A compound having a benzobisoxazole structure and an organic light emitting device using the same

Abstract

The application belongs to the technical field of organic semiconductors, and discloses a compound with a benzobisoxazole structure and an organic electroluminescent device containing the compound. The compound with the benzobisoxazole structure has the following structure: the compound is used as a charge transport material and a charge injection material, especially a hole injection layer material, in an organic electroluminescent device, and can greatly improve the voltage and service life and other performances of the organic electroluminescent device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic semiconductors, and particularly relates to a compound with a benzobisoxazole structure and an organic electroluminescent device comprising the compound. BACKGROUND

[0002] Organic light-emitting diodes (OLED) have the characteristics of self-luminescence, wide viewing angle, low driving voltage, thin device, easy realization of large-area preparation and flexibility, and are widely used in display and lighting fields.

[0003] The device structure of OLED mainly includes an ITO anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a metal cathode. The preparation methods of these functional layers mainly include vacuum evaporation and solution processing. The hole injection layer and the electron injection layer are used in OLED devices to promote the injection of charges, and the hole transport layer and the electron transport layer are used to promote the transport of charges. The hole injection layer is a functional layer formed by one or more materials. The method of one material is to use a material with a deep lowest unoccupied molecular orbital (LUMO) energy level, and the method of multiple materials is to form by doping a P-type, deep LUMO material into a hole transport material. Therefore, a deep LUMO energy level is crucial for the hole injection layer material. However, materials with a deep LUMO energy level usually have one or more strong electron-withdrawing substituents, making them difficult to synthesize. And it is difficult to simultaneously realize deep LUMO energy level, high stability and high film-forming property. Since the hole injection layer has a great influence on the voltage, efficiency and lifetime of the OLED device, it is very important and urgent to develop a P-type material with a deep LUMO energy level, high stability and high film-forming property in the field of organic electroluminescence. SUMMARY

[0004] In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present application is to provide a compound with a benzobisoxazole structure. The compound can be used as a charge transport material and a charge injection material in an organic electroluminescent device, especially a hole injection layer material, which can greatly improve the performance of the voltage and lifetime of the organic electroluminescent device.

[0005] Another purpose of the present application is to provide a preparation method of the compound with a benzobisoxazole structure.

[0006] Another purpose of the present application is to provide an electronic device comprising the compound with a benzobisoxazole structure.

[0007] A compound with a benzobisoxazole structure is a compound with a structure of formula (I):

[0008]

[0009] Wherein, Z1 and Z2 are both relatively independently selected from CR”R”'; R” and R”' are relatively independently selected from one of hydrogen, halogen, cyano, halogen-substituted alkyl, halogen-substituted aryl, halogen-substituted heteroaryl, sulfonyl-substituted aromatic, sulfonyl-substituted heteroaryl, cyano-substituted alkyl, cyano-substituted aromatic, cyano-substituted heteroaryl, cyano and halogen co-substituted aromatic, and cyano and halogen co-substituted heteroaryl.

[0010] R1 and R2, each time appearing, are selected from one of the following groups: deuterium, substituted or unsubstituted deuterated alkyl groups having 1-30 carbon atoms, substituted or unsubstituted deuterated alkoxy groups having 1-30 carbon atoms, substituted or unsubstituted deuterated aryl groups having 6-30 carbon atoms, and substituted or unsubstituted deuterated heteroaryl groups having 6-30 carbon atoms, and at least one of R1 and R2 is an electron-withdrawing group; wherein deuterated alkyl, deuterated alkoxy, and deuterated aryl refer to all hydrogen atoms on the deuterated alkyl, alkoxy, aryl, or heteroaryl group; substitution refers to at least one of the following: deuterium halogenated, -CF3, -C3F7, -C4F9, -C5F... 11 -C6F 13 , -OCF3, -OC2F5, -OC3F7, -OC4F9, -SF5, -SCF 3、 The substituted group is at least one of the following: -SO2CF3, -SO2CD3, -NO2, alkyl having 1-20 carbon atoms, cycloalkyl having 3-20 cyclic carbon atoms, heteroalkyl having 1-20 carbon atoms, alkoxy having 1-20 carbon atoms, alkenyl having 2-20 carbon atoms, alkynyl having 2-20 carbon atoms, aryl having 6-12 carbon atoms, heteroaryl having 3-12 carbon atoms, amino having 0-20 cyclic carbon atoms, acyl having 0-20 cyclic carbon atoms, carbonyl having 0-20 cyclic carbon atoms, carbonyl acid having 0-20 cyclic carbon atoms, ester having 0-20 cyclic carbon atoms, cyano having 0-20 cyclic carbon atoms, isocyano having 0-20 cyclic carbon atoms, nitro having 0-20 cyclic carbon atoms, and sulfonyl having 0-20 cyclic carbon atoms.

[0011] Preferably, the electron withdrawing group is selected from one or a combination of halogen, nitro, acyl, carbonyl, carboxylic acid, ester, cyano, SF5, sulfonyl, deuterated nitrogen heteroaromatic ring group, alkyl group having 1-20 carbon atoms, cycloalkyl group having 3-20 ring carbon atoms, heteroalkyl group having 1-20 carbon atoms, alkoxy group having 1-20 carbon atoms, alkenyl group having 2-20 carbon atoms, alkynyl group having 2-20 carbon atoms, aryl group having 6-12 carbon atoms, and heteroaryl group having 3-12 carbon atoms. More preferably, the electron withdrawing group is selected from one or a combination of F, CF3, OCF3, SF5, SO2CF3, cyano, and pyrimidinyl.

[0012] Preferably, Z1and Z2are the same or different at each occurrence and are selected from one or a combination of the following structures:

[0013]

[0014]

[0015] wherein Ar is selected from one or a combination of substituted or unsubstituted aryl group having 6-30 carbon atoms, and substituted or unsubstituted heteroaryl group having 3-30 carbon atoms at each occurrence;

[0016] In the present application, “*” indicates the position of the Z1and Z2groups connecting to the oxazole in the benzodioxazole of Formula I.

[0017] Preferably, R1and R2are the same or different at each occurrence and are selected from one or a combination of the following structures:

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] In the present application, “*” indicates the position of the R1and R2groups connecting to the benzene in the benzodioxazole of Formula I.

[0025] A method of preparing a compound having a benzodioxole structure as described above, comprising the steps of:

[0026] (1) 2,5-diamino-3,6-dibromo-benzene-1,4-diol, HC(OEt)3, Y(OTf)3 in a solvent to obtain intermediate 1;

[0027] (2) reacting intermediate 1 with R1-B(OH)2, R2-B(OH)2 in the presence of a base and a catalyst in a solvent to obtain intermediate 2;

[0028] (3) reacting intermediate 2 with n-butyllithium and then adding elemental iodine to continue the reaction to obtain intermediate 3;

[0029] (4) adding NaH to CR'R" to react, and then adding intermediate 3 to continue the reaction to obtain intermediate 4;

[0030] (5) adding PIFA to intermediate 4 to react in a solvent to obtain a compound having a benzobisoxazole structure.

[0031]

[0032] The solvent in step (1) is preferably DMSO; and the reaction is preferably stirring at 55-65°C overnight.

[0033] The solvent in step (2) is dioxane, and the reaction is preferably heated to reflux overnight.

[0034] In step (3), the reaction of intermediate 2 with n-butyllithium means stirring at -85—-95°C for 1h and then warming to -75—-85°C for 8h; and the addition of elemental iodine to continue the reaction means stirring at room temperature overnight.

[0035] In step (4), the addition of NaH to CR'R" to react means adding NaH at -10—5°C, and then warming to room temperature and stirring for 15—35min; and the addition of intermediate 3 to continue the reaction means adding intermediate 3 and then warming to 85—95°C to continue stirring for 24—48h.

[0036] In step (5), the addition of PIFA to intermediate 4 means adding at -10—5°C, and then stirring at room temperature for 2—5 days. The solvent is preferably dichloromethane.

[0037] The use of a compound having a benzobisoxazole structure as described above in an organic electroluminescent device, especially as a hole injection material.

[0038] According to one embodiment of the present application, an electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer is a hole injection layer, and the hole injection layer is formed of the compound of formula (I) alone.

[0039] According to one embodiment of the present application, an electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer is a hole injection layer, and the hole injection layer is formed of the compound of formula (I) alone.

[0040] According to one embodiment of the present application, the molar doping ratio of the compound to the hole transport material is 10:1 to 1:100.

[0041] According to another embodiment of the present application, a compound formulation comprising the compound represented by formula I is also disclosed. The specific structure of the compound is shown in the aforementioned formula (I).

[0042] The compound having a benzobisoxazole structure disclosed in the present application can be used as a charge transport material and a charge injection material in an organic electroluminescent device. These compounds can greatly improve the performance of the organic electroluminescent device, such as voltage and lifetime.

[0043] Devices manufactured according to embodiments of the present application can be incorporated into various consumer products having one or more electronic component modules of the device. Some examples of these consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, flat panel displays, flexible displays, smart phones, wearable devices, smart watches, smart phones, digital cameras, camcorders.

[0044] The present application has the following beneficial technical effects relative to the prior art:

[0045] The compound can be used as a charge transport material, a charge injection material, and a charge generation material in an electroluminescent device. These novel compounds can greatly improve the performance of the organic electroluminescent device, such as voltage and lifetime. DETAILED DESCRIPTION

[0046] The present application will be further described in conjunction with the following examples, but the embodiments of the present application are not limited thereto. In the examples, unless otherwise specified, the procedures were carried out under conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used, unless otherwise specified, were all conventional products available on the market.

[0047] Material synthesis examples:

[0048] The preparation method of the compounds of the present application is not limited, and the following compounds are exemplified typically but not limitatively, and the synthetic routes and preparation methods thereof are as follows:

[0049] Synthesis Example 1: Synthesis of compound 59

[0050] Step 1: Synthesis of intermediate M59a

[0051]

[0052] Under nitrogen protection, HC(OEt)3(11.1 g, 75 mmol), Y(OTf)3(1.07 g, 4 mmol), 2,5-diamino-3,6-dibromo-benzene-1,4-diol (4.47 g, 15 mmol), 100 mL DMSO solvent were added into a 500 mL three-necked flask. The reaction was heated and stirred overnight at 60°C. 500 mL DCM / PE (v:v = 1:1) was added into the three-necked flask, and the solid was collected by filtration and washed with acetone. After drying by filtration, a white solid (3.58 g, yield: 75%) was obtained. MALDI-TOF-MS: m / z = 317.92 (M + ). Elemental analysis (C8H2Br2N2O2): C 29.82, H 0.50, N 8.69.

[0053] Step 2: Synthesis of intermediate M59b

[0054] Under nitrogen protection, Pd(OAc)2(450 mg, 10 mol%, 2.0 mmol), XPhos (2.0 g, 4.2 mmol), intermediate M59a (6.36 g, 20 mmol), deuterated p-propoxyphenylboronic acid (11.28 g, 80 mmol), potassium carbonate (16.68 g, 120 mmol), 100 mL dioxane solvent were added into a 500 mL three-necked flask. The reaction was heated and stirred overnight at 110°C under reflux. After the reaction was completed, the reaction mixture was filtered with diatomite, washed with dichloromethane, and separated by silica gel column chromatography to obtain a white solid (6.38 g, yield: 91%). MALDI-TOF-MS: m / z = 350.36 (M + ). Elemental analysis (C 26 H2D8F 14C 45.13, H 2.50, N 3.92.

[0055] Step 3: Synthesis of intermediate M59c

[0056]

[0057] To a 500 mL three-necked flask was added intermediate M59b (3.15 g, 9 mmol) in 100 mL of dry THF under nitrogen protection. The mixture was cooled to -94 °C under stirring, then n-butyllithium (13.8 mL, 20.93 mmol, 1.6 M in hexane) was added dropwise. After the addition was completed, the mixture was stirred at -94 °C for 1 h, then the temperature was slowly raised to -78 °C and the reaction was continued for 8 h. A solution of iodine (6.93 g, 27.3 mmol) in 15 mL of THF was added dropwise. After the addition was completed, the mixture was slowly warmed to room temperature and stirred overnight. A small amount of saturated aqueous ammonium chloride solution was added to quench the reaction, then celite was added directly to the mixture. The mixture was purified by silica gel column chromatography to give the product M59c (3.25 g, yield: 60%) as a white solid. MALDI-TOF-MS: m / z = 602.15 (M + ). Elemental analysis (C 26 D8F 14 I2N2O4): C 33.10, D 1.57, N 2.86.

[0058] Step 4: Synthesis of intermediate M59d

[0059] Under nitrogen protection, malononitrile (2.78 g, 42 mmol) was added to 70 mL of dry DMF, and NaH (1.67 g, 42 mmol, 60% content) was added in portions at 0 °C. The mixture was stirred at 0 °C for 10 min, then the temperature was slowly raised to room temperature and the reaction was continued for 20 min. Then M59c (4.22 g, 7 mmol) and Pd(PPh3)4(1.62 g, 1.4 mmol) were added, and the temperature was gradually raised to 90 °C. The reaction was continued for 36 h, then the mixture was poured into ice water, and dilute hydrochloric acid was added to adjust the pH to <1. A large amount of yellow solid was precipitated after stirring, and the solid was collected by filtration. The yellow solid was washed with dichloromethane, and then washed with dichloromethane twice to give the yellow solid M59d (3.28 g, yield: 98%). MALDI-TOF-MS: m / z = 478.45 (M + ). Elemental analysis (C 32 H2D8F 14 N6O4): C 46.95, H 2.09, N 10.14.

[0060] Step 5: Synthesis of compound 59

[0061]

[0062] Into a 1000 mL three-necked flask was placed intermediate M59d (2.39 g, 5 mmol) and 150 mL of dichloromethane solvent under nitrogen protection. The reaction mixture was cooled to 0 °C under stirring, then PIFA (6.45 g, 15 mmol) was added portionwise. The reaction mixture was stirred for 1 h at 0 °C, then allowed to warm to room temperature. The reaction mixture was stirred for 3 days at room temperature, then 400 mL of n-hexane was added to the reaction mixture. The mixture was stirred for 10 min, then filtered to give a dark green solid. The solid was washed with DCM / PE mixture (v:v = 1:1) twice, then dried to give dark green solid compound 59 (1.98 g, yield: 83%). MALDI-TOF-MS: m / z = 476.44 (M+H)+. Elemental analysis (C + ). Elemental analysis (C 32 D8F 14 N6O4): C 47.02, H 1.83, N 10.18.

[0063] Synthesis Example 2: Synthesis of compound 92

[0064] Step 1: Synthesis of intermediate M92a

[0065] Into a 500 mL three-necked flask was placed Pd(OAc)2 (450 mg, 10 mol%, 2.0 mmol), XPhos (2.0 g, 4.2 mmol), intermediate M59a (6.36 g, 20 mmol), deuterated 2-trifluoromethylpyridine-4-boronic acid (15.51 g, 80 mmol), potassium carbonate (16.68 g, 120 mmol), and 100 mL of dioxane solvent under nitrogen protection. The reaction mixture was heated to 110 °C and stirred overnight. After the reaction was completed, the mixture was filtered with celite and washed with dichloromethane. The mixture was separated by silica gel column chromatography to give a white solid (7.76 g, yield: 85%). MALDI-TOF-MS: m / z = 456.34 (M+H)+. Elemental analysis (C + ). Elemental analysis (C 20 H2D6F6N4O2): C 52.50, H 2.94, N 12.12.

[0066] Step 2: Synthesis of intermediate M92b

[0067]

[0068] Into a 500 mL three-necked flask, was placed intermediate M92a (4.11 g, 9 mmol) in 100 mL of dry THF under nitrogen atmosphere. The reaction mixture was cooled to -94 °C under stirring, then n-butyllithium (13.8 mL, 20.93 mmol, 1.6 M in hexane) was added dropwise. After the addition was completed, the reaction mixture was stirred at -94 °C for 1 h, then the temperature was slowly raised to -78 °C and the reaction was continued for 8 h. Then, 15 mL of iodine (6.93 g, 27.3 mmol) in THF was added dropwise. After the addition was completed, the reaction mixture was slowly warmed to room temperature and stirred overnight. A small amount of saturated aqueous ammonium chloride solution was added to quench the reaction, then celite was added directly to the mixture. The mixture was purified by silica gel column chromatography to give the white solid product M92b (3.44 g, yield: 54 %). MALDI-TOF-MS: m / z = 708.13 (M + ). Elemental analysis (C 20 D6F6I2N4O2): C 33.80, H 1.58, N 7.75.

[0069] Step 3: Synthesis of intermediate M92c

[0070] Under nitrogen atmosphere, malononitrile (2.78 g, 42 mmol) was added to 70 mL of dry DMF, NaH (1.67 g, 42 mmol, 60 % purity) was added in portions at 0 °C, the reaction mixture was stirred at 0 °C for 10 min, then the temperature was slowly raised to room temperature and the reaction was continued for 20 min. Then, M92b (4.96 g, 7 mmol) and Pd(PPh3)4(1.62 g, 1.4 mmol) were added, the temperature was gradually raised to 90 °C and the reaction was continued for 36 h. The reaction mixture was poured into ice water, diluted with dilute hydrochloric acid to adjust pH < 1. A large amount of yellow solid was precipitated after stirring. The solid was collected by filtration, washed with dichloromethane, and then washed with dichloromethane twice to give yellow solid M92c (3.68 g, yield: 90 %). 1 H NMR (500 MHz, CDC13) δ (ppm): 4.78 (m, 2H). MALDI-TOF-MS: m / z = 584.43 (M + ). Elemental analysis (C 26 H2D6F6N8O2): C 53.35, H 2.30, N 19.02.

[0071] Step 4: Synthesis of compound 92

[0072]

[0073] Into a 1000 mL three-necked flask was placed intermediate M92c (2.92 g, 5 mmol) in 150 mL of dichloromethane solvent under nitrogen protection. The reaction mixture was cooled to 0 °C under stirring, then PIFA (6.45 g, 15 mmol) was added portionwise. The reaction mixture was stirred for 1 h at 0 °C, then allowed to warm to room temperature. The reaction mixture was stirred for 3 days at room temperature, then 400 mL of n-hexane was added to the reaction mixture. The reaction mixture was filtered after stirring for 10 min. The resulting dark green solid was washed with DCM / PE mixture (v:v = 1:1) twice, and finally dark green solid compound 92 (2.18 g, yield: 75%) was obtained. MALDI-TOF-MS: m / z = 582.42 (M + ). Elemental analysis (C 26 D6F6N8O2): C 53.49, H 1.95, N 19.11.

[0074] Synthesis Example 3: Synthesis of compound 175

[0075] Step 1: Synthesis of intermediate M175a

[0076] Into a 500 mL three-necked flask was placed Pd(OAc)2 (450 mg, 10 mol%, 2.0 mmol), XPhos (2.0 g, 4.2 mmol), intermediate M59a (6.36 g, 20 mmol), (3’-(trifluoromethoxy)-[1,1’-biphenyl]-3-yl-2,2’,4,4’,5,5’,6,6’-d8)boronic acid (23.21 g, 80 mmol), potassium carbonate (16.68 g, 120 mmol) in 100 mL of dioxane solvent under nitrogen protection. The reaction mixture was heated to 110 °C and stirred overnight. After the reaction was completed, the reaction mixture was filtered with celite and washed with dichloromethane. The resulting white solid was separated by silica gel column chromatography (10.38 g, yield: 80%). MALDI-TOF-MS: m / z = 648.62 (M + ). Elemental analysis (C 34 H2D 16 F6N2O4): C 62.79, H 5.13, N 4.12.

[0077] Step 2: Synthesis of intermediate M175b

[0078]

[0079] Into a 500 mL three-necked flask, was placed intermediate M175a (5.84 g, 9 mmol) in 100 mL of dry THF under nitrogen. The reaction mixture was cooled to -94 °C with stirring, and then n-butyllithium (13.8 mL, 20.93 mmol, 1.6 M in hexane) was added dropwise. After the addition was completed, the reaction mixture was stirred at -94 °C for 1 h, and then the temperature was slowly raised to -78 °C and stirred for 8 h. A solution of iodine (6.93 g, 27.3 mmol) in 15 mL of THF was added dropwise, and the reaction mixture was stirred at room temperature overnight. The reaction was quenched by the addition of a small amount of saturated aqueous ammonium chloride solution, and then celite was added directly to the mixture. The mixture was purified by column chromatography on silica gel to give the product M175b (4.54 g, 56% yield) as a white solid. MALDI-TOF-MS: m / z = 900.41 (M + ). Elemental analysis (C 34 D 16 F6I2N2O4): C 45.16, H 3.32, N 2.97.

[0080] Step 3: Synthesis of intermediate M175c

[0081] Under nitrogen, malononitrile (2.78 g, 42 mmol) was added to 70 mL of dry DMF, and NaH (1.67 g, 42 mmol, 60% content) was added in portions at 0 °C. The reaction mixture was stirred at 0 °C for 10 min, and then the temperature was slowly raised to room temperature. The reaction mixture was stirred at room temperature for 20 min, and then M175b (6.30 g, 7 mmol) and Pd(PPh3)4(1.62 g, 1.4 mmol) were added. The reaction mixture was heated to 90 °C, and stirred at 90 °C for 36 h. The reaction mixture was poured into ice water, and the pH was adjusted to <1 by the addition of dilute hydrochloric acid. A large amount of yellow solid was precipitated upon stirring. The solid was collected by filtration, and washed with dichloromethane. The yellow solid was washed with dichloromethane twice more, and then filtered to give M175c (4.62 g, 85% yield) as a yellow solid. MALDI-TOF-MS: m / z = 776.71 (M + ). Elemental analysis (C 40 H2D 16 F6N6O4): C 61.69, H 4.28, N 10.63.

[0082] Step 4: Synthesis of compound 175

[0083]

[0084] Into a 1000 mL three-necked flask was placed intermediate M175c (3.88 g, 5 mmol) and 150 mL of dichloromethane solvent under nitrogen protection. The reaction mixture was cooled to 0 °C under stirring, then PIFA (6.45 g, 15 mmol) was added portionwise. The reaction mixture was stirred for 1 h, then warmed to room temperature. The reaction mixture was stirred at room temperature for 3 days, then 400 mL of n-hexane was added. The reaction mixture was filtered after stirring for 10 min. The resulting dark green solid was washed with DCM / PE mixture (v:v = 1 : 1) twice, and finally dark green solid compound 175 (2.79 g, yield: 72%) was obtained. MALDI-TOF-MS: m / z = 774.69 (M + ). Elemental analysis (C 40 D 16 F6N6O4): C 61.78, H 4.01, N 10.60.

[0085] Synthesis Example 4: Synthesis of compound 234

[0086] Step 1: Synthesis of intermediate M234a

[0087] Into a 500 mL three-necked flask was placed Pd(OAc)2 (450 mg, 10 mol%, 2.0 mmol), XPhos (2.0 g, 4.2 mmol), intermediate M59a (6.36 g, 20 mmol), (2',3-di(trifluoromethyl)-[1,1'-biphenyl]-4-yl-2,3',4',5,5',6,6'-d7)boronic acid (27.29 g, 80 mmol), potassium carbonate (16.68 g, 120 mmol), and 100 mL of dioxane solvent under nitrogen protection. The reaction mixture was heated to 110 °C and stirred overnight. After the reaction was completed, the reaction mixture was filtered with celite and washed with dichloromethane. The resulting white solid was separated by silica gel column chromatography (10.96 g, yield: 73%). MALDI-TOF-MS: m / z = 750.60 (M + ).

[0088] Step 2: Synthesis of intermediate M234b

[0089]

[0090] Into a 500 mL three-necked flask, was placed intermediate M234a (6.76 g, 9 mmol) in 100 mL of dry THF under nitrogen. The reaction mixture was cooled to -94 °C under stirring, then n-butyllithium (13.8 mL, 20.93 mmol, 1.6 M in hexane) was added dropwise. After the addition was completed, the reaction mixture was stirred at -94 °C for 1 h, then the temperature was slowly raised to -78 °C and the reaction was continued for 8 h. A solution of iodine (6.93 g, 27.3 mmol) in 15 mL of THF was added dropwise. After the addition was completed, the reaction mixture was slowly warmed to room temperature and stirred overnight. A small amount of saturated aqueous ammonium chloride solution was added to quench the reaction, then celite was added directly to the mixture. The mixture was purified by silica gel column chromatography to give the product M234b (4.69 g, yield: 52%) as a white solid. MALDI-TOF-MS: m / z = 1002.4 (M + ). Elemental analysis (C 36 D 14 F 12 I2N2O2): C 42.97, H 2.63, N 2.62.

[0091] Step 3: Synthesis of intermediate M234c

[0092] Under nitrogen, malononitrile (2.78 g, 42 mmol) was added to 70 mL of dry DMF, NaH (1.67 g, 42 mmol, 60% content) was added in portions at 0 °C, the reaction mixture was stirred at 0 °C for 10 min, then the temperature was slowly raised to room temperature and the reaction was continued for 20 min. M234b (7.01 g, 7 mmol) and Pd(PPh3)4(1.62 g, 1.4 mmol) were added, the temperature was gradually raised to 90 °C and the reaction was continued for 36 h. The reaction mixture was poured into ice water, diluted with dilute hydrochloric acid to adjust pH < 1, then a large amount of yellow solid was precipitated after stirring. The solid was collected by filtration, washed with dichloromethane, and then washed with dichloromethane twice to give yellow solid M234c (5.04 g, yield: 82%). MALDI-TOF-MS: m / z = 877.69 (M + ). Elemental analysis (C 42 H2D 14 F 12 N6O2): C 57.29, H 3.30, N 9.43.

[0093] Step 4: Synthesis of compound 234

[0094]

[0095] Into a 1000 mL three-necked flask was placed intermediate M234c (4.39 g, 5 mmol) and 150 mL of dichloromethane solvent under nitrogen protection. The reaction mixture was cooled to 0 °C under stirring, then PIFA (6.45 g, 15 mmol) was added portionwise. The reaction mixture was stirred for 1 h at 0 °C, then warmed to room temperature. The reaction mixture was stirred for 3 days at room temperature, then 400 mL of n-hexane was added to the reaction mixture. The mixture was stirred for 10 min, then filtered to give a dark green solid. The solid was washed with DCM / PE mixture (v:v = 1:1) twice, then dried to give dark green solid compound 234 (3.06 g, yield: 70%). MALDI-TOF-MS: m / z = 875.67 (M + ). Elemental analysis (C 42 D 14 F 12 N6O2): C 57.39, H 3.01, N 9.43.

[0096] Synthesis Example 5: Synthesis of compound 323

[0097] Step 1: Synthesis of intermediate M323a

[0098]

[0099] Into a 500 mL three-necked flask was placed Pd(OAc)2 (450 mg, 10 mol%, 2.0 mmol), XPhos (2.0 g, 4.2 mmol), intermediate M59a (6.36 g, 20 mmol), (4-((trifluoromethyl)sulfonyl)phenyl-2,3,5,6-d4)boronic acid (20.64 g, 80 mmol), potassium carbonate (16.68 g, 120 mmol), and 100 mL of dioxane solvent under nitrogen protection. The reaction mixture was heated to 110 °C and stirred overnight. After the reaction was completed, the mixture was filtered with celite and washed with dichloromethane. The mixture was separated by silica gel column chromatography to give white solid M323a-1 (6.32 g, yield: 70%). MALDI-TOF-MS: m / z = 451.21 (M + ). According to the same preparation method as M323a-1, intermediate (4-(4,4,4,4,4,4,4,4,4-perfluoro-4λ 12 -Butane-1,3-diyl)benzene-2,3,5,6-d4)boronic acid reacted with M323a-1 to give M323a (4.83 g, yield: 65%). MALDI-TOF-MS: m / z = 670.45 (M + ). Elemental analysis (C 25 H2D8F 12 N2O4S): C 44.67, H 2.58, N 4.06.

[0100] Step 2: Synthesis of intermediate M323b

[0101]

[0102] To a 500 mL three-necked flask was added intermediate M323a (4.06 g, 9 mmol) in 100 mL of dry THF under nitrogen protection. The mixture was cooled to -94 °C under stirring, then n-butyllithium (13.8 mL, 20.93 mmol, 1.6 M in hexane) was added dropwise. After the addition was completed, the mixture was stirred at -94 °C for 1 h, then slowly warmed to -78 °C and stirred for 8 h. A solution of iodine (6.93 g, 27.3 mmol) in 15 mL of THF was added dropwise. After the addition was completed, the mixture was slowly warmed to room temperature and stirred overnight. A small amount of saturated aqueous ammonium chloride solution was added to quench the reaction, then celite was added directly to the mixture. The mixture was purified by silica gel column chromatography to give the product M323b (2.80 g, yield: 50%) as a white solid. MALDI-TOF-MS: m / z = 922.25 (M + ). Elemental analysis (C 25 D8F 12 I2N2O4S): C 32.42, H 1.60, N 2.98.

[0103] Step 3: Synthesis of intermediate M323c

[0104]

[0105] A17 (7.78 g, 42 mmol) was added to 70 mL of dry DMF under nitrogen protection, and NaH (1.67 g, 42 mmol, 60% content) was added in portions at 0 °C. The mixture was stirred at 0 °C for 10 min, then slowly warmed to room temperature and stirred for 20 min. M323b (4.92 g, 7 mmol) and Pd(PPh3)4 (1.62 g, 1.4 mmol) were added, and the mixture was gradually warmed to 90 °C and stirred for 36 h. The mixture was poured into ice water, and the pH was adjusted to <1 by adding dilute hydrochloric acid. A large amount of yellow solid was precipitated after stirring. The solid was collected by filtration, washed with dichloromethane, and washed with dichloromethane twice more to give yellow solid M323c (4.03 g, yield: 78%). MALDI-TOF-MS: m / z = 817.69 (M + ). Elemental analysis (C 43 H 10 D8F 18 N4O4S): C 49.70, H 2.39, N 5.28.

[0106] Step 4: Synthesis of compound 323

[0107]

[0108] Into a 1000 mL three-necked flask was placed intermediate M323c (4.09 g, 5 mmol) and 150 mL of dichloromethane solvent under nitrogen protection. The reaction mixture was cooled to 0 °C under stirring, then PIFA (6.45 g, 15 mmol) was added portionwise. The reaction mixture was stirred for 1 h at 0 °C, then warmed to room temperature. The reaction mixture was stirred for 3 days at room temperature, then 400 mL of n-hexane was added to the reaction mixture. The mixture was stirred for 10 min, then filtered to give a dark green solid. The solid was washed with DCM / PE mixture (v:v = 1:1) twice, then dried to give dark green solid compound 323 (2.29 g, yield: 62%). MALDI-TOF-MS: m / z = 1036.68 (M + ). Elemental analysis (C 41 H6D8F 18 N6O4S): C 47.38, H 1.96, N 7.97.

[0109] Synthesis Example 6: Synthesis of compound 328

[0110] Step 1: Synthesis of intermediate M328a

[0111] Into a 500 mL three-necked flask was placed Pd(OAc)2 (450 mg, 10 mol%, 2.0 mmol), XPhos (2.0 g, 4.2 mmol), intermediate M59a (6.36 g, 20 mmol), (4-(perfluoroethoxy)phenyl-2,3,5,6-d4)boronic acid (20.80 g, 80 mmol), potassium carbonate (16.68 g, 120 mmol), and 100 mL of dioxane solvent under nitrogen protection. The reaction mixture was heated to 110 °C and stirred overnight. After the reaction was completed, the mixture was filtered with celite and washed with dichloromethane. The mixture was separated by silica gel column chromatography to give a white solid (8.83 g, yield: 75%). MALDI-TOF-MS: m / z = 588.39 (M + ). Elemental analysis (C 24 H2D8F 10 N2O4): C 48.82, H 2.97, N 4.63.

[0112] Step 2: Synthesis of intermediate M328b

[0113]

[0114] Into a 500 mL three-necked flask, was placed intermediate M328a (5.30 g, 9 mmol) in 100 mL of dry THF under nitrogen. The mixture was cooled to -94 °C with stirring, and then n-butyllithium (13.8 mL, 20.93 mmol, 1.6 M in hexane) was added dropwise. After the addition was completed, the mixture was stirred at -94 °C for 1 h, and then the temperature was slowly raised to -78 °C and the mixture was stirred for 8 h. A solution of iodine (6.93 g, 27.3 mmol) in 15 mL of THF was added dropwise, and the mixture was stirred at room temperature overnight. A small amount of saturated aqueous ammonium chloride solution was added to quench the reaction, and then celite was added directly to the mixture. The mixture was purified by silica gel column chromatography to give the product M328b (3.78 g, 50% yield) as a white solid. MALDI-TOF-MS: m / z = 840.18 (M+). Elemental analysis for (C24D8F10I2N2O4): C 34.18, D 1.76, N 3.20.

[0115] Step 3: Synthesis of intermediate M328c

[0116]

[0117] A18 (10.72 g, 42 mmol) was added to 70 mL of dry DMF under nitrogen. NaH (1.67 g, 42 mmol, 60% content) was added in portions at 0 °C, and the mixture was stirred at 0 °C for 10 min. The temperature was then slowly raised to room temperature, and the mixture was stirred at room temperature for 20 min. M328b (5.88 g, 7 mmol) and Pd(PPh3)4 (1.62 g, 1.4 mmol) were then added, and the mixture was heated to 90 °C and stirred at 90 °C for 36 h. The mixture was then poured into ice water, and the pH was adjusted to <1 by the addition of dilute hydrochloric acid. A large amount of yellow solid was precipitated upon stirring, and the solid was collected by filtration. The solid was washed with dichloromethane, and then washed with dichloromethane twice more. The yellow solid M328c (6.51 g, 85% yield) was collected by filtration. MALDI-TOF-MS: m / z = 868.68 (M+). Elemental analysis for (C42H10D8F10N6O4): C 57.94, HD 2.90, N 9.53.

[0118] Step 4: Synthesis of compound 328

[0119]

[0120] Into a 1000 mL three-necked flask was placed intermediate M328c (5.47 g, 5 mmol) and 150 mL of dichloromethane solvent under nitrogen protection. The reaction mixture was cooled to 0 °C under stirring, then PIFA (6.45 g, 15 mmol) was added portionwise. The reaction mixture was stirred for 1 h, then warmed to room temperature. The reaction mixture was stirred at room temperature for 3 days, then 400 mL of n-hexane was added to the reaction mixture. The mixture was stirred for 10 min, then filtered to give a dark green solid. The solid was washed with DCM / PE mixture (v:v = 1:1) twice, then dried to give dark green solid compound 328 (4.04 g, yield: 74%). MALDI-TOF-MS: m / z = 866.66 (M+). Elemental analysis (C42H8D8F10N6O4): C 58.09, HD 2.63, N 9.56.

[0121] Synthesis Example 7: Synthesis of compound 329

[0122] Step 1: Synthesis of intermediate M329a

[0123] Into a 500 mL three-necked flask was placed Pd(OAc)2 (450 mg, 10 mol%, 2.0 mmol), XPhos (2.0 g, 4.2 mmol), intermediate M59a (6.36 g, 20 mmol), (2,3,5,6-tetrafluorobenzene-4-d)boronic acid (15.59 g, 80 mmol), potassium carbonate (16.68 g, 120 mmol) and 100 mL of dioxane solvent under nitrogen protection. The reaction mixture was heated to 110 °C and stirred overnight. After the reaction was completed, the mixture was filtered with celite and washed with dichloromethane. The mixture was separated by silica gel column chromatography to give a white solid (6.60 g, yield: 72%). MALDI-TOF-MS: m / z = 458.26 (M + ). Elemental analysis (C 20 H2D2F8N2O2): C 52.29, HD 1.18, N 5.97.

[0124] Step 2: Synthesis of intermediate M329b

[0125]

[0126] Into a 500 mL three-necked flask, was placed intermediate M329a (4.12 g, 9 mmol) in 100 mL of dry THF under nitrogen. The reaction mixture was cooled to -94 °C with stirring, and then n-butyllithium (13.8 mL, 20.93 mmol, 1.6 M in hexane) was added dropwise. After the addition was completed, the reaction mixture was stirred at -94 °C for 1 h, and then the temperature was slowly raised to -78 °C and the reaction was continued for 8 h. A solution of iodine (6.93 g, 27.3 mmol) in 15 mL of THF was added dropwise, and the reaction mixture was slowly warmed to room temperature and stirred overnight. The reaction was quenched by the addition of a small amount of saturated aqueous ammonium chloride solution, and then celite was added directly to the mixture. The mixture was purified by column chromatography on silica gel to give the product M329b (3.00 g, yield: 47%) as a white solid. MALDI-TOF-MS: m / z = 710.06 (M + ). Elemental analysis (C 20 D2F8I2N2O2): C 33.69, D 0.42, N 3.81.

[0127] Step 3: Synthesis of intermediate M329c

[0128]

[0129] A22 (6.01 g, 42 mmol) was added to 70 mL of dry DMF under nitrogen, and NaH (1.67 g, 42 mmol, 60% content) was added in portions at 0 °C. The reaction mixture was stirred at 0 °C for 10 min, and then the temperature was slowly raised to room temperature and the reaction was continued for 20 min. M329b (4.97 g, 7 mmol) and Pd(PPh3)4 (1.62 g, 1.4 mmol) were added, and the temperature was gradually raised to 90 °C. The reaction was continued for 36 h, and then the reaction mixture was poured into ice water and the pH was adjusted to <1 by the addition of dilute hydrochloric acid. A large amount of yellow solid was precipitated upon stirring, and the solid was collected by filtration. The solid was washed with dichloromethane, and then washed with dichloromethane twice more to give yellow solid M329c (4.20 g, yield: 81%). MALDI-TOF-MS: m / z = 740.53 (M + ). Elemental analysis (C 36 H8D2F8N8O2): C 58.25, H 1.47, N 14.98.

[0130] Step 4: Synthesis of compound 329

[0131]

[0132] Into a 1000 mL three-necked flask, was placed intermediate M329c (3.70 g, 5 mmol) and 150 mL of dichloromethane solvent under nitrogen protection. The reaction flask was cooled to 0 °C under stirring, then PIFA (6.45 g, 15 mmol) was added portionwise. The reaction was stirred for 1 h at 0 °C, then the temperature was raised to room temperature. The reaction was stirred for 3 days at room temperature, then 400 mL of n-hexane was added to the reaction mixture. The mixture was stirred for 10 min, then filtered to give a dark green solid. The solid was washed with DCM / PE mixture (v:v = 1 : 1) twice, then dried to give dark green solid compound 329 (2.51 g, yield: 68%). MALDI-TOF-MS: m / z = 738.51 (M + ). Elemental analysis (C 36 H6D2F8N8O2): C 58.41, H 1.22, N 15.03.

[0133] Device Example 1

[0134] A glass substrate with an 80 nm thick indium tin oxide (ITO) transparent anode was treated with oxygen plasma and UV ozone. The cleaned glass substrate was dried on a hot plate in a glove box. The following materials were sequentially evaporated onto the surface of the glass substrate at a rate of 0.2-2 A / s under a vacuum of about 10 -8 A compound of the present application, compound 59, was evaporated onto the surface of the glass substrate to form a 5 nm thick film as a hole injection layer (HIL). Next, compound NPB was evaporated onto the resulting HIL film to form a 120 nm thick film as a hole transport layer (HTL). Then, compound EB was evaporated onto the resulting HTL film to form a 5 nm thick film as an electron blocking layer (HBL). Next, compound BH and compound BD (mass ratio 96:4) were co-evaporated onto the HBL film to form a 25 nm thick film as an emitting layer (EML). LiQ (8-hydroxyquinoline-lithium) and compound ET (weight ratio 60:40) were co-evaporated onto the EML film to form a 30 nm thick film as an electron transport layer (ETL). Finally, Liq was evaporated to form a 1 nm thick film as an electron injection layer (EIL) and 120 nm thick aluminum was evaporated as a cathode. The device was then transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the fabrication of the device.

[0135] Device Example 2

[0136] Device Example 2 was fabricated in the same manner as Device Example 1, except that compound 92 was used instead of compound 59 to form a 5 nm thick film as a HIL.

[0137] Device Example 3

[0138] Device Example 3 was fabricated in the same manner as Device Example 1, except that Compound 175 was used instead of Compound 59 to form a 5 nm thick film as the HIL.

[0139] Device Example 4

[0140] Device Example 4 was fabricated in the same manner as Device Example 1, except that Compound 234 was used instead of Compound 59 to form a 5 nm thick film as the HIL.

[0141] Device Example 5

[0142] Device Example 5 was fabricated in the same manner as Device Example 1, except that Compound 323 was used instead of Compound 59 to form a 5 nm thick film as the HIL.

[0143] Device Example 6

[0144] Device Example 6 was fabricated in the same manner as Device Example 1, except that Compound 328 was used instead of Compound 59 to form a 5 nm thick film as the HIL.

[0145] Device Example 7

[0146] Device Example 7 was fabricated in the same manner as Device Example 1, except that Compound 329 was used instead of Compound 59 to form a 5 nm thick film as the HIL.

[0147] Detailed device layer structures and thicknesses are shown in Table 1 below. Layers for which more than one material is used are doped with the different compounds in the proportions indicated.

[0148] Device Comparative Example 1

[0149] Device Comparative Example 1 was fabricated in the same manner as Device Example 1, except that Compound HI-a was used instead of Compound 59 to form a 5 nm thick film as the HIL, wherein Compound HI-a was prepared according to the preparation of Compound 59, except that the deuterated p- propoxyphenylboronic acid was replaced with an equivalent molar amount of p-propoxyphenylboronic acid.

[0150] Device Comparative Example 2

[0151] Device Comparative Example 1 was fabricated in the same manner as Device Example 1, except that Compound HI-b was used instead of Compound 59 to form a 5 nm thick film as the HIL, wherein Compound HI-b was prepared according to the preparation of Compound 92, except that the deuterated 2-trifluoromethylpyridine-4-boronic acid was replaced with an equivalent molar amount of 2-trifluoromethylpyridine-4-boronic acid.

[0152] Device Comparative Example 3

[0153] Device Comparative Example 1 was fabricated in the same manner as Device Example 1, except that Compound HI-c was used instead of Compound 59 to form a 5 nm thick film as the HIL, wherein the preparation method of Compound HI-c was according to the preparation method of Compound 175, except that (3'-(trifluoromethoxy)-[1,1'-biphenyl]-3-yl-2,2',4,4',5,5',6,6'-d8)boronic acid was replaced with an equivalent molar amount of (3'-(trifluoromethoxy)-[1,1'-biphenyl]-3-yl-2,2',4,4',5,5',6,6'-8H)boronic acid.

[0154] Device Comparative Example 4

[0155] Device Comparative Example 1 was fabricated in the same manner as Device Example 1, except that Compound HI-d was used instead of Compound 59 to form a 5 nm thick film as the HIL, wherein the preparation method of Compound HI-d was according to the preparation method of Compound 234, except that (2',3-di(trifluoromethyl)-[1,1'-biphenyl]-4-yl-2,3',4',5,5',6,6'-d7)boronic acid was replaced with an equivalent molar amount of (2',3-di(trifluoromethyl)-[1,1'-biphenyl]-4-yl-2,3',4',5,5',6,6'-7H)boronic acid.

[0156] Device Comparative Example 5

[0157] Device Comparative Example 1 was fabricated in the same manner as Device Example 1, except that Compound HI-e was used instead of Compound 59 to form a 5 nm thick film as the HIL, wherein the preparation method of Compound HI-e was according to the preparation method of Compound 323, except that (4-((trifluoromethyl)sulfonyl)phenyl-2,3,5,6-d4)boronic acid was replaced with an equivalent molar amount of (4-((trifluoromethyl)sulfonyl)phenyl-2,3,5,6-4H)boronic acid.

[0158] Device Comparative Example 6

[0159] Device Comparative Example 1 was fabricated in the same manner as Device Example 1, except that Compound HI-f was used instead of Compound 59 to form a 5 nm thick film as the HIL, wherein the preparation method of Compound HI-f was according to the preparation method of Compound 328, except that (4-(perfluoroethoxy)phenyl-2,3,5,6-d4)boronic acid was replaced with an equivalent molar amount of (4-(perfluoroethoxy)phenyl-2,3,5,6-4H)boronic acid.

[0160] Device Comparative Example 7

[0161] Device Comparative Example 1 was fabricated in the same manner as Device Example 1, except that compound HI-g was used instead of compound 59 to form a 5 nm thick film as the HIL, wherein the preparation method of compound HI-g refers to the preparation method of compound 329, except that (2,3,5,6-tetrafluorophen-4H)boronic acid is used instead of (2,3,5,6-tetrafluorophen-4-d)boronic acid in equivalent molar amounts.

[0162] Table 1 Device structure of device examples

[0163]

[0164]

[0165] The material structures used in the devices are shown below:

[0166]

[0167]

[0168] The above devices were measured for I-V-L characteristics under 100 cd / cm 2 and 1000 cd / cm 2 V, luminous efficiency (cd / A), power efficiency (PE) and color coordinates were recorded in Table 2 below.

[0169] Table 2 Device data

[0170]

[0171] Table 3 Calculated energy level values, thermal decomposition temperature and roughness values of representative materials

[0172] Compounds LUMO a (eV) T d b (°C) RMS c (nm) 59 -6.16 406 3.80 92 -6.20 410 3.96 175 -6.25 402 3.84 234 -6.18 412 3.90 323 -6.22 418 3.92 328 -6.26 421 3.85 329 -6.21 415 3.94 HI-a -5.38 396 4.60 HI-b -5.46 390 4.55 HI-c -5.50 384 4.58 HI-d -5.42 386 4.50 HI-e -5.48 392 4.56 HI-f -5.52 388 4.62 HI-g -5.54 394 4.54

[0173] a Calculated by theory

[0174] b Measured by thermogravimetric analyzer

[0175] c Measured by atomic force microscope

[0176] As can be seen from the above table, the benzodioxazole is used as a hole injection layer, and has very excellent performance in the light-emitting device, and is a type of hole injection material with excellent performance.

[0177] The various embodiments described herein are presented only by way of example, and are not intended to limit the scope of the application. Thus, the claimed application can include variations to the examples described herein that are obvious to those of ordinary skill in the art. Many of the materials and device structures described herein can be substituted for other materials and structures without departing from the spirit of the application. It is understood that various theories as to why the application works are not intended to be limiting.

[0178] The above embodiments are the preferred embodiments of the present application, but the embodiments of the present application are not limited to the above embodiments, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principle of the present application are equivalent replacement manners and are included in the protection scope of the present application.

Claims

1. A compound having a benzobisoxazole structure, characterized by A compound having the structure of Formula (I): Formula (I) wherein Z1 and Z2 are each independently selected from the group consisting of CR'R", CR'R" is one of the following structures: R1, R2 are the same or different at each occurrence and are selected from the group consisting of one of the following structures: 。 2. A class of compounds having a benzobisoxazole structure characterized by The compound is one of the following: 。 3. A process for the preparation of a compound having a benzobisoxazole structure according to any one of claims 1-2, characterized in that The method comprises the following steps: (1) reacting 2,5-diamino-3,6-dibromo-benzene-1,4-diol, HC(OEt)3, Y(OTf)3 in a solvent to obtain intermediate product 1; (2) reacting intermediate product 1 with R1-B(OH)2, R2-B(OH)2 in the presence of a base and a catalyst in a solvent to obtain intermediate product 2; (3) reacting intermediate product 2 with n-butyllithium, then adding elemental iodine to continue the reaction to obtain intermediate product 3; (4) adding NaH to CR'R" to react, then adding intermediate product 3 to continue the reaction to obtain intermediate product 4; (5) adding PIFA to intermediate product 4 to react in a solvent to obtain a compound having a benzobisoxazole structure; The specific reaction route is shown as follows: 。 4. Use of the compound having a benzobisoxazole structure according to any one of claims 1-2 in an electroluminescent device.

5. An electroluminescent device, characterized by An electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising the compound having a benzobisoxazole structure according to any one of claims 1-2.

6. The electroluminescent device according to claim 5, wherein: The organic layer is a hole injection layer, and the hole injection layer comprises the compound having a benzobisoxazole structure according to any one of claims 1-2 and a dopant, wherein the dopant comprises at least one hole transport material; the hole transport material comprises at least one of a compound having a triarylamine unit, a spirobifluorene compound, a pentacene compound, an oligothiophene compound, and an oligophenyl compound.

7. The electroluminescent device according to claim 6, wherein: The molar doping ratio of the compound having a benzobisoxazole structure to the hole transport material is 10000:1 to 1:10000.

8. Use of the electroluminescent device according to any one of claims 5-7 in a flat panel display, a monitor, a television, a billboard, a light for indoor or outdoor illumination and / or signaling, a flexible display, a smart phone, a wearable device, a digital camera, a camcorder.

Images