Iridium-based metal complex and organic electroluminescent device

Abstract

The invention relates to the field of organic electroluminescent materials, in particular to an iridium-based metal complex which is selected from specific ligand units and further limits positions and types of substituent groups in a dibenzo five-membered ring so as to realize excellent material performance. When the iridium-based metal complex is applied to an organic electroluminescent device, the luminous efficiency of the device can be effectively improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic electroluminescent materials, in particular to an iridium-based metal complex and an organic electroluminescent device. BACKGROUND

[0002] Organic electroluminescence (OLED) as a new generation of display technology, with its self-luminous, high contrast, flexible and other characteristics, becomes a leading technology in the field of new generation of high-quality display and lighting.

[0003] In OLED, the light-emitting material is a key functional material, which directly determines the performance of the device. In order to improve the light-emitting efficiency of OLED, various fluorescent and phosphorescent light-emitting material systems have been developed. OLED using fluorescent material has high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electric field excitation. In contrast, OLED using phosphorescent material can almost achieve 100% internal luminescence quantum efficiency due to the branching ratio of 1:3 between singlet and triplet excited states of excitons. For small molecule organic matter, the formation of metal complexes by doping heavy metal centers can improve the spin-orbital coupling and easily occur intersystem crossing under electric field excitation, thereby effectively obtaining triplet excited state.

[0004] Currently, metal complexes based on metal iridium (III) have the advantages of easy modification of chemical structure and easy control of photophysical properties, and are widely used as a kind of light-emitting material for high-efficiency OLED. Among them, the homoleptic and heteroleptic tridentate iridium (III) complexes have been successfully applied in the field of display and lighting such as color display. However, the current phosphorescent OLED based on metal iridium (III) still has the problem of low efficiency, so it is necessary to continuously develop new high-performance metal complexes to further improve the photoelectric performance of OLED. SUMMARY

[0005] Therefore, the present application aims to provide a new metal complex based on metal iridium (III), which can be used as a light-emitting material in an organic electroluminescent device, so that the device exhibits better light-emitting efficiency.

[0006] To achieve the purpose of the present application, the technical solutions are as follows:

[0007] The present application provides an iridium-based metal complex, which has a structure as shown in general formula (I):

[0008]

[0009] Wherein:

[0010] Y is selected from O or S;

[0011] Each time R1 appears, it is independently selected from substituted or unsubstituted cycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 cyclic atoms.

[0012] Each occurrence of R2 is independently selected from -F, -CN, or -CF3;

[0013] R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 Each occurrence is independently selected from -H, -D, -F, -CN, -CF3, substituted or unsubstituted straight-chain alkyl with 1-10 carbon atoms, substituted or unsubstituted branched alkyl with 3-10 carbon atoms, substituted or unsubstituted cycloalkyl with 3-10 carbon atoms, substituted or unsubstituted aromatic group with 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group with 5-20 cyclic atoms;

[0014] m is selected from 1 or 2;

[0015] The term "substituted or unsubstituted" indicates that the defined group is not substituted or is substituted by one or more substituents R, wherein each substituent R is independently selected from -D, -F, -CN, -CF3, straight-chain alkyl with 1-10 carbon atoms, branched alkyl with 3-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, aromatic group with 6-20 carbon atoms, heteroaromatic group with 5-20 ring atoms, or a combination of at least two of the above groups.

[0016] In one embodiment, the iridium-based metal complex has a structure as shown in general formula (II-1) or (II-2):

[0017]

[0018] In an alternative embodiment, R1 is selected from the group being R a Substituted or unsubstituted cycloalkyl groups having 5-10 carbon atoms; the R a Each occurrence is independently selected from -D, a straight-chain alkyl group having 1-10 carbon atoms that is substituted with deuterium or not, or a branched alkyl group having 3-10 carbon atoms that is substituted with deuterium or not.

[0019] In another alternative embodiment, R1 is selected from those R b Aromatic groups having 6-20 carbon atoms, substituted or unsubstituted, or containing R bsubstituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; said R b each occurrence is independently selected from one of -D, -F, -CN, -CF3, straight chain alkyl having 1 to 10 carbon atoms, branched alkyl having 3 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, aromatic group having 6 to 10 carbon atoms, heteroaromatic group having 5 to 10 ring atoms, or a combination of at least two of the above groups.

[0020] In a particular embodiment, said R b each occurrence is independently selected from one of -D, -F, -CN, -CF3, methyl substituted or unsubstituted by deuterium, ethyl substituted or unsubstituted by deuterium, isopropyl substituted or unsubstituted by deuterium, t-butyl substituted or unsubstituted by deuterium, cyclohexyl substituted or unsubstituted by deuterium, R * substituted or unsubstituted phenyl; said R * is selected from one of -D, -F, -CN, -CF3, methyl substituted or unsubstituted by deuterium, ethyl substituted or unsubstituted by deuterium, isopropyl substituted or unsubstituted by deuterium, t-butyl substituted or unsubstituted by deuterium, or cyclohexyl substituted or unsubstituted by deuterium.

[0021] Further, said R1is selected from one of R b substituted or unsubstituted phenyl.

[0022] In an alternative embodiment, said R1is selected from any one of the following groups:

[0023]

[0024]

[0025] wherein: * indicates the point of attachment.

[0026] In one embodiment, said iridium-based metal complex has a structure as shown in any one of general formulae (III-1) to (II-4):

[0027]

[0028] wherein: r is independently at each occurrence selected from 0, 1, 2, 3, 4 or 5.

[0029] In a particular embodiment, said R2is selected from -F or -CN.

[0030] In an alternative embodiment, said R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R15 Each occurrence is independently selected from -H, -D, -F, -CN, -CF3, deuterated or unsubstituted straight-chain alkyl groups having 1-6 carbon atoms, deuterated or unsubstituted branched alkyl groups having 3-6 carbon atoms, and R-substituted alkyl groups. c Substituted or unsubstituted cycloalkyl groups having 5-10 carbon atoms, R c Aromatic groups having 6-10 carbon atoms, substituted or unsubstituted, or containing R c Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms; said R c Each occurrence is independently selected from one or a combination of at least two of the following groups: -D, -F, -CN, -CF3, straight-chain alkyl groups having 1-6 carbon atoms, branched alkyl groups having 3-6 carbon atoms, cycloalkyl groups having 5-10 carbon atoms, aromatic groups having 6-10 carbon atoms, heteroaromatic groups having 5-10 cyclic atoms.

[0031] In a specific embodiment, the R c Each occurrence is independently selected from -D, -F, -CN, -CF3, methyl (deuterated or unsubstituted), ethyl (deuterated or unsubstituted), isopropyl (deuterated or unsubstituted), tert-butyl (deuterated or unsubstituted), or phenyl (deuterated or unsubstituted).

[0032] Furthermore, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 Each occurrence is independently selected from -H, -D, -F, -CN, -CF3, or any of the following groups:

[0033]

[0034] In an alternative embodiment, the formula (I), (II-1), (II-2), or (III-1)-(II-4) described Selected from R3, R5, and R6, each appearing independently, are selected from -D, -F, -CN, -CF3, deuterated or unsubstituted straight-chain alkyl groups with 1-6 carbon atoms, deuterated or unsubstituted branched alkyl groups with 3-6 carbon atoms, and R... c Substituted or unsubstituted cycloalkyl groups having 5-10 carbon atoms, R c Aromatic groups having 6-10 carbon atoms, substituted or unsubstituted, or containing R c Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms.

[0035] In some embodiments, the R3, R5, R6are independently selected at each occurrence from -D, -F, -CN, -CF3, or a group (A-1) - (A-40).

[0036] In some embodiments, the is selected from:

[0037] In some embodiments, R9, R 13 , R 14 , R 15 are independently selected at each occurrence from -H, -D, -F, -CN, -CF3, or a group (A-1) - (A-40).

[0038] In some embodiments, the iridium-based metal complex according to the present application is selected from any one of the following structures, but not limited thereto:

[0039]

[0040]

[0041]

[0042]

[0043]

[0044] The present application also provides an organic electroluminescent device comprising the iridium-based metal complex as described above. Further, the organic electroluminescent device comprises an anode layer, a cathode layer, and a light-emitting layer between the anode layer and the cathode layer, wherein the light-emitting layer comprises the iridium-based metal complex as described above.

[0045] Preferably, the organic electroluminescent device comprises an anode layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer, which are stacked in this order; and the light-emitting layer comprises the iridium-based metal complex as described above.

[0046] In some embodiments, the organic electroluminescent device further comprises a substrate. The substrate can be located on the side of the anode away from the light-emitting layer, or on the side of the cathode away from the light-emitting layer.

[0047] The substrate can be opaque or transparent. The substrate can also be rigid or flexible, for example, the substrate can be made of plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface, and a substrate without surface defects is particularly desirable. In a preferred embodiment, the substrate is glass, poly(ethylene terephthalate) (PET), or polyethylene naphthalate (PEN).

[0048] The material of the anode can be any material known in the art for use in an anode of an organic electronic device, such as a conductive metal, a conductive metal oxide, or a conductive polymer. By way of example, the material of the anode can be selected from, but not limited to, at least one of Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, and aluminum-doped zinc oxide (AZO). Other suitable anode materials are known and can be readily selected by one of ordinary skill in the art.

[0049] The material of the cathode can be any material known in the art for use in a cathode of an organic electronic device, such as a conductive metal or a conductive metal oxide. By way of example, the material of the cathode can be selected from, but not limited to, at least one of Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, e-beam, and the like.

[0050] The hole injection layer has the function of reducing ITO surface roughness, reducing internal defects of the device, reducing hole injection barrier, and the like. The material of the hole injection layer can be any material known in the art for use in a hole injection layer, such as, but not limited to, HAT-CN, F4-TCQN, 1-TNATA, 2-TNATA, m-MTDATA, PEDOT:PSS, MoO3, AgO, and the like.

[0051] The hole transport layer has the function of improving the transport efficiency of holes in the device and blocking electrons in the light-emitting layer. The material of the hole transport layer can be any material known in the art for use in a hole transport layer, such as, but not limited to, an aromatic amine organic compound, including but not limited to NPB, CBP, TFB, TCTA, TAPC, TPD, Spiro-TAD, TDATA, and the like.

[0052] The light-emitting layer comprises a host material and a guest material. The host material comprises a thiazole derivative, a benzimidazole derivative, an arylamine derivative, a carbazole derivative, a triazine derivative, etc., but is not limited thereto. Specific examples can include 4,4'-bis(carbazol-9-yl)biphenyl (CBP), 1,3-bis(N-carbazolyl)benzene (MCP), 1,3,5-tris(carbazol-9-yl)benzene (TCP), 9,10-di(2-naphthyl)anthracene (ADN), etc., but are not limited thereto. The guest material is selected from the iridium-based metal complexes as described above.

[0053] The electron transport layer can function to facilitate electron transport. The electron transport material is a material that advantageously receives electrons from the cathode and transports the electrons to the light-emitting layer, and a material having a high electron mobility is suitable. The electron transport material can be selected from a compound containing a heterocycle, such as a pyridine derivative, a pyrimidine derivative, a triazine derivative, a benzimidazole derivative, etc.

[0054] The electron injection layer functions to lower the electron injection barrier between the cathode and the organic layer, allowing efficient injection of electrons into the organic layer. The electron injection layer material includes, but is not limited to, a metal, a metal compound, a metal oxide, etc., as described below. Specific examples can include lithium (Li), lithium fluoride (LiF), lithium 8-hydroxyquinolate (LiQ), cesium fluoride (CsF), lithium oxide (Li2O), cesium carbonate (Cs2CO3), etc., but are not limited thereto.

[0055] The present application also relates to an electronic device comprising the organic electronic device. The present application relates to the use of electroluminescent devices in various electronic devices. The electronic device can be, but is not limited to, a display device, an illumination device, a light source, a sensor, etc.

[0056] The iridium-based metal complex according to the present application, by selecting a specific ligand unit and further limiting the position and type of the substituent in the dibenzopentacene, synergistically optimizes the structure of the compound, thereby achieving excellent material performance; specifically, by limiting the position and type, the spatial configuration of the molecule is effectively improved; further introducing an electron-withdrawing unit R2, adjusts the energy level and energy gap of the metal complex. Thus, when the iridium-based metal complex is applied to an organic electroluminescent device, the luminous efficiency of the device is effectively improved. DETAILED DESCRIPTION

[0057] The embodiments described herein are only a few of all the embodiments of the present application. Based on the embodiments described herein, all other embodiments obtained by those skilled in the art without creative effort shall fall within the scope of the present application. In addition, it should be understood that the specific implementations described herein are merely intended for illustration and explanation of the present application and are not intended to limit the present application.

[0058] In the present application, the term "comprising" means "including but not limited to", the term "plurality" means "two or more", and various embodiments of the present application can exist in the form of a range. It should be understood that the description in the form of a range is merely for convenience and brevity and should not be understood as a hard limitation on the scope of the present application; therefore, it should be considered that the range described has been specifically disclosed all possible sub-ranges and single values within the range. For example, it should be considered that the range description from 1 to 6 has been specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range.

[0059] The selection range of the terms "and / or", "or / and", and "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, including any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least two conjunctions selected from "and / or", "or / and", and "and / or" are combined to connect at least three items, it should be understood that in the present application, the technical solution undoubtedly includes the technical solution connected by "logical and", and also undoubtedly includes the technical solution connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B, and A+B. For another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (i.e., the technical solution connected by "logical or"), and also includes any and all combinations of A, B, C, and D, i.e., includes the combination of any two or any three of A, B, C, and D, and also includes the four-item combination of A, B, C, and D (i.e., the technical solution connected by "logical and").

[0060] In the present application, "substituted" means that one or more hydrogen atoms in a substituent is replaced by a substituent.

[0061] In the present application, when the same substituent appears multiple times, it can be independently selected from different groups. For example, if a general formula contains multiple R, R can be independently selected from different groups.

[0062] In the present application, when the connecting site is not indicated in a group, it means that the optional connecting site in the group is connected as the connecting site. In the present application, the single bond to which a substituent is connected is throughout the corresponding ring, and it means that the substituent can be connected to the optional position of the ring, for example R is connected to any substitutable site of the benzene ring. For example may be represented as

[0063] In the present application, when a plurality of substituents with the same symbol are contained in the same group, each substituent can be the same as or different from each other, for example The 6 R's on the benzene ring can be the same as or different from each other.

[0064] In the present application, the halogen means fluorine, chlorine, bromine and iodine.

[0065] In the present application, "substituted or unsubstituted" means that the functional group described after the term can contain a substituent or can not contain a substituent.

[0066] In the present application, the "number of ring atoms" means the number of atoms among the atoms constituting the ring itself of a structural compound obtained by bonding atoms into a ring shape (for example, a monocyclic compound, a fused ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound). When the ring is substituted with a substituent, the atoms included in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of quinoline is 10, the number of ring atoms of a thienyl group is 5, the number of ring atoms of thienothiophene is 8, and the number of ring atoms of pyridine is 6.

[0067] In the present application, "aromatic group" means an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aryl group (for example, phenyl) or a polycyclic aryl group, in other words, the aromatic group can be a monocyclic aromatic group, a fused ring aromatic group, two or more monocyclic aromatic groups connected by a carbon-carbon bond in conjugation, a monocyclic aromatic group and a fused ring aromatic group connected by a carbon-carbon bond in conjugation, two or more fused ring aromatic groups connected by a carbon-carbon bond in conjugation. That is, unless otherwise specified, two or more aromatic groups connected by a carbon-carbon bond in conjugation can also be regarded as an aromatic group of the present application. Preferably, the aromatic group is selected from aromatic groups having 6 to 20 C atoms; further, the aromatic group is selected from aromatic groups having 6 to 10 C atoms; the aromatic group includes but is not limited to phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, rylene, and derivatives thereof.

[0068] In the present application, "heteroaromatic group" means a heteroaromatic ring or a derivative thereof, which contains 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, and the heteroatoms can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaromatic group or a polycyclic heteroaromatic group, in other words, the heteroaromatic group can be a single heteroaromatic ring system or a plurality of heteroaromatic ring systems connected in conjugation through carbon-carbon bonds, and any one of the heteroaromatic ring systems is a heteroaromatic monocyclic ring or a heteroaromatic fused ring. Preferably, the heteroaromatic group is selected from those having 5 to 20 ring atoms; further, the heteroaromatic group is selected from those having 5 to 10 ring atoms. The heteroaromatic group includes, but is not limited to, thienyl, furanyl, pyrrolyl, dioxazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furanopyrrolyl, furanofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, perylenyl, phenanthridinyl, perimidinyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl and derivatives thereof.

[0069] In the present application, the number of carbon atoms of the linear alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6. Non-limiting examples of the linear alkyl group include methyl (-CH3), ethyl (-C2H5), n-propyl (-C3H7), n-butyl (-C4H9), n-pentyl (-C5H 11 ), n-hexyl (-C6H 13 ), n-heptyl (-C7H 15 ), n-octyl (-C8H 17 ), n-nonyl (-C9H 19 ), -C 10 H 21 . The number of carbon atoms of the branched alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of the branched alkyl group include: isopropyl, a branched alkyl group containing 4 C atoms, a branched alkyl group containing 5 C atoms, a branched alkyl group containing 6 C atoms, a branched alkyl group containing 7 C atoms, a branched alkyl group containing 8 C atoms, a branched alkyl group containing 9 C atoms, a branched alkyl group containing 10 C atoms. The number of carbon atoms of the cyclic alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of the cyclic alkyl group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl.

[0070] In the present application, when the connection site is not specified in the group, it means that any optional connection site in the group is the connection site.

[0071] In the present application, "independently selected from" means that when one or more groups are simultaneously present and multiple times in a compound, they are all independently selected, which can be the same or different.

[0072] In the course of explaining structural elements of the present application, "comprising" or "including" and the like similar words used in the present application mean that the device or material appearing before the word covers the device or material listed after the word and its equivalents, and does not exclude other devices or materials.

[0073] "Combinations thereof", "any combination thereof", "combinations of groups", "combinations" and the like used in the present application include all suitable combinations of any two or more of the listed groups.

[0074] In the present application, "further", "furthermore", "in particular" and the like are used for the purpose of description, indicating differences in content, but should not be understood as limiting the scope of protection of the present application.

[0075] In the present application, "optionally", "optional" and "optional" mean optional, that is, selected from "yes" or "no" two parallel schemes. If there are multiple "options" in a technical solution, unless otherwise specified, there is no contradiction or mutual restriction relationship, and each "option" is independent.

[0076] In the present application, the Indicates The Indicates

[0077] Synthesis example of iridium-based metal complex

[0078] The iridium-based metal complex and the preparation method thereof of the present application will be further described in detail in combination with specific embodiments. In the following synthesis examples, the raw materials used are commercially available products or prior art, unless otherwise specified.

[0079] Synthesis example 1: synthesis of metal complex (4)

[0080]

[0081] Synthesis of compound 4-3:

[0082] Accurately weighed compound 4-1 (6.2 g, 20.0 mmol), tetrahydrofuran (20.0 mL) were added into a three-neck flask, replaced with nitrogen for three times, cooled to -20 °C, compound 4-2 (15.0 mL, 2.0 M) was added dropwise slowly, then naturally warmed to room temperature, and reacted overnight. TLC was used to monitor the reaction. After the reaction was completed, saturated ammonium chloride solution was added for quenching, water and ethyl acetate were used for liquid-liquid extraction, the aqueous phase was extracted with ethyl acetate again, the combined organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by reduced pressure distillation. Silica gel column chromatography was performed, and PE:DCM = 25:1 (volume ratio) was used as the eluent to obtain compound 4-3 about 6.13 g, with a yield of 79.1%, MS: 387.56.

[0083] Synthesis of compound 4-4:

[0084] Accurately weighed compound 4-3 (5.8 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) were added into a three-neck flask, replaced with hydrogen, and reacted overnight. TLC was used to monitor the reaction. After the reaction was completed, the reaction was cooled to room temperature, water and ethyl acetate were used for liquid-liquid extraction, the aqueous phase was extracted with ethyl acetate again, the combined organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by reduced pressure distillation. Silica gel column chromatography was performed, and PE:DCM = 30:1 (volume ratio) was used as the eluent to obtain compound 4-4 about 2.94 g, with a yield of 69.7%, MS: 281.35.

[0085] Synthesis of compound 4-6:

[0086] Accurately weighed compound 4-4 (2.8 g, 10.0 mmol), compound 4-5 (2.8 g, 11.0 mmol), potassium carbonate (2.8 g, 20.0 mmol), DMF (30 mL), distilled water (3 mL) were added into a three-neck flask, replaced with nitrogen for three times, and then 2-(triphenylphosphoranylidene)-dichloropalladium (351 mg, 0.5 mmol) was added. After being replaced with nitrogen, the reaction was carried out at 60 °C for 10 h. TLC was used to monitor the reaction. After the reaction was completed, the reaction was cooled to room temperature, water and ethyl acetate were used for liquid-liquid extraction, the aqueous phase was extracted with ethyl acetate again, the combined organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by reduced pressure distillation. Silica gel column chromatography was performed, and PE:DCM = 15:1 (volume ratio) was used as the eluent to obtain compound 4-6 about 3.05 g, with a yield of 75.0%, MS: 406.88.

[0087] Synthesis of compound 4-7:

[0088] Accurately weigh compound 4-6 (2.8 g, 7.0 mmol), 3-nitropyridine (43 mg, 0.35 mmol), tert-butyl peroxybenzoate (2.7 g, 14.0 mmol), palladium acetate (79 mg, 0.35 mmol), 1,3-dimethyl-2-imidazolidinone (10.0 mL), hexafluorobenzene (15.0 mL), replace nitrogen three times, 90 °C for 4 h. TLC monitoring reaction, when the reaction is completed, cool to room temperature, add water and ethyl acetate, separate the aqueous phase with ethyl acetate, dry the combined organic phase with anhydrous sodium sulfate, remove the excess solvent under reduced pressure, silica gel column chromatography, eluent is PE: DCM = 10: 1 (volume ratio), to obtain compound 4-7 about 2.36 g, yield 83.4%, MS: 404.12.

[0089] Synthesis of compound 4-8:

[0090] Accurately weigh compound 4-7 (1.7 g, 4.1 mmol), iridium trichloride trihydrate (353 mg, 1.0 mmol), distilled water (4.0 mL), DME (12.0 mL) are added to a two-necked flask, replace nitrogen three times, 110 °C for 6 h. When the reaction is completed, cool to room temperature, filter the reaction solution under reduced pressure, and wash with ethanol and distilled water to obtain compound 4-8 about 0.91 g, yield 88.0%, MALDI-TOF-MS: 2069.25.

[0091] Synthesis of metal complex (4):

[0092] Accurately weigh compound 4-8 (829 mg, 0.4 mmol), compound 4-9 (233 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) are sequentially added to a three-necked flask, replace nitrogen three times, 110 °C for 6 h, after the reaction is completed, cool to room temperature, remove the excess solvent under reduced pressure, recrystallize with dichloromethane / methanol to obtain metal complex (4) about 451 mg, yield 48.9%, MALDI-TOF-MS: 1153.36.

[0093] Synthesis of metal complex (13)

[0094]

[0095] Synthesis of compound 13-3:

[0096] Accurately weigh compound 13-1 (33.8 g, 120.0 mmol), compound 13-2 (14.9 g, 120.0 mmol), potassium carbonate (33.2 g, 240.0 mmol), N-methylacetamide (400.0 mL) into a three-neck flask, replace nitrogen for three times, react at room temperature overnight. TLC monitor the reaction, when the reaction is completed, add water and ethyl acetate to separate the aqueous phase, the aqueous phase is extracted with ethyl acetate again, the combined organic phase is dried with anhydrous sodium sulfate, remove the excess solvent by distillation under reduced pressure, recrystallize with ethanol to obtain compound 13-3 about 30.51 g, yield 78.1%, MS: 325.73.

[0097] Synthesis of compound 13-5:

[0098] Accurately weigh compound 13-3 (6.5 g, 20.0 mmol), tetrahydrofuran (20.0 mL) into a three-neck flask, replace nitrogen for three times, cool to-20℃, slowly add compound 13-4 (15.0 mL, 2.0 M) dropwise, then naturally warm to room temperature and react overnight. TLC monitor the reaction, when the reaction is completed, quench with saturated ammonium chloride solution, add water and ethyl acetate to separate the aqueous phase, the aqueous phase is extracted with ethyl acetate again, the combined organic phase is dried with anhydrous sodium sulfate, remove the excess solvent by distillation under reduced pressure, silica gel column chromatography, the eluent is PE:DCM=25:1 (volume ratio), to obtain compound 13-5 about 6.59 g, yield 80.6%, MS: 408.56.

[0099] Synthesis of compound 13-6:

[0100] Accurately weigh compound 13-5 (6.1 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) into a three-neck flask, replace hydrogen, react overnight. TLC monitor the reaction, when the reaction is completed, cool to room temperature, add water and ethyl acetate to separate the aqueous phase, the aqueous phase is extracted with ethyl acetate again, the combined organic phase is dried with anhydrous sodium sulfate, remove the excess solvent by distillation under reduced pressure, silica gel column chromatography, the eluent is PE:DCM=30:1 (volume ratio), to obtain compound 13-6 about 3.25 g, yield 71.8%, MS: 301.84.

[0101] Synthesis of compound 13-9:

[0102] A three-necked flask was charged with compound 13-7 (4.7 g, 20.0 mmol), compound 13-8 (4.8 g, 20.0 mmol), sodium azide (2.6 g, 40.0 mmol), cuprous iodide (381 mg, 2.0 mmol), L-proline (461 mg, 4.0 mmol), DMSO (50.0 mL) in sequence, replaced with nitrogen for three times, and reacted at 100 °C for 24 h. The reaction was monitored by TLC. After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with water and ethyl acetate. The aqueous phase was extracted with ethyl acetate again. The combined organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by distillation under reduced pressure. The sample was column chromatographed on silica gel with PE:DCM = 20:1 (volume ratio) as the eluent to obtain compound 13-9 about 6.69 g with a yield of 86.2%, MS: 388.07.

[0103] Synthesis of compound 13-10:

[0104] A three-necked flask was charged with bis(acetonitrile) palladium(II) chloride (65 mg, 0.25 mmol), bis(2-diphenylphosphinophenyl) ether (269 mg, 0.5 mmol), cesium pivalate (5.9 g, 25.0 mmol), and compound 13-6 (1.5 g, 5.0 mmol) in sequence, replaced with nitrogen for three times. Then anhydrous N,N-dimethylacetamide (30.0 mL) and compound 13-9 (2.3 g, 6 mmol) were added in sequence, and reacted at 140 °C for 24 h. The reaction was monitored by TLC. After the reaction was completed, the reaction mixture was cooled to room temperature, and quenched by adding saturated ammonium chloride solution. The reaction mixture was extracted with water and ethyl acetate. The aqueous phase was extracted with ethyl acetate again. The combined organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by distillation under reduced pressure. The sample was column chromatographed on silica gel with PE:DCM = 20:1 (volume ratio) as the eluent to obtain compound 13-10 about 1.78 g with a yield of 73.9%, MS: 481.42.

[0105] Synthesis of compound 13-11:

[0106] A two-necked flask was charged with compound 4-9 (2.6 g, 16.4 mmol), iridium trichloride trihydrate (1.4 g, 4.0 mmol), distilled water (16.0 ml), and DME (48.0 ml) in sequence, replaced with nitrogen for three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and filtered under reduced pressure. The residue was washed with ethanol and distilled water to obtain compound 13-11 about 1.62 g with a yield of 75.5%, MS: 1072.43.

[0107] Synthesis of metal complex (13):

[0108] Accurately weigh compound 13-11 (536 mg, 0.5 mmol), compound 13-10 (722 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-neck flask, replace nitrogen three times, react at 110 °C for 6 h, after the reaction is completed, cool to room temperature, remove the excess solvent under reduced pressure, recrystallize using dichloromethane / methanol to obtain metal complex (13) about 398 mg, yield 40.5%, MS: 981.92.

[0109] Synthesis Example 3: Synthesis of metal complex (18)

[0110]

[0111] Synthesis of compound 18-2:

[0112] Accurately weigh compound 4-1 (6.2 g, 20.0 mmol), tetrahydrofuran (20.0 mL) into a three-neck flask, replace nitrogen three times, cool to -20 °C, slowly drop compound 18-1 (15.0 mL, 2.0 M) under temperature control, then naturally warm to room temperature and react overnight. Refer to the synthesis route of compound 4-3 for subsequent synthesis reaction steps to obtain compound 18-2 about 6.27 g, yield 79.6%, MS: 393.81.

[0113] Synthesis of compound 18-3:

[0114] Accurately weigh compound 18-2 (5.9 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) into a three-neck flask, replace hydrogen, and react overnight. Refer to the synthesis route of compound 4-4 for subsequent synthesis reaction steps to obtain compound 18-3 about 3.18 g, yield 74.0%, MS: 286.60.

[0115] Synthesis of compound 18-5:

[0116] Accurately weigh compound 18-0 (4.7 g, 20.0 mmol), compound 18-4 (4.8 g, 20.0 mmol), sodium azide (2.6 g, 40.0 mmol), cuprous iodide (381 mg, 2.0 mmol), L-proline (461 mg, 4.0 mmol), and DMSO (50.0 mL) into a three-necked flask. Purge with nitrogen three times and react at 100 °C for 24 h. Monitor the reaction by TLC. After the reaction is complete, cool to room temperature, extract with water and ethyl acetate, and extract the aqueous phase again with ethyl acetate. Combine the organic phases and dry with anhydrous sodium sulfate. Remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:DCM = 20:1 (v / v) as eluent to obtain approximately 6.34 g of compound 18-5, yield 81.6%, MS: 388.51.

[0117] Synthesis of compound 18-6:

[0118] Accurately weigh compound 18-5 (5.8 g, 15.0 mmol), triisopropyl borate (8.5 g, 45.0 mmol), and anhydrous tetrahydrofuran (100.0 mL) into a three-necked flask, purge with nitrogen three times, and cool to -78 °C for 2 h. Add n-butyllithium (6 mL, 2.5 M) dropwise while maintaining the temperature, and react at -78 °C for 1 h. After the reaction is complete, cool to room temperature, quench the reaction mixture with sodium dihydrogen phosphate solution, and extract with water and ethyl acetate. Extract the aqueous phase again with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, remove excess solvent by vacuum distillation, and slurry with ethanol to give approximately 3.53 g of compound 18-6, yield 76.8%, MS: 306.45.

[0119] Synthesis of compound 18-7:

[0120] Accurately weigh 2.9 g (10.0 mmol) of compound 18-3, 3.4 g (11.0 mmol) of compound 18-6, 2.8 g (20.0 mmol) of potassium carbonate, 30 mL of DMF, and 3 mL of distilled water into a three-necked flask. Purge with nitrogen three times. Add 351 mg (0.5 mmol) of di-(triphenylphosphine)-palladium dichloride, purge with nitrogen again, and react at 60 °C for 10 h. Follow the same synthetic route as for compounds 4-6 to obtain approximately 3.48 g of compound 18-7, yield 74.2%, MS: 468.77.

[0121] Synthesis of compound 18-8:

[0122] Accurately weigh compound 18-7 (3.3 g, 7.0 mmol), 3-nitropyridine (43 mg, 0.35 mmol), tert-butyl peroxybenzoate (2.7 g, 14.0 mmol), palladium acetate (79 mg, 0.35 mmol), 1,3-dimethyl-2-imidazolidinone (10.0 mL), hexafluorobenzene (15.0 mL), replace nitrogen three times, react at 90 °C for 4 h. Refer to the synthesis route of compound 4-7 for subsequent synthesis reaction steps to obtain compound 18-8 about 2.19 g, yield 66.9%, MS: 467.14.

[0123] Synthesis of metal complex (18):

[0124] Accurately weigh compound 13-11 (536 mg, 0.5 mmol), compound 18-8 (700 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-necked flask in turn, replace nitrogen three times, react at 110 °C for 6 h, after the reaction is completed, cool to room temperature, remove the excess solvent under reduced pressure, recrystallize with dichloromethane / methanol to obtain metal complex (18) about 409 mg, yield 42.3%, MS: 966.05.

[0125] Synthesis Example 4: Synthesis of metal complex (25)

[0126]

[0127] Synthesis of compound 25-2:

[0128] Accurately weigh diisopropylamine (5.1 g, 50.0 mmol), anhydrous tetrahydrofuran (20 mL) into a two-necked flask in turn, replace nitrogen three times, cool to -78 °C, drop in n-butyllithium (18.0 mL, 2.5 M), after stirring at -78 °C for 10 min, drop into a solution of compound 25-1 (11.5 g, 40.0 mmol) in anhydrous tetrahydrofuran (100.0 mL) at -78 °C. Stir the reaction at -78 °C for 1 h, add N,N-dimethylformamide (4.0 mL), and stir for 20 min. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride solution, add water and extract with ethyl acetate, re-extract the aqueous phase with ethyl acetate, dry the combined organic phase with anhydrous sodium sulfate, remove the excess solvent under reduced pressure, recrystallize with ethyl acetate / n-hexane to obtain compound 25-2 about 8.80 g, yield 69.7%, MS: 315.56.

[0129] Synthesis of compound 25-4:

[0130] Accurately weighed compound 25-2 (6.3 g, 20.0 mmol), tetrahydrofuran (20.0 mL) were added into a three-neck flask, replaced with nitrogen for three times, cooled to -20 °C, compound 25-3 (15.0 mL, 2.0 M) was added dropwise slowly, then naturally warmed to room temperature and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-3, to obtain compound 25-4 about 6.56 g, yield 80.3%, MS: 408.31.

[0131] Synthesis of compound 25-5:

[0132] Accurately weighed compound 25-4 (6.1 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) were added into a three-neck flask, replaced with hydrogen, and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-4, to obtain compound 25-5 about 3.12 g, yield 68.8%, MS: 302.45.

[0133] Synthesis of compound 25-6:

[0134] Accurately weighed compound 25-5 (3.0 g, 10.0 mmol), compound 4-5 (2.8 g, 11.0 mmol), potassium carbonate (2.8 g, 20.0 mmol), DMF (30 mL), distilled water (3 mL) were added into a three-neck flask, replaced with nitrogen for three times, added with bis(triphenylphosphine)-palladium dichloride (351 mg, 0.5 mmol), replaced with nitrogen, and reacted at 60 °C for 10 h. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-6, to obtain compound 25-6 about 3.74 g, yield 87.4%, MS: 427.93.

[0135] Synthesis of compound 25-7:

[0136] Accurately weighed compound 25-6 (3.0 g, 7.0 mmol), 3-nitropyridine (43 mg, 0.35 mmol), tert-butyl peroxybenzoate (2.7 g, 14.0 mmol), palladium acetate (79 mg, 0.35 mmol), 1,3-dimethyl-2-imidazolidinone (10.0 mL), hexafluorobenzene (15.0 ml) were replaced with nitrogen for three times, and reacted at 90 °C for 4 h. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-7, to obtain compound 25-7 about 2.24 g, yield 75.1%, MS: 426.13.

[0137] Synthesis of compound 25-8:

[0138] Accurately weigh compound 25-7 (1.7 g, 4.1 mmol), iridium trichloride trihydrate (353 mg, 1.0 mmol), distilled water (4.0 mL), DME (12.0 mL) into a three-necked flask, replace nitrogen for three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, and filter the reaction solution under reduced pressure, and wash with ethanol and distilled water to obtain compound 25-8 about 0.92 g, yield 85.5%, MALDI-TOF-MS: 2153.29.

[0139] Synthesis of metal complex (25):

[0140] Accurately weigh compound 25-8 (861 mg, 0.4 mmol), compound 4-9 (233 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-necked flask, replace nitrogen for three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, and remove the excess solvent under reduced pressure, and recrystallize using dichloromethane / methanol to obtain metal complex (25) about 431 mg, yield 45.1%, MALDI-TOF-MS: 1195.10.

[0141] Synthesis of metal complex (49)

[0142]

[0143] Synthesis of compound 49-2:

[0144] Accurately weigh compound 49-1 (10.0 g, 30.0 mmol), compound 13-2 (3.7 g, 30.0 mmol), potassium carbonate (8.3 g, 60.0 mmol), N-methylacetamide (100.0 mL) into a three-necked flask, replace nitrogen for three times, and react at room temperature overnight. Refer to the synthesis route of compound 13-3 for subsequent synthesis reaction steps to obtain compound 49-2 about 8.03 g, yield 71.4%, MS: 374.73.

[0145] Synthesis of compound 49-3:

[0146] Accurately weigh compound 49-2 (7.5 g, 20.0 mmol), tetrahydrofuran (20.0 mL) into a three-necked flask, replace nitrogen for three times, cool to -20 °C, and slowly drop compound 4-2 (15.0 mL, 2.0 M) under temperature control, and then naturally warm to room temperature and react overnight. Refer to the synthesis route of compound 13-5 for subsequent synthesis reaction steps to obtain compound 49-3 about 7.38 g, yield 81.3%, MS: 453.86.

[0147] Synthesis of compound 49-4:

[0148] Compound 49-3 (6.8 g, 15.0 mmol), 10% palladium on carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) were added into a three-neck flask in turn, replaced with hydrogen, and reacted overnight. The subsequent synthesis reaction steps refer to the synthetic route of compound 13-6, to obtain compound 49-4 about 3.69 g, yield 70.8%, MS: 347.24.

[0149] Synthesis of compound 49-5:

[0150] Compound 49-0 (1.7 g, 10.0 mmol), o-diiodobenzene (3.6 g, 11.0 mmol), potassium carbonate (2.8 g, 20.0 mmol), DMF (30 mL), distilled water (3 mL) were added into a three-neck flask in turn, replaced with nitrogen three times, and then bis(triphenylphosphine)-palladium dichloride (351 mg, 0.5 mmol) was added, replaced with nitrogen, and reacted at 60°C for 10 h. The reaction was monitored by TLC, and after the reaction was completed, it was cooled to room temperature, and then extracted with water and ethyl acetate. The aqueous phase was extracted with ethyl acetate again, and the combined organic phase was dried over anhydrous sodium sulfate, and then the excess solvent was removed by reduced pressure distillation. The sample was mixed and column chromatographed on silica gel, and eluted with PE:DCM=10:1 (volume ratio) to obtain compound 49-5 about 2.18 g, yield 65.6%, MS: 332.36.

[0151] Synthesis of compound 49-6:

[0152] Bis(acetonitrile) palladium (II) chloride (65 mg, 0.25 mmol), bis(2-diphenylphosphinylphenyl) ether (269 mg, 0.5 mmol), cesium pivalate (5.9 g, 25.0 mmol), and compound 49-4 (1.7 g, 5.0 mmol) were added into a three-neck flask in turn, and replaced with nitrogen three times. Then anhydrous N,N-dimethylacetamide (30.0 mL) and compound 49-5 (2.0 g, 6 mmol) were added in turn, and reacted at 140°C for 24 h. The subsequent synthesis reaction steps refer to the synthetic route of compound 13-10, to obtain compound 49-6 about 1.57 g, yield 66.7%, MS: 470.85.

[0153] Synthesis of compound 49-8:

[0154] Accurately weigh compound 49-7 (1.4 g, 8.2 mmol), iridium trichloride trihydrate (706 mg, 2.0 mmol), distilled water (8.0 mL), DME (24.0 mL) into a three-necked flask, replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, and filter the reaction solution under reduced pressure, and wash with ethanol and distilled water to obtain compound 49-8 about 0.72 g, yield 63.8%, MALDI-TOF-MS: 1128.39.

[0155] Synthesis of metal complex (49):

[0156] Accurately weigh compound 49-8 (564 mg, 0.5 mmol), compound 49-6 (706 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-necked flask, replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, and remove the excess solvent under reduced pressure, and recrystallize using dichloromethane / methanol to obtain metal complex (49) about 393 mg, yield 39.4%, MS: 998.37.

[0157] Synthesis Example 6: Synthesis of metal complex (65)

[0158]

[0159] Synthesis of compound 65-1:

[0160] Accurately weigh compound 13-3 (6.5 g, 20.0 mmol), tetrahydrofuran (20.0 mL) into a three-necked flask, replace nitrogen three times, cool to -20 °C, and slowly drop compound 18-1 (15.0 mL, 2.0 M) while controlling the temperature, and then naturally warm to room temperature to react overnight. Refer to the synthesis route of compound 13-5 for subsequent synthesis reaction steps to obtain compound 65-1 about 7.34 g, yield 89.7%, MS: 409.19.

[0161] Synthesis of compound 65-2:

[0162] Accurately weigh compound 65-1 (6.1 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) into a three-necked flask, replace hydrogen, and react overnight. Refer to the synthesis route of compound 13-6 for subsequent synthesis reaction steps to obtain compound 65-2 about 3.20 g, yield 70.3%, MS: 303.44.

[0163] Synthesis of compound 65-3:

[0164] Accurately weigh bis(acetonitrile) palladium (II) chloride (65 mg, 0.25 mmol), bis(2- diphenylphosphinophenyl) ether (269 mg, 0.5 mmol), cesium pivalate (5.9 g, 25.0 mmol) and compound 65-2 (1.5 g, 5.0 mmol) into a three-neck flask, replace nitrogen three times. Then add anhydrous N,N-dimethylacetamide (30.0 mL) and compound 49-5 (2.0 g, 6 mmol) into the flask, respectively, and react at 140 °C for 24 h. Refer to the synthetic route of compound 13-10 for subsequent synthetic reaction steps to obtain compound 65-3 about 1.64 g, yield 76.9%, MS: 426.74.

[0165] Synthesis of compound 65-5:

[0166] Accurately weigh compound 65-4 (1.5 g, 8.2 mmol), iridium trichloride trihydrate (706 mg, 2.0 mmol), distilled water (8.0 ml), DME (24.0 ml) into a two-neck flask, replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, reduce pressure to filter the reaction solution, and wash with ethanol and distilled water to obtain compound 65-5 about 0.87 g, yield 75.4%, MALDI-TOF-MS: 1154.49.

[0167] Synthesis of metal complex (65):

[0168] Accurately weigh compound 65-5 (577 mg, 0.5 mmol), compound 65-3 (640 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-neck flask, replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, remove the excess solvent under reduced pressure, and recrystallize using dichloromethane / methanol to obtain metal complex (49) about 391 mg, yield 39.8%, MS: 982.56.

[0169] Synthesis of metal complex (66) in synthesis example 7

[0170]

[0171] Synthesis of compound 66-1:

[0172] Accurately weighed compound 13-3 (6.5 g, 20.0 mmol), tetrahydrofuran (20.0 mL) were added into a three-neck flask, replaced nitrogen for three times, cooled to -20 ℃, compound 4-2 (15.0 mL, 2.0 M) was added dropwise slowly, then naturally warmed to room temperature, and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 13-5, and compound 66-1 was obtained about 7.12 g, with a yield of 88.3%, MS: 403.17.

[0173] Synthesis of compound 66-2:

[0174] Accurately weighed compound 66-1 (6.0 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) were added into a three-neck flask, replaced hydrogen, and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 13-6, and compound 66-2 was obtained about 3.04 g, with a yield of 68.2%, MS: 297.36.

[0175] Synthesis of compound 66-4:

[0176] Accurately weighed compound 66-3 (4.4 g, 15.0 mmol), triisopropyl borate (8.5 g, 45.0 mmol), anhydrous tetrahydrofuran (100.0 mL) were added into a three-neck flask, replaced nitrogen for three times, cooled to -78 ℃, and reacted for 2 h. After cooling to room temperature, sodium dihydrogen phosphate solution was added to quench the reaction, water and ethyl acetate were added for liquid-liquid extraction, the aqueous phase was extracted with ethyl acetate again, the combined organic phase was dried with anhydrous sodium sulfate, the excess solvent was removed by reduced pressure distillation, and ethanol was used for slurry to obtain compound 66-4 about 2.82 g, with a yield of 73.4%, MS: 256.27.

[0177] Synthesis of compound 66-5:

[0178] Compound 66-4 (2.6 g, 10.0 mmol), o-diiodobenzene (3.3 g, 10.0 mmol), potassium carbonate (2.8 g, 20.0 mmol), DMF (30 mL), distilled water (3 mL) were added into a three-neck flask in turn, replaced with nitrogen for three times, then bis(triphenylphosphine)palladium dichloride (351 mg, 0.5 mmol) was added, replaced with nitrogen, and reacted at 60 °C for 10 h. The reaction was monitored by TLC. After the reaction was completed, the reaction solution was cooled to room temperature, and extracted with water and ethyl acetate. The aqueous phase was extracted with ethyl acetate again, and the combined organic phase was dried over anhydrous sodium sulfate. The excess solvent was removed by reduced pressure distillation, and the sample was column chromatographed on silica gel with PE:DCM = 15:1 (volume ratio) as the eluent to obtain compound 66-5 about 2.98 g, with a yield of 71.9%, MS: 414.42.

[0179] Synthesis of compound 66-6:

[0180] Compound 66-7 (1.4 g, 8.2 mmol), iridium trichloride trihydrate (706 mg, 2.0 mmol), distilled water (8.0 ml), DME (24.0 ml) were added into a two-neck flask in turn, replaced with nitrogen for three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and filtered under reduced pressure. The residue was washed with ethanol and distilled water to obtain compound 66-8 about 0.88 g, with a yield of 78.0%, MALDI-TOF-MS: 1128.10.

[0181] Synthesis of compound 66-8:

[0182] Compound 66-7 (1.4 g, 8.2 mmol), iridium trichloride trihydrate (706 mg, 2.0 mmol), distilled water (8.0 ml), DME (24.0 ml) were added into a two-neck flask in turn, replaced with nitrogen for three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and filtered under reduced pressure. The residue was washed with ethanol and distilled water to obtain compound 66-8 about 0.88 g, with a yield of 78.0%, MALDI-TOF-MS: 1128.10.

[0183] Synthesis of metal complex (66):

[0184] Accurately weigh into a three-necked flask, compound 66-8 (564 mg, 0.5 mmol), compound 66-6 (754 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL), replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, remove the excess solvent under reduced pressure, and recrystallize using dichloromethane / methanol to obtain about 419 mg of metal complex (66) at a yield of 40.7%, MS: 1030.48.

[0185] Synthesis Example 8: Synthesis of metal complex (93)

[0186]

[0187] Synthesis of compound 93-1:

[0188] Accurately weigh into a three-necked flask, bis(acetonitrile) palladium (II) chloride (65 mg, 0.25 mmol), bis(2-diphenylphosphinophenyl) ether (269 mg, 0.5 mmol), cesium pivalate (5.9 g, 25.0 mmol), and compound 66-2 (1.5 g, 5.0 mmol), replace nitrogen three times, and then sequentially add anhydrous N,N-dimethylacetamide (30.0 mL) and compound 13-9 (2.3 g, 6 mmol), and react at 140 °C for 24 h. Refer to the synthesis route of compound 13-10 for subsequent synthesis reaction steps to obtain about 1.75 g of compound 93-1 at a yield of 73.4%, MS: 476.99.

[0189] Synthesis of compound 93-3:

[0190] Accurately weigh into a two-necked flask, compound 93-2 (1.6 g, 8.2 mmol), iridium trichloride trihydrate (714 mg, 2.0 mmol), distilled water (8.0 mL), and DME (24.0 mL), replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, remove the reaction solution under reduced pressure, and wash with ethanol and distilled water to obtain about 0.94 g of compound 93-3 at a yield of 75.8%, MALDI-TOF-MS: 1240.75.

[0191] Synthesis of metal complex (93):

[0192] Accurately weigh compound 93-3 (620 mg, 0.5 mmol), compound 93-1 (715 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-neck flask, replace nitrogen for three times, react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, remove the excess solvent under reduced pressure, and recrystallize using dichloromethane / methanol to obtain about 409 mg of metal complex (93) with a yield of 38.6%, MS: 1060.14.

[0193] Synthesis Example 9: Synthesis of metal complex (102)

[0194]

[0195] Synthesis of compound 102-2:

[0196] Accurately weigh compound 102-1 (8.7 g, 30.0 mmol), compound 13-2 (3.7 g, 30.0 mmol), potassium carbonate (8.3 g, 60.0 mmol), N-methylacetamide (100.0 mL) into a three-neck flask, replace nitrogen for three times, and react at room temperature overnight. Refer to the synthesis route of compound 13-3 for subsequent synthesis reaction steps to obtain about 7.96 g of compound 102-2 with a yield of 79.8%, MS: 332.53.

[0197] Synthesis of compound 102-3:

[0198] Accurately weigh compound 102-2 (6.7 g, 20.0 mmol), tetrahydrofuran (20.0 mL) into a three-neck flask, replace nitrogen for three times, cool to -20 °C, slowly add compound 4-2 (15.0 mL, 2.0 M) dropwise while controlling the temperature, and then naturally warm to room temperature and react overnight. Refer to the synthesis route of compound 13-5 for subsequent synthesis reaction steps to obtain about 7.15 g of compound 102-3 with a yield of 87.1%, MS: 410.72.

[0199] Synthesis of compound 102-4:

[0200] Accurately weigh compound 102-3 (6.2 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) into a three-neck flask, replace hydrogen, and react overnight. Refer to the synthesis route of compound 13-6 for subsequent synthesis reaction steps to obtain about 3.50 g of compound 102-4 with a yield of 76.6%, MS: 304.78.

[0201] Synthesis of compound 102-5:

[0202] Accurately weigh bis(acetonitrile) palladium (II) chloride (65 mg, 0.25 mmol), bis(2- diphenylphosphinophenyl) ether (269 mg, 0.5 mmol), cesium pivalate (5.9 g, 25.0 mmol) and compound 102-4 (1.5 g, 5.0 mmol) into a three-neck flask, replace nitrogen three times. Then add anhydrous N,N-dimethylacetamide (30.0 mL) and compound 49-5 (2.0 g, 6 mmol) into the flask, respectively, and react at 140 °C for 24 h. Refer to the synthetic route of compound 13-10 for subsequent synthetic reaction steps to obtain compound 102-5 about 1.57 g, yield 73.5%, MS: 427.24.

[0203] Synthesis of compound 102-7:

[0204] Accurately weigh compound 102-6 (1.9 g, 8.2 mmol), iridium trichloride trihydrate (706 mg, 2.0 mmol), distilled water (8.0 ml), DME (24.0 ml) into a two-neck flask, replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, and reduce pressure to filter the reaction solution, and wash with ethanol and distilled water to obtain compound 102-7 about 1.12 g, yield 81.4%, MALDI-TOF-MS: 1376.52.

[0205] Synthesis of metal complex (102):

[0206] Accurately weigh compound 102-7 (688 mg, 0.5 mmol), compound 102-5 (641 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-neck flask, replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, and remove the excess solvent under reduced pressure, and recrystallize using dichloromethane / methanol to obtain metal complex (102) about 398 mg, yield 36.9%, MS: 1079.08.

[0207] Synthesis Example 10: Synthesis of metal complex (109)

[0208]

[0209] Synthesis of compound 109-2:

[0210] Accurately weighed compound 109-1 (6.2 g, 20.0 mmol), tetrahydrofuran (20.0 mL) were added into a three-neck flask, replaced with nitrogen for three times, cooled to -20 °C, compound 4-2 (15.0 mL, 2.0 M) was added dropwise slowly, then naturally warmed to room temperature, and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-3, and compound 109-2 about 6.49 g was obtained with a yield of 83.7%, MS: 387.76.

[0211] Synthesis of compound 109-3:

[0212] Accurately weighed compound 109-2 (5.8 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) were added into a three-neck flask, replaced with hydrogen, and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-4, and compound 109-3 about 3.10 g was obtained with a yield of 73.5%, MS: 281.24.

[0213] Synthesis of compound 109-4:

[0214] Accurately weighed compound 109-3 (2.8 g, 10.0 mmol), compound 4-5 (2.8 g, 11.0 mmol), potassium carbonate (2.8 g, 20.0 mmol), DMF (30 mL), distilled water (3 mL) were added into a three-neck flask, replaced with nitrogen for three times, added with bis(triphenylphosphine)-palladium dichloride (351 mg, 0.5 mmol), replaced with nitrogen, and reacted at 60 °C for 10 h. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-6, and compound 109-4 about 3.22 g was obtained with a yield of 79.2%, MS: 406.40.

[0215] Synthesis of compound 109-5:

[0216] Accurately weighed compound 109-4 (2.8 g, 7.0 mmol), 3-nitropyridine (43 mg, 0.35 mmol), tert-butyl peroxybenzoate (2.7 g, 14.0 mmol), palladium acetate (79 mg, 0.35 mmol), 1,3-dimethyl-2-imidazolidinone (10.0 mL), hexafluorobenzene (15.0 ml) were replaced with nitrogen for three times, and reacted at 90 °C for 4 h. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-7, and compound 109-5 about 2.18 g was obtained with a yield of 77.0%, MS: 404.29.

[0217] Synthesis of compound 109-6:

[0218] Compound 109-5 (1.7 g, 4.1 mmol), iridium trichloride trihydrate (353 mg, 1.0 mmol), distilled water (4.0 mL), DME (12.0 mL) were added into a three-neck flask, and replaced with nitrogen three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and filtered under reduced pressure, and washed with ethanol and distilled water to obtain compound 109-6 about 0.89 g, yield 86.0%, MALDI-TOF-MS: 2069.37.

[0219] Synthesis of metal complex (109):

[0220] Compound 109-6 (828 mg, 0.4 mmol), compound 4-9 (233 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) were added into a three-neck flask in turn, replaced with nitrogen three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the excess solvent was removed under reduced pressure, and recrystallized with dichloromethane / methanol to obtain metal complex (109) about 401 mg, yield 43.5%, MS: 1153.38.

[0221] Synthesis Example 11: Synthesis of metal complex (121)

[0222]

[0223] Synthesis of compound 121-2:

[0224] Compound 121-1 (8.7 g, 30.0 mmol), compound 13-2 (3.7 g, 30.0 mmol), potassium carbonate (8.3 g, 60.0 mmol), N-methylacetamide (100.0 mL) were added into a three-neck flask in turn, replaced with nitrogen three times, and reacted at room temperature overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 13-3 to obtain compound 121-2 about 7.81 g, yield 78.3%, MS: 332.65.

[0225] Synthesis of compound 121-3:

[0226] Compound 121-2 (6.7 g, 20.0 mmol), tetrahydrofuran (20.0 mL) were added into a three-neck flask in turn, replaced with nitrogen three times, and cooled to-20 °C, and compound 4-2 (15.0 mL, 2.0 M) was slowly added while controlling the temperature, and then naturally warmed to room temperature and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 13-5 to obtain compound 121-3 about 6.82 g, yield 83.0%, MS: 410.71.

[0227] Synthesis of compound 121-4:

[0228] Accurately weigh compound 121-3 (6.2 g, 15.0 mmol), 10% palladium on carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) into a three-neck flask, replace hydrogen gas, and react overnight. Refer to the synthetic route of compound 13-6 for subsequent synthetic reaction steps to obtain compound 121-4 about 3.36 g, yield 73.6%, MS: 304.52.

[0229] Synthesis of compound 121-6:

[0230] Accurately weigh compound 13-7 (4.7 g, 20.0 mmol), compound 121-5 (4.8 g, 20.0 mmol), sodium azide (2.6 g, 40.0 mmol), cuprous iodide (381 mg, 2.0 mmol), L-proline (461 mg, 4.0 mmol), DMSO (50.0 mL) into a three-neck flask, replace nitrogen gas three times, and react at 100°C for 24 h. Refer to the synthetic route of compound 18-5 for subsequent synthetic reaction steps to obtain compound 121-6 about 5.66 g, yield 72.9%, MS: 388.01.

[0231] Synthesis of compound 121-7:

[0232] Accurately weigh bis(acetonitrile) palladium (II) chloride (65 mg, 0.25 mmol), bis(2-diphenylphosphinophenyl) ether (269 mg, 0.5 mmol), cesium pivalate (5.9 g, 25.0 mmol), and compound 121-4 (1.5 g, 5.0 mmol) into a three-neck flask, replace nitrogen gas three times. Then, add anhydrous N,N-dimethylacetamide (30.0 mL) and compound 121-6 (2.3 g, 6 mmol) into the flask, respectively, and react at 140°C for 24 h. Refer to the synthetic route of compound 13-10 for subsequent synthetic reaction steps to obtain compound 121-7 about 2.02 g, yield 83.6%, MS: 483.29.

[0233] Synthesis of compound 121-8:

[0234] Accurately weigh compound 121-7 (2.0 g, 4.1 mmol), iridium trichloride trihydrate (353 mg, 1.0 mmol), distilled water (4.0 mL), DME (12.0 mL) into a three-necked flask, replace nitrogen for three times, react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, reduce pressure to filter the reaction solution, and wash with ethanol and distilled water to obtain compound 121-8 about 1.01 g, yield 84.7%, MALDI-TOF-MS: 2385.74.

[0235] Synthesis of metal complex (121):

[0236] Accurately weigh compound 121-8 (954 mg, 0.4 mmol), compound 4-9 (233 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-necked flask, replace nitrogen for three times, react at 110 °C for 6 h, after the reaction is completed, cool to room temperature, remove the excess solvent under reduced pressure, and recrystallize using dichloromethane / methanol to obtain metal complex (121) about 433 mg, yield 41.3%, MALDI-TOF-MS: 1311.23.

[0237] Synthesis of metal complex (135)

[0238]

[0239] Synthesis of compound 13-2:

[0240] Accurately weigh compound 135-1 (33.8 g, 120.0 mmol), compound 13-2 (14.9 g, 120.0 mmol), potassium carbonate (33.2 g, 240.0 mmol), N-methylacetamide (400.0 mL) into a three-necked flask, replace nitrogen for three times, react at room temperature overnight. Refer to the synthesis route of compound 13-3 for subsequent synthesis reaction steps to obtain compound 135-2 about 30.29 g, yield 77.5%, MS: 325.85.

[0241] Synthesis of compound 135-3:

[0242] Accurately weigh compound 135-2 (6.5 g, 20.0 mmol), tetrahydrofuran (20.0 mL) into a three-necked flask, replace nitrogen for three times, cool to -20 °C, slowly add compound 4-2 (15.0 mL, 2.0 M) under temperature control, and then naturally warm to room temperature to react overnight. Refer to the synthesis route of compound 13-5 for subsequent synthesis reaction steps to obtain compound 135-3 about 6.70 g, yield 83.1%, MS: 403.18.

[0243] Synthesis of compound 135-4:

[0244] Accurately weigh compound 135-3 (6.0 g, 15.0 mmol), 10% palladium on carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) into a three-neck flask, replace hydrogen gas, and react overnight. Refer to the synthetic route of compound 13-6 for subsequent synthetic reaction steps to obtain compound 135-4 about 3.13 g, yield 70.4%, MS: 296.48.

[0245] Synthesis of compound 135-6:

[0246] Accurately weigh compound 13-7 (4.7 g, 20.0 mmol), compound 135-5 (5.2 g, 20.0 mmol), sodium azide (2.6 g, 40.0 mmol), cuprous iodide (381 mg, 2.0 mmol), L-proline (461 mg, 4.0 mmol), DMSO (50.0 mL) into a three-neck flask, replace nitrogen gas three times, and react at 100°C for 24 h. Refer to the synthetic route of compound 18-5 for subsequent synthetic reaction steps to obtain compound 135-6 about 5.62 g, yield 68.7%, MS: 408.96.

[0247] Synthesis of compound 135-7:

[0248] Accurately weigh bis(acetonitrile) palladium (II) chloride (65 mg, 0.25 mmol), bis(2-diphenylphosphinophenyl) ether (269 mg, 0.5 mmol), cesium pivalate (5.9 g, 25.0 mmol), and compound 135-4 (1.5 g, 5.0 mmol) into a three-neck flask, replace nitrogen gas three times. Then, add anhydrous N,N-dimethylacetamide (30.0 mL) and compound 135-6 (2.5 g, 6 mmol) into the flask, respectively, and react at 140°C for 24 h. Refer to the synthetic route of compound 13-10 for subsequent synthetic reaction steps to obtain compound 135-7 about 2.11 g, yield 85.0%, MS: 496.27.

[0249] Synthesis of compound 135-9:

[0250] Accurately weigh compound 135-8 (1.4 g, 8.2 mmol), iridium trichloride trihydrate (706 mg, 2.0 mmol), distilled water (8.0 mL), DME (24.0 mL) into a three-neck flask, replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, and filter the reaction solution under reduced pressure, and wash with ethanol and distilled water to obtain compound 135-9 about 0.95 g, yield 83.3%, MALDI-TOF-MS: 1140.39.

[0251] Synthesis of metal complex (135):

[0252] Accurately weigh compound 135-9 (570 mg, 0.5 mmol), compound 135-7 (744 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) into a three-neck flask, replace nitrogen three times, and react at 110 °C for 6 h. After the reaction is completed, cool to room temperature, and remove the excess solvent under reduced pressure, and recrystallize using dichloromethane / methanol to obtain metal complex (135) about 442 mg, yield 42.9%, MS: 1030.54.

[0253] Synthesis Example 13: Synthesis of metal complex (124)

[0254]

[0255] Synthesis of compound 124-2:

[0256] Accurately weigh diisopropylamine (5.1 g, 50.0 mmol), anhydrous tetrahydrofuran (20 mL) into a three-neck flask, replace nitrogen three times, and cool to -78 °C. Drop in n-butyllithium (18.0 mL, 2.5 M), and stir at -78 °C for 10 min. Drop into a solution of compound 124-1 (11.5 g, 40.0 mmol) in anhydrous tetrahydrofuran (100.0 mL) at -78 °C. Stir the reaction at -78 °C for 1 h, add N,N-dimethylformamide (4.0 mL), and stir for 20 min. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride solution, separate the water phase and the ethyl acetate phase, dry the combined organic phase with anhydrous sodium sulfate, remove the excess solvent under reduced pressure, and recrystallize with ethyl acetate / n-hexane to obtain compound 124-2 about 8.91 g, yield 70.4%, MS: 316.53.

[0257] Synthesis of compound 124-3:

[0258] Compound 124-2 (6.3 g, 20.0 mmol), tetrahydrofuran (20.0 mL) were added into a three-neck flask successively, replaced with nitrogen for three times, cooled to -20 °C, compound 25-3 (15.0 mL, 2.0 M) was added dropwise slowly, then the temperature was increased to room temperature, and the mixture was stirred at room temperature overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-3, and compound 124-3 about 6.46 g was obtained with a yield of 79.1%, MS: 408.14.

[0259] Synthesis of compound 124-4:

[0260] Compound 124-3 (6.1 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) were added into a three-neck flask successively, replaced with hydrogen, and the mixture was stirred at room temperature overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-4, and compound 124-4 about 3.13 g was obtained with a yield of 69.0%, MS: 302.47.

[0261] Synthesis of compound 124-5:

[0262] Compound 124-4 (3.0 g, 10.0 mmol), compound 4-5 (2.8 g, 11.0 mmol), potassium carbonate (2.8 g, 20.0 mmol), DMF (30 mL), distilled water (3 mL) were added into a three-neck flask successively, replaced with nitrogen for three times, and then bis(triphenylphosphine)palladium dichloride (351 mg, 0.5 mmol) was added, replaced with nitrogen, and the mixture was stirred at 60 °C for 10 h. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-6, and compound 124-5 about 3.19 g was obtained with a yield of 74.7%, MS: 427.23.

[0263] Synthesis of compound 124-6:

[0264] Compound 124-5 (3.0 g, 7.0 mmol), 3-nitropyridine (43 mg, 0.35 mmol), tert-butyl peroxybenzoate (2.7 g, 14.0 mmol), palladium acetate (79 mg, 0.35 mmol), 1,3-dimethyl-2-imidazolidinone (10.0 mL), hexafluorobenzene (15.0 mL) were added into a three-neck flask successively, replaced with nitrogen for three times, and the mixture was stirred at 90 °C for 4 h. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-7, and compound 124-6 about 2.24 g was obtained with a yield of 75.2%, MS: 425.78.

[0265] Synthesis of compound 124-7:

[0266] Compound 124-6 (1.7 g, 4.1 mmol), iridium trichloride trihydrate (353 mg, 1.0 mmol), distilled water (4.0 mL), DME (12.0 mL) were added into a three-neck flask, and replaced with nitrogen three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and filtered under reduced pressure, and washed with ethanol and distilled water to obtain compound 124-7 about 0.94 g, yield 87.3%, MALDI-TOF-MS: 2153.36.

[0267] Synthesis of metal complex (124):

[0268] Compound 124-7 (861 mg, 0.4 mmol), compound 4-9 (233 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) were added into a three-neck flask, and replaced with nitrogen three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the excess solvent was removed under reduced pressure, and recrystallized with dichloromethane / methanol to obtain metal complex (124) about 418 mg, yield 43.7%, MALDI-TOF-MS: 1195.61.

[0269] Synthesis of metal complex (159)

[0270]

[0271] Synthesis of compound 159-2:

[0272] Compound 109-1 (6.2 g, 20.0 mmol), tetrahydrofuran (20.0 mL) were added into a three-neck flask, and replaced with nitrogen three times, and cooled to -20 °C, and compound 18-1 (15.0 mL, 2.0 M) was slowly added dropwise, and then naturally warmed to room temperature and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-3 to obtain compound 159-2 about 6.20 g, yield 78.8%, MS: 393.17.

[0273] Synthesis of compound 159-3:

[0274] Compound 159-2 (5.9 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) were added into a three-neck flask, and replaced with hydrogen, and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-4 to obtain compound 159-3 about 3.15 g, yield 73.0%, MS: 287.49.

[0275] Synthesis of compound 159-4:

[0276] Compound 159-3 (2.9 g, 10.0 mmol), compound 4-5 (2.8 g, 11.0 mmol), potassium carbonate (2.8 g, 20.0 mmol), DMF (30 mL), distilled water (3 mL) were added into a three-neck flask in turn, replaced with nitrogen for three times, then bis(triphenylphosphine)palladium dichloride (351 mg, 0.5 mmol) was added, replaced with nitrogen, and reacted at 60 °C for 10 h. The subsequent synthesis reaction steps refer to the synthetic route of compound 4-6, and compound 159-4 was obtained in about 3.24 g with a yield of 78.6%, MS: 412.23.

[0277] Synthesis of compound 159-5:

[0278] Compound 159-4 (2.9 g, 7.0 mmol), 3-nitropyridine (43 mg, 0.35 mmol), tert-butyl peroxybenzoate (2.7 g, 14.0 mmol), palladium acetate (79 mg, 0.35 mmol), 1,3-dimethyl-2-imidazolidinone (10.0 mL), hexafluorobenzene (15.0 ml) were added into a two-neck flask in turn, replaced with nitrogen for three times, and reacted at 90 °C for 4 h. The subsequent synthesis reaction steps refer to the synthetic route of compound 4-7, and compound 159-5 was obtained in about 1.85 g with a yield of 64.3%, MS: 410.72.

[0279] Synthesis of compound 159-7:

[0280] Compound 159-6 (1.7 g, 8.2 mmol), iridium trichloride trihydrate (706 mg, 2.0 mmol), distilled water (8.0 ml), DME (24.0 ml) were added into a two-neck flask in turn, replaced with nitrogen for three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure, and washed with ethanol and distilled water to obtain compound 159-7 in about 0.89 g with a yield of 68.6%, MALDI-TOF-MS: 1296.59.

[0281] Synthesis of metal complex (159):

[0282] Compound 159-7 (648 mg, 0.5 mmol), compound 159-5 (616 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) were added into a three-neck flask in turn, replaced with nitrogen for three times, and reacted at 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the excess solvent was removed under reduced pressure. Recrystallization was performed using dichloromethane / methanol to obtain metal complex (159) in about 378 mg with a yield of 37.0%, MS: 1022.65.

[0283] Synthesis of Example 15: Synthesis of metal complex (169)

[0284]

[0285] Synthesis of compound 169-2:

[0286] Accurately weighed compound 169-1 (6.2 g, 20.0 mmol), tetrahydrofuran (20.0 mL) were added into a three-neck flask, replaced with nitrogen for three times, cooled to -20 °C, and compound 169-1 (15.0 mL, 2.0 M) was added dropwise under temperature control, and then naturally warmed to room temperature for overnight reaction. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-3, and compound 169-2 was obtained about 6.56 g with a yield of 80.6%, MS: 405.66.

[0287] Synthesis of compound 169-3:

[0288] Accurately weighed compound 169-2 (6.1 g, 15.0 mmol), 10% palladium-carbon (160 mg, 1.5 mmol), methanol (60.0 mL), hydrochloric acid (0.4 mL, 1.0 M) were added into a three-neck flask, replaced with hydrogen, and reacted overnight. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-4, and compound 169-3 was obtained about 3.28 g with a yield of 73.3%, MS: 298.37.

[0289] Synthesis of compound 169-4:

[0290] Accurately weighed compound 169-3 (3.0 g, 10.0 mmol), compound 4-5 (2.8 g, 11.0 mmol), potassium carbonate (2.8 g, 20.0 mmol), DMF (30 mL), distilled water (3 mL) were added into a three-neck flask, replaced with nitrogen for three times, and then added with bis(triphenylphosphine)-palladium dichloride (351 mg, 0.5 mmol), replaced with nitrogen, and reacted at 60 °C for 10 h. The subsequent synthesis reaction steps refer to the synthesis route of compound 4-6, and compound 169-4 was obtained about 3.10 g with a yield of 73.1%, MS: 424.81.

[0291] Synthesis of compound 169-5:

[0292] Compound 169-4 (3.0 g, 7.0 mmol), 3-nitropyridine (43 mg, 0.35 mmol), tert- butyl peroxybenzoate (2.7 g, 14.0 mmol), palladium acetate (79 mg, 0.35 mmol), 1,3- dimethyl-2-imidazolidinone (10.0 mL), hexafluorobenzene (15.0 mL), replace nitrogen for three times, 90 °C for 4 h. Refer to the synthetic route of compound 4-7 for the subsequent synthetic reaction steps to obtain compound 169-5 about 1.89 g, yield 63.9%, MS: 422.75.

[0293] Synthesis of compound 169-6:

[0294] Compound 169-5 (1.7 g, 4.1 mmol), iridium trichloride trihydrate (353 mg, 1.0 mmol), distilled water (4.0 mL), DME (12.0 mL) were accurately weighed into a three-necked flask, replaced nitrogen for three times, 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure, and washed with ethanol and distilled water to obtain compound 169-6 about 0.92 g, yield 85.9%, MALDI-TOF-MS: 2141.23.

[0295] Synthesis of metal complex (169):

[0296] Compound 169-6 (857 mg, 0.4 mmol), compound 102-6 (347 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) were accurately weighed into a three-necked flask, replaced nitrogen for three times, 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the excess solvent was removed under reduced pressure, and recrystallized with dichloromethane / methanol to obtain metal complex (169) about 428 mg, yield 42.3%, MALDI-TOF-MS: 1265.52.

[0297] Synthesis of metal complex (Ref):

[0298]

[0299] Compound 13-11 (536 mg, 0.5 mmol), compound a (469 mg, 1.5 mmol), potassium carbonate (346 mg, 2.5 mmol), 2-ethoxyethanol (10.0 mL) were accurately weighed into a three-necked flask, replaced nitrogen for three times, 110 °C for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the excess solvent was removed under reduced pressure, and recrystallized with dichloromethane / methanol to obtain metal complex (Ref) about 297 mg, yield 36.6%, MS: 812.67.

[0300] Device embodiments

[0301] The structure of the OLED device provided by the present application is as follows: ITO / HI-1(10 nm) / HT-1(60 nm) / HT-2(5 nm) / EML(40 nm) / ETM:LiQ(5:5, 30 nm) / LiQ(1 nm) / Al(100 nm).

[0302] The preparation steps of the OLED-1 device are as follows:

[0303] Step a, cleaning of the ITO conductive glass substrate: the ITO conductive glass is cleaned with chloroform, ketone, and isopropanol in sequence, and then subjected to ultraviolet ozone treatment;

[0304] Step b, the cleaned conductive glass substrate is moved into a nitrogen glove box, and HI-1 is vacuum evaporated on the ITO substrate to form a hole injection layer under high vacuum (1x10 -6 -5 nm); a light-emitting auxiliary layer HT-2 is vacuum evaporated on the hole transport layer, with an evaporation thickness of 5 nm; a light-emitting layer is formed by vacuum evaporating a light-emitting host material and a light-emitting guest material on the light-emitting auxiliary layer, with a thickness of 40 nm, wherein the light-emitting host material is selected from H-Host and E-host, and the guest material is selected from metal complex (4), and the H-Host:E-host:metal complex (4) = 45:45:10 (wt%); an electron transport layer ETM:LiQ = 1:1 (wt%) is vacuum evaporated on the light-emitting layer, with a thickness of 30 nm; a LiQ electron injection layer is vacuum evaporated on the electron transport layer, with an evaporation thickness of 1 nm; then, a cathode material Al is evaporated on the electron injection layer to obtain a cathode with a thickness of 100 nm.

[0305] Step c, encapsulation: the device is encapsulated with ultraviolet hardened resin in a nitrogen glove box.

[0306] The chemical structural formulas of HI-1, HT-1, HT-2, H-Host, E-Host, and ETM are as follows:

[0307]

[0308] Preparation of OLED-2 to OLED-15 devices:

[0309] The device preparation method of OLED-2 to OLED-15 is same as OLED-1, the difference is that the light emitting guest material in the light emitting layer is selected differently, specifically, the metal complex (4) in OLED-1 is replaced by metal complex (13), metal complex (18), metal complex (25), metal complex (49), metal complex (65), metal complex (66), metal complex (93), metal complex (102), metal complex (109), metal complex (121), metal complex (124), metal complex (135), metal complex (159) and metal complex (169) respectively. For details, see Table 1.

[0310] The device preparation of OLED-Ref is as follows:

[0311] The device preparation method of OLED-Ref is same as OLED-1, the difference is that the light emitting guest material in the light emitting layer is selected differently, specifically, the metal complex (4) in OLED-1 is replaced by metal complex (Ref) respectively. For details, see Table 1.

[0312] The OLED-1 to OLED-15 and OLED-Ref devices are characterized as shown in Table 1. Among them, the luminous efficiency is the value measured under the condition that the current density is 10 mA / cm 2 .

[0313] Table 1

[0314] Light emitting layer guest material Luminous efficiency (cd / A) OLED-1 Metal complex (4) 82.66 OLED-2 Metal complex (13) 84.54 OLED-3 Metal complex (18) 81.37 OLED-4 Metal complex (25) 79.83 OLED-5 Metal complex (49) 75.32 OLED-6 Metal complex (65) 81.90 OLED-7 Metal complex (66) 80.82 OLED-8 Metal complex (93) 83.59 OLED-9 Metal complex (102) 82.05 OLED-10 Metal complex (109) 77.36 OLED-11 Metal complex (121) 78.48 OLED-12 Metal complex (124) 75.61 OLED-13 Metal complex (135) 74.29 OLED-14 Metal complex (159) 79.18 OLED-15 Metal complex (169) 75.09 OLED-Ref Metal complex (Ref) 63.29

[0315] It can be seen from Table 1 that the metal complex as a light emitting layer guest material applied to the phosphorescent OLED device has obvious improvement in luminous efficiency compared with the device comparative examples, the reason is that the iridium-based metal complex provided by the application realizes excellent material performance by selecting specific ligand units and further limiting the position and type of the substituent in the dibenzopentacyclic ring; specifically, by limiting the position and type, the spatial configuration of the molecule is effectively improved; further introducing the electron-withdrawing unit R2 adjusts the energy level and energy gap of the metal complex. Therefore, when the iridium-based metal complex is applied to the organic electroluminescent device, the luminous efficiency of the device is improved.

[0316] The technical features of the above-mentioned embodiments can be combined in any way. In order to make the description simple, all possible combinations of the technical features in the above-mentioned embodiments are not described, however, as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the present application.

[0317] The above embodiments only express several implementation ways of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation to the patent scope of the application. It should be pointed out that for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. An iridium-based metal complex, characterized in that: The metal complex has a structure as shown in general formula (I): in: Y is selected from O or S; Each time R1 appears, it is independently selected from substituted or unsubstituted cycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted aromatic groups having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5-20 cyclic atoms. Each occurrence of R2 is independently selected from -F, -CN, or -CF3; R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 Each occurrence is independently selected from -H, -D, -F, -CN, -CF3, substituted or unsubstituted straight-chain alkyl with 1-10 carbon atoms, substituted or unsubstituted branched alkyl with 3-10 carbon atoms, substituted or unsubstituted cycloalkyl with 3-10 carbon atoms, substituted or unsubstituted aromatic group with 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group with 5-20 cyclic atoms; m is selected from 1 or 2; The term "substituted or unsubstituted" indicates that the defined group is not substituted or is substituted by one or more substituents R, wherein each substituent R is independently selected from -D, -F, -CN, -CF3, straight-chain alkyl with 1-10 carbon atoms, branched alkyl with 3-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, aromatic group with 6-20 carbon atoms, heteroaromatic group with 5-20 cyclic atoms, or a combination of at least two of the above groups.

2. The iridium-based metal complex according to claim 1, characterized in that: The metal complex has a structure as shown in general formula (II-1) or (II-2):

3. The iridium-based metal complex according to claim 2, characterized in that: R1 is selected from R a Substituted or unsubstituted cycloalkyl groups having 5-10 carbon atoms; the R a Each occurrence is independently selected from -D, a straight-chain alkyl group having 1-10 carbon atoms that is substituted with deuterium or unsubstituted, or a branched alkyl group having 3-10 carbon atoms that is substituted with deuterium or unsubstituted. Alternatively, R1 is selected from R b Aromatic groups having 6-20 carbon atoms, substituted or unsubstituted, or containing R b Substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms; said R b Each occurrence is independently selected from one or a combination of at least two of the following groups: -D, -F, -CN, -CF3, straight-chain alkyl with 1-10 carbon atoms, branched alkyl with 3-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, aromatic group with 6-10 carbon atoms, heteroaromatic group with 5-10 cyclic atoms.

4. The iridium-based metal complex according to claim 1, characterized in that: R1 is selected from any of the following groups: Where: * indicates a connection site.

5. The iridium-based metal complex according to claim 3, characterized in that: The metal complex has a structure as shown in any of the general formulas (III-1)-(III-4): Wherein: each occurrence of r is independently selected from 0, 1, 2, 3, 4 or 5.

6. The iridium-based metal complex according to claim 1, characterized in that: The R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 Each occurrence is independently selected from -H, -D, -F, -CN, -CF3, deuterated or unsubstituted straight-chain alkyl groups having 1-6 carbon atoms, deuterated or unsubstituted branched alkyl groups having 3-6 carbon atoms, and R-substituted alkyl groups. c Substituted or unsubstituted cycloalkyl groups having 5-10 carbon atoms, R c Aromatic groups having 6-10 carbon atoms, substituted or unsubstituted, or containing R c Substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms; said R c Each occurrence is independently selected from one or a combination of at least two of the following groups: -D, -F, -CN, -CF3, straight-chain alkyl groups having 1-6 carbon atoms, branched alkyl groups having 3-6 carbon atoms, cycloalkyl groups having 5-10 carbon atoms, aromatic groups having 6-10 carbon atoms, heteroaromatic groups having 5-10 cyclic atoms.

7. The iridium-based metal complex according to claim 1, characterized in that: The R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 Each occurrence is independently selected from -H, -D, -F, -CN, -CF3, or any of the following groups:

8. The iridium-based metal complex according to claim 2, characterized in that: The Selected from And / or, the Selected from:

9. The iridium-based metal complex according to claim 1, characterized in that: The metal complex is selected from any of the following structures:

10. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an iridium-based metal complex as described in any one of claims 1-9.

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