Condensed ring compound and organic light-emitting device of condensed ring compound

Abstract

The invention discloses a fused ring compound and an organic light-emitting device of the fused ring compound, the fused ring compound has a structure shown in the following formula (1): # imgabs0 # formula (1), in the formula (1), A ring is independently an unsubstituted, monosubstituted or polysubstituted aryl ring, heteroaryl ring or heteroalkyl ring; when a substituent group is contained, the substituent group is substituted for one time or multiple times, and the substituent group is selected from a group consisting of H, deuterium, Si, O, N, aryl of C6-C20, alkyl of C1-C12 and naphthenic base of C3-C16. R1 and R2 represent polysubstituted groups and can be unsubstituted, monosubstituted or polysubstituted. According to the invention, interaction among luminescent molecules can be effectively inhibited through a large-steric-hindrance group. According to the organic light-emitting device, the energy transmission performance between the subject and the object can be improved, the concentration of high-energy excitons in the light-emitting layer is reduced, the organic light-emitting device can effectively have lower driving voltage, and the light-emitting efficiency is improved.

Description

Technical Field

[0001] The invention relates to a condensed ring compound and an organic light-emitting device of the condensed ring compound, belonging to the technical field of materials. Background Art

[0002] With the development of the multimedia era and the improvement of information technology requirements, the requirements for panel display performance are getting higher and higher. OLED has attracted widespread attention from the industry and academia due to its unique advantages such as simple manufacturing, low driving voltage, light weight, low cost, and fast response speed. Among them, OLED is widely used in televisions, mobile phones, cameras, smart watches and other fields due to its special advantages. Organic light-emitting diode (OLED) is an electroluminescent device. The mechanism of OLED light emission is that under the action of an external electric field, electrons and holes are injected from the positive and negative electrodes respectively, migrate, recombine and decay in the organic material to produce light. The typical structure of OLED includes one or more functional layers of cathode layer, anode layer, electron injection layer, electron transport layer, hole blocking layer, hole transport layer, hole injection layer and light-emitting layer.

[0003] OLED promotes the combination of electrons and holes after electrical excitation, forming a 1:3 ratio of singlet and triplet excitons. However, fluorescent OLED can only use singlet excitons to emit fluorescence. IQE of fluorescent OLED max The theoretical limit is about 25%. Triplet excitons account for 75% of the energy, which is converted into heat through vibration or rotational energy dissipation. Because the coupling efficiency is usually less than 20%, the EQE of fluorescent OLEDs is max About 5%, much lower than expected. In order to improve the efficiency of OLED devices, many mechanisms have been proposed, and many light-emitting devices have been designed and tested. Among them, phosphorescent materials, as the second-generation light-emitting materials, can utilize singlet and triplet phosphorescence to achieve 100% IQE through spin-orbit coupling.

[0004] Although the research progress of organic electroluminescence is very rapid, there are still many problems to be solved. At present, how to provide a high-efficiency and long-life blue light material is still the focus of technical personnel in this field. Summary of the invention

[0005] The present invention aims to provide a condensed ring compound and an organic light-emitting device thereof in view of the defects and shortcomings of the above-mentioned prior art. The present invention can effectively inhibit the interaction between light-emitting molecules through a large steric hindering group. The present invention can improve the energy transfer performance between the host and the guest, reduce the concentration of high-energy excitons in the light-emitting layer, and effectively make the organic light-emitting device have a lower driving voltage and improve the luminous efficiency.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] The present invention provides a condensed ring compound having a structure shown in the following formula (1):

[0008]

[0009] In formula (1), ring A is independently an unsubstituted, monosubstituted or polysubstituted aryl ring, heteroaryl ring or heteroalkyl ring; when it contains a substituent, the substituent is substituted once or multiple times, and the substituent is selected from the group consisting of H, deuterium, Si, O, N, C6-C20 aryl, C1-C12 alkyl, C3-C16 cycloalkyl. R1 and R2 represent polysubstituted groups, which can be unsubstituted, monosubstituted or polysubstituted.

[0010] Furthermore, the fused ring compounds R1 and R2 of the present invention are each independently selected from the group consisting of H, deuterium, oxygen, C6-C20 aryl, C6-C20 heteroaryl, C1-C15 alkyl, C12-C30 diarylamino, and C3-C14 cycloalkyl.

[0011] Furthermore, the fused ring compound of the present invention is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

[0012]

[0013]

[0014]

[0015]

[0016]

[0017] Furthermore, the present invention also provides a method for preparing a condensed ring compound material. The reaction process of the preparation method is shown in Formula 2 below. The steps of the preparation method are as follows:

[0018] Synthesis of compound 3: Under nitrogen environment: Compound 1 and compound 2 are dissolved in toluene solution, and then appropriate amounts of palladium acetate and tri-tert-butylphosphine tetrafluoroborate are added, and compound 3 is obtained after sufficient reaction.

[0019] Synthesis of compound 5: The reaction conditions are similar to those of compound 3.

[0020] Synthesis of compound 7: Under nitrogen environment: Compound 5 and compound 6 are dissolved in toluene solution, and then appropriate amounts of sodium tert-butoxide, palladium acetate, and tri-tert-butylphosphine tetrafluoroborate are added, and compound 7 is obtained after sufficient reaction.

[0021] Synthesis of compound 8: Compound 7 was added to anhydrous tert-butylbenzene, followed by slow addition of BuLi. After the reaction was complete, BBr3 and N,N-diisopropylethylamine were added, and compound 8 was obtained after sufficient reaction.

[0022]

[0023] Furthermore, the present invention also provides a use of a condensed ring compound material, which can be applied to organic electroluminescent devices, organic integrated circuits, organic field effect transistors, smart phones, tablet computers, smart wearable devices, organic thin film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, etc.

[0024] Furthermore, the present invention also provides an organic electroluminescent device applied to condensed ring compounds, and the organic electroluminescent device comprises the condensed ring compound of the present invention.

[0025] Furthermore, the present invention also provides an organic electroluminescent device applied to condensed ring compounds, comprising a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises a condensed ring compound having the general structure shown in formula (I) above.

[0026] Furthermore, the present invention also provides an organic photoelectric device applied to condensed ring compounds, comprising a first electrode, a second electrode; and a light-emitting material layer arranged between the first electrode and the second electrode, wherein the light-emitting material layer contains the condensed ring compound described in the present invention.

[0027] On the one hand, the present invention also provides the use of the condensed ring compound with the general structure shown in the above formula (I) in electronic devices.

[0028] Furthermore, the electronic devices include organic electroluminescent devices, organic integrated circuits, organic field effect transistors, smart phones, tablet computers, smart wearable devices, organic thin film transistors, organic light emitting transistors, organic solar cells, organic optical detectors, etc.

[0029] In another aspect, the present invention further provides an organic electroluminescent device, which comprises a condensed ring compound having a general structure as shown in the above formula (I).

[0030] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises a condensed ring compound having a general structure as shown in formula (I) above, and the mass percentage of the condensed ring compound is 0.1%-60%.

[0031] On the other hand, the present invention also provides an organic photoelectric device, comprising a first electrode, a second electrode; and a light-emitting material layer arranged between the first electrode and the second electrode, wherein the light-emitting material layer contains a condensed ring compound with the general structure shown in formula (I) above.

[0032] Beneficial effects:

[0033] 1. The present invention can effectively inhibit the interaction between luminescent molecules through large steric hindrance groups.

[0034] 2. The present invention can improve the energy transfer performance between the host and the guest, reduce the concentration of high-energy excitons in the light-emitting layer, and can effectively make the organic light-emitting device have a lower driving voltage and improve the luminous efficiency. DETAILED DESCRIPTION

[0035] The following is a detailed description of the present invention. The description of the constituent elements described below may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0036] By reference to the following specific embodiments and the examples contained therein, the disclosure can be more easily understood. Before disclosing and describing the compounds, devices and / or methods of the present invention, it should be understood that, unless otherwise stated, they are not limited to specific synthetic methods or specific reagents, because this can be varied. It should also be understood that the terms used in the present invention are only used to describe specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used in this practice or test, exemplary methods and materials are now described.

[0037] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include the plural forms.

[0038] Unless otherwise indicated, all commercial reagents used in the following experiments were purchased and used directly.

[0039] General synthetic route

[0040] The general synthesis route of the compound of formula (1) of the present invention is as follows:

[0041]

[0042] The preparation method of the condensed ring compound, i.e., the guest compound, and the luminescent properties of the device are further explained in detail in conjunction with the following examples.

[0043] Example 1: Synthesis of Compound 1

[0044]

[0045] Synthesis of compound 1-3: Compound 1-1 (350 mg, 2 mmol) and compound 1-2 (382 mg, 2 mmol) were dissolved in 60 mL of toluene solution. At 80 ° C, under the condition of protective gas nitrogen, sodium tert-butoxide (384 mg, 4 mmoL), palladium acetate (24 mg, 0.1 mmoL), and tri-tert-butylphosphine tetrafluoroborate (290 mg, 1 mmoL) were added. After reacting for 48 hours, the mixture was cooled to room temperature, the solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane. The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography column, and petroleum ether: dichloromethane = 3:1 (volume ratio) was used for column separation. Compound 1-3 (391 mg, yield 68%) was obtained.

[0046] Synthesis of compound 1-5: Compound 1-3 (285 mg, 1 mmol) and compound 1-41-4 (465 mg, 5 mmol) were dissolved in 80 mL of toluene solution. At 80 ° C, under the condition of protective gas nitrogen, sodium tert-butoxide (960 mg, 10 mmoL), palladium acetate (12 mg, 0.05 mmoL), tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmoL) were added. After 64 hours of reaction, the mixture was cooled to room temperature, the solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane. The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography column, and petroleum ether: dichloromethane = 3:1 (volume ratio) was used for column separation. Compound 1-5 (212 mg, yield 62%) was obtained.

[0047] Synthesis of compound 1-7: Compound 1-5 (171 mg, 0.5 mmoL) and compound 1-6 (887 mg, 2.5 mmoL) were dissolved in 50 mL of toluene solution. Sodium tert-butoxide (480 mg, 5 mmoL), palladium acetate (6 mg, 0.025 mmoL), and tri-tert-butylphosphine tetrafluoroborate (73 mg, 0.25 mmoL) were added at 60 ° C under the condition of protective gas nitrogen. After 72 hours of reaction, the mixture was cooled to room temperature, the solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane. The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography column, and petroleum ether: dichloromethane = 3:1 (volume ratio) was used for column separation. Compound 1-7 (124 mg, yield 45%) was obtained.

[0048] Synthesis of compound 1: Compound 1-7 (111 mg, 0.2 mmol) was dissolved in 60 mL of anhydrous tert-butylbenzene. The reaction system was cooled to -78 °C, and BuLi (0.2 mL, 0.4 mmoL) was slowly added. After reacting at -78 °C for 4 hours, BBr3 (50 mg, 0.2 mmoL) was slowly added. After reacting at -50 °C for 1 hour, the mixture was warmed to room temperature, and then N, N-diisopropylethylamine (78 mg, 0.6 mmoL) was added. The mixture was then heated to 120 °C for 12 hours and cooled to room temperature, and then 5 mL of sodium acetate aqueous solution was added. The mixture was cooled to room temperature, the solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane. The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography column, and petroleum ether: dichloromethane = 3:1 (volume ratio) was used for column separation. Compound 1 (68 mg, yield 68%) was obtained. Mass spectrum m / z, theoretical value 498.23; measured value M+H: 499.21.

[0049] Example 2: Synthesis of Compound 7

[0050]

[0051] Compound 7 was synthesized by referring to the synthetic route of compound 1. The yield of the final product was 51%. Mass spectrum m / z, theoretical value 720.33; measured value M+H: 721.31.

[0052] Example 3: Synthesis of Compound 14

[0053]

[0054] Compound 14 was synthesized by referring to the synthetic route of compound 7. The yield of the final product was 48%. Mass spectrum m / z, theoretical value 721.37; measured value M+H: 722.36.

[0055] Example 4: Synthesis of Compound 29

[0056]

[0057] Compound 29 was synthesized by referring to the synthetic route of compound 14. The yield of the final product was 53%. Mass spectrum m / z, theoretical value 693.33; measured value M+H: 694.31.

[0058] Example 5: Synthesis of Compound 50

[0059]

[0060] Compound 50 was synthesized by referring to the synthetic route of compound 29. The yield of the final product was 41%. Mass spectrum m / z, theoretical value 812.38; measured value M+H: 813.33.

[0061] Example 6: Synthesis of Compound 62

[0062]

[0063] Compound 62 was synthesized by referring to the synthetic route of compound 50. The yield of the final product was 45%. Mass spectrum m / z, theoretical value 706.36; measured value M+H: 707.33.

[0064] Example 7: Synthesis of Compound 69

[0065]

[0066] Compound 69 was synthesized by referring to the synthetic route of compound 62. The yield of the final product was 48%. Mass spectrum m / z, theoretical value 739.32; measured value M+H: 740.30.

[0067] Example 8: Synthesis of Compound 74

[0068]

[0069] Compound 74 was synthesized by referring to the synthetic route of compound 69. The yield of the final product was 44%. Mass spectrum m / z, theoretical value 732.36; measured value M+H: 733.31.

[0070] Example 9: Synthesis of Compound 94

[0071]

[0072] Compound 94 was synthesized by referring to the synthetic route of compound 74. The yield of the final product was 51%. Mass spectrum m / z, theoretical value 814.35; measured value M+H: 815.30.

[0073] Example 10: Synthesis of Compound 101

[0074]

[0075] Compound 101 was synthesized by referring to the synthetic route of compound 94. The yield of the final product was 46%. Mass spectrum m / z, theoretical value 832.35; measured value M+H: 833.32.

[0076] Fabrication of OLED devices:

[0077] This embodiment provides the structural components of device embodiment 1, specifically including a first electrode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a second electrode as a structure of an organic layer.

[0078] The materials of each layer are as follows:

[0079] Anode: ITO (indium tin oxide), thickness 50nm;

[0080] Hole injection layer: main material NDP-9, thickness 8nm;

[0081] Hole transport layer: HT, thickness 20nm;

[0082] Electron transport layer: ET1 (30% by mole) and LiQ (70% by mole), thickness 30 nm;

[0083] Cathode: Mg / Ag (mass ratio 8:2), thickness 30nm.

[0084] Referring to the method provided in the above-mentioned device embodiment 1, the prepared condensed ring compounds 7, 14, 29, 50, 62, 69, 74, 94, and 101 were respectively selected as the implementation objects to replace compound 1, and they were co-evaporated with the main compound in a volume ratio of 2:98 to form a light-emitting layer to prepare organic electroluminescent diodes, which were recorded as device embodiments 2 to device embodiments 10.

[0085] In the above device, the structural formula corresponding to the abbreviation of the material is as follows:

[0086]

[0087] Preparation of Comparative Example 1

[0088] Comparative Example 1 was prepared by referring to the method provided in the above device embodiment 1, except that BN-1 was used as the guest material of the light-emitting layer in Comparative Example 1 to replace the condensed ring compound of the present invention. The chemical structure of the compound BN-1 in the comparative example is as follows:

[0089]

[0090] The current efficiency, voltage, life and other characteristics of the device embodiments and comparative examples prepared above were tested by standard methods, and the device luminescence characteristic data are shown in Table 1.

[0091]

[0092]

[0093] As can be seen from Table 1, the specific condensed ring compound disclosed in the present invention is used as a dopant for the light-emitting layer in an organic electroluminescent device, and a better starting voltage is obtained compared with the comparative example, and the device life is also significantly improved. This shows that the condensed ring compound of the present invention can optimize device performance and has high commercial application value.

Claims

1. A condensed ring compound, characterized in that: The condensed ring compound has a structure shown in the following formula (1): In formula (1), each A ring is independently an unsubstituted, monosubstituted or polysubstituted aryl ring, heteroaryl ring or heteroalkyl ring; R1 and R2 represent a polysubstituted group, which may be unsubstituted, monosubstituted or polysubstituted.

2. A fused ring compound according to claim 1, characterized in that: R1 R1 and R2 are each independently selected from the group consisting of H, deuterium, oxygen, C6-C20 aryl, C6-C20 heteroaryl, C1-C15 alkyl, C12-C30 diarylamino, and C3-C14 cycloalkyl.

3. A fused ring compound according to claim 1, characterized in that: The fused ring compound is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

4. A method for preparing a condensed ring compound material as claimed in any one of claims 1 to 3, characterized in that: The reaction process of the preparation method is shown in Formula 2, and the steps of the preparation method are as follows: Synthesis of compound 3: Under nitrogen environment: Compound 1 and compound 2 are dissolved in toluene solution, and then appropriate amounts of palladium acetate and tri-tert-butylphosphine tetrafluoroborate are added, and compound 3 is obtained after sufficient reaction; Synthesis of compound 5: The reaction conditions are similar to those of compound 3; Synthesis of compound 7: Under nitrogen environment: Compound 5 and compound 6 are dissolved in toluene solution, and then appropriate amounts of sodium tert-butoxide, palladium acetate, and tri-tert-butylphosphine tetrafluoroborate are added, and compound 7 is obtained after sufficient reaction; Synthesis of compound 8: Compound 7 was added to anhydrous tert-butylbenzene, followed by slow addition of BuLi, and after the reaction was complete, BBr3 and N,N-diisopropylethylamine were added to obtain compound 8 after sufficient reaction; 5. A use of a condensed ring compound material as claimed in any one of claims 1 to 3, characterized in that: The condensed ring compound material is applied to organic electroluminescent devices, organic integrated circuits, organic field effect transistors, smart phones, tablet computers, smart wearable devices, organic thin film transistors, organic light emitting transistors, organic solar cells, and organic optical detectors.

6. An organic electroluminescent device applied to a condensed ring compound, characterized in that: The organic electroluminescent device comprises the condensed ring compound as claimed in any one of claims 1 to 3.

7. An organic electroluminescent device applied to condensed ring compounds according to claim 6, characterized in that: It comprises a cathode, an anode and an organic functional layer between the cathode and the anode; the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises a condensed ring compound having a general structure as shown in the above formula (I).

8. An organic optoelectronic device applied to condensed ring compounds, characterized in that: The invention comprises a first electrode, a second electrode; and a light-emitting material layer arranged between the first electrode and the second electrode, wherein the light-emitting material layer comprises the condensed ring compound as claimed in any one of claims 1 to 3.

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