Deuterated composition and preparation method thereof, luminescent layer and organic light-emitting device

Abstract

The present application discloses a deuterated composition and a preparation method thereof, a light-emitting layer and an organic light-emitting device, which relates to the field of organic light-emitting materials, wherein the deuterated composition includes different deuterated substances of a compound as shown in Formula I: #imgabs0#; in Formula I, Ar1 is selected from a phenyl group or a naphthyl group; in different deuterated substances of the same compound, the average deuterated rate of deuterated hydrogen on Ar1 and anthracene group is greater than 98%, and the average deuterated rate of deuterated hydrogen on phenanthrene group is 96% to 98%. When the deuterated composition of the present application is used as a light-emitting material of an organic light-emitting device, the device life can be significantly improved.

Description

Technical Field

[0001] The present application relates to the technical field of organic light-emitting materials, and in particular to a deuterated composition and a preparation method thereof, a light-emitting layer and an organic light-emitting device. Background Art

[0002] In organic light-emitting devices, the life of blue light-emitting devices is usually lower than that of red light-emitting devices and green light-emitting devices, which has become the life shortcoming of organic light-emitting devices. In order to improve the service life of blue light-emitting devices, one of the most effective ways is to improve the blue light-emitting host material.

[0003] Common blue light-emitting host materials are anthracene compounds. If the anthracene compounds are deuterated, the stability of the anthracene compounds can be improved. Although the life of blue light-emitting devices can be improved when the deuterated anthracene compounds are used as blue light-emitting host materials, the device life still needs to be further improved. Summary of the invention

[0004] The technical problem solved by the present application is to increase the lifespan of a blue light-emitting device.

[0005] In order to solve the above technical problems, the first aspect of the present application provides a deuterated composition, comprising different deuterated substances of the compound shown in Formula I:

[0006] ; In formula I, Ar1 is selected from phenyl or naphthyl; in different deuterated forms of the same compound, the average deuteration rate of deuterated hydrogen of Ar1 and anthracene is greater than 98%, and the average deuteration rate of deuterated hydrogen of phenanthryl is 96% to 98%.

[0007] The second aspect of the present application provides a deuterated composition, which is prepared by subjecting compound A1 to a first deuteration reaction to obtain compound A2, then reacting compound A2 with compound A3 to obtain compound A4, and then subjecting compound A4 to a second deuteration reaction.

[0008] The third aspect of the present application provides a method for preparing a deuterated composition, comprising the following steps: subjecting compound A1 to a first deuteration reaction to obtain compound A2; subjecting compound A2 to a reaction with compound A3 to obtain compound A4; subjecting compound A4 to a second deuteration reaction to obtain a deuterated composition comprising different deuterated substances, wherein the structural formula of the deuterated substances is as shown in Formula II:

[0009] , D(n) represents that the anthracene group is substituted by n deuteriums, and n'≤n≤8, D(m) represents that the deuterated hydrogen of the phenanthryl group is substituted by m deuteriums, and m≤9, Ar1'' is selected from a fully or partially deuterated phenyl group, a fully or partially deuterated naphthyl group, and the number of deuterated groups of Ar1'' is greater than or equal to the number of deuterated groups of Ar1'.

[0010] In the above scheme, the structural formula of the compound A1 is: , Ar1 is selected from phenyl or naphthyl; the structural formula of the compound A2 is: , D(n') represents that n' deuteriums replace the deuterated hydrogen on the anthracene group, and n'≤8, Ar1' is selected from a fully or partially deuterated phenyl group, a fully or partially deuterated naphthyl group; the structural formula of the compound A3 is: ; The structural formula of compound A4 is: .

[0011] A fourth aspect of the present application provides a light-emitting layer, comprising: the above-mentioned deuterated composition or a deuterated composition prepared by the above-mentioned method for preparing the deuterated composition.

[0012] A fifth aspect of the present application provides an organic light-emitting device, comprising a first electrode and a second electrode arranged opposite to each other and an organic layer located between the first electrode and the second electrode, wherein the organic layer comprises the above-mentioned light-emitting layer.

[0013] Device testing has verified that different deuterated compounds of the compound shown in Formula I of the present application are used as the light-emitting material of the organic light-emitting device, and when the average deuterated rate of deuterated hydrogen on Ar1 and the anthracene group is higher than the average deuterated rate of deuterated hydrogen on the phenanthrene group, the device life can be greatly improved. When the preparation method of the present application is used to deuterate anthracene compounds, the deuterated cost can be greatly reduced, which is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The following drawings describe in detail the exemplary embodiments disclosed in this application. The same reference numerals represent similar structures in several views of the drawings. Those skilled in the art will understand that these embodiments are non-limiting, exemplary embodiments, and the drawings are only used for the purpose of illustration and description, and are not intended to limit the scope of this application. Other embodiments may also accomplish the inventive intent in this application. It should be understood that the drawings are not drawn to scale. Among them:

[0015] Figure 1 This is the hydrogen nuclear magnetic spectrum of the deuterated composition prepared in Example 1 of the present application;

[0016] Figure 2 The hydrogen nuclear magnetic spectrum of the deuterated composition prepared in Comparative Example 1 of the present application;

[0017] Figure 3 The hydrogen nuclear magnetic spectrum of the deuterated composition prepared in Comparative Example 2 of the present application;

[0018] Figure 4 This is the hydrogen nuclear magnetic spectrum of the deuterated composition prepared in Comparative Example 3 of the present application;

[0019] Figure 5 This is the hydrogen nuclear magnetic spectrum of the deuterated composition prepared in Example 2 of the present application;

[0020] Figure 6 This is the hydrogen nuclear magnetic spectrum of the deuterated composition prepared in Example 3 of the present application. DETAILED DESCRIPTION

[0021] The following description provides specific application scenarios and requirements of the present application, with the purpose of enabling those skilled in the art to make and use the content in the present application. It will be apparent to those skilled in the art that various local modifications to the disclosed embodiments are apparent, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present application. Therefore, the present application is not limited to the embodiments shown, but to the widest scope consistent with the claims.

[0022] The present application provides a deuterated composition, including different deuterated substances of the compound shown in Formula I:

[0023] ;

[0024] In formula I, Ar1 is selected from phenyl or naphthyl.

[0025] In Formula I, the connection site of the phenanthryl group and the anthracene group is not limited, therefore, the Formula I represents a variety of compounds according to the different connection sites of the phenanthryl group and the anthracene group. The following are examples of compounds represented by Formula I:

[0026] .

[0027] In the present application, the deuterated composition may include different deuterated substances of only one compound of the compound shown in Formula I, or may include different deuterated substances of two or more compounds of the compound shown in Formula I. For example, the deuterated composition may include different deuterated substances of the compound shown in Formula I-1, or different deuterated substances of the compound shown in Formula I-5, or different deuterated substances of the compound shown in Formula I-6. For another example, the deuterated composition may include different deuterated substances of two or three compounds of the compound shown in Formula I-1, the compound shown in Formula I-5, and the compound shown in Formula I-6.

[0028] In the present application, different deuterated substances of the compound refer to different numbers of deuterated hydrogens of the compound replaced by deuterium. The deuterated hydrogen refers to hydrogen that can be replaced by deuterium. In Formula I, the total number of deuterated hydrogens on the anthracene group is 8, the total number of deuterated hydrogens on the phenanthryl group is 9, the total number of deuterated hydrogens when Ar1 is a phenyl group is 5, and the total number of deuterated hydrogens when Ar1 is a naphthyl group is 7.

[0029] When anthracene compounds are deuterated, it is generally believed that the higher the degree of deuteration, the better, and it is best to achieve all deuteration. However, the inventors of the present application unexpectedly found that it is not the closer to all deuterated performance, the better. In anthracene compounds, the degree of deuteration of anthracene groups and the degree of deuteration of other groups have different effects on the life of the device. When the degree of deuteration of anthracene groups is higher than that of other groups, the device shows a longer life. The reason may be that when anthracene compounds are used as luminescent host materials, anthracene groups contribute the most to the HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) of the compound, and its stability is the most critical, so the requirement for the degree of deuteration of anthracene groups is higher than that of other groups.

[0030] Specifically, the inventors of the present application have discovered that if in different deuterated products of the same compound, for example, in different deuterated products of the compound represented by formula I-1, or in different deuterated products of the compound represented by formula I-5, or in different deuterated products of the compound represented by formula I-6, the average deuterated rate of deuterated hydrogen of Ar1 and anthracene groups is greater than 98%, and the average deuterated rate of deuterated hydrogen of phenanthryl groups is 96% to 98%, then the deuterated composition containing these different deuterated products can significantly improve the life of the device when used as a luminescent material.

[0031] In the present application, the average deuteration rate of deuterated hydrogen refers to the average value of the deuteration rate of deuterated hydrogen. The average deuteration rate of deuterated hydrogen will be described below using the compound represented by Formula I-1 as an example.

[0032] In the above formula, d1 to d8 represent the sites of deuterated hydrogen of the anthracene group, d9 to d13 represent the sites of deuterated hydrogen of the phenyl group, and d14 to d22 represent the sites of deuterated hydrogen of the phenanthryl group.

[0033] When the compound shown in Formula I-1 is deuterated, each deuterated hydrogen may be deuterated or not, so the deuteration rate of each deuterated hydrogen can be calculated, and the deuteration rate can represent the degree of deuteration. Since there are many deuterated hydrogens, each deuterated hydrogen corresponds to a deuteration rate, which cannot well reflect the degree of deuteration of a part as a whole. Therefore, the average deuteration rate of deuterated hydrogen is introduced in this application to reflect the degree of deuteration, and the higher the average deuteration rate of deuterated hydrogen, the higher the degree of deuteration.

[0034] Theoretically, the deuteration rate of any deuterated hydrogen can be obtained as follows: di %=N Di / N T ×100%,D di % represents the deuteration rate of deuterated hydrogen at the i-th site, N Di is the number of deuterated species in which the deuterated hydrogen at the i-th site is replaced by deuterium, N T is the total number of such compounds (e.g., compounds of formula I-1). Then the average deuteration rate of deuterated hydrogen on Ar1 and anthracene groups can be obtained by the following method: The average deuteration rate of deuterated hydrogen on the phenanthryl group can be obtained by the following method: .

[0035] When quantitative analysis is actually performed, the average deuteration rate of deuterated hydrogen can be calculated by hydrogen nuclear magnetic resonance testing: a standard sample (such as mesitylene trimethoxybenzene, 1,4-dioxane, etc.) is prepared and dissolved and diluted in a suitable deuterated reagent (such as deuterated DMSO, deuterated chloroform, etc.) to obtain a standard sample solution, and the test sample is dissolved in the standard sample solution and subjected to hydrogen nuclear magnetic resonance testing. The molar mass of the standard sample and the test sample is calculated, and then the average degree of deuteration is calculated in combination with hydrogen nuclear magnetic resonance spectrum analysis.

[0036] In some preferred embodiments, the different deuterated substances of the compound represented by Formula I are selected from the following group:

[0037] ;

[0038] Wherein: D(n) represents that n deuteriums replace the deuterated hydrogen of the anthracene group, and n≤8; D(m) represents that m deuteriums replace the deuterated hydrogen of the phenanthryl group, and m≤9; when D(q1) appears, it represents that q1 deuteriums replace the deuterated hydrogen of the phenyl group, and q1≤5; when D(q2) appears, it represents that q2 deuteriums replace the deuterated hydrogen of the naphthyl group, and q2≤7.

[0039] In some preferred embodiments, the average deuteration rate of the anthracene group is greater than the average deuteration rate of the phenanthryl group, and the difference is p, and the value of p is 1%~4%.

[0040] When deuterating anthracene compounds, there is usually a problem of difficulty in deuteration due to the poor solubility of anthracene compounds. At present, in order to increase the deuteration rate, the conventional method is to use a large amount of deuterated reagents for multiple deuteration, but this method faces problems such as long deuteration time and high deuteration cost, and is not suitable for industrial production.

[0041] In view of this, the present application provides a method for preparing a deuterated composition, using two deuterated reactions, first deuterating an anthracene compound with good solubility, and the deuterated process only requires a small amount of deuterated reagent to make the average deuterated rate of deuterated hydrogen reach 96%. Then, the product of the first deuterated reaction is coupled with non-deuterated phenanthrene, and the coupled product is deuterated for the second time. The deuterated process also requires a small amount of deuterated reagent, and the average deuterated rate of deuterated hydrogen in the anthracene part is greater than 98%, and the average deuterated rate of deuterated hydrogen in the phenanthrene part is 96%~98%, so as to improve the life of the device. Therefore, the preparation method of the present application can obtain a deuterated composition with excellent application effect at a lower cost.

[0042] Specifically, the preparation method of the deuterated composition comprises the following steps:

[0043] S1: subjecting compound A1 to a first deuteration reaction to obtain compound A2.

[0044] The structural formula of the compound A1 is: , Ar1 is selected from the same as in Formula I, and is selected from phenyl and naphthyl.

[0045] The structural formula of the compound A2 is: , D(n') represents that n' deuterated hydrogen of the anthracene group is substituted with deuterium, and n'≤8, and Ar1' is selected from a fully or partially deuterated phenyl group and a fully or partially deuterated naphthyl group.

[0046] In some embodiments, the method for performing the first deuteration reaction comprises: placing compound A1 in a first deuteration reagent in the presence of a first catalyst to perform a deuteration reaction.

[0047] In some preferred embodiments, the first catalyst includes at least one of a protonic acid, a Lewis acid, and a polymer-bonded sulfonic acid. As an example, the protonic acid can be selected from trifluoroacetic acid, trifluoromethanesulfonic acid, perfluorobutylsulfonic acid, etc. As an example, the Lewis acid can be selected from aluminum chloride, zinc chloride, molybdenum chloride, etc.

[0048] In some preferred embodiments, the mass of the first catalyst is 3% to 20% of the mass of the compound A1.

[0049] In some preferred embodiments, the first deuterated reagent includes: deuterated benzene or deuterated water.

[0050] In some preferred embodiments, the ratio of the volume of the first deuterated reagent to the mass of the compound A1 (also referred to as the volume-to-weight ratio) is (20-50) mL:1 g. Since the compound A1 has good solubility, only a small amount of the first deuterated reagent is needed to achieve a high average deuteration rate.

[0051] In some preferred embodiments, the reaction temperature of the first deuteration reaction is reflux temperature, and the reaction time is 1 to 5 days.

[0052] S2: reacting the compound A2 with the compound A3 to obtain the compound A4.

[0053] The structural formula of the compound A3 is: The structural formula of the compound A4 is: .

[0054] In some embodiments, the method for reacting the compound A2 with the compound A3 comprises: firstly subjecting the compound A2 to a bromination reaction to obtain a bromide, and then subjecting the bromide to a coupling reaction with the compound A3 to obtain the compound A4.

[0055] In some preferred embodiments, the method for causing the compound A2 to undergo bromination reaction comprises: causing the compound A2 to react with N-bromosuccinimide, using a solvent selected from at least one of N,N-dimethylformamide, toluene, and chlorobenzene, the reaction temperature is 0°C to 40°C, and the reaction time is 1 hour to 24 hours.

[0056] In some preferred embodiments, when carrying out the coupling reaction, the catalyst is selected from platinum compounds, palladium compounds, such as Pd(dppf)Cl2, Pd2(dba)3, palladium acetate, etc., the auxiliary ligand is selected from phosphine ligands, such as 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, etc., the reaction system is alkaline, K2CO3, Cs2CO3 can be used to adjust the pH value of the system, the solvent used is selected from at least one of benzene, toluene, xylene, and chlorobenzene, the reaction temperature is from room temperature to the boiling point of the solvent, and the reaction time is 1 hour to 24 hours.

[0057] S3: subjecting the compound A4 to a second deuteration reaction to obtain a deuterated composition comprising different deuterated substances, wherein the structural formula of the deuterated substance is as shown in Formula II:

[0058] , D(n) represents that the anthracene group is substituted by n deuteriums, and n'≤n≤8, D(m) represents that the deuterated hydrogen of the phenanthryl group is substituted by m deuteriums, and m≤9, Ar1'' is selected from a fully or partially deuterated phenyl group, a fully or partially deuterated naphthyl group, and the number of deuterated groups of Ar1'' is greater than or equal to the number of deuterated groups of Ar1'.

[0059] In some embodiments, the method for performing the second deuteration reaction comprises: placing the compound A4 in a second deuteration reagent in the presence of a second catalyst to perform a deuteration reaction.

[0060] In some preferred embodiments, the second catalyst includes at least one of a protonic acid, a Lewis acid, and a polymer-bonded sulfonic acid. As an example, the protonic acid can be selected from trifluoroacetic acid, trifluoromethanesulfonic acid, perfluorobutylsulfonic acid, etc. As an example, the Lewis acid can be selected from aluminum chloride, zinc chloride, molybdenum chloride, etc.

[0061] In some preferred embodiments, the mass of the second catalyst is 3% to 20% of the mass of the compound A4.

[0062] In some preferred embodiments, the second deuterated reagent includes: deuterated benzene or deuterated water.

[0063] In some preferred embodiments, the ratio of the volume of the second deuterated reagent to the mass of the compound A4 is (40-200) mL:1 g.

[0064] In the present application, the solubility of compound A4 obtained after the introduction of the phenanthryl moiety is poor, and under the general view that the higher the degree of deuteration, the better, it is easy to think of a method of using a large amount of deuterated reagents for multiple deuterations, so that the phenanthryl moiety can also reach a high degree of deuteration equivalent to the anthracene moiety. However, based on the discovery of the inventors of the present application, the average deuteration rate of the phenanthryl moiety is not the higher the better, and when there is a difference in the average deuteration rate of the phenanthryl moiety and the anthracene moiety, it is beneficial to improve the life of the device. Therefore, the present application can still use a small amount of deuterated reagents for the second deuteration. On the one hand, due to solubility issues, the deuteration rate of the phenanthryl part will be lower than that of the anthracene part; on the other hand, the second deuteration reaction will not only deuterate the phenanthryl part, but also deuterate the undeuterated deuterated hydrogen on the anthracene part (specifically Ar1' and anthracene). As a result, the average deuteration rate of the anthracene part will be higher than that of the phenanthryl part.

[0065] In some preferred embodiments, the reaction temperature of the second deuteration reaction is reflux temperature, and the reaction time is 1 to 5 days.

[0066] The present application also provides a deuterated composition, which is prepared by subjecting compound A1 to a first deuterated reaction to obtain compound A2, then subjecting compound A2 to a reaction with compound A3 to obtain compound A4, and then subjecting compound A4 to a second deuterated reaction; wherein:

[0067] The structural formula of the compound A1 is: , Ar1 is selected from phenyl or naphthyl; the structural formula of the compound A2 is: , D(n') represents that n' deuterated hydrogen of anthracene group is substituted, and n'≤8, Ar1' is selected from a fully or partially deuterated phenyl group and a fully or partially deuterated naphthyl group; the structural formula of the compound A3 is: ; The structural formula of compound A4 is: .

[0068] In some embodiments, the first deuteration reaction is performed by placing Compound A1 in a first deuteration reagent in the presence of a first catalyst.

[0069] In some preferred embodiments, the conditions of the first deuteration reaction satisfy at least one of the following conditions:

[0070] (a) the first catalyst comprises at least one of a proton acid, a Lewis acid, and a polymer-bonded sulfonic acid; as an example, the proton acid can be selected from trifluoroacetic acid, trifluoromethanesulfonic acid, perfluorobutylsulfonic acid, etc.; as an example, the Lewis acid can be selected from aluminum chloride, zinc chloride, molybdenum chloride, etc.;

[0071] (b) the mass of the first catalyst is 3% to 20% of the mass of the compound A1;

[0072] (c) the first deuterated reagent comprises: deuterated benzene or deuterated water;

[0073] (d) The ratio of the volume of the first deuterated reagent to the mass of the compound A1 is (20-50) mL:1 g;

[0074] (e) The reaction temperature is reflux temperature, and the reaction time is 1 to 5 days.

[0075] In some embodiments, the second deuteration reaction is performed by placing the compound A4 in a second deuteration reagent in the presence of a second catalyst.

[0076] In some preferred embodiments, the conditions of the second deuteration reaction satisfy at least one of the following conditions:

[0077] (a) the second catalyst comprises at least one of a protonic acid, a Lewis acid, and a polymer-bonded sulfonic acid; as an example, the protonic acid may be selected from trifluoroacetic acid, trifluoromethanesulfonic acid, perfluorobutylsulfonic acid, etc.; as an example, the Lewis acid may be selected from aluminum chloride, zinc chloride, molybdenum chloride, etc.;

[0078] (b) the mass of the second catalyst is 3% to 20% of the mass of the compound A4;

[0079] (c) the second deuterated reagent comprises: deuterated benzene or deuterated water;

[0080] (d) The ratio of the volume of the second deuterated reagent to the mass of the compound A4 is (40-200) mL:1 g;

[0081] (e) The reaction temperature is reflux temperature, and the reaction time is 1 to 5 days.

[0082] The present application also provides a light-emitting layer, comprising: the above-mentioned deuterated composition or a deuterated composition prepared by the above-mentioned method for preparing the deuterated composition.

[0083] In some preferred embodiments, the light-emitting layer further comprises a compound as shown in Formula III:

[0084] Formula III;

[0085] wherein Q1 and Q2 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzocycloalkyl; and when substituted, the substituent is selected from hydrogen, deuterium, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 6 to 30 carbon atoms, straight-chain or branched alkyl or cycloalkyl having 1 to 10 carbon atoms; n is an integer from 0 to 3; R is selected from deuterium, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 6 to 30 carbon atoms, straight-chain or branched alkyl or cycloalkyl having 1 to 10 carbon atoms; when n is 3 and R is a straight-chain or branched alkyl having 1 to 10 carbon atoms, two adjacent alkyl groups form a ring. Ar1 and Ar2 are independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted aryl and cycloalkyl groups having 6 to 30 carbon atoms, and the substituents are selected from aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 6 to 30 carbon atoms, and straight-chain or branched alkyl or cycloalkyl groups having 1 to 10 carbon atoms.

[0086] In some preferred embodiments, the compound represented by formula III is selected from the following group:

[0087] .

[0088] In some preferred embodiments, the deuterated composition of the present application is a luminescent host material with a mass percentage of 95% to 99%, and the compound represented by formula III is a luminescent guest material with a mass percentage of 1% to 5%.

[0089] The present application also provides an organic light-emitting device, comprising a first electrode and a second electrode arranged opposite to each other and an organic layer located between the first electrode and the second electrode, wherein the organic layer comprises the above-mentioned light-emitting layer. As an example, the first electrode is an anode and the second electrode is a cathode. The cathode can be one or more layers. The organic layer can be a single-layer structure or a multi-layer series structure in which two or more organic layers are laminated. The organic layer can include at least one layer of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0090] In some specific embodiments, the structure of the organic light-emitting device can be selected from one of the following:

[0091] (1) An organic electroluminescent device comprises an anode, a hole injection layer, a first hole transport layer, a light-emitting layer, a first electron transport layer, and a cathode stacked in sequence, i.e., anode / hole injection layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode. Each device structure will be expressed in this simplified manner below.

[0092] (2) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode.

[0093] (3) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0094] (4) anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / electron injection layer / cathode.

[0095] (5) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / multilayer cathode.

[0096] (6) anode / hole injection layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode.

[0097] (7) anode / hole injection layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0098] (8) anode / hole injection layer / second hole transport layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode.

[0099] (9) anode / hole injection layer / second hole transport layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0100] (10) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / electron injection layer / cathode.

[0101] (11) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / cathode.

[0102] (12) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0103] (13) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / hole blocking layer / electron transport layer / cathode.

[0104] (14) Anode / hole injection layer / hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0105] The light emission direction of the organic light emitting device can be emitted from the anode side or the cathode side. When emitted from the cathode side, the difference from structures (1) to (14) is that an additional covering layer needs to be added on the cathode side.

[0106] Some specific functional layers in the organic light-emitting device will be described below.

[0107] Substrate:

[0108] The substrate is generally located below the anode, and the substrate may be made of plastic or glass, and may be rigid or bendable. The substrate is provided with a driving unit, which may drive the corresponding pixel to emit light.

[0109] anode:

[0110] The anode is usually required to have good conductivity, a smooth surface, and be free of cracks. There are also certain requirements for the work function, mainly to be able to match the hole injection layer and exert the hole injection effect.

[0111] When the top emission mode (light emitting from the cathode side) is adopted, the anode adopts a metal compound with a work function of 4.2eV or more, for example, indium tin oxide alloy, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, graphene, etc. The thickness is 10nm~200nm, preferably 10nm~50nm. A reflective electrode is set under the anode (close to the substrate end), and the reflective electrode is generally made of metal or metal alloy, for example, silver metal, copper metal, aluminum metal, gold metal or alloys of these metals and other metals. The reflectivity of the reflective electrode is relatively high, and the reflectivity is required to be more than 90%. The thickness is usually used at a thickness of 100nm~500nm, preferably in the range of 80nm~150nm.

[0112] When the bottom emission mode (light emitting from the substrate side) is adopted, the anode adopts a metal compound with a work function of 4.2eV or more, such as indium tin oxide alloy, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, graphene, etc. The thickness is 10nm~1μm, preferably 50nm~200nm.

[0113] The anode can be produced by forming an electrode material into a thin film by a method such as vapor deposition, sputtering, or coating.

[0114] Hole injection layer:

[0115] In order to make the light-emitting device more efficient, the hole injection layer needs to have good hole injection ability. The thickness of the hole injection layer can be 100 angstroms to 300 angstroms. Preferably, the hole injection layer uses a mixed material of a hole dopant and a hole transport host material, wherein the mass proportion of the hole dopant is 1% to 5%.

[0116] The hole transport host material has a hole mobility greater than or equal to N,N,N',N'-tetraphenylbiphenyl diamine (CAS: 164724-35-0).

[0117] In some embodiments, the hole transport host material is selected from the following compounds:

[0118] ;

[0119] In the above compounds, L1~L4, when present, are independently selected from a single bond or a phenylene group. Ar1~Ar4, when present, are independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and the substituent is selected from an alkyl group having 1 to 10 carbon atoms. Preferably, Ar1~Ar4, when present, are independently selected from phenyl, biphenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, N-phenylcarbazolyl, benzo[B]naphtho[2,3-D]furan, benzo[B]naphtho[1,2-D]furan, benzo[B]naphtho[2,1-D]furan. When R1 and R2 exist separately, they are independently selected from substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and the substituents are selected from alkyl groups having 1 to 10 carbon atoms. R1 and R2 may also be bonded to form a ring.

[0120] In some specific embodiments, the hole transport host material can be selected from the following compounds:

[0121] .

[0122] The hole dopant may be selected from an organic compound or a metal oxide. In some embodiments, the hole dopant is selected from the compounds shown in Formula 1 and Formula 2:

[0123] Formula 1, Formula 2;

[0124] In formula 1, R1~R 15 Each is independently selected from fluorine, trifluoromethyl, cyano, and nitro. In Formula 2, R1 to R2 are each independently selected from fluorine-containing aryl groups.

[0125] In some specific embodiments, the hole dopant is selected from the following compounds:

[0126] .

[0127] First hole transport layer:

[0128] The thickness of the first hole transport layer is generally 3nm~150nm. When there is no second hole transport layer, the thickness of the first hole transport layer is generally 40nm~150nm; when there is a second hole transport layer, the thickness of the first hole transport layer is generally 3nm~40nm. The material selection of the first hole transport layer can refer to the aforementioned hole transport host material, which will not be repeated here.

[0129] Second hole transport layer:

[0130] The thickness of the second hole transport layer is generally 5 nm to 150 nm. In some embodiments, the material of the second hole transport layer can be selected from the following:

[0131] ;

[0132] In the above formula, when R1 to R3 are present, they are independently selected from hydrogen, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

[0133] In some specific embodiments, the material of the second hole transport layer is selected from the following:

[0134]

[0135] Electron blocking layer:

[0136] The electron blocking layer can have both hole transport and electron blocking functions. At the same time, the higher triplet excitation energy level of the electron blocking layer can lock the excitons generated in the light-emitting layer in the light-emitting layer, thereby improving the luminous efficiency of the device.

[0137] Luminous layer:

[0138] The material of the light-emitting layer generally includes a light-emitting main material (host) and a light-emitting guest material (dopant), and the content of the light-emitting main material is greater than that of the light-emitting guest material.

[0139] Hole blocking layer:

[0140] In order to enhance the balance of hole and electron concentrations, a hole blocking layer is inserted to balance the carrier concentration and prevent exciton quenching. Generally, the hole blocking layer is located between the light-emitting layer and the electron transport layer. The hole blocking layer material must meet the conditions of strong stability, good film-forming properties, and a sufficiently high highest molecular occupied orbital.

[0141] First electron transport layer:

[0142] The thickness of the first electron transport layer can generally be 3nm~40nm, 3nm~10nm, 10nm~20nm, 20nm~30nm, 30nm~40nm or 20nm~40nm, etc. When there is no second electron transport layer, the thickness of the first electron transport layer is generally 20nm~40nm, and when there is a second electron transport layer, the thickness of the first electron transport layer is generally 5nm~10nm. The material of the electron transport layer can be a single compound or mixed with other metal compounds, such as 8-hydroxyquinoline lithium.

[0143] In some embodiments, the material of the first electron transport layer is selected from the following s-triazine compounds:

[0144] ;

[0145] Wherein L1 is selected from a single bond, phenyl, biphenyl, and naphthyl; R1 is selected from hydrogen, phenyl, and biphenyl; Ar1 ​​to Ar3 are independently selected from hydrogen, phenyl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl, 9,9'-spirofluorenyl, 9,9'-xanthenespirofluorenyl, and phenanthryl.

[0146] In some specific embodiments, the material of the first electron transport layer is selected from the following compounds:

[0147] .

[0148] Second electron transport layer:

[0149] The thickness of the second electron transport layer is generally 10 nm to 40 nm, and the material of the second electron transport layer may include a mixture of an organic electron transport material and a metal compound, or a mixture of an organic electron transport material and a metal.

[0150] When the organic electron transport material is mixed with a metal compound material, for example, it is mixed with an alkali metal compound, an alkaline earth metal compound, a rare earth metal compound, and more specifically, it is mixed with a metal lithium compound, a metal calcium compound, a metal Mg compound, a metal samarium compound, a metal ytterbium compound, etc., and more specifically, it is mixed with 8-hydroxyquinoline lithium, lithium fluoride, magnesium fluoride, ytterbium fluoride, calcium fluoride, etc. When mixed with a metal compound, the mass ratio of the organic electron transport material can be 20% to 80%, 20% to 40%, 40% to 60%, or 60% to 80%, etc.

[0151] When the organic electron transport material is mixed with a metal, for example, mixed with an alkali metal, an alkaline earth metal, or a rare earth metal, more specifically, mixed with lithium metal, magnesium metal, calcium metal, ytterbium metal, samarium metal, etc., when mixed with a metal, the mass proportion of the organic electron transport material can be 80% to 99%, 80% to 89%, 89% to 99%, 80% to 85%, 85% to 90%, 90% to 95%, or 95% to 99%, etc.

[0152] In some embodiments, the material of the second electron transport layer may be selected from the following compounds:

[0153] ;

[0154] Wherein, when L1~L4 each exist, they are independently selected from a single bond, phenyl, biphenyl, naphthyl, dimethylfluorenyl, 9,9'-spirobifluorenyl; when Ar1~Ar4 each exist, they are independently selected from a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, and a substituted or unsubstituted phosphonyl group.

[0155] In some specific embodiments, the material of the second electron transport layer may be selected from the following compounds:

[0156] .

[0157] Electron injection layer: The material may be selected from alkali metals, alkaline earth metals, rare earth metals or inorganic substances or coordination compounds thereof.

[0158] cathode:

[0159] The cathode requires a material with good electrical conductivity and good surface flatness. In order to improve the electron injection capability, a material with a small work function is usually selected. The cathode material can be a single-layer cathode, or a double-layer or multi-layer cathode, generally a metal or a metal alloy. For a single-layer cathode, silver, copper, aluminum, gold, or alloys of these metals with other metals, such as alloys with rare earth metals, alkali metals, and alkaline earth metals, can be used, which can be listed as magnesium-indium alloy, magnesium-aluminum alloy, aluminum-potassium alloy, aluminum-scandium-potassium alloy, magnesium-silver alloy, silver-ytterbium alloy, silver-samarium alloy, etc. If the cathode uses a double-layer metal, the cathode near the light-emitting layer can use alkali metals, alkaline earth metals, rare earth metals, etc., such as lithium, calcium, magnesium, ytterbium, etc., to increase the electron injection ability, and the cathode layer far from the light-emitting side is mainly used to improve the conductivity. Generally, silver, copper, aluminum, gold or alloys of these metals with other metals, such as alloys with rare earth metals, alkali metals, and alkaline earth metals can be used, which can be listed as magnesium-indium alloy, magnesium-aluminum alloy, aluminum-potassium alloy, aluminum-scandium-potassium alloy, magnesium-silver alloy, silver-ytterbium alloy, silver-samarium alloy, etc. The cathode can also be formed into a thin film by evaporation, sputtering, etc.

[0160] When light comes out from the anode side, the cathode is required to be non-transparent, and a cathode with a thickness greater than 100nm can be evaporated. When light comes out from the cathode side, the cathode is required to be transparent, and the transmittance should be greater than 40% at this time, with a thickness of 10nm~20nm.

[0161] Overlay:

[0162] When light comes out from the cathode side, photons resonate with electrons in the cathode metal to reduce the light extraction efficiency. Adding a covering layer on the side of the cathode away from the light-emitting layer can reduce this effect and effectively improve the light efficiency. When adding a covering layer, directly use a covering layer material with a high refractive index and a low absorption coefficient, for example, a material with a refractive index greater than 1.9 at a wavelength of 460nm and a material with an absorption rate less than 0.01%, preferably a material with a refractive index greater than 2.0 at a wavelength of 460nm and an absorption rate less than 0.01%, and more preferably a material with a refractive index greater than 2.1 at a wavelength of 460nm and an absorption rate less than 0.01%.

[0163] In some embodiments, the material of the covering layer is selected from the following compounds:

[0164] .

[0165] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solution of the present application. Unless otherwise specified, the reagents and raw materials used can be purchased through commercial channels. The experimental methods in the following examples that do not specify specific conditions are usually measured according to national standards. If there is no corresponding national standard, then according to general international standards, conventional methods and conditions, or according to the conditions recommended by the manufacturer, or selected according to the product specifications.

[0166] The raw materials and solvents in the following examples were purchased from Sinopharm, and some commonly used OLED intermediates and other products were purchased from domestic OLED intermediate manufacturers; the NMR data were measured using a Varian 400-MR NMR spectrometer.

[0167] Deuterated composition: BH1

[0168] Example 1

[0169] The synthetic route of the deuterated composition of this embodiment is as follows:

[0170]

[0171] The specific preparation method is as follows:

[0172] 1) Preparation of compound A1:

[0173] In a clean 1000mL three-necked flask, add 9-bromoanthracene (30.3g, 118.1mmol), phenylboronic acid (14.4g, 118.1mmol), K2CO3 (32.5g, 236.2mmol), Pd2(dba)3 (0.54g, 0.59mmol), s-phos (0.45g, 1.2mmol), then add 300mL toluene, 50mL ethanol and 100mL water, replace the system with nitrogen 3 times, heat the reaction to 95℃, reflux and stir for 16 hours, and use TLC to detect the complete reaction. The reaction solution is cooled to room temperature and separated. The organic phase is passed through a silica gel column (200~300 mesh, 50g, TOl), the column liquid is concentrated to dryness, and 200mL of a mixed solvent of n-hexane and toluene with a volume ratio of 10:1 is added. Stir at room temperature for 2 hours, and filter to obtain 24g of white solid with a yield of 80%.

[0174] 2) Preparation of compound A2:

[0175] In a clean 1000mL three-necked flask, add compound A1 (20 grams, 78mmol), perfluorobutylsulfonic acid (4.4 grams, 7.8mmol), and 400mL of deuterated benzene. The system was replaced with nitrogen three times, the reaction temperature was raised to reflux, and the reaction was stirred for 4 days. The reaction solution was cooled to room temperature and deuterated by rotary evaporation. Add 300mL of dichloromethane and 100mL of 10% sodium carbonate solution, stir for half an hour, and separate the liquids. Wash with water again and dry. The organic phase was passed through a silica gel column and rinsed with dichloromethane. The organic phase was spin-dried, pulped with 100mL of ethanol, filtered, and dried to obtain 19.5 grams of product with a yield of 97%.

[0176] 3) Preparation of Compound A4:

[0177] In a 200mL reaction bottle, 15g (56mmol) of the reaction product from the previous step, NBS (10.5g, 59mmol) and DMF (100mL) were added, and the temperature was gradually raised to 50°C, and stirred for 2 hours. TLC showed a reaction. 100mL of water was slowly added to the reaction solution, stirred for 1 hour, filtered, and the filter cake was washed with 20mL of ethanol, and slurried with 30mL of n-hexane for 2 hours. 17g of yellow solid was obtained by suction filtration, with a yield of 87.7%.

[0178] In a clean 500mL three-necked flask, add the product of the previous step (15g, 43mmol), 9-phenanthrene boronic acid (9.5g, 43mmol), K2CO3 (11.8g, 86mmol), Pd2(dba)3 (0.19g, 0.21mmol), s-phos (0.17g, 0.42mmol), and then add 200mL toluene, 50mL ethanol, and 50mL water. The system is replaced with nitrogen three times, and the reaction temperature is raised to 95°C, and the reaction is stirred under reflux for 10 hours. TLC detection shows that the reaction is complete. The reaction solution is cooled to room temperature and separated. The organic phase is passed through a silica gel column (200~300 mesh, 30g, TOl), the column liquid is concentrated to dryness, 200mL of n-hexane and toluene with a volume ratio of 10:2 is added, and stirred at room temperature for 4 hours. 14g of yellow-white solid compound A4 is obtained by suction filtration, with a yield of 73.6%.

[0179] 4) Preparation of deuterated composition BH1:

[0180] In a clean 1000mL three-necked flask, add compound A4 (12 g, 27.1 mmol), perfluorobutylsulfonic acid (1.5 g, 2.7 mmol), and 500 mL of deuterated benzene. The system was replaced with nitrogen three times, the reaction temperature was raised to reflux, and the reaction was stirred for 6 days. The reaction solution was cooled to room temperature and deuterated by rotary evaporation. Add 500 mL of dichloromethane and 300 mL of 10% sodium carbonate solution, stir for half an hour, and separate the liquids. Wash with water again and dry. The organic phase was passed through a silica gel column and rinsed with dichloromethane. The organic phase was spin-dried, pulped with 500 mL of ethanol, filtered, and dried to obtain 10.5 g of product with a yield of 86%.

[0181] The product was purified by vacuum sublimation with a vacuum degree of 3×10 -5 Pa, sublimation temperature is 245℃.

[0182] HNMR test: Weigh 65.2 mg of trimethoxybenzene and dissolve it in 1487.48 mg of DMSO-D6 as a standard sample for later use. Mix 16.9 mg of the test sample and 18.91 mg of the standard sample and dissolve them in DMSO-D6 for testing. The NMR spectrum is as follows: Figure 1 shown.

[0183] According to NMR analysis, the peaks at 9.06ppm, 8.09ppm, 8.01ppm, 7.76ppm, 7.73ppm, 7.68ppm, 7.46ppm, 7.42ppm, and 7.32ppm are attributed to hydrogen on the phenanthryl group, and the remaining displacement peaks are attributed to hydrogen on the anthracene group and the phenyl group. The hydrogen integral of the phenanthryl group is 2.37, and the hydrogen integral of the anthracene group and the phenyl group is 0.5. According to calculations, the average deuteration rate of deuterated hydrogen on the anthracene group and the phenyl group is 99.5%, and the average deuteration rate of deuterated hydrogen on the phenanthryl group is 96.5%.

[0184] The specific calculation method is as follows:

[0185] First, the molar mass of the standard sample in the test sample is calculated based on the weight of the standard sample, the dilution multiple and the molecular weight of the standard sample: the molar mass of mesitylene=18.91×(65.2÷168.2÷1487.48)=0.004928mmol. Then the molar mass of the test sample is calculated as: 16.9÷452=0.037mmol.

[0186] There are 9 hydrogen atoms in the standard sample, and the number of hydrogen atoms in the non-deuterated phenyl and anthracene groups of the test sample is 13, and the number of hydrogen atoms in the non-deuterated phenanthrene is 9. When the hydrogen integral of the standard sample is 9, the hydrogen integral of the non-deuterated phenanthrene group is: 0.037÷0.004928×9=68.28, and the hydrogen integral of the non-deuterated anthracene and phenyl groups is 98.6. According to the actual test of nuclear magnetic resonance hydrogen integral, the hydrogen integral of the methyl group of the standard sample is 9, the hydrogen integral of the phenanthrene group is 2.37, and the hydrogen integral of the anthracene and phenyl groups is 0.5.

[0187] The average deuteration degree of phenanthryl = 1-(2.37÷68.28)×100%=96.5%, the average deuteration degree of anthracenyl and phenyl = 1-(0.5÷218.29)×100%=99.5%.

[0188] Comparative Example 1

[0189] The synthetic route of the deuterated composition of this comparative example is as follows:

[0190]

[0191] The specific preparation method is as follows:

[0192] The steps are basically the same as those in Example 1, except that the first deuteration reaction is not performed on Compound A1, but two deuteration reactions are performed on Compound A4-1, and the conditions of the two deuteration reactions are the same as those of the second deuteration reaction in Example 1. The yields of the two deuteration reactions are 85% and 84%, respectively.

[0193] HNMR test: Weigh 15.76 mg of 1,4-dioxane and dissolve it in 1386.2 mg of deuterated DMSO as a standard sample for later use. Mix 15.1 mg of the test sample and 16.8 mg of the standard sample and dissolve them in deuterated DMSO for testing. The NMR spectrum is as follows: Figure 2 shown.

[0194] like Figure 2As shown, the marked peak is attributed to the hydrogen on the phenanthryl, and the remaining peaks are attributed to the hydrogen on the anthracene and phenyl. Wherein the hydrogen integration of the phenanthryl is 46.53, and the hydrogen integration of the anthracene and phenyl is 73.23. According to calculations, the average deuterated rate of the deuterated hydrogen of the anthracene and phenyl is 97.08%, and the average deuterated rate of the deuterated hydrogen of the phenanthryl is 97.31%. The calculation method is the same as in Example 1.

[0195] Comparative Example 2

[0196] The synthetic route of the deuterated composition of this comparative example is as follows:

[0197]

[0198] The NMR test method can refer to Comparative Example 1, and the NMR spectrum is as follows Figure 3 As shown. Directly compared with the hydrogen internal standard of phenanthrene, the phenanthrene group is not deuterated, and the hydrogen integral is 117.54. The theoretical integral of anthracene and phenyl groups when they are not deuterated is 117.54×13 / 9=169.78, and the actual hydrogen integral of anthracene and phenyl groups is 5.33. The average deuteration rate of deuterated hydrogen of anthracene and phenyl groups is calculated to be 1-(5.33 / 169.78)×100%=96.86%.

[0199] Comparative Example 3

[0200] The deuterated composition prepared in this comparative example is the compound A4 in Example 1, which is different from Comparative Example 2 only in that the first deuterated reaction is repeated twice.

[0201] The NMR test method can refer to Comparative Example 1, and the NMR spectrum is as follows Figure 4 As shown. Directly compared with the hydrogen internal standard of phenanthrene, the phenanthrene group is not deuterated, the hydrogen integral is 88.36, the theoretical integral of anthracene and phenyl groups is 88.36×13 / 9=127.63 when they are not deuterated, and the hydrogen integral of anthracene and phenyl groups is 1.32. The average deuteration rate of deuterated hydrogen of anthracene and phenyl groups is calculated to be 1-(1.32 / 127.63)×100%=98.97%.

[0202] Deuterated composition: BH5

[0203] Example 2

[0204] The synthetic route of the deuterated composition of this embodiment is as follows:

[0205]

[0206] The preparation method can refer to Example 1:

[0207] 1) First coupling reaction: 1-naphthaleneboric acid was used to replace the phenylboric acid in Example 1, and other conditions and molar equivalents were the same, with a yield of 81%.

[0208] 2) First deuteration reaction: The conditions were the same as those in Example 1, with a yield of 94%.

[0209] 3) Bromination reaction: The conditions were the same as those in Example 1, and the yield was 92%.

[0210] 4) Second coupling reaction: 2-phenanthrene boronic acid was used instead of 9-phenanthrene boronic acid in Example 1, with a yield of 81%.

[0211] 5) Second deuteration reaction: The conditions were the same as those in Example 1, with a yield of 86%.

[0212] HNMR test: Weigh 45.5 mg of trimethoxybenzene and dissolve it in 1321.5 mg of deuterated chloroform as a standard sample for later use. Mix 27.36 mg of the test sample and 13.16 mg of the standard sample and dissolve them in deuterated chloroform for testing. The NMR spectrum is as follows: Figure 5 As shown. The hydrogen integral of the phenanthryl group is 5.53, and the hydrogen integral of the anthracenyl group and the naphthyl group is 4.94. According to calculations, the average deuteration rate of deuterated hydrogen of the anthracenyl group and the naphthyl group is 98.36%, and the average deuteration rate of deuterated hydrogen of the phenanthryl group is 96.95%. The calculation method is the same as in Example 1.

[0213] Comparative Example 4

[0214] The synthetic route of the deuterated composition of this comparative example is as follows:

[0215]

[0216] The specific preparation method is as follows:

[0217] The steps are basically the same as those in Example 2, except that the first deuteration reaction is not performed on Compound A1, but two deuteration reactions are performed on Compound A4-1, and the conditions of the two deuteration reactions are the same as those of the second deuteration reaction in Example 2. The yields of the two deuteration reactions are 83% and 81%, respectively.

[0218] According to NMR testing and calculation, the average deuteration rate of deuterated hydrogen in anthracene and naphthyl groups is 97.1%, and the average deuteration rate of deuterated hydrogen in phenanthryl groups is 96.5%.

[0219] Deuterated composition: BH6

[0220] Example 3

[0221] The difference from the preparation method of Example 2 is that compound A3 is Replace with .

[0222] HNMR test: Weigh 26.1 mg of trimethoxybenzene and dissolve it in 1320 mg of deuterated chloroform as a standard sample for later use. Mix 25.15 mg of the test sample and 14.26 mg of the standard sample and dissolve them in deuterated chloroform for testing. The NMR spectrum is as follows: Figure 6 As shown. The hydrogen integral of the phenanthryl group is 8.74, and the hydrogen integral of the anthracenyl group and the naphthyl group is 6.57. According to calculations, the average deuteration rate of deuterated hydrogen of the anthracenyl group and the naphthyl group is 98.53%, and the average deuteration rate of deuterated hydrogen of the phenanthryl group is 96.73%. The calculation method is the same as in Example 1.

[0223] Comparative Example 5

[0224] The difference from the preparation method of Comparative Example 4 is that compound A3 is Replace with .

[0225] According to NMR testing and calculation, the average deuteration rate of deuterated hydrogen in anthracene and naphthyl groups is 96.8%, and the average deuteration rate of deuterated hydrogen in phenanthryl groups is 96.2%.

[0226] Organic light-emitting devices

[0227] Example 4

[0228] This embodiment provides an organic light-emitting device, and the preparation method thereof comprises the following steps:

[0229] (1) A mixed material of Compound 1 and Compound 2 was evaporated on the surface of the reflective anode as a hole injection layer, with a mixing ratio of 1:99 (mass ratio) and a thickness of 10 nm.

[0230] (2) Compound 2 was evaporated on the surface of the hole injection layer to obtain a first hole transport layer with a thickness of 100 nm.

[0231] (3) Compound 3 was evaporated on the surface of the first hole transport layer to obtain a second hole transport layer with a thickness of 5 nm.

[0232] (4) The light-emitting host material compound 4 and the light-emitting guest material compound 5 were co-evaporated at a mass ratio of 99:1 to form an organic light-emitting layer with a thickness of 25 nm on the surface of the second hole transport layer.

[0233] (5) Compound 6 was evaporated on the surface of the organic light-emitting layer to form a hole blocking layer with a thickness of 5 nm, and then compound 7 and LiQ with a mixing ratio of 4:6 (mass ratio) were evaporated to form an electron transport layer with a thickness of 30 nm.

[0234] (6) Metal ytterbium (Yb) is evaporated on the surface of the electron transport layer to form a 5 nm electron injection layer, and magnesium (Mg) and silver (Ag) are mixed and deposited on the surface of the electron injection layer at an evaporation rate of 1:9 to form a second electrode with a thickness of 14 nm as a cathode.

[0235] (7) Compound 8 was evaporated on the cathode surface to form a covering layer with a thickness of 60 nm.

[0236] The structural formulas of the compounds involved in the above preparation process are shown in Table 1.

[0237] Table 1 Structural formula of compounds

[0238]

[0239] Comparative Example 6

[0240] The only difference from Example 4 is that Compound 4 is replaced by the deuterated composition prepared in Comparative Example 1.

[0241] Comparative Example 7

[0242] The only difference from Example 4 is that Compound 4 is replaced by the deuterated composition prepared in Comparative Example 2.

[0243] Comparative Example 8

[0244] The only difference from Example 4 is that Compound 4 is replaced by the deuterated composition prepared in Comparative Example 3.

[0245] Example 5

[0246] The only difference from Example 4 is that Compound 4 is replaced by the deuterated composition prepared in Example 2.

[0247] Comparative Example 9

[0248] The only difference from Example 4 is that Compound 4 is replaced by the deuterated composition prepared in Comparative Example 4.

[0249] Example 6

[0250] The only difference from Example 4 is that Compound 4 is replaced by the deuterated composition prepared in Example 3.

[0251] Comparative Example 10

[0252] The only difference from Example 4 is that Compound 4 is replaced by the deuterated composition prepared in Comparative Example 5.

[0253] Device life test

[0254] The organic light-emitting devices prepared in Examples 4 to 6 and Comparative Examples 6 to 10 were tested using a Foster lifetime measurement system equipped with a power supply and a photodiode as a detection unit. The test conditions were a constant current of 50 mA / cm 2 , the device life under dark conditions is obtained, and the test results are shown in Table 2. LT95 refers to the time (hours) required for the brightness to decay from the initial brightness to 95%. The longer the device life, the more durable the device.

[0255] Table 2 Life test results

[0256]

[0257] As can be seen from Table 2, the present application can obtain a deuterated composition in which the average deuteration rate of anthracene and phenyl / naphthyl exceeds 98% and the average deuteration rate of phenanthryl is less than 98%. When the deuterated composition is used to prepare an organic light-emitting device, the device life can be significantly improved.

[0258] At the same time, the preparation method of the present application can conveniently prepare the deuterated composition of the present application, greatly reducing the deuterated cost, and is particularly suitable for industrial production, as described in detail as follows:

[0259] In Example 1, although both Example 1 and Comparative Example 1 can achieve a high level of deuteration, because the solubility of the intermediate is much greater than that of the final product, the first deuteration using the deuteration method of the present application scheme can save deuteration reagents and has low cost. For example, the volume weight ratio of deuterated benzene used in the first deuteration in Example 1 to the raw material to be deuterated is 20:1 (mL / g) (see the preparation of compound A2 in Example 1), and the volume weight ratio of deuterated benzene in the second deuteration to the raw material to be deuterated is 41.6:1 (mL / g). Compared with the final product being deuterated twice (Example 2), the amount of deuterated benzene can be saved, which is more economical.

[0260] Similarly, the products of Example 2 and Example 3 also have poor solubility, while the intermediates have good solubility, and deuterated intermediates can save deuterated reagents.

[0261] The above description of the embodiments is to facilitate those of ordinary skill in the art to understand and apply the present application. It is obvious that those familiar with the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without having to pay creative labor. Therefore, the present application is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art based on the contents disclosed in the present application without departing from the scope and spirit of the present application are within the scope of the present application.

Claims

1. A deuterated composition, characterized in that: Including different deuterated compounds of the compound shown in formula I: ； In formula I, Ar1 is selected from phenyl or naphthyl; In different deuterated products of the same compound, the average deuteration rate of deuterated hydrogen of Ar1 and anthracene group is greater than 98%, and the average deuteration rate of deuterated hydrogen of phenanthryl group is 96% to 98%.

2. The deuterated composition according to claim 1, characterized in that The different deuterated substances of the compound represented by formula I are selected from the following group: ； in: D(n) represents that n deuteriums replace the deuterated hydrogen of the anthracene group, and n≤8; D(m) means that m deuterium groups replace the deuterated hydrogen of the phenanthryl group, and m≤9; When D(q1) appears, it means that q1 deuteriums replace the deuterated hydrogen of phenyl, and q1≤5; When D(q2) appears, it means that q2 deuteriums replace the deuterated hydrogen of the naphthyl group, and q2≤7.

3. The deuterated composition according to claim 1, characterized in that The average deuteration rate of the anthracene group is greater than the average deuteration rate of the phenanthryl group, and the difference is p, and the value of p is 1% to 4%.

4. A deuterated composition, characterized in that: The deuterated composition is prepared by subjecting compound A1 to a first deuteration reaction to obtain compound A2, then subjecting compound A2 to a reaction with compound A3 to obtain compound A4, and then subjecting compound A4 to a second deuteration reaction; in: The structural formula of the compound A1 is: , Ar1 is selected from phenyl or naphthyl; The structural formula of the compound A2 is: , D(n') represents that n' deuterated hydrogen of anthracene group is substituted with deuterium, and n'≤8, and Ar1' is selected from fully or partially deuterated phenyl group and fully or partially deuterated naphthyl group; The structural formula of the compound A3 is: ; The structural formula of compound A4 is: ; In different deuterated products of the same compound of the deuterated composition, the average deuteration rate of deuterated hydrogen of Ar1 and anthracene group is greater than 98%, and the average deuteration rate of deuterated hydrogen of phenanthrene group is 96% to 98%.

5. The deuterated composition according to claim 4, characterized in that The first deuteration reaction is to place compound A1 in a first deuteration reagent for a deuteration reaction in the presence of a first catalyst, and the conditions of the first deuteration reaction meet at least one of the following conditions: (a) the first catalyst comprises at least one of a protonic acid, a Lewis acid, and a polymer-bonded sulfonic acid; (b) the mass of the first catalyst is 3% to 20% of the mass of the compound A1; (c) the first deuterated reagent comprises: deuterated benzene or deuterated water; (d) The ratio of the volume of the first deuterated reagent to the mass of the compound A1 is (20-50) mL:1 g; (e) The reaction temperature is reflux temperature, and the reaction time is 1 to 5 days.

6. The deuterated composition according to claim 4, characterized in that The second deuteration reaction is to place the compound A4 in a second deuteration reagent for a deuteration reaction in the presence of a second catalyst, and the conditions of the second deuteration reaction meet at least one of the following conditions: (a) the second catalyst comprises at least one of a protonic acid, a Lewis acid, and a polymer-bonded sulfonic acid; (b) the mass of the second catalyst is 3% to 20% of the mass of the compound A4; (c) the second deuterated reagent comprises: deuterated benzene or deuterated water; (d) The ratio of the volume of the second deuterated reagent to the mass of the compound A4 is (40-200) mL:1 g; (e) The reaction temperature is reflux temperature, and the reaction time is 1 to 5 days.

7. A method for preparing a deuterated composition, characterized in that: The following steps are involved: Compound A1 is subjected to a first deuteration reaction to obtain compound A2; wherein the structural formula of compound A1 is: , Ar1 is selected from phenyl or naphthyl; the structural formula of the compound A2 is: , D(n') represents that n' deuterated hydrogen of anthracene group is substituted with deuterium, and n'≤8, and Ar1' is selected from fully or partially deuterated phenyl group and fully or partially deuterated naphthyl group; The compound A2 is reacted with the compound A3 to obtain the compound A4; the structural formula of the compound A3 is: ; The structural formula of compound A4 is: ; The compound A4 is subjected to a second deuteration reaction to obtain a deuterated composition comprising different deuterated substances, and the structural formula of the deuterated substances is shown in Formula II: , D(n) represents that the anthracene group is substituted with n deuteriums, and n'≤n≤8, D(m) represents that the deuterated hydrogen of the phenanthryl group is substituted with m deuteriums, and m≤9, Ar1'' is selected from a fully or partially deuterated phenyl group, a fully or partially deuterated naphthyl group, and the number of deuterated groups of Ar1'' is greater than or equal to the number of deuterated groups of Ar1'; In different deuterated products of the same compound of the deuterated composition, the average deuteration rate of deuterated hydrogen of Ar1 and anthracene group is greater than 98%, and the average deuteration rate of deuterated hydrogen of phenanthrene group is 96% to 98%.

8. The method for preparing a deuterated composition according to claim 7, characterized in that: The method for performing the first deuteration reaction comprises: placing compound A1 in a first deuteration reagent in the presence of a first catalyst to perform a deuteration reaction.

9. The method for preparing a deuterated composition according to claim 8, characterized in that: The conditions of the first deuteration reaction meet at least one of the following conditions: (a) the first catalyst comprises at least one of a protonic acid, a Lewis acid, and a polymer-bonded sulfonic acid; (b) the mass of the first catalyst is 3% to 20% of the mass of the compound A1; (c) the first deuterated reagent comprises: deuterated benzene or deuterated water; (d) The ratio of the volume of the first deuterated reagent to the mass of the compound A1 is (20-50) mL:1 g; (e) The reaction temperature is reflux temperature, and the reaction time is 1 to 5 days.

10. The method for preparing a deuterated composition according to claim 7, characterized in that: The method for reacting the compound A2 with the compound A3 comprises: firstly subjecting the compound A2 to a bromination reaction to obtain a bromide, and then subjecting the bromide to a coupling reaction with the compound A3 to obtain the compound A4.

11. The method for preparing a deuterated composition according to claim 10, characterized in that: The method for reacting the compound A2 with the compound A3 satisfies at least one of the following conditions: (a1) The method for causing the compound A2 to undergo bromination reaction comprises: causing the compound A2 to react with N-bromosuccinimide, using a solvent selected from at least one of N,N-dimethylformamide, toluene, and chlorobenzene, the reaction temperature being 0° C. to 40° C., and the reaction time being 1 hour to 24 hours; (b1) When the coupling reaction is carried out, the catalyst is selected from a platinum compound and a palladium compound, the auxiliary ligand is selected from a phosphine ligand, the reaction system is alkaline, the solvent used is selected from at least one of benzene, toluene, xylene and chlorobenzene, the reaction temperature is from room temperature to the boiling point of the solvent, and the reaction time is 1 hour to 24 hours.

12. The method for preparing a deuterated composition according to claim 7, characterized in that: The method for performing the second deuteration reaction comprises: placing the compound A4 in a second deuteration reagent in the presence of a second catalyst to perform a deuteration reaction.

13. The method for preparing a deuterated composition according to claim 12, characterized in that: The conditions of the second deuteration reaction meet at least one of the following conditions: (a) the second catalyst comprises at least one of a protonic acid, a Lewis acid, and a polymer-bonded sulfonic acid; (b) the mass of the second catalyst is 3% to 20% of the mass of the compound A4; (c) the second deuterated reagent comprises: deuterated benzene or deuterated water; (d) The ratio of the volume of the second deuterated reagent to the mass of the compound A4 is (40-200) mL:1 g; (e) The reaction temperature is reflux temperature, and the reaction time is 1 to 5 days.

14. A light-emitting layer, characterized in that: include: A deuterated composition according to any one of claims 1 to 6 or a deuterated composition prepared by the method for preparing a deuterated composition according to any one of claims 7 to 13.

15. The light-emitting layer according to claim 14, characterized in that The light-emitting layer further comprises a compound as shown in formula III: ； Formula III wherein Q1 and Q2 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzocycloalkyl, and the substituent when substituted is selected from hydrogen, deuterium, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 6 to 30 carbon atoms, a linear or branched alkyl or cycloalkyl group having 1 to 10 carbon atoms; R is selected from deuterium, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 6 to 30 carbon atoms, a linear or branched alkyl group or a cycloalkyl group having 1 to 10 carbon atoms; n is an integer of 0 to 3; when n is 3 and R is a linear or branched alkyl group having 1 to 10 carbon atoms, two adjacent alkyl groups form a ring; Ar1 and Ar2 are independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted aryl and cycloalkyl groups having 6 to 30 carbon atoms, and the substituents are selected from aryl groups having 6 to 30 carbon atoms, heteroaryl groups having 6 to 30 carbon atoms, and straight-chain or branched alkyl or cycloalkyl groups having 1 to 10 carbon atoms.

16. An organic light-emitting device, characterized in that: The method comprises a first electrode and a second electrode which are arranged opposite to each other and an organic layer located between the first electrode and the second electrode, wherein the organic layer comprises the light-emitting layer according to claim 14 or 15.

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