An organic metal iridium compound and its application

Abstract

The present invention relates to an organometallic iridium compound and its application. The organometallic iridium compound has the general formula Ir(La)(Lb)(Lc), wherein La has the structure shown in formula (1) and Lb has the structure shown in formula (2). The compound provided by the present invention has advantages such as high optical and electrical stability, low sublimation temperature, narrow emission half-width, high color saturation, high luminous efficiency, and long device life, and can be used in organic electroluminescent devices. In particular, as a red light-emitting dopant, it has potential applications in the AMOLED industry, particularly in displays, lighting, and automotive taillights. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, in particular to an organic luminescent material suitable for an organic electroluminescent device, and more particularly to an organic metal iridium compound and its application in an organic electroluminescent device. Background Art

[0002] Organic light-emitting diodes (OLEDs), a next-generation display technology, are gaining increasing attention in both display and lighting applications, boasting a broad range of applications. However, compared to market requirements, OLED device performance, including luminous efficiency, driving voltage, and lifespan, still requires further improvement.

[0003] Generally speaking, the basic structure of an OLED device consists of thin films of organic functional materials with various functions sandwiched between metal electrodes, like a sandwich. Driven by an electric current, holes and electrons are injected from the cathode and anode, respectively. After traveling a certain distance, the holes and electrons recombine in the light-emitting layer and are released as light or heat, thus generating the OLED's luminescence. However, organic functional materials are the core components of organic electroluminescent devices, and the material's thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, and color saturation are all major factors affecting device performance.

[0004] Generally, organic functional materials include fluorescent materials and phosphorescent materials. Fluorescent materials are usually organic small molecule materials, which can generally only utilize 25% of the singlet state to emit light, so the luminous efficiency is relatively low. However, due to the spin-orbit coupling caused by the heavy atom effect, phosphorescent materials can utilize the energy of 75% of the triplet excitons in addition to the 25% singlet state, so the luminous efficiency can be improved. However, compared with fluorescent materials, phosphorescent materials started later, and the thermal stability, lifespan, color saturation, etc. of the materials need to be improved. This is a challenging topic. Various organometallic iridium compounds have been developed as phosphorescent materials. For example, Chou et al. published a non-patent document in 2005 (Inorg.Chem.2005,44,5677-5685) disclosing The iridium-based complex shown in the figure is used as a red luminescent material. However, the luminous efficiency of these two materials is very low and the operating voltage is very high, which requires further improvement. Wu et al. published a non-patent document (Dalton. Trans. 2020, 49, 15633-15645) in 2020. The platinum-based complex shown in the figure is used as a red luminescent material. Similarly, the luminous efficiency of this type of material is very low and the operating voltage is very high. In addition, the emission peak has multiple shoulders, which is not conducive to improving the chromatographic purity and efficiency of the device and needs to be further improved. Patent document CN107892702 discloses a type of Iridium-based and platinum-based complexes as ligands, but the operating voltage, device luminous efficiency and color purity of this type of material need to be further improved; Patent document KR101630317 discloses a type of Iridium complex, wherein for However, this type of material also has problems such as high device voltage, low current efficiency, and insufficient chromatographic purity, which need to be improved. Patent document KR10069600 discloses a type of naphthyl-bis(isoquinoline) iridium complex. This type of material also has problems such as high device voltage, low current efficiency, and insufficient chromatographic purity, which need to be improved; Patent document CN110041372 discloses a type of However, the device voltage of this type of compound is high, the current efficiency is low, the emission wavelength is too large, and it is not in the visible light region of the human eye, so it is not suitable for the field of display technology. Patent document CN111377969 discloses a type of iridium complex of dibenzofuran-isoquinoline However, the color saturation of this type of material is CIE (x, y) 0.68 and around 0.32, which needs further improvement. Summary of the Invention

[0005] In order to solve the above-mentioned defects, the present invention provides a high-performance organic electroluminescent device and an organometallic iridium compound material capable of realizing such an organic electroluminescent device.

[0006] The organometallic iridium compound of the present invention has the general formula Ir(La)(Lb)(Lc), wherein La is the structure shown in formula (1) and Lb is the structure shown in formula (2). The iridium complex provided by the present invention has advantages such as high optical and electrical stability, low sublimation temperature, narrow emission half-width, high color saturation, high luminous efficiency, and long device life, and can be used in organic electroluminescent devices. In particular, as a red light-emitting dopant, it has potential applications in the AMOLED industry, particularly in displays, lighting, and automotive taillights.

[0007] An organometallic iridium compound having the general formula of Ir(La)(Lb)(Lc), wherein La is a structure shown in formula (1),

[0008]

[0009] The dotted line indicates the position connected to the metal Ir;

[0010] wherein X1 is N or CR1, X2 is N or CR2, X3 is N or CR3, X4 is N or CR4, and X5 is N or CR5;

[0011] wherein R1-R5 are 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 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkylmono-C6-C30 arylsilyl, substituted or unsubstituted mono-C1-C10 alkyldi-C6-C30 arylsilyl, or two adjacent groups of R1-R5 are linked to form an alicyclic ring or an aromatic ring;

[0012] wherein at most one of X1-X5 is N, and when X1-X5 are CR1-CR5, at least one of R1-R5 is not H;

[0013] wherein R6-R9 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C20 cycloalkyl, and R6 is not hydrogen, deuterium or halogen;

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

[0015] wherein the substitution is substitution by an amino group, a nitrile, an isonitrile or a phosphine group substituted with deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, or C1-C6 alkyl, wherein the substitution is from a single substitution to a maximum number of substitutions;

[0016] Wherein Lb is the structure shown in formula (2),

[0017]

[0018] The dotted line indicates 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 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;

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

[0021] wherein the substitution is substituted by an amino group, a cyano group, an isonitrile group or a phosphine group substituted by deuterium, F, Cl, Br, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C3-C6 cycloalkyl group or a C1-C4 alkyl group;

[0022] Among them, Lc is a monoanionic bidentate ligand, Lc and Lb are different and are not OO type ligands;

[0023] Wherein, Lc and La are the same or different, and the difference is that the parent core structures are different, or the parent core structures are the same but the substituents are different, or the parent core structures are the same but the substituents are in different positions;

[0024] Among them, La, Lb, and Lc are connected to each other in pairs or in triplets to form a multidentate ligand.

[0025] Preferably: wherein La is a structure represented by formula (3),

[0026]

[0027] The dotted line indicates the position connected to the metal Ir;

[0028] wherein R1-R5 are 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 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkylmono-C6-C30 arylsilyl, substituted or unsubstituted mono-C1-C10 alkyldi-C6-C30 arylsilyl, or two adjacent groups of R1-R5 are linked to form an alicyclic ring or an aromatic ring, wherein at least one of R1-R5 is not H;

[0029] wherein R6-R9 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C20 cycloalkyl, and R6 is not hydrogen, deuterium or halogen;

[0030] wherein the heteroalkyl and heteroaryl groups contain at least one heteroatom of O, N or S;

[0031] Wherein, the substitution is amino, nitrile, isonitrile or phosphine substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl, wherein the substitution is from single substitution to maximum number substitution.

[0032] Preferably, in formula (3), R6 is a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C3-C10 cycloalkyl group.

[0033] Further preferably, in formula (3), R6 is a substituted or unsubstituted methyl group, a substituted or unsubstituted isopropyl group, or a substituted or unsubstituted cyclopentyl group; the substitution is by deuterium, F, Cl or Br.

[0034] Preferably: R7 is hydrogen, deuterium or halogen.

[0035] wherein at least one of R8 and R9 is not hydrogen. Preferably, neither R8 nor R9 is hydrogen.

[0036] It is further preferred that at least one of R8 and R9 is a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C3-C10 cycloalkyl group.

[0037] In formula (3), R2 and / or R5 are not hydrogen.

[0038] Preferably: in formula (3), wherein R2 is a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C3-C10 cycloalkyl group, and R1, R3-R5 are independently selected from hydrogen.

[0039] Preferably, Lc and La are different.

[0040] More preferably: wherein Lc is a structure shown in formula (4),

[0041]

[0042] The dotted line indicates the position connected to the metal Ir;

[0043] Among them, R 10 -R 17 independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, amino, amine, 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 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkylmono-C6-C30 arylsilyl, or substituted or unsubstituted mono-C1-C10 alkyldi-C6-C30 arylsilyl;

[0044] Among them, R 14 -R 17 At least two of them are not hydrogen;

[0045] Among them, R 10 -R 13 At least one group of two adjacent groups may form an aromatic ring as shown in the following formula (5);

[0046]

[0047] In formula (5)

[0048] The dotted line indicates the position of connection with the pyridine ring;

[0049] Among them, R 18 -R 21 R 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 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 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkylmono-C6-C30 arylsilyl, substituted or unsubstituted mono-C1-C10 alkyldi-C6-C30 arylsilyl, or R 18 -R 21 Two adjacent groups are connected to form an alicyclic ring or an aromatic ring;

[0050] wherein the heteroalkyl and heteroaryl groups contain at least one heteroatom of O, N or S;

[0051] Wherein, the substitution is amino, nitrile, isonitrile or phosphine substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl, wherein the substitution is from single substitution to maximum number substitution.

[0052] As a preferred organometallic iridium compound, La is preferably one of the following structural formulas, or the corresponding partially or completely deuterated or fluorinated ones,

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] As a preferred organometallic iridium compound, Lb is preferably one of the following structural formulas, or a corresponding partially or completely deuterated or fluorinated one,

[0061]

[0062]

[0063] As a preferred organometallic iridium compound, Lc is preferably one of the following structural formulas, or a corresponding partially or completely deuterated or fluorinated one,

[0064]

[0065]

[0066] Another object of the present invention is to provide an OLED phosphorescent material containing the above compound.

[0067] Another object of the present invention is to provide an OLED device containing the above compound.

[0068] The material of the present invention not only has the advantages of high optical and electrical stability, low sublimation temperature, narrow emission half-width, high color saturation, high luminous efficiency, and long device life, but also as a phosphorescent material, it can convert triplet excited states into light, thereby improving the luminous efficiency of organic electroluminescent devices and reducing energy consumption. In particular, as a red-emitting dopant, it has potential applications in the AMOLED industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 is the 1HNMR spectrum of the compound Ir(La002)2(Lb005) of the present invention in deuterated chloroform solution,

[0070] Figure 2 The UV absorption spectrum and emission spectrum of the compound Ir(La002)2(Lb005) of the present invention in dichloromethane solution are shown in FIG.

[0071] Figure 3 is the 1HNMR spectrum of the compound Ir(La003)2(Lb005) of the present invention in deuterated chloroform solution,

[0072] Figure 4 The UV absorption spectrum and emission spectrum of the compound Ir(La003)2(Lb005) of the present invention in dichloromethane solution are shown in FIG.

[0073] Figure 5 is the 1HNMR spectrum of the compound Ir(La007)2(Lb005) of the present invention in deuterated chloroform solution,

[0074] Figure 6 The UV absorption spectrum and emission spectrum of the compound Ir(La007)2(Lb005) of the present invention in dichloromethane solution are shown in FIG.

[0075] Figure 7 is the 1HNMR spectrum of the ligand La002 of the present invention in deuterated chloroform solution,

[0076] Figure 8 is the 1HNMR spectrum of the ligand La003 of the present invention in deuterated chloroform solution,

[0077] Figure 9 This is the 1HNMR spectrum of the ligand La007 of the present invention in deuterated chloroform solution. DETAILED DESCRIPTION

[0078] The compound of the present invention, an organometallic iridium compound, has the general formula of Ir(La)(Lb)(Lc), wherein La is a structure shown in formula (1),

[0079]

[0080] The dotted line indicates the position connected to the metal Ir;

[0081] wherein X1 is N or CR1, X2 is N or CR2, X3 is N or CR3, X4 is N or CR4, and X5 is N or CR5;

[0082] wherein R1-R5 are 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 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkylmono-C6-C30 arylsilyl, substituted or unsubstituted mono-C1-C10 alkyldi-C6-C30 arylsilyl, or two adjacent groups of R1-R5 may be connected to form an alicyclic ring or an aromatic ring structure;

[0083] wherein at most one of X1-X5 is N, and when X1-X5 are CR1-CR5, at least one of R1-R5 is not H;

[0084] wherein R6-R9 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C20 cycloalkyl, and R6 is not hydrogen, deuterium or halogen;

[0085] wherein the heteroalkyl and heteroaryl groups contain at least one heteroatom of O, N or S;

[0086] Wherein, the substitution is deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, nitrile, isonitrile or phosphine, wherein the substitution is a single substitution to the maximum number of substitutions.

[0087] Wherein Lb is the structure shown in formula (2),

[0088]

[0089] The dotted line indicates the position connected to the metal Ir;

[0090] 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, or substituted or unsubstituted C3-C20 heterocycloalkyl;

[0091] wherein the heteroalkyl group and heterocycloalkyl group contain at least one heteroatom of O, N or S;

[0092] wherein the substitution is deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, C1-C4 alkyl substituted amino, cyano, isonitrile or phosphine;

[0093] Among them, Ra, Rb, and Rc can be connected in pairs to form an aliphatic ring structure, and Re, Rf, and Rg can also be connected in pairs to form an aliphatic ring;

[0094] Among them, Lc is a monoanionic bidentate ligand, Lc and Lb are different and are not OO type ligands;

[0095] Wherein, Lc and La are the same or different, and the difference is that the parent core structures are different, or the parent core structures are the same but the substituents are different, or the parent core structures are the same but the substituents are in different positions;

[0096] Among them, La, Lb, and Lc can be connected to each other in pairs or in groups of three to form a multidentate ligand.

[0097] In formulae (1) to (5), when there are two or more substituents, the plurality of substituents may be the same or different.

[0098] Hereinafter, examples of each group of the compounds represented by formula (1) to formula (5) will be described.

[0099] In the present specification, the "carbon number a to b" in the expression "substituted or unsubstituted X group having a to b carbon atoms" refers to the carbon number of the unsubstituted X group and does not include the carbon number of the substituent when the X group is substituted.

[0100] The C1-C10 alkyl group is a linear or branched alkyl group, specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n-decyl and its isomers, etc., preferably, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and more preferably, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl.

[0101] Examples of the C3-C20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, and 2-norbornyl, with cyclopentyl and cyclohexyl being preferred.

[0102] Examples of the C2-C10 alkenyl group include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, and 3-hexatrienyl, with propenyl and allyl being preferred.

[0103] The C1-C10 heteroalkyl group is a linear or branched alkyl group, cycloalkyl group, etc. containing atoms other than carbon and hydrogen, and examples thereof include mercaptomethylmethane, methoxymethane, ethoxymethane, tert-butoxymethane, N,N-dimethylmethane, butylene oxide, cyclopentyl, and hexyl oxide, with methoxymethane and cyclopentyl being preferred.

[0104] Specific examples of the aryl group include phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacene, pyrene, chrysene, benzo[c]phenanthrenyl, benzo[g]chrysene, fluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, and fluoranthenyl, preferably phenyl or naphthyl.

[0105] Specific examples of heteroaryl groups include pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, isoindolyl, imidazolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, diazadibenzofuranyl, diazadibenzothiophenyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, Phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, oxadiazolyl, furazanyl, thienyl, benzothienyl, dihydroacridinyl, azacarbazolyl, diazacarbazolyl, quinazolinyl, etc., preferably pyridyl, pyrimidinyl, triazinyl, dibenzofuranyl, dibenzothienyl, azadibenzofuranyl, azadibenzothienyl, diazadibenzofuranyl, diazadibenzothienyl, carbazolyl, azacarbazolyl, diazacarbazolyl.

[0106] The following examples are only for facilitating understanding of the technical invention and should not be regarded as specific limitations of the present invention.

[0107] The raw materials and solvents involved in the synthesis of the compounds of the present invention were purchased from suppliers well known to those skilled in the art, such as Alfa and Acros.

[0108] Synthesis of ligand La002:

[0109]

[0110] Synthesis of intermediate 2:

[0111] Compound 1 (27.85 g, 0.13 mol, 1.0 eq), pinacol diboronate (67.02 g, 0.26 mol, 2.0 eq), Pd(dppf)Cl2 (9.66 g, 0.013 mol, 0.1 eq), potassium acetate (25.90 g, 0.26 mol, 2.0 eq), and 1,4-dioxane (350 ml) were added to a 1 L three-necked flask. The flask was evacuated and replaced with nitrogen three times. Under nitrogen protection, the mixture was stirred at 100°C for 2 hours. TLC monitoring indicated that the reaction of starting material 1 was complete. The mixture was cooled to room temperature and concentrated under reduced pressure to remove the organic solvent. The mixture was extracted with dichloromethane and deionized water, and the mixture was spin-dried and separated by column chromatography (eluent: ethyl acetate: n-hexane = 1:20). After concentration, a light yellow solid was obtained. 3V (90 mL) of n-hexane was added for slurrying. The mixture was stirred at 70°C for 15 min and dissolved. After heating was stopped and stirring was continued for 2 h, the mixture was filtered and the filter cake was dried to obtain a white solid as intermediate 2 (19.86 g, yield: 58.3%). The mass spectrum was 259.14 (M+H).

[0112] Synthesis of ligand La002:

[0113] Intermediate 3 (17.00 g, 0.08 mol, 1.0 eq), intermediate 2 (23.47 g, 0.09 mol, 1.1 eq), Pd(PPh3)4 (4.78 g, 0.004 mol, 0.05 eq), sodium carbonate (17.52 g, 0.16 mol, 2.00 eq), 1,4-dioxane (255 ml), and deionized water (85 ml) were added to a 1 L three-necked flask. The flask was evacuated and replaced with nitrogen three times. Under nitrogen protection, the flask was stirred at 90°C for 3 hours. TLC monitoring showed that the reaction of starting material 3 was complete. The mixture was cooled to room temperature and concentrated under reduced pressure to remove the organic solvent. The mixture was extracted with dichloromethane and deionized water. The mixture was spin-dried and separated by column chromatography (eluent: ethyl acetate: n-hexane = 1:25). After concentration, a light yellow sugar-like solid was obtained, which was compound La002 (21.48 g, yield: 86.23%). The mass spectrum was 302.38 (M+H).

[0114] Synthesis of compound Ir(La002)2(Lb005):

[0115]

[0116] Synthesis of compound Ir(La002)-1:

[0117] Compound La002 (12.30 g, 40.81 mmol, 3.5 eq) and IrCl₃.3H₂O (4.11 g, 11.66 mmol, 1.0 eq) were placed in a 500 ml single-necked round-bottom flask. Ethylene glycol ether (120 ml) and deionized water (40 ml) were added and the mixture was replaced in vacuo three times. Under nitrogen, the mixture was stirred at 110°C for 24 hours. After cooling to room temperature, the solvent was removed by concentration. DCM was added to dissolve the silica gel, and the filtrate was washed with deionized water. The organic phase was concentrated to yield a dark red oil, compound Ir(La002)-1 (9.33 g, 96.56%). The resulting compound was used directly in the next step without further purification.

[0118] Synthesis of compound Ir(La002)2(Lb005):

[0119] Compound Ir(La002)-1 (6.56 g, 7.92 mmol, 1.0 eq), Lb005 (8.41 g, 39.59 mmol, 5.0 eq) and sodium carbonate (8.39 g, 79.19 mmol, 10.0 eq) were placed in a 250 ml single-necked round-bottom flask, and ethylene glycol ethyl ether (66 ml) was added. The mixture was replaced by vacuum three times, and the mixture was stirred at 50 ° C under N2 protection for 24 hours. The reaction of Ir(La002)-1 was monitored by TLC. After cooling to room temperature, 132 ml of methanol was added and the mixture was stirred at room temperature for 2 hours. The mixture was then filtered with suction. The filter cake was dissolved in dichloromethane (100 ml) to remove the silica gel. The filtrate was washed with deionized water (120 ml). The organic phase was collected, concentrated, and dried to obtain a dark red solid. This solid was recrystallized twice from DMF / MeCN (30 V / 20 V) to obtain the dark red solid compound Ir(La002)2(Lb005) (2.65 g, yield: 33.32%). 2.65 g of crude Ir(La002)2(Lb005) was purified by sublimation to obtain pure Ir(La002)2(Lb005) (1.52 g, yield: 57.35%). Mass spectrum: 1005.28 (M+H). 1 H NMR (400MHz, CDCl3) δ8.87(d,J=8.9Hz,2H),8.21(d,J=6.4Hz,2H),7.59(s,2H),7.53(d,J=8.9Hz,2H), 7.39(d,J=2.1Hz,2H),7.23(d,J=6.4Hz,2H),7.02(s,2H),6.66(d,J=2.1Hz,2H),4.76(s,1H),3.14(dt, J = 13.5, 6.7 Hz, 2H), 1.54 (dd, J = 12.1, 3.8 Hz, 8H), 1.40 (dd, J = 6.9, 2.7 Hz, 11H), 1.33–1.12 (m, 3H), 1.14–1.02 (m, 2H), 0.75 (dd, J = 16.9, 9.6 Hz, 4H), 0.45 (t, J = 7.4 Hz, 6H), -0.20 (t, J = 7.4 Hz, 6H). Synthesis of ligand La003:

[0120]

[0121] Referring to the synthesis and purification methods of compound La002, only the corresponding raw materials need to be changed to obtain the target compound La003, mass spectrum: 316.16 (M+H).

[0122] Synthesis of compound Ir(La003)2(Lb005):

[0123]

[0124] Synthesis of compound Ir(La003)-1:

[0125] Referring to the synthesis and purification methods of compound Ir(Lb002)-1, the corresponding raw materials can be changed to obtain compound Ir(La003)-1, which is directly used in the next step without purification.

[0126] Synthesis of compound Ir(La003)2(Lb005):

[0127] Referring to the synthesis and purification methods of compound Ir(La002)2(Lb005), only the corresponding raw materials need to be changed to obtain a red solid compound Ir(La003)2(Lb005) (2.31g, yield: 32.57%). 2.31g of crude Ir(La003)2(Lb005) was purified by sublimation to obtain pure Ir(La003)2(Lb005) (1.21g, yield: 52.38%), mass spectrum: 1033.44 (M+H) 1 H NMR (400MHz, CDCl3) δ8.85(d,J=8.7Hz,2H),8.21(d,J=6.4Hz,2H),7.53(s,2H),7.45(d,J=8.8Hz,2H),7.38(d,J=2.1Hz,2H ),7.21(d,J=6.3Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),4.77(s,1H),2.70(p,J=13.4Hz,4H),2.14–2.01(m,2H),1.66–

[0128] 1.39(m,10H),1.33–1.16(m,3H),1.04(ddd,J=15.7,10.9,6.1Hz,12H),0.88(t,J=7. 4Hz, 2H), 0.77 (dd, J=14.7, 7.7Hz, 3H), 0.44 (t, J=7.4Hz, 5H), -0.20 (t, J=7.3Hz, 5H).

[0129] Synthesis of ligand La004:

[0130]

[0131] Referring to the synthesis and purification methods of compound La002, it is only necessary to change the corresponding raw materials to obtain the target compound La004, mass spectrum: 330.43 (M+H).

[0132] Synthesis of compound Ir(La004)2(Lb005):

[0133]

[0134] Synthesis of compound Ir(La004)-1:

[0135] Referring to the synthesis and purification methods of compound Ir(Lb002)-1, the corresponding raw materials can be changed to obtain compound Ir(La004)-1, which is directly used in the next step without purification.

[0136] Synthesis of compound Ir(La004)2(Lb005):

[0137] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply modify the corresponding starting materials to obtain a red solid, compound Ir(La004)2(Lb005) (1.89 g, yield: 36.21%). 1.89 g of crude Ir(La004)2(Lb005) was purified by sublimation to obtain pure Ir(La004)2(Lb005) (1.02 g, yield: 53.96%), with a mass spectrum of 1061.39 (M+H). 1 H NMR (400MHz, CDCl3) δ8.86 (d, J = 8.7Hz, 2H), 8.22 (d, J = 6.4Hz, 2H), 7.53 (s, 2H), 7.45 (d, J = 8. 8Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.3Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),4. 77(s,1H),2.70(p,J=13.4Hz,4H),1.66–1.39(m,10H),1.33–1.16(m,3H),1.04(m,18H),0.88 (t,J=7.4Hz,2H),0.77(dd,J=14.7,7.7Hz,3H),0.44(t,J=7.4Hz,5H),-0.15(t,J=7.3Hz,5H).

[0138] Synthesis of ligand La007:

[0139]

[0140] Referring to the synthesis and purification methods of compound La002, only the corresponding raw materials need to be changed to obtain the target compound La007, mass spectrum: 328.42 (M+H).

[0141] Synthesis of compound Ir(La007)2(Lb005):

[0142]

[0143] Synthesis of compound Ir(La007)-1:

[0144] Referring to the synthesis and purification method of compound Ir(La002)-1, it is only necessary to change the corresponding raw materials to obtain compound Ir(La007)-1, which is directly used in the next step without purification.

[0145] Synthesis of compound Ir(La007)2(Lb005):

[0146] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply modify the corresponding starting materials to obtain a dark red solid, compound Ir(La007)2(Lb005) (2.66 g, yield: 35.20%). 2.66 g of crude Ir(La007)2(Lb005) was purified by sublimation to obtain pure Ir(La007)2(Lb005) (1.63 g, yield: 61.27%), mass spectrum: 1057.44 (M+H). 1 H NMR (400MHz, CDCl3) δ8.86(d,J=8.8Hz,2H),8.20(d,J=6.4Hz,2H),7.60(s,2H),7.54(d,J=9.0Hz,2 H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.4Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),4.76(s,1H),3. 37–3.07(m,2H),2.19(s,4H),1.84(d,J=51.8Hz,11H),1.62–1.44(m,9H),1.24(dd,J=14.9,7.6Hz, 3H),1.16–0.97(m,2H),0.75(dd,J=16.5,8.4Hz,4H),0.45(t,J=7.4Hz,5H),-0.19(t,J=7.4Hz,5H).

[0147] Synthesis of ligand La011:

[0148]

[0149] Referring to the synthesis and purification methods of compound La002, only the corresponding raw materials need to be changed to obtain the target compound La011, mass spectrum: 370.5 (M+H).

[0150] Synthesis of compound Ir(La011)2(Lb007):

[0151]

[0152] Synthesis of compound Ir(La011)-1:

[0153] Referring to the synthesis and purification method of compound Ir(La002)-1, it is only necessary to change the corresponding raw materials to obtain compound Ir(La011)-1, which is directly used in the next step without purification.

[0154] Synthesis of compound Ir(La011)2(Lb007):

[0155] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply by changing the corresponding starting materials, a dark red solid was obtained, compound Ir(La011)2(Lb007) (2.11 g, yield: 34.91%). 2.11 g of crude Ir(La011)2(Lb007) was purified by sublimation to obtain pure Ir(La011)2(Lb007) (0.95 g, yield: 45.02%), with a mass spectrum of 1069.57 (M+H). 1 H NMR (400MHz, CDCl3) δ8.86(d,J=8.7Hz,2H),8.22(d,J=6.4Hz,2H),7.53(s,2H),7.45(d,J=8.8Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.3Hz ,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),2.22(m,2H),1.55(m,6H),1.4 7(m,16H), 1.33–1.16(m,8H), 1.03(m,12H), 0.89(m,12H), 0.77(s,6H).

[0156] Synthesis of compound Ir(La003)2(Lb006):

[0157]

[0158] Synthesis of compound Ir(La003)2(Lb006):

[0159] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply modify the corresponding starting materials to obtain a dark red solid, compound Ir(La003)2(Lb006) (1.97 g, yield: 31.70%). 1.97 g of crude Ir(La003)2(Lb006) was purified by sublimation to obtain pure Ir(La003)2(Lb006) (1.11 g, yield: 56.34%), with a mass spectrum of 1047.34 (M+H). 1 H NMR (400MHz, CDCl3) δ8.85(d,J=8.7Hz,2H),8.21(d,J=6.4Hz,2H),7.53(s,2H),7.45(d,J=8.8Hz,2H),7.38(d,J=2.1Hz,2H ),7.21(d,J=6.3Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),2.70(p,J=13.4Hz,4H),2.14–2.01(m,2H),1.88(s,3H),1.66–

[0160] 1.39(m,10H),1.33–1.16(m,3H),1.04(ddd,J=15.7,10.9,6.1Hz,12H),0.88(t,J=7. 4Hz, 2H), 0.77 (dd, J=14.7, 7.7Hz, 3H), 0.44 (t, J=7.4Hz, 5H), -0.20 (t, J=7.3Hz, 5H).

[0161] Synthesis of ligand La039:

[0162]

[0163] Synthesis of intermediate 10:

[0164] In a 1L three-necked flask, compound 8 (18.5g, 86.01mmol, 1.0eq), compound 9 (19.97g, 94.61mmol, 1.1eq), and dimethyl sulfoxide (277ml) were added. After stirring at room temperature, potassium hydroxide aqueous solution (5.79g, 103.2mmol, 1.2eq, in 150ml of deionized water) was slowly added dropwise. After completion of the addition, the reaction was heated to 120°C for 16 hours. TLC monitoring indicated complete reaction of starting material 8. After cooling to room temperature, the reaction solution was extracted with ethyl acetate (250ml) several times. The organic phase was then washed twice with deionized water (100ml / times). The organic phase was separated and concentrated to obtain compound 10 (24.3g, 81.83%) as a light yellow oil, which was directly used in the next step. Mass spectrum: 346.2 (M+H).

[0165] Synthesis of intermediate 11:

[0166] In a 1L three-necked flask, compound 10 (20.0 g, 57.93 mmol, 1.0 eq), polyphosphoric acid (100 g), and chlorobenzene (250 ml) were added and the reaction was heated to reflux for 16 hours. TLC monitoring indicated that the reaction of starting material 10 was essentially complete. After cooling to room temperature, the reaction solution was extracted with ethyl acetate (300 ml). The resulting organic phase was washed three times with 5% sodium bicarbonate solution (250 ml), then separated. The organic phase was concentrated and separated by column chromatography (eluent: n-hexane) to obtain compound 11 (6.87 g, 46.82%) as a white solid. Mass spectrum: 254.13 (M+H).

[0167] Synthesis of intermediate 12:

[0168] Referring to the synthesis and purification methods of compound 2, only the corresponding raw materials need to be changed to obtain the target compound 12, mass spectrum: 301.22 (M+H).

[0169] Synthesis of ligand La039:

[0170] Referring to the synthesis and purification methods of compound La002, only the corresponding raw materials need to be changed to obtain the target compound La039, mass spectrum: 358.49 (M+H).

[0171] Synthesis of compound Ir(La039)2(Lb006):

[0172]

[0173] Synthesis of compound Ir(La039)-1:

[0174] Referring to the synthesis and purification method of compound Ir(La002)-1, it is only necessary to change the corresponding raw materials to obtain compound Ir(La039)-1, which is directly used in the next step without purification.

[0175] Synthesis of compound Ir(La039)2(Lb006):

[0176] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply modify the corresponding starting materials to obtain a dark red solid, compound Ir(La039)2(Lb006) (2.73 g, yield: 41.72%). 2.73 g of crude Ir(La039)2(Lb006) was purified by sublimation to obtain pure Ir(La039)2(Lb006) (1.22 g, yield: 44.68%), with a mass spectrum of 1031.52 (M+H).1 H NMR (400MHz, CDCl3) δ8.87(d,J=8.8Hz,2H),8.22(d,J=6.4Hz,2H),7.60(s,2H),7.54(d,J=9.0Hz,2H),7.38(d,J=2.1Hz,2H ),7.21(d,J=6.4Hz,2H),7.01(s,2H),2.87(m,2H),2.43(m,4H),2.25(s,6H),1.87(s,3H),1.82(m,2H),1.24(m,18H),1.06–

[0177] 0.76(m,28H).

[0178] Synthesis of ligand La087:

[0179]

[0180] Synthesis of intermediate 14:

[0181] Referring to the synthesis and purification methods of compound 10, only the corresponding raw materials need to be changed to obtain the target compound 14, mass spectrum: 318.22 (M+H).

[0182] Synthesis of intermediate 15:

[0183] Referring to the synthesis and purification methods of compound 10, only the corresponding raw materials need to be changed to obtain the target compound 15, mass spectrum: 226.08 (M+H).

[0184] Synthesis of intermediate 16:

[0185] Referring to the synthesis and purification methods of compound 2, only the corresponding raw materials need to be changed to obtain the target compound 16, mass spectrum: 273.15 (M+H).

[0186] Synthesis of intermediate 17:

[0187] Referring to the synthesis and purification methods of compound La002, only the corresponding raw materials need to be changed to obtain the target compound intermediate 17, mass spectrum: 330.43 (M+H).

[0188] Synthesis of ligand La087:

[0189] Take a 1L single-necked bottle, put in intermediate 17 (9.5g, 28.84mmol, 1.0eq), 60% sodium hydride (3.46g,

[0190] 86.51 mmol, 3.0 eq) and deuterated ethanol (100 ml). The mixture was vacuum-purified and nitrogen-purged three times, then heated to 75°C under nitrogen protection and reacted for 16 hours. The reaction mixture was cooled to room temperature. Heavy water (40 mL) was added and stirred to precipitate a solid, which was collected by filtration. The crude product was separated by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1 / 30) to obtain compound La087 (5.98 g, 62.4% yield) as a pale yellow solid.

[0191] Synthesis of compound Ir(La087)2(Lb006):

[0192]

[0193] Synthesis of compound Ir(La087)-1:

[0194] Referring to the synthesis and purification method of compound Ir(La002)-1, it is only necessary to change the corresponding raw materials to obtain compound Ir(La087)-1, which is directly used in the next step without purification.

[0195] Synthesis of compound Ir(La087)2(Lb006):

[0196] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply modify the corresponding starting materials to obtain a dark red solid, compound Ir(La087)2(Lb006) (1.68 g, yield: 31.61%). 1.68 g of crude Ir(La087)2(Lb006) was purified by sublimation to obtain pure Ir(La087)2(Lb006) (0.84 g, yield: 50.0%), mass spectrum: 1081.53 (M+H). 1 H NMR (400MHz, CDCl3) δ8.84(d,J=8.7Hz,2H),8.19(d,J=6.4Hz,2H),7.53(s,2H),7.45(d,J=8.8Hz, 2H),7.38(d,J=2.1Hz,2H),7.22(d,J=6.3Hz,2H),7.02(s,2H),2.71(p,J=13.4Hz,4H),2.14–2.01( m,2H),1.88(s,3H),1.66–1.39(m,10H),1.33–1.16(m,3H),1.04(ddd,J=15.7,10.9,6.1Hz,12H), 0.88(t,J=7.4Hz,2H), 0.77(dd,J=14.7,7.7Hz,3H), 0.44(t,J=7.4Hz,5H), -0.20(t,J=7.3Hz,5H).

[0197] Synthesis of ligand La099:

[0198]

[0199] Synthesis of intermediate 19:

[0200] Referring to the synthesis and purification methods of compound 10, only the corresponding raw materials need to be changed to obtain the target compound 19, mass spectrum: 332.25 (M+H).

[0201] Synthesis of intermediate 20:

[0202] Referring to the synthesis and purification methods of compound 10, only the corresponding raw materials need to be changed to obtain the target compound 20, mass spectrum: 240.11 (M+H).

[0203] Synthesis of intermediate 21:

[0204] Referring to the synthesis and purification methods of compound 2, only the corresponding raw materials need to be changed to obtain the target compound 21, mass spectrum: 287.17 (M+H).

[0205] Synthesis of ligand La099:

[0206] Referring to the synthesis and purification methods of compound La002, it is only necessary to change the corresponding raw materials to obtain the target compound La099, mass spectrum: 344.46 (M+H).

[0207] Synthesis of compound Ir(La099)2(Lb006):

[0208]

[0209] Synthesis of compound Ir(La099)-1:

[0210] Referring to the synthesis and purification method of compound Ir(La002)-1, it is only necessary to change the corresponding raw materials to obtain compound Ir(La099)-1, which is directly used in the next step without purification.

[0211] Synthesis of compound Ir(La099)2(Lb006):

[0212] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply modify the corresponding starting materials to obtain a dark red solid, compound Ir(La099)2(Lb006) (1.89 g, yield: 33.67%). 1.89 g of crude Ir(La099)2(Lb006) was purified by sublimation to obtain pure Ir(La099)2(Lb006) (1.09 g, yield: 57.67%), with a mass spectrum of 1103.47 (M+H). 1 H NMR (400MHz, CDCl3) δ8.85(d,J=8.8Hz,2H),8.20(d,J=6.4Hz,2H),7.60(s,2H),7.54(d,J=9.0Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J= 6.4Hz,2H),2.43(s,4H),2.30(d,J=40.0Hz,12H),2.02(s,6H),1.87(s,3H),1.85–1.77(m,2H),1.27(m,8H),1.01(m,4H),0.91(m,22H).

[0213] Synthesis of ligand La111:

[0214]

[0215] Synthesis of intermediate 23:

[0216] Referring to the synthesis and purification methods of compound 10, only the corresponding raw materials need to be changed to obtain the target compound 23, mass spectrum: 360.3 (M+H).

[0217] Synthesis of intermediate 24:

[0218] Referring to the synthesis and purification methods of compound 10, only the corresponding raw materials need to be changed to obtain the target compound 24, mass spectrum: 267.16 (M+H).

[0219] Synthesis of intermediate 25:

[0220] Referring to the synthesis and purification methods of compound 2, only the corresponding raw materials need to be changed to obtain the target compound 25, mass spectrum: 315.23 (M+H).

[0221] Synthesis of ligand La111:

[0222] Referring to the synthesis and purification methods of compound La002, it is only necessary to change the corresponding raw materials to obtain the target compound La111, mass spectrum: 386.54 (M+H).

[0223] Synthesis of compound Ir(La111)2(Lb006):

[0224]

[0225] Synthesis of compound Ir(La111)-1:

[0226] Referring to the synthesis and purification method of compound Ir(La002)-1, it is only necessary to change the corresponding raw materials to obtain compound Ir(La111)-1, which is directly used in the next step without purification.

[0227] Synthesis of compound Ir(La111)2(Lb006):

[0228] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply modify the corresponding starting materials to obtain a dark red solid, compound Ir(La111)2(Lb006) (1.59 g, yield: 30.87%). 1.59 g of crude Ir(La111)2(Lb006) was purified by sublimation to obtain pure Ir(La111)2(Lb006) (0.87 g, yield: 54.71%), with a mass spectrum of 1187.63 (M+H). 1 H NMR (400MHz, CDCl3) δ8.23(d,J=6.4Hz,2H),7.61(s,2H),7.55(d,J=9.0Hz,2H),7.39(d,J=2.1Hz,2H),7.212(d,J=6.4Hz,2H),2.69(s ,6H),2.43(m,4H),2.34(s,6H),2.02(s,6H),1.87(s,3H),1.82(m,2H),1.27(m,6H),1.19(m,12H),1.07–0.90(m,18H),0.87(m,12H).

[0229] Synthesis of ligand La123:

[0230]

[0231]

[0232] Synthesis of intermediate 27:

[0233] Referring to the synthesis and purification methods of compound 10, only the corresponding raw materials need to be changed to obtain the target compound 27, mass spectrum: 386.34 (M+H).

[0234] Synthesis of intermediate 28:

[0235] Referring to the synthesis and purification methods of compound 10, only the corresponding raw materials need to be changed to obtain the target compound 28, mass spectrum: 294.20 (M+H).

[0236] Synthesis of intermediate 29:

[0237] Referring to the synthesis and purification methods of compound 2, only the corresponding raw materials need to be changed to obtain the target compound 29, mass spectrum: 341.26 (M+H).

[0238] Synthesis of ligand La123:

[0239] Referring to the synthesis and purification methods of compound La002, it is only necessary to change the corresponding raw materials to obtain the target compound La123, mass spectrum: 398.55 (M+H).

[0240] Synthesis of compound Ir(La123)2(Lb006):

[0241]

[0242] Synthesis of compound Ir(La123)-1:

[0243] Referring to the synthesis and purification method of compound Ir(La002)-1, it is only necessary to change the corresponding raw materials to obtain compound Ir(La123)-1, which is directly used in the next step without purification.

[0244] Synthesis of compound Ir(La123)2(Lb006):

[0245] Referring to the synthesis and purification methods for compound Ir(La002)2(Lb005), simply modify the corresponding starting materials to obtain a dark red solid, compound Ir(La123)2(Lb006) (1.76 g, yield: 30.87%). 1.76 g of crude Ir(La123)2(Lb006) was purified by sublimation to obtain pure Ir(La123)2(Lb006) (1.04 g, yield: 61.17%), with a mass spectrum of 1121.65 (M+H). 1 H NMR (400MHz, CDCl3) δ8.87(d,J=8.8Hz,2H),8.23(d,J=6.4Hz,2H),7.62(s,2H),7.55(d,J=9.0Hz,2H),7.39(d,J=2 .1Hz,2H),7.23(d,J=6.4Hz,2H),2.43(m,4H),2.30(m,12H),1.99–1.56(m,21H),1.27(m,6H),1.10–0.81(m,30H).

[0246] Synthesis of ligand Lc002:

[0247]

[0248] Referring to the synthesis and purification methods of compound La002, only the corresponding raw materials need to be changed to obtain the target compound Lc002, mass spectrum: 276.39 (M+H).

[0249] Synthesis of compound Ir(La004)(Lb005)(Lc002):

[0250]

[0251] Synthesis of Compound Ir(La004)-2

[0252] To a 3L three-necked flask, add the dimer Ir(La004)-1 (8.64g, 9.77mmol, 1.0eq) and dichloromethane (650ml) and stir to dissolve. Dissolve silver trifluoromethanesulfonate (5.02g, 19.54mmol, 2.0eq) in methanol (510ml) and add the resulting mixture to the original reaction flask. Vacuum replacement is performed three times, and the mixture is stirred at room temperature under N2 protection for 16 hours. The reaction mixture is then filtered through Celite, and the residue is rinsed with dichloromethane (150ml). The filtrate is then dried to dryness to yield compound Ir(La004)-2 (7.3g, 70.32%). The resulting compound is used directly in the next step without further purification.

[0253] Synthesis of Compound Ir(La004)2(Lc002)

[0254] Compound Ir(La004)-2 (6.8 g, 6.4 mmol, 1.0 eq) and Lc002 (4.41 g, 16.0 mmol, 2.5 eq) were added to a 250 ml three-necked flask, and ethanol (70 ml) was added. The mixture was replaced by vacuum three times and stirred under N2 protection for 16 hours. After cooling to room temperature, the mixture was filtered. The collected solid was dissolved in dichloromethane (150 ml) and filtered through silica gel. The filter cake was rinsed with dichloromethane (50 ml). The filtrate was dried and recrystallized twice from tetrahydrofuran / methanol (product: tetrahydrofuran:methanol = 1:5:10). The product was dried to obtain compound Ir(La004)2(Lc002) (2.92 g, 40.62%). Mass spectrum: 1124.45 (M+H). Synthesis of compound Ir(La004)2(Lc002)-1

[0255] Compound Ir(La004)2(Lc002) (5.9 g, 5.25 mmol, 1.0 eq) and zinc chloride (35.79 g, 262.5 mmol, 50 eq) were placed in a 1L single-necked flask. 1,2-dichloroethane (360 ml) was added and the mixture was replaced in vacuo three times. Under nitrogen, the mixture was stirred and refluxed for 18 hours. TLC analysis indicated that the reaction of the starting material Ir(La004)2(Lc002) was essentially complete. After cooling to room temperature, the mixture was washed three times with deionized water (150 ml). The filtrate was then dried to give compound Ir(La004)2(Lc002)-1 (3.71 g, 83.40%). The resulting compound was used directly in the next step without further purification.

[0256] Synthesis of Compound Ir(La004)(Lb005)(Lc002)

[0257] Compound Ir(La004)2(Lc002)-1(3.7g, 4.37mmol, 1.0eq), Lb005

[0258] (4.64 g, 21.58 mmol, 5.0 eq) and sodium carbonate (4.63 g, 43.71 mmol, 10.0 eq) were placed in a 250 ml single-necked round-bottom flask, and ethylene glycol ether (55 ml) was added. The mixture was replaced in vacuo three times, and stirred at 50°C under N2 protection for 24 hours. TLC monitored the complete reaction of Ir(La004)2(Lc002)-1. After cooling to room temperature, 110 ml of methanol was added and the mixture was stirred at room temperature for 2 hours. The mixture was then filtered, and the filter cake was dissolved in dichloromethane (80 ml) and filtered through silica gel. The filtrate was washed with deionized water (60 ml). The layers were separated, and the organic phase was collected, concentrated, and dried to obtain a dark red solid. The dark red solid was recrystallized twice from DMF / MeCN (30 V / 20 V) to obtain compound Ir(La004)(Lb005)(Lc002) (1.64 g, yield: 37.33%). 1.64 g of crude Ir(La004)(Lb005)(Lc002) was purified by sublimation to obtain sublimation-purified Ir(La004)(Lb005)(Lc002) (0.79 g, yield: 48.17%). Mass spectrum: 1007.34 (M+H). 1H NMR (400MHz, CDCl3) δ8.86(m,1H),8.23(d,J=6.4Hz,2H),8.07(m,2H),7.78(d,J=5.0Hz,2H),7.61(m,2H),7.49(d,J=2 0.0Hz,2H),6.92(m,2H),6.76(m,2H),4.77(s,1H),2.87(s,1H),2.36(m,12H),1.43–1.12(m,14H),1.10–0.75(m,24H).

[0259] Synthesis of ligand Lc004:

[0260]

[0261] Referring to the synthesis and purification methods of compound La002, only the corresponding raw materials need to be changed to obtain the target compound Lc004, mass spectrum: 290.41 (M+H).

[0262] Synthesis of compound Ir(La004)(Lb005)(Lc004):

[0263]

[0264] Synthesis of compound Ir(La004)2(Lc004):

[0265] Referring to the synthesis and purification methods of compound Ir(La004)2(Lc002), it is only necessary to change the corresponding raw materials to obtain the target compound Ir(La004)2(Lc004), mass spectrum: 1138.48 (M+H).

[0266] Synthesis of compound Ir(La004)2(Lc004)-1:

[0267] Referring to the synthesis and purification methods of compound Ir(La004)2(Lc002)-1, it is only necessary to change the corresponding raw materials to obtain the target compound Ir(La004)2(Lc004)-1, which is directly used in the next step without purification.

[0268] Synthesis of compound Ir(La004)(Lb005)(Lc004):

[0269] Referring to the synthesis and purification methods for compound Ir(La004)(Lb005)(Lc002), only the corresponding starting materials need to be changed to obtain a dark red solid, compound Ir(La004)(Lb005)(Lc004) (1.48 g, yield: 36.61%). 1.48 g of crude Ir(La004)(Lb005)(Lc004) was purified by sublimation to obtain pure Ir(La004)(Lb005)(Lc004) (0.78 g, yield: 52.70%), with a mass spectrum of 1121.37 (M+H). 1 H NMR (400MHz, CDCl3) δ8.85(m,1H),8.23(d,J=6.4Hz,2H),8.07(m,2H),7.78(d,J=5.0Hz,2H),7.61(m,2H),7.50(d,J=20.0Hz,2H ),6.90(m,2H),6.76(m,2H),4.77(s,1H),2.43(s,4H),2.32(m,9H),1.82(m,1H),1.27(m,8H),1.01(m,5H),0.97–0.80(m,24H).

[0270] Synthesis of ligand Lc006:

[0271]

[0272] Referring to the synthesis and purification methods of compound La002, only the corresponding raw materials need to be changed to obtain the target compound Lc006, mass spectrum: 302.42 (M+H).

[0273] Synthesis of compound Ir(La004)(Lb005)(Lc006):

[0274]

[0275] Synthesis of compound Ir(La004)2(Lc006):

[0276] Referring to the synthesis and purification method of compound Ir(La004)2(Lc002), it is only necessary to change the corresponding raw materials to obtain the target compound Ir(La004)2(Lc006), mass spectrum: 1150.48 (M+H).

[0277] Synthesis of compound Ir(La004)2(Lc006)-1:

[0278] Referring to the synthesis and purification methods of compound Ir(La004)2(Lc002)-1, it is only necessary to change the corresponding raw materials to obtain the target compound Ir(La004)2(Lc006)-1, which is directly used in the next step without purification.

[0279] Synthesis of compound Ir(La004)(Lb005)(Lc006):

[0280] Referring to the synthesis and purification methods for compound Ir(La004)(Lb005)(Lc002), only the corresponding starting materials need to be changed to obtain a dark red solid, compound Ir(La004)(Lb005)(Lc006) (1.87 g, yield: 38.98%). 1.87 g of crude Ir(La004)(Lb005)(Lc006) was purified by sublimation to obtain pure Ir(La004)(Lb005)(Lc006) (1.03 g, yield: 55.08%), mass spectrum: 1133.38 (M+H). 1 H NMR (400MHz, CDCl3) δ8.86(d,1H),8.23(d,J=6.4Hz,2H),8.07(m,2H),7.78(d,J=5.0Hz,2H),7.61(m,2H),7.50(d,J=20.0Hz,2H),6.90(m,2H), 6.76(m,2H),4.78(s,1H),2.44(s,2H),2.32(d,J=15.0Hz,9H),1.88(m, 3H),1.76(m,2H),1.66(m,4H),1.27(m,8H),1.01(m,5H),0.90(m,18H).

[0281] Application example: Fabrication of organic electroluminescent devices

[0282] A 50mm*50mm*1.0mm glass substrate with an ITO (100nm) transparent 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 mounted on the substrate holder of a vacuum evaporation apparatus. First, a 5nm thick film of HATCN was deposited on the surface of the substrate with the transparent electrode lines, covering the transparent electrode. Next, a 60nm thick film of HTM1 was deposited. A 10nm thick film of HTM2 was then deposited on the HTM1 film. Finally, a 30nm thick film of a host material and a dopant compound (comparative compound X and compound AX of the present invention) was co-deposited on the HTM2 film. The ratio of host material to dopant material was 90%:10%. An ETL layer (25nm) and a LiQ layer (1nm) were then sequentially deposited on the light-emitting layer. Finally, a 100nm thick layer of Al was deposited as the electrode.

[0283]

[0284] evaluate:

[0285] The above devices were subjected to device performance testing. In each example and comparative example, a constant current source (Keithley 2400) was used to flow a constant current density through the light-emitting element, and the emission spectrum was measured using a spectroradiometer (CS2000). The voltage value and the time it took for the brightness to reach 90% of the initial brightness (LT90) were also measured. The results are as follows:

[0286]

[0287] As can be seen from the data comparison in the table above, organic electroluminescent devices using the compounds of the present invention as dopants exhibit superior performance in terms of driving voltage, luminous efficiency, and device life compared to the comparative compounds. In particular, the compounds of the present invention surprisingly exhibit more saturated luminescence performance, a deeper red emission wavelength, and improved device life by more than 10% under conditions that reduce the conjugation and electron-donating properties of the HOMO energy level compared to comparative complex 6. Compared to comparative example 2, the change in connection mode results in a more blue-shifted emission, thereby improving the luminous efficiency.

[0288] These results demonstrate that the compounds of the present invention possess advantages such as high optical and electrical stability, low sublimation temperature, narrow emission half-width, high color saturation, high luminous efficiency, and long device life, and are therefore suitable for use in organic electroluminescent devices. In particular, as red-emitting dopants, they have potential applications in the OLED industry.

Claims

1. An organometallic iridium compound having the general formula Ir(La)(Lb)(Lc), wherein La is a structure represented by formula (3), in, The dotted line indicates the location of connection with metal Ir; wherein R1-R5 are 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, or substituted or unsubstituted C2-C17 heteroaryl; wherein at least one of R1-R5 is not H; wherein R6-R9 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C3-C20 cycloalkyl, and R6 is not hydrogen, deuterium or halogen; wherein the heteroalkyl and heteroaryl groups contain at least one heteroatom of O, N or S; wherein the substitution is substitution with deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, nitrile or isonitrile, wherein the substitution is from a single substitution to a maximum number of substitutions; Wherein Lb is the structure shown in formula (2), The dotted line indicates the position connected to the metal Ir; 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, or substituted or unsubstituted C3-C20 heterocycloalkyl; Or Lb is one of the following structural compounds: wherein the heteroalkyl group and heterocycloalkyl group contain at least one heteroatom of O, N or S; wherein the substitution is substituted by an amino group, a cyano group or an isonitrile group substituted by deuterium, F, Cl, Br, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C3-C6 cycloalkyl group or a C1-C4 alkyl group; Wherein, Lc and La are the same or different, and the difference is that the parent core structures are different, or the parent core structures are the same but the substituents are different, or the parent core structures are the same but the substituents are in different positions; When the core structures are different, Lc is the structure shown in formula (4), The dotted line indicates the position connected to the metal Ir; Among them, R 10 -R 17 independently selected from hydrogen, deuterium, halogen, cyano, hydroxy, amino, 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, or substituted or unsubstituted C2-C17 heteroaryl; Among them, R 14 -R 17 At least two of them are not hydrogen; Among them, R 10 -R 13 At least one set of two adjacent groups forms an aromatic ring as shown in the following formula (5); In formula (5) The dotted line indicates the position of connection with the pyridine ring; Among them, R 18 -R 21 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, or substituted or unsubstituted C2-C17 heteroaryl; wherein the heteroalkyl and heteroaryl groups contain at least one heteroatom of O, N or S; wherein the substitution is amino, nitrile or isonitrile substituted with deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl, wherein the substitution is from a single substitution to the maximum number of substitutions, Or Lc is one of the following structural compounds:

2. The organometallic iridium compound according to claim 1, wherein in formula (3), R6 is a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C3-C10 cycloalkyl group.

3. The organometallic iridium compound according to claim 2, wherein in formula (3), R6 is a substituted or unsubstituted methyl group, a substituted or unsubstituted isopropyl group, or a substituted or unsubstituted cyclopentyl group; and the substitution is by deuterium, F, Cl, or Br.

4. The organometallic iridium compound according to claim 3, wherein in formula (3), R7 is hydrogen, deuterium or halogen. The organometallic iridium compound according to claim 1 , wherein at least one of R 8 and R 9 is not hydrogen. The organometallic iridium compound according to claim 5 , wherein R 8 and R 9 are both not hydrogen.

7. The organometallic iridium compound according to claim 6, wherein at least one of R8 and R9 is a substituted or unsubstituted C1-C6 alkyl group or a substituted or unsubstituted C3-C10 cycloalkyl group.

8. The organometallic iridium compound according to claim 1, wherein in formula (3), R2 and / or R5 are not hydrogen.

9. The organometallic iridium compound according to claim 8, wherein in formula (3), R2 is a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C3-C10 cycloalkyl group, and R1, R3-R5 are independently selected from hydrogen.

10. The organometallic iridium compound according to claim 1, wherein Lc is different from La.

11. The organometallic iridium compound according to claim 1, wherein La is one of the following structural formulas, 12. The organometallic iridium compound according to claim 1, wherein Lb is one of the following structural formulas, 13. The organometallic iridium compound according to claim 1, wherein Lc is one of the following structural formulas, 14. Use of the organometallic iridium compound according to any one of claims 1 to 13 in an organic electroluminescent device.

15. The use according to claim 14, wherein the organometallic iridium compound according to any one of claims 1 to 13 is used as a red light-emitting dopant material in a light-emitting layer of an organic electroluminescent device.

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