Polycyclic compounds and organic electroluminescent devices comprising the same

Abstract

The application discloses a polycyclic compound and an organic electroluminescent device containing the same. The compound structure is shown as formula I, which is a boron-nitrogen material with a planar structure. By introducing a bridged cycloalkyl group, the rigidity of the polycyclic compound is increased, and the introduction of a π electron-containing structure is reduced, so that the π-π mutual attraction in the molecule is minimized. The compound has similar molecular vibration modes and energy levels as existing boron-nitrogen materials, avoids the occurrence of red shift of the emission wavelength, and has a narrow emission spectrum and a half peak width. The compound is suitable for a blue host / dopant system in a blue series of AM-OLED and an organic electroluminescent device. The organic electroluminescent device containing the compound has a high external quantum efficiency, and the lifetime performance is particularly excellent.

Description

Technical Field

[0001] This invention belongs to the field of OLED technology, specifically including a polycyclic compound and an organic electroluminescent device containing the same. Background Technology

[0002] Compared with other flat panel display elements such as liquid crystal displays (LCDs), plasma display panels (PDPs), and field emission displays (FEDs), organic light-emitting diodes (OLEDs) have a simple structure, various advantages in manufacturing processes, high brightness and excellent viewing angle characteristics, fast response speed, and are being actively developed and commercialized due to their low driving voltage. This makes them suitable for use as light sources in flat panel displays such as wall-mounted TVs, backlighting of displays, lighting, billboards, etc.

[0003] The materials used in the organic layer of organic electroluminescent devices are mostly pure organic materials or complex compounds formed by organic materials and metals. Depending on their application, they can be classified as hole injection materials, hole transport materials, luminescent materials, electron transport materials, and electron injection materials. Preferably, the luminescent layer material is a material that is stable in both oxidative and reduced states, and preferably a material with high luminous efficiency in converting excitons into light. More specifically, the luminescent layer consists of a host material and a dopant material. The dopant needs to have high quantum efficiency, and the host material preferably has a larger bandgap than the dopant material to facilitate energy transfer to the dopant. Displays used in televisions, mobile devices, etc., achieve full color using red, green, and blue colors, and the luminescent layers are respectively composed of a red host / dopant, a green host / dopant, and a blue host / dopant.

[0004] Among existing materials used for blue dopants, fluorescent molecules such as perylene, coumarin, anthracene, and pyrene are widely utilized. However, due to the broad emission spectra and full width at half maximum (FWHM) of these dopants, it is difficult to obtain pure blue light during device fabrication. This characteristic not only reduces the efficiency of blue light in the device but also makes it difficult to obtain deep blue light.

[0005] Recently, literature on boron-based dopant-based devices with narrow emission spectra and high device efficiency has been published in Adv. Mater. 2016, 28, 2777-2781 and Angew. Chem. Int. Ed. 2017, 56, 5087-5090, and also published in Korean Patent Publication No. 10-2016-0119683. In existing boron-based blue dopant materials, boron atoms are contained at the center and cyclized, thus forming only three coordination bonds and maintaining the molecular structure in a planar state. The advantage of this planar dopant structure is that the energy levels of the molecular vibrational modes are similar, resulting in a narrower emission spectrum and half-width at half-maximum (WWHM) for pure light production. However, when using this planar dopant structure to fabricate devices, the lack of outermost electrons in the boron atom increases the intensity of interactions with adjacent dopant atoms, leading to a more severe concentration quenching of the dopant.

[0006] Therefore, it is necessary to develop a novel dopant that can maintain a narrow emission spectrum and half-amplitude while solving the concentration quenching problem during device fabrication. Summary of the Invention

[0007] In view of the above-mentioned problems in the prior art, the present invention provides a polycyclic compound and an organic electroluminescent device containing the same.

[0008] To achieve the above objectives, the technical solution adopted by the present invention includes:

[0009] In a first aspect, the present invention provides a polycyclic compound having the general structural formula shown in Formula I:

[0010]

[0011] In this context, ring A indicates a carbon number of C4 to C5. 30 Substituted or unsubstituted bridged cycloalkyl groups; ring B indicates a carbon number of C6 to C6. 60 The substituted or unsubstituted aryl group has a carbon number of C5 to C6. 60 Substituted or unsubstituted heteroaryl groups with a carbon number of C6 to C5 60 Substituted or unsubstituted fused-ring aryl groups with a carbon number of C5 to C6. 60 Substituted or unsubstituted heterocyclic aryl groups;

[0012] X represents N or O;

[0013] R1 and R2 independently represent hydrogen, deuterium, halogen, and carbon atoms with numbers C1 to C2. 30 The substituted or unsubstituted alkyl group has a carbon number of C1 to C2. 30The substituted or unsubstituted alkoxy group has a carbon number of C2 to C3. 30 The substituted or unsubstituted alkenyl group has a carbon number of C3 to C4. 30 Substituted or unsubstituted cycloalkyl groups with a carbon number of C6 to C5 60 The substituted or unsubstituted aryl group has a carbon number of C6 to C6. 60 Substituted or unsubstituted heteroaryl groups with a carbon number of C6 to C5 60 Substituted or unsubstituted fused-ring aryl groups with a carbon number of C5 to C6. 60 Substituted or unsubstituted heterofused aryl groups with a carbon number of C6 to C5 60 Substituted or unsubstituted aromatic amino groups; when R1 represents a carbon number of C1 to C2. 30 When the substituted or unsubstituted alkyl or alkoxy groups are used, the two or more R1 groups can be linked together to form a ring;

[0014] m and n can each independently represent 1, 2 or 3; when m and n are 2 or 3, R1 and R2 can be the same or different.

[0015] R3 indicates hydrogen, deuterium, halogen, or carbon atoms with a carbon number of C1 to C2. 30 The substituted or unsubstituted alkyl group has a carbon number of C2 to C3. 30 The substituted or unsubstituted alkenyl group has a carbon number of C3 to C4. 30 Substituted or unsubstituted cycloalkyl groups with a carbon number of C6 to C5 60 The substituted or unsubstituted aryl group has a carbon number of C6 to C6. 60 The substituted or unsubstituted heteroaryl group, wherein R3 can be connected to R2 and ring B to form a ring;

[0016] The substituents in ring A, ring B, R1, R2, and R3 may be the same or different, and each is independently selected from deuterium, halogen, cyano, and carbon atoms with C1 to C3. 10 The alkyl group has a carbon number of C6 to C6. 60 The aryl group has a carbon number of C6 to C6. 60 The fused-ring aryl group or carbon atom number is C3 to C4. 30 One of the cycloalkyl groups, wherein two or more substituents can be linked together to form an aliphatic ring, an aromatic ring or a fused ring;

[0017] The hydrogen atoms on the ring structure of the compound shown in Formula I can be independently replaced by deuterium.

[0018] Furthermore, the ring formed by the connection of R3 and ring B is a substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

[0019] Furthermore, the ring formed by the connection of R3 and R2 is a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

[0020] Furthermore, the ring formed by the connection of two or more R1s is a substituted or unsubstituted cycloalkyl or a substituted or unsubstituted aryl group.

[0021] Furthermore, the ring B represents Or the number of carbon atoms is C3 to C4. 15 In the cycloalkyl group, any non-adjacent C in the above structures can be independently replaced by N, and any H can be independently replaced by F, D, CN, straight-chain alkyl, branched-chain alkyl, cycloalkyl, aryl, heteroaryl or aromatic amino.

[0022] Furthermore, R3 indicates a carbon number of C1 to C2. 10 Substituted or unsubstituted alkyl groups with a carbon number of C2 to C3 10 Substituted or unsubstituted alkenyl groups Each of the H atoms in the above structures can be independently replaced by F, D, straight-chain alkyl, branched alkyl, cycloalkyl, or phenyl.

[0023] Furthermore, the compound represented by Formula I is selected from any one of the following compounds:

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032] In a second aspect, the present invention provides an organic electroluminescent device comprising an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode sequentially disposed on a substrate; wherein the light-emitting layer comprises one or more of the aforementioned polycyclic compounds.

[0033] Furthermore, the light-emitting layer comprises a host material and a dopant material, wherein the dopant material comprises one or more polycyclic compounds as described above.

[0034] Beneficial effects of this invention:

[0035] This invention provides a polycyclic compound, a boron-nitrogen material with a planar structure. By introducing bridged alkyl groups, the rigidity of the polycyclic compound is increased, while the introduction of π-electron-containing structures is reduced, minimizing π-π interactions within the molecule. This compound exhibits molecular vibrational modes and energy levels similar to existing boron-nitrogen materials, avoiding redshift in emission wavelength. Furthermore, this compound possesses a narrow emission spectrum and a high full width at half maximum (FWHM).

[0036] The compounds provided by this invention are suitable for blue host / dopant systems in the blue series of AM-OLEDs and organic electroluminescent devices. Organic electroluminescent devices containing these compounds have high external quantum efficiency and particularly excellent lifetime performance. Attached Figure Description

[0037] Figure 1 This is a schematic diagram of the structure of an organic electroluminescent device containing the polycyclic compound of the present invention;

[0038] Figure 2 The mass spectrum of intermediate I13-2 from synthesis example 13;

[0039] Figure 3 The UV spectrum of synthesis example 13;

[0040] Figure 4 The PL spectrum of synthesis example 13;

[0041] Figure 5 The mass spectrum of synthesis example 13;

[0042] Figure description: 1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-light-emitting auxiliary layer, 6-light-emitting layer, 7-electron transport layer, 8-electron injection layer, 9-cathode. Detailed Implementation

[0043] To better understand the content of this invention, a detailed description will be provided in conjunction with the accompanying drawings and embodiments.

[0044] The compounds of this invention are applicable to light-emitting elements, display panels, and electronic devices, particularly organic electroluminescent devices. The electronic devices described in this invention are devices comprising at least one layer containing at least one organic compound; the devices may also comprise inorganic materials or layers formed entirely of inorganic materials. Preferably, the electronic devices are organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), and organic solar cells.

[0045] Organic dye-sensitized solar cells (O-DSSC), organic optical detectors, organic photosensors, organic field quenching devices (O-FQD), light-emitting electrochemical cells (LEC), organic laser diodes (O-laser), and organic plasma emitting devices. The electronic devices are preferably organic light-emitting devices (OLEDs). A schematic diagram of an exemplary organic light-emitting device is shown below. Figure 1 As shown.

[0046] Experimental Section

[0047] To better understand the content of this invention, the polycyclic compound, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to embodiments. Various chemical reactions can be applied to the synthesis method of the compound according to one embodiment of this invention. However, it should be noted that the synthesis method of the compound according to one embodiment of this invention is not limited to the synthesis method described below. Unless otherwise stated, subsequent synthesis is carried out in an anhydrous solvent under a protective gas atmosphere. Solvents and reagents can be purchased from conventional reagent suppliers.

[0048] compound

[0049] intermediate synthesis

[0050]

[0051] Sub1-1 (7.8 g; 30 mmol), Sub1-2 (5.64 g; 60 mmol), and Sub1-3 (5.92 g; 35 mmol) were added to toluene (100 mL). Then, under nitrogen protection, [Pd(PPh3)4] (1.73 g, 1.5 mmol) and CsCO3 (19.56 g, 60 mmol) were added to the system. The reaction mixture was then heated to 80 °C with stirring and maintained for 48 hours. After cooling to room temperature, the mixture was quenched with water and separated. The organic phase was filtered and dehydrated with anhydrous magnesium sulfate. After removing the organic solvent by rotary evaporation, the crude product was purified by column chromatography and then recrystallized from dichloromethane and n-heptane. The final product I1-1 was obtained as follows: 6.24 g (yield: 70%), MS (m / z) (M+): 298.

[0052] I1-1 (5.94 g; 20 mmol) and CF3SO3H (30 mL) were then added to cyclohexane (90 mL). Under nitrogen protection, the reaction system was heated to 125 °C with stirring and maintained for 18 hours. After cooling to room temperature, the mixture was quenched with saturated sodium bicarbonate solution and separated. The organic phase was filtered and dehydrated with anhydrous sodium sulfate. After removing the organic solvent by rotary evaporation, the crude product was purified by column chromatography and then recrystallized from dichloromethane and n-heptane. The final product, I1-2, was obtained as follows: 2.89 g (yield: 60%), MS (m / z) (M+): 241.

[0053] I1-2 (2.41 g; 10 mmol), Sub1-4 (2.25 g; 9 mmol), and sodium tert-butoxide (1.05 g, 11 mmol) were added to toluene (30 mL). Under nitrogen protection, bis(dibenzyl) and palladium (274.28 mg, 0.30 mmol) and tri-tert-butylphosphine (121.2 mg, 0.6 mmol) were introduced. The reaction mixture was then heated to reflux and maintained for 10 hours. After cooling to room temperature, the mixture was quenched with water and separated. The organic phase was filtered, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography. The final product was I1-3: 2.77 g (yield: 75%), MS (m / z) (M+): 410.

[0054] I1-3 (4.10 g; 10 mmol), Sub1-5 (2.81 g; 10 mmol), and sodium tert-butoxide (1.05 g, 11 mmol) were added to toluene (50 mL). Under nitrogen protection, bis(dibenzyl) and palladium (274.28 mg, 0.30 mmol) and tri-tert-butylphosphine (121.2 mg, 0.6 mmol) were introduced. The reaction system was then heated to reflux and maintained for 10 hours. After cooling to room temperature, the mixture was quenched with water and separated. The organic phase was filtered and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation, and the crude product was purified by column chromatography. The final product A1 was 4.88 g (yield: 80%), MS (m / z) (M+): 611.

[0055] In addition, by using a method similar to A1, I1-2 can be synthesized through a two-step Buchwald-Hartwig coupling synthesis method to obtain A3, A8, A21, A27, A34, A36, and A40.

[0056] Intermediate I2-2

[0057]

[0058] Under nitrogen protection, [Pd(OAc)2] (0.3 g, 1.3 mmol), K2CO3 (1.79 g, 13 mmol), and Bu4NBr (5 g, 16 mmol) were added to DMF (20 mL). Then, a mixed DMF solution of Sub2-1 (3.85 g; 14 mmol) and Sub1-2 (1.5 g; 16 mmol) was slowly added dropwise to the system. The reaction mixture was then heated to 105 °C with stirring and maintained for 24 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed with water, and separated. The organic phase was filtered and dehydrated with anhydrous sodium sulfate. After removing the organic solvent by rotary evaporation, the crude product was purified by column chromatography and recrystallized from dichloromethane and n-heptane. The final product was I2-2: 1.72 g (yield: 51%), MS (m / z) (M+): 241. A2 can be synthesized using a method similar to A1, through a two-step Buchwald-Hartwig coupling synthesis method.

[0059] Intermediate I4-2

[0060]

[0061] Under nitrogen protection, Sub4-1 (2.32 g, 10 mmol) and Sub4-2 (1.1 g, 10 mmol) were added to 20 mL of THF at -5 °C. Then, a 1.6 M, 1.25 mL, 20 mmol solution of n-butyllithium was slowly added dropwise. The reaction mixture was then heated to 0 °C and maintained for 2 h with stirring. After cooling to room temperature, the mixture was diluted with diethyl ether, washed with water, and separated. The organic phase was filtered, and water was removed using anhydrous sodium sulfate. After removing the organic solvent by rotary evaporation, the crude product was purified by column chromatography. Under nitrogen protection, a solution of crude product, KH (3.2 g, 8 mmol), and iodomethane (1.14 g, 8 mmol) in THF (20 mL) was heated to 40 °C and stirred for 5 h. The mixture was then cooled to room temperature, and 10 M HCl:ethanol (20 mL) was slowly added dropwise. After the addition was complete, the mixture was slowly heated to 93 °C and refluxed for 48 h. The mixture was then cooled to room temperature, neutralized with potassium hydroxide aqueous solution, and separated. The organic phase was filtered, and water was removed using anhydrous sodium sulfate. After removing the organic solvent by rotary evaporation, the crude product was purified by column chromatography and recrystallized from dichloromethane / n-heptane. The final product was I4-2: 0.53 g (yield: 22%), MS (m / z) (M+): 241. A4, A12, A24, and A33 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to that used in A1.

[0062] Intermediate I5-2

[0063]

[0064] The method is the same as for I2-2, except that Sub5-1 (3.85 g; 14 mmol) replaces Sub2-1, and Sub5-2 (1.95 g; 16 mmol) replaces Sub1-2, ultimately yielding product I5-2: 1.69 g (yield: 45%), MS (m / z) (M+): 269. A5, A16, and A20 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to A1.

[0065] Intermediate I6-2

[0066]

[0067] The method is the same as for I2-2, except that Sub6-1 (3.85 g; 14 mmol) replaces Sub2-1, and Sub6-2 (2.18 g; 16 mmol) replaces Sub1-2, ultimately yielding product I6-2: 1.58 g (yield: 40%), MS (m / z) (M+): 283. A6 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to A1.

[0068] Intermediate I7-2

[0069]

[0070] The method is the same as for I2-2, except that Sub7-1 (4.21 g; 14 mmol) is replaced with Sub2-1, finally yielding product I7-2: 1.90 g (yield: 51%), MS (m / z) (M+): 267. A7 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to A1.

[0071] Intermediate I9-2

[0072]

[0073] The method is the same as for I2-2, except that Sub6-1 (3.85 g; 14 mmol) replaces Sub2-1, and Sub9-2 (1.72 g; 16 mmol) replaces Sub1-2, ultimately yielding product I9-2: 1.46 g (yield: 41%), MS (m / z) (M+): 255. A9 and A41 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to A1.

[0074] Intermediate I10-2

[0075]

[0076] The method is the same as for I2-2, except that Sub6-1 (3.85 g; 14 mmol) is replaced with Sub2-1, finally yielding product I10-2: 1.62 g (yield: 48%), MS (m / z) (M+): 241. A10, A14, A15, A18, A22, A23, A25, A26, A28, A29, A30, A31, A35, and A39 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to A1.

[0077] Intermediate I11-2

[0078]

[0079] The method is the same as for I2-2, except that Sub11-1 (4.13 g; 14 mmol) is replaced with Sub2-1, finally yielding product I11-2: 2.00 g (yield: 55%), MS (m / z) (M+): 261. A11 can be synthesized using a similar method to A1, through a two-step Buchwald-Hartwig coupling synthesis.

[0080] Intermediate I13-2

[0081]

[0082] The method is the same as for I2-2, except that Sub13-1 (3.06 g; 14 mmol) is replaced with Sub2-1, finally yielding product I13-2: 1.42 g (yield: 55%), MS (m / z) (M+): 185. A13 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to A1.

[0083] Intermediate I17-2

[0084]

[0085] The method is the same as for I4-2, except that Sub17-1 (2.33 g; 14 mmol) is replaced by Sub4-1, and Sub17-2 (1.38 g; 16 mmol) is replaced by Sub4-2, finally yielding product I17-2: 0.54 g (yield: 20%), MS (m / z) (M+): 269. A17 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to that used for A1.

[0086] Intermediate I19-2

[0087]

[0088] The method is the same as for I2-2, except that Sub19-1 (3.85 g; 14 mmol) replaces Sub2-1, and Sub19-2 (1.47 g; 16 mmol) replaces Sub1-2, finally yielding product I19-2: 1.34 g (yield: 40%), MS (m / z) (M+): 239. A19, A32, and A37 can be synthesized using a two-step Buchwald-Hartwig coupling synthesis method similar to A1.

[0089] Intermediate I38-2

[0090]

[0091] Under nitrogen protection, Sub38-1 (4.1 g, 25 mmol) was added to glacial acetic acid (20 mL) at 60 °C and dissolved with stirring. Then, a solution of Sub38-2 (4.14 g, 30 mmol) in glacial acetic acid (10 mL) was slowly added dropwise to the system. The reaction system was then heated to reflux with stirring and maintained for 2 h. After cooling to room temperature, the solvent was removed by rotary evaporation. The crude product was purified by column chromatography. Under nitrogen protection, the crude product was dissolved in toluene (40 mL). The solution was cooled to -70 °C, and a solution of methyllithium (1.6 M, 32 mL) in n-hexane was slowly added dropwise. After the addition was complete, the temperature was raised to 0 °C, and the mixture was stirred for 5 h. The mixture was then quenched with an aqueous solution and separated. The organic phase was filtered and dehydrated with anhydrous sodium sulfate. After removing the organic solvent by rotary evaporation, the crude product was purified by column chromatography and recrystallized from dichloromethane / n-heptane. The final product I38-2 was obtained: 1.91 g (yield: 27%), MS (m / z) (M+): 283. A38 can be synthesized by a two-step Buchwald-Hartwig coupling synthesis method similar to that of A1.

[0092] Synthesis Example 1

[0093]

[0094] Add A1 (6.11 g; 10 mmol) to 1,2-dichlorobenzene (50 mL), then add boron triiodide (3.92 g, 10 mmol) under nitrogen protection. The reaction mixture was then heated to 120 °C and maintained for 12 hours. After cooling to room temperature, the mixture was quenched with ice water and separated. The organic phase was filtered, and water was removed using anhydrous magnesium sulfate. After removing the organic solvent by rotary evaporation, the crude product was purified by recrystallization from dichloromethane and n-heptane. The final product was B1: 0.74 g (yield: 12%), MS (m / z) (M+): 619.

[0095] Synthesis Example 2

[0096]

[0097] The method was the same as in Example 1, except that A2 (6.51 g; 10 mmol) was used to replace A1, and the final product B2 was obtained: 0.99 g (yield: 15%), MS (m / z) (M+): 659.

[0098] Synthesis Example 3

[0099]

[0100] The method was the same as in Example 1, except that A3 (7.43 g; 10 mmol) was used to replace A1, and the final product B3 was obtained: 0.90 g (yield: 12%), MS (m / z) (M+): 751.

[0101] Synthesis Example 4

[0102]

[0103] The method was the same as in Example 1, except that A4 (6.63 g; 10 mmol) was used to replace A1, and the final product B4 was 1.01 g (yield: 15%), MS (m / z) (M+): 671.

[0104] Synthesis Example 5

[0105]

[0106] The method was the same as in Example 1, except that A5 (6.39 g; 10 mmol) was used instead of A1, and the final product B5 was 0.52 g (yield: 8%), MS (m / z) (M+): 647.

[0107] Synthesis Example 6

[0108]

[0109] The method was the same as in Example 1, except that A6 (7.77 g; 10 mmol) was used to replace A1, and the final product B6 was 0.86 g (yield: 11%), MS (m / z) (M+): 785.

[0110] Synthesis Example 7

[0111]

[0112] The method was the same as in Example 1, except that A7 (6.92 g; 10 mmol) was replaced with A1, and the final product B7 was 0.98 g (yield: 14%), MS (m / z) (M+): 700.

[0113] Synthesis Example 8

[0114]

[0115] The method was the same as in Example 1, except that A8 (7.43 g; 10 mmol) was used instead of A1, and the final product B8 was 1.13 g (yield: 15%), MS (m / z) (M+): 751.

[0116] Synthesis Example 9

[0117]

[0118] The method was the same as in Example 1, except that A9 (7.05 g; 10 mmol) was replaced with A1, and the final product B9 was obtained: 1 g (yield: 14%), MS (m / z) (M+): 713.

[0119] Synthesis Example 10

[0120]

[0121] The method was the same as in Example 1, except that A10 (7.85 g; 10 mmol) was used to replace A1, and the final product B10 was obtained: 0.63 g (yield: 8%), MS (m / z) (M+): 793.

[0122] Synthesis Example 11

[0123]

[0124] The method was the same as in Example 1, except that A11 (6.59 g; 10 mmol) was replaced with A1, and the final product B11 was 0.93 g (yield: 14%), MS (m / z) (M+): 667.

[0125] Synthesis Example 12

[0126]

[0127] The method was the same as in Example 1, except that A12 (6.53 g; 10 mmol) was used to replace A1, and the final product B12 was 0.53 g (yield: 8%), MS (m / z) (M+): 661.

[0128] Synthesis Example 13

[0129]

[0130] The method was the same as in Example 1, except that A13 (5.96 g; 10 mmol) was used to replace A1, and the final product B13 was 0.85 g (yield: 14%), MS (m / z) (M+): 605.

[0131] Figure 3 The UV spectrum of the sample prepared in Example 13 shows that its UVmax = 451 nm and UVonset = 468 nm. Figure 4 The PL spectrum of the sample shows that PLmax = 460 nm and the half-width at half-maximum (WHM) is 23 nm, indicating that the material prepared in this invention is a blue light material with high color purity.

[0132] Synthesis Example 14

[0133]

[0134] The method was the same as in Example 1, except that A14 (7.85 g; 10 mmol) was used to replace A1, and the final product B14 was 0.87 g (yield: 11%), MS (m / z) (M+): 793.

[0135] Synthesis Example 15

[0136]

[0137] The method was the same as in Example 1, except that A15 (7.94 g; 10 mmol) was replaced with A1, and the final product B15 was 1.04 g (yield: 13%), MS (m / z) (M+): 802.

[0138] Synthesis Example 16

[0139]

[0140] The method was the same as in Example 1, except that A16 (7.36 g; 10 mmol) was used to replace A1, and the final product B16 was 0.67 g (yield: 9%), MS (m / z) (M+): 744.

[0141] Synthesis Example 17

[0142]

[0143] The method was the same as in Example 1, except that A17 (6.79 g; 10 mmol) was used instead of A1, and the final product B17 was 0.55 g (yield: 8%), MS (m / z) (M+): 687.

[0144] Synthesis Example 18

[0145]

[0146] The method was the same as in Example 1, except that A18 (6.79 g; 10 mmol) was replaced with A1, and the final product B18 was 0.89 g (yield: 13%), MS (m / z) (M+): 687.

[0147] Synthesis Example 19

[0148]

[0149] The method was the same as in Example 1, except that A19 (8.61 g; 10 mmol) was used instead of A1, and the final product B19 was 1.3 g (yield: 15%), MS (m / z) (M+): 869.

[0150] Synthesis Example 20

[0151]

[0152] The method was the same as in Example 1, except that A20 (7.41 g; 10 mmol) was replaced with A1, and the final product B20 was 0.9 g (yield: 12%), MS (m / z) (M+): 749.

[0153] Synthesis Example 21

[0154]

[0155] The method was the same as in Example 1, except that A21 (6.78 g; 10 mmol) was used to replace A1, and the final product B21 was 0.55 g (yield: 8%), MS (m / z) (M+): 686.

[0156] Synthesis Example 22

[0157]

[0158] The method was the same as in Example 1, except that A22 (6.67 g; 10 mmol) was replaced with A1, and the final product B22 was 0.88 g (yield: 13%), MS (m / z) (M+): 675.

[0159] Synthesis Example 23

[0160]

[0161] The method was the same as in Example 1, except that A23 (7.09 g; 10 mmol) was replaced with A1, and the final product was B23: 1 g (yield: 14%), MS (m / z) (M+): 717.

[0162] Synthesis Example 24

[0163]

[0164] The method was the same as in Example 1, except that A24 (8.4 g; 10 mmol) was replaced with A1, and the final product B24 was obtained: 1.1 g (yield: 13%), MS (m / z) (M+): 848.

[0165] Synthesis Example 25

[0166]

[0167] The method was the same as in Example 1, except that A25 (7.35 g; 10 mmol) was replaced with A1, and the final product B25 was 1.04 g (yield: 14%), MS (m / z) (M+): 743.

[0168] Synthesis Example 26

[0169]

[0170] The method was the same as in Example 1, except that A26 (7.87 g; 10 mmol) was replaced with A1, and the final product B26 was 1.11 g (yield: 14%), MS (m / z) (M+): 795.

[0171] Synthesis Example 27

[0172]

[0173] The method was the same as in Example 1, except that A27 (9.16 g; 10 mmol) was replaced with A1, and the final product B27 was 1.11 g (yield: 12%), MS (m / z) (M+): 924.

[0174] Synthesis Example 28

[0175]

[0176] The method was the same as in Example 1, except that A28 (6.11 g; 10 mmol) was replaced with A1, and the final product B28 was 0.8 g (yield: 13%), MS (m / z) (M+): 619.

[0177] Synthesis Example 29

[0178]

[0179] The method was the same as in Example 1, except that A29 (7.9 g; 10 mmol) was replaced with A1, and the final product B29 was 1.2 g (yield: 15%), MS (m / z) (M+): 798.

[0180] Synthesis Example 30

[0181]

[0182] The method was the same as in Example 1, except that A30 (6.93 g; 10 mmol) was replaced with A1, and the final product B30 was 0.91 g (yield: 13%), MS (m / z) (M+): 701.

[0183] Synthesis Example 31

[0184]

[0185] The method was the same as in Example 1, except that A31 (6.29 g; 10 mmol) was replaced with A1, and the final product B31 was 0.96 g (yield: 15%), MS (m / z) (M+): 637.

[0186] Synthesis Example 32

[0187]

[0188] The method was the same as in Example 1, except that A32 (7.17 g; 10 mmol) was replaced with A1, and the final product B32 was 1.02 g (yield: 14%), MS (m / z) (M+): 725.

[0189] Synthesis Example 33

[0190]

[0191] The method was the same as in Example 1, except that A33 (6.55 g; 10 mmol) was replaced with A1, and the final product B33 was 0.8 g (yield: 12%), MS (m / z) (M+): 663.

[0192] Synthesis Example 34

[0193]

[0194] The method was the same as in Example 1, except that A34 (7.71 g; 10 mmol) was replaced with A1, and the final product B34 was 0.86 g (yield: 11%), MS (m / z) (M+): 779.

[0195] Synthesis Example 35

[0196]

[0197] The method was the same as in Example 1, except that A35 (7.07 g; 10 mmol) was replaced with A1, and the final product B35 was 1.07 g (yield: 15%), MS (m / z) (M+): 715.

[0198] Synthesis Example 36

[0199]

[0200] The method was the same as in Example 1, except that A36 (5.31 g; 10 mmol) was replaced with A1, and the final product B36 was 0.7 g (yield: 13%), MS (m / z) (M+): 539.

[0201] Synthesis Example 37

[0202]

[0203] The method was the same as in Example 1, except that A37 (5.55 g; 10 mmol) was replaced with A1, and the final product B37 was 0.56 g (yield: 10%), MS (m / z) (M+): 563.

[0204] Synthesis Example 38

[0205]

[0206] The method was the same as in Example 1, except that A38 (6.85 g; 10 mmol) was replaced with A1, and the final product B38 was 0.9 g (yield: 13%), MS (m / z) (M+): 693.

[0207] Synthesis Example 39

[0208]

[0209] The method was the same as in Example 1, except that A39 (5.87 g; 10 mmol) was replaced with A1, and the final product B39 was 0.71 g (yield: 12%), MS (m / z) (M+): 595.

[0210] Synthesis Example 40

[0211]

[0212] The method was the same as in Example 1, except that A40 (8.76 g; 10 mmol) was replaced with A1, and the final product B40 was 0.88 g (yield: 10%), MS (m / z) (M+): 884.

[0213] Synthesis Example 41

[0214]

[0215] The method was the same as in Example 1, except that A41 (6.65 g; 10 mmol) was used instead of A1, and the final product B41 was 0.81 g (yield: 12%), MS (m / z) (M+): 673.

[0216] OLED manufacturing and characterization

[0217] Device Examples

[0218] The organic electroluminescent device provided by the present invention includes an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode sequentially disposed on a substrate.

[0219] Furthermore, the hole transport region includes a hole transport layer and a light-emitting auxiliary layer; the electron transport region includes an electron transport layer and an electron injection layer.

[0220] Furthermore, the light-emitting layer is composed of a host material and doped materials, and the host material of the light-emitting layer can be composed of one molecular material or multiple molecular materials.

[0221] The polycyclic compound described in this invention can be used as one or more layers of the above-mentioned organic electroluminescent device, preferably as a doping material for the light-emitting layer of the device.

[0222] In this embodiment, the anode uses a commonly used anode material in the art, such as ITO, Ag, or their multilayer structures. The hole injection unit uses a commonly used hole injection material in the art, and is doped with F4TCNQ, HATCN, NDP-9, etc. The hole transport unit uses a commonly used hole transport material in the art. The light-emitting unit uses a commonly used light-emitting material in the art, for example, it can be composed of a host material and an emitting guest material, the emitting guest material can be an organic material such as a pyrene compound, or a metal complex (such as metal Ir, Pt, etc.). The electron transport unit uses a commonly used electron transport material in the art. The electron injection layer uses a commonly used electron injection material in the art, such as Liq, LiF, Yb, etc. The cathode uses a commonly used material in the art, such as metal Al, Ag, or metal mixtures (Ag-doped Mg, Ag-doped Ca, etc.).

[0223] The electrode fabrication method and the deposition method of each functional layer in this embodiment are conventional methods in the art, such as vacuum thermal evaporation or inkjet printing, and will not be described in detail here. Only some process details and testing methods in the fabrication process are supplemented as follows:

[0224] Device Example 1

[0225] In the fabrication of blue light-emitting devices, firstly, a hole injection layer is formed on the ITO layer (anode) formed on the substrate by vacuum deposition of HTL and F4TCNQ (mass ratio 97:3) with a thickness of 10 nm. Secondly, on the hole injection layer, a hole transport layer is formed by vacuum deposition of HTL with a thickness of 120 nm. Next, on the hole transport layer, a light-emitting auxiliary layer is formed by vacuum deposition of B prime with a thickness of 10 nm. Then, on the light-emitting auxiliary layer, a light-emitting layer is formed by vacuum deposition of a mixture of BH as the host and B1 as the dopant with a mass ratio of 98:2, with a thickness of 20 nm. Next, on the light-emitting layer, an electron transport layer is formed by vacuum deposition of TmPyPb and Liq with a thickness of 40 nm. Then, on the electron transport layer, an electron injection layer is formed by depositing Liq with a thickness of 0.2 nm. Finally, on the electron injection layer, an aluminum (Al) cathode is formed by depositing with a thickness of 150 nm, thus fabricating a blue organic light-emitting device.

[0226]

[0227] Organic electroluminescent devices were prepared by using the above method to manufacture the compounds described in the examples. Specifically, blue light-emitting organic electroluminescent devices (Examples 2-41) were prepared by replacing B1 with B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12, B13, B14, B15, B16, B17, B18, B19, B20, B21, B22, B23, B24, B25, B26, B27, B28, B29, B30, B31, B32, B33, B34, B35, B36, B37, B38, B39, B40, and B41.

[0228] Device Comparison

[0229] Using the above method, an organic light-emitting device was fabricated using compound 1BD-01 as a comparative example. Specifically, a blue organic light-emitting device was fabricated by replacing B1 with BD-01 as comparative example 1.

[0230]

[0231] The OLED devices described above were tested using standard methods. For this purpose, J = 10 mA / cm² was used. 2The driving voltage, luminance, electroluminescent current efficiency (in cd / A), and external quantum efficiency (EQE, in percentage) of the organic electroluminescent device were determined at a given current density, calculated as a function of luminescence density from the current / voltage / luminescence density characteristic line (IVL characteristic line) exhibiting Lambertian emission characteristics, and the emission spectrum. The lifetime LT was defined as the time after which, when operating at a constant current J, the luminance decreased from the initial luminance L0 to a specific proportion L1; J = 50 mA / cm². 2 The statement L1 = 90% refers to a value of 50 mA / cm. 2 When operating below the threshold, the luminous intensity decreases to 90% of its initial value L0 after time LT. Similarly, J = 20 mA / cm² 2 L1 = 80% means that at 20 mA / cm 2 When operating below the threshold, the luminous intensity drops to 80% of its initial value L0 after time LT.

[0232] The data for various OLED devices are summarized in Table 1. The parameters of the examples and comparative examples are compared to demonstrate the performance data of the various OLED devices.

[0233] The testing instruments and methods used to perform performance testing on the OLED devices of the above embodiments and comparative examples are as follows:

[0234] Brightness was tested using a PhotoResearch PR-635 spectral scanner;

[0235] Current density and turn-on voltage: tested using a Keithley 2400 digital source meter;

[0236] Life test: The LT-96ch life test device was used.

[0237] The performance test results of the above devices are listed in Table 1.

[0238] Table 1 Performance test results of blue light devices

[0239]

[0240]

[0241] As shown in Table 1 above, the organic electroluminescent device prepared from the polycyclic organic compound of this invention exhibits significantly improved external quantum efficiency and lifetime compared to Comparative Example 1. This is because the bridge ring structure in the material structure facilitates the uniform dispersion of the dopant material within the host material, preventing SSA quenching and thus improving device efficiency. The device in the above embodiment achieves an external quantum efficiency of 20 mA / cm². 2When operating, the time it takes for the luminous intensity to drop to 90% of its initial value L0 is significantly longer compared to the comparative device. This is because, compared to conventional aromatic rings, the bridge ring does not have a large number of conjugated π electrons, thus significantly reducing the electron cloud density of connected N electrons and effectively avoiding redshift of luminescence. At the same time, the bridge ring has a certain rigidity, fewer unsaturated bonds, and good thermal stability. Therefore, the organic electroluminescent device prepared using the organic compound of this invention has a longer lifespan.

[0242] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A polycyclic compound, characterized by, The compound is selected from one of the following structures: 。 2. The polycyclic compound of claim 1, wherein In the polycyclic compound, each hydrogen atom in the ring structure is independently replaced by deuterium.

3. An organic electroluminescent device, characterized by comprising It includes an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode sequentially disposed on a substrate; wherein the light-emitting layer includes a host material and a dopant material, and the dopant material includes one or more polycyclic compounds as described in claim 1 or 2.

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