Boron-containing compound for organic electroluminescent device
A boron-containing compound with specific structural features addresses the challenge of achieving high efficiency and color purity in OLEDs by enabling multiple resonance effects, enhancing blue light emission and efficiency without the need for filters, thus offering improved performance and industrial relevance.
Patent Information
- Application Number
- CN202510133628.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-06
- Publication Date
- 2025-03-18
AI Technical Summary
Commercial OLEDs face challenges in achieving high efficiency and color purity due to the wide emission spectra of π-conjugated molecules, requiring the use of narrow-band filters that compromise light output efficiency, while developing MR-TADF materials for blue light is complex and demanding.
A boron-containing compound with a specific structure that enables high single and triplet energy levels and a small energy gap, facilitating multiple resonance effects to enhance color purity and efficiency in OLEDs without the need for filters.
The boron compound significantly improves color purity and efficiency in OLEDs, with current efficiency values increasing by 10.0% to 76.1% and a narrower emission spectrum, demonstrating its potential for industrial applications.
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Figure CN119638734A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of organic electroluminescent materials and relates to a boron-containing compound used for an organic electroluminescent device. Background Art
[0002] Organic electroluminescent device (OLED) is a flat panel display technology that drives organic semiconductor thin film by electric current to achieve the purpose of light emission and display. It has the advantages of high brightness, fast response, wide viewing angle, simple process and flexibility. It has been widely used in smart phones, televisions, car displays, head-mounted displays, industrial control equipment displays, transparent displays, wearable displays and other fields. Its light-emitting principle is that under the action of an external electric field, electrons and holes are injected from the cathode and anode into the organic thin film layer sandwiched between the electrodes, and the injected electrons and holes migrate from the electron transport layer and the hole transport layer to the light-emitting layer, respectively. The electrons and holes meet in the light-emitting layer to generate excitons. The excitons continue to diffuse freely in the organic solid film and are deactivated in a radiative or non-radiative manner. When the excitons return to the ground state from the excited state by radiative transition, the electroluminescence phenomenon can be observed.
[0003] OLED achieves the purpose of luminescence and display by driving organic semiconductor films with electric current. However, most organic light-emitting molecules based on π-conjugated structures exhibit a wide luminescence spectrum, resulting in insufficient color purity. In order to improve color purity, commercial OLED displays usually need to be combined with narrow-band filters, but this often sacrifices light output efficiency. Therefore, how to improve color purity while maintaining high efficiency has become an urgent problem to be solved in the field of OLED. Multiple resonance thermally activated delayed fluorescence (MR-TADF) materials have broad application prospects in constructing narrow-spectrum OLEDs. MR-TADF materials have a rigid molecular skeleton and a fine distribution of frontier orbital electron clouds. The local (LE) excited state properties account for a large proportion, so they have a small half-maximum width (FWHM) and can achieve narrow-band luminescence without filters, thereby achieving high external quantum efficiency and color purity in OLED devices at the same time.
[0004] However, the conditions for achieving thermally active delayed fluorescent blue light materials with multiple resonance effects are very harsh. It is necessary to ensure a wide band gap and to satisfy the small enough energy level difference between singlet and triplet states, while also achieving the resonance effect. How to construct new compounds to obtain MR-TADF materials is a hot topic and difficulty in the industry. Therefore, providing a MR-TADF material is of great significance to solving the color purity problem of blue light devices. Summary of the invention
[0005] In order to solve the above technical problems, the present invention provides a boron-containing compound for an organic electroluminescent device. The boron-containing compound has sufficiently high singlet and triplet energy while ensuring large distortion, a small singlet and triplet energy difference, and holes and electrons act simultaneously in the molecule to produce a multiple resonance effect. When used as a MR-TADF luminescent material in an organic electroluminescent device, the color purity of the organic electroluminescent device can be significantly improved to achieve high efficiency.
[0006] To achieve the technical purpose of the present invention, on the one hand, the present invention provides a boron-containing compound having a structure as shown in formula (I),
[0007]
[0008] X in the formula (I) 1 , X 2 Each independently selected from NR 1 , O, S, Se, CR 2 R 3 One of;
[0009] Y in the formula (I) 1 Selected from O, S, Se, NR 4 , CR 5 R 6 One of;
[0010] Y in the formula (I) 2 , Y 3 Each independently selected from O, S, Se, NR 7 One of;
[0011] Ar in the formula (I) 1 ~Ar 4 Each of them is independently selected from a hydrogen atom, a deuterium atom, a C1-C5 alkyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
[0012] Furthermore, in the boron-containing compound provided by the present invention, the NR 1 R 1 is a substituted or unsubstituted phenyl group; the CR 2 R 3 R 2 , R 3 Each of them is independently selected from a methyl group and a phenyl group.
[0013] Furthermore, in the boron-containing compound provided by the present invention, the NR 4 R 4is one of substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, said CR 5 R 6 R 5 , R 6 Each independently selected from a methyl group and a phenyl group, wherein the NR 7 R 7 is substituted or unsubstituted phenyl.
[0014] Furthermore, in the boron-containing compound provided by the present invention, the NR 1 R 1 Connected to N by a single bond or bonded to an adjacent benzene ring to form a ring, the NR 7 R 7 It is connected to N by a single bond or to an adjacent benzene ring to form a ring. 1 ~Ar 4 All hydrogen atoms in the boron-containing compound can be arbitrarily deuterated.
[0015] Furthermore, the boron-containing compound provided by the present invention has the structures shown in A1 to A5,
[0016]
[0017] Furthermore, in the boron-containing compound provided by the present invention, A1 to A5 have the following structures:
[0018]
[0019]
[0020]
[0021]
[0022]
[0023] On the other hand, the present invention claims protection for the use of the above-mentioned boron-containing compound in an organic electroluminescent device, wherein the boron-containing compound is used as a light-emitting layer material in the organic electroluminescent device.
[0024] Furthermore, the present invention simulates and calculates the physicochemical properties of boron-containing compounds and finds that the boron-containing compounds have more suitable HOMO / LUMO and higher triplet energy, and can be used as multi-resonance blue light emitting materials to effectively improve the luminous efficiency and color purity of the device.
[0025] In another aspect, the present invention claims protection for an organic electroluminescent device comprising a light-emitting layer, wherein the material of the light-emitting layer comprises the boron-containing compound.
[0026] Furthermore, the present invention applies the prepared boron-containing compound as a blue light emitting material to OLED, which has excellent performance, and its current efficiency value is improved by 10.0% to 76.1% compared with the existing material BD01, and the half-peak width is 17 to 26nm. Compared with the existing material BD01 applied to OLED, after the compound of the present invention is applied as a blue light emitting material to OLED, the luminous efficiency of the light-emitting device is significantly improved, the half-peak width of the emission spectrum is narrower, and the color purity is higher. It has great application value in the application of OLED and has good industrialization prospects.
[0027] Furthermore, the present invention seeks to protect a display component comprising the above-mentioned organic electroluminescent device.
[0028] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages:
[0029] (1) The boron-containing compound prepared by the present invention is centered on a five-membered heterocyclic ring and is constructed by direct bonding of B atoms with N, O, S, and Se atoms. The boron-containing compound has sufficiently high singlet and triplet energies while ensuring large distortion, a small singlet and triplet energy difference (△st), and holes and electrons act simultaneously in the molecule to produce a multiple resonance effect. The present invention simulates and calculates the physicochemical properties of the boron-containing compound and finds that the boron-containing compound has a more suitable HOMO / LUMO and a higher triplet energy. As a multiple resonance blue light emitting material, it can effectively improve the luminous efficiency and color purity of the device.
[0030] (2) The boron-containing compound prepared by the present invention can be applied to organic electroluminescent devices as MR-TADF luminescent materials, which can significantly improve the color purity of organic electroluminescent devices and achieve high efficiency. The boron-containing compound of the present invention is applied to OLED as a blue light luminescent material, and has excellent performance. Its current efficiency value is increased by 10.0% to 76.1% compared with the existing material BD01, and the half-peak width is 17 to 26nm. Compared with the existing material BD01 applied to OLED, after the compound of the present invention is applied to OLED as a blue light luminescent material, the luminous efficiency of the luminescent device is significantly improved, the half-peak width of the emission spectrum is narrower, and the color purity is higher. It has great application value in the application of OLED and has good industrialization prospects. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention.
[0032] Figure 1 Schematic diagram of the structure of an organic electroluminescent device, wherein 1 is a substrate, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking 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
[0033] The technical scheme of the present invention is described below in conjunction with the embodiments, but the present invention is not limited to the following embodiments. The experimental methods and detection methods described in each embodiment are conventional methods unless otherwise specified; the reagents and materials described are all commercially available unless otherwise specified.
[0034] Example 1
[0035] This example provides compound 1 (X 1 and X 2 All are O, Y 1 , Y 2 and Y 3 All O, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 The synthesis of (all C4 alkyl) is as follows, and specifically comprises the following steps:
[0036]
[0037] S1: Under nitrogen protection, raw material 1 (80.40 g, 350.9 mmol), raw material 2 (82.00 g, 350.9 mmol), potassium carbonate (72.64 g, 526.4 mmol), toluene (500 mL), ethanol (200 mL) and water (200 mL) were added in sequence to a three-necked flask equipped with a condenser, and then Pd(OAc) was added. 2 (0.25 g, 1.05 mmol), X-Phos (1.47 g, 3.1 mmol) were heated to 72 °C for 6 h. Cooled to room temperature, washed with water until neutral, and washed with MgSO 4 The residue was dried, filtered and concentrated, passed through a silica gel column and recrystallized to obtain intermediate 1-1 (50.50 g, yield 46%).
[0038] S2: Under nitrogen protection, add intermediate 1-1 (50.50 g, 161.6 mmol), raw material 3 (17.42 g, 73.5 mmol), potassium carbonate (38.41 g, 220.4 mmol) and DMF (500 mL) to a three-necked flask equipped with a condenser, and heat to reflux for 10 h. After the reaction is completed, cool to room temperature, pour into water to form a white precipitate, and filter. Wash the precipitate with water and ethanol in turn, and finally pass through a silica gel column and recrystallize to obtain intermediate 1-2 (55.30 g, yield 95%).
[0039] S3: Under nitrogen protection, add intermediate 1-2 (55.30 g, 70.1 mmol) and dichloromethane (500 mL) to a three-necked flask equipped with a condenser, cool to 0-5°C, and then slowly drop boron tribromide (17.52 g, 70.1 mmol). After the reaction is completed, pour the system into a large amount of ice water, filter, wash the filter cake with water and ethanol in turn, and finally pass through a silica gel column to recrystallize to obtain intermediate 1-3 (20.20 g, yield 38%).
[0040] S4: Under nitrogen protection, add intermediate 1-3 (20.20 g, 26.5 mmol) and o-dichlorobenzene (100 mL) to a three-necked flask equipped with a condenser, then slowly drop boron tribromide (53.08 g, 212.3 mmol), heat to 150-160 ° C and react for 8 hours. After the reaction is completed, the system is cooled to room temperature, a large amount of water is added, and a white precipitate is generated, which is filtered. The filter cake is washed with water and ethanol in turn, and finally passed through a silica gel column and recrystallized to obtain compound 1 (10.35 g, yield 52%).
[0041] The characterization results of compound 1 are as follows: HRMS: measured value: 777.3906 [M+H] + ; Exact mass: 777.3917. C 52 H 50 O 5 B 2 (%) Calculated value: C, 80.42%; H, 6.49%; Found value: C, 80.35%; H, 6.38%.
[0042] Example 2
[0043] This example provides compound 17 (X 1 and X 2 All NR 1 , R 1 is a phenyl group substituted by a methyl group at the 2 and 6 positions, Y 1 , Y 2 and Y 3 All O, Ar 1 ,Ar 3All are C4 alkyl, Ar 2 ,Ar 4 The synthesis of the 2-hydroxy-2-nitropropene (2-hydroxy-2-nitropropene) is as follows, which specifically comprises the following steps:
[0044]
[0045]
[0046] S1: Under nitrogen protection, raw material 4 (80.10 g, 213.4 mmol), raw material 5 (21.86 g, 213.4 mmol), sodium tert-butoxide (24.61 g, 256.1 mmol), toluene (800 mL) were added in sequence to a three-necked flask equipped with a condenser, and then Pd(OAc) was added. 2 (0.25 g, 1.05 mmol), X-Phos (1.47 g, 3.1 mmol) were heated to 100 °C for 2 h. Cooled to room temperature, washed with water until neutral, and washed with MgSO 4 The residue was dried, filtered and concentrated, passed through a silica gel column and recrystallized to obtain Intermediate 17-1 (50.00 g, yield 65%).
[0047] S2: Under nitrogen protection, intermediate 17-1 (50.00 g, 139.1 mmol), raw material 6 (21.59 g, 66.2 mmol), sodium tert-butoxide (19.09 g, 198.7 mmol), toluene (500 mL) were added in sequence to a three-necked flask equipped with a condenser, and then Pd 2 (dba) 3 (0.51 g, 0.56 mmol), X-Phos (0.53 g, 1.12 mmol) were heated to 104 °C for 4 h. Cooled to room temperature, washed with water until neutral, and washed with MgSO 4 The residue was dried, filtered and concentrated, passed through a silica gel column and recrystallized to obtain intermediate 17-2 (58.30 g, yield 99.7%).
[0048] S3: Under nitrogen protection, add intermediate 17-2 (58.30 g, 66.0 mmol) and dichloromethane (600 mL) to a three-necked flask equipped with a condenser, cool to 0-5°C, and then slowly drop boron tribromide (16.52 g, 66.0 mmol). After the reaction is completed, pour the system into a large amount of ice water and filter. The filter cake is washed with water and ethanol in turn, and finally passed through a silica gel column and recrystallized to obtain intermediate 17-3 (24.50 g, yield 43%).
[0049] S4: Under nitrogen protection, add intermediate 17-3 (24.50 g, 28.7 mmol) and o-dichlorobenzene (100 mL) to a three-necked flask equipped with a condenser, then slowly drop boron tribromide (42.98 g, 171.9 mmol), heat to 160-170 ° C and react for 8 hours. After the reaction is completed, the system is cooled to room temperature, a large amount of water is added, and a white precipitate is generated, which is filtered. The filter cake is washed with water and ethanol in turn, and finally passed through a silica gel column and recrystallized to obtain compound 17 (10.68 g, yield 58%).
[0050] The characterization results of compound 17 are as follows: HRMS: measured value: 871.4226 [M+H] + ; Exact mass: 871.4237. C 60 H 52 O 3 B 2 N 2 (%) Calculated value: C, 82.67%; H, 6.13%; N, 3.21%; Found value: C, 82.59%; H, 6.01%; N, 3.13%.
[0051] Example 3
[0052] This example provides compound 19 (X 1 and X 2 All NR 1 , R 1 is a phenyl group substituted by a methyl group at the 2 and 6 positions, Y 1 Se, Y 2 and Y 3 All O, Ar 1 ,Ar 3 All are C4 alkyl, Ar 2 ,Ar 4 The synthesis route is as follows. The synthesis method refers to the synthesis of compound 17. In S2, raw material 6 is replaced by raw material 7 to obtain compound 19 (9.98 g, yield 49%).
[0053]
[0054] The characterization results of compound 19 are as follows: LC-MS: measured value: 933.6746 [M+H] + ; Exact mass: 933.6753. C 60 H 52 O 2 N 2 Se (%) calculated value: C, 77.19%; H, 5.61%; N, 3.00%; measured value: C, 77.11%; H, 5.52%; N, 2.92%.
[0055] Example 4
[0056] This example provides compound 30 (X 1 and X 2 All NR 1 , R 1 is a phenyl group substituted by a methyl group at the 2 and 6 positions, Y 1 For S, Y 2 and Y 3 All NR 7 , R 7 Phenyl, Ar 1 ,Ar 3 All are C4 alkyl, Ar 2 ,Ar 4 The synthesis method of S3 is shown below. The synthesis method of S4 refers to compound 17, and compound 30 (9.95 g, yield 48%) is obtained by synthesis.
[0057]
[0058] S3: Under nitrogen protection, intermediate 30-2 (50.00 g, 55.1 mmol), raw material 10 (12.82 g, 137.6 mmol), sodium tert-butoxide (15.87 g, 198.7 mmol), toluene (500 mL) were added in sequence to a three-necked flask equipped with a condenser, and then Pd 2 (dba) 3 (0.40 g, 0.44 mmol), X-Phos (0.42 g, 0.88 mmol), heated to 104 °C for 4 h. Cooled to room temperature, washed with water until neutral, and washed with MgSO 4 The residue was dried, filtered and concentrated, passed through a silica gel column and recrystallized to obtain intermediate 30-3 (44.20 g, yield 80%).
[0059] The characterization results of compound 30 are as follows: LC-MS: measured value: 1036.4864 [M+H] + ; Exact mass: 1036.4876. C 72 H 62 B 2 N 4 S(%) calculated value: C, 83.39%; H, 6.03%; N, 5.40%; measured value: C, 83.31%; H, 5.94%; N, 5.32%.
[0060] Example 5
[0061] This example provides compound 33 (X 1 and X 2 All NR 1 , R 1 is phenyl, Y 1 For O, Y 2 and Y 3 All NR 7 , R 7 is a phenyl group substituted by a tert-butyl group at the 4-position, and R 7 Bonded with adjacent benzene ring to form a ring, Ar 1 ,Ar 3 are all hydrogen atoms, Ar 2 ,Ar 4 The synthesis route is as follows. The synthesis method refers to the synthesis of compound 17. In S1, raw material 4 is replaced by raw material 11, and in S1, raw material 5 is replaced by raw material 12. S3 is removed to obtain compound 33 (10.62 g, yield 59%).
[0062]
[0063] The characterization results of compound 33 are as follows: HRMS: measured value: 1073.5486 [M+H] + ; Exact mass: 1073.5495. C 76 H 66 OB 2 N 4 (%) Calculated value: C, 85.07%; H, 6.20%; N, 5.22%; Found value: C, 84.98%; H, 6.09%; N, 5.13%.
[0064] Example 6
[0065] This example provides compound 46 (X 1 and X 2 All are O, Y 1 For S, Y 2 and Y 3 All NR 7 , R 7 Phenyl, Ar 1 ,Ar 3 All are C4 alkyl, Ar 2 ,Ar 4 The synthesis route is as follows. The synthesis method refers to the synthesis of compound 30, without performing S1. In S2, intermediate 30-1 is replaced by raw material 13 to obtain compound 46 (9.45 g, yield 45%).
[0066]
[0067]
[0068] The characterization results of compound 46 are as follows: HRMS: measured value: 831.3373 [M+H] + ; Exact mass: 831.3382. C 56 H 44 O 2 B 2 N 2 S (%) calculated value: C, 80.97%; H, 5.34%; N, 3.37%; measured value: C, 80.88%; H, 5.26%; N, 3.27%.
[0069] Example 7
[0070] This example provides compound 102 (X 1 and X 2 All are O, Y 1 NR 4 , R 4 is a phenyl group substituted with 5 deuterium atoms, Y 2 and Y 3 All NR 7 , R 7 is a phenyl group, bonded to the adjacent benzene ring, Ar 1 ,Ar 3 All are C4 alkyl, Ar 2 ,Ar 4 The synthesis route is as follows. The synthesis method refers to the synthesis of compound 46. In S1, raw material 9 is replaced by raw material 14, and raw material 13 is replaced by raw material 15 to obtain compound 102 (10.28 g, yield 46%).
[0071]
[0072] The characterization results of compound 102 are as follows: HRMS: measured value: 891.4078 [M+H] + ; Exact mass: 891.4084. C 62 H 40 D 5 B 2 N 3 O 2 (%) Calculated value: C, 83.61%; H, 5.66%; N, 4.72%; Found value: C, 83.52%; H, 5.50%; N, 4.64%.
[0073] Example 8
[0074] This example provides compound 106 (X 1 and X2 All are O, Y 1 NR 4 , R 4 is a phenyl group substituted with 5 deuterium atoms, Y 2 and Y 3 All NR 7 , R 7 Phenyl, Ar 1 ,Ar 3 All are C4 alkyl, Ar 2 ,Ar 4 The synthesis route is as follows. The synthesis method refers to the synthesis of compound 30, without performing S1. In S2, intermediate 30-1 is replaced by raw material 16, and raw material 9 is replaced by raw material 14, and compound 106 (8.28 g, yield 41%) is synthesized.
[0075]
[0076] The characterization results of compound 106 are as follows: HRMS: measured value: 895.4385 [M+H] + ; Exact mass: 895.4397. C 62 H 44 D 5 O 2 B 2 N 3 (%) Calculated value: C, 84.08%; H, 5.12%; N, 4.74%; Found value: C, 83.97%; H, 5.01%; N, 4.66%.
[0077] Example 9
[0078] This example provides compound 111 (X 1 and X 2 Both S, Y 1 NR 4 , R 4 is a phenyl group substituted with 5 deuterium atoms, Y 2 and Y 3 All O, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 The synthesis route is as follows. The synthesis method refers to the synthesis of compound 1. In S1, raw material 1 is replaced by raw material 17, and in S2, raw material 3 is replaced by raw material 18, and compound 111 (9.60 g, yield 44%) is synthesized.
[0079]
[0080] The characterization results of compound 111 are as follows: HRMS: measured value: 889.4238 [M+H] + ; Exact mass: 889.4247. C 58 H 50 D 5 B 2 NO 2 S 2 (%) Calculated value: C, 78.37%; H, 6.80%; N, 1.58%; Found value: C, 85.01%; H, 5.84%; N, 2.49%.
[0081] Example 10
[0082] This example provides compound 121 (X 1 and X 2 All NR 1 , R 1 Y is a phenyl group whose 2- and 6-positions are substituted by methyl groups and whose 4-position is substituted by tert-butyl groups; 1 NR 4 , R 4 is a phenyl group substituted with 5 deuterium atoms; Y 2 and Y 3 All O, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 The synthesis route is as follows. The synthesis method refers to the synthesis of compound 19. In S1, intermediate 17-1 is replaced by raw material 19, and raw material 7 is replaced by raw material 14 to obtain compound 121 (11.35 g, yield 50%).
[0083]
[0084]
[0085] The characterization results of compound 121 are as follows: HRMS: measured value: 951.5019 [M+H] + ; Exact mass: 951.5023. C 66 H 52 D 5 B 2 N 3 O 2 (%) Calculated value: C, 83.37%; H, 6.57%; N, 4.42%; Found value: C, 83.26%; H, 6.48%; N, 4.34%.
[0086] Embodiment 11
[0087] This example provides compound 125 (X1 and X 2 All NR 1 , R 1 is a phenyl group substituted by a tert-butyl group at the 3-position, and R 1 Bonded to the adjacent benzene ring; Y 1 NR 4 , R 4 is a phenyl group substituted with 5 deuterium atoms; Y 2 and Y 3 All O, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 The synthesis route is as follows. The synthesis method refers to the synthesis of compound 121. In S1, raw material 19 is replaced by raw material 20 to obtain compound 125 (12.16 g, yield 52%).
[0088]
[0089]
[0090] The characterization results of compound 125 are as follows: HRMS: measured value: 1003.5324 [M+H] + ; Exact mass: 1003.5336. C 70 H 56 D 5 B 2 N 3 O 2 (%) Calculated value: C, 83.83%; H, 6.63%; N, 4.19%; Found value: C, 83.71%; H, 6.54%; N, 4.10%.
[0091] Example 12
[0092] This example performs simulation calculations on the physicochemical properties of the compound.
[0093] Compound 1, compound 10, compound 17, compound 20, compound 22, compound 30, compound 33, compound 37, compound 45, compound 48, compound 49, compound 57, compound 60, compound 73, compound 77, compound 84, compound 85, compound 93, compound 102, compound 106, compound 109, compound 111, compound 118, compound 121, compound 125, compound 132 and comparative material BD01 were respectively subjected to S 1 , T 1 Energy level and HOMO, LUMO simulation calculation. HOMO, LUMO, S 1 , T1 To simulate the calculated data, the B3LYP hybrid functional was used with the basis set 6-31g (d, P). The calculation results are shown in Table 1.
[0094] Table 1 Simulation results of the physicochemical properties of the compounds
[0095]
[0096]
[0097] As can be seen from Table 1, the compounds prepared in the present invention have more suitable HOMO / LUMO and higher triplet energy, and can effectively improve the luminous efficiency and color purity of the device as a multi-resonance blue light emitting material.
[0098] Embodiment 13
[0099] This embodiment provides the use of the compound as a light-emitting material in an organic electroluminescent device.
[0100] The structure of organic electroluminescent devices is as follows Figure 1 As shown, it includes a substrate 1, an anode layer 2, a hole injection layer 3, a hole transport layer 4, an electron blocking 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 which are stacked in sequence.
[0101] Among them, the material of the anode layer 2 is indium tin oxide (ITO) with a high work function; the material of the hole injection layer 3 is HI-1 with a thickness of 10nm; the material of the hole transport layer 4 is HT1 doped with HI-1, the mass ratio of HT1 to HI-1 is 95%:5%, and the thickness is 60nm; the material of the electron blocking layer 5 is EB1 with a thickness of 15nm; the light-emitting layer 6 uses BH1 as the main material and BD01 or a compound as the light-emitting material, with a doping mass ratio of 5% and a thickness of 30nm; the material of the hole blocking layer 7 is HB with a thickness of 10nm; the electron transport layer 8 is composed of ET-1 doped with Liq, with a doping concentration of 50% and a thickness of 30nm; the material of the electron injection layer 9 is Liq with a thickness of 2nm; the material of the cathode layer is Al with a thickness of 100nm.
[0102] The material structure used in each functional layer of the device is as follows:
[0103]
[0104] The preparation of an organic electroluminescent device comprises the following steps:
[0105] 1) Clean the ITO anode on the transparent glass or plastic substrate, and ultrasonically clean it with deionized water, acetone, and ethanol for 20 minutes respectively, and then perform plasma treatment for 5 minutes in an oxygen atmosphere; 2) Vacuum evaporation is used to deposit a hole injection layer on the ITO anode layer; 3) Vacuum co-evaporation is used to deposit a hole transport layer HT1:HI-1 (mass ratio is 5%) on the hole injection layer; 4) Vacuum evaporation is used to deposit an electron blocking layer on the hole transport layer HT1:HI-1; 5) On the electron blocking layer, The light-emitting layer is co-deposited by vacuum evaporation, using BH1 as the main material and BD01 or a compound as the light-emitting material, with a doping mass ratio of 5% and a thickness of 30nm; 6) On the light-emitting layer, a hole blocking layer is deposited by vacuum evaporation; 7) On the hole blocking layer, an electron transport material layer ET-1:Liq is deposited by vacuum co-evaporation, with a doping concentration of 50%; 8) On the electron transport layer, an electron injection layer is deposited by vacuum evaporation; 9) On the electron injection layer, cathode Al is deposited by vacuum evaporation.
[0106] The cathode and anode of the organic electroluminescent device are connected by a known driving circuit, and the voltage-efficiency-current density relationship of the OLED is tested by a standard method using a Keithley 2400 power supply combined with a PR670 photometer. The device performance of the organic electroluminescent device prepared using BD01 or the compound as the luminescent material is shown in Table 2.
[0107] Table 2 Performance parameters of organic electroluminescent devices
[0108]
[0109]
[0110] As shown in Table 2, the compounds of the present invention are applied as blue light emitting materials in OLEDs and have excellent performance. The current efficiency value is increased by 10.0% to 76.1% compared with the existing material BD01, and the half-peak width is 17 to 26nm. Compared with the existing material BD01 applied to OLEDs, after the compounds of the present invention are applied as blue light emitting materials to OLEDs, the luminous efficiency of the light-emitting device is significantly improved, the half-peak width of the emission spectrum is narrower, and the color purity is higher. It has great application value in the application of OLEDs and has good industrialization prospects.
[0111] The embodiments described above are part of the embodiments of the present invention, rather than all of the embodiments. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. All other embodiments obtained without creative work and related deductions and substitutions made by ordinary technicians in the field under the conditions of the concept of the present invention belong to the scope of protection of the present invention.
Claims
1. A compound, characterized in that Having a structure as shown in formula (I), X1 and X2 in the formula (I) are independently selected from one of NR1, O, S, Se, and CR2R3; Y1 in the formula (I) is selected from one of O, S, Se, NR4, and CR5R6; Y2 and Y3 in the formula (I) are independently selected from one of O, S, Se and NR7; Ar1, Ar2, Ar3, and Ar4 in the formula (I) are independently selected from a hydrogen atom, a deuterium atom, a C1-C5 alkyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C6-C30 heteroaryl group.
2. The compound according to claim 1, characterized in that R1 in the NR1 is a substituted or unsubstituted phenyl group; R2 and R3 in the CR2R3 are independently selected from methyl and phenyl.
3. The compound according to claim 1, characterized in that R4 in the NR4 is one of substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl; R5 and R6 in the CR5R6 are independently selected from methyl and phenyl.
4. The compound according to claim 1, characterized in that R7 in the NR7 is a substituted or unsubstituted phenyl group.
5. The compound according to claim 1, characterized in that The R1 in the NR1 is connected to N by a single bond or is bonded to an adjacent benzene ring to form a ring; R7 in the NR7 is connected to N via a single bond or is bonded to an adjacent benzene ring to form a ring.
6. The compound according to claim 1, characterized in that Having the structures shown in A1 to A5, 7. The compound according to claim 6, characterized in that The structures of A1 to A5 are as follows:
8. Use of the compound according to any one of claims 1 to 7 in an organic electroluminescent device, characterized in that: The compound is used as a light-emitting layer material in an organic electroluminescent device.
9. An organic electroluminescent device comprising a light-emitting layer, characterized in that: The material of the light-emitting layer includes the compound according to any one of claims 1 to 7.
10. A display component, characterized in that: An organic electroluminescent device comprising the organic electroluminescent device according to claim 9.