Organometallic compound and organic electroluminescent device

Abstract

The invention provides an organic metal compound and an organic electroluminescent device, the organic metal compound has a structure shown in a general formula I. After the organic metal compound is used as a specific doping material of a luminescent layer and is applied to the organic electroluminescent device, the starting voltage of the device is reduced, the luminous efficiency is improved, and the service life is prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of organic photoelectric materials, and in particular relates to an organic metal compound and an organic electroluminescent device. Background Art

[0002] Organic electronic devices include, but are not limited to, organic light-emitting diodes (OLEDs), organic field-effect transistors (O-FETs), organic light-emitting transistors (OLETs), organic photovoltaic devices (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field-effect devices (OFQDs), light-emitting electrochemical cells (LECs), organic laser diodes, and organic plasmonic light-emitting devices.

[0003] The emission color of OLEDs can be achieved by designing the structure of the luminescent material. OLEDs can include one luminescent layer or multiple luminescent layers to achieve the desired spectrum. Currently, green and red organic electroluminescent devices have been commercialized. Blue phosphorescent devices still have problems such as unsaturated blue, short device life and high operating voltage.

[0004] Therefore, how to develop a high-performance phosphorescent material that enables an organic electroluminescent device to have comprehensive characteristics such as high efficiency, long life and low voltage is a technical problem that people in this field need to solve urgently. Summary of the invention

[0005] In view of the deficiencies of the prior art, the object of the present invention is to provide an organic metal compound and an organic electroluminescent device. By changing the combination of substituents on 2-(naphtho[1,2-b]benzofuran-10-yl)pyridine, adding branched alkyl, substituted or unsubstituted aryl and substituted or unsubstituted cycloalkyl to generate an organic metal compound, the intermolecular spatial configuration is improved, and the compound has a good spatial twisting ability, thereby avoiding carrier migration. After the compound is used as a specific doping material for the light-emitting layer and applied to an organic electroluminescent device, the starting voltage of the device is reduced, thereby avoiding carrier migration, and the driving voltage is significantly reduced, and the luminous efficiency and life are significantly improved.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In one aspect, the present invention provides an organometallic compound having a structure shown in Formula I:

[0008]

[0009] Wherein, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from any one or a combination of at least two of hydrogen, -D (deuterium), -T (tritium), -CN, -F, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C24 heteroaryl, substituted or unsubstituted C3-C24 alkynyl, substituted or unsubstituted methoxy, trimethylgermanium, trimethylsilyl;

[0010] Furthermore, R5 and R6 are not hydrogen at the same time;

[0011] R9, R 10 , R 11 , R 12 , R 13 , R 14 and R 15 Each is independently selected from any one or a combination of at least two of -H, -D, -T, -CN, -F, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-15-membered cycloalkyl, and substituted or unsubstituted C1-C6 alkoxy;

[0012] As mentioned above, hydrogen in the radical may be deuterated.

[0013] Preferably, R1, R2, R3, R4, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 and R 15 Each is independently selected from hydrogen, -D, -T, -CN, -F, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, C1-C6 alkyl fully or partially substituted by deuterium, cyclopentyl, cyclohexyl, phenyl;

[0014] The C1-C6 alkyl group completely substituted by deuterium is preferably -CD3 or -C2D5;

[0015] Preferably, R5 and R6 are each independently selected from methyl, ethyl, propyl, butyl, pentyl, phenyl, furyl, naphthyl, thienyl, methoxy, C1-C6 alkyl-substituted phenyl, C1-C6 alkyl-substituted biphenyl, C1-C6 alkyl-substituted naphthyl, tert-butyl, cyclopentyl, cyclohexyl, tert-butylphenyl, deuterated tert-butylphenyl, deuterated phenyl, cyano-substituted phenyl, cyano-substituted naphthyl, fluorine-substituted phenyl, cyclopropyl, tert-butylnaphthyl, deuterated naphthyl, trimethylgermanium, trimethylsilicon, tetramethylcyclohexane, -F, -CN, -D, -CD3, -CT3, -CF3, -CH2F, -CHF2;

[0016] In the present invention, the C1-C6 alkyl groups are each independently selected from a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted branched-chain alkyl group, or a substituted or unsubstituted cycloalkyl group; the C1-C6 alkyl group is partially deuterated, fully deuterated, or undeuterated.

[0017] In the present invention, the substituents on the substituted groups as described above are selected from one or a combination of at least two of hydrogen, methyl, ethyl, propyl, butyl, pentyl, phenyl, furan, naphthyl, thiophene, methoxy, phenyl, biphenyl, naphthyl, phenanthryl, tert-butyl, cyclopentyl, cyclohexyl, tert-butylbenzene, deuterated tert-butylbenzene, deuterated phenyl, cyano-substituted phenyl, cyano-substituted naphthyl, fluorine-substituted phenyl, cyclopropyl, tert-butylnaphthyl, deuterated naphthyl, trimethylgermanium, trimethylsilyl, tetramethylcyclohexane, -F, -CN, -D, -CD3, -CT3, -CF3, -CH2F, -CHF2.

[0018] Preferably, the organometallic compound is selected from one of the following structures, but is not limited thereto:

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] In the present invention, the preparation process of the organometallic compound of formula I is as follows:

[0092]

[0093] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 and R 15 As defined above, no further elaboration is required.

[0094] Under nitrogen protection, ligand formula Za-1 and IrC13·3H2O were placed in the reaction system, and a mixed solution of ethylene glycol ethyl ether and purified water was added for reflux reaction to obtain intermediate formula Za-2;

[0095] Silver trifluoromethanesulfonate is added to the intermediate formula Za-2, and then dichloromethane and methanol are added to the system for reflux reaction to obtain the intermediate formula Za-3;

[0096] Add the ligand Zb-1 to the intermediate Za-2, and then add anhydrous ethanol to the system for reflux reaction to obtain the organometallic compound shown in formula I.

[0097] In another aspect, the present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic material layer disposed between the anode and the cathode, wherein the organic material layer comprises at least one of the above-mentioned organic metal compounds.

[0098] Preferably, the organic material layer comprises a light-emitting layer, the light-emitting layer comprises a host material and a doping material, and the doping material comprises at least one of the organic metal compounds described above.

[0099] Preferably, the organic material layer further includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer or an electron injection layer.

[0100] Preferably, the organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode which are arranged in sequence.

[0101] Generally speaking, an organic electroluminescent device includes a first electrode (anode) and a second electrode (cathode), and an organic material layer located between the electrodes. The organic material can be divided into multiple regions. For example, the organic material layer can include a hole transport region, a light-emitting layer, and an electron transport region.

[0102] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0103] The first electrode can be formed by sputtering or depositing a material used as the first electrode on a substrate. When the first electrode is used as an anode, transparent conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and any combination thereof can be used. In addition, the anode material can also be selected from materials and combinations thereof that facilitate hole injection other than the listed anode materials, including materials known to be suitable for anodes. When the first electrode is used as a cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and any combination thereof can be used. In addition to the cathode materials listed above, the cathode material can also be a material and a combination thereof that facilitates electron injection, including materials known to be suitable for cathodes.

[0104] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing and the like. The compound used as the organic material layer can be an organic small molecule, an organic macromolecule and a polymer, and a combination thereof. The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a hole transport layer (HTL) of a single-layer structure, including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0105] The material of the hole transport layer can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA), polyaniline / poly(4-styrenesulfonate) (PANI / PSS), aromatic amine derivatives such as the compounds shown in LB-1 to LB-30 below; or any combination thereof.

[0106]

[0107]

[0108] But it is not limited to the above materials.

[0109] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of the above LB-1 to LB-30, or one or more compounds of the following LC-1 to LC-3; or one or more compounds of LB-1 to LB-30 can be doped with one or more compounds of the following LC-1 to LC-3:

[0110]

[0111] But it is not limited to the above materials.

[0112] The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0113] In one aspect of the present application, the electron transport layer material can be selected from, but not limited to, one or more combinations of LD-1 to LD-36 listed below, but not limited to the above materials.

[0114]

[0115]

[0116]

[0117] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes but is not limited to one or more combinations of the following: LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca.

[0118] Compared with the prior art, the present invention has the following beneficial effects:

[0119] After the organic metal compound of the present invention is applied to an organic electroluminescent device, the starting voltage of the device is reduced, so that the luminous efficiency and life are significantly improved. DETAILED DESCRIPTION

[0120] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0121] The following will be clearly and completely described in conjunction with the technical solutions of the synthesis examples and embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments of the present application, all embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0122] In addition, it should be noted that the numerical values ​​given in the following examples are as accurate as possible, but those skilled in the art understand that due to unavoidable measurement errors and experimental operation problems, each number should be understood as an approximate number rather than an absolutely accurate value.

[0123] Example 1

[0124] This embodiment provides an organometallic compound Z-16, that is, a compound numbered Z-16, and the specific synthesis steps are as follows:

[0125]

[0126] Under nitrogen protection, compound 1-fluoro-2,4-dibromonaphthalene (CAS: 341-49-1) (180 mmol) and anhydrous potassium carbonate (540 mmol) were placed in the reaction system, 1000 mL of toluene, 500 mL of anhydrous ethanol, and 500 mL of purified water were added, and Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection, and 3-chloro-2-methoxyphenylboronic acid (CAS: 179898-50-1) (180 mmole) was added in three batches every 1 hour. ol), after the addition, reflux at 100 ° C for 24h under nitrogen protection, then cool to 25 ° C. After the reaction is cooled, it is extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product is subjected to column chromatography (200-300 mesh, 450g) to remove impurities, the developing agent EA:PE=1:10, the receiving liquid is vortexed until no liquid flows out, and vacuum dried to obtain the intermediate 1 (30.79g, yield 47%) of the compound shown, and its HPLC purity is greater than 99.5%.

[0127] Mass spectrum: Test value is 363.97.

[0128]

[0129] Under nitrogen protection system, add intermediate 1 (80mmol), dichloromethane (847mL), N2 replacement three times and N2 protection, put into 0℃ ice bath and stir for 10 minutes, slowly drip boron tribromide, after complete dripping, warm to room temperature and stir for 12h. After the reaction is complete, quench with ice water under ice bath, neutralize with saturated sodium bicarbonate aqueous solution, a large amount of solid product precipitates and is directly filtered, washed with water three times, and dried under reduced pressure to obtain intermediate 2 (21.28g, yield 76%), with HPLC purity greater than 99.5%.

[0130] Mass spectrum: Test value is 349.95.

[0131]

[0132] Under nitrogen protection, intermediate 2 (70 mmol), potassium carbonate (210 mmol) and DMF (500 mL) were added to the reaction system in sequence, and then heated and stirred at 100 ° C for 15 h. After the reaction was complete, it was cooled, filtered through diatomaceous earth, and the organic phase was washed with saturated brine, extracted with ethyl acetate three times, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by column chromatography to remove impurities, and eluted with 20% (v / v) dichloromethane / petroleum ether solution to obtain intermediate 3 (11.09 g, yield 48%), with an HPLC purity of more than 99.5%.

[0133] Mass spectrum: Test value is 329.94.

[0134]

[0135] Under nitrogen protection, intermediate 3 (180 mmol) and anhydrous potassium carbonate (540 mmol) were put into the reaction system, 1000 mL toluene, 500 mL anhydrous ethanol, and 500 mL purified water were added, Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection, and 2-pyridineboric acid (CAS: 197958-29-5) (180 mmol) was added in three batches every 1 hour. After the addition was completed, the mixture was refluxed at 100°C for 24 h under nitrogen protection, and then cooled to 25°C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was subjected to column chromatography (200-300 mesh, 500 g) to remove impurities, and the developing agent EA:PE=1:20. The receiving solution was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate 4 (31.56 g, yield 47%) of the compound shown, and its HPLC purity was greater than 99.5%.

[0136] Mass spectrum: Test value is 373.01

[0137]

[0138] Under nitrogen protection, intermediate 4 (180 mmol) and anhydrous potassium carbonate (540 mmol) were put into the reaction system, 1000 mL toluene, 500 mL anhydrous ethanol and 500 mL purified water were added under nitrogen protection, Pd(PPh3)4 (1.5 mmol) was added, 1-naphthaleneboric acid (CAS: 13922-41-3) (180 mmol) was added in three batches every half an hour, after the addition was completed, refluxed at 100°C for 24 h under nitrogen protection, and then cooled to 25°C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was chromatographed on a column (200-300 mesh, 500 g) to remove impurities, the developing agent EA:PE=1:20, the receiving liquid was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate 5 (36.39 g, yield 48%) of the compound shown, and its HPLC purity was greater than 99.5%.

[0139] Mass spectrum: Test value is 421.15

[0140]

[0141] Under nitrogen protection system, add intermediate ML-1 (CAS: 27012-22-2) (55mmol), DMSO-d6 (1485mmol), NaOH (60.5mmol), N2 replacement three times and N2 protection, and heat the reaction at 100°C for 12h. After the reaction is completed, extract with ethyl acetate, wash with saturated brine three times, and concentrate under reduced pressure. The crude product is purified by column chromatography, eluted with PE:EA = 10:1 to 5:1 (v / v) gradient, and the intermediate ML-2 has a mass of 8.99g and a yield of 95%.

[0142] Mass spectrum: Test value is 172.11.

[0143] 1 H NMR (400 MHz, deuterated chloroform) δ8.28 (d, 1H), 7.99–7.93 (m, 2H), 7.58–7.51 (m, 2H),

[0144] 7.51–7.44(m,2H),7.44–7.36(m,1H).

[0145]

[0146] Under nitrogen protection system, weigh the ligand ML-2 (50mmol), IrC13·3H2O (22.72mmol) into the reaction system, add a mixed solution of 420mL ethylene glycol ethyl ether and 140mL pure water, reflux for 24 hours under nitrogen protection, then cool to room temperature, a precipitate is precipitated, the precipitate is filtered, rinsed and dried with water, anhydrous ethanol and petroleum ether in turn, and the bridging ligand ML-3 is obtained with a mass of 7.25g and a yield of 56%.

[0147]

[0148] Weigh the intermediate formula ML-3 (10 mmol), add silver trifluoromethanesulfonate (22 mmol), then add 600 mL of dichloromethane to the system, add 200 mL of methanol, reflux for 24 hours under nitrogen protection, cool to room temperature, and concentrate the column chromatography filtrate until solid precipitates to obtain the iridium complex intermediate formula ML-4 (7.78 g, yield 97%).

[0149]

[0150] Weigh ML-4 (10 mmol), add intermediate 5 (22 mmol), and then add 150 mL of anhydrous ethanol to the system. Under nitrogen protection, reflux for 24 hours, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use silica gel column chromatography, concentrate the filtrate, and solid precipitate to obtain the final compound Z-16 (3.73 g, yield 39%).

[0151] The organometallic compound Z-16 was subjected to the following analytical tests:

[0152] HPLC purity: greater than 99.5%;

[0153] Mass spectrum: Test value is 955.30.

[0154] Elemental Analysis:

[0155] Calculated values: C: 69.16; H: 4.64; N: 4.40; O: 1.67

[0156] Test values: C:69.18; H:4.62N:4.42; O:1.64

[0157] 1 H NMR (400 MHz, deuterated chloroform) δ8.68 (dd, 1H), 8.33 (d, 2H), 8.11 (td, 3H), 7.99–7.83 (m, 4H), 7.77 (dd, 1H), 7.68 (dt, 3H), 7.68–7.55 (m, 5H), 7.52–7.38 (m, 8H), 7.28 (td, 2H), 7.23 (td, 1H), 7.13 (td, 2H).

[0158] Embodiment 2:

[0159] This embodiment provides an organometallic compound Z-64, that is, a compound numbered Z-64, and the specific synthesis steps are as follows:

[0160]

[0161] Under nitrogen protection, intermediate 4 (180 mmol) and anhydrous potassium carbonate (540 mmol) were put into the reaction system, 1000 mL toluene, 500 mL anhydrous ethanol, and 500 mL purified water were added, Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection, and dibenzofuran-4-boric acid (CAS: 100124-06-9) (180 mmol) was added in three batches every half an hour. After the addition was completed, the mixture was refluxed at 100° C. for 24 h under nitrogen protection, and then cooled to 25° C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was subjected to column chromatography (200-300 mesh, 500 g) to remove impurities, and the developing agent EA:PE=1:20. The receiving solution was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate 6 (39.84 g, yield 48%) of the compound shown, and its HPLC purity was greater than 99.5%.

[0162] Mass spectrum: Test value is 461.14.

[0163]

[0164] Weigh ML-4 (10 mmol), add intermediate 6 (22 mmol), and then add 150 mL of anhydrous ethanol to the system. Under nitrogen protection, reflux for 24 hours, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use silica gel column chromatography, concentrate the filtrate, and solid precipitate to obtain the final compound Z-64 (4.08 g, yield 41%).

[0165] Mass spectrum: Test value: 995.30.

[0166] Elemental Analysis:

[0167] Calculated values: C: 68.79; H: 4.46; N: 4.22; O: 3.22

[0168] Test values: C:68.81; H:4.44; N:4.23; O:3.19

[0169] 1 H NMR (400 MHz, deuterated chloroform) δ8.68 (dd, 1H), 8.33 (d, 2H), 8.17–8.08 (m, 3H), 8.02 (ddd, 2H), 7.94–7.87 (m, 1H), 7.83 (dd, 1H), 7.77 (dd, 1H), 7.71–7.64 (m, 3H), 7.64 (d, 2H), 7.61–

[0170] 7.55(m,2H),7.53–7.34(m,9H),7.28(td,2H),7.23(td,1H),7.13(td,2H).

[0171] Example 3

[0172] This synthesis example provides an organometallic compound Z-234, i.e., a compound numbered Z-234. The specific synthesis steps are as follows:

[0173]

[0174] Under nitrogen protection, intermediate 4 (180 mmol) and anhydrous potassium carbonate (540 mmol) were put into the reaction system, 1000 mL toluene, 500 mL anhydrous ethanol, 500 mL purified water were added, Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection, 3,5-dimethylphenylboronic acid (CAS: 1172975-69-8) (180 mmol) was added in three batches every half an hour, after the addition was completed, refluxed at 100°C for 24 h under nitrogen protection, and then cooled to 25°C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was subjected to column chromatography (200-300 mesh, 500 g) to remove impurities, the developing agent EA:PE=1:15, the receiving liquid was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate 7 (35.21 g, yield 49%) of the compound shown, and its HPLC purity was greater than 99.5%.

[0175] Mass spectrum: Test value is 399.16.

[0176]

[0177] Under nitrogen protection system, weigh the ligand ML-5 (50mmol), IrC13·3H2O (22.72mmol) and put it into the reaction system, add a mixed solution of 420mL ethylene glycol ethyl ether and 140mL pure water, reflux for 24 hours under nitrogen protection, and then cool to room temperature. A precipitate is precipitated, and the precipitate is filtered, rinsed and dried with water, anhydrous ethanol and petroleum ether in turn to obtain the bridged ligand ML-6 with a mass of 5.85g and a yield of 56%.

[0178] Weigh the intermediate formula ML-6 (10 mmol), add silver trifluoromethanesulfonate (22 mmol), then add 600 mL of dichloromethane to the system, add 200 mL of methanol, reflux for 24 hours under nitrogen protection, cool to room temperature, and concentrate the filtrate by column chromatography (short column) until solid precipitates to obtain the iridium complex intermediate formula ML-7 (7.37 g, yield 96%).

[0179]

[0180] Weigh ML-7 (10 mmol), add intermediate 7 (22 mmol), and then add 150 mL of anhydrous ethanol to the system. Under nitrogen protection, reflux for 24 hours, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use silica gel column chromatography, concentrate the filtrate, and solid precipitate to obtain the final compound Z-234 (3.51 g, yield 39%).

[0181] Mass spectrum: Test value is 899.25.

[0182] Elemental Analysis:

[0183] Calculated values: C: 68.13; H: 4.04; N: 4.67; O: 1.78

[0184] Test values ​​are C:68.16; H:4.01; N:4.69; O:1.75

[0185] 1 H NMR (400 MHz, deuterated chloroform) δ8.68 (dd, 1H), 8.64 (dt, 2H), 8.10 (ddd, 3H), 7.90 (dd, 1H), 7.77 (dd, 1H), 7.75–7.64 (m, 5H), 7.64–7.57 (m, 2H), 7.52–7.43 (m, 3H), 7.45–7.38 (m, 2H), 7.31–7.20 (m, 5H), 7.13 (td, 2H), 6.89–6.83 (m, 3H), 2.27 (s, 6H).

[0186] Embodiment 4:

[0187] This synthesis example provides an organometallic compound Z-316, that is, a compound numbered Z-316, and the specific synthesis steps are as follows:

[0188]

[0189] Under nitrogen protection, intermediate 4 (180 mmol) and anhydrous potassium carbonate (540 mmol) were put into the reaction system, 1000 mL toluene, 500 mL anhydrous ethanol, 500 mL purified water were added, Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection, 3,4-dimethylphenylboronic acid (CAS: 55499-43-9) (180 mmol) was added in three batches every half an hour, after the addition was completed, the mixture was refluxed at 100°C for 24 h under nitrogen protection, and then cooled to 25°C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was subjected to column chromatography (200-300 mesh, 450 g) to remove impurities, the developing agent EA:PE=1:20, the receiving solution was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate 8 (34.49 g, yield 48%) of the compound shown, and its HPLC purity was greater than 99.5%.

[0190] Mass spectrum: Test value is 399.16.

[0191]

[0192] Under nitrogen protection system, add intermediate ML-8 (CAS: 3430-26-0) (55mmol), DMSO-d6 (1485mmol), NaOH (60.5mmol), N2 replacement three times and N2 protection, and heat the reaction at 100°C for 12h. After the reaction is completed, extract with ethyl acetate, wash with saturated brine three times, and concentrate under reduced pressure. The crude product is purified by column chromatography, eluted with PE:EA = 10:1 to 5:1 (v / v) gradient, and the intermediate ML-9 mass is 14.75g, and the yield is 95%.

[0193] Mass spectrum: Test value is 282.21.

[0194]

[0195] Under nitrogen protection system, weigh the ligand ML-9 (50mmol), IrC13·3H2O (22.72mmol) and put them into the reaction system, add a mixed solution of 420mL ethylene glycol ethyl ether and 140mL pure water, reflux for 24 hours under nitrogen protection, then cool to room temperature, a precipitate is precipitated, filter the precipitate, rinse and dry with water, anhydrous ethanol and petroleum ether in turn, and obtain the bridging ligand ML-10 with a mass of 10.41g and a yield of 58%.

[0196]

[0197] Weigh the intermediate formula ML-10 (10 mmol), add silver trifluoromethanesulfonate (22 mmol), then add 600 mL of dichloromethane to the system, add 200 mL of methanol, reflux for 24 hours under nitrogen protection, cool to room temperature, and concentrate the column chromatography filtrate until solid precipitates to obtain the iridium complex intermediate formula ML-11 (9.82 g, yield 96%).

[0198] Weigh ML-11 (10 mmol), add intermediate 8 (22 mmol), and then add 150 mL of anhydrous ethanol to the system. Under nitrogen protection, reflux for 24 hours, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use silica gel column chromatography, concentrate the filtrate, and solid precipitate to obtain the final compound Z-316 (4.38 g, yield 38%).

[0199] Mass spectrum: Test value is 1153.52.

[0200] Elemental Analysis:

[0201] Calculated values: C: 71.84; H: 6.46; N: 3.64; O: 1.39

[0202] Test values ​​are C:71.86; H:6.48; N:3.65; O:1.37

[0203] 1 H NMR (400 MHz, deuterated chloroform) δ8.71 (dd, 1H), 8.31 (s, 2H), 8.10 (d, 1H), 8.05 (dd, Hz, 1H), 8.00 (s, 2H), 7.88 (ddd, 2H), 7.80–7.72 (m, 2H), 7.63–7.57 (m, 3H), 7.52–7.12 (m, 18H), 2.35 (s, 3H), 2.29 (d, 3H).

[0204] Embodiment 5:

[0205] This synthesis example provides an organometallic compound Z-349, i.e., a compound numbered Z-349. The specific synthesis steps are as follows:

[0206]

[0207] Under nitrogen protection, intermediate 4 (180 mmol) and anhydrous potassium carbonate (540 mmol) were put into the reaction system, 1000 mL toluene, 500 mL anhydrous ethanol, 500 mL purified water were added, Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection, and neopentylboric acid (CAS701261-35-0) (180 mmol) was added in three batches every half an hour. After the addition was completed, the mixture was refluxed at 100°C for 24 h under nitrogen protection, and then cooled to 25°C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was subjected to column chromatography (200-300 mesh, 450 g) to remove impurities, and the developing agent EA:PE=1:20. The receiving solution was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate 9 (29.58 g, yield 45%) of the compound shown, and its HPLC purity was greater than 99.5%.

[0208] Mass spectrum: Test value is 365.18.

[0209]

[0210] Under nitrogen protection system, add intermediate ML-12 (CAS: 27063-84-9) (55mmol), DMSO-d6 (1485mmol), NaOH (60.5mmol), N2 replacement three times and N2 protection, and heat the reaction at 100°C for 12h. After the reaction is completed, extract with ethyl acetate, wash with saturated brine three times, and concentrate under reduced pressure. The crude product is purified by column chromatography, eluted with PE:EA = 10:1 to 5:1 (v / v) gradient, and the intermediate ML-13 mass is 9.88g, and the yield is 95%.

[0211] Mass spectrum: Test value is 189.14.

[0212] 1 H NMR (400 MHz, deuterated chloroform) δ8.23 (s, 1H), 7.94–7.88 (m, 2H), 7.62 (s, 1H), 7.50–7.43 (m, 2H), 7.42–7.34 (m, 1H).

[0213] Under nitrogen protection system, weigh the ligand ML-13 (50mmol), IrC13·3H2O (22.72mmol) and put it into the reaction system, add a mixed solution of 420mL ethylene glycol ethyl ether and 140mL pure water, reflux for 24 hours under nitrogen protection, and then cool to room temperature. A precipitate is precipitated, and the precipitate is filtered, rinsed and dried with water, anhydrous ethanol and petroleum ether in turn, to obtain the bridging ligand ML-14 with a mass of 7.96g and a yield of 58%.

[0214]

[0215] Weigh the intermediate formula ML-14 (10 mmol), add silver trifluoromethanesulfonate (22 mmol), then add 600 mL of dichloromethane to the system, add 200 mL of methanol, reflux for 24 hours under nitrogen protection, cool to room temperature, and concentrate the column chromatography filtrate until solid precipitates to obtain the iridium complex intermediate formula ML-15 (8.03 g, yield 96%).

[0216]

[0217] Weigh ML-15 (10 mmol), add intermediate 9 (22 mmol), and then add 150 mL of anhydrous ethanol to the system. Under nitrogen protection, reflux for 24 hours, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use silica gel column chromatography, concentrate the filtrate, and solid precipitate to obtain the final compound Z-349 (3.55 g, yield 38%).

[0218] Mass spectrum: Test value is 933.40.

[0219] Elemental Analysis:

[0220] Calculated values ​​are C: 66.92; H: 6.26; N: 4.50; O: 1.71.

[0221] The test values ​​are C: 66.94; H: 6.24; N: 4.51; O: 1.73.

[0222] 1H NMR (400MHz, deuterated chloroform) δ8.68 (dd, 1H), 8.28 (s, 2H), 8.14 (dd, 1H), 8.08 (dd, 2H),

[0223] 7.92(dd,1H),7.77(dd,1H),7.67(td,1H),7.59(d,1H),7.58(s,2H),7.50–7.3 6(m,6H),7.27(td,2H),7.23(td,1H),7.14(td,2H),2.91(s,2H),0.96(s,9H).

[0224] Embodiment 6:

[0225] This synthesis example provides an organometallic compound Z-438, that is, a compound numbered Z-438, and the specific synthesis steps are as follows:

[0226]

[0227] Under nitrogen protection, intermediate 4 (180 mmol) and anhydrous potassium carbonate (540 mmol) were put into the reaction system, 1000 mL toluene, 500 mL anhydrous ethanol, 500 mL purified water were added, Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection, 4-methylphenylboronic acid (CAS: 5720-05-8) (180 mmol) was added in three batches every half an hour, after the addition was completed, the mixture was refluxed at 100°C for 24 h under nitrogen protection, and then cooled to 25°C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was subjected to column chromatography (200-300 mesh, 450 g) to remove impurities, the developing agent EA:PE=1:20, the receiving solution was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate 10 (33.97 g, yield 49%) of the compound shown, and its HPLC purity was greater than 99.5%.

[0228] Mass spectrum: Test value is 385.15.

[0229]

[0230] Under nitrogen protection system, add intermediate ML-16 (808142-70-3) (55mmol), DMSO-d6 (1485mmol), NaOH (60.5mmol), N2 replacement three times and N2 protection, and heat the reaction at 100°C for 12h. After the reaction is completed, extract with ethyl acetate, wash with saturated brine three times, and concentrate under reduced pressure. The crude product is purified by column chromatography, eluted with PE:EA = 10:1 to 5:1 (v / v) gradient, and the intermediate ML-17 is 12.97g in mass and 95% in yield.

[0231] Mass spectrum: Test value is 248.14.

[0232] 1 H NMR (400 MHz, deuterated chloroform) δ 8.37 (d, 1H), 8.05–7.99 (m, 2H), 7.65–7.58 (m, 4H), 7.61–7.51 (m, 2H), 7.49–7.42 (m, 2H), 7.40–7.33 (m, 1H).

[0233]

[0234] Under a nitrogen protection system, the ligand ML-17 (50 mmol) and IrC13·3H2O (22.72 mmol) were weighed and put into the reaction system, and a mixed solution of 420 mL of ethylene glycol ethyl ether and 140 mL of pure water was added. The mixture was refluxed for 24 hours under nitrogen protection, and then cooled to room temperature. A precipitate was precipitated. The precipitate was filtered, rinsed and dried with water, anhydrous ethanol and petroleum ether in turn, and the bridging ligand ML-18 was obtained with a mass of 9.19 g and a yield of 56%.

[0235]

[0236] Weigh the intermediate formula ML-18 (10 mmol), add silver trifluoromethanesulfonate (22 mmol), then add 600 mL of dichloromethane to the system, add 200 mL of methanol, reflux for 24 hours under nitrogen protection, cool to room temperature, and concentrate the column chromatography filtrate until solid precipitates to obtain the iridium complex intermediate formula ML-19 (9.16 g, yield 96%).

[0237]

[0238] Weigh ML-19 (10 mmol), add intermediate 10 (22 mmol), and then add 150 mL of anhydrous ethanol to the system. Under nitrogen protection, reflux for 24 hours, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use silica gel column chromatography, concentrate the filtrate, and solid precipitate to obtain the final compound Z-438 (3.98 g, yield 37%).

[0239] Mass spectrum: Test value is 1076.36.

[0240] Elemental Analysis:

[0241] Calculated values ​​are C: 64.42; H: 40.12; N: 3.01; O: 1.01.

[0242] The test values ​​are C: 64.44; H: 40.10; N: 3.03; O: 1.03.

[0243] 1 H NMR (400 MHz, deuterated chloroform) δ8.68 (dd, 1H), 8.33 (d, 2H), 8.11 (dd, 1H), 7.91 (dd, 1H), 7.77 (dd, 1H), 7.74–7.64 (m, 8H), 7.61–7.53 (m, 9H), 7.47 (td, 1H), 7.44–7.31 (m, 10H), 7.30–7.26 (m, 2H), 7.23 (td, 1H), 2.39 (d, 3H).

[0244] Embodiment 7:

[0245] This synthesis example provides an organometallic compound Z-492, i.e., a compound numbered Z-492. The specific synthesis steps are as follows:

[0246]

[0247] Under nitrogen protection, intermediate 4 (180 mmol) and anhydrous potassium carbonate (540 mmol) were placed in the reaction system, 1000 mL of toluene, 500 mL of anhydrous ethanol, and 500 mL of purified water were added, and Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection. (7-phenyldibenzo[b, d]furan-4-yl)boric acid (CAS: 2233599-85-2) (180 mmol) was added in three batches every half an hour. After the addition was completed, The mixture was refluxed at 100°C for 24 h under nitrogen protection, and then cooled to 25°C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was subjected to column chromatography (200-300 mesh, 450 g) to remove impurities, with the developing agent EA:PE=1:20. The receiving liquid was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate compound 11 (47.38 g, yield 49%), with an HPLC purity of more than 99.5%.

[0248] Mass spectrum: Test value is 537.17.

[0249]

[0250] Under nitrogen protection system, add intermediate ML-20 (CAS: 85237-71-4) (55mmol), DMSO-d6 (1485mmol), NaOH (60.5mmol), N2 replacement three times and N2 protection, and heat the reaction at 100°C for 12h. After the reaction is completed, extract with ethyl acetate, wash with saturated brine three times, and concentrate under reduced pressure. The crude product is purified by column chromatography, eluted with PE:EA = 10:1 to 5:1 (v / v) gradient, and the intermediate ML-21 mass is 9.99g, and the yield is 96%.

[0251] Mass spectrum: Test value is 189.14.

[0252] 1 H NMR (400 MHz, deuterated chloroform) δ 8.33 (d, 1H), 7.90–7.85 (m, 2H), 7.59–7.51 (m, 2H), 7.34–7.28 (m, 2H).

[0253]

[0254] Under nitrogen protection system, weigh the ligand ML-21 (50mmol), IrC13·3H2O (22.72mmol) and put it into the reaction system, add a mixed solution of 420mL ethylene glycol ethyl ether and 140mL pure water, reflux for 24 hours under nitrogen protection, and then cool to room temperature. A precipitate is precipitated, and the precipitate is filtered, rinsed and dried with water, anhydrous ethanol and petroleum ether in turn, to obtain the bridged ligand ML-22 with a mass of 7.00g and a yield of 51%.

[0255]

[0256] Weigh the intermediate formula ML-22 (10 mmol), add silver trifluoromethanesulfonate (22 mmol), then add 600 mL of dichloromethane to the system, add 200 mL of methanol, reflux for 24 hours under nitrogen protection, cool to room temperature, and concentrate the column chromatography filtrate until solid precipitates to obtain the iridium complex intermediate formula ML-23 (8.03 g, yield 96%).

[0257]

[0258] Weigh ML-23 (10 mmol), add intermediate 11 (22 mmol), and then add 150 mL of anhydrous ethanol to the system. Under nitrogen protection, reflux for 24 hours, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use silica gel column chromatography, concentrate the filtrate, and solid precipitate to obtain compound Z-492 (3.98 g, yield 36%).

[0259] Mass spectrum: Test value is 1105.40.

[0260] Elemental Analysis:

[0261] Calculated values: C: 70.63; H: 5.29; N: 3.80; O: 2.89

[0262] The test values ​​are C:70.65; H:5.27; N:3.79; O:2.91.

[0263] 1H NMR (400 MHz, deuterated chloroform) δ8.68 (dd, 1H), 8.36 (d, 2H), 8.17–8.10 (m, 1H), 8.03 (dd, 1H), 7.94–7.87 (m, 1H), 7.84 (dd, 1H), 7.81–7.75 (m, 2H), 7.75 (dd, 2H), 7.70 (dd, 2H), 7.67 (td, 1H), 7.66–7.56 (m, 6H), 7.56–7.50 (m, 3H), 7.48–7.33 (m, 8H), 7.31 (dd, 2H), 7.23 (td, 1H).

[0264] Embodiment 8:

[0265] This synthesis example provides an organometallic compound Z-577, i.e., a compound numbered Z-577. The specific synthesis steps are as follows:

[0266]

[0267] Under nitrogen protection, intermediate 4 (180 mmol) and anhydrous potassium carbonate (540 mmol) were put into the reaction system, 1000 mL toluene, 500 mL anhydrous ethanol, and 500 mL purified water were added, Pd(PPh3)4 (1.5 mmol) was added under nitrogen protection, and dibenzothiophene-4-ylboronic acid (CAS: 108847-20-7) (180 mmol) was added in three batches every half an hour. After the addition was completed, the mixture was refluxed at 100°C for 24 h under nitrogen protection, and then cooled to 25°C. After the reaction was cooled, it was extracted with ethyl acetate, washed three times with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was subjected to column chromatography (200-300 mesh, 450 g) to remove impurities, and the developing agent EA:PE=1:20. The receiving solution was vortexed until no liquid flowed out, and vacuum dried to obtain the intermediate 12 (41.22 g, yield 48%) of the compound shown, and its HPLC purity was greater than 99.5%.

[0268] Mass spectrum: Test value is 477.12.

[0269]

[0270] Under nitrogen protection system, weigh the ligand ML-24 (50mmol), IrC13·3H2O (22.72mmol) and put them into the reaction system, add a mixed solution of 420mL ethylene glycol ethyl ether and 140mL pure water, reflux for 24 hours under nitrogen protection, and then cool to room temperature. A precipitate is precipitated, and the precipitate is filtered, rinsed and dried with water, anhydrous ethanol and petroleum ether in turn, to obtain a bridging ligand ML-25 with a mass of 7.80g and a yield of 58%.

[0271]

[0272] Weigh the intermediate formula ML-25 (10 mmol), add silver trifluoromethanesulfonate (22 mmol), then add 600 mL of dichloromethane to the system, add 200 mL of methanol, reflux for 24 hours under nitrogen protection, cool to room temperature, and concentrate the filtrate by column chromatography (short column) until solid precipitates to obtain iridium complex intermediate formula ML-26 (7.91 g, yield 96%).

[0273]

[0274] Weigh ML-26 (10 mmol), add intermediate 12 (22 mmol), and then add 150 mL of anhydrous ethanol to the system. Under nitrogen protection, reflux for 24 hours, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use silica gel column chromatography, concentrate the filtrate, and solid precipitate to obtain the final compound Z-577 (3.93 g, yield 38%).

[0275] Mass spectrum: Test value is 1033.27.

[0276] Elemental Analysis:

[0277] Calculated values ​​are C: 68.58; H: 4.10; N: 4.07; O: 1.55; S: 3.10.

[0278] The test values ​​are C:68.59; H:4.09; N:4.08; O:1.57; S:3.11.

[0279] 1 H NMR (400 MHz, deuterated chloroform) δ8.72–7.95 (m, 5H), 7.92–7.85 (m, 2H), 7.77 (dt, 2H),

[0280] 7.73–7.64(m,3H),7.61–7.52(m,4H),7.51–7.42(m,6H),7.42–7.37(m,2H),7.33(td,1H),7.30–7.20(m,5H),2.41(s,6H),2.28(s,6H).

[0281] The synthesis methods of other compounds are the same as above, and are not described here one by one. The mass spectra or molecular formulas of other synthesis examples are shown in Table 1 below:

[0282] Table 1

[0283] Compound Molecular formula Mass spectrometry test value Z-16 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 55 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 32 <h2 style=";text-align:left;direction:ltr"> D6IrN3O]]><h2 style=";text-align:left;direction:ltr"> 955.30 Z-36 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 59 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 38 <h2 style=";text-align:left;direction:ltr"> D6IrN3O]]><h2 style=";text-align:left;direction:ltr"> 1009.35 Z-64 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 57 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 32 <h2 style=";text-align:left;direction:ltr"> D6IrN3O2<h2 style=";text-align:left;direction:ltr"> 995.30 Z-155 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 59 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 37 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 1024.47 Z-234 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 51 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 36 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 899.25 Z-302 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 63 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 34 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 1077.49 Z-316 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 69 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 38 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 1153.52 Z-349 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 52 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 34 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 933.40 Z-391 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 59 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 32 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> IrN3OS]]><h2 style=";text-align:left;direction:ltr"> 1043.33 Z-438 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 64 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 40 <h2 style=";text-align:left;direction:ltr"> D6IrN3O]]><h2 style=";text-align:left;direction:ltr"> 1071.36 Z-463 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 54 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 30 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 953.37 Z-492 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 65 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 34 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> IrN3O2<h2 style=";text-align:left;direction:ltr"> 1105.40 Z-577 <![CDATA[C 59 H 42 IrN3OS]]> 1033.27 Z-589 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 66 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 60 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 1103.44 Z-602 <![CDATA[C 56 H 53 GeIrN4O]]> 1064.31 Z-688 <![CDATA[C 62 H 50 D6IrN3OSi2]]> 1113.40 Z-781 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 46 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 36 <h2 style=";text-align:left;direction:ltr"> IrN3OSi]]><h2 style=";text-align:left;direction:ltr"> 867.23 Z-800 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 64 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 38 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> GeIrN3O]]><h2 style=";text-align:left;direction:ltr"> 1167.44

[0284] Device Example 1: Preparation of an organic electroluminescent device using an organometallic compound of formula Z-16

[0285] The coating thickness is The ITO glass substrate was washed twice in distilled water and ultrasonically washed for 30 minutes. After the distilled water washing, it was ultrasonically washed with isopropyl alcohol, acetone, methanol and other solvents in sequence, dried, and transferred to a plasma cleaning machine. The above substrate was washed for 10 minutes and sent to a vapor deposition machine. First, the ITO (anode) was vapor-deposited with a thickness of The hole injection layer of HI-02 is then deposited on the hole injection layer with a thickness of The hole transport layer of HT-02 is then evaporated to a thickness of The main material 4,4'-N,N'-biphenyl dicarbazole ("CBP") and the dopant material compound Z-16 are in a weight ratio of 90:10 to form a light-emitting layer, and then a layer with a thickness of 1000 nm is deposited on the light-emitting layer. The electron transport layer of ET-02 is then evaporated with a thickness of The electron injection layer material Liq is finally deposited on the electron injection layer with a thickness of The cathode material Al is added to obtain an organic electroluminescent device. The performance and luminescence characteristics of the obtained device are tested by using a KEITHLEY 2400 source measurement unit and a CS-2000 spectroradiometer to evaluate the driving voltage, lifespan, and luminous efficiency.

[0286] Device Comparative Example 1: An organic electroluminescent device was prepared in the same manner as in Device Example 1, and the structure of the green light-emitting doping compound in the light-emitting layer was as follows:

[0287]

[0288] Device Comparative Example 2: An organic electroluminescent device was prepared in the same manner as in Device Example 1, and the structure of the green light-emitting doping compound in the light-emitting layer was as follows:

[0289]

[0290] Device Comparative Example 3: An organic electroluminescent device was prepared in the same manner as in Device Example 1, and the structure of the green light-emitting doping compound in the light-emitting layer was as follows:

[0291]

[0292] Device Comparative Example 4: An organic electroluminescent device was prepared in the same manner as in Device Example 1, and the structure of the green light-emitting doping compound in the light-emitting layer was as follows:

[0293]

[0294] Device Comparative Example 5: An organic electroluminescent device was prepared in the same manner as in Device Example 1, and the structure of the green light-emitting doping compound in the light-emitting layer was as follows:

[0295]

[0296] Device Comparative Example 6: An organic electroluminescent device was prepared in the same manner as in Device Example 1, and the structure of the green light-emitting doping compound in the light-emitting layer was as follows:

[0297]

[0298] Device Comparative Example 7: An organic electroluminescent device was prepared in the same manner as in Device Example 1, and the structure of the green light-emitting doping compound in the light-emitting layer was as follows:

[0299]

[0300] Device Comparative Example 8: An organic electroluminescent device was prepared in the same manner as in Device Example 1, and the structure of the green light-emitting doping compound in the light-emitting layer was as follows:

[0301]

[0302] Device Example 2: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-36.

[0303] Device Example 3: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-64.

[0304] Device Example 4: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-155.

[0305] Device Example 5: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-234.

[0306] Device Example 6: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-302.

[0307] Device Example 7: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-316.

[0308] Device Example 8: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-349.

[0309] Device Example 9: Refer to the method of the above-mentioned device example 1, the only difference is that the doping material Z-16 is replaced by Z-391.

[0310] Device Example 10: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-438.

[0311] Device Example 11: Refer to the method of the above device example 1, the only difference is that the doping material Z-16 is replaced by Z-463.

[0312] Device Example 12: Refer to the method of the above-mentioned device example 1, the only difference is that the doping material Z-16 is replaced by Z-492.

[0313] Device Example 13: Refer to the method of the above-mentioned device example 1, the only difference is that the doping material Z-16 is replaced by Z-577.

[0314] Device Example 14: Refer to the method of the above-mentioned device example 1, the only difference is that the doping material Z-16 is replaced by Z-589.

[0315] Device Example 15: Refer to the method of the above-mentioned device example 1, the only difference is that the doping material Z-16 is replaced by Z-602.

[0316] Device Example 16: Refer to the method of the above-mentioned device example 1, the only difference is that the doping material Z-16 is replaced by Z-688.

[0317] Device Example 17: Refer to the method of the above-mentioned device example 1, the only difference is that the doping material Z-16 is replaced by Z-781.

[0318] Device Example 18: Refer to the method of the above-mentioned device example 1, the only difference is that the doping material Z-16 is replaced by Z-800.

[0319] The driving voltage, luminous efficiency and life of the organic electroluminescent devices obtained in the above device embodiments and device comparative examples were characterized at a brightness of 15000 (nits). The test results are shown in Table 2 below:

[0320] Table 2

[0321]

[0322]

[0323] It can be seen from Table 2 that:

[0324] 1. By comparing the comparative examples 1, 2, 3, 4, 5, 6, 7, and 8 with the organometallic compounds Z-16, Z-64, Z-234, Z-316, Z-349, Z-438, Z-492, and Z-577 of the present application, it can be seen that by changing the combination of substituents on 2-phenylpyridine and 2-(naphtho[1,2-b]benzofuran-10-yl)pyridine, adding branched alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted cycloalkyl to generate an organometallic compound, the intermolecular spatial configuration is improved, the compound has good spatial torsion ability, and the HOMO and LUMO energy levels are effectively adjusted, thereby avoiding carrier migration. When the compound is used as a specific doping material for the light-emitting layer and applied to an organic electroluminescent device, the starting voltage of the device is reduced, and the luminous efficiency and life of the device are improved. Thus, carrier migration is avoided, so that the organic electroluminescent device prepared by using the compound of the present application as a doping material for the light-emitting layer has a significantly lower driving voltage, and a significantly improved luminous efficiency and life compared with the organic electroluminescent device prepared in the comparative example.

[0325] 2. Compared with the organic electroluminescent devices prepared by using the compounds provided in the present application as the doping materials for the light-emitting layer, the driving voltage of the organic electroluminescent devices prepared by using the compounds provided in the present application as the doping materials for the light-emitting layer is significantly reduced, and the luminous efficiency is improved. The above embodiments only list the effect data of the devices made of a part of the structural formulas, which is a representative sampling test. According to the experimental data, the overall data is not much different, which can represent the effects of other structures not listed.

[0326] The applicant declares that the present invention illustrates the organometallic compound and the preparation method thereof and the organic electroluminescent device of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An organometallic compound, characterized in that The organometallic compound has a structure shown in general formula I: Wherein, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from any one or a combination of at least two of hydrogen, -D (deuterium), -T (tritium), -CN, -F, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C24 heteroaryl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted methoxy, trimethylgermanium, trimethylsilyl; Furthermore, R5 and R6 are not hydrogen at the same time; R9, R 10 , R 11 , R 12 , R 13 , R 14 and R 15 Each is independently selected from any one or a combination of at least two of -H, -D, -T, -CN, -F, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-15-membered cycloalkyl, and substituted or unsubstituted C1-C6 alkoxy; As mentioned above, hydrogen in the radical may be deuterated.

2. The organometallic compound according to claim 1, characterized in that R1, R2, R3, R4, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 and R 15 Each is independently selected from hydrogen, -D, -T, -CN, -F, -CH3, -CT3, -CF3, -CH2F, -CHF2, methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, C1-C6 alkyl fully or partially substituted by deuterium, cyclopentyl, cyclohexyl or phenyl; 3. The organometallic compound according to claim 2, characterized in that The C1-C6 alkyl group fully substituted by deuterium is selected from -CD3 or -C2D5.

4. The organometallic compound according to any one of claims 1 to 3, characterized in that R5 and R6 are each independently selected from methyl, ethyl, propyl, butyl, pentyl, phenyl, furanyl, naphthyl, thienyl, methoxy, C1-C6 alkyl-substituted phenyl, C1-C6 alkyl-substituted biphenyl, C1-C6 alkyl-substituted naphthyl, tert-butyl, cyclopentyl, cyclohexyl, tert-butylphenyl, deuterated tert-butylphenyl, deuterated phenyl, cyano-substituted phenyl, cyano-substituted naphthyl, fluorine-substituted phenyl, cyclopropyl, tert-butylnaphthyl, deuterated naphthyl, trimethylgermanium, trimethylsilicon, tetramethylcyclohexanyl, -F, -CN, -D, -CD3, -CT3, -CF3, -CH2F or -CHF2.

5. The organometallic compound according to claim 1, characterized in that The substituents on the substituted group are selected from one or a combination of at least two of hydrogen, methyl, ethyl, propyl, butyl, pentyl, phenyl, furan, naphthyl, thiophene, methoxy, phenyl, biphenyl, naphthyl, phenanthryl, tert-butyl, cyclopentyl, cyclohexyl, tert-butylbenzene, deuterated tert-butylbenzene, deuterated phenyl, cyano-substituted phenyl, cyano-substituted naphthyl, fluorine-substituted phenyl, cyclopropyl, tert-butylnaphthyl, deuterated naphthyl, trimethylgermanium, trimethylsilyl, tetramethylcyclohexane, -F, -CN, -D, -CD3, -CT3, -CF3, -CH2F or -CHF2.

6. The organometallic compound according to any one of claims 1 to 5, characterized in that The organometallic compound is preferably selected from one of the following structures:

7. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic material layer disposed between the anode and the cathode, wherein the organic material layer comprises at least one of the organic metal compounds according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, characterized in that: The organic material layer comprises a light-emitting layer, the light-emitting layer comprises a host material and a doping material, and the doping material comprises at least one of the organic metal compounds according to any one of claims 1 to 5.

9. The organic electroluminescent device according to claim 7 or 8, characterized in that: The organic material layer further includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer or an electron injection layer.

10. The organic electroluminescent device according to any one of claims 7 to 9, characterized in that: The organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode which are arranged in sequence.

Images