Organic metal iridium complex, preparation method and organic electroluminescent device containing organic metal iridium complex

Abstract

The invention belongs to the field of organic electroluminescence, and provides an organic metal iridium complex, a preparation method and an organic electroluminescent device containing the organic metal iridium complex. The structural general formula of the organic metal iridium complex is shown in the specification. After the organic metal iridium complex provided by the invention is applied to the organic electroluminescent device, the starting voltage of the device is reduced, the luminous efficiency of the device is improved, and the service life of the device is prolonged.

Description

Technical Field

[0001] The invention belongs to the field of organic electroluminescence, and in particular relates to an organic metal iridium complex, a preparation method and an organic electroluminescent device containing the same. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a type of device with a sandwich-like structure, including positive and negative electrode film layers and organic functional material layers sandwiched between the electrode film layers. When voltage is applied to the electrodes of the OLED device, positive charges are injected from the positive electrode and negative charges are injected from the negative electrode. Under the action of the electric field, the positive and negative charges migrate in the organic layer and meet to combine and emit light. Due to the advantages of high brightness, fast response, wide viewing angle, simple process, and flexibility, OLED devices have attracted much attention in the fields of new display technology and new lighting technology. At present, OLED has been widely used in display panels of new lighting fixtures, smart phones, tablet computers and other products, and will further expand to the application fields of large-size display products such as TVs. It is a new display technology with fast development and high technical requirements.

[0003] Therefore, the research on high-efficiency phosphorescent organic electroluminescent devices provides an important impetus for the development of flat panel and portable display industries. How to develop a high-performance phosphorescent material that enables organic electroluminescent devices 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

[0004] In view of this, the present invention provides an organometallic iridium complex, a preparation method and an organic electroluminescent device comprising the same. When the organometallic iridium complex of the present invention is used in an organic electroluminescent device, not only the starting voltage of the device is reduced, but also the luminous efficiency and life of the device are improved.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] The first technical purpose of the present invention is to provide an organic metal iridium complex, the chemical formula of which is Ir(L A )2(L B );L A and L B All are ligands, with the following structural formulas:

[0007]

[0008] in,

[0009] Ar1 independently represents none or is selected from substituted or unsubstituted C 6- C 18Aryl, and the aryl group may be fused at the 1,2, 2,3 or 3,4 position of dibenzofuran;

[0010] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 and R 12 are independently selected from -H, -D, -T, -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, silicon, germanium, substituted or unsubstituted C2-C 10 Alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C 20 any one of an aryl group, a substituted or unsubstituted 4- to 8-membered heterocyclic group, wherein R1, R2, R3, R4, R5, R6, R7 and R8 are independently formed with other substituents on the ring to form a substituted or unsubstituted C3-C 10 Aliphatic ring, substituted or unsubstituted C6-C 10 Aromatic ring, substituted or unsubstituted C4-C 10 Aromatic heterocyclic ring, substituted or unsubstituted C 10 -C 18 Condensed ring;

[0011] S 13 , S 14 , S 15 is unsubstituted, monosubstituted or polysubstituted; S 13 , S 14 , S 15 independently selected from -H, -D, -T, -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, silicon, germanium substituted or unsubstituted C2-C 10 Alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C 20 Any one of aryl, substituted or unsubstituted 4-8 membered heterocyclic group; wherein S 15 At least one of the substituents is phenyl.

[0012] Specifically, the substituents on the above-mentioned substituent groups are at least selected from one or more of -H, -D, -T, -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, and -CHF2.

[0013] Furthermore, L B The ligand is selected from any of the following structures:

[0014]

[0015] Ar1 independently represents none or is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl.

[0016] And, according to S 15 The substitution position of the phenyl group in B The ligand is selected from any of the following structures:

[0017]

[0018] Furthermore, L B The following structures are preferred:

[0019]

[0020]

[0021] Furthermore, L A The ligand is selected from any one of the following structures LA-1 to LA-110:

[0022]

[0023]

[0024]

[0025]

[0026] Furthermore, the organometallic iridium complex is selected from any one of the following structures:

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

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[0042]

[0043]

[0044]

[0045]

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[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

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[0064]

[0065]

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[0067]

[0068]

[0069]

[0070]

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[0072]

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[0075]

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[0080]

[0081]

[0082]

[0083]

[0084] Only some specific structural forms are listed above, but this series of organometallic iridium complexes are not limited to the above molecular structures. Other specific molecular structures can be obtained by simple changes of some simple groups and their substituted groups and substitution positions, which will not be described one by one here.

[0085] The second object of the present invention is to provide a method for preparing the above-mentioned organometallic iridium complex. The organometallic iridium complex of the present invention can be prepared by a synthetic method known to those skilled in the art. Alternatively, the following reaction process is preferably used for preparation, and the specific synthetic route is as follows:

[0086]

[0087] Step 1: Add raw material LA, iridium trichloride trihydrate, ethylene glycol ethyl ether and water under nitrogen, react at 120°C for 48 hours, filter, rinse with ethanol and petroleum ether, and dry to obtain intermediate L-A1;

[0088] Step 2: Add intermediate L-A1, silver trifluoromethanesulfonate, isopropanol and dichloromethane under nitrogen, react at 25°C for 48 hours, pass through a silica gel funnel, rinse with dichloromethane until there is no product, combine the organic phases and spin dry to obtain intermediate L-A2;

[0089] Step 3: Add intermediate L-A2, LB, and ethanol under nitrogen conditions, react at 90°C for 48 hours, then filter and obtain product L by column chromatography.

[0090] The third object of the present invention is to provide the use of the above-mentioned organometallic iridium complex in an organic electroluminescent device.

[0091] An electroluminescent device, comprising the organic metal iridium complex. The organic electroluminescent device comprises: a first electrode, a second electrode and an organic layer disposed between the two electrodes, wherein the organic layer comprises the organic metal iridium complex of the present invention; the organic metal iridium complex is in a single form or mixed with other substances and exists in the organic layer.

[0092] The organic layer at least includes one or more of a hole injection layer, a hole transport layer, a layer having both hole injection and hole transport skills, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer having both electron transport and electron injection skills.

[0093] The organic electroluminescent device comprises at least one functional layer, namely the organic metal iridium complex of the present invention.

[0094] The organic electroluminescent device comprises a light-emitting layer, and the light-emitting layer contains the organic metal iridium complex of the present invention.

[0095] The light-emitting layer of the organic electroluminescent device comprises a main material and a doping material, wherein the doping material is the organic metal iridium complex of the present invention, and the mixing ratio of the main material to the doping material is 90:10 to 99.5:0.5.

[0096] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0097] The invention provides an organic metal iridium complex. By introducing functional groups such as benzene and naphthalene into a dibenzofuran ring body and adding some electron-withdrawing groups such as cyano or methyl, the compound of the invention changes the molecular configuration, increases the conjugated system, and adjusts the electrochemical properties of the compound compared with a comparative example compound. After the obtained organic compound is used in an organic electroluminescent device, the starting voltage of the device is not only reduced, but also the luminous efficiency and life of the device are improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0098] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0099] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of L-559 in Example 4. DETAILED DESCRIPTION

[0100] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0101] The embodiments of the present invention disclose an organic metal iridium complex, a preparation method and an organic electroluminescent device containing the same.

[0102] 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.

[0103] Example 1 Preparation of organometallic compound L-1

[0104] The specific operation and process route are as follows:

[0105]

[0106] Step 1: Under nitrogen conditions, weigh intermediate A-1 (CAS: 50548-45-3, 404 mmol), B-1 (CAS: 475156-28-6, 445 mmol), tetrakistriphenylphosphine palladium (7.91 mmol), 1000 ml of toluene, 500 ml of ethanol, 500 ml of water, and potassium carbonate (1.18 mol), react at 100 ° C for 24 hours, separate and dry, and column chromatography to obtain intermediate C-1 (64.2 g, yield 65%);

[0107] HPLC purity:>99%

[0108] Mass spectrum: Test value 244.10

[0109]

[0110] Step 2: Under nitrogen, weigh the raw material C-1 (245 mmol), add 600 ml of DMF into a three-necked flask, and stir for 5 minutes; add NBS (220 mmol) at room temperature and stir for 2 hours; add saturated brine (700 ml), and obtain intermediate D-1 (46.8 g, yield 59%) by column chromatography;

[0111] HPLC purity:>99%

[0112] Mass spectrum:; Test value 322.01

[0113]

[0114] Step 3: Under nitrogen, weigh intermediate D-1 (123 mmol), E-1 (CAS: 372963-49-0135 mmol), tetrakistriphenylphosphine palladium (2.42 mmol), 400 ml of toluene, 200 ml of ethanol, 200 ml of water, and potassium carbonate (374 mmol), react at 100 ° C for 24 h, separate and dry, and obtain intermediate F-1 (25 g, yield 63%) by column chromatography;

[0115] HPLC purity:>99%

[0116] Mass spectrum: Test value 335.15

[0117]

[0118] Step 4: Under nitrogen, weigh the raw material G-1 (CAS: 1622235-49-759.8mmol), iridium trichloride (27.2mmol), ethylene glycol ether 200ml, water 67ml, react at 120℃ for 48h. Filter and wash, and dry to obtain the intermediate H-1 (12.5g, yield 80%);

[0119] Step 5: Under nitrogen, weigh the raw material H-1 (10.6 mmol), silver trifluoromethanesulfonate (23.3 mmol), 242 ml of dichloromethane, and 60 ml of isopropanol, and react at 25°C for 48 h. Pass through a silica gel funnel and spin dry to obtain the intermediate I-1 (12 g, yield 75%)

[0120]

[0121] Step 6: Under nitrogen conditions, weigh the raw materials I-1 (11.2 mmol), F-1 (28 mmol), and 220 ml of ethanol, react at 90° C. for 48 h, and filter and column chromatograph to obtain the final product L-1 (5.7 g, 60% yield);

[0122] HPLC purity>99%

[0123] Mass spectrum: Test value 869.31

[0124] Elemental analysis: calculated value; C 66.34%; H, 4.87%; N, 4.84%; O 1.84%.

[0125] Measured values: C, 66.35%; H 4.88%; N 4.86%; O 1.87%

[0126] Nuclear magnetic field: NMR (400MHz, Chloroform-d) δ8.43(d,1H),8.33(d,2H),8.11(dd,2H),8.01(dd,1H),7.89(s,1H),7.72(dq,1H), 7.69(dd,2H),7.64(dd,2H),7.57(ddd,4H),7.49-7.41(m,5H),7.38-7.25(m,4H),7.13(td,2H),2.30-2.26(m,3H).

[0127] Example 2 Preparation of organometallic compound L-253

[0128] The specific operation and process route are as follows:

[0129]

[0130] Step 1: Under nitrogen conditions, weigh intermediate A-253 (CAS: 2411141-56-3395mmol), B-253 (434mmol), tetrakistriphenylphosphine palladium (7.91mmol), 1000ml toluene, 500ml ethanol, 500ml water, potassium carbonate (1.18mol), react at 100°C for 24h, separate and dry, and column chromatography to obtain intermediate C-235 (90.48g, yield 78%);

[0131] HPLC purity:>99%

[0132] Mass spectrum: Test value 294.12

[0133]

[0134] Step 2: Weigh the raw material C-253 (305 mmol) under nitrogen, add 600 ml of DMF into a three-necked flask, and stir for 5 minutes; add NBS (335 mmol) at room temperature and stir for 2 hours; add saturated brine (700 ml), and obtain intermediate D-253 (74.1 g, yield 65%) by column chromatography;

[0135] HPLC purity:>99%

[0136] Mass spectrometry test value 372.03

[0137]

[0138] Step 3: Under nitrogen, weigh the intermediate D-253 (187 mmol), E-253 (CAS 197958-29-5206 mmol), tetrakistriphenylphosphine palladium (3.74 mmol), 700 ml of toluene, 350 ml of ethanol, 350 ml of water, and potassium carbonate (562 mmol), react at 100 ° C for 24 hours, separate and dry, and obtain the intermediate F-253 (49.4 g, yield 71%) by column chromatography;

[0139] HPLC purity>99%

[0140] Mass spectrum: Test value 371.15

[0141]

[0142] Step 4: Under nitrogen, weigh the raw material G-253 (CAS: 1008-89-596.6mmol), iridium trichloride (32.2mmol), 220ml of ethylene glycol ether, and 73ml of water, and react at 120°C for 48h. Filter, rinse, and dry to obtain the intermediate H-253 (14.1g, yield 82%);

[0143] Step 5: Under nitrogen, weigh the raw material H-253 (11.2 mmol), silver trifluoromethanesulfonate (24.6 mmol), 240 ml of dichloromethane, and 60 ml of isopropanol, and react at 25°C for 48 hours. Pass through a silica gel funnel and spin dry to obtain the intermediate I-253 (12.9 g, yield 81%);

[0144]

[0145] Step 6: Under nitrogen, weigh the raw materials I-253 (9.63 mmol), F-253 (24.09 mmol), and 160 ml of ethanol, react at 90° C. for 48 h; filter and column chromatography to obtain the final product L-253 (4.61 g, yield 55%);

[0146] HPLC purity>99%

[0147] Mass spectrum: Test value 871.24

[0148] Elemental analysis: calculated value: C, 67.57%; H, 3.70%; N, 4.82%; O, 1.84%. Measured value: C, 67.57%; H 3.73%; N 4.83%; O, 1.86%

[0149] Nuclear magnetic field: NMR (400MHz, Chloroform-d) δ8.70-8.62(m,3H),8.17(dd,1H),8.09(dd2H),7.93-7.88(m,2H),7.86(dd,1H),7.77-7.64(m,7H),7. 59-7.53(m,2H),7.52-7.41(m,5H),7.40(td,1H),7.38-7.31(m,1H),7.28(td,2H),7.27-7.21(m,2H),7.24-7.19(m,1H),7.13(td,2H).

[0150] Example 3 Preparation of organometallic compound L-325

[0151] The specific operation and process route are as follows:

[0152]

[0153] Step 1: Under nitrogen conditions, weigh intermediate A-325 (CAS: 2411141-56-3395mmol), B-325 (434mmol), tetrakistriphenylphosphine palladium (7.91mmol), 1000ml of toluene, 500ml of ethanol, 500ml of water, and potassium carbonate (1.18mol), react at 100°C for 24h, separate and dry, and obtain intermediate C-325 (90.48g, yield 78%) by column chromatography;

[0154] HPLC purity:>99%

[0155] Mass spectrum:; Test value 294.11

[0156]

[0157] Step 2: Under nitrogen, weigh the raw material C-325 (305 mmol), add DMF 600 ml into a three-necked flask, and stir for 5 minutes; add NBS (335 mmol) at room temperature and stir for 2 hours, add saturated brine (700 ml), and perform column chromatography to obtain the intermediate D-325 (74.1 g, yield 65%);

[0158] HPLC purity:>99%

[0159] Mass spectrum: Test value 372.03

[0160]

[0161] Step 3: Under nitrogen, weigh the intermediate D-325 (187 mmol), E-325 (CAS 197958-29-5206 mmol), tetrakistriphenylphosphine palladium (3.74 mmol), 700 ml of toluene, 350 ml of ethanol, 350 ml of water, and potassium carbonate (562 mmol), react at 100 ° C for 24 hours, separate and dry, and obtain the intermediate F-325 (49.4 g, yield 71%) by column chromatography;

[0162] HPLC purity>99%

[0163] Mass spectrum: Test value 371.14

[0164]

[0165] Step 4: Weigh raw materials G-325 (CAS: 701261-35-0490mmol), H-325 (CAS: 53939-30-3490mmol), potassium carbonate (1.4mol), 500ml toluene, 250ml ethanol, react at 70°C for 8h; spin dry column chromatography to obtain intermediate I-325 (63g, yield 70%);

[0166] HPLC purity>99%

[0167] Mass spectrum: Test value 183.10

[0168]

[0169] Step 5: Weigh the raw materials I-325 (342 mmol), O-325 (CAS 5720-05-8342 mmol), potassium carbonate (1.02 mol), 630 ml of toluene, 315 ml of ethanol, and 315 ml of water, and react at 90° C. for 12 h; spin dry column chromatography to obtain intermediate K-325 (53 g, yield 65%);

[0170] HPLC purity>99%

[0171] Mass spectrum: Test value 224.22

[0172] Step 6: Weigh the raw material K-325 (221 mmol), potassium hydroxide (442 mmol), and dimethyl sulfoxide 280 ml, react at 90° C. for 48 h; separate the liquid and perform spin-drying column chromatography to obtain the intermediate J-325 (27.5 g, yield 50.9%);

[0173]

[0174] Step 7: Under nitrogen, weigh the raw material J-325 (22.8 mmol), iridium trichloride (50.3 mmol), ethylene glycol ethyl ether 514 ml, and water 171 ml, and react at 120° C. for 48 h; filter, rinse, and dry to obtain the intermediate M-325 (22.2 g, yield 60%);

[0175] Step 8: Under nitrogen, weigh the raw material M-325 (15.3 mmol), silver trifluoromethanesulfonate (33.8 mmol), 440 ml of dichloromethane, and 89 ml of isopropanol, and react at 25° C. for 48 h; pass through a silica gel funnel and spin dry to obtain the intermediate N-325 (17.5 g, yield 60%);

[0176]

[0177] Step 9: Under nitrogen, weigh the raw materials N-325 (9.69 mmol), F-325 (24.22 mmol), and 200 ml of ethanol, react at 90° C. for 48 h; filter and column chromatography to obtain the final product L-325 (6.2 g, yield 61%);

[0178] HPLC purity>99%

[0179] Mass spectrum: Test value 1049.48

[0180] Elemental analysis: calculated value: C, 69.82%; H, 6.34%; N, 4.00%; O, 1.52%. Found value: C 69.83%; H 6.36%; N 4.02%; O, 1.53%

[0181] Nuclear magnetic field: NMR (400MHz, Chloroform-d) δ8.72 (dd, 1H), 8.40-8.34 (m, 1H), 8.31 (s, 1H), 8.25 (d, 2H), 7.97-7.89 (m, 3H), 7. 87(d,2H),7.83(d,2H),7.75(d,1H),7.70(dd,1H),7.57(dd,2H),7.50-7.28(m,11H),7.25(ddd,1H),1.19(s,18H).

[0182] Example 4 Preparation of organometallic compound L-559

[0183] The specific operation and process route are as follows:

[0184]

[0185] Step 1: Under nitrogen conditions, weigh intermediate A-559 (CAS: 86-76-0404mmol), B-559 (445mmol), tetrakistriphenylphosphine palladium (7.91mmol), 1000ml toluene, 500ml ethanol, 500ml water, potassium carbonate (1.18mol), react at 100°C for 24h, separate and dry, and column chromatography to obtain intermediate C-559 (64.2g, yield 65%);

[0186] HPLC purity:>99%

[0187] Mass spectrum: Test value 244.10

[0188]

[0189] Step 2: Under nitrogen, weigh the raw material C-559 (245 mmol), add DMF 600 ml into a three-necked flask, and stir for 5 minutes; add NBS (220 mmol) at room temperature and stir for 2 hours, add saturated brine (700 ml), and perform column chromatography to obtain the intermediate D-559 (24.5 g, yield 31%);

[0190] HPLC purity:>99%

[0191] Mass spectrum: Test value 322.01

[0192]

[0193] Step 3: Under nitrogen conditions, weigh the intermediate D-559 (74.25mmol), E-559 (CAS: 197958-29-581.61mmol), tetrakistriphenylphosphine palladium (1.23mmol), 240ml of toluene, 120ml of ethanol, 120ml of water, and potassium carbonate (222mmol), react at 100°C for 24h, separate and spin dry, and column chromatography to obtain the intermediate F-559 (20.8g, yield 70%);

[0194] HPLC purity>99%

[0195] Mass spectrum: Test value 321.14

[0196]

[0197] Step 4: weigh raw material G-559 (CAS: 27012-22-296.3mmol), iridium trichloride (32.1mmol), ethylene glycol ether 218ml, water 71ml, react at 120°C for 48h; filter, wash, and dry to obtain intermediate H-559 (13.8g, yield 82%);

[0198] Step 5: Under nitrogen, weigh the raw material H-559 (11.1 mmol), silver trifluoromethanesulfonate (24.4 mmol), 238 ml of dichloromethane, and 60 ml of isopropanol, and react at 25°C for 48 hours; pass through a silica gel funnel and spin dry to obtain the intermediate I-559 (12.5 g, yield 78%);

[0199]

[0200] Step 6: Under nitrogen, weigh the raw materials I-559 (11.18 mmol), F-559 (27.96 mmol), and 180 ml of ethanol, react at 90°C for 48 hours, and filter and column chromatograph to obtain the final product L-559 (5.97 g, yield 63%);

[0201] HPLC purity>99%

[0202] Mass spectrum: Test value 849.25

[0203] Elemental analysis: calculated value: C, 66.49%; H, 4.04%; N, 4.95%; O, 1.88%. Found value: C 66.50%; H 4.05%; N 4.97%; O, 1.89%

[0204] Nuclear magnetic field: NMR (400MHz, Chloroform-d) δ8.68 (dd, 1H), 8.43-8.39 (m, 2H), 8.13 (dd, 2H), 8.02-7.95 (m, 2H), 7. 82-7.73(m,3H),7.71-7.64(m,3H),7.59-7.53(m,3H),7.49-7.19(m,10H),7.12(td,2H),2.28(d,6H).

[0205] Example 5 Preparation of organometallic compound L-469

[0206] The specific operation and process route are as follows:

[0207]

[0208] Step 1: Under nitrogen, weigh raw material A-469 (CAS: 605-87-8514mmol), 1.5L chloroform, and 600ml acetic acid, and stir for 5 minutes; add NBS (566mmol) at room temperature and stir for 2 hours, add saturated brine (700ml), and column chromatography to obtain intermediate B-469 (95.2g, yield 68%);

[0209] HPLC purity:>99%

[0210] Mass spectrum: Test value 271.99

[0211]

[0212] Step 2: Under nitrogen conditions, weigh the raw material B-469 (329 mmol), biboric acid pinacol ester (657 mmol), 1.4-dioxane (1.8 l), potassium acetate 0.82 mol), and add them to the reaction system in sequence, replace the nitrogen twice, add tris (dibenzylideneacetone) dipalladium (3.28 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (26.31 mmol) under nitrogen conditions, and reflux for 24 hours; after the reaction stops, the system is cooled to room temperature, the system is passed through a silica gel funnel, spin-dried, and column chromatography is performed to obtain intermediate C-469 (73.8 g, yield 70%);

[0213] HPLC purity: ≥99%

[0214]

[0215] Step 3: Under nitrogen, weigh C-469 (218 mmol), D-469 (218 mmol CAS: 31928-44-6), potassium carbonate (652 mmol), toluene (700 ml), ethanol (305 ml), water (350 ml), replace nitrogen twice, add tetrakistriphenylphosphine palladium (4.36 mmol) under nitrogen, react at 70 ° C for 24 hours, cool to room temperature after the reaction is completed, separate with ethyl acetate, spin dry, and column chromatography to obtain intermediate E-469;

[0216] Under nitrogen protection, add intermediate E-469 (144 mmol), potassium carbonate (432 mmol) and DMF (1500 mL) to the reaction system in sequence, then heat and stir at 100°C to react for 12 h; after the reaction is complete, cool, filter on diatomaceous earth, wash the organic phase with saturated brine, extract twice with ethyl acetate, dry with anhydrous magnesium sulfate, and concentrate under reduced pressure; purify the crude product by column chromatography, and elute with 20% (v / v) dichloromethane / petroleum ether solution to obtain intermediate F-469 (33.18 g, yield 60%);

[0217] HPLC purity: ≥99%

[0218] Mass spectrum: Test value 302.06.

[0219]

[0220] Step 4: Under nitrogen, weigh the intermediate F-469 (109 mmol), phenylboronic acid (119 mmol), tetrakistriphenylphosphine palladium (2.16 mmol), 330 ml of toluene, 150 ml of ethanol, 150 ml of water, and potassium carbonate (326 mmol), react at 100 ° C for 24 h, separate and dry, and perform column chromatography to obtain the intermediate G-469 (26.2 g, yield 70%);

[0221] HPLC purity:>99%

[0222] Mass spectrum: Test value 344.13

[0223]

[0224] Step 5: Under nitrogen, weigh the raw material G-469 (75.49 mmol), add 300 ml of DMF into a three-necked flask, and stir for 5 minutes; add NBS (83.03 mmol) at room temperature and stir for 2 hours, add saturated brine (350 ml), and perform column chromatography to obtain the intermediate H-469 (13.1 g, yield 41%);

[0225] HPLC purity:>99%

[0226] Mass spectrum; Test value 422.04

[0227]

[0228] Step 6: Under nitrogen, weigh the intermediate H-469 (30.71 mmol), I-469 (33.76 mmol), tetrakistriphenylphosphine palladium (0.61 mmol), 130 ml of toluene, 65 ml of ethanol, 65 ml of water, and potassium carbonate (92.02 mmol), react at 100 ° C for 24 hours, separate and dry, and obtain the intermediate J-469-A (9.06 g, yield 70%) by column chromatography;

[0229] HPLC purity>99%

[0230] Mass spectrum: Test value 421.17

[0231]

[0232] Step 7: Under nitrogen, weigh J-469-1 (CAS: 27012-22-273.2mmol), 123ml of dimethyl sulfoxide, and sodium hydroxide (146mmol), react at 90°C for 48h, separate the liquid and spin dry it through a funnel to obtain intermediate J-469-2 (17g, yield 85%);

[0233] Step 8: Under nitrogen, weigh the raw material J-469-2 (60.2 mmol), iridium trichloride (27.4 mmol), ethylene glycol ether 192 ml, and water 64 ml, react at 120° C. for 48 h, filter and wash, and dry to obtain the intermediate J-469-3 (16.9 g, yield 78%);

[0234] Step 9: Under nitrogen, weigh the raw material J-469-3 (10.1 mmol), silver trifluoromethanesulfonate (22.4 mmol), 320 ml of dichloromethane, and 59 ml of isopropanol, react at 25°C for 48 hours, pass through a silica gel funnel, and spin dry to obtain the intermediate J-469-4 (14.1 g, yield 68%);

[0235]

[0236] Step 10: Under nitrogen, weigh the raw materials J-469-4 (8.51 mmol), J-469-A (21.35 mmol), and 160 ml of ethanol, react at 90°C for 48 h, and filter and column chromatograph to obtain the final product L-469 (6.3 g, yield 63%);

[0237] HPLC purity>99%

[0238] Mass spectrum: Test value 1175.51

[0239] Elemental analysis: calculated value; C, 72.54%; H, 6.17%;; N, 3.57%; O, 1.36%. Found value; C, 72.56%; H, 6.18%; N, 3.58%; O, 1.38% NMR: NMR (400MHz, Chloroform-d) δ8.84 (dd, 1H), 8.67 (dd, 1H), 8.29 (s, 2H), 7.94-7.89 (m, 2H), 7.87 (dd, 1H), 7.81 (d, 1H), 7.74 (dd, 1H), 7.68 (td, 1H), 7.63-7.38 (m, 18H), 7.38-7.30 (m, 3H), 7.30-7.24 (m, 4H), 7.24-7.19 (m, 1H).

[0240] The synthesis methods of other organometallic iridium complexes L-7, L-9, L-10, L-76, L-77, L-181, L-217, L-361, L-505, and L-595 are the same as those in the above embodiments and are not described in detail here. The molecular formula and mass spectrum of the synthesized organometallic iridium complexes are shown in Table 1 below.

[0241] Table 1

[0242] Compound Molecular formula Mass spectrometry test value L-7 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 48 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 30 <h2 style=";text-align:left;direction:ltr"> D6IrN3O]]><h2 style=";text-align:left;direction:ltr"> 869.30 L-9 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 48 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 30 <h2 style=";text-align:left;direction:ltr"> D6IrN3O]]><h2 style=";text-align:left;direction:ltr"> 869.30 L-10 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 48 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 30 <h2 style=";text-align:left;direction:ltr"> D6IrN3O]]><h2 style=";text-align:left;direction:ltr"> 869.30 L-76 <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"> 32 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 835.24 L-77 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 47 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 34 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 849.25 L-181 <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"> 30 <h2 style=";text-align:left;direction:ltr"> D6IrN3O]]><h2 style=";text-align:left;direction:ltr"> 905.30 L-217 <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"> 899.27 L-361 <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"> 955.33 L-505 <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"> 48 <h2 style=";text-align:left;direction:ltr"> D<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> IrN3O]]><h2 style=";text-align:left;direction:ltr"> 1099.49 L-595 <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"> 32 <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"> 1074.48

[0243] Device Embodiment

[0244] Device Example 1: Preparation of an organic electroluminescent device using an organometallic compound of formula L-1

[0245] The coating thickness is The ITO glass substrate was cleaned twice in distilled water and ultrasonically washed for 30 minutes. After the distilled water cleaning, it was ultrasonically cleaned in sequence with isopropanol, acetone, methanol and other solvents, dried, and transferred to a plasma cleaning machine. The above substrate was washed for 5 minutes and sent to a vapor deposition machine.

[0246] First, the thickness of the ITO (anode) vapor deposition is 4,4',4"-tri[2-naphthylphenylamino]triphenylamine ("2-TNATA") is used as a hole injection layer, and then a layer with a thickness of 1000 nm is deposited on the hole injection layer. N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) was used as a hole transport layer, and then a layer with a thickness of 1000 nm was evaporated on the hole transport layer. A light-emitting layer of a main material 4,4'-N,N'-biphenyldicarbazole ("CBP") and a dopant compound of formula L-1 (the weight ratio of the main material to the dopant is 90:10) is then deposited on the light-emitting layer with a thickness of ALq3 is used as the electron transport layer, and then the thickness of the electron transport layer is evaporated on the electron transport layer. The electron injection layer material Liq is finally deposited on the electron injection layer with a thickness of By adding Al as cathode material, an organic electroluminescent device can be obtained.

[0247] The luminescence characteristics of the obtained device were tested using a KEITHLEY 2400 source measurement unit and a CS-2000 spectroradiometer to evaluate the driving voltage, lifespan, and luminescence efficiency.

[0248] Device Comparative Example 1-Device Comparative Example 7:

[0249] An organic electroluminescent device was prepared in the same manner as in device example L-1, and the structure of the green light-emitting doping compound in the luminescent layer was as follows:

[0250]

[0251]

[0252] Device Example 2-Device Example 15:

[0253] Referring to the method of the above device embodiment L-1, the only difference is that the doping material L-1 is replaced by L-181, L-217, L-253, L-325, L-361, L-469, L-505, L-559, L-595, L-7, L-9, L-10, L-76, and L-77.

[0254] The driving voltage, luminous efficiency and life of the organic electroluminescent devices obtained from the above device embodiments and device comparative examples were characterized at a brightness of 2000 (nits). The test results are shown in Table 2 below.

[0255] Table 2

[0256] Devices Driving voltage(V) Luminous efficiency (cd / A) <![CDATA[T 95 (h)]]> Device Comparison Example 1 4.05 40.4 527 Device Comparison Example 2 3.95 48.5 613 Device Comparison Example 3 4.10 46.2 588 Device Comparison Example 4 3.99 49.6 609 Device Comparison Example 5 3.89 47.3 596 Device Comparative Example 6 3.62 50.5 601 Device Comparison Example 7 3.79 49.3 590 Device Example 1 3.52 68.1 691 Device Example 2 3.34 67.8 693 Device Example 3 3.50 69.2 689 Device Example 4 3.42 78.3 695 Device Example 5 3.43 72.6 773 Device Example 6 3.24 73.4 696 Device Example 7 3.51 67.4 683 Device Example 8 3.53 66.1 702 Device Example 9 3.49 68.8 656 Device Example 10 3.48 62.6 754 Device Example 11 3.51 68.8 692 Device Example 12 3.53 68.5 688 Device Example 13 3.55 68.6 689 Device Example 14 3.45 69.3 691 Device Example 15 3.55 69.2 692

[0257] By comparing the device data L-1, L-7, L-9, L-10, and L-559 with Comparative Example 6, it can be seen that adding methyl groups to the pyridine ring and the benzofuran ring enhances their electron adsorption capacity, and by changing their spatial structure, the driving voltage is significantly reduced, and the luminous efficiency and life are significantly improved.

[0258] In addition, other comparative examples also show that adding benzene or naphthalene to the benzofuran ring increases its conjugated system, making its structure more stable and thus greatly improving the service life of the device.

[0259] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one 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. An organometallic iridium complex, characterized in that: The chemical formula of the organometallic iridium complex is Ir(L A )2(L B );L A and L B All are ligands, with the following structural formulas: in, Ar1 independently represents none or is selected from substituted or unsubstituted C 6- C 18 Aryl, and the aryl group may be fused at the 1,2, 2,3 or 3,4 position of dibenzofuran; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 and R 12 are independently selected from -H, -D, -T, -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, silicon, germanium, substituted or unsubstituted C2-C 10 Alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C 20 any one of an aryl group, a substituted or unsubstituted 4- to 8-membered heterocyclic group, wherein R1, R2, R3, R4, R5, R6, R7 and R8 are independently formed with other substituents on the ring to form a substituted or unsubstituted C3-C 10 Aliphatic ring, substituted or unsubstituted C6-C 10 Aromatic ring, substituted or unsubstituted C4-C 10 Aromatic heterocyclic ring, substituted or unsubstituted C 10 -C 18 Condensed ring; S 13 , S 14 , S 15 is unsubstituted, monosubstituted or polysubstituted; S 13 , S 14 , S 15 independently selected from -H, -D, -T, -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, -CHF2, silicon, germanium substituted or unsubstituted C2-C 10 Alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C 20 Any one of aryl, substituted or unsubstituted 4-8 membered heterocyclic group; wherein S 15 At least one of the substituents is phenyl.

2. The organometallic iridium complex according to claim 1, characterized in that The substituent on the substituted group is at least selected from one or more of -H, -D, -T, -F, -CN, -CH3, -CD3, -CT3, -CF3, -CH2F, and -CHF2.

3. The organometallic iridium complex according to claim 1 or 2, characterized in that: L B The ligand is selected from any of the following structures: Ar1 independently represents none or is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl.

4. The organometallic iridium complex according to claim 1, characterized in that L B The ligand is selected from any of the following structures:

5. The organometallic iridium complex according to claim 1, characterized in that L A The ligand is selected from any one of the following structures LA-1 to LA-110: L B The ligand is selected from any of the following structures:

6. The organometallic iridium complex according to claim 1, characterized in that The organometallic iridium complex is selected from any one of the following compounds:

7. A method for preparing an organometallic iridium complex as claimed in claim 1, characterized in that: The method specifically comprises the following steps: Step 1: Add raw material LA, iridium trichloride trihydrate, ethylene glycol ethyl ether and water under nitrogen, react at 120°C for 48 hours, filter, rinse with ethanol and petroleum ether, and dry to obtain intermediate L-A1; Step 2: Add intermediate L-A1, silver trifluoromethanesulfonate, isopropanol and dichloromethane under nitrogen, react at 25°C for 48 hours, pass through a silica gel funnel, rinse with dichloromethane until there is no product, combine the organic phases and spin dry to obtain intermediate L-A2; Step 3: Add intermediate L-A2, LB, and ethanol under nitrogen conditions, react at 90°C for 48 hours, filter, and obtain product L by column chromatography; The specific synthetic route is as follows: Among them, R1-R 12 , S 13 -S 15 , Ar1 are as defined in claim 1; and the ligand LB can be replaced by L B -2~L B -6.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the organometallic iridium complex according to claim 1.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic electroluminescent device comprises a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode; the organic layer comprises the organic metal iridium complex as claimed in claim 1.

10. The organic electroluminescent device according to claim 9, characterized in that: The organic electroluminescent device comprises a light-emitting layer; the light-emitting layer comprises a main material and a doping material, the doping material is the organic metal iridium complex, and the mixing ratio of the main material to the doping material is 90:10 to 99.5:0.5.

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