Deuterated compositions, methods of making, uses, and organic electroluminescent devices

Abstract

This application discloses a deuterated composition, its preparation method, uses, and organic electroluminescent devices, relating to the field of organic light-emitting materials. The deuterated composition comprises different deuterated derivatives of the compound shown in Formula 1; in Formula 1, Ar1 is selected from phenyl or naphthyl; among the different deuterated derivatives of the same compound, the average deuteration rate of the anthracene group and the naphthyl group bonded to the anthracene group is greater than 98%, and the average deuteration rate of the Ar1 group and the phenylene group bonded to Ar1 is 95%-97%. When the deuterated composition of this application is used as a light-emitting material in an organic electroluminescent device, it can significantly improve the device lifetime.

Description

Technical Field

[0001] This application relates to the field of organic light-emitting materials technology, specifically to a deuterated composition, its preparation method, uses, and organic electroluminescent devices. Background Technology

[0002] Currently, in organic light-emitting diodes (OLEDs), the lifespan of blue OLEDs is far shorter than that of red and green OLEDs. This shortcoming directly limits the overall lifespan of full-color OLED devices, becoming a key issue restricting their promotion to high-end applications. The light-emitting layer is the core functional layer of an OLED device, and its performance directly affects the device's luminous efficiency, color purity, and lifespan. Among these, the performance of the main light-emitting material is particularly crucial.

[0003] Anthracene compounds are currently the most widely used blue OLED host materials due to their suitable energy level structure and excellent charge carrier transport performance. Studies have shown that deuteration modification of anthracene compounds can improve their chemical stability, thereby extending the lifespan of blue OLED devices. However, the modification effect of existing deuterated anthracene host materials is limited, and the corresponding device lifespan still cannot meet the needs of high-end displays, long-lasting lighting, and other applications, indicating significant room for improvement. Summary of the Invention

[0004] The technical problem addressed by this application is to improve the lifespan of blue light-emitting devices.

[0005] To address the aforementioned technical problems, a first aspect of this application provides a deuterated composition comprising different deuterated derivatives of the compound shown in Formula 1: ; In Formula 1, Ar1 is selected from phenyl or naphthyl; Among the different deuterated derivatives of the same compound, the average deuteration rate of anthracene and naphthyl groups bonded to anthracene is greater than 98%, and the average deuteration rate of Ar1 and phenylene groups bonded to Ar1 is 95%-97%.

[0006] A second aspect of this application provides a deuterated composition, which is prepared by the following steps: subjecting a first intermediate compound to a first deuteration reaction to obtain a second intermediate compound; reacting the second intermediate compound with a halogenated compound to obtain a halogenated product; reacting the halogenated product with a boric acid compound to obtain a third intermediate compound; and subjecting the third intermediate compound to a second deuteration reaction to obtain the deuterated composition. in: The structural formula of the first intermediate compound is: ; The structural formula of the boric acid compound is: Ar1 is selected from phenyl or naphthyl; In different deuterated derivatives of the same compound in the deuterated composition, the average deuteration rate of the anthracene group and the naphthyl group bonded to the anthracene group is greater than 98%, and the average deuteration rate of the Ar1 group and the phenylene group bonded to the Ar1 group is 95%-97%.

[0007] A third aspect of this application provides a method for preparing a deuterated composition, comprising the following steps: The first intermediate compound was subjected to a first deuteration reaction to obtain the second intermediate compound; The second intermediate compound is reacted with the halide to give the halide product; The halogenated product is reacted with a boric acid compound to obtain a third intermediate compound. The third intermediate compound is subjected to a second deuteration reaction to obtain the deuterated composition; in: The structural formula of the first compound is: ; The structural formula of the boric acid compound is: Ar1 is selected from phenyl or naphthyl; In different deuterated derivatives of the same compound in the deuterated composition, the average deuteration rate of the anthracene group and the naphthyl group bonded to the anthracene group is greater than 98%, and the average deuteration rate of the Ar1 group and the phenylene group bonded to the Ar1 group is 95%-97%.

[0008] The fourth aspect of this application provides the use of a deuterated composition prepared by a method described in the first or second aspect, or by a method described in the third aspect, in the preparation of an organic electroluminescent device.

[0009] The fifth aspect of this application provides an organic electroluminescent device, comprising a first electrode, a second electrode, and at least one light-emitting layer located between the first electrode and the second electrode, wherein the light-emitting layer comprises a deuterated composition as described in the first or second aspect, or a deuterated composition prepared by a method for preparing a deuterated composition as described in the third aspect.

[0010] Device testing results show that when different deuterated compounds of the compound shown in Formula 1 are used as luminescent materials for organic electroluminescent devices, the average deuteration rate of deuterable hydrogens of anthracene and naphthyl bonded to anthracene is higher than 98%, and the average deuteration rate of deuterable hydrogens of Ar1 and phenylene bonded to Ar1 is controlled at 95%-97%, the device lifespan can be significantly improved.

[0011] Meanwhile, in preparing the deuterated composition, this application uses a process of deuterating intermediate compounds. Compared with directly deuterating the final product, this can effectively save the amount of deuterating reagents used, thereby reducing the cost of deuteration and making it more suitable for the needs of large-scale industrial production. Attached Figure Description

[0012] The following accompanying drawings describe in detail the exemplary embodiments disclosed in this application. The same reference numerals denote similar structures in several views of the drawings. Those skilled in the art will understand that these embodiments are non-limiting and exemplary, and the drawings are for illustrative purposes only and are not intended to limit the scope of this application. Other embodiments may similarly fulfill the inventive intent of this application. It should be understood that the drawings are not drawn to scale. Wherein: Figure 1 The hydrogen nuclear magnetic resonance spectrum of the deuterated composition prepared in Example 1 of this application; Figure 2 The hydrogen nuclear magnetic resonance spectrum of the deuterated composition prepared in Comparative Example 1 of this application; Figure 3 The hydrogen nuclear magnetic resonance spectrum of the deuterated composition prepared in Comparative Example 2 of this application; Figure 4 The hydrogen nuclear magnetic resonance spectrum of the deuterated composition prepared in Comparative Example 3 of this application; Figure 5 The hydrogen nuclear magnetic resonance spectrum of the deuterated composition prepared in Example 2 of this application; Figure 6 The hydrogen nuclear magnetic resonance spectrum of the deuterated composition prepared in Comparative Example 4 of this application; Figure 7 This is a schematic diagram of the structure of the organic electroluminescent device prepared in Example 3 of this application. Detailed Implementation

[0013] The following description provides specific application scenarios and requirements for this application, intended to enable those skilled in the art to make and use the content of this application. Various partial modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of this application. Therefore, this application is not limited to the embodiments shown, but rather to the widest scope consistent with the claims.

[0014] This application provides a deuterated composition comprising different deuterated derivatives of the compound shown in Formula 1: Ar1 is selected from phenyl or naphthyl.

[0015] The deuterated compounds described in this application are obtained by replacing some or all of the deuteratable hydrogen atoms in the molecular structure of the compound shown in Formula 1 with deuterium. The deuteratable hydrogen atoms refer to hydrogen atoms that can be replaced by deuterium atoms. In the compound shown in Formula 1, the total number of deuteratable hydrogen atoms on the anthracene group is 8; the total number of deuteratable hydrogen atoms on the naphthyl group bonded to the anthracene group is 7; the total number of deuteratable hydrogen atoms when Ar1 is a phenyl group is 5; the total number of deuteratable hydrogen atoms when Ar1 is a naphthyl group is 7; and the total number of deuteratable hydrogen atoms on the phenylene group bonded to Ar1 is 4.

[0016] The “different deuterated derivatives of the compound shown in Formula 1” described in this application are defined based on the molecular structural characteristics of the compound, specifically referring to derivatives formed after the parent skeleton is completely identical to that of the compound shown in Formula 1, and some or all of the deuterated hydrogen atoms in the molecular structure are replaced by deuterated atoms; this statement does not represent or limit the preparation method of the deuterated derivatives.

[0017] Specifically, the different deuterated derivatives of the compound shown in Formula 1 described in this application can be prepared by various routes, including but not limited to: directly deuterating the undeuterated compound shown in Formula 1 as a starting material, or by using the stepwise deuteration process of the intermediate compound described below. That is, the structural definition of "different deuterated derivatives of the compound shown in Formula 1" in this application is intended to cover all products that conform to this structural feature, regardless of their preparation method or process route.

[0018] The differences between the various deuterated compounds are specifically manifested in one or more of the following situations: different compound structures, different deuteration sites, and different numbers of deuterated groups. Among these, differences in compound structure are at least reflected in the different linkage sites between the naphthyl and anthracene groups, the different types of Ar1, and the different linkage sites between Ar1 and phenylene. The following are examples of compounds with different structures as shown in Formula 1: .

[0019] The deuterated composition may contain only one deuterated product of the compounds shown in Formula 1, or it may contain different deuterated products of two or more compounds shown in Formula 1. For example, the deuterated composition may contain only one deuterated product of the compounds shown in Formulas 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, or 1-9; or it may contain a combination of any two, three, four, five, six, seven, eight, or nine different deuterated products of the compounds shown in Formulas 1-1 to 1-9.

[0020] The prevailing view is that the higher the degree of deuteration, the better the lifespan of organic electroluminescent devices. The ideal state is to achieve full deuteration of the compound molecular structure to significantly improve the device lifespan. Therefore, many research directions focus on how to achieve full deuteration of the compound molecular structure.

[0021] However, the inventors of this application unexpectedly discovered that for the compound shown in Formula 1, it is not necessary to perform full deuteration on its molecular structure. Instead, by breaking away from the conventional thinking of full deuteration and selectively controlling the degree of deuteration in different structural regions of the molecule, the lifespan of organic electroluminescent devices can be significantly improved. Specifically, for different deuterated products of the same compound shown in Formula 1, the average deuteration rate of deuteratable hydrogens of the anthracene group and the naphthyl group bonded to the anthracene group is controlled to be greater than 98%, while the average deuteration rate of deuteratable hydrogens of Ar1 and the phenylene group bonded to Ar1 is controlled to be 95%-97%. By achieving this differentiated control of the degree of deuteration in each structural region, a significant improvement in the lifespan of organic electroluminescent devices can be effectively achieved.

[0022] In this application, the average deuteration rate of the deuterated hydrogen refers to the average deuteration rate of the deuterated hydrogen. The average deuteration rate of the deuterated hydrogen will be explained below using a compound shown in Formula 1-1 as an example.

[0023] ; In the above formula, d1-d8 represent the deuterated hydrogen sites of the anthracene group, d9-d15 represent the deuterated hydrogen sites of the naphthyl group bonded to the anthracene group, d16-d19 represent the deuterated hydrogen sites of the phenylene group bonded to Ar1, and d20-d26 represent the deuterated hydrogen sites of Ar1 when Ar1 is a naphthyl group.

[0024] When deuterating the compound shown in Formula 1-1, each deuteratable hydrogen may or may not be deuterated. Therefore, the deuteration rate of each deuteratable hydrogen can be calculated, which can represent the degree of deuteration. Since there are many deuteratable hydrogens, each deuteratable hydrogen corresponds to a deuteration rate, which cannot well reflect the overall degree of deuteration of a certain part. Therefore, this application introduces the average deuteration rate of deuteratable hydrogens to represent the degree of deuteration, and the higher the average deuteration rate of deuteratable hydrogens, the higher the degree of deuteration.

[0025] Theoretically, the deuteration rate of any deuteratizable hydrogen can be obtained in the following way: D di %=N di / N T ×100%, D di % represents the deuteration rate of the deuteratizable hydrogen at the i-th site, N di N represents the number of deuterated compounds in which the deuteratable hydrogen at the i-th site is replaced by deuterium. TThis represents the total number of compounds of this type (e.g., the compounds shown in Formula 1-1). The average deuteration rate of the anthracene group and the deuteratizable hydrogen atom bonded to the anthracene group can be obtained as follows: The average deuteration rate of Ar1 and the deuterable hydrogen atom bonded to Ar1 can be obtained as follows: .

[0026] In actual quantitative analysis, the average deuteration rate of the deuterated hydrogen can be quantitatively calculated through NMR spectroscopy. The specific method is as follows: First, prepare a standard sample solution. Select a standard sample (such as trimethoxybenzene, 1,4-dioxane, etc.), dissolve and dilute it in a suitable deuteration reagent (such as deuterated DMSO, deuterated chloroform, etc.), and shake well. Then, add the test sample to the above standard sample solution, dissolve and shake well, and perform NMR spectroscopy. After the test is completed, calculate the molar amounts of the standard sample and the test sample based on their weighing mass, molecular weight, and dilution ratio. Then, analyze and calculate the average deuteration rate of the deuterated hydrogen using the hydrogen integral signal in the NMR spectrum.

[0027] In some preferred embodiments, the different deuterated derivatives of the compound represented by Formula 1 are selected from one or more of the following formulas: ; Wherein, D(m) represents the m deuterated hydrogen atoms of the naphthyl group bonded to the anthracene group being replaced by deuterium, and m≤7; D(n) represents the n deuterated hydrogen atoms of the anthracene group being replaced by deuterium, and n≤8; D(p) represents the p deuterated hydrogen atoms of the phenylene group bonded to Ar1 being replaced by deuterium, and p≤4; D(q1) represents the q1 deuterated hydrogen atoms of Ar1 being replaced by deuterium when Ar1 is a naphthyl group, and q1≤7; D(q2) represents the q2 deuterated hydrogen atoms of Ar1 being replaced by deuterium when Ar1 is a phenyl group, and q2≤5.

[0028] More preferably, the different deuterated derivatives of the compound shown in Formula 1 are selected from one or more of the following formulas: .

[0029] When preparing the target deuterated composition by directly carrying out a deuteration reaction using the undeuterated compound shown in Formula 1 as a raw material, the poor solubility of the undeuterated compound often leads to insufficient deuteration reaction and low deuteration efficiency. Currently, the industry's conventional approach to improve the deuteration rate is to use a large amount of deuteration reagent and carry out multiple deuteration reactions. However, this method significantly increases the consumption of deuteration reagent, raises the cost of deuteration production, and cannot meet the needs of large-scale industrial production.

[0030] To address the aforementioned technical problems, in some preferred embodiments of this application, the deuterated composition is prepared by deuterating an intermediate compound. Specifically, the steps are as follows: a first deuteration reaction is performed on a first intermediate compound to obtain a second intermediate compound; the second intermediate compound is reacted with a halogenated product to obtain a halogenated product; the halogenated product is reacted with a boric acid compound to obtain a third intermediate compound; and the third intermediate compound is subjected to a second deuteration reaction to obtain the deuterated composition.

[0031] The structural formula of the first intermediate compound is: The structural formula of the boric acid compound is: Ar1 is selected from phenyl or naphthyl.

[0032] In the deuterated compositions prepared by the above-described stepwise deuteration process, different deuterated derivatives of the same compound exhibit specific deuteration rate distribution characteristics. The average deuteration rate of deuterable hydrogens of the anthracene group and the naphthyl group bonded to the anthracene group is greater than 98%, and the average deuteration rate of deuterable hydrogens of Ar1 and the phenylene group bonded to Ar1 is 95%-97%. This application achieves the above-mentioned target deuteration rate and overcomes the shortcomings of conventional processes by abandoning the conventional approach of directly deuterating the poorly soluble Formula 1 compound and instead deuterating the first and third intermediate compounds, which have better solubility, respectively. During the first deuteration reaction of the first intermediate compound, its excellent solubility allows only a small amount of deuterating reagent to achieve an average deuteration rate of over 98% for the anthracene group and the naphthyl group bonded to the anthracene group. Similarly, during the second deuteration reaction of the third intermediate compound, its solubility advantage allows only a small amount of deuterating reagent to control the average deuteration rate of the Ar1 group and the phenylene group bonded to Ar1 group at 95%-97%. Compared to conventional techniques that require large amounts of deuterating reagent and multiple deuteration reactions to achieve the target deuteration rate, the stepwise deuteration strategy of this application significantly reduces the consumption of deuterating reagent, substantially lowers overall production costs, and better meets the practical needs of large-scale industrial production.

[0033] Furthermore, it is a common understanding in the art that the higher the degree of deuteration of a compound, the better the lifetime of the corresponding organic electroluminescent device. Based on this understanding, conventional processes usually employ high-dose deuteration reagents and multiple deuteration processes to strive for a uniformly high level of deuteration rate among the various groups in the compound. However, the inventors of this application unexpectedly discovered through research that when there are reasonable differences in the deuteration rate among the various groups in the compound, it is actually more beneficial to improve the lifetime of organic electroluminescent devices. The stepwise deuteration process of this application can precisely achieve this differentiated deuteration rate distribution. Because the first and third intermediate compounds differ in structural characteristics and solubility, their deuteration reaction efficiencies also differ. Without the need to introduce complex deuteration control methods, the above-mentioned process route optimization design can naturally form a differentiated distribution with an average deuteration rate of over 98% for anthracene-based and naphthyl groups bonded to anthracene-based groups, and an average deuteration rate of 95%-97% for Ar1 and phenylene groups bonded to Ar1. This balances the convenience of the production process with the practical application effect of the device.

[0034] In some preferred embodiments, the first deuteration reaction satisfies at least one of the following conditions: (a) The process is carried out in the presence of a first catalyst, wherein the first catalyst comprises at least one of a protic acid, a Lewis acid, and a polymerically bonded sulfonic acid; (b) The process is carried out in the presence of a first catalyst, wherein the mass of the first catalyst is 3%-20% of the mass of the first intermediate compound; (c) A first deuterated reagent is used, wherein the first deuterated reagent comprises deuterated benzene and / or deuterated water; (d) A first deuterated reagent is used, and the ratio of the volume of the first deuterated reagent to the mass of the first intermediate compound is (15-50) mL:1 g; (e) Use a first deuterated reagent, the reaction temperature is the reflux temperature of the corresponding first deuterated reagent, and the reaction time is 1-5 days.

[0035] In some preferred embodiments, the second deuteration reaction satisfies at least one of the following conditions: a) The process is carried out in the presence of a second catalyst, wherein the second catalyst comprises at least one of a protic acid, a Lewis acid, and a polymerically bonded sulfonic acid; b) The process is carried out in the presence of a second catalyst, wherein the mass of the second catalyst is 3%-20% of the mass of the third intermediate compound; c) A second deuterated reagent is used, wherein the second deuterated reagent comprises deuterated benzene and / or deuterated water; d) A second deuterated reagent is used, and the volume ratio of the second deuterated reagent to the mass ratio of the third intermediate compound is (30-50) mL:1 g; e) Use a second deuterated reagent, and the reaction temperature is the reflux temperature of the corresponding second deuterated reagent, with a reaction time of 1-6 days.

[0036] Based on the above-described stepwise deuteration process for intermediates, this application also provides a method for preparing a deuterated composition, comprising the following steps: S1: The first intermediate compound is subjected to a first deuteration reaction to obtain the second intermediate compound; S2: React the second intermediate compound with the halide to obtain the halide product; S3: React the halogenated product with a boric acid compound to obtain a third intermediate compound; S4: The third intermediate compound is subjected to a second deuteration reaction to obtain the deuterated composition.

[0037] In step S1, the structural formula of the first intermediate compound is as follows: .

[0038] In step S2, the halogenated product may be selected from chlorinated, brominated, or iodinated products. As an example, the halogenated product is N-bromosuccinimide. In the structural formula of the halogenated product, the naphthyl group or its deuterated group is located in the para position of the anthracene group to the halogen atom.

[0039] In step S3, the structural formula of the boric acid compound is: Ar1 is selected from phenyl or naphthyl.

[0040] In different deuterated derivatives of the same compound in the prepared deuterated composition, the average deuteration rate of the anthracene group and the naphthyl group bonded to the anthracene group is greater than 98%, and the average deuteration rate of the Ar1 group and the phenylene group bonded to the Ar1 group is 95%-97%.

[0041] In some preferred embodiments, in step S1, the first deuteration reaction is carried out in the presence of a first catalyst, and the first catalyst includes at least one selected from protic acids, Lewis acids, and polymerically bonded sulfonic acids. As an example, the protic 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.

[0042] In some preferred embodiments, in step S1, the first deuteration reaction is carried out in the presence of a first catalyst, and the mass of the first catalyst is 3%-20% of the mass of the first intermediate compound.

[0043] In some preferred embodiments, in step S1, the first deuteration reaction uses a first deuteration reagent, and the first deuteration reagent includes deuterated benzene and / or deuterated water.

[0044] In some preferred embodiments, in step S1, the first deuteration reaction uses a first deuteration reagent, and the volume ratio (also known as the volume-to-weight ratio) of the first deuteration reagent to the first intermediate compound is (15-50) mL:1 g; preferably (15-20) mL:1 g. Because the first intermediate compound has good solubility, only a small amount of the first deuteration reagent is needed to achieve a high average deuteration rate.

[0045] In some preferred embodiments, in step S1, the first deuteration reaction uses a first deuteration reagent, the reaction temperature is the reflux temperature of the corresponding first deuteration reagent, and the reaction time is 1-5 days.

[0046] In some preferred embodiments, in step S1, the first intermediate compound is prepared by reacting a 9-haloanthracene with 1-naphthoboronic acid.

[0047] In some preferred embodiments, in step S2, the second deuteration reaction is carried out in the presence of a second catalyst, and the second catalyst includes at least one selected from protic acids, Lewis acids, and polymerically bonded sulfonic acids. As an example, the protic 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.

[0048] In some preferred embodiments, in step S2, the second deuteration reaction is carried out in the presence of a second catalyst, and the mass of the second catalyst is 3%-20% of the mass of the third intermediate compound.

[0049] In some preferred embodiments, in step S2, the second deuteration reaction employs a second deuteration reagent, and the second deuteration reagent includes deuterated benzene and / or deuterated water.

[0050] In some preferred embodiments, in step S2, the second deuteration reaction uses a second deuteration reagent, and the volume ratio of the second deuteration reagent to the mass ratio of the second intermediate compound is (30-50) mL:1 g; preferably (30-40) mL:1 g.

[0051] In some preferred embodiments, in step S2, the second deuteration reaction uses a second deuterated reagent, the reaction temperature is the reflux temperature of the corresponding second deuterated reagent, and the reaction time is 1-6 days.

[0052] This application also provides the use of the above-described deuterated composition or the deuterated composition prepared by the above-described method in the preparation of organic electroluminescent devices.

[0053] This application also provides an organic electroluminescent device, including a first electrode, a second electrode, and at least one light-emitting layer located between the first electrode and the second electrode, wherein the light-emitting layer comprises the above-described deuterated composition or a deuterated composition prepared by the above-described method for preparing the deuterated composition.

[0054] In some preferred embodiments, the light-emitting layer further includes a compound as shown in Formula 2: ; Wherein, Q1 and Q2 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzocycloalkyl, and the substituent when substituted is selected from deuterium, C6-C30 aryl, C6-C30 heteroaryl, C1-C10 alkyl or C3-C10 cycloalkyl; R is selected from deuterium, C6-C30 aryl, C6-C30 heteroaryl, C1-C10 alkyl or C3-C10 cycloalkyl; n1 is an integer from 0 to 3; when n1 is 3 and R is a C1-C10 alkyl, the two adjacent alkyl groups form a ring; Ar2 and Ar3 are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted C6-C30 arylcycloalkyl, and the substituent when substituted is selected from C6-C30 aryl, C6-C30 heteroaryl, C1-C10 alkyl or C3-C10 cycloalkyl.

[0055] Unless otherwise specified, "a certain group of Cn-Cm" in this article refers to a certain group having n to m carbon atoms. For example, "an aryl group of C6-C30" refers to an aryl group having 6 to 30 carbon atoms.

[0056] Unless otherwise specified, "aryl" in this document can refer to monocyclic or polycyclic aryl groups; monocyclic aryl groups include, but are not limited to, phenyl and tolyl; polycyclic aryl groups include fused-ring aryl groups, biphenyl-type aryl groups, and polyphenylalanine groups, wherein fused-ring aryl groups include, but are not limited to, naphthyl, anthraceneyl, phenanthryl, and fluorenyl, and biphenyl-type aryl groups include biphenyl; polyphenylalanine groups are structures formed by multiple aromatic rings linked by alkyl groups, such as diphenylmethyl ( ); the “” in the structure of this article "All of these represent connection sites."

[0057] Unless otherwise specified, "heteroaryl" in this document refers to an aryl group containing at least one of B, N, O, P, S, Si, and Se, including but not limited to pyridyl, pyrroloyl, pyrimidinyl, pyridazinyl, furanyl, thiopheneyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, diazolyl, thiadiazolyl, tetrazolyl, pyrazinyl, thiazolyl, triazinyl, tetraazinyl, quinolinyl, isoquinolinyl, indolyl, indoleyl, indoleyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, benzothiazolyl, benzooxazolyl, benzoimidazolyl, benzothiopheneyl, benzofuranyl, dibenzofuranyl, dibenzothiopheneyl, imidazopyridyl, phenanthrolinel, imidazophenanthridyl, naphridinyl, quinazolinyl, quinoxolinyl, etc.

[0058] Unless otherwise specified, "alkyl" in this article may be a straight-chain or branched structure, such as methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl), pentyl (n-pentyl, isopentyl, neopentyl, tert-pentyl), hexyl, heptyl, octyl, nonyl, decyl.

[0059] Unless otherwise specified, "cycloalkyl" in this document refers to a saturated cyclic aliphatic hydrocarbon, which may be a monocycloalkyl or polycycloalkyl; the monocycloalkyl includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, etc.; the polycycloalkyl can be a bridged cycloalkyl, spirocycloalkyl, or a structure formed by multiple monocycloalkyl groups linked by alkyl groups, wherein the bridged cycloalkyl includes, but is not limited to, bicyclic [2.2.1]heptyl ( ), bicyclic [2.2.2] octyl ( ), etc., spirocycloalkyl includes but is not limited to spiro[3,4]octyl, spiro[4,4]nonyl ( )wait.

[0060] In some preferred embodiments, the compound represented by Formula 2 is selected from one or more of the following formulas: .

[0061] In some preferred embodiments, the content of the deuterated composition is 80wt%-99.9wt%, and the content of the compound shown in Formula 2 is 0.1wt%-20wt%.

[0062] In some embodiments, the organic layer may further include at least one functional layer selected from the following: hole injection layer, hole transport layer, electron blocking layer, hole blocking layer, electron transport layer, and electron injection layer. Each functional layer may be a single-layer structure or a multi-layer structure.

[0063] In some specific embodiments, the structure of the organic electroluminescent device may be selected from one of the following: (1) An organic electroluminescent device includes 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, that is, anode / hole injection layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode. The structure of each device will be expressed in this simplified way below.

[0064] (2) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode.

[0065] (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.

[0066] (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.

[0067] (5) Anode / hole injection layer / second hole transport layer / first hole transport layer / light emission layer / first electron transport layer / second electron transport layer / multilayer cathode.

[0068] (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.

[0069] (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.

[0070] (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.

[0071] (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.

[0072] (10) Anode / hole injection layer / hole transport layer / electron blocking layer / light emission layer / electron transport layer / electron injection layer / cathode.

[0073] (11) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / cathode.

[0074] (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.

[0075] (13) Anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / cathode.

[0076] (14) Anode / hole injection layer / hole transport layer / light emission layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0077] The light emission direction of the organic electroluminescent device can be either from the anode side or the cathode side. When emitting from the cathode side, the difference from the structure (1)-(14) is that an additional covering layer needs to be added to the cathode side.

[0078] The following describes some specific functional layers in the organic electroluminescent device.

[0079] Substrate: The substrate is typically located below the anode and can be made of plastic or glass, and can be rigid or flexible. The substrate has driving units that can drive the corresponding pixels to emit light.

[0080] anode: Anodes typically need to meet requirements such as good conductivity, smooth surface, and resistance to cracking. They also have certain requirements for work function, mainly to match the hole injection layer and achieve the hole injection effect.

[0081] When using a top-emitting method (cathode-side light emission), the anode is a metal compound with a work function of 4.2 eV or higher, such as indium tin oxide, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, graphene, etc. The thickness is 10 nm-200 nm. A reflective electrode is placed below the anode (near the substrate end). The reflective electrode is generally made of metal or metal alloy, such as silver, copper, aluminum, gold, or alloys of these metals with other metals. The reflective electrode has high reflectivity, requiring a reflectivity of over 90%, and its thickness is typically between 100 nm and 500 nm, preferably in the range of 80 nm-150 nm.

[0082] When using a bottom-emitting method (substrate-side light emission), the anode is a metal compound with a work function of 4.2 eV or higher, such as indium tin oxide alloy, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, graphene, etc. The thickness is 10 nm to 1 μm, preferably 50 nm to 200 nm. The anode can be fabricated by forming a thin film from the electrode material using methods such as vapor deposition, sputtering, or coating.

[0083] Hole injection layer: The thickness of the hole injection layer can range from 3 nm to 50 nm. The hole injection layer uses a hybrid material of hole dopant and hole transport host material, wherein the mass percentage of hole dopant can be 0.5% to 10%.

[0084] The hole mobility of the hole transport host material is greater than or equal to that of N,N,N',N'-tetraphenylbenzidine diamine (CAS: 164724-35-0). The hole transport host material can be selected from the following group: , , , Wherein: L1-L4, when present individually, are independently selected from single bonds or phenylene. Ar1-Ar4, when present individually, are independently selected from substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C3-C30 heteroaryl groups, and the substituents in the case of substitution are selected from C1-C10 alkyl groups. Preferably, Ar1-Ar4, when present individually, are independently selected from phenyl, biphenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, N-phenylcarbazoyl, benzo[B]naphtho[2,3-D]furanyl, benzo[B]naphtho[1,2-D]furanyl, and benzo[B]naphtho[2,1-D]furanyl. When R1 and R2 are present individually, they are independently selected from substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C3-C30 heteroaryl groups, and the substituents in the case of substitution are selected from C1-C10 alkyl groups. R1 and R2 can also be bonded to form a ring.

[0085] The hole dopant may be selected from organic compounds or metal oxides. For example, the hole dopant may be selected from compounds shown in Formula 3 or Formula 4: Formula 3 Equation 4; In Equation 3, R1-R 15 Each of the R1-R2 is independently selected from fluorine, trifluoromethyl, cyano, and nitro. In Formula 4, each of R1-R2 is independently selected from fluorinated aryl groups.

[0086] As an example, the hole dopant is selected from the following compounds: , .

[0087] Hole transport layer: The thickness of the hole transport layer can range from 3 nm to 150 nm. Material selection can refer to the aforementioned hole transport host materials, and will not be repeated here. The hole transport layer can be a single layer or multiple layers. As an example, the hole transport layer may include a first hole transport layer and / or a second hole transport layer.

[0088] Electron blocking layer: The electron blocking layer can function as both a hole transport layer and an electron blocking layer. Simultaneously, the higher triplet excitation energy level of the electron blocking layer can confine excitons generated in the emissive layer, thereby improving the luminous efficiency of the device. The thickness is selected from 1-40 nm, preferably 5-20 nm.

[0089] Emissive layer: The luminescent layer typically consists of a host material and a dopant material, with the host material comprising a larger proportion than the dopant material. The host material's role is to facilitate the binding of electrons and holes to form electron-hole pairs, i.e., excitons, and to transfer the excitons' energy to the dopant material, thereby emitting light. This requires the host material to possess both considerable electron and hole mobility, as well as a certain triplet energy level.

[0090] To further improve the carrier transport balance of the host material, two or more host materials are used to form the host light-emitting layer through blending or co-evaporation. The guest material determines the emission wavelength and full width at half maximum (FWHM) of the device, i.e., the color of the light. The mass percentage of the guest material in the overall light-emitting layer material can be selected from 1%-3%, 3%-5%, 5%-8%, 8%-10%, 10%-15%, 15%-20%, etc., preferably 1%-3%.

[0091] The thickness of the light-emitting layer can be 10nm-50nm, preferably 15nm-25nm. When a two-layer light-emitting layer structure is used, the first light-emitting layer is in contact with the second light-emitting layer. The thickness of the first light-emitting layer is selected from 5nm-40nm, preferably 10nm-20nm. The thickness of the second light-emitting layer is selected from 1nm-20nm, preferably 3nm-10nm.

[0092] Cavity blocking layer: To enhance the balance between hole and electron concentrations, a hole blocking layer is inserted to balance carrier concentration and prevent exciton quenching. Typically, the hole blocking layer is located between the emissive layer and the electron transport layer. The hole blocking layer material must meet conditions such as high stability, good film-forming properties, and a sufficiently high highest molecular occupied orbital (HOO). The thickness is selected from 1-20 nm, preferably 3-10 nm.

[0093] Electron transport layer: The electron transport layer can be made of a single compound, such as a triazine compound, or it can be mixed with other metals or metal compounds. For example, it can be mixed with lithium compounds, calcium compounds, magnesium compounds, samarium compounds, ytterbium compounds, etc. More specifically, it can be mixed with lithium 8-hydroxyquinoline, lithium fluoride, magnesium fluoride, ytterbium fluoride, calcium fluoride, etc. The electron transport layer can be a single layer or multiple layers. As an example, the electron transport layer may include a first electron transport layer and / or a second electron transport layer. The thickness is selected from 5-50 nm, preferably 15-40 nm.

[0094] Electron injection layer: The electron injection layer can lower the potential barrier for electrons to be injected from the cathode into the organic layer, improving electron injection efficiency and thus optimizing device performance. The material selection for the electron injection layer needs to consider its work function matching with the cathode material. Options include alkali metal compounds (such as LiF), metal oxides (such as Cs₂CO₃), metals (such as Li, Yb), and some small organic molecules or polymers. The thickness is selected from 1-20 nm, preferably 2-10 nm.

[0095] cathode: The cathode requires materials with good electrical conductivity and surface smoothness. To improve electron injection capability, materials with low work function are usually selected. Cathode materials can be single-layer, double-layer, or multi-layer cathodes, and are generally made of metals or metal alloys. Thin films can be formed by methods such as vapor deposition and sputtering.

[0096] Overlay: When light exits from the cathode side, photons resonate with electrons in the cathode metal, reducing the light extraction efficiency. Adding a capping layer on the side of the cathode furthest from the light-emitting layer can reduce this effect and effectively improve the light efficiency. When adding a capping layer, a capping layer material with high refractive index and low absorption coefficient should be used directly. For example, a material with a refractive index greater than 1.9 and an absorption rate less than 0.01% at a wavelength of 460 nm is preferred, a material with a refractive index greater than 2.0 and an absorption rate less than 0.01% at a wavelength of 460 nm is preferred, and a material with a refractive index greater than 2.1 and an absorption rate less than 0.01% at a wavelength of 460 nm is even more preferred.

[0097] The technical solution of this application will be clearly and completely described below with reference to the embodiments of this application. Unless otherwise specified, the reagents and raw materials used can be purchased commercially. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national standards. If there is no corresponding national standard, then general international standards, conventional methods and conditions, or conditions recommended by the manufacturer, or the product instructions shall be followed.

[0098] The raw materials and solvents used in the following examples were purchased from Sinopharm, and some commonly used OLED intermediate compounds were purchased from domestic OLED intermediate manufacturers; NMR data were measured using a Varian 400-MR NMR spectrometer.

[0099] Example 1 The synthetic route of the deuterated composition BH1 in this embodiment is as follows: ; The specific preparation method of the deuterated composition BH1 is as follows: 1) Preparation of compound A1: In a clean 1000 mL three-necked flask, 9-bromoanthracene (30.3 g, 118.1 mmol), 1-naphthenic acid (20.3 g, 118.1 mmol), K₂CO₃ (32.5 g, 236.2 mmol), Pd₂(dba)₃ (0.54 g, 0.59 mmol), and 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (S-Phos, 0.45 g, 1.2 mmol) were added sequentially. Then, 300 mL of toluene, 50 mL of ethanol, and 100 mL of water were added. The system was purged with nitrogen three times. The reaction mixture was heated to 95 °C and refluxed with stirring for 16 hours. The reaction was monitored for completeness using TLC. The reaction solution was cooled to room temperature and then separated. The organic phase was passed through a silica gel column (200-300 mesh, 50 g, toluene). The column chromatography solution was concentrated to dryness, and 200 mL of a mixed solvent of n-hexane and toluene in a volume ratio of 10:1 was added. The mixture was stirred at room temperature for 2 hours and filtered to obtain 32.3 g of white solid, with a yield of 90%.

[0100] 2) Preparation of compound A2: In a clean 1000 mL three-necked flask, compound A1 (23.7 g, 78 mmol), perfluorobutylsulfonic acid (4.4 g, 7.8 mmol), and 400 mL of deuterium benzene were added. The system was purged with nitrogen three times, and the reaction was heated to reflux and stirred for 4 days. The reaction solution was cooled to room temperature, and the deuterium benzene was removed by rotary evaporation. 300 mL of dichloromethane and 100 mL of 10% sodium carbonate solution were added, and the mixture was stirred for half an hour. The mixture was separated. It was washed once with water and dried. The organic phase was passed through a silica gel column and eluted with dichloromethane. The organic phase was evaporated to dryness, slurried with 100 mL of ethanol, filtered, and dried to give 23.1 g of product, with a yield of 92.8%.

[0101] 3) Preparation of compound A4: 17.8 g (56 mmol) of compound A2, 10.5 g (59 mmol) of N-bromosuccinimide (NBS, 10.5 g, 59 mmol), and 100 mL of N,N-dimethylformamide (DMF, 100 mL) were added to a 200 mL reaction flask. The mixture was gradually heated to 50 °C and stirred for 2 hours. The reaction was observed by TLC. 100 mL of water was slowly added dropwise to the reaction mixture, and the mixture was stirred for 1 hour. The mixture was filtered, and the filter cake was washed with 20 mL of ethanol and then slurried with 30 mL of n-hexane for 2 hours. The mixture was then filtered to obtain 20 g of a yellow solid, with a yield of 89.2%.

[0102] In a clean 500 mL three-necked flask, the product from the previous reaction (17.1 g, 43 mmol), compound A3 (4-(2-naphthyl)phenylboronic acid, 10.7 g, 43 mmol), K2CO3 (11.8 g, 86 mmol), Pd2(dba)3 (0.19 g, 0.21 mmol), and S-Phos (0.17 g, 0.42 mmol) were added, followed by 200 mL of toluene, 50 mL of ethanol, and 50 mL of water. The system was purged with nitrogen three times, and the reaction was heated to 95 °C and stirred under reflux for 10 hours. The reaction was confirmed to be complete by TLC. The reaction solution was cooled to room temperature and separated. The organic phase was passed through a silica gel column (200-300 mesh, 30 g, toluene). The column chromatography solution was concentrated to dryness, and 200 mL of n-hexane and toluene (1:1 v / v) was added. The mixture was stirred at room temperature for 4 hours, and the solution was filtered to obtain 20.2 g of a yellowish-white solid compound A4, with a yield of 90.0%.

[0103] 4) Preparation of the deuterated composition BH1: In a clean 1000 mL three-necked flask, compound A4 (14.1 g, 27.1 mmol), perfluorobutylsulfonic acid (1.5 g, 2.7 mmol), and 500 mL of deuterium benzene were added. The system was purged with nitrogen three times, and the reaction was heated to reflux and stirred for 6 days. The reaction solution was cooled to room temperature, and the deuterium benzene was removed by rotary evaporation. 500 mL of dichloromethane and 300 mL of 10% sodium carbonate solution were added, and the mixture was stirred for half an hour. The mixture was separated. It was washed once with water and dried. The organic phase was passed through a silica gel column and eluted with dichloromethane. The organic phase was evaporated to dryness, slurried with 500 mL of ethanol, filtered, and dried to give 13.5 g of product, with a yield of 93.7%.

[0104] The product was purified by vacuum sublimation at a vacuum level of 3 × 10⁻⁶. -5 Pa, sublimation temperature is 280℃.

[0105] 1 ¹H NMR assay: Weigh 57.08 mg of trimethoxybenzene and dissolve it in 1207.8 mg of DMSO-D6 to prepare a standard sample for later use. Mix 5.36 mg of the test sample and 14 mg of the standard sample and dissolve them in DMSO-D6 to complete the test sample preparation and assay.1 HNMR testing yielded the following NMR spectrum: Figure 1 As shown.

[0106] First, calculate the amount of substance of the standard sample based on its weight, dilution factor, and molecular weight: Amount of trimethoxybenzene = 57.08 × 14 ÷ 168.2 ÷ 1207.8 = 0.003934 mmol. Then calculate the amount of substance of the test sample as: 5.36 ÷ 532 = 0.01008 mmol.

[0107] Trimethoxybenzene contains three hydrogen atoms and can be used as an internal standard for quantitative analysis. Based on the target peak integral, the number of internal standard hydrogens, the amount of internal standard substance, and the amount of test sample substance, the average deuteration rate of deuterated hydrogens in the corresponding region can be calculated.

[0108] For the anthracene group and the corresponding naphthyl group bonded to the anthracene group, the theoretical total number of deuterated hydrogens is 15, and the NMR integral is 1.6. Therefore, the average deuteration rate is 100% - 1.6 × 3 × 0.003934 ÷ 0.01008 ÷ 150 × 100% = 98.7%. For Ar1 (naphthyl) and the corresponding phenylene group bonded to Ar1, the theoretical total number of deuterated hydrogens is 11, and the NMR integral is 3.56. Therefore, the average deuteration rate is 100% - 3.56 × 3 × 0.003934 ÷ 0.01008 ÷ 110 × 100% = 96.2%.

[0109] Therefore, the average deuteration rate of anthracene and naphthyl groups bonded to anthracene is 98.7%, and the average deuteration rate of Ar1 and phenylene groups bonded to Ar1 is 96.2%.

[0110] Comparative Example 1 The synthetic route for the deuterated composition in this comparative example is as follows: .

[0111] In this comparative example, the specific preparation method of the deuterated composition BH1 is basically the same as that in Example 1, except that compound A1 is not subjected to the first deuteration treatment, but compound A5 is subjected to two deuteration treatments instead. The two deuteration treatment processes are as follows: In a clean 1000 mL three-necked flask, compound A5 (15.2 g, 30 mmol), perfluorobutylsulfonic acid (1.7 g, 3 mmol), and 540 mL of deuterium benzene were added. The system was purged with nitrogen three times, and the reaction was heated to reflux and stirred for 6 days. The reaction solution was cooled to room temperature, and deuterium benzene was removed by rotary evaporation. 500 mL of dichloromethane and 300 mL of 10% sodium carbonate solution were added, and the mixture was stirred for half an hour to complete the first deuteration treatment. The mixture was separated. It was washed once with water and dried. The organic phase was passed through a silica gel column and eluted with dichloromethane. The organic phase was evaporated to dryness, slurried with 500 mL of ethanol, filtered, and dried to give 14.1 g of product, with a yield of 92.8%. The obtained solid was then added to fluorobutylsulfonic acid (1.7 g, 3 mmol) and 500 mL of deuterium benzene. The system was purged with nitrogen three times, and the reaction was heated to reflux and stirred for 6 days. The reaction solution was cooled to room temperature, and deuterated benzene was removed by rotary evaporation. 500 mL of dichloromethane and 300 mL of 10% sodium carbonate solution were added, and the mixture was stirred for half an hour to complete the second deuteration treatment. The mixture was then separated. It was washed once more with water and dried. The organic phase was passed through a silica gel column and eluted with dichloromethane. The organic phase was evaporated to dryness, slurried with 500 mL of ethanol, filtered, and dried to give product 12.7, with a yield of 90.1%.

[0112] 1 ¹H NMR assay: Weigh 57.08 mg of trimethoxybenzene and dissolve it in 1207.8 mg of DMSO-D6 to prepare a standard sample for later use. Mix 11.2 mg of the test sample and 7.0 mg of the standard sample and dissolve them in DMSO-D6 to complete the test sample preparation and assay. 1 HNMR testing yielded the following NMR spectrum: Figure 2 As shown.

[0113] First, calculate the amount of substance of the standard sample based on its weight, dilution factor, and molecular weight: Amount of mesitylene trimethoxybenzene = 57.08 × 7.0 ÷ 168.2 ÷ 1207.8 = 0.001966 mmol. Then calculate the amount of substance of the test sample: 11.2 ÷ 532 = 0.02105 mmol.

[0114] The theoretical total number of deuterable hydrogens for anthracene and the naphthyl group bonded to anthracene is 15, with an NMR integral of 19.4. The average deuteration rate is calculated as 100% - 19.4 × 3 × 0.001966 ÷ 0.02105 ÷ 150 × 100% = 96.4%. The theoretical total number of deuterable hydrogens for Ar1 (naphthyl) and the phenylene group bonded to Ar1 is 11, with an NMR integral of 14.9. The average deuteration rate is calculated as 100% - 14.9 × 3 × 0.001966 ÷ 0.02105 ÷ 110 × 100% = 96.3%.

[0115] Comparative Example 2 The synthetic route for the deuterated composition in this comparative example is as follows: .

[0116] The specific preparation method is basically the same as that in Example 1, except that: compound A4 is not subjected to a second deuteration treatment, and the reaction conditions for the first deuteration are the same as those for the first deuteration in Example 1.

[0117] 1 ¹H NMR assay: Weigh 57.08 mg of trimethoxybenzene and dissolve it in 1207.8 mg of DMSO-D6 to prepare a standard sample for later use. Mix 12 mg of the test sample and 5.2 mg of the standard sample and dissolve them in DMSO-D6 to complete the test sample preparation and assay. 1 HNMR testing yielded the following NMR spectrum: Figure 3 As shown.

[0118] First, calculate the amount of substance of the standard sample based on its weight, dilution factor, and molecular weight: Amount of trimethoxybenzene = 57.08 × 5.2 ÷ 168.2 ÷ 1207.8 = 0.001461 mmol. Then calculate the amount of substance of the test sample as: 12 ÷ 521 = 0.02303 mmol.

[0119] The theoretical total number of deuterable hydrogens of Ar1 (naphthyl) and the phenylene bonded to Ar1 is 11, with an NMR integral of 54.5; therefore, the average deuteration rate of anthracene and naphthyl is 100% - (0.02303 ÷ 0.001461 × 11 ÷ 3 - 54.5) ÷ (0.02303 ÷ 0.001461 × 15 ÷ 3) = 95.8%.

[0120] Comparative Example 3 The method for preparing the deuterated composition in this comparative example is basically the same as that in Example 1, except that: instead of performing a second deuteration treatment on compound A4, the first deuteration reaction of Example 1 is repeated twice.

[0121] 1 ¹H NMR assay: Weigh 21.0 mg of trimethoxybenzene and dissolve it in 1100.3 mg of DMSO-D6 to prepare a standard sample for later use. Mix 10.5 mg of the test sample and 8.2 mg of the standard sample and dissolve them in DMSO-D6 to complete the test sample preparation and assay. 1 HNMR testing yielded the following NMR spectrum: Figure 4 As shown.

[0122] First, calculate the amount of substance of the standard sample based on its weight, dilution factor, and molecular weight: Amount of mesitylene trimethoxybenzene = 21.0 × 8.2 ÷ 168.2 ÷ 1100.3 = 0.0009307 mmol. Then calculate the amount of substance of the test sample as: 10.5 ÷ 521 = 0.02015 mmol.

[0123] The theoretical total number of deuterable hydrogens of Ar1 (naphthyl) and the phenylene bonded to Ar1 is 11, with an NMR integral of 78.87. Therefore, the average deuteration rate of anthracene and naphthyl is 100% - (0.02015 ÷ 0.0009307 × 11 ÷ 3 - 78.87) ÷ (0.02015 ÷ 0.0009307 × 15 ÷ 3) = 99.5%.

[0124] Example 2 The synthetic route of the deuterated composition BH2 in this embodiment is as follows: .

[0125] The preparation method of the deuterated composition BH2 in this embodiment is basically the same as that in Example 1, except that compound A3 is changed from 4-(2-naphthyl)phenylboronic acid to 4-biphenylboronic acid.

[0126] 1 ¹H NMR assay: Weigh 21.0 mg of trimethoxybenzene and dissolve it in 1100.3 mg of DMSO-D6 to prepare a standard sample for later use. Mix 5.1 mg of the test sample and 22.5 mg of the standard sample and dissolve them in DMSO-D6 to complete the test sample preparation and assay. 1 HNMR testing yielded the following NMR spectrum: Figure 5 As shown.

[0127] First, calculate the amount of substance of the standard sample based on its weight, dilution factor, and molecular weight: Amount of mesitylene trimethoxybenzene = 22.5 × 21 ÷ 168.2 ÷ 1100.3 = 0.002553 mmol. Then calculate the amount of substance of the test sample as: 5.1 ÷ 480 = 0.01062 mmol.

[0128] The NMR integral of the 15 theoretically deuterated hydrogens on the anthracene group and the naphthyl group bonded to the anthracene group is 0.22, and its average deuteration rate is 100% - 0.22 × 3 × 0.002553 ÷ 0.01062 ÷ 15 × 100% = 98.9%; the NMR integral of the 9 theoretically deuterated hydrogens on Ar1 (biphenyl) is 0.45, and its average deuteration rate is 100% - 0.45 × 3 × 0.002553 ÷ 0.01062 ÷ 9 × 100% = 96.3%.

[0129] Comparative Example 4 .

[0130] The difference between the preparation method of the deuterated composition BH2 in this comparative example and that in Example 2 is that the product compound A5 is deuterated twice.

[0131] 1 ¹H NMR assay: Weigh 21.0 mg of trimethoxybenzene and dissolve it in 1100.3 mg of DMSO-D6 to prepare a standard sample for later use. Mix 9.8 mg of the test sample and 12.0 mg of the standard sample and dissolve them in DMSO-D6 to complete the test sample preparation and assay. 1 HNMR testing yielded the following NMR spectrum: Figure 6 As shown.

[0132] First, calculate the amount of substance of the standard sample based on its weight, dilution factor, and molecular weight: Amount of mesitylene trimethoxybenzene = 12.0 × 21 ÷ 168.2 ÷ 1100.3 = 0.001362 mmol. Then calculate the amount of substance of the test sample as: 9.8 ÷ 480 = 0.02042 mmol.

[0133] The NMR integral of the 15 theoretically deuterated hydrogens on the anthracene group and the naphthyl group bonded to the anthracene group is 2.04, and its average deuteration rate is 100% - 2.04 × 3 × 0.001362 ÷ 0.02042 ÷ 15 × 100% = 97.3%; the NMR integral of the 9 theoretically deuterated hydrogens on Ar1 (biphenyl) is 1.75, and its average deuteration rate is 100% - 1.75 × 3 × 0.001362 ÷ 0.02042 ÷ 9 × 100% = 96.1%.

[0134] Example 3 refer to Figure 7 This embodiment provides an organic electroluminescent device, the preparation method of which includes the following steps: (1) A hole injection layer 103 is formed by vapor deposition of a mixture of compound 1 and compound 2 on the surface of the reflective anode 102 on the substrate 101, with a mass ratio of 1:99 and a thickness of 10 nm.

[0135] (2) Compound 2 is deposited on the surface of hole injection layer 103 to form a first hole transport layer 104 with a thickness of 100 nm.

[0136] (3) Compound 3 is vapor-deposited on the surface of the first hole transport layer 104 to form a second hole transport layer 105 with a thickness of 5 nm.

[0137] (4) Compound 4 and compound 5 are co-deposited at a mass ratio of 99:1 to form a light-emitting layer 106 with a thickness of 25 nm on the surface of the second hole transport layer 105.

[0138] (5) A hole blocking layer 107 with a thickness of 5 nm is formed by evaporating compound 6 on the surface of the light-emitting layer 106, and then an electron transport layer 108 with a thickness of 30 nm is formed by evaporating compound 7 and LiQ with a mass ratio of 4:6.

[0139] (6) A 5 nm electron injection layer 109 is formed by evaporating ytterbium (Yb) on the surface of electron transport layer 108. Magnesium (Mg) and silver (Ag) are mixed and deposited on the surface of electron injection layer 109 at a evaporation rate of 1:9 to form a second electrode with a thickness of 14 nm as cathode 110.

[0140] (7) A 60 nm thick capping layer 111 is formed by vapor deposition of compound 8 on the surface of cathode 110.

[0141] The structural formulas of the compounds involved in the above preparation process are shown in Table 1.

[0142] Table 1. Structural Formulas of Compounds

[0143] Comparative Example 5 This comparative example provides an organic electroluminescent device, which differs from Example 3 only in that compound 4 is replaced with the deuterated composition prepared in Comparative Example 1.

[0144] Comparative Example 6 This comparative example provides an organic electroluminescent device, which differs from Example 3 only in that compound 4 is replaced with the deuterated composition prepared in Comparative Example 2.

[0145] Comparative Example 7 This comparative example provides an organic electroluminescent device, which differs from Example 3 only in that compound 4 is replaced with the deuterated composition prepared in Comparative Example 3.

[0146] Example 4 This embodiment provides an organic electroluminescent device, which differs from Example 3 only in that compound 4 is replaced with the deuterated composition BH2 prepared in Example 2.

[0147] Comparative Example 8 This comparative example provides an organic electroluminescent device, which differs from Example 4 only in that compound 4 is replaced with the deuterated composition prepared in Comparative Example 4.

[0148] Device lifetime testing The organic electroluminescent devices prepared in the examples and comparative examples were tested using a Fostar lifetime measurement system equipped with a power supply and a photodiode as detection units. The test conditions were a constant current of 50 mA / cm². 2The device lifetime LT95 under dark conditions was obtained. LT95 refers to the time required for the brightness to decay from the initial brightness to 95%. The longer the device lifetime, the more durable the device. The test results are shown in Table 2. The color coordinates were obtained by testing with a PR650 spectral scanning luminance meter.

[0149] Table 2 Lifetime Test Results

[0150] As shown in Table 2, this application can prepare deuterated compositions with an average deuteration rate of over 98% for anthracene and naphthyl groups and an average deuteration rate of 95%-97% for Ar1 and phenylene groups. When used to prepare organic electroluminescent devices, the device lifespan can be significantly improved, with an LT95 lifespan of over 200 hours, which is far superior to the comparative examples with substandard deuteration rates.

[0151] Meanwhile, the preparation method of this application can easily prepare the target deuterated composition, significantly reducing the cost of deuteration, and is particularly suitable for industrial production. For example, compared with Comparative Example 1, the deuteration rate of Example 1 is higher than that of Comparative Example 1, and the stepwise deuteration scheme of this application has a significant advantage in terms of reagent usage. Specifically, in Example 1, the volume weight ratio of deuterated benzene to the raw material to be deuterated (compound A1) used in the preparation of compounds 1-2 (first deuteration reaction) is 16.88:1 (mL / g); the volume weight ratio of deuterated benzene to the raw material to be deuterated (compound A4) used in the preparation of deuterated composition BH1 (second deuteration reaction) is 35.46:1 (mL / g). In Comparative Example 1, when the final product underwent two deuteration treatments, the corresponding volume-to-weight ratios of deuterated benzene to the product to be deuterated were 35.53:1 (mL / g) and 35.46:1 (mL / g). The amount of deuterated benzene used in the first deuteration treatment of Comparative Example 1 was 2.1 times that used in the first deuteration treatment of Example 1. Therefore, this application significantly reduces the amount of deuterated benzene used, resulting in better economic efficiency. Similarly, the target product in Example 2 also exhibits poor solubility, while its intermediate compound has good solubility. Using the intermediate compound for deuteration can further save on deuteration reagents.

[0152] The above description of the embodiments is intended to enable those skilled in the art to understand and apply this application. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without creative effort. Therefore, this application is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of this application without departing from the scope and spirit of this application are within the scope of this application.

Claims

1. A deuterated composition, characterized in that, Different deuterated derivatives of the compound shown in Formula 1: ； In Formula 1, Ar1 is selected from phenyl or naphthyl; Among the different deuterated derivatives of the same compound, the average deuteration rate of anthracene and naphthyl groups bonded to anthracene is greater than 98%, and the average deuteration rate of Ar1 and phenylene groups bonded to Ar1 is 95%-97%.

2. The deuterated composition according to claim 1, characterized in that, Different deuterated derivatives of the compound shown in Formula 1 are selected from one or more of the following formulas: ； in: D(m) represents the m deuterable hydrogen atoms of the naphthyl group bonded to the anthracene group being replaced by deuterium, and m≤7; D(n) represents the n deuterable hydrogen atoms of anthracene group that are replaced by deuterium, and n≤8; D(p) represents the p deuterable hydrogen atoms of the phenylene bonded to Ar1 being replaced by deuterium, and p≤4; D(q1) represents the q1 deuterable hydrogens in Ar1 that are replaced by deuterium when Ar1 is naphthyl, and q1≤7; D(q2) represents the substitution of q2 deuterated hydrogens in Ar1 by deuterium when Ar1 is phenyl, and q2≤5.

3. A deuterated composition, characterized in that, The deuterated composition is prepared by the following steps: subjecting a first intermediate compound to a first deuteration reaction to obtain a second intermediate compound; reacting the second intermediate compound with a halogenated compound to obtain a halogenated product; reacting the halogenated product with a boric acid compound to obtain a third intermediate compound; and subjecting the third intermediate compound to a second deuteration reaction to obtain the deuterated composition. in: The structural formula of the first intermediate compound is: ; The structural formula of the boric acid compound is: Ar1 is selected from phenyl or naphthyl; In different deuterated derivatives of the same compound in the deuterated composition, the average deuteration rate of the anthracene group and the naphthyl group bonded to the anthracene group is greater than 98%, and the average deuteration rate of the Ar1 group and the phenylene group bonded to the Ar1 group is 95%-97%.

4. The deuterated composition according to claim 3, characterized in that, The first deuteration reaction satisfies at least one of the following conditions: (a) The process is carried out in the presence of a first catalyst, wherein the first catalyst comprises at least one of a protic acid, a Lewis acid, and a polymerically bonded sulfonic acid; (b) The process is carried out in the presence of a first catalyst, wherein the mass of the first catalyst is 3%-20% of the mass of the first intermediate compound; (c) A first deuterated reagent is used, wherein the first deuterated reagent comprises deuterated benzene and / or deuterated water; (d) A first deuterated reagent is used, and the ratio of the volume of the first deuterated reagent to the mass of the first intermediate compound is (15-50) mL:1 g; (e) Use a first deuterated reagent, the reaction temperature is the reflux temperature of the corresponding first deuterated reagent, and the reaction time is 1-5 days.

5. The deuterated composition according to claim 3, characterized in that, The second deuteration reaction satisfies at least one of the following conditions: a) The process is carried out in the presence of a second catalyst, wherein the second catalyst comprises at least one of a protic acid, a Lewis acid, and a polymerically bonded sulfonic acid; b) The process is carried out in the presence of a second catalyst, wherein the mass of the second catalyst is 3%-20% of the mass of the third intermediate compound; c) A second deuterated reagent is used, wherein the second deuterated reagent comprises deuterated benzene and / or deuterated water; d) A second deuterated reagent is used, and the volume ratio of the second deuterated reagent to the mass ratio of the third intermediate compound is (30-50) mL:1 g; e) Use a second deuterated reagent, and the reaction temperature is the reflux temperature of the corresponding second deuterated reagent, with a reaction time of 1-6 days.

6. A method for preparing a deuterated composition, characterized in that, Includes the following steps: The first intermediate compound was subjected to a first deuteration reaction to obtain the second intermediate compound; The second intermediate compound is reacted with the halide to give the halide product; The halogenated product is reacted with a boric acid compound to obtain a third intermediate compound. The third intermediate compound is subjected to a second deuteration reaction to obtain the deuterated composition; in: The structural formula of the first intermediate compound is: ; The structural formula of the boric acid compound is: Ar1 is selected from phenyl or naphthyl; In different deuterated derivatives of the same compound in the deuterated composition, the average deuteration rate of the anthracene group and the naphthyl group bonded to the anthracene group is greater than 98%, and the average deuteration rate of the Ar1 group and the phenylene group bonded to the Ar1 group is 95%-97%.

7. The method for preparing the deuterated composition according to claim 6, characterized in that, The first deuteration reaction satisfies at least one of the following conditions: (a) The process is carried out in the presence of a first catalyst, wherein the first catalyst comprises at least one of a protic acid, a Lewis acid, and a polymerically bonded sulfonic acid; (b) The process is carried out in the presence of a first catalyst, wherein the mass of the first catalyst is 3%-20% of the mass of the first intermediate compound; (c) A first deuterated reagent is used, wherein the first deuterated reagent comprises deuterated benzene and / or deuterated water; (d) A first deuterated reagent is used, and the ratio of the volume of the first deuterated reagent to the mass of the first intermediate compound is (15-50) mL:1 g; (e) Use a first deuterated reagent, the reaction temperature is the reflux temperature of the corresponding first deuterated reagent, and the reaction time is 1-5 days.

8. The method for preparing the deuterated composition according to claim 6, characterized in that, The second deuteration reaction satisfies at least one of the following conditions: a) The process is carried out in the presence of a second catalyst, wherein the second catalyst comprises at least one of a protic acid, a Lewis acid, and a polymerically bonded sulfonic acid; b) The process is carried out in the presence of a second catalyst, wherein the mass of the second catalyst is 3%-20% of the mass of the third intermediate compound; c) A second deuterated reagent is used, wherein the second deuterated reagent comprises deuterated benzene and / or deuterated water; d) A second deuterated reagent is used, and the volume ratio of the second deuterated reagent to the mass ratio of the third intermediate compound is (30-50) mL:1 g; e) Use a second deuterated reagent, and the reaction temperature is the reflux temperature of the corresponding second deuterated reagent, with a reaction time of 1-6 days.

9. Use of a deuterated composition prepared by any one of claims 1 to 5 or any one of claims 6 to 8 in the preparation of an organic electroluminescent device.

10. An organic electroluminescent device, characterized in that, It includes a first electrode, a second electrode, and at least one light-emitting layer located between the first electrode and the second electrode, wherein the light-emitting layer comprises a deuterated composition prepared by the method of any one of claims 1 to 5 or the method of preparing the deuterated composition according to any one of claims 6 to 8.

11. The organic electroluminescent device according to claim 10, characterized in that, The light-emitting layer also includes a compound as shown in Formula 2: ； Wherein, Q1 and Q2 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzocycloalkyl, and the substituent when substituted is selected from deuterium, C6-C30 aryl, C6-C30 heteroaryl, C1-C10 alkyl or C3-C10 cycloalkyl; R is selected from deuterium, C6-C30 aryl, C6-C30 heteroaryl, C1-C10 alkyl or C3-C10 cycloalkyl; n1 is an integer from 0 to 3; when n1 is 3 and R is a C1-C10 alkyl, the two adjacent alkyl groups form a ring; Ar2 and Ar3 are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted C6-C30 arylcycloalkyl, and the substituent when substituted is selected from C6-C30 aryl, C6-C30 heteroaryl, C1-C10 alkyl or C3-C10 cycloalkyl.

12. The organic electroluminescent device according to claim 11, characterized in that, The content of the deuterated composition is 80wt%-99.9wt%, and the content of the compound shown in Formula 2 is 0.1wt%-20wt%.

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