific test results are shown in table 14 below:
TABLE 14
As can be seen from the contents of table 14, the prepared organic electroluminescent device has better overall performance using the deuterated mixture provided by the present invention as EBL (electron blocking layer) material.
In summary, in the invention, the compound A is subjected to deuteration reaction to obtain a deuterated mixture, and the obtained deuterated mixture is used as a hole layer material, so that the prepared OLED device has lower driving voltage, higher current efficiency and longer service life; meanwhile, the deuteration reaction process for preparing the deuteration mixture is simple, the reaction conditions are mild, a complicated purification process is not needed, the post-treatment is simple, and the method is suitable for preparing the organic electroluminescent device.
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. A deuterated composition comprising a deuterated mixture prepared from compound a via a deuteration reaction;
the compound A has a structure shown in a formula I:
wherein Ar is 11 、Ar 12 、Ar 21 、Ar 22 Ar is independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C12-C20 heteroaryl;
Ar 11 、Ar 12 can be connected by single bond, ar 21 、Ar 22 The two can be connected through a single bond; ar, ar 12 Can be connected by single bond, ar 11 Can be connected by single bond, ar 21 Can be connected by single bond, ar 22 The two can be connected through a single bond;
n is selected from 0 or 1;
Ar 11 、Ar 12 、Ar 21 、Ar 22 the substituent groups of Ar are respectively and independently selected from at least one of C1-C12 alkyl, C1-C12 alkoxy and C6-C12 aryl.
2. The deuterated composition of claim 1, wherein Ar 11 、Ar 12 、Ar 21 、Ar 22 Ar is independently selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, triphenylenyl, fluoranthracenyl, pyrenyl, perylenyl, spirofluorenyl, indenofluorenyl, hydrogenated benzanthrenyl, dibenzofuran, dibenzothiophene, naphthobenzofuran, naphthobenzothiophene, dinaphthiophene, dinaphthofuran, dibenzofuran;
the substituted substituent groups are respectively and independently selected from at least one of C1-C12 alkyl, C1-C12 alkoxy and C6-C12 aryl;
preferably, the Ar 11 、Ar 12 、Ar 21 、Ar 22 The substituents substituted in Ar are each independently selected from at least one of methyl, ethyl, tert-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl or naphthyl.
3. The deuterated composition according to claim 1 or 2, wherein Ar is selected from any of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, phenanthryl, anthracyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothiophenyl, triphenylene, fluorenyl, benzofluorenyl;
The substituent group of the substituent group is selected from at least one of methyl, ethyl, tertiary butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothienyl or naphthyl;
preferably, the Ar 11 、Ar 12 、Ar 21 、Ar 22 Each independently selected from any one of the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, triphenylene, fluoranthenyl, 9-dimethylfluorenyl, 9-diphenyl fluorenyl, spirofluorenyl, dibenzofuranyl, diphenylBenzothienyl, dibenzobenzofuranyl, dibenzothienothioyl;
the substituted substituents are each independently selected from at least one of methyl, ethyl, t-butyl, adamantyl, cyclohexyl, cyclopentyl, 1-methylcyclopentyl, 1-methylcyclohexyl, methoxy, phenyl, biphenyl, 9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, or naphthyl.
4. The deuterated composition according to any of claims 1-3 wherein compound a is selected from any of the following compounds:
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5. the deuterated composition according to any of claims 1-4 wherein the deuteration reaction comprises the steps of:
In the presence of a catalyst, placing a compound A in D 2 O and solvent, carrying out deuteration reaction to obtain the deuteration mixture.
6. The deuterated composition of claim 5 wherein the catalyst is selected from PdCl 2 、NiCl 2 Any one or a combination of at least two of triphenylphosphine or tri-o-tolylphosphine; further preferred is PdCl 2 And NiCl 2 Is a combination of PdCl 2 、NiCl 2 And triphenylphosphine, pdCl 2 、NiCl 2 And any one or a combination of at least two of tri-o-tolylphosphine;
preferably, the PdCl 2 And NiCl 2 PdCl in combination of (a) 2 And NiCl 2 The ratio of the amounts of the substances (1-2) to (1), more preferably 1:1;
preferably, the PdCl 2 、NiCl 2 And triphenylphosphine, the amount of triphenylphosphine material and PdCl 2 And NiCl 2 The ratio of the sum of the amounts of the substances is (1 to 3): 1, more preferably (2 to 2.5): 1;
preferably, the PdCl 2 、NiCl 2 And tri-o-tolylphosphine in combination with PdCl 2 And NiCl 2 The ratio of the sum of the amounts of the substances is (1 to 3): 1, more preferably (2 to 2.2): 1.
7. The deuterated composition according to claim 6 wherein the solvent is selected from benzene, toluene, ethyl acetate, or C 6 D 6 Any one or a combination of at least two, further preferably C 6 D 6 ；
Preferably, the temperature of the deuteration reaction is 60-200 ℃;
preferably, the deuteration reaction is performed in a hydrogen atmosphere;
preferably, the pressure of the deuteration reaction is 0.01-2 MPa;
preferably, the deuteration ratio of the deuterated mixture is 15-99%, more preferably 28-90%.
8. The deuterated composition according to any of claims 1-5 further comprising compound B;
the compound B is selected from any one of the following HI-1 to HI-9 compounds:
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preferably, the volume percentage of compound B in the deuterated composition is between 3 and 5%.
9. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode;
the material of the organic thin film layer comprising the deuterated composition of any of claims 1-8;
preferably, the organic thin film layer includes a hole layer including a hole injection layer, a hole transport layer, and an electron blocking layer;
preferably, the material of the cavitation layer comprises the deuterated composition as recited in any one of claims 1-8.
10. A display device characterized in that the display device comprises the organic electroluminescent device according to claim 9.
CN202210420136.2A 2022-04-20 2022-04-20 Deuterated composition, organic electroluminescent device and display device Pending CN116986997A (en)

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