Doping material in light-emitting layer of organic light-emitting device and device

Abstract

The invention belongs to the field of organic photoelectric materials, and provides a doping material in a luminescent layer of an organic electroluminescent device, a preparation method of the doping material and the organic electroluminescent device containing the doping material. The organic electroluminescent device prepared from the doping material has the technical effects of high luminous efficiency, long service life and improved driving voltage.

Description

Technical Field

[0001] The invention relates to the field of organic synthesis and organic photoelectric materials, and more particularly to a doping material and device in a light-emitting layer of an organic electroluminescent device. Background Art

[0002] Organic electronic devices include but are not limited to the following categories: 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] As organic electroluminescent diodes for next-generation flat panel display applications, organic optoelectronic semiconductor materials require: 1. High luminous efficiency; 2. Excellent electron and hole stability; 3. Suitable luminescent color; 4. Excellent film-forming processability. For various reasons, optoelectronic devices using organic materials have become increasingly popular. Many materials used to manufacture the devices are relatively cheap, so organic optoelectronic devices have the potential to have cost advantages over inorganic devices. In addition, the inherent properties of organic materials (such as their flexibility) can make them more suitable for specific applications, such as manufacturing on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

[0004] However, up to now, the efficiency of phosphorescent OLEDs rapidly decreases under high brightness conditions, and the phosphorescent materials used in organic light-emitting devices in the prior art have low efficiency and short life. Therefore, it is an urgent problem for those skilled in the art to have lower driving voltage, higher efficiency and longer device life. Summary of the invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an organic electroluminescent material and a device thereof. The organic electroluminescent device provided by the present invention adopts a doping material with a specific atomic structure, and by fusing one or more benzene ring groups on a benzofuran or benzothiophene ring, the spatial structure size and morphology of the obtained substance are adjusted, the spatial configuration of the compound molecule is extended, the electrochemical properties of the compound are adjusted, and the symmetrical dipole moment between molecules is improved, so that the obtained organic compound, after being used in an organic electroluminescent device, makes the device have the characteristics of long life, high efficiency and low driving voltage.

[0006] To achieve the aforementioned objectives of the present invention, the present invention provides a display panel, comprising a substrate, a first electrode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic electroluminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a second electrode arranged in sequence.

[0007] The light-emitting layer may include a light-emitting dye (i.e., a dopant) that can emit light of different wavelength spectra, and may also include a host material (Host) at the same time. The light-emitting layer may be a monochrome light-emitting layer that emits a single color such as red, green, or blue. A plurality of monochrome light-emitting layers of different colors may be arranged in a plane according to a pixel pattern, or may be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they may be separated from each other or may be connected to each other. The light-emitting layer may also be a single color light-emitting layer that can simultaneously emit different colors such as red and green.

[0008] According to different technologies, the luminescent layer material can be made of different materials such as phosphorescent electroluminescent materials and thermally activated delayed fluorescent luminescent materials. In an OLED device, a single luminescent technology can be used, or a combination of multiple different luminescent technologies can be used. These different luminescent materials classified by technology can emit light of the same color or different colors.

[0009] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. Preferably, the doping material in the light-emitting layer of the organic electroluminescent device has a compound with a structure shown in the following formula I: M(L A )2(L B );

[0010] Wherein, M is metal;

[0011] Where L A and L B Both are ligands, a type of organic compound.

[0012] Preferably, L A and L B is a compound having the following general structural formula,

[0013]

[0014] In the general formula, R1-R8, Ar1, Ar2, Ar3 and Ar4 are independently selected from any one of -H, -D (deuterium), -T (tritium), -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, -Ge(Me)3, -Si(Me)3, substituted or unsubstituted C2-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C20 aryl and substituted or unsubstituted 4-8 membered aromatic heterocyclic group;

[0015] Wherein, m, n, p and q are integers representing integers between no substitution and maximum substitution in the ring;

[0016] X is O or S;

[0017] H1 and H2 are independently selected from hydrogen or a benzene ring, and are connected to the benzene ring by substitution or by forming a condensed ring;

[0018] M is preferably metal Ir;

[0019] Specifically, formula L A The specific structure is as follows:

[0020]

[0021]

[0022] Among them, R1-R8, Ar1-Ar4 are the same as above and will not be repeated here;

[0023] m1, m2, m3, m4, p3, p4, p5 and n5 are integers between 0 and 4, q1 and q2 are integers between 0 and 2, n1, n2, n3 and n4 are integers between 0 and 1;

[0024] The hydrogen atoms in the above formulae are independently substituted with deuterium or not.

[0025] Further, R1-R8, Ar1-Ar4 are selected from the following groups: -H, -D (deuterium), -T (tritium), -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, -Ge(Me)3, -Si(Me)3, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, thiolane, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrene yl, anthracenyl, triphenylene, tetraphenyl, fluoranthene, furanyl, thienyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, triazine, tetrazine, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl and the like or any combination thereof.

[0026] Preferably, the doping material is selected from one of the following structures:

[0027]

[0028]

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[0055]

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[0089] In the present invention, the preparation process of the compound of formula I is as follows:

[0090]

[0091] The definitions in the above formula are consistent with those mentioned above and will not be repeated here.

[0092] The specific synthesis steps are as follows:

[0093] 1. Under nitrogen protection, formula L A The structural compound and IrC13·3H2O are placed in a reaction system, and a mixed solution of ethylene glycol ethyl ether and purified water is added, and the mixture is refluxed under nitrogen protection, and then cooled to room temperature, a precipitate is precipitated, and the precipitate is filtered, washed with water, anhydrous ethanol, and petroleum ether in turn, and dried to obtain the bridged ligand compound of formula II shown in the figure.

[0094] 2. Weigh the intermediate compound of formula II and anhydrous potassium carbonate, add ethylene glycol ether, and then add the ligand of formula L B , under nitrogen protection, reflux reaction, suction filtration, alcohol washing, drying. Using dichloromethane as solvent, silica gel column chromatography, the filtrate is concentrated to precipitate solids, and the final product of compound formula I is obtained.

[0095] 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.

[0096] Generally speaking, an organic electroluminescent device includes a first electrode, a second electrode, and an organic material layer 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.

[0097] 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.

[0098] 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.

[0099] 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).

[0100] 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 HT-1 to HT-34 below; or any combination thereof.

[0101]

[0102]

[0103]

[0104] But it is not limited to the above materials.

[0105] 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 HT-1 to HT-34 mentioned above, or one or more compounds of HI-1 to HI-3 below; or one or more compounds of HT-1 to HT-34 can be doped with one or more compounds of HI-1 to HI-3 below:

[0106]

[0107] But it is not limited to the above materials.

[0108] 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).

[0109] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-57 listed below.

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116] But it is not limited to the above materials.

[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] With respect to the prior art, the present invention has the following beneficial effects:

[0119] 1. By fusing one or more benzene ring groups on the benzofuran or benzothiophene ring, the spatial structure size and morphology of the obtained substance are adjusted, the spatial configuration of the compound molecule is extended, the electrochemical properties of the compound are adjusted, and the symmetrical dipole moment between molecules is improved, so that when the compound is used in an organic electroluminescent device, the starting voltage is reduced, the efficiency is improved, and the life is increased.

[0120] 2. In the study of the diketone ligand part of the iridium complex, a complete theoretical system has not yet been formed. Because the carbon atoms on the side chain do not participate in conjugation, they have a certain influence on the electron cloud distribution but the influence is not significant. At the same time, the study found that the length, configuration, and group size of the side chain alkyl group will have a certain degree of influence on the performance indicators such as the wavelength, half-peak width, efficiency, life, and CIE coordinates of the doped material. More importantly, for different RH materials, the molecular structure of the diketone ligand is regulated to match RH and RD with each other. At present, this matching basically has no directional guidance and needs to be verified through massive experiments.

[0121] The light-emitting layer of the organic electroluminescent device of the present invention adopts a structure composed of specific doping materials and main materials, and cooperates with other layer materials to make the obtained organic electroluminescent device effectively reduce the starting and dropping voltage, improve the efficiency, and improve the problem of low lifespan.

[0122] The following will be clearly and completely described in conjunction with the technical solutions of the synthesis examples and embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0123] Synthesis example 1

[0124] This synthesis example provides an organometallic compound Ⅰ-181, i.e., a compound numbered Ⅰ-181. The specific synthesis steps are as follows:

[0125]

[0126] Under nitrogen protection system, 9-chlorophenanthrene (CAS: 947-72-8) (820mmol) and methanol (1000ml) were added in sequence, and sodium methoxide (2870mmol) was added in batches. After adding, the temperature was raised and refluxed for 5 hours. After the reaction was completed, activated carbon (8.2mmol) was added to the reaction solution for decolorization, filtered, concentrated to dryness, 100g of ice water was added, stirred and slurried, filtered, and the filter cake was dried at 50℃ to obtain the compound shown in formula L AD -181 (97.58 g, yield 88%), the intermediate compound formula L AD -181 The following analytical tests were performed:

[0127] HPLC purity: greater than 99.5%;

[0128] Mass spectrum: Test value is 212.13.

[0129]

[0130] Under nitrogen protection system, compound formula L AD -181 (720 mmol) was added to 1700 mL of anhydrous methanol, and then trifluoroacetic acid (7.20 mmol) was added. Under nitrogen protection, the temperature was lowered to 0°C, and N-bromosuccinimide (NBS) (720 mmol) was added in batches, and the internal temperature was controlled not to exceed 25°C. After the addition was completed, the mixture was stirred for 2 hours, and then the temperature was raised to room temperature and stirred overnight. The raw material compound formula L was detected by TLC. AD -181 disappeared. Then the reaction solution was slowly poured into 2L H2O with stirring, and the stirring was continued for 2h. Then the solid was filtered out, washed with water, crushed and vacuum dried to obtain the intermediate L shown in the figure. AC -181 (72.07 g, yield 35%), the intermediate compound of formula L AC -181 The following analytical tests were performed:

[0131] HPLC purity: greater than 99.5%;

[0132] Mass spectrometry test value: 286.26.

[0133]

[0134] Under nitrogen protection system, compound formula L AC -181 (250 mmol), biboric acid pinacol ester (250 mmol), X-Phos (50 mmol), palladium acetate (5.0 mmol), potassium acetate (750 mmol) and dioxane (900 mL) were added to the reaction system, replaced with N2 three times and protected with N2, and heated and stirred at 100 ° C overnight. After the reaction was completed, diatomaceous earth and anhydrous magnesium sulfate were filtered, washed with ethyl acetate twice, and the organic phase was collected and concentrated under reduced pressure to obtain a crude product intermediate of formula L AB -181 was used directly in the next step.

[0135]

[0136] Under nitrogen protection system, weigh compound formula L AB-181 (250mmol), 3-amino-2-bromoquinoline (CAS: 17127-83-2) (250mmo1), anhydrous potassium carbonate (750mmol) were placed in the reaction system, 1600ml toluene, 800mL anhydrous ethanol, 800mL purified water were added, Pd (PPh3) 4 (5.0mmol) was added under nitrogen protection, refluxed at 100°C for 26h under nitrogen protection, after the reaction was completed, the liquid was separated, extracted with ethyl acetate, washed with saturated brine three times, and concentrated under reduced pressure. 400ml of dichloromethane was added to dissolve, the solution was column chromatographed (200-300 mesh, 1250g) with developing agent DCM: PE = 1:2, and the receiving liquid was vortexed until no liquid flowed out to obtain the compound shown in formula L AA -181 (42.89 g, yield 49%), the intermediate compound formula L AA -181 The following analytical tests were performed:

[0137] HPLC purity: greater than 99.5%;

[0138] The mass spectrometry test value is 350.31.

[0139]

[0140] Under nitrogen protection system, weigh compound formula L AA -181 (120 mmol) was dissolved in THF (650 mL) in the reaction system. After the temperature reached 55°C to 57°C, the heating was stopped, copper acetate (120 mmol) was added, and then 70 mL of THF solution containing tert-butyl nitrite (144 mmol) was carefully dripped into the above system. The system released heat and gas. After the addition was completed, the temperature was kept for 1.5 h to complete the reaction. The reaction solution was directly concentrated to dryness under reduced pressure, and then DCM (750 mL) was added to reflux and dissolve to make it clear. The solution was passed through a silica gel column. After the column liquid was collected, it was concentrated under reduced pressure to a remaining volume of about 100 ml. After solid precipitation, the temperature was lowered to below 20°C, filtered, drained, and dried to obtain compound L A -181 (16.08 g, yield 42%), the intermediate compound formula L A -181 The following analytical tests were performed:

[0141] HPLC purity: greater than 99.5%;

[0142] The mass spectrometry test value is 319.38.

[0143]

[0144] Under nitrogen protection system, weigh the ligand formula L A-181 (50mmol), IrC13·3H2O (22mmol) were placed in the reaction system, and a mixed solution of 510ml of ethylene glycol ethyl ether and 170ml of pure water was added. The mixture was refluxed for 28 hours under nitrogen protection, and then cooled to room temperature. A precipitate was precipitated, and the precipitate was filtered, rinsed and dried with water, anhydrous ethanol, and petroleum ether in turn. The bridging ligand Ⅱ-181 (11.22g, yield 59%) was obtained as a dark red powder.

[0145]

[0146] Weigh the bridged ligand II-181 (5.5 mmol), add anhydrous potassium carbonate (55 mmol), then add 205 ml of ethylene glycol ether to the system, replace nitrogen three times, and add formula L under nitrogen. B -181 compound (CAS: 872802-98-7) (16.5mmol), under nitrogen protection, reflux for 23 hours, cool, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use neutral alumina column chromatography, concentrate the filtrate and precipitate solid, and finally obtain the organic phosphorus luminescent material shown in Ⅰ-181 (3.55g, its yield is 31%). The organic metal compound Ⅰ-181 is subjected to the following analytical tests:

[0147] HPLC purity: greater than 99.5%;

[0148] The mass spectrometry test value is 1040.48;

[0149] Elemental analysis: calculated values ​​are C, 68.12; H, 4.55; N, 2.69; O, 6.15.

[0150] The test values ​​are C, 67.89; H, 4.69; N, 2.82; O, 6.33;

[0151] 1H NMR(400MHz,Chloroform-d)δ8.75–8.70(m,1H),8.62(d,2H),8.33(dd,2H),8.28–8.23(m,1H),8.14–8.07(m,3H),7.98–7.89(m,4H),7.82 –7.76(m,3H),7.71(tdd,2H),7.64(td,1H),7.60–7.46(m,5H),5.65(dd,1H),2.76(pd,1H),2.48(pd,1H),1.61–1.41(m,8H),0.89(t,12H).

[0152] Synthesis example 2

[0153] This synthesis example provides an organometallic compound I-526, i.e., a compound numbered I-526. The specific synthesis steps are as follows:

[0154]

[0155] Under nitrogen protection system, weigh compound 9-bromo-10-chloroanthracene (CAS: 22273-72-9) (2390mmol), isopropylboric acid (CAS: 80041-89-0) (2390mmo1), anhydrous potassium carbonate (7170mmol) into the reaction system, add 4400ml toluene, 2200mL anhydrous ethanol, 2200mL pure water, add Pd (PPh3) 4 (23.90mmol) under nitrogen protection, reflux at 100℃ for 23h under nitrogen protection, after the reaction is completed, separate the liquid, extract with ethyl acetate, wash three times with saturated brine, and concentrate under reduced pressure. Add 900ml dichloromethane to dissolve, and the solution is column chromatographed (200-300 mesh, 2000g) with developing agent DCM: PE = 1:2, and the receiving liquid is vortexed until no liquid flows out to obtain the compound shown in formula L AE -526 (285.42 g, yield 47%), the intermediate compound formula L AE -526 performs the following analysis tests:

[0156] HPLC purity: greater than 99.5%;

[0157] The mass spectrometry test value was 254.28.

[0158]

[0159] Under nitrogen protection system, compound formula L AE -526 (950mmol), cuprous bromide (950mmmol), anhydrous sodium methylthiolate (2850mmol), added to DMF (2000mL), then added water (180mL), N2 replaced three times and N2 protected, heated at 140℃ and stirred for 43h. After the reaction was completed, cooled to room temperature, the reaction solution was poured into 3 times the volume of water, solid precipitated, filtered, the solid was dissolved with DCM, the filtrate was passed through a silica gel funnel, DCM was rinsed, and the filtrate was spin-dried to obtain a crude product intermediate of formula L AD -526 was directly used in the next reaction.

[0160]

[0161] Under nitrogen protection system, compound formula L AD-526 (950 mmol) was added to 1900 mL of anhydrous methanol, and then trifluoroacetic acid (9.50 mmol) was added. Under nitrogen protection, the temperature was lowered to 0°C, and N-bromosuccinimide (NBS) (950 mmol) was added in batches, and the internal temperature was controlled not to exceed 25°C. After the addition was completed, the mixture was stirred for 2 hours, and then the temperature was raised to room temperature and stirred overnight. The raw material compound formula L was detected by TLC. AD -526 disappeared. Then the reaction solution was slowly poured into stirred H2O (2L), and the stirring was continued for 2h. Then the solid was filtered out, washed with water, crushed and vacuum dried to obtain the intermediate L shown in the figure. AD -526 (104.58 g, yield 32%), the intermediate compound of formula L AD -526 performs the following analysis tests:

[0162] HPLC purity: greater than 99.5%;

[0163] The mass spectrometry test value was 344.20.

[0164]

[0165] Under nitrogen protection system, compound formula L AC -526 (300 mmol), biboric acid pinacol ester (300 mmol), X-Phos (60 mmol), palladium acetate (6.0 mmol), potassium acetate (900 mmol) and dioxane (1200 mL) were added to the reaction system, replaced with N2 three times and protected with N2, and heated and stirred at 100°C overnight. After the reaction was completed, the mixture was filtered with diatomaceous earth and anhydrous magnesium sulfate, washed twice with ethyl acetate, and the organic phase was collected and concentrated under reduced pressure to obtain a crude product intermediate of formula L AB -526 is used directly in the next step.

[0166]

[0167] Under nitrogen protection system, weigh compound formula L AB -526 (300mmol), 3-amino-2-bromoquinoline (CAS: 17127-83-2) (300mmo1), anhydrous potassium carbonate (900mmol) were placed in the reaction system, 2400ml toluene, 1200mL anhydrous ethanol, 1200mL purified water were added, Pd (PPh3) 4 (6.0mmol) was added under nitrogen protection, refluxed at 100°C for 26h under nitrogen protection, after the reaction was completed, the liquid was separated, extracted with ethyl acetate, washed with saturated brine three times, and concentrated under reduced pressure. 400ml of dichloromethane was added to dissolve, the solution was column chromatographed (200-300 mesh, 1450g) with a developing agent of DCM: PE = 1:4, and the receiving liquid was vortexed until no liquid flowed out to obtain the compound shown in formula LAA -526 (56.33 g, yield 46%), the intermediate compound formula L AA -526 performs the following analysis tests:

[0168] HPLC purity: greater than 99.5%;

[0169] The mass spectrometry test value is 408.39.

[0170]

[0171] Under nitrogen protection system, weigh compound formula L AA -526 (135 mmol) was dissolved in THF (850 mL) in the reaction system. After the temperature reached 55°C to 57°C, the heating was stopped, and copper acetate (135 mmol) was added. Then, a THF (70 mL) solution containing tert-butyl nitrite (162 mmol) was carefully dripped into the above system. The system released heat and gas. After the addition was completed, the temperature was kept for 1.5 h to complete the reaction. The reaction solution was directly concentrated to dryness under reduced pressure, and then DCM (850 mL) was added to reflux and dissolve to make it clear. The solution was passed through a silica gel column. After the column liquid was collected, it was concentrated under reduced pressure to a remaining volume of about 100 ml. After solid precipitation, the temperature was lowered to below 20°C, filtered, drained, and dried to obtain compound L A -526 (19.35 g, yield 38%), the intermediate compound formula L A -526 performs the following analysis tests:

[0172] HPLC purity: greater than 99.5%;

[0173] The mass spectrometry test value is 377.43.

[0174]

[0175] Under nitrogen protection system, weigh the ligand formula L A -526 (55mmol), IrC13·3H2O (22mmol) were placed in the reaction system, and a mixed solution of 480ml of ethylene glycol ethyl ether and 160ml of pure water was added. The mixture was refluxed for 28 hours under nitrogen protection, and then cooled to room temperature. A precipitate was precipitated, and the precipitate was filtered, rinsed and dried with water, anhydrous ethanol, and petroleum ether in turn. The bridging ligand Ⅱ-526 (13.37g, yield 62%) was obtained as a dark red powder.

[0176]

[0177] Weigh the bridged ligand II-526 (5.5 mmol), add anhydrous potassium carbonate (55 mmol), then add 235 ml of ethylene glycol ether to the system, replace nitrogen three times, and add formula L under nitrogen.B -526 compound (CAS: 2529711-94-0) (22mmol), under nitrogen protection, reflux for 23 hours, cool, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use neutral alumina column chromatography, concentrate the filtrate and precipitate solid, and finally obtain the organic phosphorus luminescent material shown in Ⅰ-526 (3.60g, its yield is 28%). The organic metal compound Ⅰ-526 is subjected to the following analytical tests:

[0178] HPLC purity: greater than 99.5%;

[0179] The mass spectrometry test value is 1070.48;

[0180] Elemental analysis: calculated values ​​are C, 67.72; H, 5.25; N, 2.39; O, 2.73; S, 5.48.

[0181] The test values ​​are C, 67.52; H, 5.46; N, 2.43; O, 2.83; S, 5.62;

[0182] 1H NMR(400MHz,Chloroform-d)δ8.26–8.18(m,4H),8.02–7.95(m,4H),7.85(ddd,2H),7.77–7.67(m,4H),7.54–7.42(m,8H),5.63(d,1 H),3.95(hept,2H),2.80(pd,1H),1.72(qd,4H),1.61–1.52(m,2H),1.52–1.42(m,2H),1.35(dd,12H),1.18(s,3H),0.87(dt,12H).

[0183] Synthesis example 3

[0184] This synthesis example provides an organometallic compound Ⅰ-551, i.e., a compound numbered Ⅰ-551. The specific synthesis steps are as follows:

[0185]

[0186] Under nitrogen protection system, weigh the compound 3-bromo-9-hydroxyphenanthrene (CAS: 111196-62-4) (2400mmol) and put it into the reaction system, add 2000mL THF, cool to -78°C, start to drop n-BuLi (2.5M, 960mL), keep the internal temperature at 78±5°C, after the drop, keep the temperature for 4h, start to drop TMSCl (2400mmol), keep the internal temperature at 78±5°C, after the drop, keep the temperature for 4h, then slowly return to room temperature for 10h, extract with ethyl acetate, wash three times with saturated brine, dry with anhydrous magnesium sulfate, concentrate under reduced pressure, and remove impurities by column chromatography (200-300 mesh, 2400g) of the crude product, with the developing agent EA:PE=1:15, rotate the receiving liquid until no liquid flows out, and dry under vacuum to obtain the intermediate L of the compound shown AF -551 (281.01 g, yield 44%), the intermediate compound formula L AF -551 performs the following analytical tests:

[0187] Its HPLC purity is greater than 99.5%.

[0188] Mass spectrometry test value: 266.28.

[0189]

[0190] Under nitrogen protection system, weigh the intermediate compound L AF -551 (1050mmmol), add POCl3 (1500mL) and o-DCB (150ml), protect with nitrogen, react at 100℃ for 18h, and cool to room temperature after the reaction. The POCl3 in the rotary evaporation part is sticky, then add ice water, stir to quench the POCl3 thoroughly, then extract the reaction liquid with dichloromethane, concentrate under reduced pressure, and remove impurities by column chromatography (200-300 mesh, 2500g) of the crude product, with the developing agent DCM:PE=1:2, and rotate the receiving liquid until no liquid flows out, and vacuum dry to obtain the intermediate L shown in the compound AE -551 (274.42 g, yield 92%), the intermediate compound formula L AE -551 performs the following analytical tests:

[0191] HPLC purity was greater than 99.5%.

[0192] The mass spectrometry test value was 284.23.

[0193]

[0194] Under nitrogen protection system, add intermediate compound formula L AE-551 (960mmol) and methanol (2000ml), sodium methoxide (3360mmol) was added in batches, and the temperature was raised and refluxed for 5 hours. After the reaction was completed, activated carbon (9.6mmol) was added to the reaction solution for decolorization, filtered, concentrated to dryness, added 200g of ice water, stirred and slurried, filtered, and the filter cake was dried at 50℃ to obtain the compound shown in formula L AD -551 (225.90 g, yield 84%), the intermediate compound formula L AD -551 performs the following analytical tests:

[0195] HPLC purity: greater than 99.5%;

[0196] The mass spectrometry test value was 280.31.

[0197]

[0198] Under nitrogen protection system, compound formula L AD -551 (800 mmol) was added to 1800 mL of anhydrous methanol, and then trifluoroacetic acid (8.0 mmol) was added. Under nitrogen protection, the temperature was lowered to 0°C, and N-bromosuccinimide (NBS) (800 mmol) was added in batches, and the internal temperature was controlled not to exceed 25°C. After the addition was completed, the mixture was stirred for 2.5 hours, and then the temperature was raised to room temperature and stirred overnight. The raw material compound formula L was detected by TLC. AD -551 disappeared. Then the reaction solution was slowly poured into stirred H2O (2.5L), and the stirring was continued for 2h. Then the solid was filtered out, washed with water, crushed and vacuum dried to obtain the intermediate L shown in the figure. AC -551 (85.93 g, yield 30%), the intermediate compound of formula L AC -551 performs the following analytical tests:

[0199] HPLC purity: greater than 99.5%;

[0200] The mass spectrometry test value is 358.26.

[0201]

[0202] Under nitrogen protection system, compound formula L AC -551 (240mmol), biboric acid pinacol ester (240mmol), X-Phos (48mmol), palladium acetate (4.8mmol), potassium acetate (720mmol) and dioxane (850mL) were added to the reaction system, replaced with N2 three times and protected with N2, and heated and stirred at 100°C overnight. After the reaction was completed, the mixture was filtered with diatomaceous earth and anhydrous magnesium sulfate, washed twice with ethyl acetate, and the organic phase was collected and concentrated under reduced pressure to obtain a crude product intermediate of formula LAB -551 was used directly in the next step.

[0203]

[0204] Under nitrogen protection system, weigh compound formula L AB -551 (240mmol), 3-amino-2-bromoquinoline (CAS: 17127-83-2) (240mmo1), anhydrous potassium carbonate (720mmol) were placed in the reaction system, 1500ml toluene, 750mL anhydrous ethanol, 750mL purified water were added, Pd (PPh3) 4 (4.8mmol) was added under nitrogen protection, refluxed at 100°C for 26h under nitrogen protection, after the reaction was completed, the liquid was separated, extracted with ethyl acetate, washed with saturated brine three times, and concentrated under reduced pressure. 400ml of dichloromethane was added to dissolve, the solution was column chromatographed (200-300 mesh, 1600g) with the developing agent DCM: PE = 1:1, and the receiving liquid was vortexed until no liquid flowed out to obtain the compound shown in formula L AA -551 (48.64 g, yield 48%), the intermediate compound formula L AA -551 performs the following analytical tests:

[0205] HPLC purity: greater than 99.5%;

[0206] The mass spectrometry test value is 422.37.

[0207]

[0208] Under nitrogen protection system, weigh compound formula L AA -551 (115 mmol) was dissolved in THF (620 mL) in the reaction system. After the temperature reached 55°C to 57°C, the heating was stopped, copper acetate (115 mmol) was added, and then 65 mL of THF solution containing tert-butyl nitrite (138 mmol) was carefully dripped into the above system. The system released heat and gas. After the addition was completed, the temperature was kept for 2.5 h to complete the reaction. The reaction solution was directly concentrated to dryness under reduced pressure, and then DCM (700 mL) was added to reflux and dissolved to become clear. The solution was passed through a silica gel column (200-300 mesh, 1600 g) with a developing agent of DCM:PE=1:3. After the column liquid was collected and concentrated under reduced pressure to a remaining volume of about 100 ml, a solid was precipitated. The temperature was lowered to below 20°C, filtered, drained, and dried to obtain compound L A -551 (19.79 g, yield 44%), the intermediate compound formula L A -551 performs the following analytical tests:

[0209] HPLC purity: greater than 99.5%;

[0210] The mass spectrometry test value is 391.47.

[0211]

[0212] Under nitrogen protection system, weigh the ligand formula L A -551 (50.6mmol), IrC13·3H2O (22mmol) were put into the reaction system, and a mixed solution of 600ml ethylene glycol ethyl ether and 200ml pure water was added. The mixture was refluxed for 28 hours under nitrogen protection, and then cooled to room temperature. A precipitate was precipitated. The precipitate was filtered, washed and dried with water, anhydrous ethanol, and petroleum ether in turn. The bridged ligand Ⅱ-551 (14.20g, yield 64%) was obtained as a dark red powder.

[0213]

[0214] Weigh the bridged ligand II-551 (5.5 mmol), add anhydrous potassium carbonate (55 mmol), then add 320 ml of ethylene glycol ether to the system, replace nitrogen three times, and add formula L under nitrogen. B -551 compound (CAS: 865193-73-3) (22mmol), under nitrogen protection, reflux for 23 hours, cool, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use neutral alumina column chromatography, concentrate the filtrate and precipitate solid, and finally obtain the organic phosphorus luminescent material shown in Ⅰ-551 (2.80g, its yield is 21%). The organic metal compound Ⅰ-551 is subjected to the following analytical tests:

[0215] HPLC purity: greater than 99.5%;

[0216] The mass spectrometry test value is 1212.49;

[0217] Elemental analysis: calculated values ​​are C, 66.36; H, 5.57; N, 2.31; O, 5.28; Si, 4.63.

[0218] The test values ​​are C, 66.15; H, 5.78; N, 2.58; O, 5.48; Si, 4.78;

[0219] 1H NMR(400MHz,Chloroform-d)δ8.90(dd,2H),8.68(d,2H),8.44(d,2H),8.12–8.07(m,2H),7.91(d,2H),7.82–7.76(m,4H) ,7.72(dtd,4H),7.50(ddd,4H),5.58(s,1H),1.78–1.63(m,8H),1.18(s,3H),1.08(s,3H),0.85(td,12H),0.32(d,18H).

[0220] Synthesis example 4

[0221] This synthesis example provides an organometallic compound I-919, i.e., a compound numbered I-919. The specific synthesis steps are as follows:

[0222]

[0223] Under nitrogen protection system, weigh compound 4-bromoquinolin-3-amine (CAS: 36825-34-0) (710mmol), neopentylboronic acid (CAS: 701261-35-0) (781mmo1), anhydrous potassium carbonate (2130mmol) into the reaction system, add 2200ml toluene, 1100mL anhydrous ethanol, 1100mL pure water, add Pd (PPh3) 4 (7.10mmol) under nitrogen protection, reflux at 100℃ for 23h under nitrogen protection, after the reaction is completed, separate the liquid, extract with ethyl acetate, wash three times with saturated brine, and concentrate under reduced pressure. Add 400ml dichloromethane to dissolve, and the solution is column chromatographed (200-300 mesh, 1200g) with developing agent DCM: PE = 1:2, and the receiving liquid is vortexed until no liquid flows out to obtain the compound shown in formula L ABA -919 (98.83 g, yield 65%), the intermediate compound of formula L ABA -919 performs the following analytical tests:

[0224] HPLC purity: greater than 99.5%;

[0225] The mass spectrometry test value was 214.26.

[0226]

[0227] Under nitrogen protection system, compound formula L ABA -919 (460 mmol) was added to 1350 mL of anhydrous methanol, and then trifluoroacetic acid (4.60 mmol) was added. Under nitrogen protection, the temperature was lowered to 0°C, and N-bromosuccinimide (NBS) (460 mmol) was added in batches, and the internal temperature was controlled not to exceed 25°C. After the addition was completed, the mixture was stirred for 2.5 hours, and then the temperature was raised to room temperature and stirred overnight. The raw material compound formula L was detected by TLC. ABA -919 disappeared. The reaction solution was then slowly poured into stirred H2O (1.5 L), and the stirring was continued for 2 h. The solid was then filtered to obtain a solid, which was washed with water, crushed and vacuum dried to obtain the intermediate compound L shown in FIG. AB -919 (65.83 g, yield 49%), the intermediate compound of formula L AB -919 performs the following analytical tests:

[0228] HPLC purity: greater than 99.5%;

[0229] The mass spectrometry test value was 292.32.

[0230]

[0231] Under nitrogen protection system, the intermediate compound 9-bromo-1-chlorophenanthrene (CAS: 2170029-70-4) (1160mmol) and methanol (2500ml) were added in sequence, and sodium methoxide (1160mmol) was added in batches. After the addition, the temperature was raised and refluxed for 5 hours. After the reaction was completed, activated carbon (11.6mmol) was added to the reaction solution for decolorization, filtered, concentrated to dryness, 200g of ice water was added, stirred and slurried, filtered, and the filter cake was dried at 50°C to obtain the compound shown in formula L AF -919 (210.58 g, yield 75%), the intermediate compound formula L AF -919 performs the following analytical tests:

[0232] HPLC purity: greater than 99.5%;

[0233] The mass spectrometry test value was 242.33.

[0234]

[0235] Under nitrogen protection system, weigh compound formula L AF -919 (870mmol), neopentylboronic acid (CAS: 701261-35-0) (957mmol), anhydrous potassium carbonate (2610mmol) were placed in the reaction system, 3700ml toluene, 1850ml anhydrous ethanol, 1850ml purified water were added, Pd (PPh3) 4 (8.7mmol) was added under nitrogen protection, refluxed at 100°C for 23h under nitrogen protection, after the reaction was completed, the liquid was separated, extracted with ethyl acetate, washed three times with saturated brine, and concentrated under reduced pressure. 900ml of dichloromethane was added to dissolve, the solution was column chromatographed (200-300 mesh, 2000g) with developing agent DCM: PE = 1:2, and the receiving liquid was vortexed until no liquid flowed out to obtain the compound shown in formula L AE -919 (166.98 g, yield 69%), the intermediate compound formula L AE -919 performs the following analytical tests:

[0236] HPLC purity: greater than 99.5%;

[0237] The mass spectrometry test value was 278.26.

[0238]

[0239] Under nitrogen protection system, compound formula L AE -919 (600 mmol) was added to 1750 mL of anhydrous methanol, and then trifluoroacetic acid (6.0 mmol) was added. Under nitrogen protection, the temperature was lowered to 0°C, and N-bromosuccinimide (NBS) (600 mmol) was added in batches, and the internal temperature was controlled not to exceed 25°C. After the addition was completed, the mixture was stirred for 1.5 hours, and then the temperature was raised to room temperature and stirred overnight. The raw material compound formula L was detected by TLC. AE -919 disappeared. The reaction solution was then slowly poured into stirred H2O (1.5 L), and the stirring was continued for 2 h. The solid was then filtered to obtain a solid, which was washed with water, crushed and vacuum dried to obtain the intermediate compound L shown in FIG. AD -919 (81.19 g, yield 38%), the intermediate compound of formula L AD -919 performs the following analytical tests:

[0240] HPLC purity: greater than 99.5%;

[0241] The mass spectrometry test value is 356.27.

[0242]

[0243] Under nitrogen protection system, compound formula L AD -919 (225 mmol), biboric acid pinacol ester (225 mmol), X-Phos (45 mmol), palladium acetate (4.5 mmol), potassium acetate (675 mmol) and dioxane (1000 mL) were added to the reaction system, replaced with N2 three times and protected with N2, and heated and stirred at 100°C overnight. After the reaction was completed, the mixture was filtered with diatomaceous earth and anhydrous magnesium sulfate, washed twice with ethyl acetate, and the organic phase was collected and concentrated under reduced pressure to obtain a crude product intermediate of formula L AC -919 is used directly in the next step.

[0244]

[0245] Under nitrogen protection system, weigh compound formula L AC -919 (225 mmol), compound formula L AB-919 (225mmol), anhydrous potassium carbonate (675mmol) were placed in the reaction system, 1800ml toluene, 900mL anhydrous ethanol, 900mL pure water were added, Pd (PPh3) 4 (4.5mmol) was added under nitrogen protection, refluxed at 100℃ for 26h under nitrogen protection, after the reaction was completed, the liquid was separated, extracted with ethyl acetate, washed with saturated brine three times, and concentrated under reduced pressure. 350ml of dichloromethane was added to dissolve, the solution was column chromatographed (200-300 mesh, 1350g) with developing agent DCM: PE = 1:4, and the receiving liquid was vortexed until no liquid flowed out to obtain the compound shown in formula L AA -919 (57.37 g, yield 52%), the intermediate compound formula L AA -919 performs the following analytical tests:

[0246] HPLC purity: greater than 99.5%;

[0247] The mass spectrometry test value was 490.45.

[0248]

[0249] Under nitrogen protection system, weigh compound formula L AA -919 (115 mmol) was dissolved in THF (650 mL) in the reaction system. After the temperature reached 55°C to 57°C, heating was stopped, copper acetate (115 mmol) was added, and then a THF (60 mL) solution containing tert-butyl nitrite (138 mmol) was carefully dripped into the above system. The system released heat and gas. After the addition was completed, the temperature was kept for 2 hours to complete the reaction. The reaction solution was directly concentrated to dryness under reduced pressure, and then DCM (650 mL) was added to reflux and dissolve to make it clear. The solution was passed through a silica gel column. After the column liquid was collected, it was concentrated under reduced pressure to a remaining volume of about 100 ml. After solid precipitation, the temperature was lowered to below 20°C, filtered, drained, and dried to obtain compound L A -919 (23.77 g, yield 45%), the intermediate compound formula L A -919 performs the following analytical tests:

[0250] HPLC purity: greater than 99.5%;

[0251] The mass spectrometry test value is 459.33.

[0252]

[0253] Under nitrogen protection system, weigh the ligand formula L A-919 (48.4mmol), IrC13·3H2O (22mmol) were placed in the reaction system, and a mixed solution of 480ml of ethylene glycol ethyl ether and 160ml of pure water was added. The mixture was refluxed for 28 hours under nitrogen protection, and then cooled to room temperature. A precipitate was precipitated, and the precipitate was filtered, washed and dried with water, anhydrous ethanol, and petroleum ether in turn. The bridging ligand Ⅱ-919 (16.62g, yield 66%) was obtained as a dark red powder.

[0254]

[0255] Weigh the bridged ligand II-919 (5.5 mmol), add anhydrous potassium carbonate (55 mmol), then add 195 ml of ethylene glycol ether to the system, replace nitrogen three times, and add formula L under nitrogen. B -919 compound (CAS: 865193-73-3) (16.5mmol), under nitrogen protection, reflux for 26 hours, cool, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use neutral alumina column chromatography, concentrate the filtrate and precipitate solid, and finally obtain the organic phosphorus luminescent material shown in Ⅰ-919 (3.86g, its yield is 26%). The organic metal compound Ⅰ-919 is subjected to the following analytical tests:

[0256] HPLC purity: greater than 99.5%;

[0257] The mass spectrometry test value is 1348.81;

[0258] Elemental analysis: calculated values ​​are C, 72.13; H, 6.80; N, 2.08; O, 4.74.

[0259] The test values ​​are C, 71.95; H, 6.98; N, 2.22; O, 4.89;

[0260] 1H NMR(400MHz,Chloroform-d)δ8.74(dd,2H),8.63(d,2H),8.38(d,2H),8.09–8.05(m,2H),8.04–7.99(m,2H),7.73(s,2H),7.60–7.49(m,4H),7. 45(t,2H),7.21(dd,2H),5.58(s,1H),3.10(s,4H),2.91(s,4H),1.78–1 .63(m,8H),1.18(s,3H),1.08(s,3H),1.01–0.95(m,36H),0.85(t,12H).

[0261] Synthesis example 5

[0262] This synthesis example provides an organometallic compound I-946, i.e., a compound numbered I-946. The specific synthesis steps are as follows:

[0263]

[0264] Under nitrogen protection system, compound 9-bromo-1-chlorophenanthrene (CAS: 2170029-70-4) (1500mmol), cuprous bromide (1500mmmol), anhydrous sodium methyl mercaptan (1500mmol) were added in sequence, added to DMF (3500mL), and then water (350mL) was added, N2 was replaced three times and N2 was protected, and the reaction was stirred at 140°C for 44h. After the reaction was completed, it was cooled to room temperature, and the reaction solution was poured into 3 times the volume of water, solids were precipitated, filtered, and the solids were dissolved with DCM. The filtrate was passed through a silica gel funnel, washed with DCM, and the filtrate was spin-dried to obtain a crude product intermediate of formula L AG -946 was directly used in the next reaction.

[0265]

[0266] Under nitrogen protection system, weigh compound formula L AG -946 (1500mmol), neopentylboronic acid (CAS: 701261-35-0) (1650mmo1), anhydrous potassium carbonate (4500mmol) were placed in the reaction system, 4800ml toluene, 2400ml anhydrous ethanol, 2400ml purified water were added, Pd (PPh3) 4 (15mmol) was added under nitrogen protection, refluxed at 100°C for 23h under nitrogen protection, after the reaction was completed, the liquid was separated, extracted with ethyl acetate, washed with saturated brine three times, and concentrated under reduced pressure. 1200ml dichloromethane was added to dissolve, the solution was column chromatographed (200-300 mesh, 3500g) with developing agent DCM: PE = 1:2, and the receiving liquid was vortexed until no liquid flowed out to obtain the compound shown in formula L AF -946 (286.79 g, yield 65%), the intermediate compound formula L AF -946 performs the following analysis tests:

[0267] HPLC purity: greater than 99.5%;

[0268] The mass spectrometry test value was 294.26.

[0269]

[0270] Under nitrogen protection system, compound formula L AF-946 (970 mmol) was added to 2100 mL of anhydrous methanol, and then trifluoroacetic acid (9.7 mmol) was added. Under nitrogen protection, the temperature was lowered to 0°C, and N-bromosuccinimide (NBS) (970 mmol) was added in batches, and the internal temperature was controlled not to exceed 25°C. After the addition was completed, the mixture was stirred for 2 hours, and then the temperature was raised to room temperature and stirred overnight. The raw material compound formula L was detected by TLC. AF -946 disappeared. Then the reaction solution was slowly poured into stirred H2O (2.5 L), and the stirring was continued for 2 h. Then the solid was filtered out, washed with water, crushed and vacuum dried to obtain the intermediate compound L shown in FIG. AE -946 (104.66 g, yield 29%), the intermediate compound of formula L AE -946 performs the following analysis tests:

[0271] HPLC purity: greater than 99.5%;

[0272] The mass spectrometry test value is 372.32.

[0273]

[0274] Under nitrogen protection system, compound formula L AE -946 (280 mmol), biboric acid pinacol ester (280 mmol), X-Phos (56 mmol), palladium acetate (5.6 mmol), potassium acetate (840 mmol) and dioxane (1200 mL) were added to the reaction system, replaced with N2 three times and protected with N2, and heated and stirred at 100°C overnight. After the reaction was completed, the mixture was filtered with diatomaceous earth and anhydrous magnesium sulfate, washed twice with ethyl acetate, and the organic phase was collected and concentrated under reduced pressure to obtain a crude product intermediate of formula L AD -946 is used directly in the next step.

[0275]

[0276] Among them, formula L AC The synthesis method of compound -946 is shown in Synthesis Example 4 and will not be repeated here.

[0277] Under nitrogen protection system, weigh compound formula L AD -946 (280 mmol), compound formula L AC-946 (280mmol), anhydrous potassium carbonate (840mmol) were placed in the reaction system, 2300ml toluene, 1150mL anhydrous ethanol, 1150mL pure water were added, Pd (PPh3) 4 (5.6mmol) was added under nitrogen protection, and refluxed at 100°C for 28h under nitrogen protection. After the reaction was completed, the liquid was separated, extracted with ethyl acetate, washed with saturated brine three times, and concentrated under reduced pressure. 450ml of dichloromethane was added to dissolve, and the solution was column chromatographed (200-300 mesh, 1350g) with a developing agent of DCM: PE = 1:3, and the receiving liquid was vortexed until no liquid flowed out to obtain the compound shown in formula L AB -946 (70.88 g, yield 50%), the intermediate compound formula L AB -946 performs the following analysis tests:

[0278] HPLC purity: greater than 99.5%;

[0279] The mass spectrometry test value is 506.38.

[0280]

[0281] Under nitrogen protection system, weigh compound formula L AB -946 (140 mmol) was dissolved in THF (800 mL) in the reaction system. After the temperature reached 55°C to 57°C, heating was stopped, copper acetate (140 mmol) was added, and then a THF (80 mL) solution containing tert-butyl nitrite (168 mmol) was carefully dripped into the above system. The system released heat and gas. After the addition was completed, the temperature was kept for 2 h to complete the reaction. The reaction solution was directly concentrated to dryness under reduced pressure, and then DCM (650 mL) was added to reflux and dissolve to make it clear. The solution was passed through a silica gel column. After the column liquid was collected, it was concentrated under reduced pressure to a remaining volume of about 100 ml. Solid precipitated, and the temperature was lowered to below 20°C, filtered, drained, and dried to obtain compound L AA -946 (33.93 g, yield 51%), the intermediate compound formula L AA -946 performs the following analysis tests:

[0282] HPLC purity: greater than 99.5%;

[0283] The mass spectrometry test value was 475.40.

[0284]

[0285] Under nitrogen protection system, compound formula L AA-946 (70 mmol), DMSO-d6 (2100 mmol), KOH (210 mmol), N2 replacement three times and N2 protection, heating at 100 ° C for 38 hours. After the reaction is completed, ethyl acetate is extracted, washed three times with saturated brine, and concentrated under reduced pressure. The crude product is purified by column chromatography with a gradient elution of DCM:EA = 50:1 to 10:1 (v / v) to obtain the intermediate compound shown in formula L A -946 (24.15 g, yield 72%), the intermediate compound formula L A -946 performs the following analysis tests:

[0286] HPLC purity: greater than 99.5%;

[0287] The mass spectrometry test value is 479.43;

[0288] 1H NMR(400MHz,Chloroform-d)δ8.74(dd,1H),8.66(dd,1H),8.46(dd,1H),8.21–8.15(m,1H),7.93– 7.86(m,1H),7.83(t,1H),7.62(s,1H),7.55–7.46(m,3H),7.30(dd,1H),1.14(s,9H),1.10(s,9H).

[0289]

[0290] Under nitrogen protection system, weigh the ligand formula L A -946 (52.8mmol), IrC13·3H2O (22mmol) were placed in the reaction system, and a mixed solution of 420ml of ethylene glycol ethyl ether and 130ml of pure water was added. The mixture was refluxed for 28 hours under nitrogen protection, and then cooled to room temperature. A precipitate was precipitated, and the precipitate was filtered, washed and dried with water, anhydrous ethanol, and petroleum ether in turn. The bridged ligand II-946 (14.85g, yield 57%) was obtained.

[0291]

[0292] Weigh the bridged ligand II-946 (5.5 mmol), add anhydrous potassium carbonate (55 mmol), then add 255 ml of ethylene glycol ether to the system, replace nitrogen three times, and add formula L under nitrogen. B-946 compound (CAS: 1821143-86-5) (27.5mmol), under nitrogen protection, reflux for 26 hours, cool, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use neutral alumina column chromatography, concentrate the filtrate and precipitate solid, and finally obtain the organic phosphorus luminescent material shown in Ⅰ-946 (5.14g, its yield is 33%). The organic metal compound Ⅰ-946 is subjected to the following analytical tests:

[0293] HPLC purity: greater than 99.5%;

[0294] The mass spectrometry test value is 1416.98;

[0295] Elemental analysis: calculated values ​​are C, 70.35; H, 7.33; N, 1.98; O, 2.26; S, 4.52;

[0296] The test values ​​are C, 70.17; H, 7.46; N, 2.14; O, 2.43; S, 4.60;

[0297] 1H NMR(400MHz,Chloroform-d)δ8.77–8.72(m,2H),8.69(d,2H),8.45(d,2H),8.22–8.15(m,2H),7.99–7.92(m,2H),7.64(s,2H),7.54–7. 46(m,6H),7.29(dd,2H),5.61(dd,1H),2.66(td,1H),2.14(ddd,1H),2.00(dq,2H),1.85(dq,2H),1.13–1.04(m,36H),0.92(ddd,24H).

[0298] Synthesis example 6

[0299] This synthesis example provides an organometallic compound Ⅰ-1099, i.e., a compound numbered Ⅰ-1099. The specific synthesis steps are as follows:

[0300]

[0301] Under nitrogen protection system, compound 10-bromo-1-chlorophenanthrene (CAS: 3028153

[0302] -16-1) (290mmol), biboric acid pinacol ester (290mmol), X-Phos (58mmol), palladium acetate (5.8mmol), potassium acetate (870mmol) and dioxane (1250mL) were added to the reaction system, replaced with N2 three times and protected with N2, and heated and stirred at 100°C overnight. After the reaction was completed, diatomaceous earth and anhydrous magnesium sulfate were filtered, washed with ethyl acetate twice, and the organic phase was collected and concentrated under reduced pressure to obtain a crude product intermediate of formula L AD -1099 is used directly in the next step.

[0303]

[0304] Under nitrogen protection system, add intermediate compound formula L AD -1099 (290mmol) and methanol (1300ml), sodium methoxide (290mmol) was added in batches, and the temperature was raised and refluxed for 5 hours. After the reaction was completed, activated carbon (2.9mmol) was added to the reaction solution for decolorization, filtered, concentrated to dryness, 80g of ice water was added, stirred and slurried, filtered, and the filter cake was dried at 50℃ to obtain the compound shown in formula L AC -1099 (81.4 g, yield 84%), the intermediate compound formula L AC -1099 performs the following analytical tests:

[0305] HPLC purity: greater than 99.5%;

[0306] The mass spectrometry test value is 334.26.

[0307]

[0308] Among them, formula L AB The synthesis method of compound -1099 is shown in Synthesis Example 4 and will not be repeated here.

[0309] Under nitrogen protection system, weigh compound formula L AC -1099 (242 mmol), compound formula L AB -1099 (220mmol), anhydrous potassium carbonate (660mmol) were placed in the reaction system, 1400ml toluene, 700mL anhydrous ethanol, 700mL pure water were added, Pd (PPh3) 4 (4.4mmol) was added under nitrogen protection, refluxed at 100℃ for 28h under nitrogen protection, after the reaction was completed, the liquid was separated, extracted with ethyl acetate, washed with saturated brine three times, and concentrated under reduced pressure. 250ml dichloromethane was added to dissolve, the solution was column chromatographed (200-300 mesh, 1050g) with developing agent DCM: PE = 1:3, and the receiving liquid was vortexed until no liquid flowed out to obtain the compound shown in formula L AA-1099 (51.77 g, yield 56%), the intermediate compound formula L AA -1099 performs the following analytical tests:

[0310] HPLC purity: greater than 99.5%;

[0311] The mass spectrometry test value is 420.38.

[0312]

[0313] Under nitrogen protection system, weigh compound formula L AA -1099 (120 mmol) was dissolved in THF (760 mL) in the reaction system. After the temperature reached 55°C to 57°C, the heating was stopped, copper acetate (120 mmol) was added, and then a THF (76 mL) solution containing tert-butyl nitrite (144 mmol) was carefully dripped into the above system. The system released heat and gas. After the addition was completed, the temperature was kept for 2 hours to complete the reaction. The reaction solution was directly concentrated to dryness under reduced pressure, and then DCM (610 mL) was added to reflux and dissolve to make it clear. The solution was passed through a silica gel column. After the column liquid was collected, it was concentrated under reduced pressure to a remaining volume of about 100 ml. After solid precipitation, the temperature was lowered to below 20°C, filtered, drained, and dried to obtain compound L A -1099 (20.08 g, yield 43%), the intermediate compound formula L A -1099 performs the following analytical tests:

[0314] HPLC purity: greater than 99.5%;

[0315] The mass spectrometry test value was 389.44.

[0316]

[0317] Under nitrogen protection system, weigh the ligand formula L A -1099 (50.6mmol), IrC13·3H2O (22mmol) were put into the reaction system, and a mixed solution of 390ml of ethylene glycol ethyl ether and 130ml of pure water was added. The mixture was refluxed for 28 hours under nitrogen protection, and then cooled to room temperature. A precipitate was precipitated, and the precipitate was filtered, washed and dried with water, anhydrous ethanol, and petroleum ether in turn. The bridged ligand II-1099 (13.16g, yield 60%) was obtained.

[0318]

[0319] Weigh the bridged ligand II-1099 (5.5 mmol), add anhydrous potassium carbonate (55 mmol), then add 220 ml of ethylene glycol ether to the system, replace nitrogen three times, and add formula L under nitrogen. B-1099 compound (CAS: 865193-73-3) (16.5mmol), under nitrogen protection, reflux for 23 hours, cool, filter, wash with alcohol, and dry. Use dichloromethane as solvent, use neutral alumina column chromatography, concentrate the filtrate and precipitate solid, and finally obtain the organic phosphorus luminescent material shown in Ⅰ-1099 (1.86g, its yield is 14%). The organic metal compound Ⅰ-1099 is subjected to the following analytical tests:

[0320] HPLC purity: greater than 99.5%;

[0321] The mass spectrometry test value is 1208.68;

[0322] Elemental analysis: calculated values ​​are C, 70.56; H, 5.92; N, 2.32; O, 5.30;

[0323] The test values ​​are C, 70.65; H, 6.21; N, 2.48; O, 5.52;

[0324] 1H NMR(400MHz,Chloroform-d)δ8.84(dd,2H),8.14(dd,2H),8.10–7.99(m,4H),7.63–7.53(m,8H),7.53–7.46(m,4H), 7.17(dd,2H),5.57(s,1H),3.10(s,4H),1.79–1.62(m,8H),1.18(s,3H),1.08(s,3H),0.98(d,18H),0.85(td,12H).

[0325] The synthesis methods of other compounds are the same as above, and are not described one by one here. The mass spectra or molecular formulas of other synthesis examples are shown in Table 1 below:

[0326]

[0327]

[0328] The present invention also provides an organic electroluminescent device, which is made of the organic luminescent material, more specifically, made of the organic luminescent material of the compound of chemical formula I.

[0329] In order to further describe the present invention, more specific embodiments are listed below.

[0330] Example 1

[0331] Device fabrication

[0332] All example devices were passed through a high vacuum (<10 -7 The anode electrode is made by thermal evaporation. Indium tin oxide (ITO). The cathode is made of Liq (8-hydroxyquinoline lithium) and subsequently All devices were packaged with epoxy-sealed glass lids in a nitrogen glove box (H2O and O2 <1 ppm) immediately after fabrication, and a desiccant was incorporated inside the package. The organic stack of the device example consisted of the following in order: an ITO surface, a HT-9 as hole transport layer (HTL) HT-9 as an electron blocking layer (EBL) EBM; containing RH-01 as a red host and 3% of the emitter formula Ⅰ-1 compound of an emission layer (EML); and an electron transport layer (ETL) doped with 35% ET-19 Table 2 shows the thickness and materials of the device layers.

[0333] Table 2: Device layer materials and thicknesses

[0334]

[0335] Example 2-23

[0336] Referring to the method of the above-mentioned embodiment 1, the only difference is that the doping material Ⅰ-1 is replaced by Ⅰ-45, Ⅰ-121, Ⅰ-181, Ⅰ-268, Ⅰ-346, Ⅰ-371, Ⅰ-414, Ⅰ-499, Ⅰ-526, Ⅰ-551, Ⅰ-600, Ⅰ-686, Ⅰ-728, Ⅰ-790, Ⅰ-808, Ⅰ-858, Ⅰ-919, Ⅰ-920, Ⅰ-946, Ⅰ-975, Ⅰ-989, Ⅰ-1099 respectively.

[0337] Comparative Examples 1-8

[0338] An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound of the structure of Comparative Example 1-8 was used instead of the compound of doping compound I-1 in Example 1.

[0339] The structures of EBM, RH-01 and Comparative Examples 1-8 are as follows:

[0340]

[0341] 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 3 below:

[0342]

[0343]

[0344] It can be seen from Table 3 that, compared with the organic electroluminescent device prepared by using the compound provided by the present invention as the doping material of the light-emitting layer, the present invention selects a specific ligand compound, and changes the spatial configuration and stereostructure between molecules by fusing one or more benzene rings on the benzofuran or benzothiophene ring, sets the molecular orientation, increases the planarity between molecules, and matches the device structure of the present invention, so that the OLED device has the advantages of long life, high efficiency, and low driving voltage.

[0345] The above embodiments only list the effect data of devices made of a part of the structural formulas. This is a representative sampling test. According to the experimental data, the overall data is not much different and can represent the effects of other unlisted structures.

[0346] It will be apparent to those skilled in the art that many modifications and variations of the present invention are possible without departing from the spirit and scope of the present invention. It is therefore contemplated that the present invention covers modifications and variations of the present invention provided within the scope of the appended claims and their equivalents.

[0347] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A doping material, characterized in that: Having the structure shown in general formula Ⅰ: M(L A )2(L B ); Wherein, M is metal; Where L A and L B are all ligands, a type of organic compound; preferably, L A and L B is a compound having the following general structural formula, In the formula, R1-R8, Ar1, Ar2, Ar3 and Ar4 are independently selected from any one of -H, -D (deuterium), -T (tritium), -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, -Ge(Me)3, -Si(Me)3, substituted or unsubstituted C2-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C20 aryl and substituted or unsubstituted 4-8 membered aromatic heterocyclic group; Wherein, m, n, p and q are integers representing integers between no substitution and maximum substitution in the ring; X is O or S; H1 and H2 are independently selected from hydrogen or a benzene ring, and are connected to the benzene ring by substitution or by forming a condensed ring; M is preferably metal Ir.

2. The doping material according to claim 1, characterized in that Formula L A The specific structure is as follows: Among them, R1-R8, Ar1-Ar4 are the same as above; m1, m2, m3, m4, p3, p4, p5 and n5 are integers between 0 and 4, q1 and q2 are integers between 0 and 2, and n1, n2, n3 and n4 are integers between 0 and 1.

3. The doping material according to claim 1, wherein the hydrogen atoms are independently substituted by deuterium or are not substituted by deuterium.

4. The doping material according to claim 1, characterized in that R1-R8, Ar1-Ar4 are each independently selected from the following groups: -H, -D, -T, -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, -Ge(Me)3, -Si(Me)3, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, thiolane, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl , anthracenyl, triphenylene, tetraphenyl, fluoranthene, furanyl, thienyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, triazine, tetrazine, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl or any combination thereof.

5. The doping material according to claim 1, characterized in that The doping material is selected from any one of the compounds represented by the following structural formulas:

6. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an organic layer; the organic layer contains the doping material as claimed in claim 1.

7. The organic electroluminescent device according to claim 6, characterized in that: The organic electroluminescent device further comprises a first electrode and a second electrode; the organic layer is disposed between the first electrode and the second electrode; in, The organic layer includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a luminescence auxiliary layer, a luminescent layer, a hole blocking layer, an electron transport layer and an electron injection layer; and the luminescent layer contains the doping material.

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