Imidazole fused ring compound and application thereof in organic electroluminescent device

Abstract

The application belongs to the technical field of organic electroluminescent materials, and relates to an imidazole fused ring compound and application thereof in an organic electroluminescent device. The compound has a naphthalene six-membered heterocycle and imidazole as a mother nucleus, and is obtained through group modification. The compound has suitable front orbital energy level and triplet state energy, and can be applied to the organic electroluminescent device as a light-emitting host material and a hole blocking material. After the compound is used in the organic electroluminescent device, the performance of the device, such as light-emitting efficiency and service life, is significantly improved, the light-emitting efficiency is increased by 16-56%, and the LT 95 life of the device is increased by 25-69%.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic electroluminescent materials, and relates to an imidazole fused ring compound and application thereof in an organic electroluminescent device. BACKGROUND

[0002] An organic electroluminescent (OLED) device is a current-driven organic light-emitting device, which has the advantages of high efficiency, low power consumption, high contrast, lightness, flexibility and the like. In the display field, an OLED screen can realize more vivid colors, deeper black performance and a wider viewing angle, and has been widely applied to various electronic products such as smart phones, tablet computers, televisions and the like. In the lighting field, an OLED lamp has the characteristics of bendability, lightness, soft and uniform light, and can be applied to indoor decorative lighting, automotive interior lighting and the like. Under the action of an external electric field, the physical process inside the OLED device is as follows: holes are injected from the anode to the organic layer, and electrons are injected from the cathode to the organic layer. When these injected holes and electrons meet in the light-emitting layer, they will combine to form excitons. When the excitons retransition to the ground state, energy will be released, which is emitted in the form of light, thereby realizing the light-emitting effect.

[0003] The OLED device is a multilayer structure, and the transmission rates of holes and electrons are inconsistent, which will affect the performance of the OLED device. A hole / electron transmission material with excellent mobility can ensure that the electrons and holes in the light-emitting layer are transmitted at a suitable speed, thereby realizing carrier balance. How to realize carrier balance in the light-emitting layer while effectively avoiding energy backflow has become an important means to improve the performance of the device. This puts higher requirements on the performance of functional materials, especially the hole blocking layer adjacent to the light-emitting layer. The hole blocking layer is mainly used to block the holes from the anode, so that the holes are enriched in the light-emitting layer, thereby improving the light-emitting efficiency. At the same time, it also solves the problem of unstable electron flow of the anode caused by high temperature and the like, plays a buffering role, and thereby prolongs the working life of the device, which is very important for improving the performance of the device.

[0004] In order to improve the photoelectric performance such as efficiency, brightness and life of the device, the light-emitting material usually needs to be doped in a suitable host material to reduce the exciton quenching effect and thereby improve the light-emitting performance of the device. Therefore, a high-performance host material and a hole blocking layer material are very important for obtaining a high-quality OLED device. At present, although some host materials and hole blocking layer materials have been developed and applied to OLED devices, they still have certain limitations in performance, which cannot meet the increasing demand for higher quality OLED devices. Therefore, it is very important to develop a high-performance light-emitting layer host material and a hole blocking layer material for obtaining a high-quality OLED device. SUMMARY

[0005] To solve the above technical problems, the application provides an imidazole fused ring compound and application thereof in an organic electroluminescent device.The compound has a naphthalene six-membered heterocycle and imidazole as a mother nucleus, and is obtained by modifying groups, and has suitable front orbital energy level and triplet energy, and is applied to the organic electroluminescent device as a light-emitting host material and a hole blocking material, and plays a key role in improving the light-emitting efficiency, service life and other performances of the device.

[0006] To achieve the technical purpose of the application, in one aspect, the application provides a compound having a structure as shown in formula (I),

[0007] ;

[0008] Y in the formula (I) is selected from CR1R2, O, S, SiR1R2;

[0009] X in the formula (I) is C or N;

[0010] Z1-Z6 in the formula (I) are C or N, and at most two are N;

[0011] L1 in the formula (I) is a single bond or a bridging group;

[0012] Ar1 in the formula (I) is selected from one of a phenyl group, a naphthyl group, a biphenyl group and a pyridine group;

[0013] Ar2 in the formula (I) has a structure as shown in formula (II),

[0014] ;

[0015] T1-T5 in the formula (II) are selected from one of a single bond, C and N, and at most one is a single bond;

[0016] R3 in the formula (II) is selected from hydrogen, deuterium, C1-C10 alkane, C1-C10 alkene, substituted or unsubstituted C6-C30 aryl group and substituted or unsubstituted C3-C30 heteroaryl group;

[0017] m in the formula (II) is any one of 1, 2 and 3;

[0018] * indicates a connecting position;

[0019] Unsubstituted hydrogen atoms on L1, Ar1 and Ar2 can be replaced by deuterium;

[0020] R1 and R2 are selected from a methyl group or a phenyl group; the bridging group is selected from one of a phenyl group, a naphthyl group, a biphenyl group, a pyridine group, a pyrazine group, a pyrimidine group, a pyridazine group and a triazine group; the heteroatom in the heteroaryl group is N or O; when m>1, the plurality of R3 are the same or different from each other.

[0021] The Ar2 is a combination of one or more of phenyl, naphthyl, biphenyl, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, quinoline, quinoxaline, imidazole.

[0022] Further, the Ar2 has a structure as shown in formula (II-1)~(II-3),

[0023]

[0024] .

[0025] Further, when two adjacent T1~T5 are CR3, the adjacent R3 form a ring, the Ar2 has a structure as shown in formula (II-1)~(II-3),

[0026] ;

[0027] Preferably, the Ar2 has a structure as shown in formula (II-1)~(II-3),

[0028]

[0029]

[0030] .

[0031] Further, the formula (I) has a structure as shown in formula (I-1) or (I-2),

[0032] .

[0033] Further, the formula (I-1) and the formula (I-2) have a structure as shown in formula 1~10,

[0034]

[0035]

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[0037] .

[0038] Further, the compound of the present application has a structure as shown in formula (I-1)~(I-2),

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[0138] .

[0139] In another aspect, the present application claims the use of the above-mentioned compound in an organic electroluminescence device.

[0140] Further, the present application claims an organic electroluminescence device comprising an anode layer, a cathode layer and an organic thin film layer between the anode layer and the cathode layer, the organic thin film layer comprising a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, the light emitting layer and / or the hole blocking layer containing the above-mentioned compound.

[0141] Compared with the prior art, the technical scheme provided by the present application has at least the following beneficial effects or advantages:

[0142] (1) The imidazole fused ring compound provided by the present application takes naphthalene polyheterocyclic imidazole as a mother nucleus, the mother nucleus structure has a bipolar characteristic, a nitrogen-containing group having an electron-withdrawing ability is connected to the electron-donating N atom of the imidazole in the mother nucleus structure of the naphthalene polyheterocyclic imidazole, the compound constructed has suitable front-line orbital energy level and triplet energy, when used as a phosphorescent light emitting host material, the energy transfer between the host and the guest is ensured, the device brightness efficiency and the service life are obviously improved; when used as a hole blocking material, the holes from the anode can be effectively blocked, so that the holes are enriched in the light emitting layer, and the light emitting efficiency is improved, and the compound has a good application prospect. For example, in device example 6, the compound 1-75 is used as a light emitting host material, compared with RH1 in the comparative example, the device light emitting efficiency and service life are significantly improved, the light emitting efficiency is increased by 56%, and the device service life is increased by 65%; in example 44, the compound 5-57 is used as a hole blocking material, compared with HB1 in the comparative example, the device light emitting efficiency is increased by 49%, and the device service life is increased by 36%.

[0143] (2) The present application provides an imidazole fused ring compound and its application in an organic electroluminescent device. The compound takes naphthalene hexaheterocyclic imidazole as a mother nucleus, and the compound obtained by modifying the group has suitable front-line orbital energy level and triplet energy, and is applied to an organic electroluminescent device as a light emitting host material and a hole blocking material, and plays a key role in improving the light emitting efficiency, service life and other properties of the device. BRIEF DESCRIPTION OF DRAWINGS

[0144] In order to more clearly illustrate the technical schemes in the embodiments of the present application or the prior art, the drawings needed in the following embodiment or prior art description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0145] Figure 1 It is a schematic diagram of the structure of an organic electroluminescent element. Among them, 1 is a substrate, 2 is an anode layer, 3 is a hole injection layer, 4 is a first hole transport layer, 5 is a second hole transport layer, 6 is a light emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. DETAILED DESCRIPTION

[0146] The technical solutions of the present application are described below in combination with examples, but the present application is not limited to the following examples. The experimental methods and detection methods described in each example are all conventional methods unless otherwise specified; the reagents and materials described are all commercially available unless otherwise specified; and the % in the following examples is mass percentage content unless otherwise specified.

[0147] Example 1

[0148] This example provides the synthesis of an intermediate compound.

[0149] 1. Synthesis of intermediate 1, the synthesis route is shown below, which specifically comprises the following steps:

[0150]

[0151] S1: Under nitrogen protection, a three-necked flask was added with raw material 1 (263 g, 1 mol), raw material 2 (216 g, 1 mol), Pd(PPh3)4 (tetra (triphenylphosphine) palladium, 46.2 g, 0.04 mol), K2CO3 (276.0 g, 2 mol), TBAB (tetrabutylammonium bromide, 25.8 g, 0.08 mol), toluene (2000 mL), ethanol (1000 mL), water (500 mL), and stirred and heated to 78°C, and after reaction for 6 h, cooled to room temperature, washed with water until neutral, and then the organic phase was dried with anhydrous magnesium sulfate, filtered, the filtrate was passed through a silica gel column, and then recrystallized with toluene / petroleum ether mixed solvent (volume ratio 3:1) to obtain intermediate 1-1 (280 g), with a HPLC detection content of 98.1492% and a yield of 79%.

[0152] S2: Under nitrogen protection, a three-necked flask was added with intermediate 1-1 (142 g, 0.4 mol), HBr (800 mL), acetic acid (400 mL), stirred and heated to 100°C for reaction, and then after the raw material was detected by TLC, cooled to room temperature, added with 400 mL of toluene, fully stirred, and then repeatedly washed with water, and then the organic phase was dried with anhydrous magnesium sulfate, passed through a silica gel column, and recrystallized with toluene / ethanol mixed solvent (volume ratio 3:1) to obtain intermediate 1-2 (90 g), with a HPLC detection content of 98.5264% and a yield of 76%.

[0153] S3: Under nitrogen protection, intermediate 1-2 (59 g, 0.2 mol), tetrahydrofuran (200 mL) were added into a three-neck flask, the system was stirred uniformly, then liquid nitrogen was used to cool to -78°C, and then butyllithium (138 mL, 0.22 mol, 1.6 M) was added dropwise, and the reaction was kept for 1 h, then trimethyl borate (41.6 g, 0.4 mol) was added dropwise, and the reaction was kept for 1 h, and then the reaction was continued for 2 h after being naturally increased to room temperature. After the reaction was completed, the reaction was quenched with saturated aqueous ammonium chloride solution, diluted hydrochloric acid was added to adjust pH = 3, 300 mL of toluene was added for extraction, and then water washing was repeated, the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated, and then ethanol was used for extrusion and beating, and then intermediate 1-3 (42 g) was obtained by purification, the HPLC detection content was 99.5921%, and the yield was 80%.

[0154] S4: Under nitrogen protection, intermediate 1-3 (26 g, 0.1 mol), benzamidine hydrochloride (47 g, 0.3 mol), Cu(OAc)2 (copper acetate, 37 g, 0.2 mol), NaOPiv (sodium pivalate, 25 g, 0.2 mol), DMF (300 mL) were added into a three-neck flask, and then heating was conducted to 50°C, and then the reaction was stirred for 26 h, nitrogen protection was removed, heating was conducted to 120°C, and then the reaction was continued for 15 h, and then the reaction was quenched by adding saturated aqueous ammonium hydroxide solution, 300 mL of dichloroethane was added for stirring and water washing was repeated for multiple times, the organic phase was dried over anhydrous magnesium sulfate, and then purification was conducted by silica gel column and recrystallization with toluene / petroleum ether mixed solvent to obtain intermediate 1 (16 g), the HPLC detection content was 98.4456%, and the yield was 49%.

[0155] 2, Synthesis of intermediate 2, the synthesis route is shown below, and the synthesis method refers to the synthesis of intermediate 1, and the difference lies in that in S1, the raw material 2 is replaced by the raw material 3, and intermediate 2 (10 g) is synthesized, the HPLC detection content is 97.9858%, and the yield is 22%.

[0156]

[0157] 3, Synthesis of intermediate 3, the synthesis route is shown below, and the synthesis method specifically includes the following steps:

[0158]

[0159]

[0160] S1: Under nitrogen protection, raw material 4 (269 g, 1 mol), acetic anhydride (102 g, 1 mol), pyridine (1000 mL) were added into a three-neck flask, stirring was conducted and heating was conducted to 100°C, the reaction was kept for 2 h, the raw material was detected by TLC, the reaction was cooled to room temperature after being completed, the solvent was removed by concentration under reduced pressure, recrystallization was conducted with ethanol to obtain intermediate 3-1 (255 g), the HPLC detection content was 99.6218%, and the yield was 82%.

[0161] S2: Refer to S1 in the synthesis of intermediate 1, the difference is that raw material 1 and raw material 2 are replaced by intermediate 3-1 and raw material 5 respectively;

[0162] S3-S5 refer to S2-S4 in the synthesis of intermediate 1, to obtain intermediate 3 (21g), the content of which is 98.9712% detected by HPLC, and the total yield is 28%.

[0163] 4, synthesis of intermediate 4, the synthesis route is shown below, the synthesis method refers to the synthesis of intermediate 1, the difference is that in S1, raw material 1 and raw material 2 are replaced by intermediate 3-1 and raw material 6 respectively, to obtain intermediate 4 (9g), the content of which is 96.9753% detected by HPLC, and the total yield is 18%.

[0164]

[0165] 5, synthesis of intermediate 5, the synthesis route is shown below, which specifically includes the following steps:

[0166]

[0167]

[0168] S1: Refer to S1 in the synthesis of intermediate 1, the difference is that raw material 1 and raw material 2 are replaced by raw material 7 and raw material 8 respectively, to obtain intermediate 5-1 (194g), the content of which is 97.3912% detected by HPLC, and the yield is 70%;

[0169] S2: Under the protection of argon, tetrahydrofuran (600mL), MTPB (bromomethyl triphenylphosphonium salt, 232g, 0.65mol) were added into the reaction bottle in turn, potassium tert-butoxide (72.8g, 0.65mol) was added under stirring at room temperature, the temperature was controlled between 25℃-30℃, intermediate 5-1 (162g, 0.5mol) and tetrahydrofuran (400mL) were added dropwise, and the reaction was stirred for 1h after dropwise addition, water (50mL) was added, and concentrated under negative pressure (45℃, 0.08MPa) until no solvent flowed out, methylcyclohexane (500mL) was added and stirred uniformly, then filtered, and the filtrate was concentrated and slurried with ethanol (500mL), then filtered to obtain intermediate 5-2 (116g), the content of which is 98.3177% detected by HPLC, and the yield is 72%.

[0170] S3: Under argon protection, intermediate 5-2 (97 g, 0.3 mol), BF3-OEt2 (71 g, 0.5 mol), dichloromethane (600 mL) were sequentially added into a reaction bottle, and the reaction was stirred at room temperature for 6 h. The reaction solution was repeatedly washed with water for several times, and the organic phase was concentrated under reduced pressure (50°C, 0.08 MPa) until no solvent flowed out. Methylcyclohexane and ethanol mixed solvent (volume ratio 1:1) was added to precipitate the solid product. After filtration, the product was recrystallized with toluene / petroleum ether mixed solvent to obtain intermediate 5-3 (56 g), with a HPLC detection content of 96.3794%, and a yield of 58%.

[0171] S4-S5 refer to S3-S4 in the synthesis of intermediate 1, to obtain intermediate 5 (17 g), with a HPLC detection content of 98.2941%, and a yield of 47%.

[0172] 6, synthesis of intermediate 6, the synthesis route is shown below, the synthesis method refers to the synthesis of intermediate 5, the difference is that in S1, the raw material 8 is replaced by the raw material 9, and the intermediate 6 (20 g) is synthesized, with a HPLC detection content of 99.0216%, and a yield of 23%.

[0173]

[0174]

[0175] 7, synthesis of intermediate 7, the synthesis route is shown below, which specifically includes the following steps:

[0176]

[0177]

[0178] S1: refer to S1 in the synthesis of intermediate 1, the difference is that the raw material 1 and the raw material 2 are replaced by the raw material 10 and the raw material 8 respectively, to obtain intermediate 7-1 (204 g), with a HPLC detection content of 98.3597%, and a yield of 68%;

[0179] S2: under nitrogen protection, intermediate 7-1 (170 g, 0.5 mol), tetrahydrofuran (300 mL) were added into a three-necked flask, and phenylmagnesium bromide in tetrahydrofuran (1.0 M-THF, 1000 mL) was slowly added at room temperature. After the addition was completed, the reaction was continued at 50°C for 6 h. The reaction solution was cooled to room temperature, and then quenched with an aqueous solution of ammonium chloride. The pH was adjusted to 3 with dilute hydrochloric acid, and then 500 mL of dichloroethane was added. After stirring uniformly, the organic phase was washed with water repeatedly, dried with anhydrous magnesium sulfate, filtered and concentrated. The solid was precipitated with ethanol and purified to obtain intermediate 7-2 (160 g), with a HPLC detection content of 99.2145%, and a yield of 69%.

[0180] S3: Under nitrogen protection, intermediate 7-2 (134 g, 0.3 mol), methanesulfonic acid (58 g, 0.6 mol), toluene (500 mL) were added into a three-necked flask, and the mixture was heated to 108°C for 3 h. After the reaction solution was cooled to room temperature, it was repeatedly washed with water. The organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated, and recrystallized from a mixture of toluene and ethanol to obtain intermediate 7-3 (107 g) with a content of 98.5632% detected by HPLC, and a yield of 80%.

[0181] S4-S5 refer to S3-S4 in the synthesis of intermediate 1, to obtain intermediate 7 (26 g) with a content of 98.3927% detected by HPLC, and a yield of 42%.

[0182] 8, synthesis of intermediate 8, the synthesis route is shown below, the synthesis method refers to the synthesis of intermediate 7, the difference is that in S1, the raw material 8 is replaced by the raw material 9, and the intermediate 8 (21 g) is synthesized, with a content of 99.0695% detected by HPLC, and a total yield of 27%.

[0183]

[0184]

[0185] 9, synthesis of intermediate 9, the synthesis route is shown below, which specifically comprises the following steps:

[0186]

[0187] S1: refer to S1 in the synthesis of intermediate 1, the difference is that raw material 1 and raw material 2 are replaced by raw material 11 and raw material 12 respectively, to obtain intermediate 9-1 (285 g) with a content of 99.8164% detected by HPLC, and a yield of 65%;

[0188] S2: under nitrogen protection, intermediate 9-1 (219 g, 0.5 mol), tetrahydrofuran (300 mL) were added into a three-necked flask, the system was stirred uniformly, and then cooled to-10°C. Butyllithium (626 mL, 1 mol, 1.6 M) was slowly added dropwise, and the reaction was maintained for 1 h. Then, a solution of diphenyldichlorosilane in tetrahydrofuran (126 g, 0.5 mol, 150 mL of tetrahydrofuran) was added dropwise, and the reaction was continued for 1 h. Then, the reaction was naturally raised to room temperature and continued for 2 h. After the reaction was completed, the reaction was quenched with an aqueous solution of ammonium chloride, 500 mL of toluene was added for extraction, and the organic phase was repeatedly washed with water. The organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated, and recrystallized from a mixture of toluene and n-heptane to obtain 173 g of intermediate 5-2 with a content of 99.4712% detected by HPLC, and a yield of 75 %.

[0189] S3~S4 were prepared by referring to S3~S4 in the synthesis of intermediate 1 to obtain intermediate 9 (13 g). The content of intermediate 9 was 99.2890% by HPLC, and the yield was 38%.

[0190] 10. Synthesis of intermediate 10. The synthesis route is shown below. The synthesis method refers to the synthesis of intermediate 9, except that raw material 12 is replaced by raw material 13 in S1 to obtain intermediate 10 (12 g). The HPLC detection content is 98.6627%, and the total yield is 19%.

[0191]

[0192] 11. Synthesis of intermediate 11. The synthesis route is shown below. The synthesis method refers to the synthesis of intermediate 2, except that raw material 1 is replaced by raw material 14 in S1 to obtain intermediate 11 (11 g). The HPLC detection content is 98.9204%, and the total yield is 21%.

[0193]

[0194] Referring to the synthesis of intermediates 1 to 11 above, other intermediates of the same series can be synthesized. The only difference is that the corresponding reactant raw materials are selected according to the different N-doping positions. The structures of some of the synthesized intermediates are shown below.

[0195]

[0196]

[0197]

[0198] Example 2

[0199] This example provides the synthesis of the compound.

[0200] 1. The synthesis of compound 1-1 (Y is O, Z1-Z6 are all C, X is C, L1 is a single bond, Ar1 is phenyl, T1, T3, and T5 in Ar2 are all N, T2 and T4 in Ar2 are all C, R3 is phenyl, and m is 2) is as follows. The synthesis route specifically comprises the following steps:

[0201]

[0202] Under argon, a three-necked flask was charged with intermediate 1 (6.7 g, 0.02 mol), starting material B-1 (6.2 g, 0.02 mol), Pd2(dba)3(three bis(dibenzylideneacetone)dipalladium, 0.9 g, 1 mmol), P(t-Bu)3(tri-tert-butylphosphine, 0.4 g, 2 mmol), sodium tert-butoxide (19.2 g, 0.2 mol), toluene (100 mL), stirred and heated to 110 °C reflux for 3 h. After the reaction was completed, it was cooled to room temperature, washed with water to neutral, the organic phase was dried with anhydrous magnesium sulfate, filtered, the filtrate was concentrated on silica gel column, the column liquid was concentrated, purified by recrystallization with THF and dried, and then sublimed at 305 °C under high vacuum to obtain white crystal compound 1-1 (6.9 g), HPLC = 99.9928%, yield 61%.

[0203] The results of mass spectrometric detection of the compound 1-1 sample were: HR-MS (APCI): m / z 565.1903 [M+H] + ; C 38 H 23 N5O (%) calculated: C, 80.6911; H, 4.0987; N, 12.3816; O, 2.8285; found (%): C, 80.6883; H, 4.1019; N, 12.3735; O, 2.8363.

[0204] 2, Synthesis of compound 1-33 (Y is O, Z1-Z6 are all C, X is N, L1 is a bridging group (triazinyl), Ar1 is phenyl, T1, T3, T5 in Ar2 are all N, T2, T4 in Ar2 are all C, R3 is biphenyl, and m is 2), the synthesis route is shown below, and the synthesis method refers to the synthesis of compound 1-1, except that intermediate 1 and starting material B-1 are replaced by intermediate 1-N and starting material B-2, and then sublimed at 330 °C under high vacuum after recrystallization with THF and drying to obtain white crystal compound 1-33, HPLC = 99.9836%, yield 53%.

[0205]

[0206] The results of mass spectrometric detection of the compound 1-33 sample were: HR-MS (APCI): m / z 718.2481 [M+H] + ; C 49 H 30 N6O (%) calculated: C, 81.8757; H, 4.2069; N, 11.6917; O, 2.2257; found (%): C, 81.8634; H, 4.2159; N, 11.6889; O, 2.2318.

[0207] 3. Synthesis of compound 1-49 (Y is O, Z1-Z6 are all C, X is N, L1 is bridging group (biphenyl), Ar1 is phenyl, T1, T3, T5 in Ar2 are all N, T2, T4 in Ar2 are all C, R3 is phenyl, m is 2), the synthetic route is shown below, the synthetic method is referred to the synthesis of compound 1-1, the difference is that intermediate 1 and raw material B-1 are replaced by intermediate 2 and raw material B-3, white crystal compound 1-49 is obtained, HPLC = 99.9893%, yield 60%.

[0208]

[0209] The result of sample mass spectrum detection is: HR-MS (APCI): m / z 718.2481 [M+H] + ; C 49 H 30 N6O (%) calculated value: C, 81.8757; H, 4.2069; N, 11.6917; O, 2.2257; measured value (%): C, 81.8635; H, 4.2177; N, 11.6894; O, 2.2294.

[0210] 4. Synthesis of compound 1-82 (Y is O, Z2 is N, Z1, Z3-Z6 are all C, X is N, L1 is single bond, Ar1 is phenyl, T1-T5 in Ar2 are all C, R3 is nitrogen-containing C7 heteroaryl (benzimidazole) substituted by phenyl, m is 1), the synthetic route is shown below, the synthetic method is referred to the synthesis of compound 1-1, the difference is that intermediate 1 and raw material B-1 are replaced by intermediate 2-N and raw material B-4, THF is recrystallized, purified and dried, then sublimated at 295°C under high vacuum, white melt compound 1-82 is obtained, HPLC = 99.9811%, yield 54%.

[0211]

[0212] The result of liquid chromatography-mass spectrometry detection of compound 1-82 is: LC-MS: m / z 604.2012 [M+]. The result of sample mass spectrum detection of compound 1-82 is: HR-MS (APCI): m / z 554.1565 [M+H] + ; C 40 H 24 N6O (%) calculated value: C, 79.4545; H, 4.0008; N, 13.8988; O, 2.6459; measured value (%): C, 79.4617; H, 3.9879; N, 13.8991; O, 2.6513.

[0213] 5. Synthesis of compound 2-11 (Y is S, Z1~Z6 are C, X is C, L1 is single bond, Ar1 is phenyl, T1, T3 in Ar2 are N, T2, T4, T5 in Ar2 are C, R3 is phenyl and C2-containing alkenyl (vinyl), and the two adjacent C-vinyls form a ring to obtain phenyl, and m is 3), the synthesis route is shown below, and the synthesis method is referred to the synthesis of compound 1-1, except that intermediate 1 and raw material B-1 are replaced by intermediate 3 and raw material B-5, THF is recrystallized and dried, and then sublimated at 300°C under high vacuum to obtain white crystal compound 2-11, HPLC = 99.9942%, and the yield is 55%.

[0214]

[0215] The results of sample mass spectrometric detection of compound 2-11 are: HR-MS (APCI): m / z 554.1565 [M+H] + ; C 37 H 22 N4S (%) calculated value: C, 80.1208; H, 3.9980; N, 10.1011; S, 5.7800; measured value (%): C, 80.1109; H, 4.0020; N, 10.1120; S, 5.7751.

[0216] 6. Synthesis of compound 2-38 (Y is S, Z1~Z6 are C, X is N, L1 is single bond, Ar1 is phenyl, T1, T3, T5 in Ar2 are N, T2, T4 in Ar2 are C, R3 is biphenyl, and m is 2), the synthesis route is shown below, and the synthesis method is referred to the synthesis of compound 1-1, except that intermediate 1 and raw material B-1 are replaced by intermediate 4 and raw material B-2, THF is recrystallized and dried, and then sublimated at 330°C under high vacuum to obtain white crystal compound 2-38, HPLC = 99.9873%, and the yield is 51%.

[0217]

[0218] The results of sample mass spectrometric detection of compound 2-38 are: HR-MS (APCI): m / z 734.2253 [M+H] + ; C 49 H 30 N6S (%) calculated value: C, 80.0863; H, 4.1150; N, 11.4361; S, 4.3626; measured value (%): C, 80.0762; H, 4.1347; N, 11.4294; S, 4.3597.

[0219] 7. Synthesis of compound 3-27 (Y is CR1R2, R1, R2 are both methyl, Z1~Z6 are all C, X is N, L1 is bridging group (phenyl), Ar1 is phenyl, T1~T5 in Ar2 are all C, R3 is nitrogen-containing C7 heteroaromatic group (benzimidazole substituted by phenyl), m is 1), the synthetic route is shown below, the synthetic method is referred to the synthesis of compound 1-1, the difference is that intermediate 1 and raw material B-1 are replaced by intermediate 5-N and raw material B-4, THF is recrystallized, purified and dried, then sublimed under high vacuum at 285℃, to obtain white compound 3-27 in a molten state, HPLC = 99.9827%, yield 54%.

[0220]

[0221] The result of mass spectrometric detection of compound 3-27 sample is: HR-MS (APCI): m / z 629.2579 [M+H] + ; C 44 H 31 N5 (%) calculated value: C, 83.9174; H, 4.9618; N, 11.1208; measured value (%): C, 83.9096; H, 4.9754; N, 11.1150.

[0222] 8. Synthesis of compound 3-57 (Y is CR1R2, R1, R2 are both methyl, Z1~Z6 are all C, X is N, L1 is single bond, Ar1 is phenyl, T1~T5 in Ar2 are all C, m is 2), the synthetic route is shown below, the synthetic method is referred to the synthesis of compound 1-1, the difference is that intermediate 1 and raw material B-1 are replaced by intermediate 6 and raw material B-6, THF is recrystallized, purified and dried, then sublimed under high vacuum at 300℃, to obtain white compound 3-57 in a crystal state, HPLC = 99.9907%, yield 60%.

[0223]

[0224] The result of mass spectrometric detection of compound 3-57 sample is: HR-MS (APCI): m / z 565.2266 [M+H] + ; C 39 H 27 N5 (%) calculated value: C, 82.8081; H, 4.8112; N, 12.3807; measured value (%): C, 82.8134; H, 4.8174; N, 12.3692.

[0225] 9. Synthesis of compound 4-34 (Y is CR1R2, R1, R2 are both phenyl, Z1~Z6 are all C, X is N, L1 is bridging group (biphenyl), Ar1 is phenyl, T1, T3, T5 in Ar2 are all N, T2, T4 in Ar2 are both C, R3 is phenyl, m is 2), the synthetic route is shown below, the synthetic method is referred to the synthesis of compound 1-1, the difference is that intermediate 1 and raw material B-1 are replaced by intermediate 7-N and raw material B-3, THF is recrystallized, purified and dried, then sublimed under high vacuum at 310℃ to obtain white crystal compound 4-34, HPLC = 99.9917%, yield 50%.

[0226]

[0227] The result of sample mass spectrum detection of compound 4-34 is: HR-MS (APCI): m / z 868.3314 [M+H] + ; C 62 H 40 N6 (%) calculated value: C, 85.6898; H, 4.6396; N, 9.6706; measured value (%): C, 85.6779; H, 4.6409; N, 9.6812.

[0228] 10. Synthesis of compound 4-68 (Y is CR1R2, R1, R2 are both phenyl, Z1~Z6 are all C, X is N, L1 is single bond, Ar1 is phenyl, T1~T5 in Ar2 are all C, R3 is nitrogen-containing C8 heteroaryl (benzopyrimidine) substituted by phenyl, m is 1), the synthetic route is shown below, the synthetic method is referred to the synthesis of compound 1-1, the difference is that intermediate 1 and raw material B-1 are replaced by intermediate 8 and raw material B-7, THF is recrystallized, purified and dried, then sublimed under high vacuum at 315℃ to obtain white crystal compound 4-68, HPLC = 99.9828%, yield 55%.

[0229]

[0230] The result of sample mass spectrum detection of compound 4-68 is: HR-MS (APCI): m / z 765.2892 [M+H] + ; C 55 H 35 N5 (%) calculated value: C, 86.2499; H, 4.6062; N, 9.1439; measured value (%): C, 86.2418; H, 4.6200; N, 9.1382.

[0231] 11. Synthesis of compound 5-16 (Y is SiR1R2, R1, R2 are phenyl, Z1~Z6 are C, X is C, L1 is single bond, Ar1 is phenyl, T1~T5 in Ar2 are C, m is 2), the synthetic route is shown below, the synthetic method is referred to the synthesis of compound 1-1, the difference is that intermediate 1 and raw material B-1 are replaced by intermediate 9 and raw material B-6, THF is recrystallized, purified and dried, then sublimated under high vacuum at 330℃ to obtain white crystal compound 5-16, HPLC = 99.9806%, yield 45%.

[0232]

[0233] The result of mass spectrum detection of compound 5-16 sample is: HR-MS (APCI): m / z 704.2396 [M+H] + ; C 49 H 32 N4Si (%) calculated value: C, 83.4916; H, 4.5759; N, 7.9483; Si, 3.9842; measured value (%): C, 83.4793; H, 4.5947; N, 7.9511; Si, 3.9749.

[0234] 12. Synthesis of compound 5-71 (Y is SiR1R2, R1, R2 are phenyl, Z1~Z6 are C, X is N, L1 is bridging group (phenyl), Ar1 is phenyl, T1, T5 in Ar2 are N, T2~T4 in Ar2 are C, R3 is phenyl and C2-containing alkenyl (vinyl), two adjacent C-vinyls form a ring to obtain phenyl, m is 3), the synthetic route is shown below, the synthetic method is referred to the synthesis of compound 1-1, the difference is that intermediate 1 and raw material B-1 are replaced by intermediate 10 and raw material B-7, THF is recrystallized, purified and dried, then sublimated under high vacuum at 340℃ to obtain white crystal compound 5-71, HPLC = 99.9893%, yield 41%.

[0235]

[0236] The result of mass spectrum detection of compound 5-71 sample is: HR-MS (APCI): m / z 781.2662 [M+H] + ; C 54 H 35 N5Si (%) calculated value: C, 82.9410; H, 4.5115; N, 8.9560; Si, 3.5915; measured value (%): C, 82.9293; H, 4.5234; N, 8.9591; Si, 3.5882.

[0237] 13. Synthesis of compound 5-80 (Y is SiR1R2, R1, R2 are both phenyl, Z2 is N, Z1, Z3~Z6 are all C, X is N, L1 is single bond, Ar1 is phenyl, T1~T5 in Ar2 are all C, R3 is nitrogen-containing C7 heteroaromatic group (benzimidazole) substituted by phenyl, m is 1), the synthesis route is shown below, and the synthesis method is the same as that of compound 1-1, except that intermediate 1 and raw material B-1 are replaced by intermediate 10-N and raw material B-4, THF is recrystallized and dried, and then sublimated at 320℃ under high vacuum to obtain white crystalline compound 5-80, HPLC = 99.9863%, yield 49%.

[0238]

[0239] The results of sample mass spectrometric detection of compound 5-80 are: HR-MS (APCI): m / z 770.2614 [M+H] + ;C 52 H 34 N6Si (%) calculated: C, 81.0111; H, 4.4453; N, 10.9008; Si, 3.6428; found (%): C, 81.0181; H, 4.4442; N, 10.9041; Si, 3.6336.

[0240] According to the synthesis method of the above compound, all other compounds in the application can be synthesized, and the only difference is that different intermediates and modification groups need to be used to replace according to the different products, and the mass of the intermediate is changed according to the different molar amounts.

[0241] Example 3

[0242] In this example, the physicochemical properties of the compound are simulated and calculated.

[0243] The performance parameters (including HOMO energy level and LUMO energy level, triplet energy T1) of the compound synthesized in the application and the existing OLED material RH1, HB1 are determined, and the results are shown in Table 1.

[0244] Table 1 Determination results of performance parameters of compounds and existing materials

[0245]

[0246]

[0247] Note: The highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and the triplet energy T1 are obtained by simulation calculations in Gaussian 09 software using the B3LYP hybrid functional and basis set 6-31g(d).

[0248] As can be seen from Table 1, the compounds prepared in the present invention have suitable triplet energy, HOMO energy level and LUMO energy level, which are beneficial to the transport of carriers and the transfer of energy between host and guest in OLED devices. The compounds of the present invention are suitable for use as light-emitting hosts and hole-blocking materials.

[0249] Example 4

[0250] This embodiment provides an organic electroluminescent device, the structure of which is as follows: Figure 1 As shown, it includes a substrate 1, an anode layer 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9 and a cathode layer 10 stacked in sequence.

[0251] In the comparative example, the substrate 1 is a glass substrate with a thickness of 0.7 mm, the material of the anode layer 2 is indium tin oxide (ITO) with a high work function; the hole injection layer 3 is HAT-CN with a thickness of 5 nm; the material of the first hole transport layer 4 is HT1 with a thickness of 60 nm; the material of the second hole transport layer 5 is HT2 with a thickness of 10 nm; the light-emitting layer 6 uses RD01 as the light-emitting material and RH1 as the main material, with a doping mass ratio of 5% and a thickness of 30 nm; the material of the hole blocking layer 7 is HB1 with a thickness of 10 nm; the material of the electron transport layer 8 is ET1 with a thickness of 35 nm; the material of the electron injection layer 9 is Liq with a thickness of 2 nm; the material of the cathode layer is Al with a thickness of 100 nm.

[0252] The basic material structures used in each functional layer of the device are as follows:

[0253]

[0254] .

[0255] The specific preparation steps of the above-mentioned organic electroluminescent device are as follows:

[0256] 1) Clean the ITO anode on the transparent glass or plastic substrate by ultrasonic cleaning with deionized water, acetone, and ethanol for 20 minutes each, and then perform plasma treatment in an oxygen atmosphere for 5 minutes;

[0257] 2) On the ITO anode layer, a hole injection layer material HAT-CN is evaporated by vacuum evaporation, with a thickness of 5 nm, which serves as a hole injection layer;

[0258] 3) On the hole injection layer, a first hole transport material HT1 is evaporated by vacuum evaporation, with a thickness of 60 nm, which serves as a first hole transport layer;

[0259] 4) On the first hole transport layer HT1, a second hole transport material HT2 is evaporated by vacuum evaporation, with a thickness of 15 nm, which serves as a second hole transport layer;

[0260] 5) On the second hole transport layer, a light-emitting layer is evaporated by co-evaporation, using RH1 as a host material and RD01 as a doping material, with a doping mass ratio of 5%, and a thickness of 30 nm;

[0261] 6) On the light-emitting layer, a hole blocking material HB1 is evaporated by vacuum evaporation, with a thickness of 10 nm, which serves as a hole blocking layer;

[0262] 7) On the hole blocking layer, an electron transport material ET1 is evaporated by vacuum evaporation, with a thickness of 35 nm, which serves as an electron transport layer;

[0263] 8) On the electron transport layer, an electron injection material Liq is evaporated by vacuum evaporation, with a thickness of 2 nm, which serves as an electron injection layer;

[0264] 9) On the electron injection layer, a cathode Al is evaporated by vacuum evaporation, with a thickness of 100 nm, which serves as a cathode conductive electrode, which is the cathode layer.

[0265] The device preparation processes of the device embodiments 1-21 are the same as above, and the difference lies in that the compound (compound 1-1, compound 1-15, compound 1-33, compound 1-49, compound 1-57, compound 1-75, compound 2-3, compound 2-11, compound 2-22, compound 2-29, compound 2-38, compound 2-46, compound 3-1, compound 3-2, compound 3-7, compound 3-13, compound 3-18, compound 4-3, compound 4-9, compound 4-21, compound 5-1) synthesized by the application is used as a red light-emitting layer host material instead of RH1.

[0266] The device preparation processes of device examples 22-46 are the same as above, except that the compound (compound 1-82, compound 2-62, compound 3-27, compound 3-46, compound 3-57, compound 3-75, compound 3-80, compound 4-26, compound 4-34, compound 4-45, compound 4-54, compound 4-57, compound 4-58, compound 4-60, compound 4-68, compound 4-74, compound 5-6, compound 5-13, compound 5-16, compound 5-26, compound 5-37, compound 5-40, compound 5-57, compound 5-71, compound 5-80) synthesized according to the application is used as the hole blocking layer material instead of HB1.

[0267] The organic electroluminescent devices of each group are connected by a known driving circuit with the cathode and the anode, and the voltage-efficiency-current density relationship of the OLED device is tested by a standard method using a Keithley 2400 power supply combined with a PR670 luminometer; the lifetime of the device is tested by a constant current method, and the test condition is a constant current density of 1000 cd / cm 2 , and the time for the luminance to decay to 95% of the initial luminance, i.e. the device LT 95 lifetime. The device structure and test results of the devices prepared according to device examples 1-46 and the comparative examples of the application are shown in Table 2, and the test data are relative values (%).

[0268] Table 2 Performance results of each group of organic electroluminescent devices

[0269]

[0270]

[0271] As can be seen from Table 2, the device performance is improved when the compound prepared according to the application is used as the main body material of the light-emitting layer or the hole blocking layer material in the OLED device, and the luminous efficiency is increased by 16-56%, and the device LT 95The life is increased by 25-69%. Especially, in device example 6, compound 1-75 is used as the light-emitting host material, compared with the comparative example using RH1 as the light-emitting host material, the light-emitting efficiency and the service life of the device are significantly improved, the light-emitting efficiency is increased by 56%, and the service life of the device is increased by 65%; in device example 44, compound 5-57 is used as the hole blocking material, compared with the comparative example using HB1 as the hole blocking material, the light-emitting efficiency of the device is increased by 49%, and the service life of the device is increased by 36%. It can be seen that, compared with the existing OLED light-emitting device, the light-emitting efficiency and the service life performance of the device using the compound of the present application as the light-emitting layer host material or the hole blocking material are greatly improved, the compound prepared by the present application has great application value in the application of OLED device, and has good industrialization prospect.

[0272] As described above, the basic principles, main features and advantages of the present application are better described. The above examples and descriptions are only for describing the preferred embodiments of the present application, and the present application is not limited by the above examples. Various changes and improvements to the technical solutions of the present application made by those skilled in the art without departing from the spirit and scope of the present application shall fall within the scope of protection of the present application.

Claims

1. A compound, characterized in that Having a structure as shown in formula (I), ； Y in the formula (I) is selected from one of CR1R2, O, S, and SiR1R2; X in the formula (I) is C or N; In the formula (I), Z1 to Z6 are C or N, with at most two being N; L1 in the formula (I) is a single bond or a bridging group; Ar1 in the formula (I) is selected from one of phenyl, naphthyl, biphenyl and pyridine; Said R1 and R2 are selected from methyl or phenyl; The bridging group is selected from one of phenyl, naphthyl, biphenyl, pyridine, pyrazine, pyrimidine, pyridazine, and triazine; The Ar2 has the structure shown below, 。 2. The compound according to claim 1, characterized in that The formula (I) has a structure as shown in formula (I-1) or formula (I-2), 。 3. The compound according to claim 2, characterized in that The formula (I-1) and the formula (I-2) have the structures shown in formulas 1 to 10, 。 4. The compound according to claim 1, characterized in that Has the structure shown below, 。 5. Use of the compound according to any one of claims 1 to 4 in an organic electroluminescent device.

6. An organic electroluminescent device comprising an anode layer, a cathode layer, and an organic thin film layer located between the anode layer and the cathode layer, wherein the organic thin film layer comprises a hole injection layer, a first hole transport layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, characterized in that: The light-emitting layer and / or the hole-blocking layer contains the compound according to any one of claims 1 to 4.

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