A metal iridium complex and an organic electroluminescent device

Abstract

This application relates to a metal iridium complex and an organic electroluminescent device. The metal iridium complex has a general formula of Ir(La)(Lb)(Lc), and its structure is shown in Formula (1). The metal iridium complex provided by this application has the advantages of low evaporation temperature, high photo- and electrochemical stability, narrow full width at half maximum, high color saturation, high luminous efficiency, long device life, etc. It can be used in organic light-emitting devices, especially as a red-emitting phosphorescent material, and has the potential to be applied in the AMOLED industry.

Description

Technical Field

[0001] The present application relates to the technical field of organic electroluminescence, in particular to organic light-emitting materials, and particularly to a metal iridium complex and an organic electroluminescent device using the metal iridium complex. Background Art

[0002] Currently, organic electroluminescent devices (OLEDs), as a new generation of display technology, have received increasing attention in both display and lighting technologies and have very broad application prospects. However, compared with the requirements of market applications, the performance of OLED devices, such as luminous efficiency, driving voltage, service life, etc., still needs to be further enhanced and improved.

[0003] Generally, the basic structure of an OLED device is that various organic functional material thin films are sandwiched between metal iridium electrodes, just like a sandwich structure. Under the drive of current, holes and electrons are respectively injected from the anode and cathode. After moving a certain distance, the holes and electrons recombine in the light-emitting layer and are released in the form of light or heat, thereby generating the light emission of the OLED.

[0004] However, organic functional materials are the core components of organic electroluminescent devices. The thermal stability, photochemical stability, electrochemical stability, quantum yield, film-forming stability, crystallinity, color saturation, etc. of the materials are the main factors affecting the performance of the devices.

[0005] Generally, organic functional materials include fluorescent materials and phosphorescent materials. Fluorescent materials are usually organic small molecule materials and generally can only utilize 25% singlet emission, so the luminous efficiency is relatively low. Due to the spin-orbit coupling effect caused by the heavy atom effect, phosphorescent materials can utilize the energy of 75% triplet excitons in addition to 25% singlet, so the luminous efficiency can be greatly improved. However, compared with fluorescent materials, phosphorescent materials started relatively late, and the thermal stability, lifespan, color saturation, etc. of the materials still need to be improved, which is a challenging topic. Various organometallic iridium compounds have been developed as such phosphorescent materials. For example, the patent literature CN1589307A discloses a metal iridium complex with a compound in which quinoline, isoquinoline are linked to a benzene ring as a ligand Especially iridium complexes can provide light emission in the range of 500 - 700 nm, and it is pointed out that the emission color of the compound can be adjusted by selecting electron-donating or electron-withdrawing groups at specific positions; the patent literature CN102627671B discloses an iridium compound in which isoquinoline and phenyl are bridged by an atom which can improve the oxidation stability and obtain high thermal stability, and is helpful for improving the device lifespan. The patent literature CN104885248B discloses an iridium complex with a ligand of benzisoquinoline-linked phenyl The applicant points out that by adjusting the combination and composition of the light-emitting layer, higher device efficiency and lifespan can be provided; the invention patent document US20170012223A1 discloses an iridium complex in which isoquinoline is bridged with a benzene ring substituted with an alkyl group through a dimethyl bridge However, the light emission of this compound is orange light, and the light color of the emission does not meet the application requirements. The invention patent document US20220306666A1 reports an iridium complex of benzoisoquinoline bridged with a benzene ring This type of compound has a narrow full-width at half-maximum, good light-emitting efficiency, but the light emission is orange-yellow light, the light color of the emission does not meet the application requirements, and at the same time, the device lifespan also needs to be improved. The invention patents CN115260243A and CN114437134A disclose iridium complexes in which quinoline / isoquinoline is bridged with a naphthalene structure through an oxygen atom, and organic electroluminescent devices and compounds containing such complexes This type of compound has a narrow full-width at half-maximum, but the device efficiency and lifespan still need to be further improved to meet the growing market demand. Therefore, the applicant still hopes to further develop new materials that can improve the performance of organic electroluminescent devices Summary of the Invention

[0006] This application is completed to solve the above problems, and the purpose is to provide a high-performance organic electroluminescent device and a new material that can realize such an organic electroluminescent device

[0007] In order to achieve the foregoing purpose, the applicant has repeatedly conducted in-depth research, and as a result, it has been found that by using a metal iridium complex containing the structure represented by the following formula (1) as a ligand, a high-performance organic electroluminescent device can be obtained

[0008] One of the purposes of this application is to provide a metal iridium complex, which has the advantages of high photo and electrochemical stability, narrow full-width at half-maximum, high color saturation, high light-emitting efficiency, long device lifespan, etc., and can be used in organic electroluminescent devices. Especially as a red light-emitting dopant, it has the possibility of being applied to the OLED industry

[0009] A metal iridium complex having a general formula of Ir(La)(Lb)(Lc), and its structural formula is shown in formula (1)

[0010]

[0011] Wherein is ligand La

[0012] Wherein Z is independently selected from CR A R B ;

[0013] Wherein, X1-X9 are independently N or CR0, and adjacent substituents R0 can optionally be connected to form a ring;

[0014] Among them, at least two adjacent CR0s among X1-X5 can be connected to each other to form an aromatic ring with 6-30 carbon atoms or a heteroaromatic ring with 3-30 carbon atoms;

[0015] Wherein R0, R, R A , R B are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C3-C30 alkylgermyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 arylsilyl, substituted or unsubstituted C0-C20 alkylamino, cyano, isocyano, phosphino;

[0016] Wherein, the substitution of the said R0, R, R A , R B is substituted by deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, amino substituted by C1-C4 alkyl, C6-C10 aryl, C6-C10 aryl substituted by C1-C4 alkyl, cyano, isocyano, phosphino;

[0017] Wherein, the heteroatom in the said heteroalkyl, heterocycloalkyl, heteroaromatic ring or heteroaryl is at least one of S, O, Se, B, P, N, Si, Ge;

[0018] Wherein, both Lb and Lc are monoanionic bidentate ligands, or any two of La, Lb and Lc are connected to each other to form a multidentate ligand, or the three are connected through a group;

[0019] Wherein, the structural formula of Lb or / and Lc is as shown in ligand La shown.

[0020] As the iridium metal complex in some embodiments of the present application, wherein, ligand La has one of the following structural formulas of formula (2)-formula (19):

[0021]

[0022] wherein Y is selected from O, S, Se, CR A R B , SiR A R B , GeR A R B , NR A R B , BR A R B , PR A R B ;

[0023] Y1 - Y8 are independently N or CR0, or the adjacent substituents R0 of CR0 in Y1 - Y8 can optionally be connected to form a ring;

[0024] wherein, X1 - X9, R0, R, R A , R B , Z are as defined above.

[0025] As the iridium metal complex in some embodiments of the present application, wherein, Lb is the structure shown in formula (21):

[0026]

[0027] wherein, the dotted line position represents the position connected to the iridium metal Ir;

[0028] wherein, R a -R g are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1 - 10 main chain carbon atoms, substituted or unsubstituted cycloalkyl with 3 - 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 - 10 main chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3 - 20 ring carbon atoms or R a , R b , R c are connected pairwise to form an aliphatic ring structure, R e , R f , R g are connected pairwise to form an aliphatic ring structure; wherein, the substitution in the R a -R g is substituted by deuterium, F, Cl, Br, C1 - C4 alkyl, C1 - C4 alkoxy, C3 - C6 cycloalkyl, amino group substituted by C1 - C4 alkyl, cyano group, isocyano group, phosphino group.

[0029] R a , R b , R c , R e , R f, R g independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, or R a , R b , R c are connected pairwise to form an alicyclic structure, and R e , R f , R g are connected pairwise to form an alicyclic structure; R d is selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-10 main-chain carbon atoms, wherein the substitution in the R a -R g is substituted by deuterium, F, Cl, Br, C1-C4 alkyl, or C3-C6 cycloalkyl.

[0030] R a , R b , R c are respectively the same as R e , R f , R g .

[0031] As the iridium metal complex in some embodiments of the present application, wherein R is alkyl with 1-10 carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted C3-C30 alkylsilyl, or substituted or unsubstituted C3-C30 alkylgermyl.

[0032] As the iridium metal complex in some embodiments of the present application, wherein the ligand La has the following structural formula of formula (22):

[0033]

[0034] Among them, X1-X5, R0, R, and Z are the same as those defined above; R1-R4 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 arylsilyl, substituted or unsubstituted C0-C20 alkylamino, cyano, isocyano, phosphino, and adjacent substituents R1-R4 can optionally be connected to form a ring, and the substitution in R1-R4 is substituted by deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, amino substituted by C1-C4 alkyl, C6-C10 aryl, C6-C10 aryl substituted by C1-C4 alkyl, cyano, isocyano.

[0035] As the iridium metal complex in some embodiments of the present application, among them, the ligand La has one of the following structural formulas (23)-(24):

[0036]

[0037] Among them, X1-X3 are independently N or CR0, and two adjacent CR0 in X1-X3 can be connected to each other to form an aromatic ring with 6-30 carbon atoms or a heteroaromatic ring with 3-30 carbon atoms.

[0038] Among them, R0, R, and Z are the same as defined above; R1-R6 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-8 main-chain carbon atoms, substituted or unsubstituted cycloalkyl with 3-10 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1-8 main-chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3-10 ring carbon atoms, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, substituted or unsubstituted C3-C20 arylsilyl, substituted or unsubstituted C0-C10 alkylamino, cyano, isocyano, phosphino, or adjacent substituents R1-R4, R5-R6 can optionally be connected to form a ring, and the substitution in the above R1-R6 is substituted by deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, amino substituted by C1-C4 alkyl, C6-C10 aryl, C6-C10 aryl substituted by C1-C4 alkyl, cyano, isocyano.

[0039] In some embodiments of the iridium metal complex of the present application, in ligand La, X1-X3 are independently N or CR0; Z is independently selected from CR A R B ; R, R A 、R B 、R1-R6 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryloxy; two adjacent CR0 are connected to form an aromatic ring with 6-30 carbon atoms or a heteroaromatic ring with 3-30 carbon atoms, or R5-R6 are connected to form an aromatic ring with 6-30 carbon atoms or a heteroaromatic ring with 3-30 carbon atoms.

[0040] In some embodiments of the iridium metal complex of the present application, Lc and La have the same structure to form a (La)2Ir(Lb) structure.

[0041] As the iridium metal complex in some embodiments of the present application, La is independently selected from one of the following structural formulas or their corresponding partial or complete deuterated products or their corresponding partial or complete fluorinated products:

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051] As a metal iridium complex in some embodiments of the present application, where Lb is independently selected from one of the following structural formulas or their corresponding partial or complete deuterated or fluorinated compounds:

[0052]

[0053]

[0054] Another object of the present invention is to provide an electroluminescent device, which includes: a cathode, an anode, and an organic layer disposed between the cathode and the anode, and the organic layer contains the metal iridium complex.

[0055] Wherein the organic layer includes a light-emitting layer, and the metal iridium complex is used as a doping material for the light-emitting layer, preferably a red light-emitting doping material.

[0056] The materials of the present application have the advantages of high photo and electrochemical stability, narrow full width at half maximum, high color saturation, high luminous efficiency, and long device life. As a phosphorescent material, the materials of the present application can convert triplet excited states into light, so as to improve the luminous efficiency of organic electroluminescent devices and thus reduce energy consumption. Description of the Drawings

[0057] Figure 1 For the 1 HNMR spectrum of compound La016

[0058] Figure 2 For the 1 HNMR spectrum of compound Ir(La016)2(Lb007)

[0059] Figure 3 For the UV-PL spectrum of compound Ir(La016)2(Lb007) Detailed implementation mode

[0060] A metal iridium complex having the general formula Ir(La)(Lb)(Lc), and its structural formula is shown in Formula (1).

[0061]

[0062] wherein is ligand La;

[0063] wherein Z is independently selected from CR A R B ;

[0064] wherein X1-X9 are independently N or CR0, and adjacent substituents R0 can optionally be connected to form a ring;

[0065] wherein at least two adjacent CR0s among X1-X5 can be connected to each other to form an aromatic ring having 6-30 carbon atoms or a heteroaromatic ring having 3-30 carbon atoms;

[0066] wherein R0, R, R A 、R B are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-10 main chain carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1-10 main chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C3-C30 alkylgermyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl and fused-ring aryl, substituted or unsubstituted C3-C30 heteroaryl and fused-ring heteroaryl, substituted or unsubstituted C3-C30 arylsilyl, substituted or unsubstituted C0-C20 alkylamino, cyano, isocyano, phosphino;

[0067] wherein the substitution of the said R0, R, R A 、R B is substituted by deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, amino substituted by C1-C4 alkyl, C6-C10 aryl, C6-C10 aryl substituted by C1-C4 alkyl, cyano, isocyano, phosphino;

[0068] wherein the heteroatoms in the said heteroalkyl, heterocycloalkyl or heteroaryl are at least one of S, O, Se, P, B, N, Si, Ge;

[0069] Among them, both Lb and Lc are monoanionic bidentate ligands, or any two of La, Lb, and Lc are connected to each other pairwise to form a polydentate ligand, or the three are connected through a group;

[0070] Among them, the structural formula of Lb or / and Lc is like that of ligand La as shown.

[0071] In some embodiments of the present application, the metal iridium complex, wherein the ligand La has one of the following structural formulas of formula (2)-formula (19):

[0072]

[0073] Wherein Y is selected from O, S, Se, CR A R B , SiR A R B , GeR A R B , NR A R B , BR A R B , PR A R B ;

[0074] Y1 - Y8 are independently N or CR0, and adjacent substituents R0 can optionally be connected to form a ring;

[0075] Wherein, X1 - X9, R0, R, R A , R B , Z are as defined above;

[0076] In some embodiments of the present application, the metal iridium complex, wherein Lb has the structure shown in formula (21):

[0077]

[0078] Wherein, the dotted position indicates the position connected to the metal iridium Ir;

[0079] Wherein, R a - R g are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1 - 10 main chain carbon atoms, substituted or unsubstituted cycloalkyl with 3 - 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 - 10 main chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3 - 20 ring carbon atoms, or R a , R b , R c are connected pairwise to form an aliphatic ring structure, R e, R f , R g are connected pairwise to form an alicyclic structure; wherein, the R a -R g is substituted by deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, an amino group substituted by C1-C4 alkyl, cyano, isocyano, or phosphino.

[0080] In some embodiments of the present application, a metal iridium complex, wherein Lc and La have the same structure, forming a (La)2Ir(Lb) structure.

[0081] R a , R b , R c are respectively the same as R e , R f , R g .

[0082] R a , R b , R c , R e , R f , R g are independently selected from hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl with 1-10 main chain carbon atoms, a substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, or R a , R b , R c are connected pairwise to form an alicyclic structure, and R e , R f , R g are connected pairwise to form an alicyclic structure; R d is selected from hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl with 1-10 main chain carbon atoms, wherein the substitution in the R a -R g is substituted by deuterium, F, Cl, Br, C1-C4 alkyl, or C3-C6 cycloalkyl.

[0083] In some embodiments of the present application, a metal iridium complex, wherein R is hydrogen, a substituted or unsubstituted alkyl with 1-10 carbon atoms, a substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, a substituted or unsubstituted C3-C30 alkylsilyl, or a substituted or unsubstituted C3-C30 alkylgermyl.

[0084] In some embodiments of the present application, a metal iridium complex, wherein the ligand La has the following structural formula of formula (22):

[0085]

[0086] Among them, X1-X5, R0, R, and Z are the same as defined above; R1-R4 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted cycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1-10 main-chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3-20 ring carbon atoms, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 arylsilyl, substituted or unsubstituted C0-C20 alkylamino, cyano, isocyano, phosphino, and adjacent substituents R1-R4 can optionally be connected to form a ring.

[0087] In some embodiments of the present application, for the iridium metal complex, the ligand La has one of the following structural formulas (23)-(24):

[0088]

[0089] Among them, X1-X3 are independently N or CR0, and two adjacent CR0 in X1-X3 can be connected to each other to form an aromatic ring with 6-30 carbon atoms or a heteroaromatic ring with 3-30 carbon atoms.

[0090] Among them, R0, R, and Z are the same as defined above; R1-R6 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1-8 main-chain carbon atoms, substituted or unsubstituted cycloalkyl with 3-10 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1-8 main-chain carbon atoms, substituted or unsubstituted heterocycloalkyl with 3-10 ring carbon atoms, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, substituted or unsubstituted C3-C20 arylsilyl, substituted or unsubstituted C0-C10 alkylamino, cyano, isocyano, and adjacent substituents R1-R4, R5-R6 can optionally be connected to form a ring.

[0091] Hereinafter, examples of each group of the compound represented by formula (1) will be described.

[0092] It should be noted that in this specification, the "carbon number a to b of the X group, which may be substituted or unsubstituted" in this expression means the carbon number of the X group when it is unsubstituted, and does not include the carbon number of the substituent when the X group is substituted.

[0093] As the C1-C10 alkyl group, it is a linear or branched alkyl group. Specifically, it is 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. In some embodiments of the present application, it is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. In some embodiments of the present application, it is propyl, isopropyl, isobutyl, sec-butyl, tert-butyl.

[0094] As the C3-C20 cycloalkyl group, examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. In some embodiments of the present application, it is cyclopentyl, cyclohexyl.

[0095] As the C2-C10 alkenyl group, examples include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, 3-hexatrienyl, etc. In some embodiments of the present application, it is propenyl, allyl.

[0096] As the C1-C10 heteroalkyl group, it is a linear or branched alkyl group, cycloalkyl group, etc. containing atoms other than carbon and hydrogen. Examples include mercaptomethylmethyl, methoxymethyl, ethoxymethyl, tert-butoxymethyl, N,N-dimethylmethyl, epoxybutyl, epoxypropyl, epoxyhexyl, etc. In some embodiments of the present application, it is methoxymethyl, epoxypropyl.

[0097] Aryl includes monocyclic aryl, or fused-ring aryl or non-fused-ring aryl. Specific examples of aryl are phenyl, naphthyl, anthryl, phenanthryl, tetraphenyl, pyrenyl, chrysenyl, benzo[c]phenanthryl, benzo[g]chrysenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, fluoranthenyl, etc. In some embodiments of the present application, it is phenyl, naphthyl.

[0098] Heteroaryl includes monocyclic heteroaryl, or fused-ring heteroaryl or non-fused-ring heteroaryl. As specific examples of heteroaryl, pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, isoindolyl, imidazolyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, dibenzothiophenyl, azadibenzofuryl, azadibenzothiophenyl, diazadibenzofuryl, diazadibenzothiophenyl, quinolinyl, isoquinolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, oxadiazolyl, furazanyl, thienyl, benzothiophenyl, dihydroacridinyl, azacarbazolyl, diazacarbazolyl, quinazolinyl, etc. can be cited. In some embodiments of the present application, they are pyridyl, pyrimidinyl, triazinyl, dibenzofuryl, dibenzothiophenyl, azadibenzofuryl, azadibenzothiophenyl, diazadibenzofuryl, diazadibenzothiophenyl, carbazolyl, azacarbazolyl, diazacarbazolyl.

[0099] The adjacent substituents R0 can optionally be connected to form a ring, which can be an aromatic ring, a heteroaromatic ring, or an aliphatic ring. For example, two R0s on adjacent X1 and X2 are bonded to each other and together with the C atoms on the aryl or heteroaryl where X1 and X2 are located to form an aromatic ring, a heteroaromatic ring, or an aliphatic ring. Similarly, between X2 and X3, between X3 and X4, between X4 and X5, between X6 and X7, between X7 and X8, between X8 and X9 can be bonded to form an aromatic ring, a heteroaromatic ring, or an aliphatic ring. Similarly, the adjacent substituents R1 - R4, R5 - R6 can optionally be connected to form an aromatic ring, a heteroaromatic ring, or an aliphatic ring.

[0100] The following examples are only for facilitating the understanding of the technical invention and should not be regarded as specific limitations of the present application.

[0101] The raw materials, solvents, etc. involved in the synthesis of the compounds in the present application are all purchased from suppliers well-known to those skilled in the art such as Alfa, Acros, etc.

[0102] Synthesis of ligand La008

[0103]

[0104] Synthesis of compound La008 - 3

[0105] Compound La008-1 (50.00 g, 333.47 mmol), La008-2 (84.52 g, 333.47 mmol), tetrakis(triphenylphosphine)palladium (3.85 g, 3.33 mmol), potassium carbonate (92.17 g, 666.93 mmol), tetrahydrofuran (750 ml), and deionized water (250 ml) were added to a 2000 ml three-necked round-bottom flask. The flask was evacuated and purged with nitrogen three times. Under nitrogen protection, the mixture was stirred at 65 °C for 3 hours. Monitored by TLC (developing solvent: ethyl acetate: petroleum ether = 1:20), the raw material La008-2 was completely reacted.

[0106] Cooled to room temperature, the organic solvent was removed by concentration under reduced pressure. Ethyl acetate (800 ml) was added, and the mixture was washed with deionized water (3 × 300 ml). After standing for liquid separation, the organic phase was concentrated under reduced pressure at 65 °C and then subjected to silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate: petroleum ether = 1:30). After elution, it was concentrated under reduced pressure at 65 °C for 1 hour to obtain a white solid, which was compound La008-3 (63.70 g, purity: 99.67%, yield: 82.45%). Mass spectrum: 232.05 (M+H).

[0107] Synthesis of compound La008-4

[0108] Compound La008-3 (62.00 g, 267.61 mmol), potassium tert-butoxide (60.06 g, 535.22 mmol), and N,N-dimethylformamide (900 ml) were added to a 2000 ml three-necked round-bottom flask. The flask was evacuated and purged with nitrogen three times. Under nitrogen protection, the mixture was stirred at 120 °C for 6 hours. Monitored by TLC (developing solvent: ethyl acetate: petroleum ether = 1:10), the raw material La008-3 was completely reacted.

[0109] The N,N-dimethylformamide was directly removed by concentration. Ethyl acetate (600 ml) was added, and the mixture was washed with deionized water (3 × 300 ml). After liquid separation, the organic phase was concentrated and then subjected to silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate: petroleum ether = 1:25). After concentration, a white solid was obtained, which was compound La008-4 (37.74 g, purity: 99.86%, yield: 66.00%). Mass spectrum: 214.04 (M+H).

[0110] Synthesis of compound La008-7

[0111] Add the compound La008-5 (40.00 g, 179.32 mmol), La008-6 (36.16 g, 215.18 mmol), tetrakis(triphenylphosphine)palladium (2.07 g, 1.79 mmol), potassium carbonate (49.56 g, 358.63 mmol), tetrahydrofuran (600 ml), and deionized water (200 ml) into a 2000 ml three-necked round-bottom flask. Replace the air with vacuum and nitrogen for 3 times. Under nitrogen protection, stir at 70 °C in an oil bath for 1 hour. Monitor by TLC (the developing solvent is ethyl acetate: petroleum ether = 1:20), and the raw material La008-5 has completely reacted.

[0112] Cool to room temperature, concentrate under reduced pressure to remove the organic solvent, add ethyl acetate (500 ml), wash with deionized water (3 * 150 ml), let it stand for liquid separation. After concentrating the organic phase under reduced pressure at 65 °C, perform silica gel column chromatography (200 - 300 mesh silica gel, the eluent is ethyl acetate: petroleum ether = 1:30). After elution, concentrate under reduced pressure at 65 °C for 1 hour to obtain a light brown oily liquid, which is compound La008-7 (28.29 g, purity: 99.53%, yield: 85.62%). Mass spectrum: 185.28 (M+H).

[0113] Synthesis of compound La008-8

[0114] Add the compound La008-7 (27.00 g, 146.55 mmol), dichloromethane (350 ml), and triethylamine (29.65 g, 293.10 mmol) into a 1000 ml three-necked round-bottom flask. Replace the air with vacuum and nitrogen for 3 times. Under nitrogen protection, then cool the system to 0 °C, and use a constant pressure dropping funnel to dropwise add trifluoromethanesulfonic anhydride (53.74 g, 190.51 mmol). Finish the dropping in 30 minutes, and maintain this temperature and stir for 30 minutes. Monitor by TLC (the developing solvent is ethyl acetate: petroleum ether = 1:20), and the raw material La008-7 has completely reacted.

[0115] Add 100 ml of deionized water into the system, let it stand for liquid separation. After concentrating the organic phase under reduced pressure at 65 °C, perform silica gel column chromatography (200 - 300 mesh silica gel, the eluent is petroleum ether). After elution, concentrate under reduced pressure at 65 °C for 1 hour to obtain a light yellow oily liquid, which is compound La008-8 (41.72 g, purity: 99.32%, yield: 90.00%). Mass spectrum: 317.02 (M+H)

[0116] Synthesis of compound La008-10

[0117] Compound La008-8 (38.00 g, 120.14 mmol), La008-9 (36.61 g, 144.17 mmol), 1,1-bis(diphenylphosphino)ferrocene palladium dichloride (1.74 g, 2.40 mmol), potassium acetate (23.58 g, 240.28 mmol), and 1,4-dioxane (400 ml) were added to a 1000 ml three-necked round-bottom flask, and the system was evacuated and replaced with nitrogen three times. Under nitrogen protection, the system was heated to 80 °C and reacted for 4 hours. Monitored by TLC (the developing agent was ethyl acetate:petroleum ether = 1:20), the raw material La008-8 reacted completely.

[0118] 1,4-Dioxane was removed by concentration, ethyl acetate (500 ml) was added, washed with deionized water (3 * 200 ml), allowed to stand for liquid separation, the organic phase was concentrated under reduced pressure at 65 °C and then subjected to silica gel column chromatography (200-300 mesh silica gel, the eluent was ethyl acetate:petroleum ether = 1:30). After elution, it was concentrated under reduced pressure at 65 °C for 1 hour to obtain a white solid as compound La008-10 (26.74 g, purity: 98.55%, yield: 75.64%), MS: 295.22 (M+H)

[0119] Synthesis of compound La008-11

[0120] Compound La008-4 (18.00 g, 84.24 mmol), La008-10 (26.02 g, 88.46 mmol), bis(4-dimethylaminophenyl)di-tert-butylphosphine palladium dichloride (1.19 g, 1.68 mmol), potassium carbonate (23.28 g, 168.48 mol), toluene (270 ml), ethanol (90 ml), and deionized water (90 ml) were added to a 1000 ml three-necked flask, and the system was evacuated and replaced with nitrogen three times. Under nitrogen protection, it was heated to 65 °C and stirred for 5 hours. Monitored by TLC (the developing agent was ethyl acetate:petroleum ether = 1:15), the raw material La008-4 reacted completely.

[0121] Cooled to room temperature, the organic solvents were removed by concentration under reduced pressure, ethyl acetate (600 ml) was added, washed with deionized water (3 * 200 ml), separated, the organic phase was concentrated and then subjected to silica gel column chromatography (200-300 mesh silica gel, the eluent was ethyl acetate:petroleum ether = 1:25). After concentration, a white solid was obtained as compound La008-11 (24.24 g, purity: 99.45%, yield: 83.31%), MS: 346.16 (M+H).

[0122] Synthesis of compound La008

[0123] Compound La008-11 (20.00 g, 57.90 mmol) and methanesulfonic acid (200 ml) were added to a 500-ml three-necked flask, and the flask was evacuated and filled with nitrogen three times. Under nitrogen protection, the mixture was heated to 100 °C and stirred for 6 hours. Monitored by TLC (the developing solvent was ethyl acetate: petroleum ether = 1:15), the raw material La008-11 was completely reacted.

[0124] The reaction was cooled to 5 °C, and 200 ml of deionized water was added to quench the reaction. The precipitated solid was filtered by suction, and the filter cake was washed with deionized water (200 ml) to obtain a white solid. Crystallization was carried out using 15 times the volume of toluene and 5 times the volume of methanol. The precipitated solid was filtered by suction, and the filter cake was dried under vacuum at 90 °C for 5 hours to obtain a white solid, which was compound La008 (11.03 g, purity: 99.86%, yield: 55.14%). Mass spectrum: 346.16 (M+H).

[0125] Synthesis of compound Ir(La008)2(Lb005)

[0126]

[0127] Synthesis of compound Ir(La008)-1

[0128] Compound La008 (10.00 g, 29.00 mmol) and iridium(III) chloride trihydrate (3.40 g, 9.66 mmol) were added to a 500-ml three-necked round-bottom flask. Ethylene glycol monoethyl ether (130 ml) and deionized water (42 ml) were added, and the flask was evacuated and filled with nitrogen three times. Then, the mixture was heated to 110 °C and stirred under reflux for 24 hours.

[0129] After cooling to room temperature, methanol (150 ml) was added, and the mixture was slurried at room temperature for 1 hour. The mixture was filtered by suction, and the filter cake was washed with methanol (50 ml). The solid was dried under vacuum at 80 °C to obtain compound Ir(La008)-1 (6.86 g, yield: 77.51%). The obtained compound was used directly in the next step without purification.

[0130] Synthesis of compound Ir(La008)2(Lb005)

[0131] Compound Ir(La008)-1 (6.60 g, 3.60 mmol), Lb005 (3.82 g, 18.00 mmol), sodium carbonate (3.81 g, 36.00 mmol), and ethylene glycol monoethyl ether (66 ml) were added to a 250-ml single-necked round-bottom flask. The flask was evacuated and filled with nitrogen three times, and the mixture was stirred at 60 °C for 24 hours. Monitored by TLC (the developing solvent was methanol: dichloromethane = 1:100), Ir(La008)-1 was completely reacted.

[0132] After cooling to room temperature, methanol (100 ml) was added and the mixture was slurried at room temperature for 1.5 hours. It was then filtered by suction. The filter cake was dissolved in dichloromethane (100 ml), and 300 - 400 mesh silica gel (50 g) was added. The filtrate was washed with deionized water (3 * 50 ml), and concentrated under reduced pressure at 60 °C to obtain a red solid. Recrystallization from toluene and methanol twice gave a red solid, which was compound Ir(La008)2(Lb005) (3.44 g, purity: 99.83%, yield: 43.77%). After sublimation purification of 3.44 g of the crude Ir(La008)2(Lb005), sublimation-pure Ir(La008)2(Lb005) was obtained (2.48 g, purity: 99.80%, yield: 72.10%). Mass spectrum: 1093.44 (M + H).

[0133] 1 H NMR (400 MHz, CDCl3) δ 8.40 (dd, J = 6.0, 3.4 Hz, 2H), 8.29 (d, J = 2.2 Hz, 2H), 8.24 - 8.19 (m, 2H), 8.18 - 8.14 (m, 3H), 8.13 (s, 1H), 7.95 (m, 2H), 7.89 - 7.83 (m, 2H), 7.55 - 7.49 (m, 4H), 7.46 (m, 2H), 7.33 (m, 2H), 7.27 (d, J = 9.5 Hz, 2H), 4.79 (s, 1H), 2.71 (m, 2H), 1.67 - 1.54 (m, 16H), 1.42 - 1.28 (m, 4H), 0.95 - 0.83 (m, 12H).

[0134] Synthesis of ligand La013

[0135]

[0136] Synthesis of compound La013-2

[0137] Referring to the synthesis and purification method of compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La013-2 (65.04 g, purity: 99.68%, yield: 83.22%). Mass spectrum: 310.08 (M + H)

[0138] Synthesis of compound La013-3

[0139] Referring to the synthesis and purification method of compound La008-4, only the corresponding raw materials need to be changed to obtain the target compound La013-3 (38.59 g, purity: 99.74%, yield: 65.42%). Mass spectrum: 292.04 (M + H)

[0140] Synthesis of compound La013-4

[0141] The compound La013-3 (36.00 g, 123.05 mmol), isobutylboronic acid (25.09 g, 246.10 mmol), tris(dibenzylideneacetone)dipalladium(0) (2.25 g, 2.46 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (2.09 g, 4.92 mmol), potassium phosphate (52.24 g, 246.10 mmol), and toluene (550 ml) were added to a 1000 ml three-necked round-bottom flask. The flask was evacuated and purged with nitrogen three times. Under nitrogen protection, the mixture was stirred at 110 °C for 2 hours. Monitored by TLC (eluent: ethyl acetate:petroleum ether = 1:10), the raw material La013-3 was completely reacted.

[0142] The reaction mixture was cooled to room temperature, ethyl acetate (200 ml) was added, and the mixture was washed with deionized water (3 × 300 ml). After liquid separation, the organic phase was concentrated and then subjected to silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate:petroleum ether = 1:20). After concentration, a white sugar-like solid, compound La013-4 (24.92 g, purity: 99.83%, yield: 75.06%), was obtained. Mass spectrum: 270.12 (M+H).

[0143] Synthesis of compound La013-5

[0144] Referring to the synthesis and purification method of compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La013-5 (35.07 g, purity: 99.74%, yield: 85.06%). Mass spectrum: 402.22 (M+H)

[0145] Synthesis of compound La013

[0146] Referring to the synthesis and purification method of compound La008, only the corresponding raw materials need to be changed to obtain the target compound La013 (25.12 g, purity: 99.75%, yield: 64.33%). Mass spectrum: 402.22 (M+H)

[0147] Synthesis of compound Ir(La013)2(Lb005)

[0148]

[0149] Synthesis of compound Ir(La013)-1

[0150] Referring to the synthesis and purification method of compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La013)-1 (10.65 g, yield: 76.21%). It was used directly in the next step without purification.

[0151] Synthesis of Compound Ir(La013)2(Lb005)

[0152] Referring to the synthesis and purification method of compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La013)2(Lb005) (6.04 g, purity: 99.78%, yield: 47.77%). After sublimation purification of 6.04 g of the crude product of Ir(La013)2(Lb005), sublimation-pure Ir(La013)2(Lb005) (3.95 g, purity: 99.75%, yield: 61.59%) was obtained. Mass spectrum: 1205.52 (M+H).

[0153] 1 H NMR (400 MHz, CDCl3) δ 8.56 (d, J = 2.2 Hz, 2H), 8.24 - 8.19 (m, 2H), 8.18 - 8.14 (m, 3H), 8.13 (s, 1H), 7.88 - 7.82 (m, 4H), 7.60 (m, 2H), 7.46 (m, 2H), 7.33 (m, 2H), 7.27 (d, J = 9.5 Hz, 2H), 7.20 (m, 2H), 4.79 (s, 1H), 2.71 (m, 2H), 2.62 (dt, J = 7.0, 0.9 Hz, 4H), 1.92 (m, 2H), 1.69 - 1.50 (m, 16H), 1.45 - 1.26 (m, 4H), 0.91 - 0.84 (m, 24H).

[0154] Synthesis of Ligand La016

[0155]

[0156] Synthesis of Compound La016-2

[0157] Referring to the synthesis and purification method of compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La016-2 (40.21 g, purity: 99.84%, yield: 85.26%). Mass spectrum: 250.05 (M+H)

[0158] Synthesis of Compound La016-3

[0159] Referring to the synthesis and purification method of compound La008-4, only the corresponding raw materials need to be changed to obtain the target compound La016-3 (23.00 g, purity: 99.71%, yield: 63.62%). Mass spectrum: 232.14 (M+H)

[0160] Synthesis of Compound La016-4

[0161] Referring to the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La016-4 (18.62 g, purity: 99.46%, yield: 84.51%). Mass spectrum: 364.14 (M+H)

[0162] Synthesis of compound La016

[0163] Referring to the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La016 (10.03 g, purity: 99.87%, yield: 56.03%). Mass spectrum: 364.14 (M+H).

[0164] 1 H NMR (400 MHz, CDCl3) δ 9.34 (s, 1H), 8.91 (d, J = 5.6 Hz, 1H), 8.43 (d, J = 8.3 Hz, 1H), 8.37 (d, J = 5.6 Hz, 1H), 8.31 (s, 1H), 8.14 (s, 1H), 8.05 - 8.03 (m, 1H), 7.90 - 7.88 (m, 1H), 7.62 - 7.57 (m, 1H), 7.54 - 7.47 (m, 2H), 7.42 - 7.37 (m, 1H), 1.93 (s, 6H).

[0165] Synthesis of compound Ir(La016)2(Lb005)

[0166]

[0167] Synthesis of compound Ir(La016)-1

[0168] Referring to the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La016)-1 (7.06 g, yield: 78.05%). It is directly used in the next step without purification.

[0169] Synthesis of compound Ir(La016)2(Lb005)

[0170] For the synthesis and purification method of the reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain a red solid, which is the compound Ir(La016)2(Lb005) (4.68 g, purity: 99.85%, yield: 48.06%). After sublimation purification of 4.68 g of the crude product of Ir(La016)2(Lb005), sublimation-pure Ir(La016)2(Lb005) (3.02 g, purity: 99.81%, yield: 64.53%) was obtained. Mass spectrum: 1129.40 (M+H).

[0171] 1 H NMR(400MHz,CDCl3)δ8.62(s,2H),8.34(dd,J=7.6,0.8Hz,2H),8.24-8.18(m,4H),8.16(d,J=2.2Hz,2H),7.88-7.82(m,2H),7.53(t,J=7.6Hz,2H),7.46(td,J=7.4,1.5Hz,2H),7.33(td,J=7.2,1.1Hz,2H),7.29-7.23(m,4H),4.79(s,1H),2.71(m,2H),1.67-1.55(m,16H),1.42-1.30(m,4H),0.90-0.86(m,12H).

[0172] Synthesis of the compound Ir(La016)2(Lb007)

[0173]

[0174] Synthesis of the compound Ir(La016)2(Lb007)

[0175] For the synthesis and purification method of the reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain a red solid, which is the compound Ir(La016)2(Lb007) (5.36 g, purity: 99.88%, yield: 49.06%). After sublimation purification of 5.36 g of the crude product of Ir(La016)2(Lb007), sublimation-pure Ir(La016)2(Lb007) (3.48 g, purity: 99.85%, yield: 64.93%) was obtained. Mass spectrum: 1157.42 (M+H).

[0176] 11H NMR (400 MHz, CDCl3) δ 8.44 (s, 2H), 8.41 (d, J = 8.3 Hz, 2H), 8.17 (d, J = 6.5 Hz, 2H), 7.95 (d, J = 6.6 Hz, 2H), 7.65 - 7.59 (m, 6H), 7.45 - 7.40 (m, 2H), 7.10 - 7.06 (m, 2H), 6.48 - 6.45 (m, 4H), 5.32 (s, 1H), 2.20 (s, 6H), 1.88 (s, 6H), 1.38 - 1.27 (m, 4H), 1.06 - 1.01 (m, 2H), 0.98 - 0.92 (m, 2H), 0.71 (s, 6H), 0.31 (t, J = 7.4 Hz, 6H), 0.16 (t, J = 7.3 Hz, 6H).

[0177] Synthesis of Ligand La018

[0178]

[0179] Synthesis of Compound La018-3

[0180] Add compound La018-2 (41.02 g, 499.37 mmol) and tetrahydrofuran (410 ml) into a 2000 ml three-necked round-bottom flask. Replace the air with vacuum and nitrogen for 3 times. Under the protection of nitrogen, cool the system to -50 °C. After the internal temperature drops to the specified temperature, add n-butyllithium solution (313 ml, 1.6 mol / L n-hexane solution) dropwise. The addition is completed in 1 hour, and stir at -50 °C for 1 hour. Dissolve La018-1 (30.00 g, 249.69 mmol) in 150 ml and add it dropwise to the above low-temperature system. The addition is completed in 30 minutes, and continue to stir for 30 minutes. Monitor by TLC (developing solvent: ethyl acetate: petroleum ether = 1:15), and the raw material La018-1 has completely reacted.

[0181] Add deionized water (100 ml) dropwise to quench the reaction, warm up to room temperature, concentrate under reduced pressure to remove the organic solvent, add ethyl acetate (900 ml), wash with deionized water (3 * 300 ml), let it stand for liquid separation. The organic phase is concentrated under reduced pressure at 65 °C and then subjected to silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate: petroleum ether = 1:25). After elution, concentrate under reduced pressure at 65 °C for 1 hour to obtain a light yellow liquid, which is compound La018-3 (43.14 g, purity: 99.76%, yield: 85.41%). Mass spectrum: 203.12 (M + H).

[0182] Synthesis of Compound La018-4

[0183] Compound La018-3 (40.00 g, 197.73 mmol) and dichloromethane (800 ml) were added to a 2000-ml three-necked round-bottom flask. Stirring was started at room temperature, and Dess-Martin periodinane (88.05 g, 207.61 mmol) was added in portions over 1 hour. After addition, the mixture was stirred at room temperature for 2 hours and monitored by TLC (eluent: ethyl acetate: petroleum ether = 1:10). The reaction of starting material La018-3 was complete.

[0184] It was washed with deionized water (3 × 400 ml), allowed to stand for liquid separation. The organic phase was concentrated under reduced pressure at 65 °C and then subjected to silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate: petroleum ether = 1:20). After elution, it was concentrated under reduced pressure at 65 °C for 1 hour to obtain a light yellow liquid, which was compound La018-4 (35.66 g, purity: 99.88%, yield: 90.05%). Mass spectrum: 201.02 (M+H).

[0185] Synthesis of compound La018-5

[0186] Compound La018-4 (32.00 g, 159.78 mmol) and acetonitrile (350 ml) were added to a 1000-ml three-necked round-bottom flask. The flask was evacuated and purged with nitrogen three times. Stirring was started at room temperature, and iodine monochloride (51.88 g, 319.55 mmol) was added dropwise over 15 minutes. After addition, the mixture was stirred at room temperature for 4 hours and monitored by TLC (eluent: ethyl acetate: petroleum ether = 1:15). The reaction of starting material La018-4 was complete.

[0187] The reaction was quenched by adding saturated aqueous sodium bisulfite solution (100 ml), and the mixture was stirred at room temperature for 30 minutes. The organic phase was concentrated. Ethyl acetate (600 ml) was added thereto, and it was washed with deionized water (3 × 250 ml), allowed to stand for liquid separation. The organic phase was concentrated under reduced pressure at 65 °C and then subjected to silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate: petroleum ether = 1:25). After elution, it was concentrated under reduced pressure at 65 °C for 1 hour to obtain a white liquid, which was compound La018-5 (36.51 g, purity: 99.80%, yield: 70.06%). Mass spectrum: 327.02 (M+H).

[0188] Synthesis of compound La018-6

[0189] Referring to the synthesis and purification method of compound La008-7, only the corresponding starting materials need to be changed to obtain compound La018-6 (26.51 g, purity: 99.00%, yield: 85.14%). Mass spectrum: 241.06 (M+H)

[0190] Synthesis of compound La018-7

[0191] Referring to the synthesis and purification method of reference compound La008-8, only the corresponding raw materials need to be changed to obtain compound La018-7 (38.09 g, purity: 99.52%, yield: 88.67%). Mass spectrum: 373.12 (M+H)

[0192] Synthesis of compound La018-8

[0193] Referring to the synthesis and purification method of reference compound La008-10, only the corresponding raw materials need to be changed to obtain compound La018-8 (25.33 g, purity: 98.75%, yield: 80.06%). Mass spectrum: 351.22 (M+H)

[0194] Synthesis of compound La018-9

[0195] Referring to the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed to obtain compound La018-9 (30.05 g, purity: 99.66%, yield: 84.11%). Mass spectrum: 420.20 (M+H)

[0196] Synthesis of compound La018

[0197] Referring to the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain compound La018 (21.03 g, purity: 99.81%, yield: 56.26%). Mass spectrum: 420.20 (M+H)

[0198] Synthesis of compound Ir(La018)2(Lb005)

[0199]

[0200] Synthesis of compound Ir(La018)-1

[0201] Referring to the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La018)-1 (14.65 g, yield: 78.78%). It is directly used in the next step without purification.

[0202] Synthesis of compound Ir(La018)2(Lb005)

[0203] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid as compound Ir(La018)2(Lb005) (8.95 g, purity: 99.89%, yield: 56.51%). After sublimation purification of 8.95 g of crude Ir(La018)2(Lb005), sublimation-pure Ir(La018)2(Lb005) (6.74 g, purity: 99.83%, yield: 75.31%) was obtained, and the mass spectrum was 1241.54 (M+H).

[0204] 1 H NMR(400MHz,CDCl3)δ8.53(s,2H),8.34(dd,J=7.6,0.8Hz,2H),8.23-8.15(m,4H),7.82(dd,J=6.8,1.6Hz,2H),7.53(t,J=7.6Hz,2H),7.47(m,2H),7.37(td,J=7.6,1.3Hz,2H),7.29-7.23(m,4H),4.79(s,1H),2.71(m,2H),1.67-1.54(m,4H),1.51(s,12H),1.38(s,22H),0.90-0.85(m,12H).

[0205] Synthesis of ligand La029

[0206]

[0207] Synthesis of compound La029-2

[0208] Referring to the synthesis and purification method of reference compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La029-2 (35.12 g, purity: 99.62%, yield: 83.52%), and the mass spectrum was 257.06 (M+H)

[0209] Synthesis of compound La029-3

[0210] Referring to the synthesis and purification method of reference compound La008-4, only the corresponding raw materials need to be changed to obtain the target compound La029-3 (26.06 g, purity: 99.75%, yield: 67.16%), and the mass spectrum was 239.14 (M+H)

[0211] Synthesis of compound La029-5

[0212] For the synthesis and purification method of reference compound La008-10, only the corresponding raw materials need to be changed to obtain the target compound La029-5 (32.85 g, purity: 98.02%, yield: 76.45%). Mass spectrum: 285.12 (M+H)

[0213] Synthesis of compound La029-6

[0214] For the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La029-6 (30.25 g, purity: 99.53%, yield: 82.12%). Mass spectrum: 361.14 (M+H)

[0215] Synthesis of compound La029-7

[0216] For the synthesis and purification method of reference compound La008-8, only the corresponding raw materials need to be changed to obtain the target compound La029-7 (43.33 g, purity: 99.62%, yield: 89.56%). Mass spectrum: 493.06 (M+H)

[0217] Synthesis of compound La029-8

[0218] For the synthesis and purification method of reference compound La008-7, only the corresponding raw materials need to be changed to obtain the target compound La029-8 (31.23 g, purity: 99.68%, yield: 84.23%). Mass spectrum: 385.12 (M+H)

[0219] Synthesis of compound La029

[0220] For the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La029 (16.02 g, purity: 99.89%, yield: 54.33%). Mass spectrum: 385.12 (M+H)

[0221] Synthesis of compound Ir(La029)2(Lb005)

[0222]

[0223] Synthesis of compound Ir(La029)-1

[0224] For the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La029)-1 (13.63 g, yield: 72.11%). It is directly used in the next step without purification.

[0225] Synthesis of Compound Ir(La029)2(Lb005)

[0226] Referring to the synthesis and purification method of compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La029)2(Lb005) (9.85 g, purity: 99.88%, yield: 43.56%). After sublimation purification of 9.85 g of the crude product of Ir(La029)2(Lb005), sublimation-pure Ir(La029)2(Lb005) (7.41 g, purity: 99.84%, yield: 75.23%) was obtained. Mass spectrum: 1171.22 (M+H).

[0227] 1 H NMR (400 MHz, CDCl3) δ 8.52 - 8.47 (m, 4H), 8.36 (dd, J = 7.4, 1.5 Hz, 2H), 8.20 (d, J = 9.5 Hz, 2H), 7.84 (dd, J = 7.7, 1.5 Hz, 2H), 7.71 (dd, J = 6.8, 1.3 Hz, 2H), 7.52 (t, J = 6.6 Hz, 2H), 7.46 - 7.33 (m, 4H), 7.27 (d, J = 9.5 Hz, 2H), 4.82 (s, 1H), 2.73 - 2.68 (m, 2H), 2.34 (s, 6H), 1.67 - 1.54 (m, 16H), 1.42 - 1.30 (m, 4H), 0.92 - 0.87 (m, 12H).

[0228] Synthesis of Ligand La048

[0229]

[0230] Synthesis of Compound La048-2

[0231] Referring to the synthesis and purification method of compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La048-2 (25.45 g, purity: 99.51%, yield: 84.76%). Mass spectrum: 346.16 (M+H)

[0232] Synthesis of Compound La048

[0233] Referring to the synthesis and purification method of compound La008, only the corresponding raw materials need to be changed to obtain the target compound La048 (14.65 g, purity: 99.89%, yield: 56.12%). Mass spectrum: 346.16 (M+H)

[0234] Synthesis of Compound Ir(La048)2(Lb007)

[0235]

[0236] Synthesis of Compound Ir(La048)-1

[0237] Referring to the synthesis and purification method of compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La048)-1 (15.22 g, yield: 75.21%). It is directly used in the next step without purification.

[0238] Synthesis of Compound Ir(La048)2(Lb007)

[0239] Referring to the synthesis and purification method of compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La048)2(Lb007) (8.95 g, purity: 99.80%, yield: 45.45%). After sublimation purification of 8.95 g of the crude product of Ir(La048)2(Lb007), sublimation-pure Ir(La048)2(Lb007) (6.62 g, purity: 99.75%, yield: 73.97%) is obtained. Mass spectrum: 1121.42 (M+H).

[0240] 1 H NMR(400MHz,CDCl3)δ8.63(dd,J=7.3,1.3Hz,2H),8.28(dd,J=7.7,1.4Hz,2H),8.24-8.19(m,2H),8.18-8.10(m,4H),7.88-7.82(m,2H),7.53(dd,J=7.5,1.1Hz,2H),7.50-7.39(m,6H),7.37-7.29(m,4H),4.82(s,1H),1.68-1.57(m,16H),1.43-1.33(m,4H),1.05(d,J=15.2Hz,6H),0.88-0.82(m,12H).

[0241] Synthesis of Ligand La055

[0242]

[0243] Synthesis of Compound La055-3

[0244] Referring to the synthesis and purification method of compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La055-3 (38.42 g, purity: 99.42%, yield: 78.08%). Mass spectrum: 280.05 (M+H)

[0245] Synthesis of Compound La055-4

[0246] Compound La055-3 (35.00 g, 125.10 mmol), (methoxymethyl)triphenylphosphonium chloride (85.77 g, 250.20 mmol), potassium tert-butoxide (28.07 g, 250.20 mmol), and tetrahydrofuran (530 ml) were added to a 2000-ml three-necked round-bottom flask. The flask was evacuated and purged with nitrogen three times. Under nitrogen protection, the mixture was stirred at room temperature for 4 hours. Monitored by TLC (developing solvent: ethyl acetate: petroleum ether = 1:10), the raw material La055-3 was completely reacted.

[0247] 200 ml of deionized water was slowly added to the system to quench the reaction. The organic solvent was removed by concentration under reduced pressure. Ethyl acetate (800 ml) was added, and the mixture was washed with deionized water (3 * 300 ml). After standing for liquid separation, the organic phase was concentrated under reduced pressure at 65 °C and then subjected to silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate: petroleum ether = 1:20). After elution, it was concentrated under reduced pressure at 65 °C for 1 hour to obtain a white solid, which was Compound La055-4 (33.89 g, purity: 99.75%, yield: 88.00%). Mass spectrum: 308.06 (M+H).

[0248] Synthesis of Compound La055-5

[0249] Referring to the synthesis and purification method of Compound La008, only the corresponding raw materials need to be changed to obtain the target compound La055-5 (22.32 g, purity: 99.62%, yield: 83.03%). Mass spectrum: 276.05 (M+H)

[0250] Synthesis of Compound La055-6

[0251] Referring to the synthesis and purification method of Compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La055-6 (24.89 g, purity: 99.73%, yield: 84.21%). Mass spectrum: 408.16 (M+H)

[0252] Synthesis of Compound La055

[0253] Referring to the synthesis and purification method of Compound La008, only the corresponding raw materials need to be changed to obtain the target compound La055 (11.44 g, purity: 99.81%, yield: 52.01%). Mass spectrum: 408.16 (M+H)

[0254] Synthesis of Compound Ir(La055)2(Lb005)

[0255]

[0256] Synthesis of Compound Ir(La055)-1

[0257] Referring to the synthesis and purification method of Compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain Compound Ir(La055)-1 (17.77 g, yield: 74.04%). It is directly used in the next step without purification.

[0258] Synthesis of Compound Ir(La055)2(Lb005)

[0259] Referring to the synthesis and purification method of Compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid Compound Ir(La055)2(Lb005) (8.06 g, purity: 99.84%, yield: 46.56%). After sublimation purification of 8.06 g of the crude product of Ir(La055)2(Lb005), sublimation-pure Ir(La055)2(Lb005) (5.55 g, purity: 99.78%, yield: 68.86%) is obtained. Mass spectrum: 1217.46 (M+H).

[0260] 1 H NMR (400 MHz, CDCl3) δ8.44 (d, J = 9.0 Hz, 2H), 8.24 - 8.19 (m, 4H), 8.16 (d, J = 2.3 Hz, 2H), 7.88 - 7.82 (m, 2H), 7.46 - 7.33 (m, 4H), 7.25 (d, J = 9.1 Hz, 2H), 7.06 (m 2H), 4.72 (s, 1H), 2.73 - 2.66 (m, 6H), 1.93 (dt, J = 13.7, 6.8 Hz, 2H), 1.67 - 1.55 (m, 16H), 1.36 - 1.34 (m, 4H), 0.92 - 0.84 (m, 24H).

[0261] Synthesis of Ligand La070

[0262]

[0263] Synthesis of Compound La070-3

[0264] Referring to the synthesis and purification method of Compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La070-3 (32.22 g, purity: 99.53%, yield: 80.65%). Mass spectrum: 304.03 (M+H)

[0265] Synthesis of Compound La070-4

[0266] The compound La070-3 (30.00 g, 98.76 mmol), cesium carbonate (64.35 g, 197.51 mmol), and N,N-dimethylformamide (450 ml) were added to a 1000 ml three-necked round-bottom flask. The flask was evacuated and purged with nitrogen three times. Under nitrogen protection, the mixture was heated to 100 °C and stirred for 2 hours. Monitored by TLC (the developing solvent was ethyl acetate: petroleum ether = 1:15), the raw material La070-3 reacted completely.

[0267] The organic solvent was removed by concentration under reduced pressure. Ethyl acetate (600 ml) was added, and the mixture was washed with deionized water (3 * 200 ml). After standing for liquid separation, the organic phase was concentrated under reduced pressure at 65 °C and then subjected to silica gel column chromatography (200 - 300 mesh silica gel, the eluent was ethyl acetate: petroleum ether = 1:30). After elution, it was concentrated under reduced pressure at 65 °C for 1 hour to obtain a white solid, which was compound La070-4 (21.19 g, purity: 99.85%, yield: 75.60%). Mass spectrum: 284.02 (M+H).

[0268] Synthesis of compound La070-5

[0269] Referring to the synthesis and purification method of compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La070-5 (18.06 g, purity: 99.86%, yield: 83.54%). Mass spectrum: 416.12 (M+H)

[0270] Synthesis of compound La070

[0271] Referring to the synthesis and purification method of compound La008, only the corresponding raw materials need to be changed to obtain the target compound La070 (10.02 g, purity: 99.78%, yield: 54.33%). Mass spectrum: 416.12 (M+H)

[0272] Synthesis of compound Ir(La070)2(Lb005)

[0273]

[0274] Synthesis of compound Ir(La070)-1

[0275] Referring to the synthesis and purification method of compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La070)-1 (14.33 g, yield: 72.11%). It was used directly in the next step without purification.

[0276] Synthesis of compound Ir(La070)2(Lb005)

[0277] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain a red solid, which is compound Ir(La070)2(Lb005) (7.62 g, purity: 99.80%, yield: 47.62%). After sublimation purification of 7.62 g of the crude product of Ir(La070)2(Lb005), sublimation-pure Ir(La070)2(Lb005) (5.35 g, purity: 99.78%, yield: 70.21%) was obtained, and the mass spectrum was 1233.40 (M+H).

[0278] 1 H NMR(400MHz,CDCl3)δ8.37(d,J=9.1Hz,2H),8.28-8.14(m,8H),7.88-7.82(m,2H),7.46-7.42(m,2H),7.38-7.30(m,4H),7.28-7.22(m,4H),4.72(s,1H),2.71-2.69(m,2H),2.60(d,J=0.7Hz,6H),1.68-1.54(m,16H),1.43-1.28(m,4H),0.88-0086(m,12H).

[0279] Synthesis of compound Ir(La070)2(Lb031)

[0280]

[0281] Synthesis of compound Ir(La070)2(Lb031)

[0282] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain a red solid, which is compound Ir(La070)2(Lb031) (8.33 g, purity: 99.82%, yield: 48.52%). After sublimation purification of 8.33 g of the crude product of Ir(La070)2(Lb031), sublimation-pure Ir(La070)2(Lb031) (6.14 g, purity: 99.78%, yield: 73.71%) was obtained, and the mass spectrum was 1257.40 (M+H).

[0283] 11H NMR (400 MHz, CDCl3) δ 8.37 (d, J = 9.2 Hz, 2H), 8.28 - 8.14 (m, 8H), 7.88 - 7.82 (m, 2H), 7.46 (td, J = 7.4, 1.5 Hz, 2H), 7.38 - 7.30 (m, 4H), 7.28 - 7.22 (m, 4H), 4.51 (s, 1H), 2.60 (d, J = 0.7 Hz, 6H), 2.50 (m, 4H), 1.88 - 1.76 (m, 2H), 1.63 - 1.55 (m, 13H), 1.55 - 1.50 (m, 6H), 1.49 (m, 1H), 1.46 - 1.37 (m, 4H), 1.35 - 1.21 (m, 4H).

[0284] Synthesis of Ligand La079

[0285]

[0286] Synthesis of Compound La079 - 2

[0287] Referring to the synthesis and purification method of reference compound La008 - 3, only the corresponding raw materials need to be changed to obtain the target compound La079 - 2 (40.56 g, purity: 99.64%, yield: 85.48%), mass spectrometry: 290.20 (M + H)

[0288] Synthesis of Compound La079 - 3

[0289] Referring to the synthesis and purification method of reference compound La070 - 4, only the corresponding raw materials need to be changed to obtain the target compound La079 - 3 (35.41 g, purity: 99.83%, yield: 86.56%), mass spectrometry: 270.02 (M + H)

[0290] Synthesis of Compound La079 - 5

[0291] Add compound La079 - 4 (35.00 g, 128.90 mmol) and tetrahydrofuran (350 ml) into a 1000 ml three - necked round - bottom flask, replace with vacuum nitrogen 3 times. Under nitrogen protection, cool the system to - 78 °C. After the internal temperature drops to the specified temperature, add n - butyllithium solution (88.70 ml, 1.6 mol / L n - hexane solution, 141.79 mmol) dropwise. The addition is completed in 40 minutes, and stir at - 70 °C for 1 hour. Use a constant - pressure dropping funnel to add trimethylchlorosilane (28.00 g, 257.80 mmol) dropwise to the above low - temperature system. The addition is completed in 15 minutes, and continue to stir for 1 hour. Monitor by TLC (developing agent: ethyl acetate: petroleum ether = 1:20), and the raw material La079 - 4 has completely reacted.

[0292] Quench the reaction by dropping deionized water (100 ml) into the system, raise the temperature to room temperature, concentrate under reduced pressure to remove the organic solvent, add ethyl acetate (600 ml), wash with deionized water (3×200 ml), let it stand for liquid separation. After concentrating the organic phase under reduced pressure at 65 °C, perform silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate:p petroleum ether = 1:35). After elution, concentrate under reduced pressure at 65 °C for 1 hour to obtain a light yellow liquid, which is compound La079 - 5 (23.23 g, purity: 99.87%, yield: 68.06%). Mass spectrum: 265.06 (M + H).

[0293] Synthesis of compound La079 - 6

[0294] Add compound La079 - 5 (23.00 g, 86.85 mmol) and dichloromethane (300 ml) to a 500 ml three - necked round - bottom flask, replace the air with vacuum nitrogen for 3 times. Under nitrogen protection, cool the system to - 20 °C. After the internal temperature drops to the specified temperature, dropwise add boron tribromide (26.11 g, 104.22 mmol), complete the addition in 30 minutes, maintain the temperature at - 20 °C and stir for 1 hour. Monitor by TLC (developing agent: ethyl acetate:p petroleum ether = 1:10), and the raw material La079 - 5 reacts completely.

[0295] Then quench the reaction by dropping deionized water (100 ml) into the system, cool to room temperature, let it stand for liquid separation, wash with deionized water (3×150 ml), let it stand for liquid separation. After concentrating the organic phase under reduced pressure at 65 °C, perform silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate:p petroleum ether = 1:20). After elution, concentrate under reduced pressure at 65 °C for 1 hour to obtain a light yellow liquid, which is compound La079 - 6 (20.70 g, purity: 99.90%, yield: 95.02%). Mass spectrum: 251.06 (M + H).

[0296] Synthesis of compound La079 - 7

[0297] Refer to the synthesis and purification method of compound La008 - 10, just change the corresponding raw materials to obtain the target compound La079 - 7 (18.61 g, purity: 99.78%, yield: 77.06%). Mass spectrum: 343.18 (M + H)

[0298] Synthesis of compound La079 - 8

[0299] Refer to the synthesis and purification method of compound La008 - 11, just change the corresponding raw materials to obtain the target compound La079 - 8 (17.24 g, purity: 99.82%, yield: 82.45%). Mass spectrum: 450.12 (M + H)

[0300] Synthesis of Compound La079-9

[0301] Referring to the synthesis and purification methods of compound La008-8, only the corresponding raw materials need to be changed to obtain the target compound La079-9 (28.05 g, purity: 99.85%, yield: 92.22%). Mass spectrum: 582.08 (M+H)

[0302] Synthesis of Compound La079-10

[0303] Referring to the synthesis and purification methods of compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La079-10 (31.58 g, purity: 99.81%, yield: 79.69%). Mass spectrum: 474.16 (M+H)

[0304] Synthesis of Compound La079

[0305] Referring to the synthesis and purification methods of compound La008, only the corresponding raw materials need to be changed to obtain the target compound La079 (15.23 g, purity: 99.64%, yield: 55.87%). Mass spectrum: 474.16 (M+H)

[0306] Synthesis of Compound Ir(La079)2(Lb005)

[0307]

[0308] Synthesis of Compound Ir(La079)-1

[0309] Referring to the synthesis and purification methods of compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La070)-1 (18.96 g, yield: 74.19%). It is directly used in the next step without purification.

[0310] Synthesis of Compound Ir(La079)2(Lb005)

[0311] Referring to the synthesis and purification methods of compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La079)2(Lb005) (10.00 g, purity: 99.79%, yield: 46.52%). After sublimation purification of 10.00 g of the crude product of Ir(La079)2(Lb005), sublimation-pure Ir(La070)2(Lb005) (7.35 g, purity: 99.71%, yield: 73.50%) is obtained. Mass spectrum: 1349.44 (M+H).

[0312] 1 1H NMR (400 MHz, CDCl3) δ 8.37 (d, J = 9.2 Hz, 2H), 8.26 - 8.21 (m, 2H), 8.20 - 8.15 (m, 2H), 8.09 (s, 2H), 7.94 - 7.89 (m, 2H), 7.88 - 7.83 (m, 2H), 7.54 - 7.47 (m, 4H), 7.38 - 7.30 (m, 4H), 7.25 (d, J = 9.2 Hz, 2H), 4.72 (s, 1H), 2.71 (m, 2H), 1.68 (s, 6H), 1.66 - 1.54 (m, 10H), 1.43 - 1.30 (m, 4H), 0.92 - 0.88 (m, 12H), 0.46 (s, 18H).

[0313] Synthesis of Ligand La090

[0314]

[0315] Synthesis of Compound La090 - 3

[0316] Referring to the synthesis and purification method of reference compound La008 - 3, only the corresponding raw materials need to be changed to obtain the target compound La090 - 3 (33.25 g, purity: 99.56%, yield: 82.11%), mass spectrum: 346.08 (M + H)

[0317] Synthesis of Compound La090 - 4

[0318] Referring to the synthesis and purification method of reference compound La070 - 4, only the corresponding raw materials need to be changed to obtain the target compound La090 - 4 (24.25 g, purity: 99.71%, yield: 74.32%), mass spectrum: 326.06 (M + H)

[0319] Synthesis of Compound La090 - 5

[0320] Referring to the synthesis and purification method of reference compound La008 - 11, only the corresponding raw materials need to be changed to obtain the target compound La090 - 5 (28.79 g, purity: 99.83%, yield: 85.41%), mass spectrum: 458.20 (M + H)

[0321] Synthesis of Compound La090

[0322] Referring to the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La090 (16.55 g, purity: 99.78%, yield: 52.11%), mass spectrum: 458.20 (M + H)

[0323] Synthesis of Compound Ir(La090)2(Lb005)

[0324]

[0325] Synthesis of Compound Ir(La090)-1

[0326] Referring to the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La090)-1 (18.96 g, yield: 72.43%). It is directly used in the next step without purification.

[0327] Synthesis of Compound Ir(La090)2(Lb005)

[0328] Referring to the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La090)2(Lb005) (8.53 g, purity: 99.78%, yield: 42.45%). After sublimation purification of 8.53 g of the crude product of Ir(La090)2(Lb005), sublimation-pure Ir(La090)2(Lb005) (6.51 g, purity: 99.68%, yield: 76.31%) is obtained, and the mass spectrum is 1317.42 (M+H).

[0329] 1 H NMR(400MHz,CDCl3)δ8.45(d,J=2.5Hz,2H),8.24-8.20(m,2H),8.20-8.15(m,2H),8.02(d,J=2.1Hz,2H),7.93(dd,J=9.3,2.2Hz,2H),7.88-7.82(m,2H),7.46(m,2H),7.38-7.33(m,4H),7.33-7.26(m,2H),7.10(m,2H),4.82(s,1H),2.75-2.66(m,6H),1.90-1.88(m,2H),1.67-1.60(m,9H),1.60-1.54(m,1H),1.52(s,6H),1.43-1.28(m,4H),0.92-0.84(m,24H).

[0330] Synthesis of Ligand La095

[0331]

[0332] Synthesis of Compound La095-2

[0333] Referring to the synthesis and purification method of reference compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La095-2 (36.98 g, purity: 99.76%, yield: 86.11%). Mass spectrum: 290.01 (M+H)

[0334] Synthesis of compound La095-3

[0335] Referring to the synthesis and purification method of reference compound La070-4, only the corresponding raw materials need to be changed to obtain the target compound La095-3 (25.08 g, purity: 99.68%, yield: 74.32%). Mass spectrum: 270.02 (M+H)

[0336] Synthesis of compound La095-4

[0337] Referring to the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La095-4 (18.77 g, purity: 99.73%, yield: 82.51%). Mass spectrum: 458.20 (M+H)

[0338] Synthesis of compound La095

[0339] Referring to the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La095 (10.09 g, purity: 99.86%, yield: 54.99%). Mass spectrum: 458.20 (M+H)

[0340] Synthesis of compound Ir(La095)2(Lb005)

[0341]

[0342] Synthesis of compound Ir(La095)-1

[0343] Referring to the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La095)-1 (15.44 g, yield: 68.98%). It is directly used in the next step without purification.

[0344] Synthesis of compound Ir(La095)2(Lb005)

[0345] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain a red solid, which is compound Ir(La095)2(Lb005) (7.22 g, purity: 99.86%, yield: 45.55%). After sublimation purification of 7.22 g of crude Ir(La095)2(Lb005), sublimation-pure Ir(La095)2(Lb005) (5.67 g, purity: 99.68%, yield: 78.53%) was obtained. Mass spectrum: 1317.40 (M+H).

[0346] 1 H NMR(400MHz,CDCl3)δ8.53(d,J=2.4Hz,2H),8.26-8.21(m,2H),8.18(dd,J=7.3,1.5Hz,2H),7.96-7.89(m,4H),7.82(dd,J=6.8,1.6Hz,2H),7.54-7.50(m,2H),7.50-7.44(m,4H),7.40-7.32(m,4H),4.78(s,1H),2.71-2.68(m,2H),1.67-1.55(m,4H),1.51(s,6H),1.47(s,6H),1.38(s,22H),0.88-0.86(qm,12H).

[0347] Synthesis of compound Ir(La095)2(Lb043)

[0348]

[0349] Synthesis of compound Ir(La095)2(Lb043)

[0350] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain a red solid, which is compound Ir(La095)2(Lb043) (6.21 g, purity: 99.80%, yield: 41.12%). After sublimation purification of 6.21 g of crude Ir(La095)2(Lb043), sublimation-pure Ir(La095)2(Lb043) (4.22 g, purity: 99.71%, yield: 67.96%) was obtained. Mass spectrum: 1287.37 (M+H).

[0351] 11H NMR (400 MHz, CDCl3) δ 8.53 (d, J = 2.4 Hz, 2H), 8.24 (m, 2H), 8.18 (dd, J = 7.3, 1.5 Hz, 2H), 7.96 - 7.89 (m, 4H), 7.82 (dd, J = 6.8, 1.5 Hz, 2H), 7.55 - 7.44 (m, 6H), 7.40 - 7.32 (m, 4H), 4.64 (s, 1H), 2.79 - 2.76 (m, 1H), 1.51 (s, 6H), 1.47 (s, 6H), 1.38 (s, 18H), 1.07 (d, J = 6.1 Hz, 6H).

[0352] Synthesis of Ligand La103

[0353]

[0354] Synthesis of Compound La103 - 2

[0355] Referring to the synthesis and purification method of reference compound La008 - 3, only the corresponding raw materials need to be changed to obtain the target compound La103 - 2 (38.01 g, purity: 99.73%, yield: 82.77%). Mass spectrum: 274.04 (M + H)

[0356] Synthesis of Compound La103 - 3

[0357] Referring to the synthesis and purification method of reference compound La070 - 4, only the corresponding raw materials need to be changed to obtain the target compound La103 - 3 (31.02 g, purity: 99.81%, yield: 75.45%). Mass spectrum: 254.04 (M + H)

[0358] Synthesis of Compound La103 - 4

[0359] Referring to the synthesis and purification method of reference compound La008 - 11, only the corresponding raw materials need to be changed to obtain the target compound La103 - 4 (38.21 g, purity: 99.75%, yield: 79.91%). Mass spectrum: 386.15 (M + H)

[0360] Synthesis of Compound La103

[0361] Referring to the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La103 (16.77 g, purity: 99.81%, yield: 54.23%). Mass spectrum: 386.15 (M + H)

[0362] Synthesis of Compound Ir(La103)2(Lb005)

[0363]

[0364] Synthesis of Compound Ir(La103)-1

[0365] Referring to the synthesis and purification method of Compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain Compound Ir(La103)-1 (18.96 g, yield: 76.68%). It is directly used in the next step without purification.

[0366] Synthesis of Compound Ir(La103)2(Lb005)

[0367] Referring to the synthesis and purification method of Compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid Compound Ir(La103)2(Lb005) (9.84 g, purity: 99.79%, yield: 42.41%). After sublimation purification of 9.84 g of the crude product of Ir(La103)2(Lb005), sublimation-pure Ir(La103)2(Lb005) (7.35 g, purity: 99.68%, yield: 74.70%) is obtained, and the mass spectrum is 1173.42 (M+H).

[0368] 1 H NMR(400MHz,CDCl3)δ8.70(s,2H),8.24 - 8.19(m,2H),8.16(d,J=2.3Hz,2H),8.01 - 7.95(m,2H),7.88 - 7.81(m,4H),7.66 - 7.61(m,2H),7.50 - 7.39(m,6H),7.33(m,2H),7.23(d,J=10.8Hz,2H),4.79(s,1H),2.71 - 2.67(m,2H),1.68 - 1.54(m,16H),1.43 - 1.28(m,4H),0.88 - 0.85(m,12H).

[0369] Synthesis of Ligand La112

[0370]

[0371]

[0372] Synthesis of Compound La112-2

[0373] Referring to the synthesis and purification method of Compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La112-2 (32.12 g, purity: 99.88%, yield: 80.14%), and the mass spectrum is 288.04 (M+H)

[0374] Synthesis of Compound La112-3

[0375] Referring to the synthesis and purification method of compound La070-4, only the corresponding raw materials need to be changed to obtain the target compound La112-3 (22.01 g, purity: 99.75%, yield: 76.56%), mass spectrometry: 268.05 (M+H)

[0376] Synthesis of Compound La112-4

[0377] Referring to the synthesis and purification method of compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La112-4 (28.11 g, purity: 99.68%, yield: 80.03%), mass spectrometry: 390.10 (M+H)

[0378] Synthesis of Compound La112-4

[0379] Referring to the synthesis and purification method of compound La008-8, only the corresponding raw materials need to be changed to obtain the target compound La112-4 (40.56 g, purity: 99.79%, yield: 92.11%), mass spectrometry: 522.08 (M+H)

[0380] Synthesis of Compound La112-6

[0381] Referring to the synthesis and purification method of compound La008-7, only the corresponding raw materials need to be changed to obtain the target compound La112-6 (29.89 g, purity: 99.84%, yield: 86.46%), mass spectrometry: 414.16 (M+H)

[0382] Synthesis of Compound La112

[0383] Referring to the synthesis and purification method of compound La008, only the corresponding raw materials need to be changed to obtain the target compound La112 (14.53 g, purity: 99.74%, yield: 52.63%), mass spectrometry: 414.16 (M+H)

[0384] Synthesis of Compound Ir(La112)2(Lb005)

[0385]

[0386] Synthesis of Compound Ir(La112)-1

[0387] For the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La112)-1 (12.65 g, yield: 72.11%). It is directly used in the next step without purification.

[0388] Synthesis of Compound Ir(La112)2(Lb005)

[0389] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La112)2(Lb005) (6.53 g, purity: 99.74%, yield: 42.12%). After sublimation purification of 6.53 g of the crude product of Ir(La112)2(Lb005), sublimation-pure Ir(La112)2(Lb005) (4.45 g, purity: 99.70%, yield: 68.15%) is obtained. Mass spectrum: 1229.46 (M+H).

[0390] 1 H NMR(400MHz,CDCl3)δ8.64(s,2H),8.36 - 8.34(m,2H),8.04(d,J=7.8Hz,2H),7.87 - 7.81(m,4H),7.46 - 7.33(m,4H),7.23(d,J=10.8Hz,2H),7.19 - 7.13(m,2H),6.90 - 6.86(m,2H),4.79(s,1H),2.71 - 6.68(m,2H),2.34(d,J=8.7Hz,12H),1.67 - 1.54(m,16H),1.43 - 1.28(m,4H),0.90 - 0.87(m,12H).

[0391] Synthesis of Compound Ir(La112)2(Lb007)

[0392]

[0393] Synthesis of Compound Ir(La112)2(Lb007)

[0394] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain a red solid as compound Ir(La112)2(Lb007) (7.05 g, purity: 99.78%, yield: 43.25%). After sublimation purification of 7.05 g of the crude product of Ir(La112)2(Lb007), sublimation-pure Ir(La112)2(Lb007) (5.35 g, purity: 99.70%, yield: 75.89%) was obtained, and the mass spectrum was 1257.20 (M+H).

[0395] 1 H NMR(400MHz,CDCl3)δ8.63(s,2H),8.36(dd,J=7.4,1.5Hz,2H),8.04(d,J=7.8Hz,2H),7.87-7.81(m,4H),7.46-7.33(m,4H),7.23(d,J=10.8Hz,2H),7.16(m,2H),6.90-6.86(m,2H),5.83(s,1H),2.34(d,J=8.7Hz,12H),1.69-1.57(m,4H),1.56(s,12H),1.44-1.32(m,4H),1.05(d,J=15.2Hz,6H),0.88-0.82(m,12H).

[0396] Synthesis of ligand La132

[0397]

[0398] Synthesis of compound La132-3

[0399] Referring to the synthesis and purification method of reference compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La132-3 (40.52 g, purity: 99.80%, yield: 82.66%), and the mass spectrum was 298.02 (M+H)

[0400] Synthesis of compound La132-4

[0401] Add compound La132-3 (35.00 g, 117.55 mmol) and tetrahydrofuran (350 ml) to a 1000 ml three-necked round-bottom flask, replace with vacuum nitrogen 3 times. Under nitrogen protection, cool the system to 0 °C. After the internal temperature drops to the specified temperature, add dropwise methylmagnesium chloride solution (86.21 ml, 3 mol / L tetrahydrofuran solution, 258.62 mmol). The addition is completed in 1 hour, and stir at 0 °C for 1 hour. Monitor by TLC (the developing agent is ethyl acetate: petroleum ether = 1:15), and the raw material La132-3 has completely reacted.

[0402] The reaction was quenched by dropwise addition of aqueous hydrochloric acid solution (133 ml, 4 mol / L, 530.00 mmol) to the system. The organic solvent was removed by concentration under reduced pressure. Ethyl acetate (700 ml) was added, and the mixture was washed with deionized water (3 × 300 ml). After standing for liquid separation, the organic phase was concentrated under reduced pressure at 65 °C and then subjected to silica gel column chromatography (silica gel 200 - 300 mesh, eluent: ethyl acetate:p petroleum ether = 1:30). After elution, it was concentrated under reduced pressure at 65 °C for 1 hour to obtain a light yellow liquid, which was compound La132-4 (28.74 g, purity: 99.79%, yield: 82.11%). Mass spectrum: 298.08 (M+H).

[0403] Synthesis of compound La132-5

[0404] Compound La132-4 (25.00 g, 83.95 mmol) and dichloromethane (250 ml) were added to a 500 ml three-necked round-bottom flask. The system was evacuated and replaced with nitrogen three times. Under nitrogen protection, the temperature of the system was cooled to 0 °C. After the internal temperature reached the specified temperature, methanesulfonic acid (16.14 g, 167.91 mmol) was added dropwise, and the mixture was stirred at 0 °C for 1 hour. TLC monitoring was carried out (developing agent: ethyl acetate:p petroleum ether = 1:25), and the raw material La132-3 reacted completely.

[0405] 100 ml of deionized water was added to the system to quench the reaction. After standing for liquid separation, the organic solvent was removed by concentration under reduced pressure. Silica gel column chromatography was carried out (silica gel 200 - 300 mesh, eluent: ethyl acetate:p petroleum ether = 1:25). After elution, it was concentrated under reduced pressure at 65 °C for 1 hour to obtain a light yellow liquid, which was compound La132-5 (20.07 g, purity: 99.83%, yield: 85.47%). Mass spectrum: 280.08 (M+H)

[0406] Synthesis of compound La132-6

[0407] Referring to the synthesis and purification methods of compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La132-6 (27.60 g, purity: 99.80%, yield: 82.56%). Mass spectrum: 468.26 (M+H)

[0408] Synthesis of compound La132

[0409] Referring to the synthesis and purification methods of compound La008, only the corresponding raw materials need to be changed to obtain the target compound La132 (12.44 g, purity: 99.73%, yield: 51.01%). Mass spectrum: 468.26 (M+H)

[0410] Synthesis of Compound Ir(La132)2(Lb005)

[0411]

[0412] Synthesis of Compound Ir(La132)-1

[0413] Referring to the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La132)-1 (10.67 g, yield: 74.22%). It is directly used in the next step without purification.

[0414] Synthesis of Compound Ir(La132)2(Lb005)

[0415] Referring to the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La132)2(Lb005) (5.89 g, purity: 99.87%, yield: 41.01%). After sublimation purification of 5.89 g of the crude product of Ir(La132)2(Lb005), sublimation-pure Ir(La132)2(Lb005) (4.22 g, purity: 99.77%, yield: 71.65%) is obtained, and the mass spectrum is 1337.24 (M+H).

[0416] 1 H NMR (400 MHz, CDCl3) δ 8.26 (s, 2H), 8.21 - 8.12 (m, 4H), 8.00 - 7.95 (m, 2H), 7.82 (dd, J = 6.8, 1.6 Hz, 2H), 7.58 (dd, J = 7.3, 1.5 Hz, 2H), 7.51 - 7.44 (m, 4H), 7.40 - 7.33 (m, 6H), 4.79 (s, 1H), 2.71 (m, 2H), 1.75 (s, 12H), 1.68 - 1.54 (m, 4H), 1.51 (s, 12H), 1.38 (s, 22H), 0.91 - 0.88 (m, 12H). Synthesis of Ligand La162

[0417]

[0418]

[0419] Synthesis of Compound La162-2

[0420] For the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La162-2 (22.90 g, purity: 99.85%, yield: 81.60%), mass spectrometry: 392.10 (M+H)

[0421] Synthesis of compound La162-3

[0422] For the synthesis and purification method of reference compound La008-8, only the corresponding raw materials need to be changed to obtain the target compound La162-3 (35.23, purity: 99.75%, yield: 88.97%), mass spectrometry: 524.06 (M+H)

[0423] Synthesis of compound La162-4

[0424] For the synthesis and purification method of reference compound La008-7, only the corresponding raw materials need to be changed to obtain the target compound La162-4 (20.67, purity: 99.68%, yield: 82.69%), mass spectrometry: 416.14 (M+H)

[0425] Synthesis of compound La162

[0426] For the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La162 (11.34, purity: 99.78%, yield: 50.05%), mass spectrometry: 416.14 (M+H)

[0427] Synthesis of compound Ir(La162)2(Lb005)

[0428]

[0429] Synthesis of compound Ir(La162)-1

[0430] For the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La162)-1 (16.88 g, yield: 71.09%). It is directly used in the next step without purification.

[0431] Synthesis of compound Ir(La162)2(Lb005)

[0432] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid as compound Ir(La162)2(Lb005) (9.93 g, purity: 99.87%, yield: 43.78%). After sublimation purification of 9.93 g of the crude product of Ir(La162)2(Lb005), sublimation-pure Ir(La162)2(Lb005) (7.75 g, purity: 99.80%, yield: 78.04%) was obtained, and the mass spectrum was 1233.40 (M+H).

[0433] 1 H NMR(400MHz,CDCl3)δ8.41-8.34(m,4H),8.22-8.15(m,2H),7.91-7.81(m,4H),7.56-7.47(m,6H),7.46-7.33(m,6H),4.72(s,1H),2.71-2.68(m,2H),2.34(s,6H),1.68-1.54(m,4H),1.52(s,12H),1.43-1.28(m,4H),0.88-0.86(m,12H).

[0434] Synthesis of ligand La175

[0435]

[0436] Synthesis of compound La175-2

[0437] Referring to the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La175-2 (18.56 g, purity: 99.81%, yield: 82.05%), and the mass spectrum was 386.16 (M+H)

[0438] Synthesis of compound La175

[0439] Referring to the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La175 (8.90, purity: 99.77%, yield: 50.00%), and the mass spectrum was 386.16 (M+H)

[0440] Synthesis of compound Ir(La175)2(Lb005)

[0441]

[0442] Synthesis of compound Ir(La175)-1

[0443] With respect to the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound I Ir(La175)-1 (12.44 g, yield: 72.57%). It is directly used in the next step without purification.

[0444] Synthesis of compound Ir(La175)2(Lb005)

[0445] With reference to the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La175)2(Lb005) (7.66 g, purity: 99.83%, yield: 40.00%). After sublimation purification of 7.66 g of the crude product of Ir(La175)2(Lb005), sublimation-pure Ir(La175)2(Lb005) (4.77 g, purity: 99.80%, yield: 62.28%) is obtained, and the mass spectrum is 1173.42 (M+H).

[0446] 1 H NMR (400 MHz, CDCl3) δ 8.24 - 8.19 (m, 2H), 8.16 (d, J = 2.3 Hz, 2H), 7.97 (dd, J = 9.5, 1.4 Hz, 2H), 7.89 - 7.82 (m, 4H), 7.56 - 7.54 (m, 4H), 7.50 - 7.30 (m, 10H), 4.79 (s, 1H), 2.71 (m, 2H), 1.68 - 1.54 (m, 16H), 1.43 - 1.28 (m, 4H), 0.89 - 0.86 (m, 12H).

[0447] Synthesis of ligand La181

[0448]

[0449] Synthesis of compound La181-3

[0450] With reference to the synthesis and purification method of reference compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La181-3 (28.88 g, purity: 99.74%, yield: 80.01%), and the mass spectrum is 282.02 (M+H)

[0451] Synthesis of compound La181-4

[0452] With reference to the synthesis and purification method of reference compound La008-4, only the corresponding raw materials need to be changed to obtain the target compound La181-4 (12.35 g, purity: 99.79%, yield: 68.06%), and the mass spectrum is 264.03 (M+H)

[0453] Synthesis of Compound La181-5

[0454] Referring to the synthesis and purification methods of Compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La181-5 (19.25 g, purity: 99.83%, yield: 85.41%). Mass spectrum: 452.22 (M+H)

[0455] Synthesis of Compound La181

[0456] Referring to the synthesis and purification methods of Compound La008, only the corresponding raw materials need to be changed to obtain the target compound La181 (9.33 g, purity: 99.80%, yield: 53.32%). Mass spectrum: 452.22 (M+H)

[0457] Synthesis of Compound Ir(La181)2(Lb005)

[0458]

[0459] Synthesis of Compound Ir(La181)-1

[0460] Referring to the synthesis and purification methods of Compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain Compound Ir(La181)-1 (15.35 g, yield: 73.33%). It is directly used in the next step without purification.

[0461] Synthesis of Compound Ir(La181)2(Lb005)

[0462] Referring to the synthesis and purification methods of Compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid Compound Ir(La181)2(Lb005) (8.55 g, purity: 99.80%, yield: 42.22%). After sublimation purification of 8.55 g of the crude product of Ir(La181)2(Lb005), sublimation-pure Ir(La181)2(Lb005) (6.41 g, purity: 99.80%, yield: 74.97%) is obtained. Mass spectrum: 1305.52 (M+H).

[0463] 11H NMR (400 MHz, CDCl3) δ 8.59 (d, J = 8.9 Hz, 2H), 8.54 (s, 2H), 8.45 - 8.40 (m, 2H), 8.23 - 8.15 (m, 4H), 7.96 (d, J = 9.2 Hz, 2H), 7.92 - 7.87 (m, 2H), 7.82 (dd, J = 6.9, 1.5 Hz, 2H), 7.56 - 7.44 (m, 6H), 7.37 (td, J = 7.6, 1.3 Hz, 2H), 7.27 (d, J = 9.5 Hz, 2H), 4.80 (s, 1H), 2.71 - 2.67 (m, 2H), 1.67 - 1.54 (m, 4H), 1.51 (s, 12H), 1.38 (s, 22H), 0.90 - 0.88 (m, 12H).

[0464] Synthesis of ligand La202

[0465]

[0466] Synthesis of compound La202-1

[0467] Referring to the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La202-1 (35.06 g, purity: 99.74%, yield: 81.11%), mass spectrum: 376.12 (M+H)

[0468] Synthesis of compound La202-2

[0469] Referring to the synthesis and purification method of reference compound La008-8, only the corresponding raw materials need to be changed to obtain the target compound La202-2 (46.56 g, purity: 99.76%, yield: 88.62%), mass spectrum: 508.04 (M+H)

[0470] Synthesis of compound La202-3

[0471] Referring to the synthesis and purification method of reference compound La008-7, only the corresponding raw materials need to be changed to obtain the target compound La202-3 (37.06 g, purity: 99.83%, yield: 84.21%), mass spectrum: 400.06 (M+H)

[0472] Synthesis of compound La202-4

[0473] Referring to the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La202-4 (18.52 g, purity: 99.78%, yield: 53.63%), mass spectrum: 400.06 (M+H)

[0474] Synthesis of Compound La202

[0475] Add La202-4 (15.00 g, 37.55 mmol), potassium tert-butoxide (8.43 g, 75.10 mmol), and deuterated dimethyl sulfoxide (150 ml) into a 500-ml three-necked round-bottom flask. Replace the air with vacuum and nitrogen three times, heat to 90 °C and react overnight for 24 h, and monitor the reaction completion of La202-4 by NMR.

[0476] Drop the reaction solution into deionized water (500 ml), add ethyl acetate (500 ml), stir at room temperature for 30 minutes, separate the layers, wash the organic layer with deionized water (3 * 150 ml), separate the layers again, concentrate the organic layer and perform silica gel column chromatography (200 - 300 mesh silica gel, eluent: ethyl acetate : petroleum ether = 1 : 10). After concentration, a white solid is obtained as Compound La202 (14.37 g, purity: 99.82%, deuteration rate: 99.46%, yield: 95.55%). Mass spectrum: 401.16 (M+H).

[0477] Synthesis of Compound Ir(La202)2(Lb005)

[0478]

[0479] Synthesis of Compound Ir(La202)-1

[0480] Refer to the synthesis and purification method of Compound Ir(La008)-1, only need to change the corresponding raw materials, and Compound Ir(La202)-1 (16.56 g, yield: 7565%) can be obtained. Use it directly in the next step without purification.

[0481] Synthesis of Compound Ir(La202)2(Lb005)

[0482] Refer to the synthesis and purification method of Compound Ir(La008)2(Lb005), only need to change the corresponding raw materials, and a red solid of Compound Ir(La202)2(Lb005) (9.63 g, purity: 99.82%, yield: 43.13%) can be obtained. After sublimation purification of 9.63 g of the crude product of Ir(La202)2(Lb005), sublimation-pure Ir(La202)2(Lb005) (7.56 g, purity: 99.80%, yield: 78.52%) is obtained. Mass spectrum: 1203.44 (M+H).

[0483] 11H NMR (400 MHz, CDCl3) δ 8.63 (s, 2H), 8.36 (dd, J = 7.4, 1.5 Hz, 2H), 8.01 - 7.95 (m, 2H), 7.89 (s, 2H), 7.84 (m, 2H), 7.66 - 7.61 (m, 2H), 7.44 - 7.39 (m, 6H), 7.37 - 7.34 (m, 2H), 4.79 (s, 1H), 2.71 - 2.67 (m, 2H), 2.34 (s, 6H), 1.67 - 1.54 (m, 16H), 1.42 - 1.30 (m, 4H), 0.89 - 0.87 (m, 12H).

[0484] Synthesis of Ligand La210

[0485]

[0486] Synthesis of Compound La210-2

[0487] Referring to the synthesis and purification method of reference compound La008-3, only the corresponding raw materials need to be changed, and at the same time, the reaction time is extended to 15 hours, then the target compound La210-2 (20.03 g, purity: 99.74%, yield: 65.03%) can be obtained. Mass spectrum: 215.03 (M + H)

[0488] Synthesis of Compound La210-3

[0489] Referring to the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed, then the target compound La210-3 (18.65 g, purity: 99.65%, yield: 85.96%) can be obtained. Mass spectrum: 347.15 (M + H)

[0490] Synthesis of Compound La2101

[0491] Referring to the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed, then the target compound La210 (10.85 g, purity: 99.76%, yield: 60.00%) can be obtained. Mass spectrum: 347.15 (M + H)

[0492] Synthesis of Compound Ir(La210)2(Lb005)

[0493]

[0494] Synthesis of Compound Ir(La210)-1

[0495] For the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain compound Ir(La210)-1 (12.63 g, yield: 76.36%). It is directly used in the next step without purification.

[0496] Synthesis of Compound Ir(La210)2(Lb005)

[0497] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid compound Ir(La210)2(Lb005) (8.33 g, purity: 99.82%, yield: 43.13%). After sublimation purification of 8.33 g of the crude product of Ir(La210)2(Lb005), sublimation-pure Ir(La210)2(Lb005) (6.00 g, purity: 99.80%, yield: 72.03%) is obtained. Mass spectrum: 1095.41 (M+H).

[0498] 1 H NMR (400 MHz, CDCl3) δ 8.33 - 8.27 (m, 2H), 8.25 - 8.17 (m, 6H), 8.02 (dd, J = 7.5, 1.4 Hz, 2H), 7.88 - 7.82 (m, 2H), 7.69 - 7.62 (m, 2H), 7.52 - 7.43 (m, 4H), 7.33 (td, J = 7.2, 1.1 Hz, 2H), 7.25 (d, J = 9.5 Hz, 2H), 4.79 (s, 1H), 2.74 - 2.71 (m, 2H), 1.68 (s, 12H), 1.66 - 1.54 (m, 4H), 1.43 - 1.28 (m, 4H), 0.88 - 0.86 (m, 12H).

[0499] Synthesis of Ligand La214

[0500]

[0501]

[0502] Synthesis of Compound La214-2

[0503] For the synthesis and purification method of reference compound La008-3, only the corresponding raw materials need to be changed to obtain the target compound La214-2 (25.96 g, purity: 99.33%, yield: 83.52%). Mass spectrum: 286.15 (M+H)

[0504] Synthesis of Compound La214-3

[0505] For the synthesis and purification method of reference compound La008-11, only the corresponding raw materials need to be changed to obtain the target compound La214-3 (22.11 g, purity: 99.45%, yield: 78.98%). Mass spectrum: 355.12 (M+H)

[0506] Synthesis of Compound La214-4

[0507] For the synthesis and purification method of reference compound La008-8, only the corresponding raw materials need to be changed to obtain the target compound La214-4 (19.88 g, purity: 99.60%, yield: 75.96%). Mass spectrum: 487.07 (M+H)

[0508] Synthesis of Compound La214

[0509] For the synthesis and purification method of reference compound La008, only the corresponding raw materials need to be changed to obtain the target compound La214 (18.75 g, purity: 99.78%, yield: 62.75%). Mass spectrum: 379.15 (M+H)

[0510] Synthesis of Compound Ir(La214)2(Lb005)

[0511]

[0512] Synthesis of Compound Ir(La214)-1

[0513] For the synthesis and purification method of reference compound Ir(La008)-1, only the corresponding raw materials need to be changed to obtain Compound Ir(La214)-1 (14.63 g, yield: 77.06%). It is directly used in the next step without purification.

[0514] Synthesis of Compound Ir(La214)2(Lb005)

[0515] For the synthesis and purification method of reference compound Ir(La008)2(Lb005), only the corresponding raw materials need to be changed to obtain the red solid Compound Ir(La214)2(Lb005) (10.52 g, purity: 99.80%, yield: 46.75%). After sublimation purification of 10.52 g of the crude product of Ir(La214)2(Lb005), sublimation-pure Ir(La214)2(Lb005) (7.86 g, purity: 99.75%, yield: 74.71%) is obtained. Mass spectrum: 1159.41 (M+H).

[0516] 11H NMR (400 MHz, CDCl3) δ 8.78 (dd, J = 4.1, 2.1 Hz, 2H), 8.53 (s, 2H), 8.46 (dd, J = 7.4, 2.1 Hz, 2H), 8.34 (dd, J = 7.6, 0.8 Hz, 2H), 8.20 (d, J = 9.3 Hz, 2H), 7.53 (t, J = 7.6 Hz, 2H), 7.29 - 7.20 (m, 6H), 4.79 (s, 1H), 2.92 (s, 6H), 2.74 - 2.68 (m, 2H), 1.68 - 1.54 (m, 16H), 1.43 - 1.28 (m, 4H), 0.88 - 0.85 (m, 12H).

[0517] Application Example: Fabrication of Organic Electroluminescent Devices

[0518] A glass substrate with an ITO anode electrode of 50 mm * 50 mm * 1.0 mm was ultrasonically cleaned in ethanol for 10 minutes, dried at 150 °C, and then treated with N2 Plasma for 30 minutes. The washed glass substrate was mounted on the substrate holder of a vacuum evaporation device. First, the compounds HTM1 and P-dopant (in a ratio of 97%:3%) were co-evaporated on the side with the anode electrode wire in a mode covering the electrode to form a film with a thickness of Then, a layer of HTM1 was evaporated to form a film with a thickness of Next, a layer of HTM2 was evaporated on the HTM1 film to form a film with a thickness of Then, on the HTM2 film layer, the host material H1, the host material H2, and the doping compound (in a ratio of 48.5%:48.5%:3%, comparative compound X, compound of the present application) were co-evaporated, and the film thickness was On the light-emitting layer, ETL: LiQ ( in a ratio of 50%:50%) was co-evaporated, and then Yb was evaporated on the electron transport layer material Finally, a layer of metal iridium Ag was evaporated as the electrode.

[0519]

[0520]

[0521]

[0522]

[0523] Evaluation: The above-mentioned device was subjected to device performance tests. In each of the examples and comparative examples, a constant current power supply (Keithley 2400) was used, and a fixed current density flow (20 mA / cm 2 ) was used to test the IVL data, and a spectroradiometer (CS2000) was used to test the emission spectrum. At the same time, the voltage value and the time when the test brightness was 95% of the initial brightness (LT95) were measured. The results are as follows: The device current efficiency and lifetime were calculated with the values of Comparative Compound 3 as 100%,

[0524]

[0525]

[0526] From the data comparison in the above table, it can be seen that the iridium complex prepared from the compound of the present application using a specific phenylisoquinoline-locked naphthyl as a ligand has a strong rigid structure, inhibits the vibration of the molecule, and the compound has a narrow full width at half maximum. As a doped organic electroluminescent device, in the same device, compared with Comparative Compounds 1-3, it shows more excellent performance in driving voltage, luminous efficiency, and device lifetime.

[0527] The present application unexpectedly provides better device luminous efficiency and improved lifetime, has a narrow full width at half maximum, and can achieve saturated red emission through the special combination of substituents compared with the prior art. The above results show that the compound of the present application has the advantages of low sublimation temperature, high photo- and electrochemical stability, high color saturation, high luminous efficiency, and long device lifetime, and can be used in organic electroluminescent devices. Especially as a red light-emitting dopant, it has the possibility of being applied to the OLED industry, especially for displays, lighting, and automotive tail lights.

Claims

1. A metal iridium complex having the general formula Ir(La)(Lb)(Lc), and its structural formula is shown in Formula (1). Among them is ligand La; Lc and La have the same structure, forming the structure of (La)2Ir(Lb). Among them, The ligand La has one of the following structural formulas of Formula (2) - Formula (19): wherein Y is selected from O, S, Se, CR A R B , Y1 - Y8 are independently N or CR0; wherein Z is independently selected from CR A R B ; Wherein, X1 - X9 are independently N or CR0; R A 、R B are independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted alkyl having 1 to 10 main chain carbon atoms; wherein R is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 10 main chain carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C3-C30 alkylgermyl, cyano, isocyano; wherein R0 is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 10 main chain carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, cyano, isocyano; Among them, the substitution in the R0, R, R A , R B is replaced by deuterium, F, Cl, Br, C1-C4 alkyl, cyano, isocyano; Wherein, Lb is the structure shown in Formula (21): Wherein, the dotted line position indicates the position connected to the metal iridium Ir; wherein, R a -R g is independently selected from hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 10 main-chain carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 10 main-chain carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 20 ring carbon atoms, or R a and R b and R c are connected pairwise to form an aliphatic ring structure, and R e and R f and R g are connected pairwise to form an aliphatic ring structure; wherein, the substitution in the R a -R g is substitution by deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, an amino group substituted by C1-C4 alkyl, cyano, or isocyano.

2. The iridium metal complex according to claim 1, wherein, R is hydrogen, a substituted or unsubstituted alkyl group with 1 - 10 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 - 10 ring carbon atoms, a substituted or unsubstituted C3 - C30 alkylsilyl group or a substituted or unsubstituted C3 - C30 alkylgermyl group.

3. The metal iridium complex according to claim 1, wherein La is independently selected from one of the following structural formulas:

4. The iridium metal complex according to claim 1, wherein R a , R b , R c are respectively the same as R e , R f、 R g .

5. The metal iridium complex according to claim 1, wherein Lb is independently selected from one of the following structural formulas:

6. An electroluminescent device, comprising: A cathode, an anode, and an organic layer disposed between the cathode and the anode, wherein the organic layer contains the metal iridium complex according to any one of claims 1 - 5.

7. The electroluminescent device according to claim 6, wherein the organic layer includes a light-emitting layer, and the metal iridium complex is used as a light-emitting doping material in the light-emitting layer.

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