Metal iridium complex and use thereof

Abstract

The application relates to a kind of metal iridium complex and its application.The metal iridium compound has the general formula of Ir (La) (Lb) (Lc), wherein La is the structure shown in formula (1), and Lb is the structure shown in formula (2).The compound provided by the application has the advantages of good light and electrical stability, high luminous efficiency, long service life, high color saturation, etc., and can be used in organic light-emitting devices, especially as red light-emitting phosphor materials, and has the possibility of being applied to the AMOLED industry, especially for display, lighting and automobile tail light.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescence, in particular to an organic light-emitting material, and particularly to an iridium complex and the application thereof in an organic electroluminescence device. BACKGROUND

[0002] At present, the organic electroluminescence device (OLED) as a new generation of display technology has obtained more and more attention in the aspects of display and lighting technology, and has a very wide application prospect. However, compared with the market application requirements, the performance of the OLED device such as the luminous efficiency, the driving voltage and the service life still needs to be continuously strengthened and improved.

[0003] Generally, the basic structure of the OLED device is a sandwich structure with various different functional organic functional material films sandwiched in the middle of the metal electrode, and under the driving of the current, the holes and the electrons are injected from the cathode and the anode respectively, and the holes and the electrons are combined in the light-emitting layer after moving a distance, and are released in the form of light or heat, thereby generating the light emission of the OLED. However, the organic functional material is the core component of the organic electroluminescence device, and the thermal stability, the photochemical stability, the electrochemical stability, the quantum yield, the film-forming stability, the crystallinity and the color saturation of the material are all the main factors affecting the performance of the device.

[0004] Generally, the organic functional material includes a fluorescent material and a phosphorescent material. The fluorescent material is usually an organic small molecule material, and generally can only utilize 25% singlet state light emission, so the luminous efficiency is relatively low. The phosphorescent material can utilize the energy of 75% triplet state excitons in addition to 25% singlet state due to the spin-orbital coupling caused by the heavy atom effect, so the luminous efficiency can be improved. However, compared with the fluorescent material, the phosphorescent material started relatively late, and the thermal stability, the service life and the color saturation of the material still need to be improved, which is a challenging topic. Various compounds have been developed as phosphorescent materials. For example, the patent document CN107973823 discloses a class of iridium compounds of quinoline, but the color saturation and the device performance of the compound, especially the luminous efficiency and the device service life, still need to be improved; the patent document CN106459114 discloses a class of iridium compounds coordinated by a beta-diketone ligand, but the sublimation temperature of the compound is high, the color saturation is not good, and in particular, the device performance, especially the luminous efficiency and the device service life, is not ideal, and needs to be further improved; and the patent document CN111377969 discloses a class of iridium complexes of dibenzofuran bisisoquinoline However, the device performance of the two types of materials, especially the color saturation, cannot meet the display color gamut requirements of BT2020, and needs to be further improved to meet the market demand for OLED light-emitting materials; patent document CN108290914A discloses the structure of quinoline and benzopentaheterocyclic ring As a red light-emitting material, the device color index of this type of material cannot meet the wide color gamut requirement, and the connection and combination mode of the present application disclosed and taught by the patent cannot improve the device performance and emission wavelength; patent document CN111848689A discloses the structure of isoquinoline and benzofuran As a red light-emitting material, the device color index of this type of material cannot meet the wide color gamut requirement, and the connection and combination mode of the present application disclosed and taught by the patent cannot improve the device performance and emission wavelength; patent document CN111848689A discloses the structure of isoquinoline and benzofuran SUMMARY

[0005] The present application is completed to solve the above-mentioned problems, and aims to provide a high-performance organic electroluminescent device and a new material capable of realizing such an organic electroluminescent device.

[0006] The present inventors have repeatedly conducted in-depth research in order to achieve the aforementioned object, and as a result, it has been found that a high-performance organic electroluminescent device can be obtained by using a metal iridium complex including ligands represented by the following formula (1) and formula (2).

[0007] The metal iridium complex has a general formula of Ir(La)(Lb)(Lc), wherein La is a structure represented by formula (1), and Lb is a structure represented by formula (2). The complex provided by the present application has the advantages of good optical and electrical stability, high luminous efficiency, long service life, high color saturation, and the like, and can be used in an organic light-emitting device, especially as a red light-emitting phosphor material, and has the potential to be applied to the AMOLED industry, especially for display, lighting, and automobile tail lights.

[0008] A metal iridium compound has a general formula of Ir(La)(Lb)(Lc), wherein La is a structure represented by formula (1),

[0009]

[0010] wherein the dotted line represents the position connected to the metal Ir;

[0011] wherein X is O, S, Se, C(R0)2, Si(R0)2;

[0012] wherein R0-R 13each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted tri C1-C10 alkyl silyl, substituted or unsubstituted tri C6-C12 aryl silyl, substituted or unsubstituted di C1-C10 alkyl mono C6-C30 aryl silyl, substituted or unsubstituted mono C1-C10 alkyl di C6-C30 aryl silyl, or R 10 -R 13 two adjacent groups are connected to each other to form an aliphatic ring;

[0013] wherein R8 is not hydrogen, deuterium, halogen, cyano;

[0014] wherein the heteroalkyl and heterocycloalkyl groups contain at least one O, N, or S heteroatom;

[0015] wherein the substitution is by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkylamino, nitrile, isonitrile, or phosphine, and the number of substitutions is from mono-substitution to the maximum number of substitutions;

[0016] wherein Lb is a structure represented by formula (2),

[0017]

[0018] wherein the dotted line position represents the position connected to the metal Ir;

[0019] wherein Ra-Rg are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, or two of Ra, Rb, Rc are connected to form an aliphatic ring, and two of Re, Rf, Rg are connected to form an aliphatic ring;

[0020] wherein the heteroalkyl and heterocycloalkyl groups contain at least one O, N, or S heteroatom;

[0021] wherein the substitution is by deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, C1-C4 alkylamino, cyano, nitrile, isonitrile, or phosphine;

[0022] wherein Lc is a monoanionic bidentate ligand, Lc is not the same as Lb and is not an OO-type ligand;

[0023] wherein Lc is the same as or different from La, the difference being that the core structure is different or the core structure is the same but the substituents are different or the core structure is the same and the substituents are the same but the positions of the substituents are different;

[0024] wherein La, Lb, Lc are connected to each other to form a polydentate ligand.

[0025] As a preferred metal iridium complex, wherein X is O, S, C(R0)2, Si(R0)2, wherein R0 is substituted or unsubstituted C1-C6 alkyl.

[0026] As a preferred metal iridium complex, wherein at least one of R2-R7 is not H.

[0027] As a preferred metal iridium complex, wherein at least one of R1-R7 is F, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, the substitution being by deuterium, F, C1-C5 alkyl or C3-C6 cycloalkyl.

[0028] As a preferred metal iridium complex, wherein R8 is substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, the substitution being by deuterium, F, C1-C5 alkyl or C3-C6 cycloalkyl.

[0029] As a preferred metal iridium complex, wherein R8 is methyl or deuterated methyl.

[0030] As a preferred metal iridium complex, wherein R9-R 13 is hydrogen.

[0031] As a preferred metal iridium complex, wherein Lc is different from La.

[0032] As a preferred metal iridium complex, wherein Lc is a structure represented by formula (3),

[0033]

[0034] wherein R 21 -R 28independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, amino, imino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C17 heteroaryl, substituted or unsubstituted tri C1-C10 alkyl silyl, substituted or unsubstituted tri C6-C12 aryl silyl, substituted or unsubstituted di C1-C10 alkyl mono C6-C30 aryl silyl, substituted or unsubstituted mono C1-C10 alkyl di C6-C30 aryl silyl, or R

[0035] wherein R 25 -R 28 at least two of which are not hydrogen;

[0036] wherein R 21 -R 24 at least one pair of two adjacent groups form an aromatic ring as shown in formula (4);

[0037]

[0038] in formula (4)

[0039] wherein the dotted line indicates the position of the connection to the pyridine ring;

[0040] wherein R 31 -R 34 independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C17 heteroaryl, substituted or unsubstituted tri C1-C10 alkyl silyl, substituted or unsubstituted tri C6-C12 aryl silyl, substituted or unsubstituted di C1-C10 alkyl mono C6-C30 aryl silyl, substituted or unsubstituted mono C1-C10 alkyl di C6-C30 aryl silyl, or R 31 -R 34 two adjacent groups are connected to each other to form an alicyclic ring or an aromatic ring;

[0041] wherein the heteroalkyl and heteroaryl contain at least one O, N or S heteroatom;

[0042] wherein the substitution is by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkylamino, nitrile, isonitrile or phosphine, and the number of substitutions is from mono-substitution to the maximum number of substitutions.

[0043] Among them, R 21 With R 23 Or R 21 With R 23 An aromatic ring as shown in formula (4) is formed between them, R 31 -R 34 It is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroalkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C2-C10 heteroaryl.

[0044] As a preferred metal-iridium complex, Lc is one of the following structural formulas, or the corresponding partially or completely deuterated or fluorinated.

[0045]

[0046]

[0047] As a preferred metal iridium complex, La is one of the following structural formulas, or the corresponding partially or completely deuterated or fluorinated.

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] As a preferred metal iridium complex, Lb is one of the following structural formulas, or the corresponding partially or completely deuterated or fluorinated.

[0055]

[0056] The ligand La has the following structural formula:

[0057]

[0058] Where R1-R 13 X is as shown above.

[0059] The present application also aims to provide an electroluminescent device, which comprises a cathode, an anode and an organic layer disposed between the cathode and the anode, wherein the organic layer comprises the metal iridium complex.

[0060] The organic layer comprises a light-emitting layer, and the metal iridium complex is used as a red light-emitting dopant of the light-emitting layer; or the organic layer comprises a hole injection layer, and the metal iridium complex is used as a hole injection material in the hole injection layer.

[0061] The material of the present application has the advantages of high photochemical stability, high color saturation, high light-emitting efficiency, long device life, etc., and can be used in organic light-emitting devices, especially as a red light-emitting phosphor material, and has the possibility of application in the AMOLED industry, especially in display, lighting and automobile tail lights. As a phosphor material, the material of the present application can convert a triplet excited state into light, so as to improve the light-emitting efficiency of an organic electroluminescent device and reduce energy consumption. BRIEF DESCRIPTION OF DRAWINGS

[0062] Figure 1 is a 1H NMR spectrum of a deuterated chloroform solution of the compound La001 of the present application,

[0063] Figure 2 is a 1H NMR spectrum of a deuterated chloroform solution of the compound Ir(La002)2Lb005 of the present application,

[0064] Figure 3 is an ultraviolet absorption spectrum and an emission spectrum of a dichloromethane solution of the compound Ir(La001)2Lb005 of the present application. DETAILED DESCRIPTION

[0065] The organic metal iridium compound of the present application has a general formula of Ir(La)(Lb)(Lc), wherein La is a structure shown in formula (1),

[0066]

[0067] wherein the dotted line represents a position connected to the metal Ir;

[0068] wherein X is O, S, Se, C(R0)2, Si(R0)2;

[0069] wherein R0-R 13each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted tri C1-C10 alkyl silyl, substituted or unsubstituted tri C6-C12 aryl silyl, substituted or unsubstituted di C1-C10 alkyl mono C6-C30 aryl silyl, substituted or unsubstituted mono C1-C10 alkyl di C6-C30 aryl silyl, or R 10 -R 13 two adjacent groups are connected to each other to form an alicyclic ring;

[0070] wherein R8 is not hydrogen, deuterium, halogen, cyano;

[0071] wherein the heteroalkyl and heterocycloalkyl contain at least one O, N, or S heteroatom;

[0072] wherein the substitution is substitution with deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, nitrile, isonitrile, or phosphine, wherein the substitution is mono-substitution to the maximum number of substitution;

[0073] wherein Lb is a structure represented by formula (2),

[0074]

[0075] wherein the dotted line position represents the position connected to the metal Ir;

[0076] wherein Ra-Rg are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, or two of Ra, Rb, Rc are connected to form an aliphatic ring, and two of Re, Rf, Rg are connected to form an aliphatic ring;

[0077] wherein the heteroalkyl and heterocycloalkyl contain at least one O, N, or S heteroatom;

[0078] wherein the substitution is substitution with deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, C1-C4 alkyl substituted amine, cyano, nitrile, isonitrile, or phosphine;

[0079] wherein Lc is a monanionic bidentate ligand, Lc is not the same as Lb and is not an OO-type ligand;

[0080] wherein Lc is the same as or not the same as La, the not the same is that the mother nucleus structures are not the same, or the mother nucleus structures are the same but the substituents are different, or the mother nucleus structures are the same and the substituents are the same but the positions of the substituents are not the same;

[0081] wherein La, Lb, Lc are connected to each other to form a polydentate ligand.

[0082] Hereinafter, examples of each group of the compounds represented by formula (1) to formula (4) are described.

[0083] Note that, in the present specification, "carbon number a ~ b" in the expression "X group having a carbon number a ~ b which is substituted or unsubstituted" means the carbon number in the case where the X group is unsubstituted, and does not include the carbon number of the substituent when the X group is substituted.

[0084] As the C1-C10 alkyl group, straight-chain or branched-chain alkyl groups are exemplified, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group and its isomers, n-hexyl group and its isomers, n-heptyl group and its isomers, n-octyl group and its isomers, n-nonyl group and its isomers, n-decyl group and its isomers, and the like, preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, more preferably propyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group.

[0085] As the C3-C20 cycloalkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, 1-norbornyl group, 2-norbornyl group, and the like are exemplified, preferably cyclopentyl group, cyclohexyl group.

[0086] As the C2-C10 alkenyl group, ethenyl group, propenyl group, allyl group, 1-butyldienyl group, 2-butyldienyl group, 1-hexatrienyl group, 2-hexatrienyl group, 3-hexatrienyl group, and the like are exemplified, preferably propenyl group, allyl group.

[0087] As the C1-C10 heteroalkyl group, straight-chain or branched-chain alkyl groups, cycloalkyl groups, and the like which contain atoms other than carbon and hydrogen are exemplified, specifically, mercaptomethylmethane group, methoxymethylmethane group, ethoxymethylmethane group, t-butoxymethylmethane group, N,N-dimethylmethane group, epoxybutane group, epoxy pentane group, epoxyhexane group, and the like, preferably methoxymethylmethane group, epoxy pentane group.

[0088] As the aryl group, specific examples are phenyl group, naphthyl group, anthryl group, phenanthryl group, naphthacene group, pyrenyl group, chrysenyl group, benzo[c]phenanthryl group, benzo[g]chrysenyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, biphenyl group, terphenyl group, quaterphenyl group, fluoranthenyl group, and the like, preferably phenyl group, naphthyl group.

[0089] As specific examples of the heteroaryl group, there can be mentioned pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, isoindolyl, imidazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, diazadibenzofuranyl, diazadibenzothiophenyl, quinolyl, isoquinolyl, quinoxalyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, oxadiazolyl, furazanyl, thiophenyl, benzothiophenyl, dihydroacridinyl, azacarbazolyl, diazacarbazolyl, quinazolinyl, and the like, preferably pyridyl, pyrimidinyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, diazadibenzofuranyl, diazadibenzothiophenyl, carbazolyl, azacarbazolyl, diazacarbazolyl.

[0090] The following examples are merely for the purpose of facilitating the understanding of the technical invention and should not be regarded as specific limitations of the present invention.

[0091] The raw materials and solvents involved in the synthesis of the compounds in the present application are purchased from Alfa, Acros and other suppliers well known to those skilled in the art.

[0092] Synthesis of compound La001:

[0093]

[0094] Synthesis of compound 3:

[0095] Compound 1 (13.00 g, 49.9 mmol, 1.0 eq), compound 2 (7.23 g, 52.4 mmol, 1.05 eq), dichloro-di-tert-butyl-(4-dimethylaminophenyl) palladium (II) (176.7 mg, 0.25 mmol, 0.05 eq), sodium carbonate (10.58 g, 99.8 mmol, 2.00 eq), tetrahydrofuran (195 ml), deionized water (65 ml) were added into a 500 mL three-necked flask, vacuumed and replaced by nitrogen for 3 times, under the protection of nitrogen, the temperature was raised to 50 °C and the reaction was stirred for 4 hours. TLC monitoring showed that compound 1 was completely reacted. After cooling to room temperature, the mixture was allowed to stand and separate, the organic phase was collected and rotary evaporated to dryness, followed by column chromatography separation (eluent: tetrahydrofuran: n-hexane = 1:10), and concentrated to obtain white solid as compound 3 (9.5 g, yield: 69.54%), mass spectrum: 274.69 (M+H).

[0096] Compound 3 (9.5 g, 34.7 mmol, 1.0 eq), compound 4 (8.63 g, 38.2 mmol, 1.05 eq), tetrakis triphenylphosphine palladium (2.0 g, 1.73 mmol, 0.05 eq), sodium carbonate (7.36 g, 69.4 mmol, 2.00 eq), tetrahydrofuran (142.5 ml), methanol (47.5 ml), deionized water (47.5 ml) were added into a 500 mL three-necked flask, vacuumed and replaced by nitrogen for 3 times, under the protection of nitrogen, the reaction was stirred at 50 °C for 4.5 h. TLC monitoring, compound 3 was completely reacted. Cooled to room temperature, standing and separating, the aqueous phase was extracted with ethyl acetate (100 ml*3), the organic phase was collected and concentrated, and then column chromatography separation was performed (eluent: tetrahydrofuran: n-hexane = 1:4), and then concentrated to obtain white solid as compound 5 (13.1 g, yield: 90.03%), mass spectrum: 420.45 (M+H).

[0097] Synthesis of compound La001:

[0098] Compound 5 (13.1 g, 31.2 mmol, 1.0 eq), potassium carbonate (12.93 g, 93.7 mmol, 3.0 eq), N,N-dimethylformamide (524 ml) were added into a 1 L three-necked flask, vacuumed and replaced by nitrogen for 3 times, under the protection of nitrogen, the reaction was stirred at 110 °C for 16 h. TLC monitoring, compound 5 was completely reacted. Cooled to room temperature, the reaction solution was slowly added into deionized water (2.5 L), stirred for 1 h, and then filtered to obtain solid, which was recrystallized twice in N,N-dimethylformamide (product: N,N-dimethylformamide = 1:5), and then dried to obtain white solid as compound La001 (8.6 g, yield: 99.91%), mass spectrum: 400.44 (M+H). 1 HNMR (400 MHz, D8-THF) δ 8.83 (d, J = 5.6 Hz, 1H), 8.32 (d, J = 5.7 Hz, 1H), 8.16 - 8.05 (m, 3H), 8.02 (s, 1H), 7.83 (d, J = 8.3 Hz, 1H), 7.77 (d, J = 8.8 Hz, 1H), 7.59 (s, 2H), 7.46 (d, J = 7.2 Hz, 1H), 7.37 (dd, J = 15.3, 6.6 Hz, 3H), 2.62 (s, 3H).

[0099] Synthesis of compound Ir(La001)2(Lb005):

[0100]

[0101] Synthesis of compound Ir(La001)-1:

[0102] Compound La001 (8.0 g, 20.03 mmol, 3.5 eq), IrCl3.3H2O (2.02 g, 5.72 mmol, 1.0 eq) were placed in a 500 ml single necked round bottom flask, THF (240 ml) and deionized water (24 ml) were added, the mixture was vacuumed and replaced for 3 times, the mixture was stirred at 80 °C for 48 h under N2. After cooling to room temperature, methanol (250 ml) was added to stir to precipitate solid, the solid was collected by filtration and dried to get dark red oil as compound Ir(La001)-1 (5.48 g, 93.54 %). The obtained compound was used directly in the next step without further purification.

[0103] Synthesis of compound Ir(La001)2(Lb005):

[0104] Compound Ir(La001)-1 (5.48 g, 5.35 mmol, 1.0 eq), Lb005 (5.68 g, 26.74 mmol, 5.0 eq), Na2CO3 (5.67 g, 53.49 mmol, 10.0 eq) were placed in a 500 ml single necked round bottom flask, THF (180 ml) was added, the mixture was vacuumed and replaced for 3 times, the mixture was stirred at 60 °C for 48 h under N2. TLC was used to monitor the reaction of Ir(La001)-1 was completed. After cooling to room temperature, 180 ml methanol was added to stir for 1 h, the mixture was filtered, the filter cake was dissolved in CH2Cl2(40 ml) and clarified, then the mixture was filtered through silica gel, the filtrate was washed with deionized water (20 ml) for 3 times, the organic phase was collected and concentrated, dried to get dark red solid, the solid was recrystallized in THF / MeOH (product / THF / MeOH = 1 g / 9 ml / 9 ml) for 2 times, dried to get red solid as compound Ir(La001)2(Lb005) (3.87 g, yield: 60.26 %). The 3.87 g crude Ir(La001)2(Lb005) was purified by sublimation to get sublimed Ir(La001)2(Lb005) (1.96 g, yield: 50.64 %). Mass: 1201.40 (M+H). 1HNMR (400 MHz, CDC13) δ 8.94 (d, J = 9.0 Hz, 2H), 8.51 (d, J = 6.4 Hz, 2H), 8.22 (d, J = 8.9 Hz, 2H), 8.18 (d, J = 7.4 Hz, 2H), 7.97 (d, J = 6.2 Hz, 2H), 7.84 (d, J = 7.1 Hz, 2H), 7.79 (d, J = 8.2 Hz, 2H), 7.61 (t, J = 7.2 Hz, 2H), 7.56 - 7.45 (m, 4H), 7.42 (s, 2H), 7.37 (t, J = 7.8 Hz, 2H), 7.30 (t, J = 7.0 Hz, 2H), 4.83 (s, 1H), 1.71 (s, 5H), 1.53 (s, 1H), 1.31 (dd, J = 15.4, 7.0 Hz, 4H), 1.16 - 1.06 (m, 2H), 0.79 (dd, J = 14.4, 6.7 Hz, 4H), 0.50 (t, J = 7.4 Hz, 6H), -0.23 (t, J = 7.4 Hz, 6H).

[0105] Synthesis of compound La005:

[0106]

[0107] Synthesis of compound 7:

[0108] Referring to the synthesis and purification method of compound 3, only the corresponding starting materials need to be changed to obtain the target compound 7, mass spectrum: 292.68 (M+H).

[0109] Synthesis of compound 8:

[0110] Referring to the synthesis and purification method of compound 5, only the corresponding starting materials need to be changed to obtain the target compound 8, mass spectrum: 438.44 (M+H).

[0111] Synthesis of compound La005:

[0112] Referring to the synthesis and purification method of compound La001, only the corresponding starting materials need to be changed to obtain the target compound La005, mass spectrum: 418.43 (M+H).

[0113] Synthesis of compound Ir(La005)2(Lb005):

[0114]

[0115] Synthesis of compound Ir(La005)-1:

[0116] The synthesis and purification method of compound Ir(La001)-1 was referred to, and the corresponding raw materials were changed to obtain compound Ir(La005)-1, which was directly used in the next step without purification.

[0117] Synthesis of compound Ir(La005)2(Lb005):

[0118] The synthesis and purification method of compound Ir(La001)2(Lb005) was referred to, and only the corresponding raw materials needed to be changed to obtain red solid compound Ir(La005)2(Lb005) (3.21 g, yield: 46.77%). After sublimation purification of 3.21 g of crude Ir(La005)2(Lb005), sublimed Ir(La005)2(Lb005) (1.89 g, yield: 58.87%) was obtained, and the mass spectrum was 1237.38 (M+H). 1 H NMR (400 MHz, CDCl3) δ 8.92 (d, J = 8.7 Hz, 2H), 8.49 (d, J = 6.5 Hz, 2H), 8.21 (d, J = 7.7 Hz, 2H), 7.94 (d, J = 6.4 Hz, 2H), 7.81 (d, J = 7.1 Hz, 2H), 7.72 (d, J = 8.4 Hz, 2H), 7.60 (t, J = 7.6 Hz, 2H), 7.54-7.42 (m, 4H), 7.38 (s, 2H), 7.34 (t, J = 7.6 Hz, 2H), 7.28 (t, J = 7.2 Hz, 2H), 4.81 (s, 1H), 1.69 (s, 5H), 1.52 (s, 1H), 1.32 (dd, J = 15.4, 7.0 Hz, 4H), 1.16-1.06 (m, 2H), 0.82 (dd, J = 14.4, 6.7 Hz, 4H), 0.61 (t, J = 7.4 Hz, 6H), -0.18 (t, J = 7.4 Hz, 6H).

[0119] Synthesis of compound La007:

[0120]

[0121] Synthesis of compound 10:

[0122] The synthesis and purification method of compound 3 was referred to, and only the corresponding raw materials needed to be changed to obtain target compound 10, and the mass spectrum was 292.68 (M+H).

[0123] Synthesis of compound 11:

[0124] The synthesis and purification method of compound 5 was referred to, and only the corresponding raw materials needed to be changed to obtain target compound 11, and the mass spectrum was 438.44 (M+H).

[0125] Synthesis of compound La007:

[0126] Referring to the synthesis and purification method of compound La001, only the corresponding starting materials need to be changed to obtain the target compound La007, mass spectrum: 418.43 (M+H).

[0127] Synthesis of compound Ir(La007)2(Lb005):

[0128]

[0129] Synthesis of compound Ir(La007)-1:

[0130] Referring to the synthesis and purification method of compound Ir(La001)-1, only the corresponding starting materials need to be changed to obtain compound Ir(La007)-1, which is directly used in the next step without purification.

[0131] Synthesis of compound Ir(La007)2(Lb005):

[0132] Referring to the synthesis and purification method of compound Ir(La001)2(Lb005), only the corresponding starting materials need to be changed to obtain red solid compound Ir(La007)2(Lb005) (3.17 g, yield: 44.92%). After sublimation purification of 3.17 g of crude Ir(La007)2(Lb005), sublimed Ir(La007)2(Lb005) (1.78 g, yield: 56.15%) was obtained, mass spectrum: 1237.38 (M+H). 1 H NMR (400 MHz, CDC13) δ 8.95 (s, 2H), 8.46 (d, J = 6.1 Hz, 2H), 8.25 (d, J = 7.9 Hz, 2H), 8.21 (d, J = 7.6 Hz, 2H), 7.83 (d, J = 7.1 Hz, 2H), 7.77 (d, J = 8.2 Hz, 2H), 7.62 (t, J = 7.2 Hz, 2H), 7.51 - 7.42 (m, 4H), 7.39 (s, 2H), 7.35 (t, J = 7.8 Hz, 2H), 7.31 (t, J = 7.0 Hz, 2H), 4.82 (s, 1H), 1.72 (s, 5H), 1.54 (s, 1H), 1.26 (dd, J = 15.4, 7.0 Hz, 4H), 1.18 - 1.09 (m, 2H), 0.82 (dd, J = 14.4, 6.7 Hz, 4H), 0.52 (t, J = 7.4 Hz, 6H), -0.19 (t, J = 7.4 Hz, 6H).

[0133] Synthesis of compound La011:

[0134]

[0135] Synthesis of compound 13:

[0136] Referring to the synthesis and purification method of compound 3, only the corresponding starting materials need to be changed to obtain the target compound 13, mass spectrum: 299.7 (M+H).

[0137] Synthesis of compound 14:

[0138] Referring to the synthesis and purification method of compound 5, only the corresponding starting materials need to be changed to obtain the target compound 14, mass spectrum: 445.46 (M+H).

[0139] Synthesis of compound La011:

[0140] Referring to the synthesis and purification method of compound La001, only the corresponding starting materials need to be changed to obtain the target compound La011, mass spectrum: 425.45 (M+H).

[0141] Synthesis of compound Ir(La011)2(Lb005):

[0142]

[0143] Synthesis of compound Ir(La011)-1:

[0144] Referring to the synthesis and purification method of compound Ir(La001)-1, only the corresponding starting materials need to be changed to obtain compound Ir(La011)-1, which is directly used in the next step without purification.

[0145] Synthesis of compound Ir(La011)2(Lb005):

[0146] Referring to the synthesis and purification method of compound Ir(La001)2(Lb005), only the corresponding starting materials need to be changed to obtain the red solid compound Ir(La011)2(Lb005) (2.86 g, yield: 45.67%). After sublimation purification of 2.86 grams of crude Ir(La011)2(Lb005), sublimation pure Ir(La011)2(Lb005) (1.69 g, yield: 59.09%) was obtained, mass spectrum: 1251.42 (M+H). 1H NMR (400 MHz, CDC13) δ 8.93 (d, J = 9.1 Hz, 2H), 8.51 (d, J = 6.3 Hz, 2H), 8.22 (d, J = 7.3 Hz, 2H), 7.96 (d, J = 6.4 Hz, 2H), 7.83 (d, J = 7.2 Hz, 2H), 7.74 (d, J = 7.8 Hz, 2H), 7.62 (t, J = 6.8 Hz, 2H), 7.55 - 7.44 (m, 4H), 7.37 (s, 2H), 7.35 (t, J = 7.8 Hz, 2H), 7.27 (t, J = 7.0 Hz, 2H), 4.83 (s, 1H), 1.71 (s, 5H), 1.55 (s, 1H), 1.34 (dd, J = 15.4, 7.0 Hz, 4H), 1.17 - 1.07 (m, 2H), 0.84 (dd, J = 14.4, 6.7 Hz, 4H), 0.63 (t, J = 7.4 Hz, 6H), -0.24 (t, J = 7.4 Hz, 6H).

[0147] Synthesis of compound La014

[0148]

[0149] Synthesis of compound 16:

[0150] Referring to the synthesis and purification method of compound 3, only the corresponding starting materials need to be changed to obtain the target compound 16, mass spectrum: 330.8 (M+H).

[0151] Synthesis of compound 17:

[0152] Referring to the synthesis and purification method of compound 5, only the corresponding starting materials need to be changed to obtain the target compound 17, mass spectrum: 476.55 (M+H).

[0153] Synthesis of compound La014:

[0154] Referring to the synthesis and purification method of compound La001, only the corresponding starting materials need to be changed to obtain the target compound La014, mass spectrum: 456.55 (M+H).

[0155] Synthesis of compound Ir(La014)2(Lb005):

[0156]

[0157] Synthesis of compound Ir(La014)-1:

[0158] The synthesis and purification method of compound Ir(La001)-1 was referred to, and the corresponding raw materials were changed to obtain compound Ir(La014)-1 which was directly used in the next step without purification.

[0159] Synthesis of compound Ir(La014)2(Lb005):

[0160] The synthesis and purification method of compound Ir(La001)2(Lb005) was referred to, and only the corresponding raw materials needed to be changed to obtain red solid compound Ir(La014)2(Lb005) (3.05 g, yield: 48.61 %). After sublimation purification of 3.05 grams of crude Ir(La014)2(Lb005), sublimed Ir(La014)2(Lb005) (1.92 g, yield: 62.95 %) was obtained, mass spectrum: 1313.61 (M+H). 1 H NMR (400 MHz, CDC13) δ 8.90 (d, J = 9.2 Hz, 2H), 8.49 (d, J = 6.3 Hz, 2H), 8.21 (d, J = 8.7 Hz, 2H), 8.16 (d, J = 7.3 Hz, 2H), 7.97 (d, J = 6.2 Hz, 2H), 7.84 (d, J = 6.8 Hz, 2H), 7.79 (d, J = 7.8 Hz, 2H), 7.61 (s, 2H), 7.56 - 7.45 (m, 4H), 7.42 (s, 2H), 7.30 (t, J = 6.8 Hz, 2H), 4.83 (s, 1H), 2.34 (m, 2H), 1.88 (d, 4H), 1.71 (s, 5H), 1.53 (s, 1H), 1.31 (dd, J = 14.8, 7.3 Hz, 4H), 1.16 - 1.06 (m, 2H), 0.79 (dd, J = 14.6, 6.8 Hz, 4H), 0.66 (d, 12H), 0.50 (t, J = 7.1 Hz, 6H), -0.23 (t, J = 7.3 Hz, 6H). Synthesis of compound La026:

[0161]

[0162] Synthesis of compound 19:

[0163] The synthesis and purification method of compound 3 was referred to, and only the corresponding raw materials needed to be changed to obtain target compound 19, mass spectrum: 342.81 (M+H).

[0164] Synthesis of compound 20:

[0165] The synthesis and purification method of compound 5 was referred to, and only the corresponding raw materials needed to be changed to obtain target compound 20, mass spectrum: 488.56 (M+H).

[0166] Synthesis of compound La026:

[0167] The synthesis and purification of compound La001 were followed, only by changing the corresponding starting materials, to give the target compound La026, mass: 468.56 (M+H).

[0168] Synthesis of compound Ir(La026)2(Lb008):

[0169]

[0170] Synthesis of compound Ir(La026)-1:

[0171] The synthesis and purification of compound Ir(La001)-1 were followed, only by changing the corresponding starting materials, to give compound Ir(La026)-1 which was used directly in the next step without purification.

[0172] Synthesis of compound Ir(La026)2(Lb008):

[0173] The synthesis and purification of compound Ir(La001)2(Lb005) were followed, only by changing the corresponding starting materials, to give red solid compound Ir(La026)2(Lb008) (2.74 g, yield: 41.43%). After sublimation purification of 2.74 g crude Ir(La026)2(Lb008), sublimed Ir(La026)2(Lb008) (1.64 g, yield: 59.85%) was obtained, mass: 1379.72 (M+H). 1 H NMR (400 MHz, CDC13) δ 8.88 (s, 2H), 8.44 (d, J = 6.3 Hz, 2H), 8.26 (d, J = 7.7 Hz, 2H), 8.18 (d, J = 7.2 Hz, 2H), 7.81 (d, J = 7.3 Hz, 2H), 7.77 (d, J = 8.2 Hz, 2H), 7.62 (t, J = 6.8 Hz, 2H), 7.51 - 7.42 (m, 4H), 7.39 (s, 2H), 7.35 (t, J = 7.8 Hz, 2H), 7.31 (t, J = 7.0 Hz, 2H), 2.38 (m, 2H), 2.13 (s, 3H), 1.72 (s, 5H), 1.54 (s, 1H), 1.26 (dd, J = 15.4, 7.0 Hz, 4H), 1.08 (m, 8H), 0.82 (dd, J = 14.4, 6.7 Hz, 4H), 0.64 (s, 6H), 0.52 (t, J = 7.4 Hz, 6H), -0.19 (t, J = 7.4 Hz, 6H).

[0174] Synthesis of compound La041:

[0175]

[0176] Synthesis of compound 22:

[0177] Refer to the synthesis and purification method of compound 5, only need to change the corresponding raw material, the target compound 22 was obtained, mass: 501.56 (M+H).

[0178] Synthesis of compound La041:

[0179] Refer to the synthesis and purification method of compound La001, only need to change the corresponding raw material, the target compound La041 was obtained, mass: 481.56 (M+H).

[0180] Synthesis of compound Ir(La041)2(Lb031):

[0181]

[0182] Synthesis of compound Ir(La041)-1:

[0183] Refer to the synthesis and purification method of compound Ir(La001)-1, only need to change the corresponding raw material, the target compound Ir(La041)-1 was obtained, which was used directly in the next step without purification.

[0184] Synthesis of compound Ir(La041)2(Lb031):

[0185] Refer to the synthesis and purification method of compound Ir(La001)2(Lb005), only need to change the corresponding raw material, the target compound Ir(La041)2(Lb031) was obtained as a red solid (2.69 g, yield: 40.23%). After sublimation purification of 2.69 grams of crude Ir(La041)2(Lb031), sublimation pure Ir(La041)2(Lb031) (1.53 g, yield: 56.87%) was obtained, mass: 1387.65 (M+H). 1H NMR (400 MHz, CDC13) δ 8.90 (d, J = 9.2 Hz, 2H), 8.49 (d, J = 6.3 Hz, 2H), 8.21 (d, J = 8.7 Hz, 2H), 8.16 (d, J = 7.3 Hz, 2H), 7.97 (d, J = 6.2 Hz, 2H), 7.84 (d, J = 6.8 Hz, 2H), 7.79 (d, J = 7.8 Hz, 2H), 7.61 (s, 2H), 7.56 - 7.45 (m, 4H), 7.42 (s, 2H), 4.83 (s, 1H), 2.34 (m, 2H), 1.88 (d, 4H), 1.76 (m, 2H), 1.42 (dd, J = 13.8, 7.6 Hz, 4H), 0.79 (dd, J = 13.8, 6.6 Hz, 4H), 0.66 (d, 12H), 0.50 (t, J = 7.1 Hz, 6H), 0.33 (m, 12H). 0.12 (m, 4H).

[0186] Synthesis of compound La052:

[0187]

[0188]

[0189] Synthesis of compound 25:

[0190] Referring to the synthesis and purification method of compound 3, only the corresponding starting material needs to be changed to obtain the target compound 25, mass spectrum: 316.73 (M+H).

[0191] Synthesis of compound 26:

[0192] Compound 25 (11.3 g, 35.79 mmol, 1.0 eq), tetrahydrofuran (110 ml) was added to a 500 mL three-necked flask, vacuumed and replaced with nitrogen for 3 times, and then 2M methyl magnesium bromide (12.8 g, 107.37 mmol, 3.0 eq) was slowly added dropwise at 0°C, and the temperature was increased to 50°C after the addition was completed. Stirring for 2 hours. TLC monitoring, compound 25 reaction was complete. Cooled to room temperature, added deionized water (110 ml) to quench, then added ethyl acetate (150 ml) to extract and separate, collected the organic phase and dried, then column chromatography separation (eluent dichloromethane: n-hexane = 1:10), concentrated to obtain white solid compound 26 (7.06 g, yield: 62.44%), mass spectrum: 316.77 (M+H).

[0193] Synthesis of compound 27:

[0194] Compound 26 (6.5 g, 20.58 mmol, 1.0 eq), 36% mass fraction hydrochloric acid solution (2.08 g, 20.58 mmol, 1.0 eq), acetic acid (65 ml) were added into a 250 mL three-necked flask, vacuumed and replaced by nitrogen for 3 times, nitrogen protection, heated to 100 ℃, stirred for 4 hours. TLC monitoring, compound 26 reaction was completed. Cooled to room temperature, added deionized water (130 ml) and stirred, then added ethyl acetate (150 ml) and extracted, the organic phase was collected and rotary evaporated, then column chromatography separation (eluent: dichloromethane: n-hexane = 1:15) was performed, and concentrated to obtain white solid compound 27 (4.71 g, yield: 76.84%), mass spectrum: 298.75 (M+H).

[0195] Synthesis of compound La052:

[0196] Referring to the synthesis and purification method of compound La001, only the corresponding raw materials need to be changed to obtain the target compound La052, mass spectrum: 444.51 (M+H).

[0197] Synthesis of compound Ir(La052)2(Lb005):

[0198]

[0199] Synthesis of compound Ir(La052)-1:

[0200] Referring to the synthesis and purification method of compound Ir(La001)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La052)-1, which is directly used in the next step without purification.

[0201] Synthesis of compound Ir(La052)2(Lb005):

[0202] Referring to the synthesis and purification method of compound Ir(La001)2(Lb005), only the corresponding raw materials need to be changed to obtain red solid compound Ir(La052)2(Lb005) (2.14 g, yield: 38.64%). After sublimation purification of 2.14 g of crude Ir(La052)2(Lb005), sublimed Ir(La052)2(Lb005) (1.32 g, yield: 61.68%) was obtained, mass spectrum: 1289.54 (M+H). 1H NMR (400 MHz, CDC13) δ 8.87 (d, J = 8.8 Hz, 2H), 8.48 (d, J = 6.8 Hz, 2H), 8.21 (d, J = 7.3 Hz, 2H), 7.88 (d, J = 6.8 Hz, 2H), 7.78 (d, J = 6.8 Hz, 2H), 7.74 (d, J = 7.8 Hz, 2H), 7.58 (t, J = 6.5 Hz, 2H), 7.52 - 7.39 (m, 4H), 7.38 (s, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.24 (t, J = 7.0 Hz, 2H), 4.83 (s, 1H), 1.71 (s, 5H), 1.56 (s, 1H), 1.38 (dd, J = 15.6, 7.0 Hz, 4H), 1.17 - 1.07 (m, 2H), 0.88 (dd, J = 14.4, 6.7 Hz, 4H), 0.78 (s, 12H), 0.66 (t, J = 7.4 Hz, 6H), -0.24 (t, J = 7.4 Hz, 6H).

[0203] Synthesis of compound Ir(La052)2(Lb008):

[0204]

[0205] The synthesis and purification method of reference compound Ir(La001)2(Lb005) was referred to, only the corresponding raw materials were changed, to obtain compound Ir(La052)2(Lb008) (2.21 g, yield: 37.45%) as a red solid. After sublimation purification of 2.21 g of crude Ir(La052)2(Lb008), sublimation pure Ir(La052)2(Lb008) (1.26 g, yield: 57.01%) was obtained, mass spectrum: 1331.62 (M+H). 1 H NMR (400 MHz, CDC13) δ 8.87 (d, J = 8.8 Hz, 2H), 8.48 (d, J = 6.8 Hz, 2H), 8.21 (d, J = 7.3 Hz, 2H), 7.88 (d, J = 6.8 Hz, 2H), 7.78 (d, J = 6.8 Hz, 2H), 7.74 (d, J = 7.8 Hz, 2H), 7.58 (t, J = 6.5 Hz, 2H), 7.52 - 7.39 (m, 4H), 7.38 (s, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.24 (t, J = 7.0 Hz, 2H), 4.83 (s, 1H), 1.71 (s, 6H), 1.16 (s, 6H), 1.08 (s, 3H), 0.91 (m, 8H), 0.78 (s, 12H), 0.66 (m, 12H).

[0206] Synthesis of compound La078:

[0207]

[0208]

[0209] Synthesis of compound 29:

[0210] Referring to the synthesis and purification method of compound 3, only the corresponding starting material needs to be changed, and the target compound 29 is obtained, mass spectrum: 344.61 (M+H).

[0211] Synthesis of compound 30:

[0212] Compound 30 (13.2 g, 38.42 mmol, 1.0 eq), tetrahydrofuran (132 ml) was added to a 500 mL three-necked flask, vacuumed and replaced with nitrogen for 3 times, and 1.5 M n-butyllithium (30.73 ml, 46.1 mmol, 1.2 eq) was slowly added dropwise at -78°C. After 1 h of stirring, dimethylchlorosilane (5.45 g, 57.62 mmol, 1.5 eq) was slowly added dropwise, and the reaction was stirred at room temperature for 2 h. TLC monitoring showed that compound 30 was completely reacted. Deionized water (130 ml) was slowly added to quench the reaction, and ethyl acetate (150 ml) was added to extract the solution. The organic phase was collected and rotary evaporated to dryness, and then column chromatography separation was performed (eluent: dichloromethane: n-hexane = 1:20). After concentration, white solid compound 30 (8.76 g, yield: 70.62%) was obtained, mass spectrum: 323.86 (M+H).

[0213] Synthesis of compound 31:

[0214] Compound 30 (8.0 g, 24.78 mmol, 1.0 eq), chloro(triphenylphosphine)rhodium (0.22 g, 0.24 mmol, 0.01 eq), and dioxane (80 ml) were added to a 250 mL three-necked flask, vacuumed and replaced with nitrogen for 3 times, and the reaction was stirred at 130°C for 2 h under nitrogen protection. TLC monitoring showed that compound 30 was completely reacted. After cooling to room temperature, the organic phase was rotary evaporated to dryness, and then column chromatography separation was performed (eluent: ethyl acetate: n-hexane = 1:20). After concentration, white solid compound 31 (5.75 g, yield: 72.3%) was obtained, mass spectrum: 321.85 (M+H).

[0215] Synthesis of compound La078:

[0216] Referring to the synthesis and purification method of compound La001, only the corresponding starting material needs to be changed, and the target compound La078 is obtained, mass spectrum: 467.6 (M+H).

[0217] Synthesis of compound Ir(La078)2(Lb005):

[0218]

[0219] Synthesis of compound Ir(La078)-1:

[0220] Referring to the synthesis and purification method of compound Ir(La001)-1, the corresponding raw materials are changed, and compound Ir(La078)-1 is obtained directly for the next step without purification.

[0221] Synthesis of compound Ir(La078)2(Lb005):

[0222] Referring to the synthesis and purification method of compound Ir(La001)2(Lb005), only the corresponding raw materials need to be changed, and red solid compound Ir(La078)2(Lb005) (2.62 g, yield: 36.63%) is obtained. After sublimation purification of 2.62 grams of crude Ir(La078)2(Lb005), sublimed Ir(La078)2(Lb005) (1.48 g, yield: 56.48%) is obtained, mass spectrum: 1335.73 (M+H). 1 H NMR (400 MHz, CDC13) δ 8.90 (d, J = 8.6 Hz, 2H), 8.42 (d, J = 6.2 Hz, 2H), 8.23 (d, J = 7.5 Hz, 2H), 7.86 (d, J = 7.2 Hz, 2H), 7.78 (d, J = 7.4 Hz, 2H), 7.76 (d, J = 6.6 Hz, 2H), 7.61 (t, J = 6.5 Hz, 2H), 7.53 - 7.40 (m, 4H), 7.38 (s, 2H), 7.32 (t, J = 7.6 Hz, 2H), 7.22 (t, J = 7.0 Hz, 2H), 4.83 (s, 1H), 1.71 (s, 5H), 1.56 (s, 1H), 1.38 (dd, J = 15.6, 7.0 Hz, 4H), 1.17 - 1.07 (m, 2H), 0.88 (dd, J = 14.4, 6.7 Hz, 4H), 0.72 (s, 12H), 0.66 (t, J = 7.4 Hz, 6H), -0.24 (t, J = 7.4 Hz, 6H).

[0223] Synthesis of compound Ir(La078)2(Lb008):

[0224]

[0225] The synthesis and purification method of reference compound Ir(La001)2(Lb005) was referred to, only the corresponding raw materials were changed, to obtain the target compound Ir(La078)2(Lb008) as a red solid (2.53 g, yield: 37.23%). After sublimation purification of 2.53 g of crude Ir(La078)2(Lb008), sublimation pure Ir(La078)2(Lb008) (1.26 g, yield: 49.8%) was obtained, mass spectrum: 1377.81 (M+H). 1 H NMR (400 MHz, CDC13) δ 8.89 (d, J = 8.6 Hz, 2H), 8.54 (d, J = 7.2 Hz, 2H), 8.21 (d, J = 7.6 Hz, 2H), 7.82 (d, J = 6.6 Hz, 2H), 7.76 (d, J = 6.2 Hz, 2H), 7.68 (d, J = 7.8 Hz, 2H), 7.54 (t, J = 6.7 Hz, 2H), 7.52 - 7.39 (m, 4H), 7.39 (s, 2H), 7.35 (t, J = 7.6 Hz, 2H), 7.25 (t, J = 7.0 Hz, 2H), 4.81 (s, 1H), 1.75 (s, 6H), 1.13 (s, 6H), 1.12 (s, 3H), 0.88 (m, 8H), 0.73 (s, 12H), 0.64 (m, 12H).

[0226] Synthesis of compound Lc004:

[0227]

[0228] The synthesis and purification method of reference compound La001 was referred to, only the corresponding raw materials were changed, to obtain the target compound Lc004, mass spectrum: 290.41 (M+H).

[0229] Synthesis of compound Ir(La078)(Lb005)(Lc004):

[0230]

[0231] Synthesis of compound Ir(La078)-2

[0232] In a 3L 3-necked flask, compound Ir(La078)-1 (7.65g, 6.6mmol, 1.0 eq) was dissolved in dichloromethane (574ml) with stirring. Silver triflate (3.39g, 13.2mmol, 2.0 eq) was dissolved in methanol (380ml) and added to the reaction flask. The mixture was stirred at room temperature under N2for 16 hours. The reaction mixture was then filtered through celite, and the filter cake was rinsed with dichloromethane (150ml). The filtrate was evaporated to dryness to give compound Ir(La078)-2 (6.96g, 78.84%). The resulting compound was used directly in the next step without purification.

[0233] Synthesis of compound Ir(La078)2(Lc004)

[0234] Compound Ir(La078)-2 (6.85g, 5.13mmol, 1.0 eq) and Lc004 (3.71g, 12.81mmol, 2.5 eq) were added to a 250ml 3-necked flask. Ethanol (102ml) was added, and the mixture was stirred and refluxed under N2for 16 hours. After cooling to room temperature, the mixture was filtered, and the solid was dissolved in dichloromethane (180ml). The solution was filtered through silica gel, and the filter cake was rinsed with dichloromethane (80ml). The filtrate was evaporated to dryness, and the resulting compound was recrystallized twice from tetrahydrofuran / methanol (product: tetrahydrofuran:methanol = 1:8:10). The resulting compound was dried to give compound Ir(La078)2(Lc004) (3.52g, 48.66%). Mass: 1412.82 (M+H).

[0235] Synthesis of compound Ir(La078)2(Lc004)-1

[0236] Compound Ir(La078)2(Lc004) (4.2g, 2.97mmol, 1.0 eq) and zinc chloride (20.27g, 148.4mmol, 50 eq) were added to a 1L single-necked flask. 1,2-dichloroethane (210ml) was added, and the mixture was stirred and refluxed under N2for 18 hours. TLC monitoring showed that the starting material Ir(La078)2(Lc004) was substantially consumed. After cooling to room temperature, the mixture was washed with deionized water (100ml x 3). The filtrate was evaporated to dryness to give compound Ir(La078)2(Lc004)-1 (2.36g, 80.67%). The resulting compound was used directly in the next step without purification.

[0237] Synthesis of compound Ir(La078)(Lb005)(Lc004)

[0238] Compound Ir(La078)2(Lc004)-1 (3.5 g, 3.57 mmol, 1.0 eq), Lb005 (3.79 g, 17.83 mmol, 5.0 eq), sodium carbonate (3.78 g, 35.65 mmol, 10.0 eq) were placed in a 250 ml single-necked round-bottom flask, ethylene glycol ether (52 ml) was added, vacuum replaced 3 times, the mixture was stirred at 50 °C for 24 hours under the protection of N2, TLC monitoring Ir(La078)2(Lc004)-1 reaction was complete. After cooling to room temperature, 104 ml of methanol was added and stirred at room temperature for 2 h, filtered, the filter cake was dissolved with dichloromethane (100 ml) and filtered through silica gel, then the filter cake was washed with dichloromethane (50 ml), the filtrate was collected and washed with deionized water 3 times (60 ml / time), separated, the organic phase was concentrated and dried to obtain dark red solid, which was recrystallized 3 times with tetrahydrofuran / methanol (product: tetrahydrofuran:methanol = 1:8:10) to obtain red solid as compound Ir(La078)(Lb005)(Lc004) (1.9 g, yield: 46.71 %). After sublimation purification of 1.9 g of crude Ir(La078)(Lb005)(Lc004), sublimed Ir(La078)(Lb005)(Lc004) (0.96 g, yield: 50.52 %) was obtained. Mass spectrum: 1158.45 (M+H). 1 HNMR (400 MHz, CDC13) δ 8.87 (d, 1H), 8.45 (d, 1H), 8.27 (d, 1H), 8.07 (d, 1H), 7.95 (m, 3H), 7.78 (d, 1H), 7.69 (d, J = 5.0 Hz, 2H), 7.60 (d, 1H), 7.57 - 7.48 (m, 5H), 7.39 (d, 1H), 7.31 (d, 1H), 6.92 (d, 1H), 4.81 (s, 1H), 2.43 (d, 2H), 2.32 (d, J = 15.0 Hz, 6H), 1.82 (m, 1H), 1.27 (m, 8H), 1.01 (m, 5H), 0.94 (m, 12H), 0.87 (d, 6H), 0.66 (s, 6H).

[0239] Synthesis of compound Lc024:

[0240]

[0241] Referring to the synthesis and purification method of compound La001, only the corresponding starting materials need to be changed to obtain the target compound Lc024, mass spectrum: 406.41 (M+H).

[0242] Synthesis of compound Ir(La078)(Lb005)(Lc024):

[0243]

[0244]

[0245] Synthesis of compound Ir(La078)2(Lc024):

[0246] The synthesis and purification method of reference compound Ir(La078)2(Lc004) was referred to, only the corresponding raw materials were changed, and the target compound Ir(La078)2(Lc024) was obtained. Mass spectrum: 1558.71 (M+H).

[0247] Synthesis of compound Ir(La078)2(Lc024)-1:

[0248] The synthesis and purification method of reference compound Ir(La078)2(Lc004)-1 was referred to, only the corresponding raw materials were changed, and the compound Ir(La078)2(Lc024)-1 was obtained without purification and directly used in the next step.

[0249] Synthesis of compound Ir(La078)(Lb005)(Lc024):

[0250] The synthesis and purification method of reference compound Ir(La078)(Lb005)(Lc004) was referred to, only the corresponding raw materials were changed, and the red solid compound Ir(La078)(Lb005)(Lc024) (2.27 g, yield: 36.27%) was obtained. After sublimation purification of 2.27 g of crude Ir(La078)(Lb005)(Lc024), sublimed Ir(La078)(Lb005)(Lc024) (1.14 g, yield: 50.22%) was obtained. Mass spectrum: 1274.51 (M+H). 1 HNMR (400 MHz, CDC13) δ 8.86 (d, 1H), 8.42 (d, 1H), 8.27 (s, 1H), 8.02 - 7.89 (m, 3H), 7.81 - 7.65 (m, 4H), 7.64 - 7.48 (m, 4H), 7.42 (d, J = 30.0 Hz, 2H), 7.36 (m, 3H), 7.31 (s, 1H), 7.21 (m, 2H), 4.81 (s, 1H), 2.63 (t, 2H), 2.50 (s, 3H), 1.89 (m, 2H), 1.66 (d, 2H), 1.27 (m, 8H), 1.09 - 0.88 (m, 15H), 0.66 (s, 6H).

[0251] Synthesis of compound Lc025:

[0252]

[0253] The starting material was changed according to the synthesis and purification process of compound La001 to give the target compound Lc025, mass: 366.47 (M+H).

[0254] Synthesis of compound Ir(La078)(Lb005)(Lc025):

[0255]

[0256] Synthesis of compound Ir(La078)2(Lc025):

[0257] The starting material was changed according to the synthesis and purification process of compound Ir(La078)2(Lc004) to give the target compound Ir(La078)2(Lc025), mass: 1488.87 (M+H).

[0258] Synthesis of compound Ir(La078)2(Lc025)-1:

[0259] The starting material was changed according to the synthesis and purification process of compound Ir(La078)2(Lc004)-1 to give the target compound Ir(La078)2(Lc025)-1, which was used directly in the next step without purification.

[0260] Synthesis of compound Ir(La078)(Lb005)(Lc025):

[0261] The starting material was changed according to the synthesis and purification process of compound Ir(La078)(Lb005)(Lc004) to give the target compound Ir(La078)(Lb005)(Lc025) as a red solid (2.46 g, yield: 39.65%). After sublimation purification, 1.45 g of sublimation-purified Ir(La078)(Lb005)(Lc025) was obtained (yield: 54.87%), mass: 1234.59 (M+H). 1HNMR(400MHz, CDCl3)δ8.88(d,1H),8.45(d,1H),8.24(s,1H),8.10–7.92(m,3H),7 .82–7.66(m,4H),7.62–7.46(m,4H),7.42(d,J=30.0Hz,2H),7.38(m,3H),7.32(s,1 H),7.21(m,2H),4.81(s,1H),2.63(t,2H),2.50(s,3H),2.32(m,1H)1.89(m,2H),1. 66(d,2H),1.34(d,6H),1.27(m,8H),1.09–0.88(m,15H),0.66(s,6H),0.23(m,4H).

[0262] Application example: Fabrication of organic electroluminescent devices

[0263] A 50mm*50mm*1.0mm ITO-containing material The glass substrate for the anode electrode was ultrasonically cleaned in ethanol for 10 minutes, dried at 150°C, and then treated with N2 Plasma for 30 minutes. The cleaned glass substrate was then mounted on the substrate support of a vacuum evaporation apparatus. First, on the side with the anode electrode lines, compound HTM1 and P-dopant (97%:3%) were co-deposited using a coating electrode method, forming a film with a thickness of [missing information]. A thin film is formed, followed by the deposition of an HTM1 layer to form a film with a thickness of [missing information]. A thin film of about 100 mm thick is formed by depositing an HTM2 layer onto the HTM1 film. The thin film was then deposited on the HTM2 film layer using a co-evaporation method, followed by the deposition of host material 1 and host material 2 and a doped compound (in a ratio of 48.5%:48.5%:3%, comparative compound X or the compound of this invention), with a film thickness of [missing information]. The ratio of the host material to the dopant material is 90%:10%, and ETL:LiQ is deposited on the light-emitting layer using a co-evaporation method. The ratio is 50%:50%, and then Yb is deposited on the electron transport layer material. Finally, a layer of Ag metal is deposited. As an electrode.

[0264]

[0265]

[0266]

[0267] Evaluation: The above devices were subjected to device performance testing, in each of the examples and comparative examples, a constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and a spectroradiometric luminance meter (CS 2000) was used to test the light-emitting spectrum. The voltage value was measured at the same time, and the time (LT90) at which the brightness was 90% of the initial brightness was tested. The results are as follows: current efficiency and device lifetime were both calculated with the values of comparative compound 5 as 100%,

[0268]

[0269] From the data comparison in the above table, it can be seen that the organic electroluminescent device using the compound of the present application as a dopant has more superior performance in driving voltage, luminous efficiency and device lifetime than the comparative compound in the device of the same color scale.

[0270] Emission wavelength comparison in dichloromethane solution: defined as: the emission wavelength of the corresponding compound was tested by using a 10 - 5 mol / L solution of dichloromethane, and the wavelength at the maximum emission of the emission peak was obtained by using a Hitachi (HITACH) F2700 fluorescence spectrophotometer. The test results are as follows:

[0271] Materials PL peak wavelength / nm [Ir(La001)2(Lb005)] 626 [Ir(La005)2(Lb005)] 628 [Ir(La007)2(Lb005)] 629 [Ir(La011)2(Lb005)] 627 [Ir(La014)2(Lb005)] 627 [Ir(La026)2(Lb008)] 627 [Ir(La041)2(Lb031)] 625 [Ir(La052)2(Lb005)] 629 [Ir(La052)2(Lb008)] 630 [Ir(La078)2(Lb005)] 631 [Ir(La078)2(Lb008)] 632 Ir(La078)(Lb005)(Lc004) 629 Ir(La078)(Lb005)(Lc024) 629 Ir(La078)2Lb005)(Lc025) 629 Comparative compound 1 610 Comparative compound 2 637 Comparative compound 3 611 Comparative compound 4 608 Comparative compound 5 616 Comparative compound 7 626

[0272] From the data comparison in the above table, it can be seen that the metal iridium complex of the present application has a larger red shift than the comparative compound, which can meet the needs of industrialization for deep red light, especially BT2020 color gamut.

[0273] The present application unexpectedly provides better device light-emitting efficiency and improved lifetime, provides lower sublimation temperature, more saturated red light-emitting, compared with the prior art, by special collocation of substituents. The above results show that the compound of the present application has the advantages of high photoelectrochemical stability, high color saturation, high light-emitting efficiency, long device lifetime, etc., and can be used in organic electroluminescent devices. In particular, as a red light-emitting dopant, it has the possibility of application in the OLED industry, especially for display, lighting and automobile tail lights.

Claims

1. A metallic iridium complex having the general formula Ir(La)(Lb)(Lc), wherein La has the structure shown in formula (1), in, The dashed line indicates the location where it connects to the metal Ir; Where X represents O, S, Se, C(R0)2, and Si(R0)2; Wherein, R0 is independently selected from substituted or unsubstituted C1-C10 alkyl groups, R1-R 13 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C2-C30 heteroaryl; Among them, R8 is not hydrogen, deuterium, halogen, or cyano; Wherein, the heteroalkyl, heterocycloalkyl, and heteroaryl groups contain at least one O, N, or S heteroatom; Wherein, the substitution is by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl or cyano, and the number of substitutions ranges from monosubstituted to the maximum number of substitutions; Where Lb is the structure shown in equation (2), The dashed line indicates the position where it connects to the metal Ir; Ra-Rg are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, or Ra, Rb, and Rc are connected in pairs to form an aliphatic ring, and Re, Rf, and Rg are connected in pairs to form an aliphatic ring. Wherein, the heteroalkyl and heterocycloalkyl groups contain at least one O, N or S heteroatom; Wherein, the substitution is by being replaced by deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy or C3-C6 cycloalkyl; Wherein, Lc and La are the same or different, and the difference is that the parent nucleus structure is different, or the parent nucleus structure is the same but the substituents are different, or the parent nucleus structure is the same but the substituents are the same but the substituent positions are different. When the Lc and La parent nuclei have different structures, Lc has the following structure: Alternatively, Lc can be the structure shown in equation (3). Among them, R 21 -R 28 It is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C18 aryl, or substituted or unsubstituted C2-C17 heteroaryl. Among them, R 25 -R 28 At least two of them are not hydrogen; Among them, R 21 -R 24 At least one set of two adjacent groups forms an aromatic ring as shown in formula (4); In formula (4) The dashed lines indicate the positions where the pyridine ring is attached. Among them, R 31 -R 34 It is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C18 aryl, or substituted or unsubstituted C2-C17 heteroaryl. Wherein, the heteroalkyl and heteroaryl groups contain at least one O, N or S heteroatom; Wherein, the substitution is by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl or cyano, and the number of substitutions ranges from monosubstituted to the maximum number of substitutions.

2. The iridium complex according to claim 1, wherein X is O, S, C(RO)2, Si(RO)2, and RO is a substituted or unsubstituted C1-C6 alkyl group.

3. The iridium complex according to claim 2, wherein at least one of R2-R7 is not H.

4. The iridium complex according to claim 3, wherein at least one of R1-R7 is F, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, wherein the substitution is by being substituted with deuterium, F, C1-C5 alkyl or C3-C6 cycloalkyl.

5. The iridium complex according to claim 1, wherein, R8 is a substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, wherein the substitution is by being substituted with deuterium, F, C1-C5 alkyl or C3-C6 cycloalkyl.

6. The iridium complex according to claim 5, wherein, R8 is methyl or deuterated methyl.

7. The iridium complex according to claim 1, wherein, R9-R 13 It is hydrogen.

8. The iridium complex according to claim 1, wherein, R 21 With R 22 Or R 22 With R 23 An aromatic ring as shown in formula (4) is formed between them, R 31 -R 34 It is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroalkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C10 aryl, or substituted or unsubstituted C2-C10 heteroaryl.

9. The iridium complex according to claim 1, wherein Lc is one of the following structural formulas, 10. The iridium complex according to claim 1, wherein La is one of the following structural formulas:

11. The iridium complex according to claim 3, wherein Lb is one of the following structural formulas, 12. An electroluminescent device, comprising: A cathode, an anode, and an organic layer disposed between the cathode and the anode, said organic layer comprising the metal iridium complex according to any one of claims 1-11.

13. The electroluminescent device of claim 12, wherein the organic layer includes a light-emitting layer, and the metal iridium complex serves as a red light-emitting dopant material of the light-emitting layer; or wherein the organic layer includes a hole injection layer, and the metal iridium complex serves as a hole injection material in the hole injection layer.

14. The ligand La has the following structural formula: Where R1-R 13 X is as described in any one of claims 1-7.

Images