Spiro-chiral tetradentate platinum (II) and / or palladium (II) complex circularly polarized luminescent material based on pyridine-carbazole-phenyl carbene and derived structure thereof, and use thereof

Abstract

The present invention relates to the technical field of the preparation of circularly polarized luminescent materials, and particularly relates to a spiro-chiral tetradentate platinum (II) and / or palladium (II) complex circularly polarized luminescent material based on pyridine-carbazole-phenyl carbene and a derived structure thereof, and the use thereof. By means of a remote central chiral fragment within the chiral substituted pyridine, the provided complex molecule can autonomously induce the entire tetradentate ligand to coordinate with metal ions in a less sterically hindered manner, so as to form an optically-pure spiro-chiral metal complex circularly polarized luminescent material. Such a spiro-chiral metal complex circularly polarized luminescent material does not require chiral resolution, and has high molecular thermodynamic stability and important applications in circularly polarized luminescent elements.

Description

Spiral chiral tetradentate platinum (II) and / or palladium (II) complex circularly polarized luminescent material based on pyridine-carbazole-phenyl carbene and its derivative structure and application thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of circularly polarized luminescent material preparation, and particularly relates to a spiral chiral tetradentate platinum (II) and / or palladium (II) complex circularly polarized luminescent material based on pyridine-carbazole-phenyl carbene and its derivative structure and application thereof. BACKGROUND

[0002] Circularly polarized luminescence (CPL) is a phenomenon that left-handed or right-handed circularly polarized light is emitted after chiral luminescent substances are excited, and therefore, the design and development of chiral luminescent materials are the key in this field. With in-depth research by researchers, so far, circularly polarized luminescent materials have important applications in the fields of 3D display, data storage, quantum computing, optical anti-counterfeiting, biological imaging and asymmetric synthesis.

[0003] The phosphorescent material of the cyclometalated platinum (II) and palladium (II) complex can make full use of all singlet and triplet excitons generated by electrically excited due to its heavy atom effect, so that the maximum theoretical quantum efficiency can be as high as 100%, and therefore, such complexes are an ideal luminescent material. The bidentate cyclometalated platinum (II) and palladium (II) complex has low rigidity, and since the two bidentate ligands are easy to twist and vibrate, the energy of the excited state material molecules is consumed in a non-radiative manner, resulting in a decrease in luminescence quantum efficiency; although the cyclometalated platinum (II) and palladium (II) complex based on tridentate ligands can improve the luminescence quantum efficiency due to the enhanced molecular rigidity, the second monodentate ligand (such as Cl - , phenoxy anion, alkyne anion, carbene, etc.) contained therein greatly reduces the chemical stability and thermal stability of the complex, and it is difficult to sublimate and purify for the preparation of OLED devices; therefore, the luminescent material based on the bidentate and tridentate ligand cyclometalated complex is not conducive to its application in stable and efficient OLED devices. The central metal ions of the divalent cyclometalated platinum (II) and palladium (II) complex are both dsp 2Hybrid, easy and four-tooth ligand coordination to form stable and rigid planar square configuration molecules; high molecular rigidity can inhibit the non-radiative relaxation caused by molecular vibration and rotation, reduce the energy loss of the excited state material molecules, and thus improve the luminescence quantum efficiency of the material molecules. Due to the steric hindrance of the two aryl groups at the end of the four-tooth ligand of the ring metal platinum (II) and palladium (II) complex, the material molecules exhibit a twisted square configuration, which theoretically has the property of helical chirality. However, the molecule is easily racemized by the up-and-down vibration of the two aryl groups at the end of the ligand in solution or during the sublimation process, and cannot be separated into its enantiomers, making it extremely difficult to obtain optically pure ring metal platinum (II) and palladium (II) complex material molecules, which makes it not have the property of circularly polarized luminescence. Therefore, how to design and develop optically pure ring metal platinum (II) and palladium (II) complex material molecules with high chemical stability and thermodynamic stability, and with the property of circularly polarized luminescence, is of great significance and great practical value for its application in circularly polarized luminescence OLED devices (CP-OLED), and is also a problem that needs to be solved in the field of CP-OLED. SUMMARY

[0004] The purpose of the present application is to provide a helical chirality four-tooth platinum (II) and / or palladium (II) complex circularly polarized luminescent material based on pyridine-carbazole-phenyl carbine and its derivative structure and its application in view of the deficiencies in the current research and development of circularly polarized luminescent materials. The provided complex molecules can induce the entire four-tooth ligand to coordinate with metal ions in a small steric hindrance manner by a chiral substituted remote center chiral fragment in pyridine, forming an optically pure helical chirality metal complex circularly polarized light luminescent material. Such helical chirality metal complex circularly polarized luminescent material does not need to be chiral separated, and has high molecular thermodynamic stability, and has important application in circularly polarized luminescent elements.

[0005] The purpose of the present application is realized by the following technical solutions:

[0006] The present application provides a helical chirality four-tooth platinum (II) and / or palladium (II) complex circularly polarized luminescent material based on pyridine-carbazole-phenyl carbine and its derivative structure, which has a chemical formula as shown in general formula (I), (I'), (II) and (II'), wherein (I) and (I'), (II) and (II') are enantiomers of each other:

[0007] Wherein, M is Pt or Pd;

[0008] L is O, S, CR x R y , C=O, SiR x R y , GeR x R y, NR z , PR z , R z P = O, AsR z , R z As = O, S = O, SO2, Se, Se = O, SeO2, BH, BR z , R z Bi = O or BiR z ; R x , R y and R z each independently is one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl;

[0009] " " is a carbon atom with a central chirality;

[0010] X 1 , X 2 , X 3 , X 4 each independently is CR 2 or N; Y 1 , Y 2 , Y 3 each independently is CR 3 or N;

[0011] Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 each independently is CR 4 or N;

[0012] R 1 , R 2 , R 3 , R 4 each independently represents mono-, di-, tri-, tetra-, penta- substitution or no substitution; R 1 - R 4each independently is one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl;

[0013] R a , R b , R m and R n each independently is one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl. Two or more adjacent substituents can optionally be joined to form a fused ring or unsaturated ring system.

[0014] Preferably, R a , R b , R m and R n R x , R y and R z each independently is one or more of hydrogen, deuterium, fluorine atom, C1-C24 alkyl, C3-C24 cycloalkyl, substituted or unsubstituted C6-C18 aryl, C1-C24 heteroalkyl, C3-C24 heterocycloalkyl, C6-C18 heteroaryl, deuterated C1-C24 alkyl, halo C1-C24 alkyl; when containing a substituent, the substituent is selected from the group consisting of hydrogen, deuterium, fluorine atom, C1-C14 alkyl.

[0015] Preferably, R x , R y and R z each independently is selected from the group consisting of hydrogen, deuterium, fluorine atom, C1-C24 alkyl, substituted or unsubstituted C6-C18 aryl, C1-C24 heteroalkyl, C6-C18 heteroaryl, deuterated C1-C24 alkyl, halo C1-C24 alkyl; when containing a substituent, the substituent is selected from the group consisting of hydrogen, deuterium, fluorine atom, C1-C14 alkyl.

[0016] Preferably, R 1each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino; when containing substitution, the substituents are selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl.

[0017] each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino; when containing substitution, the substituents are selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl. 2 each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino; when containing substitution, the substituents are selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl.

[0018] each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino; when containing substitution, the substituents are selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl. 3 each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino; when containing substitution, the substituents are selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl.

[0019] each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino; when containing substitution, the substituents are selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl. 4 each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino; when containing substitution, the substituents are selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl.

[0020] In many embodiments, two or more adjacent substituents can be linked to form a fused ring or unsaturated ring system.

[0021] In many embodiments, the chiral-at-metal, distal induction, helical, tetradentate, ring metal platinum(II) or palladium(II) complex circularly polarized luminescent material of the present application can have the following structure, but is not limited thereto, wherein "D" represents deuterium: each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino; when containing substitution, the substituents are selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazolyl.

[0022] According to one or more embodiments, the present application also provides use of the circularly polarized luminescent material having the structure of formula (I) and / or (I'), formula (II) and / or (II') as above in the preparation of an electronic device.

[0023] Further, the electronic device is a light-emitting device, a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device, or a biological imaging device. The light-emitting device is preferably an organic electroluminescent device or an organic optoelectronic device.

[0024] According to one or more embodiments, the present application also provides an organic electroluminescent device, comprising a cathode, an anode, and an organic functional layer between the two; the organic functional layer comprises a circularly polarized luminescent material having the structure of formula (I) and / or (I'), formula (II) and / or (II') as above.

[0025] Further, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises a circularly polarized luminescent material having the structure of formula (I) and / or (I'), formula (II) and / or (II'). The mass percentage of the circularly polarized luminescent material is 0.01% to 50%.

[0026] According to one or more embodiments, the present application also provides an organic optoelectronic device, comprising a first electrode; a second electrode facing the first electrode; and a luminescent material layer disposed between the first electrode and the second electrode, wherein the luminescent material layer comprises a circularly polarized luminescent material having the structure of formula (I) and / or (I'), formula (II) and / or (II'). For example, the circularly polarized luminescent material can be included in the luminescent material layer as a guest material or a dopant.

[0027] According to one or more embodiments, the present application also provides a display or lighting device, including but not limited to a full-color display, a light-emitting display device, etc.; comprising the organic electroluminescent device and / or the organic optoelectronic device described above.

[0028] The present application also provides a composition comprising a circularly polarized luminescent material having a structure as shown in formula (I) and / or (I'), formula (II) and / or (II') above.

[0029] The present application also provides a preparation comprising a circularly polarized luminescent material having a structure as shown in formula (I) and / or (I'), formula (II) and / or (II') above or the composition described above and at least one solvent. The solvent is not particularly limited, and solvents well known to those skilled in the art, such as unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents, halogenated unsaturated hydrocarbon solvents, ether solvents, or ester solvents, can be used; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetralin, n-butylbenzene, sec-butylbenzene, or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene, or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; and the ester solvent is benzoic acid alkyl ester.

[0030] The present application also provides a display or lighting device comprising one or more of the organic electroluminescent devices described above.

[0031] The present application has the following advantages:

[0032] (1) The generation of central chiral remote autonomous induction of helicity: The present application designs and develops a tetradentate ligand containing a chiral substituted pyridine central chiral fragment, which utilizes the steric hindrance effect between the terminal ligand chiral substituted pyridine and the substituted carbine to make the entire tetradentate ring metal platinum(II) and palladium(II) complex molecule into a twisted quadrilateral configuration; at the same time, the chiral substituted pyridine central chiral fragment can autonomously and remotely induce the entire tetradentate ligand to coordinate with the metal ion in a small steric hindrance manner, and form an optically pure P configuration helical tetradentate ring metal platinum(II) or palladium(II) complex circularly polarized light emitting material centered on the metal ion with diastereoselectivity, compared with which the M configuration helical tetradentate platinum(II) complex is not detected due to the large terminal ligand steric hindrance leading to thermodynamic instability.

[0033] (2) Low cost without chiral resolution: The materials used in the present application can be purchased through commercial channels and are economically available, facilitating mass production of chiral optically pure tetradentate ligands. Furthermore, the prepared helical tetradentate ring metal platinum (II) or palladium (II) complexes do not need to be separated and purified by chiral column, and are not limited by high-cost chiral resolution, greatly reducing the cost of material preparation.

[0034] (4) High chemical stability and thermal stability of the material: The designed and developed tetradentate ligand can be well coordinated with dsp 2 The hybrid platinum (II) or palladium (II) metal ion forms a thermodynamically stable and rigid square planar configuration molecule, which has high chemical stability and does not racemize in solution or solid state, losing the circularly polarized luminescent property. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 is a diagram of the design idea of optically pure metal ion-centered helical tetradentate ring metal complex circularly polarized light emitting material;

[0036] Figure 2 is a circularly polarized luminescence spectrum of optically pure P-Pt1 in dichloromethane solution at room temperature under oxygen-free conditions;

[0037] Figure 3 is a circularly polarized luminescence spectrum of optically pure P-Pt2 in dichloromethane solution at room temperature under oxygen-free conditions;

[0038] Figure 4 is a circularly polarized luminescence spectrum of optically pure P-Pt3 in dichloromethane solution at room temperature under oxygen-free conditions;

[0039] Figure 5 is a circularly polarized luminescence spectrum of optically pure P-Pt4 in dichloromethane solution at room temperature under oxygen-free conditions;

[0040] Figure 6 is a circularly polarized luminescence spectrum of optically pure P-Pt5 in dichloromethane solution at room temperature under oxygen-free conditions;

[0041] Figure 7 is a circularly polarized luminescence spectrum of optically pure P-Pt7 in dichloromethane solution at room temperature under oxygen-free conditions;

[0042] Figure 8 is a circularly polarized luminescence spectrum of optically pure P-Pt9 in dichloromethane solution at room temperature under oxygen-free conditions;

[0043] Figure 9 is a circularly polarized luminescence spectrum of optically pure P-Pt11 in dichloromethane solution at room temperature under oxygen-free conditions;

[0044] Figure 10 is a circularly polarized luminescence spectrum of optically pure P-Pt40 in dichloromethane solution at room temperature under oxygen-free conditions;

[0045] Figure 11 is an emission spectrum of optically pure helical material molecules of some of the compounds of the present application in a 5% PMMA film at room temperature in the absence of oxygen; (a) is optically pure P-Pt1 and P-Pt2, (b) is optically pure P-Pt3 and P-Pt4, (c) is optically pure P-Pt5 and P-Pt11, (d) is optically pure P-Pt21 and P-Pt40, (e) is optically pure P-Pt7 and P-Pt9, (f) is optically pure P-Pt23 and P-Pt24, (g) is optically pure P-Pt151 and P-Pt152, (h) is optically pure P-Pt16 and P-Pt25, (i) is optically pure P-Pt161 and P-Pt10;

[0046] Figure 12 is a schematic diagram of the structure of a specific organic light emitting element that can be referred to; in the figure, 110 represents a substrate, 120 represents an anode, 130 represents a hole injection layer, 140 represents a hole transport layer, 150 represents a light emitting layer, 160 represents a hole blocking layer, 170 represents an electron transport layer, 180 represents an electron injection layer, and 190 represents a cathode. DETAILED DESCRIPTION

[0047] The following describes the present application in detail. The following description of the components is sometimes based on a representative embodiment or specific example of the present application, but the present application is not limited to such an embodiment or specific example.

[0048] The following describes specific examples of the circularly polarized light emitting material of the present application represented by the above general formula, but is not to be construed as limiting the present application.

[0049] The present disclosure can be more easily understood and further advantages and benefits can be obtained, by reference to the following detailed description and examples included therein. Before the present compounds, devices, and / or methods are disclosed and described, it is to be understood that the aspects described herein are not limited to specific synthetic methods or specific reagents, as such may, in other instances, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, example methods and materials are now described.

[0050] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" can include mixtures comprising two or more components.

[0051] The term "optional" or "optionally", as used herein, means that the subsequently described event or circumstance can or can not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0052] Disclosed are components that can be used to prepare compositions described herein, as well as compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be specifically enumerated, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules containing the compound are discussed, then each and every combination and permutation of the compound is specifically contemplated unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then each and every combination and permutation of the compounds A, B, C, D, E, and F is specifically contemplated unless specifically indicated to the contrary. Likewise, any subset or combination of these is also specifically contemplated. For example, subgroups of A-E, B-F, and C-E are also specifically contemplated. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions. Thus, if there are a variety of additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods.

[0053] The linking atom used herein is capable of linking two groups, e.g., linking N and C. The linking atom can optionally have other chemical groups attached (if the valence allows). For example, an oxygen atom will not have any other chemical groups attached because the valence is already satisfied upon bonding two atoms (e.g., N or C). In contrast, when carbon is the linking atom, two additional chemical groups can be attached to the carbon atom. Suitable chemical groups include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, =0, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

[0054] The term "cyclic structure" or similar terms used herein refer to any cyclic chemical structure, including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

[0055] The term "substituted" or a similar term as used herein encompasses all permissible substituents of organic compounds. Broadly speaking, permissible substituents include all cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. For example, illustrative substituents are described below. Permissible substituents can be one or more, and the same or different for each organic compound. For organic compounds, a heteroatom (e.g., nitrogen, oxygen, sulfur, silicon, germanium, etc.) can have a hydrogen substituent, and / or any permissible substituents described herein that satisfy the valencies of the heteroatom. The present application is not intended to be limited in any way by the permissible substituents of organic compounds. Also, the term "substitution" or "substituted with" includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). In certain aspects, unless explicitly described otherwise, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0056] In defining various terms, "R 1 " "R 2 " "R 3 " through "R n " are selected from an integer from 1 to 10; and are used in the present application as generic symbols to represent various specific substituents. These symbols can be any substituents, not limited to those disclosed herein, and when they are defined as certain substituents in one instance, they can also be defined as some other substituents in another instance.

[0057] The term "alkyl" as used herein refers to a branched or unbranched, saturated hydrocarbon group of from 1 to 30 carbon atoms, preferably from 1 to 24 carbon atoms, more preferably from 1 to 12 carbon atoms. For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, thio-oxo, and thiol groups as described herein. A "lower alkyl" group is an alkyl group containing from 1 to 6 (e.g., 1 to 4) carbon atoms.

[0058] Throughout the specification, "alkyl" generally refers to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to in the application by specifying the particular substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, and the like. When "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another instance, it is not meant to imply that the term "alkyl" does not also refer to the specific term such as "alkyl alcohol" and the like.

[0059] This approach is also used for other groups described in the application. That is, when a general term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moieties can additionally be specifically identified in the application; for example, a specifically substituted cycloalkyl group can be referred to as, for example, "alkylcycloalkyl." Similarly, a substituted alkoxy group can be specifically referred to as, for example, "haloalkoxy," a specific substituted alkenyl group can be, for example, "enol," and the like. Likewise, the use of a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" does not mean that the general term does not also encompass the specific term.

[0060] The term "cycloalkyl" as used in the application is a non-aromatic carbon-based ring of 3 to 30 carbon atoms, preferably 3 to 14 carbon atoms, composed of at least three carbon atoms, which can be optionally substituted with 1 to 6 alkyl groups. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is encompassed within the meaning of the term "cycloalkyl," wherein at least one ring carbon atom is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, thio-oxo, and thiol groups as described in the application.

[0061] The terms "alkoxy" and "alkoxy group" as used in the application refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms bonded through an ether linkage; that is, "alkoxy" can be defined as — OR 1 where R 1 is an alkyl or cycloalkyl group as defined above. "Alkoxy" also encompasses the alkoxylated polymers just described; that is, the alkoxy group can be a polyether such as — OR 1 — OR 2 — OR 1 — OR 2 — OR a — OR 3where "a" is an integer from 1 to 500 and R 1 , R 2 , and R 3 are each independently alkyl, cycloalkyl, or a combination thereof.

[0062] The term "alkenyl" as used herein is a hydrocarbon group of 2 to 30 carbon atoms having at least one carbon-carbon double bond in its structure. Asymmetric structures such as (R 1 R 2 )C=C(R 3 R 4 ) include both E and Z isomers. This can be inferred in the structural formulae of the present application where an asymmetric alkene is present or it can be explicitly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0063] The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms which is composed of at least 3 carbon atoms and contains at least one carbon-carbon double bond, i.e., C=C. Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, and the like. The term "heterocycloalkenyl" is a class of cycloalkenyl as defined above and is included in the meaning of the term "cycloalkenyl" wherein at least one carbon atom of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0064] The term "alkynyl" as used herein is a hydrocarbon group of 2 to 30 carbon atoms having at least one carbon-carbon triple bond in its structure. The alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0065] The term "cycloalkynyl" as used herein is a non-aromatic carbocyclic ring containing at least 7 carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a cycloalkenyl as defined above and is included within the meaning of the term "cycloalkynyl," wherein at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl groups can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo, or thiol groups as described herein.

[0066] The term "aryl" as used herein refers to any carbocyclic aromatic group containing 60 carbon atoms and less, preferably 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. Included, but not limited to, are phenyl, naphthyl, phenanthryl, biphenyl, phenoxyphenyl, anthryl, phenanthryl, and the like. The term "aryl" also includes "heteroaryl," which is defined as an aromatic group containing at least one heteroatom within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, silicon, or germanium. Also, the term "non-heteroaryl" (which is also included within the term "aryl") defines an aromatic group containing no heteroatoms. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo, or thiol groups as described herein. The term "biaryl" is a specific type of aryl and is included within the definition of "aryl." Biaryl refers to two aryl groups joined together via a fused ring structure, as in naphthalene, or joined by one or more carbon-carbon bonds, as in biphenyl.

[0067] The term "aldehyde" as used herein is represented by the formula— C(O)H. Throughout the specification, "C(O)" is a shorthand form for carbonyl (i.e., C=O).

[0068] The term "amine" or "amino" as used herein is represented by the formula— NR 1 R 2 wherein R 1 and R 2 may be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.

[0069] The term "alkylamino" as used herein is represented by the formula— NH(-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, t-butylamino, pentylamino, isopentylamino, t-pentylamino, hexylamino, and the like.

[0070] The term "carboxylic acid" as used herein is represented by the formula— C(O)OH.

[0071] The term "ester" as used herein is represented by the formula— OC(O)R 1 or— C(O)OR 1 wherein R 1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyester" as used herein is represented by the formula— (R 1 O(O)C-R 2 -C(O)O) a — or— (R 1 O(O)C-R 2 -OC(O)) a — wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein and "a" is an integer from 1 to 500. The term "polyester" is used to describe a group that is produced by a reaction between a compound having at least two carboxylic acid groups and a compound having at least two hydroxyl groups.

[0072] The term "ether" as used herein is represented by the formula R 1 OR 2 wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyether" as used herein is represented by the formula— (R 1 O-R 2 O) a — wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

[0073] The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine, and iodine.

[0074] The term "heterocyclyl" as used herein refers to 3- to 30-membered monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems of not more than 60 carbon atoms: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including oxazolyl of 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, and 1,3,4-oxadiazolyl), piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, tetrazolyl including 1,2,3,4-tetrazolyl and 1,2,4,5-tetrazolyl, thiadiazolyl including 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, and 1,3,4-thiadiazolyl, thiazolyl, thienyl, triazinyl including 1,3,5-triazinyl and 1,2,4-triazinyl, triazolyl including 1,2,3-triazolyl and 1,3,4-triazolyl, and the like.

[0075] The term "hydroxyl" as used herein is represented by the formula—OH.

[0076] The term "keto" as used herein is represented by the formula—O 1 C(O)R 2 wherein R 1 and R 2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described herein.

[0077] The term "azido" as used herein is represented by the formula—N3.

[0078] The term "nitro" as used herein is represented by the formula—NO2.

[0079] The term "nitrile" as used herein is represented by the formula—CN.

[0080] The term "silyl" as used herein is represented by the formula—SiR 1 R 2 R 3 wherein R 1 , R 2 and R 3 may independently be hydrogen or alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described herein.

[0081] The term "sulfoxy" as used herein is represented by the formula—S(O)R 1 , —S(O)2R 1 , —OS(O)2R 1or -OS(O)2OR 1 represents, wherein R 1 may be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout the specification, "S(O)" is a shorthand notation for S=O. The term "sulfinyl" as used herein refers to a sulfinyl group represented by the formula -S(O)R 1 wherein R 1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group. The term "sulfone" as used herein refers to a sulfone group represented by the formula R 1 S(O)2R 2 wherein R 1 and R 2 may be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfoxide" as used herein refers to a sulfoxide group represented by the formula R 1 S(O)R 2 wherein R 1 and R 2 may be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

[0082] The term "mercapto" as used herein refers to a group represented by the formula -SH.

[0083] The "R 1 ", "R 2 ", "R 3 ",... "R n " (wherein n is an integer) can independently have one or more of the groups listed above. For example, if R 1 is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be replaced with a hydroxyl, alkoxy, alkyl, halogen, etc. Depending on the group selected, the first group can be embedded within the second group, or the first group can be attached (i.e., linked) to the second group. For example, for the phrase "an alkyl group comprising an amino group", the amino group can be embedded within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is embedded or attached to the second group.

[0084] The compounds described herein can contain "optionally substituted" moieties. In general, the term "substituted" whether preceded by the term "optionally" or not, means that one or more hydrogens of the designated moiety are replaced by a suitable substituent. Unless otherwise indicated, "optionally substituted" groups can have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted with more than one substituent, the substituents can be either the same or different at every position. Combinations of substituents envisioned are those that result in the formation of stable or chemically feasible compounds. Also, it is envisioned that in certain aspects, each substituent group can further optionally be substituted (i.e., further substituted or unsubstituted).

[0085] The term "fused ring" as used herein means that two substituents that are adjacent can be fused five- or six-membered aromatic or heteroaromatic rings, such as benzene, pyridine, pyrazine, pyridazine, pyrimidine, and the like, as well as saturated six- or seven-membered carbocyclic or heterocyclic rings, and the like.

[0086] Opto-electronic devices that make use of organic materials are becoming increasingly important for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential to be lower cost than alternative devices that use inorganic materials. In addition, the inherent properties of organic materials, such as their flexibility, can make them well suited for particular applications such as fabrication on flexible substrates. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic

[0087] Excitons decay from singlet excited states to the ground state to produce prompt luminescence, which is fluorescence. If excitons decay from triplet excited states to the ground state to produce luminescence, this is phosphorescence. Phosphorescent metal complexes, such as platinum complexes, have demonstrated the potential to harness both singlet and triplet excitons due to the strong spin-orbit coupling of heavy metal atoms between singlet and triplet excited states, effectively enhancing intersystem crossing (ISC), achieving 100% internal quantum efficiency. As a result, phosphorescent metal complexes are good candidates for dopants in the emissive layer of organic light emitting devices (OLEDs), and have received great attention in both academic and industrial fields. In the past decade, many achievements have been made, leading to the profitable commercialization of this technology, for example, OLEDs have been used in advanced displays for smartphones, televisions, and digital cameras.

[0088] However, to date, blue electroluminescent devices remain the most challenging area in the technology, with stability of blue devices being a major issue. It has been demonstrated that the choice of host material is very important for the stability of blue devices. However, the triplet excited state (T1) of blue light emitting materials is very high in energy, which means that the triplet excited state (T1) of the host material of blue devices should be higher. This leads to the difficulty of developing host materials for blue devices.

[0089] The metal complexes of the present invention can be tailored or tuned to specific applications that are desired to have specific emission or absorption properties. The optical properties of the metal complexes in the present disclosure can be adjusted by changing the structure of the ligand around the metal center or changing the structure of the fluorescent emitters on the ligand. For example, metal complexes with ligands having electron donating substituents or electron withdrawing substituents can generally exhibit different optical properties in the emission and absorption spectra. The color of the metal complex can be adjusted by modifying the conjugated groups on the fluorescent emitters and the ligand.

[0090] The emission of such complexes of the present invention can be adjusted, for example, from ultraviolet to near infrared, by changing the ligand or fluorescent emitter structure. A fluorescent emitter is a group of atoms in an organic molecule that can absorb energy to create a singlet excited state, which rapidly decays to produce immediate luminescence. In one aspect, the complexes of the present invention can provide emission across a large portion of the visible spectrum. In particular examples, the complexes of the present invention can emit light in the range of about 400 nm to about 700 nm. In another aspect, the complexes of the present invention have improved stability and efficiency relative to conventional emissive complexes. Additionally, the complexes of the present invention can be used as luminescent markers for, for example, biological applications, anticancer agents, emitters in organic light emitting diodes (OLEDs), or combinations thereof. In another aspect, the complexes of the present invention can be used in light emitting devices, such as compact fluorescent lamps (CFLs), light emitting diodes (LEDs), incandescent lamps, and combinations thereof.

[0091] Disclosed herein are compounds or complexed complexes comprising platinum. The terms compound or complex are used interchangeably in the present invention. Additionally, the compounds disclosed herein have a neutral charge.

[0092] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be adjusted by selecting appropriate ligands. In another aspect, the present invention can exclude any one or more of the compounds, structures, or portions thereof specifically recited herein.

[0093] The compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices, such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices, or devices capable of both light absorption and emission, and as markers for biological applications.

[0094] As described above, the disclosed compounds are platinum complexes. Also, the compounds disclosed herein can be used as host materials for OLED applications, such as full color displays.

[0095] The compounds disclosed herein can be used in various applications. As light emitting materials, the compounds can be used in organic light emitting diodes (OLEDs), light emitting devices and displays, and other light emitting devices.

[0096] The compounds of the present application can be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0097] The compounds disclosed herein can be delayed fluorescence and / or phosphorescence emitters. In one aspect, the compounds disclosed herein can be delayed fluorescence emitters. In one aspect, the compounds disclosed herein can be phosphorescence emitters. In another aspect, the compounds disclosed herein can be both delayed fluorescence and phosphorescence emitters.

[0098] The present disclosure relates to polypyridyl dinuclear cyclometalated platinum or platinum complexes that can be used as light emitting materials and host materials in OLED devices.

[0099] Unless otherwise indicated, all commercial reagents used in the following experiments were used as received without further purification. Nuclear magnetic resonance hydrogen and carbon spectra were measured in deuterated chloroform (CDCI3) or deuterated dimethyl sulfoxide (DMSO-d6) solution, hydrogen spectra were measured using a 400 or 500 megahertz nuclear magnetic resonance spectrometer, carbon spectra were measured using a 100 or 126 megahertz nuclear magnetic resonance spectrometer, and chemical shifts were referenced to tetramethylsilane (TMS) or residual solvent. If CDCI3 was used as the solvent, hydrogen and carbon spectra were measured using TMS (δ = 0.00 ppm) and CDCI3 (δ = 77.00 ppm) as internal standards, respectively. If DMSO-d6 was used as the solvent, hydrogen and carbon spectra were measured using TMS (δ = 0.00 ppm) and DMSO-d6 (δ = 39.52 ppm) as internal standards, respectively. The following abbreviations (or combinations) were used to interpret hydrogen spectra: s = singlet, d = doublet, t = triplet, q = quartet, p = pentuplet, m = multiplet, br = broad. High resolution mass spectra were measured on an ESI-QTOF mass spectrometer from Applied Biosystems, with sample ionization mode as electrospray ionization.

[0100] Example 1: Tetradentate cyclometalated platinum (II) complex Pt1 synthesis route:

[0101] (1) Synthesis of intermediate chiral 1-OMe: Into a reaction flask was added OTf (1.0 g, 3.11 mmol, 1.2 equiv), Cz-OMe (512 mg, 2.59 mmol, 1.0 equiv), Pd2(dba)3 (71 mg, 0.08 mmol, 3 mol%), XPhos (148 mg, 0.31 mmol, 12 mol%) and potassium phosphate (1.65 g, 7.77 mmol, 3.0 equiv) successively, and the flask was purged with nitrogen three times. Toluene (25 mL) was added, and the reaction was stirred at 110 °C for 42 h. The solvent was removed by distillation under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 930 mg of a yellow solid, yield 98%. 1 H NMR (500 MHz, CDC13) δ 0.76 (s, 3H), 1.34 (d, J = 10.0 Hz, 1H), 1.47 (s, 3H), 2.35 - 2.39 (m, 1H), 2.78 (dt, J = 10.0, 6.0 Hz, 1H), 2.95 (t, J = 5.5 Hz, 1H), 3.09 (d, J = 2.5 Hz, 2H), 3.89 (s, 3H), 6.92 (dd, J = 8.5, 2.5 Hz, 1H), 7.23 - 7.29 (m, 1H), 7.31 (d, J = 2.5 Hz, 1H), 7.35 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.40 (t, J = 1.0 Hz, 1H), 7.69 (dt, J = 8.0, 1.0 Hz, 1H), 7.97 (d, J = 8.5 Hz, 1H), 8.00 - 8.02 (m, 1H), 8.24 (s, 1H).

[0102] (2) Synthesis of intermediate chiral 1-OH: Into a reaction flask was added 1-OMe (930 mg, 2.53 mmol, 1.0 equiv), hydrobromic acid (48%) (9 mL), acetic acid (6 mL) successively, and the reaction was stirred at 120 °C for 16 h. The reaction was cooled to room temperature. The reaction was neutralized with aqueous NaHC03solution, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The product 1-OH was obtained as a white solid by slurrying with petroleum ether / ethyl acetate, 710 mg, yield 79%. 1H NMR (500 MHz, DMSO-d6) δ 0.70 (s, 3H), 1.24 (d, J = 9.5 Hz, 1H), 1.44 (s, 3H), 2.26 - 2.35 (m, 1H), 2.76 (dt, J = 9.5, 5.5 Hz, 1H), 2.96 (t, J = 5.5 Hz, 1H), 3.03 - 3.18 (m, 2H), 6.76 (dd, J = 8.5, 2.0 Hz, 1H), 7.13 (d, J = 2.0 Hz, 1H), 7.23 (ddd, J = 7.5, 7.0, 1.0 Hz, 1H), 7.31 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.51 (s, 1H), 7.65 (dt, J = 8.5, 1.0 Hz, 1H), 7.97 (d, J = 8.5 Hz, 1H), 8.04 (dq, J = 7.5, 1.0 Hz, 1H), 8.26 (s, 1H), 9.56 (s, 1H).

[0103] (3) Synthesis of intermediate chiral 1-Cl: Into a reaction flask was added 1-OH (670 mg, 1.89 mmol, 1.0 eq), m-chlorobromobenzene (434 mg, 2.27 mmol, 1.2 eq), cuprous iodide (36 mg, 0.19 mmol, 10 mol%), 2-picolinic acid (47 mg, 0.38 mmol, 20 mol%), and potassium phosphate (802 mg, 3.78 mmol, 2.0 eq) sequentially, and the flask was purged with nitrogen three times. Dimethyl sulfoxide (10 mL) was added. The reaction was stirred at 100 °C for 48 h, diluted with water, extracted with ethyl acetate three times, washed with brine once, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1-10:1, to give 731 mg of a white solid, yield 83%. 1H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.32 (d, J = 10.0 Hz, 1H), 1.46 (s, 3H), 2.34 - 2.38 (m, 1H), 2.77 (dt, J = 10.0, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.08 (d, J = 3.0 Hz, 2H), 6.91 (ddd, J = 8.5, 2.5, 1.0 Hz, 1H), 6.98 (dd, J = 8.5, 2.0 Hz, 1H), 7.01 (t, J = 2.0 Hz, 1H), 7.03 (ddd, J = 8.0, 2.0, 1.0 Hz, 1H), 7.22 (t, J = 8.0 Hz, 1H), 7.31 (ddd, J = 8.0, 6.0, 1.0 Hz, 1H), 7.37 (s, 1H), 7.42 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.49 (d, J = 2.0 Hz, 1H), 7.75 (dt, J = 8.5, 1.0 Hz, 1H), 8.06 - 8.08 (m, 2H), 8.21 (s, 1H).

[0104] (4) Synthesis of intermediate chiral 1-NH2: Into a reaction flask was added 1-Cl (700 mg, 1.51 mmol, 1.0 equiv), tBuNH2 (491 mg, 1.66 mmol, 1.1 equiv), Pd2(dba)3 (41 mg, 0.045 mmol, 3 mol%), John Phos (54 mg, 0.18 mmol, 12 mol%) and sodium tert-butoxide (290 mg, 3.02 mmol, 2.0 equiv) sequentially, and the flask was purged with nitrogen three times. Toluene (7 mL) was added, and the reaction was stirred at 110 °C for 17 h. The solvent was removed by distillation under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 30:1-10:1, to give 1.01 g of yellow solid with a yield of 92%. The compound was easily oxidized and used directly for the next step without characterization.

[0105] (5) Synthesis of ligand 1-L: Into a schlenk tube was added 1-NH2 (1.0 g, 1.38 mmol, 1.0 equiv), ammonium hexafluorophosphate (674 mg, 4.14 mmol, 3.0 equiv) sequentially, and the flask was purged with nitrogen three times. Triethyl orthoformate (7 mL) was added sequentially, and the reaction was carried out at 75 °C for 9 h. The solvent was removed by distillation under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1- dichloromethane / methanol = 200:1, to finally give 581 mg of ligand foam solid with a yield of 48%. 1H NMR (500 MHz, DMSO-d6) δ 0.67 (s, 3 H), 1.20 (d, J = 9.0 Hz, 1 H), 1.37 (s, 18 H), 1.42 (s, 3 H), 2.28 - 2.31 (m, 1 H), 2.74 (dt, J = 10.5, 5.5 Hz, 1 H), 2.94 (t, J = 5.5 Hz, 1 H), 3.04 - 3.13 (m, 2 H), 7.18 (dd, J = 8.5, 2.0 Hz, 1 H), 7.32 - 7.35 (m, 1 H), 7.42 - 7.48 (m, 2 H), 7.57 - 7.58 (m, 2 H), 7.62 (d, J = 2.0 Hz, 1 H), 7.64 - 7.67 (m, 3 H), 7.73 (t, J = 1.5 Hz, 1 H), 7.74 - 7.82 (m, 4 H), 7.88 - 7.90 (m, 1 H), 7.93 - 7.95 (m, 1 H), 8.22 - 8.25 (m, 2 H), 8.32 (d, J = 8.5 Hz, 1 H), 10.49 (s, 1 H). HRMS (ESI): C 51 H 51 N4O[M] + Calcd 735.4057, Found 735.4062.

[0106] (6) Synthesis of complex Pt1: Ligand 1-L (500 mg, 0.57 mmol, 1.0 eq), Pt(COD)Cl2(212 mg, 0.57 mmol, 1.0 eq) and sodium acetate (140 mg, 1.70 mmol, 3.0 eq) were added into a sealed tube successively, and the tube was purged with nitrogen for three times. Diethyleneglycol dimethyl ether (7 mL) was added, and the tube was purged with nitrogen for 30 min. The tube was heated at 120 °C for 70 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 4:1-1:1 as eluent. Complex Pt1 was obtained as yellow-green solid, 272 mg, yield 51%. 1H NMR (500 MHz, CDC13) δ 0.31 (s, 3H), 0.90 (d, J = 9.5 Hz, 1H), 1.13 (s, 9H), 1.22 (s, 3H), 1.48 (s, 9H), 2.15 - 2.18 (m, 1H), 2.22 (t, J = 5.5 Hz, 1H), 2.59 (dt, J = 10.5, 5.5 Hz, 1H), 2.68 (dd, J = 17.5, 1.5 Hz, 1H), 2.85 (dd, J = 17.5, 2.5 Hz, 1H), 7.17 (dd, J = 8.0, 1.0 Hz, 1H), 7.32 - 7.39 (m, 5H), 7.43 (d, J = 8.0 Hz, 1H), 7.45 - 7.48 (m, 2H), 7.66 - 7.76 (m, 4H), 7.79 (s, 1H), 7.86 (d, J = 8.0 Hz, 1H), 8.05 (dd, J = 7.5, 1.0 Hz, 1H), 8.24 (d, J = 8.0 Hz, 1H), 8.41 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.28, 25.66, 31.27, 31.42, 32.91, 33.05, 34.90, 35.13, 39.19, 39.25, 43.79, 107.79, 109.92, 112.00, 112.18, 112.51, 114.01, 114.24, 115.01, 115.52, 116.70, 119.97, 120.00, 122.11, 122.24, 122.32, 123.22, 123.39, 124.68, 124.89, 129.03, 132.36, 136.21, 136.32, 136.96, 138.80, 144.19, 147.83, 147.91, 150.03, 150.31, 151.40, 152.54, 152.78, 154.28, 190.58. HRMS (ESI): C51H49N4OPt [M + H] + Calcd 928.3548, Found 928.3549.

[0107] Example 2: Tetradentate cyclometalated platinum (II) complex Pt2synthesis route:

[0108] (1) Synthesis of intermediate chiral 2-Cl: Into a reaction flask was added 1-OH (4.60 g, 12.98 mmol, 1.0 eq), 1-bromo-3-tert-butyl-5-chlorobenzene (3.86 g, 15.57 mmol, 1.2 eq), cuprous iodide (248 mg, 1.30 mmol, 10 mol%), 2-picolinic acid (320 mg, 2.60 mmol, 20 mol%), and potassium phosphate (5.51 g, 25.96 mmol, 2.0 eq) sequentially, and the flask was purged with nitrogen three times. Dimethyl sulfoxide (40 mL) was added. The reaction was stirred at 100 °C for 26 h, diluted with water, extracted with ethyl acetate three times, washed with brine once, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. Purification was performed on a silica gel column eluted with petroleum ether / ethyl acetate = 20:1-10:1 to give 5.49 g of white solid in 81% yield. 1 H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.27 (s, 9H), 1.32 (d, J = 10.0 Hz, 1H), 1.46 (s, 3H), 2.34 - 2.38 (m, 1H), 2.77 (dt, J = 10.0, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.07 (d, J = 2.5 Hz, 2H), 6.78 (t, J = 2.0 Hz, 1H), 6.98 (dd, J = 8.5, 2.0 Hz, 1H), 7.01 (t, J = 2.0 Hz, 1H), 7.06 (t, J = 1.5 Hz, 1H), 7.30 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.37 (s, 1H), 7.41 (ddd, J = 8.5, 7.0, 1.0 Hz, 1H), 7.48 (d, J = 2.0 Hz, 1H), 7.75 (dt, J = 8.0, 1.0 Hz, 1H), 8.05 - 8.08 (m, 2H), 8.20 (s, 1H).

[0109] (2) Synthesis of intermediate chiral 2-NH2: Into a reaction flask was added 2-Cl (600 mg, 1.15 mmol, 1.0 eq), tBuNH2(410 mg, 1.38 mmol, 1.2 eq), Pd2(dba)3(32 mg, 0.035 mmol, 3 mol%), John Phos (41 mg, 0.14 mmol, 12 mol%), and sodium tert-butoxide (221 mg, 2.3 mmol, 2.0 eq) sequentially, and the flask was purged with nitrogen three times. Toluene (6 mL) was added. The reaction was stirred at 105 °C for 34 h, and the solvent was removed under reduced pressure. Purification was performed on a silica gel column eluted with petroleum ether / ethyl acetate = 50:1-10:1 to give 861 mg of white solid in 96% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0110] (3) Synthesis of Ligand 2-L: Into a schlenk tube was added 2-NH2(859 mg, 1.10 mmol, 1.0 equiv), ammonium hexafluorophosphate (359 mg, 2.20 mmol, 2.0 equiv) successively, and the nitrogen gas was exchanged for three times, and then triethyl orthoformate (2 mL) was added successively, and the reaction was carried out at 75 °C for 7 h. The solvent was removed by distillation under reduced pressure, and the product was separated and purified by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate = 20:1 ~ dichloromethane / methanol = 200:1, and finally the ligand 2-L was obtained as a foamy solid 930 mg with a yield of 90%. 1 H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.19 (d, J = 9.5 Hz, 1H), 1.35 (s, 18H), 1.36 (s, 9H), 1.41 (s, 3H), 2.27-2.30 (m, 1H), 2.71-2.75 (m, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.02-3.11 (m, 2H), 7.18 (dd, J = 8.5, 2.0 Hz, 1H), 7.29-7.34 (m, 2H), 7.44 (ddd, J = 8.5, 6.0, 1.5 Hz, 1H), 7.52 (t, J = 2.0 Hz, 1H), 7.56 (s, 1H), 7.60 (d, J = 2.0 Hz, 1H), 7.62 (d, J = 1.5 Hz, 2H), 7.64 (t, J = 2.0 Hz, 1H), 7.72 (t, J = 2.0 Hz, 1H), 7.73-7.77 (m, 3H), 7.85-7.90 (m, 2H), 8.21-8.23 (m, 2H), 8.30 (d, J = 8.5 Hz, 1H), 10.44 (s, 1H). HRMS (ESI): C 55 H 59 N4O[M] + Calcd 791.4683,Found 791.4688.

[0111] (4) Synthesis of Complex Pt2: Ligand 2-L (900 mg, 0.96 mmol, 1.1 equiv), Pt(COD)Cl2(327 mg, 0.87 mmol, 1.0 equiv) and sodium acetate (215 mg, 2.62 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (10 mL), and the nitrogen gas was bubbled for 30 min, and the reaction was carried out at 120 °C for 70 h. The solvent was removed by distillation under reduced pressure, and the product was separated and purified by silica gel column chromatography, and the eluent was petroleum ether / dichloromethane = 4:1 ~ 1:1, and finally the complex Pt2 was obtained as a yellow-green solid 693 mg with a yield of 81%. 1H NMR (500 MHz, CDC13) δ 0.32 (s, 3 H), 0.92 (d, J = 9.5 Hz, 1 H), 1.14 (s, 9 H), 1.23 (s, 3 H), 1.50 (s, 9 H), 1.52 (s, 9 H), 2.16 - 2.20 (m, 1 H), 2.22 (t, J = 5.5 Hz, 1 H), 2.58 - 2.63 (m, 1 H), 2.69 (d, J = 18.0 Hz, 1 H), 2.86 (dd, J = 18.0, 2.5 Hz, 1 H), 7.23 (d, J = 1.5 Hz, 1 H), 7.34 - 7.40 (m, 4 H), 7.45 (d, J = 8.0 Hz, 1 H), 7.48 - 7.51 (m, 2 H), 7.68 (s, 1 H), 7.71 - 7.77 (m, 3 H), 7.84 (s, 1 H), 7.87 (d, J = 8.0 Hz, 1 H), 8.06 (dd, J = 7.5, 1.5 Hz, 1 H), 8.23 (d, J = 8.0 Hz, 1 H), 8.41 (s, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.27, 25.70, 31.31, 31.48, 31.67, 32.94, 33.04, 34.89, 35.16, 39.26, 39.29, 43.84, 105.85, 106.30, 111.05, 111.97, 112.23, 112.48, 114.02, 115.09, 115.17, 115.47, 116.61, 119.97, 122.10, 122.30, 123.17, 123.37, 124.89, 129.08, 132.43, 136.31, 136.36, 136.95, 138.87, 144.37, 147.78, 147.87, 148.51, 149.86, 150.35, 151.42, 152.11, 152.80, 154.53, 190.84. HRMS (ESI): C 55 H 57 N4OPt [M + H] + Calcd 984.4175, Found 984.4177.

[0112] Example 3: Tetradentate cyclometalated platinum (II) complex Pt3 synthesis route:

[0113] (1) Synthesis of intermediate chiral 3-NH2: Into a reaction flask was added 2-Cl (600 mg, 1.15 mmol, 1.0 eq), diPr-NH2 (370 mg, 1.38 mmol, 1.2 eq), Pd2(dba)3 (32 mg, 0.035 mmol, 3 mol%), John Phos (41 mg, 0.14 mmol, 12 mol%) and NaOt-Bu (221 mg, 2.3 mmol, 2.0 eq) successively, and the flask was purged with nitrogen three times, and toluene (6 mL) was added. The reaction was carried out at 105 °C for 34 h, and the product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 830 mg of a white solid, in 96% yield. The compound was easily oxidized and used directly in the next step without characterization.

[0114] (2) Synthesis of ligand 3-L: The synthesis was carried out according to the same procedure as 1-L in Example 1, with 3-NH2 (828 mg, 1.10 mmol, 1.0 eq), ammonium hexafluorophosphate (359 mg, 2.20 mmol, 2.0 eq), and triethyl orthoformate (2 mL) as the starting materials. The final product was obtained as a solid in 91% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.01 (d, J = 7.0 Hz, 6H), 1.11 (d, J = 7.0 Hz, 6H), 1.19 (d, J = 9.6 Hz, 1H), 1.36 (s, 9H), 1.41 (s, 3H), 2.28 - 2.37 (m, 3H), 2.73 (dt, J = 10.0, 6.0 Hz, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.02 - 3.12 (m, 2H), 7.20 (dd, J = 8.5, 2.0 Hz, 1H), 7.32 - 7.35 (m, 1H), 7.44 - 7.47 (m, 2H), 7.50 (t, J = 2.0 Hz, 1H), 7.51 - 7.53 (m, 1H), 7.56 (s, 1H), 7.57 (s, 2H), 7.61 (d, J = 2.0 Hz, 1H), 7.64 (t, J = 1.5 Hz, 1H), 7.71 - 7.78 (m, 4H), 7.99 (d, J = 8.5 Hz, 1H), 8.20 (s, 1H), 8.23 (dt, J = 7.5, 1.0 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H), 10.63 (s, 1H). HRMS (ESI): C 53 H 55 N4O[M] + Calcd 763.4371, Found 763.4377.

[0115] (3) Synthesis of complex Pt3: The synthetic procedure was identical to that of Pt1 in Example 1, with the reaction charge of ligand 3-L (900 mg, 0.99 mmol, 1.1 equiv), Pt(COD)Cl2(337 mg, 0.90 mmol, 1.0 equiv), sodium acetate (222 mg, 2.70 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (10 mL), and the final product was obtained as a yellow-green solid 732 mg in 85% yield. 1 H NMR (500 MHz, CDC13) δ 0.29 (s, 3H), 0.60 (d, J = 6.5 Hz, 3H), 0.97 (d, J = 7.0 Hz, 3H), 1.15 (d, J = 10.0 Hz, 1H), 1.17 (d, J = 6.5 Hz, 3H), 1.27 (s, 3H), 1.31 (d, J = 6.5 Hz, 3H), 1.50 (s, 9H), 2.16 - 2.23 (m, 1H), 2.34 (t, J = 5.5 Hz, 1H), 2.50 - 2.57 (m, 1H), 2.66 - 2.71 (m, 2H), 2.92 (dd, J = 18.5, 3.0 Hz, 1H), 3.68 - 3.75 (m, 1H), 6.91 (d, J = 8.0 Hz, 1H), 7.08 (dd, J = 7.5, 1.0 Hz, 1H), 7.21 (d, J = 2.0 Hz, 1H), 7.23 - 7.31 (m, 2H), 7.33 - 7.45 (m, 5H), 7.66 (d, J = 2.0 Hz, 1H), 7.69 (s, 1H), 7.74 (d, J = 8.0 Hz, 2H), 7.98 (dd, J = 7.0, 1.0 Hz, 1H), 8.13 (d, J = 9.5 Hz, 2H). 13 C NMR (126 MHz, CDC13) δ 21.21, 21.25, 24.04, 25.32, 25.90, 28.26, 28.47, 31.63, 32.59, 33.14, 34.85, 38.70, 38.97, 43.36, 106.03, 107.77, 111.43, 111.69, 112.12, 112.85, 114.28, 114.39, 115.95, 116.31, 120.05, 122.05, 122.90, 123.56, 123.97, 124.56, 129.21, 130.14, 131.40, 132.58, 136.86, 137.68, 139.17, 144.84, 145.97, 147.81, 147.93, 148.07, 148.67, 149.23, 149.56, 154.11, 155.62, 191.87. HRMS (ESI): C 53 H53 N4OPt[M+H] + Calcd 956.3862, Found 956.3864.

[0116] Example 4: Tetradentate cyclometalated platinum(II) complex Pt4 synthesis route:

[0117] (1) Synthesis of intermediate chiral 4-NH2: Into a reaction flask was added 2-Cl (600 mg, 1.15 mmol, 1.0 eq), PytBuNH2(376 mg, 1.27 mmol, 1.1 eq), Pd2(dba)3(32 mg, 0.035 mmol, 3 mol%), BrettPhos (75 mg, 0.14 mmol, 12 mol%) and sodium tert-butoxide (221 mg, 2.3 mmol, 2.0 eq) successively, and the flask was purged with nitrogen three times, and then toluene (6 mL) was added. The reaction was carried out at 105 °C for 21 h, and the product was isolated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 850 mg of white solid in 95% yield. The compound was easily oxidized and used directly in the next step without characterization.

[0118] (2) Synthesis of ligand 4-L: The synthesis was performed according to the procedure described in Example 1 for the synthesis of 1-L, with 4-NH2(850 mg, 1.09 mmol, 1.0 eq), ammonium hexafluorophosphate (354 mg, 2.17 mmol, 2.0 eq), and triethyl orthoformate (3 mL) as the starting materials. The final product was obtained as a solid in 84% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.19 (d, J = 9.5 Hz, 1H), 1.35 (s, 9H), 1.36 (s, 18H), 1.41 (s, 3H), 2.27 - 2.30 (m, 1H), 2.73 (dt, J = 10.0, 6.0 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.02 - 3.10 (m, 2H), 7.14 (dd, J = 8.5, 2.0 Hz, 1H), 7.32 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.42 - 7.46 (m, 2H), 7.49 (t, J = 2.0 Hz, 1H), 7.56 (s, 1H), 7.58 (d, J = 2.5 Hz, 1H), 7.64 (d, J = 1.5 Hz, 2H), 7.73 - 7.77 (m, 3H), 7.83 (dd, J = 8.5, 4.5 Hz, 1H), 8.20 - 8.22 (m, 2H), 8.30 (d, J = 8.5 Hz, 1H), 8.43 (dd, J = 8.5, 1.5 Hz, 1H), 8.80 (dd, J = 5.0, 1.5 Hz, 1H), 10.72 (s, 1H). HRMS (ESI): C 54 H 58 N5O[M] + Calcd 792.4636, Found 792.4635.

[0119] (3) Synthesis of complex Pt4: The synthesis procedure was referenced to the synthesis of Pt1 in Example 1. The reaction was carried out with ligand 4-L (750 mg, 0.80 mmol, 1.1 equiv), Pt(COD)Cl2(272 mg, 0.73 mmol, 1.0 equiv), sodium acetate (179 mg, 2.18 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (6 mL). The final product was 641 mg of yellow solid with 89% yield. 1H NMR (500 MHz, CDC13) δ 0.31 (s, 3 H), 0.88 (d, J = 9.5 Hz, 1 H), 1.13 (s, 9 H), 1.22 (s, 3 H), 1.49 (s, 9 H), 1.51 (s, 9 H), 2.17 - 2.21 (m, 2 H), 2.58 (dt, J = 10.0, 5.5 Hz, 1 H), 2.68 (d, J = 18.0 Hz, 1 H), 2.83 - 2.87 (m, 1 H), 7.24 (d, J = 2.0 Hz, 1 H), 7.29 (dd, J = 8.0, 5.0 Hz, 1 H), 7.33 - 7.39 (m, 3 H), 7.46 (d, J = 8.0 Hz, 1 H), 7.62 (s, 1 H), 7.73 - 7.77 (m, 3 H), 7.87 (d, J = 8.0 Hz, 2 H), 8.05 (dd, J = 7.0, 2.0 Hz, 1 H), 8.39 (s, 1 H), 8.59 (dd, J = 5.0, 1.5 Hz, 1 H), 8.79 (d, J = 2.0 Hz, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.27, 25.68, 31.31, 31.44, 31.68, 32.93, 33.00, 35.00, 35.13, 39.27, 39.31, 43.82, 105.29, 108.68, 111.17, 112.64, 114.00, 114.97, 115.19, 115.42, 116.82, 118.24, 118.88, 119.18, 119.96, 122.16, 122.51, 123.40, 128.52, 129.07, 136.14, 137.00, 138.85, 144.34, 145.45, 146.36, 147.87, 147.92, 148.64, 149.01, 150.22, 151.75, 154.66, 192.68. HRMS (ESI): C 53 H 53 N4OPt [M + H] + Calcd 956.3862, Found 956.3864.

[0120] Example 5: Tetradentate cyclometalated platinum (II) complex Pt5 synthesis route:

[0121] (1) Synthesis of intermediate chiral 5-NH2: Into a reaction vial was added 2-Cl (300 mg, 0.58 mmol, 1.0 equiv), PydiPrNH2 (212 mg, 0.75 mmol, 1.3 equiv), Pd2(dba)3 (16 mg, 0.017 mmol, 3 mol%), BrettPhos (19 mg, 0.035 mmol, 6 mol%) and sodium tert-butoxide (111 mg, 1.15 mmol, 2.0 equiv) successively, and the vial was purged with nitrogen for three times. Toluene (3 mL) was added. The reaction was stirred at 100 °C for 16 h. The reaction mixture was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 432 mg of white solid in 97% yield. The compound was easily oxidized and used directly for the next step without characterization.

[0122] (2) Synthesis of ligand 5-L: The synthesis was performed according to the procedure described in the synthesis of 1-L in Example 1, with 5-NH2 (430 mg, 0.56 mmol, 1.0 equiv), ammonium hexafluorophosphate (183 mg, 1.12 mmol, 2.0 equiv), and triethyl orthoformate (3 mL). The final product was obtained as a solid in 87% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.66 (s, 3H), 0.99 (d, J = 6.5 Hz, 6H), 1.13 (d, J = 7.0 Hz, 6H), 1.16 (d, J = 7.0 Hz, 1H), 1.36 (s, 9H), 1.41 (s, 3H), 2.29 - 2.31 (m, 1H), 2.34 - 2.42 (m, 2H), 2.60 (s, 3H), 2.72 - 2.76 (m, 1H), 2.93 (t, J = 5.0 Hz, 1H), 3.04 - 3.13 (m, 2H), 7.20 (dd, J = 8.5, 2.0 Hz, 1H), 7.34 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.44 - 7.48 (m, 2H), 7.50 (t, J = 2.0 Hz, 1H), 7.53 (d, J = 7.5 Hz, 2H), 7.58 (s, 1H), 7.62 (d, J = 2.5 Hz, 1H), 7.64 (t, J = 2.0 Hz, 1H), 7.68 - 7.73 (m, 2H), 7.77 (dt, J = 8.5, 1.0 Hz, 1H), 8.20 (s, 1H), 8.24 (dt, J = 7.5, 1.0 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H), 8.45 (d, J = 8.5 Hz, 1H), 10.74 (s, 1H). HRMS (ESI): C 53 H 56 N5O[M] +Calcd 778.4479, Found 778.4482.

[0123] (3) Synthesis of complex Pt5: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1, with ligand 5-L (360 mg, 0.39 mmol, 1.0 equiv), Pt(COD)Cl2(146 mg, 0.39 mmol, 1.0 equiv), sodium acetate (96 mg, 1.17 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (6 mL). The final product was obtained as a yellow solid 238 mg, 63% yield. 1 H NMR (500 MHz, CDC13) δ 0.30 (s, 3H), 0.60 (d, J = 6.5 Hz, 3H), 0.98 (d, J = 7.0 Hz, 3H), 1.21 (d, J = 9.5 Hz, 1H), 1.23 (d, J = 6.5 Hz, 3H), 1.28 (s, 3H), 1.31 (d, J = 7.0 Hz, 3H), 1.50 (s, 9H), 2.19 - 2.23 (s, 1H), 2.39 (t, J = 5.0 Hz, 1H), 2.43 - 2.48 (m, 1H), 2.53 (s, 3H), 2.66 - 2.76 (m, 2H), 2.95 (dd, J = 18.5, 3.0 Hz, 1H), 3.75 - 3.81 (m, 1H), 7.06 (dd, J = 7.5, 1.5 Hz, 1H), 7.21 - 7.23 (m, 2H), 7.31 - 7.41 (m, 5H), 7.54 (d, J = 2.0 Hz, 1H), 7.70 (s, 1H), 7.76 - 7.79 (m, 2H), 8.01 (d, J = 7.5 Hz, 1H), 8.09 (s, 1H), 8.25 (d, J = 8.5 Hz, 1H). 13C NMR (126 MHz, CDC13) δ 20.86, 21.24, 23.97, 24.16, 24.84, 24.92, 25.88, 28.65, 28.77, 31.59, 32.53, 33.15, 34.81, 38.65, 38.96, 43.35, 105.42, 107.83, 111.69, 112.81, 114.31, 114.39, 115.87, 115.97, 116.50, 118.97, 119.29, 120.04, 122.03, 122.08, 123.40, 123.64, 124.14, 129.12, 130.01, 131.98, 136.95, 139.15, 144.75, 146.29, 147.32, 147.90, 148.05, 148.77, 149.05, 149.20, 149.50, 153.45, 154.07, 155.47, 192.84. HRMS (ESI): C 53 H 54 N5OPt[M+H] + Calcd 971.3971, Found 971.3980.

[0124] Example 6: Tetradentate cyclometalated platinum(II) complex Pt7 synthesis route:

[0125] (1) Synthesis of intermediate dBr-tBuNH2: Into a reaction flask was added p-tert-butylaniline (15.0 g, 100 mmol, 1.0 equiv), dissolved in dichloromethane (150 mL), N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equiv), and the reaction was allowed to proceed at room temperature for 48 hours. Concentration and silica gel column chromatography afforded 25.6 g of a red liquid in 80% yield. Directly used in the subsequent reaction.

[0126] (2) Synthesis of intermediate dBr-tBuNO2: Into a reaction flask was added dBr-tBuNH2(5 g, 16.3 mmol, 1.0 equiv) dissolved in N-methylpyrrolidone (50 mL), sodium hydride (1.96 g, 49 mmol, 3.0 equiv), and o-fluoronitrobenzene (3.45 g, 24.5 mmol, 1.5 equiv), and the reaction was allowed to proceed at room temperature for 48 hours. Concentration and silica gel column chromatography afforded 5.08 g of a yellow solid in 70% yield. 1H NMR (500 MHz, CDC13) δ 1.35 (s, 9H), 6.45 (dd, J = 8.5, 1.0 Hz, 1H), 6.79 - 6.87 (m, 1H), 7.31 - 7.41 (m, 1H), 7.66 (s, 2H), 8.25 (dd, J = 8.5, 1.5 Hz, 1H), 9.22 (s, 1H).

[0127] (3) Synthesis of intermediate dBr-tBu2NH2: Into a reaction flask was added dBr-tBuNO2(4.8 g, 11.2 mmol, 1.0 eq), stannous chloride (10.1 g, 44.8 mmol, 4.0 eq), ethyl acetate (50 mL) and ethanol (50 mL). The reaction was stopped after 24 h at 78 °C, concentrated, and column chromatography on silica gel to give white solid 3.43 g, 90% yield. 1 H NMR (500 MHz, DMSO-d6) δ 1.35 (s, 9H), 4.44 (s, 2H), 5.57 (s, 1H), 6.05 (dd, J = 8.0, 1.5 Hz, 1H), 6.12 (td, J = 7.5, 1.5 Hz, 1H), 6.25 (td, J = 7.6, 1.5 Hz, 1H), 6.31 (dd, J = 7.5, 1.5 Hz, 1H), 7.20 - 7.16 (m, 2H), 7.25 (t, J = 7.5 Hz, 4H), 7.28 (s, 2H), 7.43 - 7.41 (m, 4H).

[0128] (4) Synthesis of intermediate dPhNH2: Into a reaction flask was added dBr-tBu2NH2(3.2 g, 8 mmol, 1.0 eq), phenylboronic acid (2.93 g, 24 mmol, 3.0 eq), palladium tetrakis(triphenylphosphine) (185 mg, 0.16 mmol, 0.02 eq), sodium carbonate (2.8 g, 20 mmol, 2.5 eq), dioxane (40 mL) and water (15 mL). The reaction was stopped after 24 h at 90 °C, concentrated, and column chromatography on silica gel to give white solid 2.66 g, 90% yield. 1 H NMR (500 MHz, DMSO-d6) δ 1.35 (s, 9H), 4.44 (s, 2H), 5.57 (s, 1H), 6.05 (dd, J = 8.0, 1.5 Hz, 1H), 6.12 (td, J = 7.5, 1.5 Hz, 1H), 6.25 (td, J = 7.6, 1.5 Hz, 1H), 6.31 (dd, J = 7.5, 1.5 Hz, 1H), 7.20 - 7.16 (m, 2H), 7.25 (t, J = 7.5 Hz, 4H), 7.28 (s, 2H), 7.43 - 7.41 (m, 4H).

[0129] (5) Synthesis of intermediate chiral 7-NH2: Into a reaction flask was added 2-Cl (600 mg, 1.15 mmol, 1.0 eq), dPhNH2 (542 mg, 1.38 mmol, 1.2 eq), Pd2(dba)3 (32 mg, 0.035 mmol, 3 mol%), JohnPhos (41 mg, 0.14 mmol, 12 mol%) and NaOt-Bu (221 mg, 2.3 mmol, 2.0 eq) successively, and the flask was purged with nitrogen three times, and toluene (6 mL) was added. The reaction was carried out at 105 °C for 18 h, and the product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 950 mg of white solid, yield 94%. The compound was easily oxidized and was used directly in the next step without characterization.

[0130] (6) Synthesis of ligand 7-L: The synthesis was carried out according to the same procedure as 1-L in Example 1, and the reaction was carried out using 7-NH2 (950 mg, 1.10 mmol, 1.0 eq), ammonium hexafluorophosphate (353 mg, 2.20 mmol, 2.0 eq) and triethyl orthoformate (3 mL). Finally, 1.0 g of solid was obtained, yield 90%. 1 H NMR (500 MHz, DMSO-d6) δ 0.64 (s, 3H), 1.19 (d, J = 9.5 Hz, 1H), 1.30 (s, 9H), 1.41 (s, 3H), 1.44 (s, 9H), 2.27-2.31 (m, 1H), 2.71-2.75 (m, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.02-3.12 (m, 2H), 6.75 (t, J = 2.0 Hz, 1H), 6.95 (t, J = 2.0 Hz, 1H), 7.08-7.16 (m, 11H), 7.33-7.37 (m, 1H), 7.44-7.48 (m, 3H), 7.51-7.58 (m, 4H), 7.69-7.72 (m, 3H), 7.78 (d, J = 8.5 Hz, 1H), 8.20 (s, 1H), 8.26 (dt, J = 7.5, 1.0 Hz, 1H), 8.34 (d, J = 8.5 Hz, 1H), 10.22 (s, 1H). HRMS (ESI): C 63 H 59 N4O[M] + Calcd 887.4678, Found 887.4678.

[0131] (7) Synthesis of complex Pt7: The synthetic procedure was identical to that of Pt1 in Example 1 with the reaction charge of ligand 7-L (900 mg, 0.87 mmol, 1.1 equiv), Pt(COD)Cl2(296 mg, 0.79 mmol, 1.0 equiv), sodium acetate (195 mg, 2.38 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (8 mL), and the final product was obtained as a yellow solid 641 mg in 75% yield. 1 H NMR (500 MHz, CDC13) δ 0.24 (s, 3H), 1.08 (s, 3H), 1.20 (d, J = 9.5 Hz, 1H), 1.42 (s, 9H), 1.45 (s, 9H), 2.03 (t, J = 5.5 Hz, 1H), 2.14 - 2.17 (m, 1H), 2.47 - 2.52 (m, 1H), 2.69 (d, J = 18.0 Hz, 1H), 2.84 - 2.89 (m, 1H), 6.16 (t, J = 7.5 Hz, 2H), 6.47 (t, J = 7.5 Hz, 1H), 6.52 (d, J = 4.5 Hz, 2H), 6.84 (d, J = 8.0 Hz, 1H), 7.02 (t, J = 7.5 Hz, 1H), 7.09 (d, J = 1.5 Hz, 1H), 7.19 - 7.28 (m, 4H), 7.31 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 2.0 Hz, 1H), 7.40 (t, J = 7.0 Hz, 1H), 7.45 - 7.51 (m, 3H), 7.61 (d, J = 7.0 Hz, 2H), 7.74 (s, 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 8.11 (d, J = 7.0 Hz, 1H), 8.92 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.20, 25.70, 31.28, 31.60, 32.08, 33.06, 34.75, 34.97, 39.40, 39.63, 42.89, 105.73, 107.50, 110.67, 111.24, 111.98, 112.31, 113.17, 114.57, 115.09, 115.90, 116.76, 120.12, 122.06, 122.64, 123.61, 123.93, 125.54, 127.07, 127.43, 127.70, 128.08, 128.25, 128.68, 128.95, 129.47, 129.60, 131.79, 136.39, 136.75, 138.01, 138.69, 142.32, 144.43, 146.86, 147.63, 149.61, 150.26, 152.27, 152.47, 154.64, 193.96. HRMS (ESI): C 63 H 57 N4OPt[M+H] + Calcd 1080.4175, Found 1080.4191.

[0132] Example 7: Tetradentate cyclometalated platinum(II) complex Pt8 synthesis route:

[0133] (1) Synthesis of intermediate chiral 8-NH2: Into a reaction flask was added 2-Cl (400 mg, 0.77 mmol, 1.0 equiv), dPhNNH2 (333 mg, 0.92 mmol, 1.2 equiv), Pd2(dba)3 (21 mg, 0.023 mmol, 3 mol%), JohnPhos (27 mg, 0.092 mmol, 12 mol%) and sodium tert-butoxide (148 mg, 1.54 mmol, 2.0 equiv) successively, and the flask was purged with nitrogen three times, and toluene (5 mL) was added. The mixture was stirred at 85 °C for 12 h, and then separated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 550 mg of white solid in 85% yield. The compound was easily oxidized and used directly in the next step without characterization.

[0134] (2) Synthesis of ligand 7-L: The synthesis was performed according to the procedure described in Example 1 for the synthesis of 1-L, with 7-NH2 (550 mg, 0.65 mmol, 1.0 equiv), ammonium hexafluorophosphate (212 mg, 1.30 mmol, 2.0 equiv), and triethyl orthoformate (3 mL) as the starting materials to give 230 mg of solid in 35% yield. 1H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.31 (d, J = 9.5 Hz, 1H), 1.32 (s, 9H), 1.45 (s, 3H), 2.35 - 2.38 (m, 1H), 2.77 (dt, J = 10.0, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.10 (d, J = 2.0 Hz, 2H), 6.50 (t, J = 2.0 Hz, 1H), 6.72 (t, J = 2.0 Hz, 1H), 7.05 (dd, J = 8.5, 2.0 Hz, 1H), 7.09 - 7.21 (m, 11H), 7.31 - 7.36 (m, 2H), 7.40 - 7.52 (m, 4H), 7.54 - 7.60 (m, 1H), 7.62 (d, J = 2.0 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.89 (s, 2H), 8.12 (d, J = 7.5 Hz, 1H), 8.16 (d, J = 8.5 Hz, 1H), 8.20 (s, 1H), 9.38 (s, 1H).

[0135] (3) Synthesis of complex Pt8: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1, with ligand 8-L (210 mg, 0.21 mmol, 1.0 equiv), Pt(COD)Cl2(82 mg, 0.22 mmol, 1.05 equiv), sodium acetate (52 mg, 0.63 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (5 mL). The final product was obtained as a yellow solid 188 mg, 85% yield. 1H NMR (500 MHz, CDC13) δ 0.26 (s, 3H), 1.12 (s, 3H), 1.31 (d, J = 10.0 Hz, 1H), 1.45 (s, 9H), 1.96 (t, J = 5.0 Hz, 1H), 2.19 - 2.25 (m, 1H), 2.69 - 2.75 (m, 2H), 3.04 (dd, J = 18.0, 3.0 Hz, 1H), 6.32 (t, J = 7.5 Hz, 2H), 6.53 - 6.61 (m, 3H), 6.79 (d, J = 8.0 Hz, 1H), 7.06 (t, J = 7.5 Hz, 1H), 7.13 (d, J = 1.5 Hz, 1H), 7.24 - 7.30 (m, 5H), 7.43 (t, J = 7.5 Hz, 1H), 7.47 - 7.58 (m, 4H), 7.62 (d, J = 2.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.84 (d, J = 2.0 Hz, 1H), 7.88 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 8.11 (dd, J = 16.5, 8.0 Hz, 2H), 8.68 (s, 1H). MS: 1049.35 [M+H] + .

[0136] Example 8: Tetradentate cyclometalated platinum (II) complex Pt9 synthesis route:

[0137] (1) Synthesis of intermediate chiral 9-NH2: Into a reaction flask was added 2-Cl (600 mg, 1.15 mmol, 1.0 eq), dPhFNH2 (591 mg, 1.38 mmol, 1.2 eq), Pd2(dba)3 (32 mg, 0.035 mmol, 3 mol%), JohnPhos (41 mg, 0.14 mmol, 12 mol%) and sodium tert-butoxide (221 mg, 2.3 mmol, 2.0 eq) successively, and the flask was purged with nitrogen three times, then toluene (6 mL) was added. The reaction was carried out at 105 °C for 18 h, and the product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 450 mg of white solid, yield 43%. The compound was easily oxidized and used directly in the next step without characterization.

[0138] (2) Synthesis of ligand 9-L: The synthesis was performed according to the same procedure as 1-L in Example 1, with 9-NH2 (450 mg, 0.49 mmol, 1.0 eq), ammonium hexafluorophosphate (161 mg, 0.99 mmol, 2.0 eq), and triethyl orthoformate (2 mL) as the reactants. Finally, 441 mg of solid was obtained, yield 84%. 1H NMR (500 MHz, DMSO-d6) δ 0.63 (s, 3H), 1.18 (d, J = 9.5 Hz, 1H), 1.29 (s, 9H), 1.41 (s, 3H), 1.44 (s, 9H), 2.26 - 2.30 (m, 1H), 2.70 - 2.75 (m, 1H), 2.92 (t, J = 5.5 Hz, 1H), 2.99 - 3.10 (m, 2H), 6.88 (t, J = 2.0 Hz, 1H), 6.97 - 7.03 (m, 4H), 7.05 (t, J = 2.0 Hz, 1H), 7.15 (dd, J = 8.5, 2.0 Hz, 1H), 7.20 - 7.24 (m, 4H), 7.34 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.44 - 7.51 (m, 3H), 7.53 - 7.61 (m, 4H), 7.73 - 7.78 (m, 4H), 8.19 (s, 1H), 8.24 (dt, J = 7.5, 1.0 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H), 10.26 (s, 1H). HRMS (ESI): C 63 H 57 F2N4O[M] + Calcd 923.4495, Found 923.4500.

[0139] (3) Synthesis of complex Pt9: The synthetic procedure was identical to that of Pt1 in Example 1, with ligand 9-L (400 mg, 0.37 mmol, 1.1 equiv), Pt(COD)Cl2(127 mg, 0.34 mmol, 1.0 equiv), sodium acetate (84 mg, 1.02 mmol, 3.0 equiv), diethylene glycol dimethyl ether (5 mL) as the reaction feed. The final product was obtained as a yellow solid, 350 mg, 92% yield. 1H NMR (500 MHz, CDC13) δ 0.24 (s, 3H), 1.10 (s, 3H), 1.20 (d, J = 8.5 Hz, 1H), 1.41 (s, 9H), 1.46 (s, 9H), 1.99 (t, J = 5.5 Hz, 1H), 2.14 - 2.18 (m, 1H), 2.49 - 2.53 (m, 1H), 2.69 (d, J = 17.5 Hz, 1H), 2.84 - 2.88 (m, 1H), 5.86 (t, J = 8.5 Hz, 2H), 6.48 (s, 2H), 6.80 (d, J = 8.0 Hz, 1H), 6.97 (t, J = 8.5 Hz, 2H), 7.05 (t, J = 7.5 Hz, 1H), 7.11 (d, J = 1.5 Hz, 1H), 7.27 - 7.31 (m, 2H), 7.32 (d, J = 8.0 Hz, 1H), 7.41 (td, J = 7.5, 1.0 Hz, 1H), 7.44 - 7.50 (m, 3H), 7.56 - 7.59 (m, 2H), 7.73 (s, 1H), 7.80 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 8.5 Hz, 1H), 8.11 (dd, J = 7.5, 1.0 Hz, 1H), 8.82 (s, 1H). HRMS (ESI): C 63 H 55 F2N4OPt[M+H] + Calcd 1116.3986, Found 1116.3978.

[0140] Example 9: Tetradentate cyclometalated platinum (II) complex Pt10 synthesis route:

[0141] (1) Synthesis of intermediate (2BrNO): To a three-necked flask was added 2,6-dibromoaniline (40 g, 159.4 mmol, 1.0 eq), 350 ml DMF, 60% sodium hydride (19.13 g, 478.2 mmol, 3.0 eq) was added slowly under ice bath, after stirring for 1 hour, o-fluoronitrobenzene (29.2 g, 207.2 mmol, 1.3 eq) was added, then the temperature was raised to room temperature and stirred for 12 hours. Extracted with water and ethyl acetate, the solvent was removed by reduced pressure distillation, then separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 60:1-30:1, 56.75 g of yellow solid was obtained, yield 95%. No structure characterization was carried out, it was directly used in the next step.

[0142] (2) Synthesis of intermediate (2BrNH): Into a three-neck flask was added 2BrNO (56.75 g, 152.5 mmol, 1.0 eq), stannous chloride (115.7 g, 610.2 mmol, 4.0 eq), and ethanol and ethyl acetate was added under nitrogen protection. The reaction was carried out at 78 °C for 18 h. The product was extracted with water and ethyl acetate, and then the solvent was removed by distillation under reduced pressure. The product was obtained as a white solid (44.9 g, 86% yield) after slurry with dichloromethane and petroleum ether. 1 H NMR (500 MHz, CDC13) δ 3.72 (br, 2H), 5.40 (s, 1H), 6.49 (dd, J = 8.0, 1.5 Hz, 1H), 6.67 (td, J = 7.5, 1.0 Hz, 1H), 6.80 - 6.85 (m, 2H), 6.93 (td, J = 7.5, 1.0 Hz, 1H), 7.54 (s, 1H), 7.56 (s, 1H).

[0143] (3) Synthesis of intermediate (4tBuNH): Into a Schlenk tube was added 2BrNH (9.92 g, 29 mmol, 1.0 eq), 2tbu-pin (27.5 g, 86.9 mmol, 3.0 eq), tetrakis(triphenylphosphine)palladium (1.0 g, 0.87 mmol, 0.03 eq), and potassium carbonate (10 g, 72.5 mmol, 2.5 eq). The reaction was carried out at 95 °C for 10 h under nitrogen protection. The product was extracted with ethyl acetate, and then the solvent was removed by distillation under reduced pressure. The product was obtained as a solid (14.8 g, 91% yield) after separation by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 8:1-5:1. 1 H NMR (500 MHz, CDC13) δ 3.72 (br, 2H), 5.40 (s, 1H), 6.49 (dd, J = 8.0, 1.5 Hz, 1H), 6.67 (td, J = 7.5, 1.0 Hz, 1H), 6.80 - 6.85 (m, 2H), 6.93 (td, J = 7.5, 1.0 Hz, 1H), 7.54 (s, 1H), 7.56 (s, 1H).

[0144] (4) Synthesis of intermediate (10-NH2): Into a Schlenk tube was added 2-Cl (400 mg, 0.77 mmol, 1.0 eq), Ph4tBuNH (473 mg, 0.84 mmol, 1.1 eq), Pd2(dba)3(21 mg, 0.023 mmol, 3 mol%), JohnPhos (14 mg, 0.046 mmol, 6 mol%) and sodium tert-butoxide (147 mg, 1.53 mmol, 2.0 eq). After purging with nitrogen for three times, toluene (6 mL) was added. The reaction was heated at 110 °C for 12 h. After removing the solvent by distillation under reduced pressure, the residue was separated by silica gel column chromatography with petroleum ether / ethyl acetate = 100:1-50:1 as eluent to give 506 mg of white solid with 63% yield. No structural characterization was performed and it was used directly for the next step.

[0145] (5) Synthesis of ligand 10-L: The synthesis was performed according to the procedure described in Example 1 for the synthesis of 1-L with 10-NH2(506 mg, 0.484 mmol, 1.0 eq), ammonium hexafluorophosphate (158 mg, 0.97 mmol, 2.0 eq), triethyl orthoformate (4 mL) as reactants. Finally, 360 mg of solid was obtained with 62% yield. 1 H NMR (500 MHz, CDC13) δ 0.74 (s, 3H), 0.99 (s, 36H), 1.27 (s, 9H), 1.32 (d, J = 10.0 Hz, 1H), 1.45 (s, 3H), 2.35 - 2.38 (m, 1H), 2.75 - 2.79 (m, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.10 (s, 2H), 6.45 (t, J = 2.0 Hz, 1H), 6.70 (t, J = 1.5 Hz, 1H), 6.98 (d, J = 2.0 Hz, 4H), 7.01 (dd, J = 8.5, 2.5 Hz, 1H), 7.14 (t, J = 2.0 Hz, 2H), 7.23 (d, J = 8.5 Hz, 1H), 7.28 - 7.34 (m, 3H), 7.39 - 7.46 (m, 4H), 7.61 (d, J = 2.0 Hz, 1H), 7.67 (s, 1H), 7.68 (s, 1H), 7.73 - 7.81 (m, 2H), 8.09 (t, J = 8.0 Hz, 2H), 8.20 (s, 1H), 9.29 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.55, 25.93, 30.91, 30.99, 31.78, 32.99, 34.60, 35.33, 39.35, 39.89, 44.32, 103.42, 110.07, 110.99, 112.84, 113.10, 114.50, 115.88, 117.56, 118.31, 119.91, 120.89, 121.13, 121.44, 121.51, 122.82, 123.66, 125.80, 127.38, 127.71, 128.23, 130.27, 130.36, 131.62, 132.04, 132.31, 136.13, 140.26, 140.83, 141.03, 141.09, 142.38, 145.35, 147.75, 149.56, 151.35, 153.87, 156.65, 159.71. HRMS (ESI): C 75 H 83 N4O[M] + Calcd 1055.6561, Found 1055.6521.

[0146] (6) Synthesis of Pt10: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1 with ligand 10-L (300 mg, 0.25 mmol, 1.0 equiv), Pt(COD)Cl2(93 mg, 0.25 mmol, 1.0 equiv), sodium acetate (61 mg, 0.75 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (7 mL). The final product was obtained as a yellow solid 203 mg in 65% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.22 (s, 3H), 0.35 (s, 18H), 1.02 (s, 3H), 1.12 (s, 18H), 1.22 (d, J = 10.0 Hz, 2H), 1.92 - 1.95 (m, 1H), 2.16 (s, 1H), 2.77 (d, J = 18.5 Hz, 1H), 3.01 (d, J = 18.5 Hz, 1H), 6.54 (s, 2H), 6.72 (s, 1H), 6.87 (s, 1H), 7.03 (d, J = 8.0 Hz, 1H), 7.08 - 7.17 (m, 3H), 7.26 - 7.27 (m, 1H), 7.31 (t, J = 7.5 Hz, 1H), 7.36 - 7.40 (m, 3H), 7.42 (s, 1H), 7.48 (t, J = 7.5 Hz, 1H), 7.58 - 7.59 (m, 2H), 7.80 (d, J = 8.0 Hz, 1H), 7.86 (s, 1H), 8.05 (d, J = 8.5 Hz, 2H), 8.12 (d, J = 7.5 Hz, 1H), 8.77 (s, 1H). 13 CNMR (100 MHz, CDC13) δ 21.40, 25.78, 30.14, 31.19, 31.55, 32.45, 33.07, 33.78, 34.67, 34.79, 38.74, 39.27, 43.00, 104.72, 106.52, 110.41, 111.10, 112.21, 112.79, 114.47, 114.51, 115.52, 115.63, 116.02, 119.67, 120.64, 121.42, 121.95, 122.23, 122.48, 122.83, 123.11, 123.74, 129.09, 129.12, 129.30, 130.63, 131.86, 132.25, 136.50, 136.63, 136.68, 137.36, 137.76, 139.00, 140.06, 144.47, 147.14, 147.25, 147.38, 149.98, 151.04, 151.55, 154.49, 193.94. HRMS (ESI): C 75 H 81 N4OPt [M+H] + Calcd 1248.6053, Found 1248.6060.

[0147] Example 10: Tetradentate cyclometalated platinum (II) complex Pt11 synthesis route:

[0148] (1) Synthesis of intermediate chiral 11-NH2: Into a reaction flask was added 2-Cl (600 mg, 1.15 mmol, 1.0 eq), diPrPhNH2(475 mg, 1.38 mmol, 1.2 eq), Pd2(dba)3(32 mg, 0.035 mmol, 3 mol%), JohnPhos (41 mg, 0.14 mmol, 12 mol%), and NaOtBu (221 mg, 2.3 mmol, 2.0 eq) successively, and the flask was purged with nitrogen three times, and toluene (6 mL) was added. The reaction was carried out at 105 °C for 24 h, and the product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 907 mg of a white solid, in 95% yield. The compound was easily oxidized and was used directly in the next step without characterization.

[0149] (2) Synthesis of ligand 11-L: The synthesis was performed according to the procedure for 1-L in Example 1, with 11-NH2(907 mg, 1.09 mmol, 1.0 eq), ammonium hexafluorophosphate (357 mg, 2.19 mmol, 2.0 eq), and triethyl orthoformate (3 mL) as the reactants. The final product was obtained as a solid in 94% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.09 (d, J = 6.5 Hz, 6H), 1.16 (d, J = 7.5 Hz, 1H), 1.18 (d, J = 6.5 Hz, 6H), 1.36 (s, 9H), 1.41 (s, 3H), 2.28 - 2.30 (m, 1H), 2.36 - 2.41 (m, 2H), 2.71 - 2.75 (m, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.03 - 3.13 (m, 2H), 7.21 (dd, J = 8.5, 2.5 Hz, 1H), 7.33 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.43 - 7.49 (m, 3H), 7.51 (t, J = 2.0 Hz, 1H), 7.52 - 7.58 (m, 3H), 7.62 (d, J = 2.0 Hz, 1H), 7.63 - 7.65 (m, 1H), 7.66 (t, J = 2.0 Hz, 1H), 7.71 - 7.80 (m, 5H), 7.80 - 7.85 (m, 2H), 8.00 (d, J = 8.0 Hz, 1H), 8.20 (s, 1H), 8.23 (dt, J = 7.5, 1.0 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H), 10.64 (s, 1H).

[0150] (3) Synthesis of complex Pt11: The synthetic procedure was the same as Pt1 in Example 1, the reaction was charged with ligand 11-L (900 mg, 0.91 mmol, 1.1 equiv), Pt(COD)Cl2 (311 mg, 0.83 mmol, 1.0 equiv), sodium acetate (204 mg, 2.49 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (8 mL), and finally 755 mg of yellow solid was obtained in 88% yield. 1 H NMR (500 MHz, CDC13) δ 0.23 (s, 3H), 0.61 (d, J = 4.5 Hz, 1H), 0.62 (d, J = 6.5 Hz, 3H), 1.03 (d, J = 6.5 Hz, 3H), 1.18 (s, 3H), 1.26 (d, J = 6.5 Hz, 3H), 1.37 (d, J = 6.5 Hz, 3H), 1.50 (s, 9H), 1.94 - 2.02 (m, 1H), 2.16 - 2.20 (m, 1H), 2.34 (t, J = 5.5 Hz, 1H), 2.59 (d, J = 17.5 Hz, 1H), 2.62 - 2.68 (m, 1H), 2.73 - 2.77 (m, 1H), 3.81 - 3.86 (m, 1H), 6.94 (d, J = 8.0 Hz, 1H), 7.22 - 7.28 (m, 2H), 7.32 (t, J = 7.5 Hz, 1H), 7.37 - 7.41 (m, 3H), 7.44 (t, J = 7.5 Hz, 2H), 7.54 (t, J = 7.5 Hz, 2H), 7.62 - 7.69 (m, 5H), 7.75 - 7.78 (m, 2H), 8.00 (dd, J = 7.5, 1.0 Hz, 1H), 8.14 (d, J = 8.5 Hz, 1H), 8.32 (s, 1H).

[0151] Example 11: Tetradentate cyclometalated platinum(II) complex Pt12 synthesis route:

[0152] (1) Synthesis of intermediate chiral 12-NH2: Into a reaction vial was added 2-Cl (400 mg, 0.77 mmol, 1.0 equiv), diPrPhFNH2 (340 mg, 0.92 mmol, 1.2 equiv), Pd2(dba)3 (21 mg, 0.023 mmol, 3 mol%), JohnPhos (27 mg, 0.092 mmol, 12 mol%), and sodium tert-butoxide (221 mg, 2.3 mmol, 2.0 equiv) successively, and the flask was purged with nitrogen for three times, then toluene (5 mL) was added. The reaction was stirred at 85 °C for 18 h, and then purified by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 430 mg of white solid in 65% yield. The compound was easily oxidized and used directly for the next step without characterization.

[0153] (2) Synthesis of Ligand 12-L: The synthesis procedure was consistent with 1-L in Example 1, with reaction feed of 12-NH2(430 mg, 0.50 mmol, 1.0 equiv), ammonium hexafluorophosphate (164 mg, 1.01 mmol, 2.0 equiv), triethyl orthoformate (3 mL), to give 201 mg of solid, 40% yield. 1 H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.08 (dd, J = 6.5, 1.5 Hz, 6H), 1.28 (dd, J = 6.5, 2.5 Hz, 6H), 1.31 (d, J = 9.5 Hz, 1H), 1.41 (s, 9H), 1.45 (s, 3H), 2.21 - 2.29 (m, 2H), 2.34 - 2.38 (m, 1H), 2.76 (dt, J = 10.0, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.06 - 3.14 (m, 2H), 7.06 (t, J = 2.0 Hz, 1H), 7.16 (dd, J = 8.5, 2.0 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 7.37 (d, J = 8.5 Hz, 1H), 7.42 - 7.46 (m, 4H), 7.55 (s, 2H), 7.62 - 7.68 (m, 2H), 7.70 - 7.77 (m, 4H), 7.79 - 7.81 (m, 2H), 7.92 (d, J = 8.5 Hz, 1H), 8.09 (d, J = 7.5 Hz, 1H), 8.15 (d, J = 8.5 Hz, 1H), 8.20 (s, 1H), 9.78 (s, 1H).

[0154] (3) Synthesis of Complex Pt12: The synthesis procedure was consistent with Pt1 in Example 1, with reaction feed of Ligand 12-L (173 mg, 0.17 mmol, 1.1 equiv), Pt(COD)Cl2(67 mg, 0.18 mmol, 1.0 equiv), sodium acetate (42 mg, 0.51 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (5 mL), to give 120 mg of yellow solid, 67% yield. 1H NMR (500 MHz, CDC13) δ 0.26 (s, 3H), 0.64 (d, J = 7.0 Hz, 3H), 1.06 (d, J = 7.0 Hz, 3H), 1.20 (s, 3H), 1.28 (d, J = 7.0 Hz, 3H), 1.39 (d, J = 7.0 Hz, 3H), 1.45 (d, J = 4.0 Hz, 1H), 1.52 (s, 9H), 2.02 - 2.06 (m, 1H), 2.18 (dt, J = 10.5, 5.5 Hz, 1H), 2.33 (t, J = 5.5 Hz, 1H), 2.59 - 2.71 (m, 2H), 2.76 (d, J = 19.0 Hz, 1H), 3.91 (p, J = 6.5 Hz, 1H), 6.93 (d, J = 8.0 Hz, 1H), 7.25 (d, J = 1.5 Hz, 1H), 7.32 - 7.36 (m, 1H), 7.38 - 7.43 (m, 3H), 7.47 (t, J = 7.5 Hz, 1H), 7.66 (d, J = 2.0 Hz, 1H), 7.69 (d, J = 1.5 Hz, 1H), 7.72 (s, 1H), 7.76 - 7.88 (m, 7H), 8.02 (dd, J = 7.5, 1.5 Hz, 1H), 8.17 (d, J = 8.5 Hz, 1H), 8.32 (s, 1H). MS: 1057.41 [M+H] + .

[0155] Example 12: Synthesis route of tetradentate cyclometalated platinum (II) complex Pt13

[0156] (1) Synthesis of intermediate (tBu-NH2): Into a three-necked flask was added 3.5-di-tert-butylphenylboronic acid pinacol ester (3.0 g, 9.5 mmol, 1.5 eq), 4-bromo-2-methyl aniline (1.08 g, 6.3 mmol, 1.0 eq), potassium carbonate (2.6 g, 18.9 mmol, 3.0 eq), and tetrakis(triphenylphosphine)palladium (146 mg, 0.13 mmol, 2 mol%). After purging with nitrogen three times, ethylene glycol dimethyl ether / water = 1:1 (10 mL:10 mL) was added. The reaction was carried out at 80 °C for 72 hours, extracted with water and ethyl acetate, and the solvent was removed by distillation under reduced pressure. The product was separated by silica gel column chromatography with eluent of petroleum ether / ethyl acetate / dichloromethane = 20:1:1 to obtain 1.16 g of solid, with a yield of 66%.

[0157] (2) Synthesis of intermediate (Br-NH2): To a single-neck flask was added tBu-NH2(1.5 g, 5.3 mmol, 1.0 eq), dissolved with dichloromethane (15 mL), N-bromosuccinimide (2.0 g, 11.2 mmol, 2.1 eq) was added at low temperature, and it was moved to room temperature for 11 hours. Concentration, silica gel column chromatography gave 872 mg of solid, with a yield of 38%. 1 H NMR (500 MHz, CDC13) δ 1.37 (s, 18H), 4.58 (s, 2H), 7.28 (d, J = 2.0 Hz, 2H), 7.40 (s, 1H), 7.60 (s, 2H).

[0158] (3) Synthesis of intermediate (Br-NO): To a three-neck flask was added Br-NH2(825 mg, 1.88 mmol, 1.0 eq), dissolved with N,N-dimethylformamide (5 mL), 60% sodium hydride (226 mg, 5.6 mmol, 2.1 eq) was added at low temperature, and it was moved to room temperature for 11 hours. Concentration, silica gel column chromatography gave 918 mg of solid, with a yield of 87%. 1 H NMR (500 MHz, CDC13) δ 1.39 (s, 18H), 6.54 (dd, J = 8.5, 1.5 Hz, 1H), 6.86 (ddd, J = 8.5, 7.0, 1.0 Hz, 1H), 7.34 - 7.43 (m, 3H), 7.50 (t, J = 2.0 Hz, 1H), 7.86 (s, 2H), 8.27 (dd, J = 8.5, 1.5 Hz, 1H), 9.30 (s, 1H).

[0159] (4) Synthesis of intermediate (Br-NH): To a three-neck flask was added Br-NO (868 mg, 1.35 mmol, 1.0 eq), stannous chloride (1.2 g, 6.20 mmol, 4.0 eq), dissolved with ethyl acetate / ethanol (5 mL:5 mL), and it was reacted at 78°C for 11 hours. Extraction with water and ethyl acetate, removal of the solvent under reduced pressure, and separation using a silica gel column gave 741 mg of solid, with a yield of 90%.

[0160] (5) Synthesis of intermediate (dPhdtBuNH2): Into a three-neck flask was added Br-NH (741 mg, 1.4 mmol, 1.0 eq), phenylboronic acid (511 mg, 4.2 mmol, 3.0 eq), potassium carbonate (387 mg, 2.8 mmol, 2.0 eq), and tetrakis(triphenylphosphine)palladium (48.5 mg, 0.04 mmol, 3 mol%). After purging with nitrogen three times, 1,4-dioxane / water = 4:1 (8 mL:2 mL) was added. The reaction was carried out at 90 °C for 12 h, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The product was separated by silica gel column chromatography with petroleum ether / ethyl acetate / dichloromethane = 20:1:1 as the eluent to give 690 mg of a solid with a yield of 94%. 1 H NMR (500 MHz, DMSO-d6) δ 1.33 (s, 17H), 4.52 (s, 2H), 5.64 (s, 1H), 6.12-6.19 (m, 2H), 6.28-6.35 (m, 2H), 7.19-7.22 (m, 2H), 7.27-7.30 (m, 4H), 7.40 (t, J = 2.0 Hz, 1H), 7.46-7.52 (m, 8H).

[0161] (6) Synthesis of intermediate (13-NH2): Into a three-neck flask was added dPhdtBuNH2 (657 mg, 1.25 mmol, 1.1 eq), 2-Cl (593 mg, 1.14 mmol, 1.0 eq), Pd2(dba)3 (31 mg, 0.03 mmol, 3 mol%), SPhos (28 mg, 0.07 mmol, 6 mol%), and sodium tert-butoxide (219 mg, 2.18 mmol, 2.0 eq). After purging with nitrogen three times, toluene (10 mL) was added. After the reaction was carried out at 90 °C for 4.5 h, the product was extracted with water and ethyl acetate. After removing the solvent under reduced pressure, the product was separated by silica gel column chromatography with petroleum ether / ethyl acetate = 20:1 as the eluent to give 1.09 g of a solid with a yield of 95%.

[0162] (7) Synthesis of ligand 13-L: The synthesis was carried out according to the procedure described in Example 1 for the synthesis of 1-L, with 13-NH2 (1.09 g, 1.08 mmol, 1.0 eq), ammonium hexafluorophosphate (352 mg, 2.16 mmol, 2.0 eq), and triethyl orthoformate (10 mL) as the reactants. Finally, 967 mg of a solid was obtained with a yield of 77%. 1H NMR (500 MHz, CDC13) δ 0.74 (s, 3H), 1.33 (s, 10H), 1.40 (s, 18H), 1.45 (s, 3H), 2.36 (dt, J = 6.0, 3.0 Hz, 1H), 2.77 (dt, J = 11.5, 6.0 Hz, 1H), 2.94 (t, J = 5.5 Hz, 1H), 3.11 (s, 2H), 6.51 (t, J = 2.0 Hz, 1H), 6.73 (t, J = 1.5 Hz, 1H), 7.07 - 7.15 (m, 7H), 7.21 - 7.23 (m, 4H), 7.28 (d, J = 1.0 Hz, 1H), 7.31 - 7.34 (m, 2H), 7.42 - 7.44 (m, 3H), 7.46 - 7.49 (m, 1H), 7.50 (d, J = 1.5 Hz, 2H), 7.52 - 7.54 (m, 2H), 7.62 (d, J = 2.0 Hz, 1H), 7.75 (dt, J = 8.5 Hz, J = 1.0 Hz, 1H), 7.78 (s, 3H), 8.11 (dt, J = 8.0 Hz, 1.0 Hz, 1H), 8.16 (d, J = 8.5 Hz, 1H), 8.21 (s, 1H), 9.28 (s, 1H).

[0163] (8) Synthesis of Pt13: The synthesis was performed according to the procedure described for the synthesis of Pt1 in Example 1, with ligand 13-L (840 mg, 0.72 mmol, 1.0 equiv), Pt(COD)Cl2(283 mg, 0.76 mmol, 1.05 equiv), sodium acetate (177 mg, 2.16 mmol, 3.0 equiv), diethylene glycol dimethyl ether (40 mL). The final product was obtained as a yellow solid 398 mg, 46% yield. 1H NMR (400 MHz, DMSO-d6) δ 0.20 (s, 3H), 0.48 (d, J = 12.0 Hz, 1H), 0.99 (s, 3H), 1.42 (s, 9H), 1.46 (s, 16H), 1.91 - 1.94 (m, 2H), 2.14 - 2.19 (m, 1H), 2.61 - 2.75 (m, 2H), 6.20 (t, J = 7.5 Hz, 2H), 6.55 (t, J = 7.5 Hz, 1H), 6.67 (d, J = 7.5 Hz, 2H), 6.92 (d, J = 2.0 Hz, 1H), 7.05 (d, J = 8.0 Hz, 1H), 7.14 - 7.18 (m, 2H), 7.24 (d, J = 9.0 Hz, 1H), 7.34 - 7.28 (m, 3H), 7.46 (t, J = 7.5 Hz, 1H), 7.52 - 7.58 (m, 6H), 7.66 (d, J = 7.5 Hz, 2H), 7.80 (d, J = 2.0 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.90 (s, 1H), 8.14 (d, J = 8.5 Hz, 1H), 8.21 (t, J = 9.5 Hz, 2H), 8.66 (s, 1H).

[0164] Example 13: Synthesis route of tetradentate cyclometalated platinum(II) complex Pt14:

[0165] Synthesis of intermediate F-12: Into a 100 mL three-necked flask was added p-fluorobenzoic acid (3 g, 21.4 mmol, 1.3 eq), p-bromoaniline (2.83 g, 16.5 mmol, 1.0 eq), tetrakis(triphenylphosphine)palladium (381 mg, 0.33 mmol, 0.02 eq), potassium carbonate (6.8 g, 49.4 mmol, 3.0 eq), and the flask was purged with nitrogen three times. Then 1,4-dioxane and water (40 mL / 10 mL) were added, and the reaction was stirred at 90 °C for 11 h. The temperature was increased to 100 °C, and the reaction was continued for 25 h. The reaction mixture was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography using petroleum ether / ethyl acetate / dichloromethane = 100:2:1 as the eluent to give intermediate F-12 as a white solid, 1.73 g, 56% yield.

[0166] Synthesis of intermediate F-Br-12: Into a 250 mL single necked flask was placed F-12 (1.7 g, 9.1 mmol, 1.0 eq), dichloromethane (50 mL), cooled to -10 °C, liquid bromine (3.04 g, 19.1 mmol, 2.1 eq) was added slowly (dissolved in 50 mL dichloromethane), the reaction was stirred at room temperature for 36 h, 0.5 mL of liquid bromine was added and the reaction was stirred for another 24 h. The reaction was quenched with sodium thiosulfate solution, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 40:1, to give intermediate F-Br-12 as white solid 1.76 g, yield 56%.

[0167] Synthesis of intermediate F-Br-NO2-12: Into a 250 mL three necked flask was placed F-Br-12 (1.7 g, 4.92 mmol, 1.0 eq), N,N-dimethylformamide (50 mL), cooled to -10 °C, sodium hydride (591 mg, 14.7 mmol, 3.0 eq) was added slowly, the temperature was kept low for 1 h, o-fluoro-nitrobenzene (765 mg, 5.42 mmol, 1.1 eq) was added, the reaction was stirred at room temperature for 48 h. The reaction was quenched with water, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 50:1, the fraction that did not pass through the column was slurry with petroleum ether and ethyl acetate, to give intermediate F-Br-NO2-12 as a solid 2.7 g.

[0168] Synthesis of intermediate F-Br-NH2-12: Into a 250 mL three necked flask was placed intermediate F-Br-NH2-12 (2.7 g, 5.8 mmol, 1.0 eq), stannous chloride (4.39 g, 23.17 mmol, 4.0 eq), the flask was purged with nitrogen three times, ethyl acetate and ethanol (30 + 30 mL) was added, the reaction was stirred at 78 °C for 11 h. The reaction was neutralized with aqueous sodium bicarbonate solution, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 10:1, to give intermediate F-Br-NH2-12 as a solid 2.3 g, yield 91%.

[0169] Synthesis of intermediate F-Ph-NH2-12: Into a 100 mL three-necked flask was placed F-Br-NH2-12 (2.3 g, 5.2 mmol, 1.0 eq), phenylboronic acid (1.93 g, 15.8 mmol, 3.0 eq), Pd2(dba)3 (243 mg, 0.21 mmol, 0.04 eq), potassium carbonate (3.6 g, 26.3 mmol, 5.0 eq), and the flask was purged with nitrogen three times, 1,4-dioxane and water (28 mL / 7 mL) was added, nitrogen was bubbled for 30 min, the reaction was stirred at 100 °C for 5 h. The reaction was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate / dichloromethane = 20:1:1, to give intermediate F-Ph-NH2-12 as a solid 2.04 g in 90% yield. 1 H NMR (500 MHz, CDC13) δ 3.42 (s, 2H), 4.87 (s, 1H), 6.40 (dd, J = 7.5, 1.5 Hz, 1H), 6.46 (td, J = 8.0, 1.5 Hz, 1H), 6.61 (td, J = 7.5, 1.5 Hz, 1H), 6.65 (dd, J = 7.5, 1.5 Hz, 1H), 7.09 - 7.14 (m, 2H), 7.19 - 7.24 (m, 2H), 7.26 - 7.31 (m, 4H), 7.39 - 7.44 (m, 4H), 7.48 (s, 2H), 7.58 - 7.63 (m, 2H).

[0170] Synthesis of intermediate 14-NH2: Into a schlenk tube was placed intermediate F-Ph-NH2-12 (453 mg, 1.05 mmol, 1.2 eq), intermediate 2-Cl (457 mg, 0.87 mmol, 1.0 eq), Pd2(dba)3 (48 mg, 0.053 mmol, 0.06 eq), SPhos (43 mg, 0.104 mmol, 0.12 eq), sodium tert-butoxide (167 mg, 1.74 mmol, 2.0 eq), and the flask was purged with nitrogen three times, toluene (10 mL) was added, the reaction was stirred at 90 °C for 5 h, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate / dichloromethane = 100:2:1, to give intermediate F-NH-12 as a green solid 735 mg in 92% yield. The product was unstable and used directly in the following reaction.

[0171] Synthesis of Ligand 14-L: Into a schlenk tube, F-NH-12 (735 mg, 0.8 mmol, 1.0 eq), ammonium hexafluorophosphate (262 mg, 1.6 mmol, 2.0 eq) were added successively, and the system was purged with nitrogen for three times, then triethyl orthoformate (10 mL) was added successively, and the system was heated at 70 °C for 15 min. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 1:1 ~ 1:5 ~ dichloromethane:methanol = 500:1, finally ligand 14-L was obtained as a foamy solid 750 mg, yield 87%.1H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.31 - 1.32 (m, 1H), 1.33 (s, 9H), 1.45 (s, 3H), 2.34 - 2.39 (m, 1H), 2.73 - 2.81 (m, 1H), 2.94 (t, J = 5.5 Hz, 1H), 3.12 (s, 2H), 6.51 (t, J = 2.0 Hz, 1H), 6.73 (s, 1H), 7.06 - 7.10 (m, 2H), 7.10 (s, 3H), 7.10 - 7.14 (m, 3H), 7.18 (s, 1H), 7.19 - 7.20 (m, 1H), 7.20 - 7.22 (m, 3H), 7.27 - 7.30 (m, 1H), 7.31 - 7.35 (m, 2H), 7.42 - 7.45 (m, 2H), 7.45 - 7.50 (m, 2H), 7.52 - 7.55 (m, 1H), 7.61 (d, J = 2.0 Hz, 1H), 7.66 - 7.70 (m, 2H), 7.72 - 7.76 (m, 3H), 8.10 - 8.13 (m, 1H), 8.16 (d, J = 8.5 Hz, 1H), 8.22 (s, 1H), 9.36 (s, 1H).13C NMR (125 MHz, CDC13) δ 21.52, 25.90, 30.90, 31.75, 32.99, 35.34, 39.32, 39.86, 44.28, 103.26, 109.99, 110.96, 113.19, 113.42, 114.08, 115.85, 115.90, 116.07, 117.88, 118.38, 119.97, 120.95, 121.04, 121.48, 123.66, 125.82, 126.93, 128.06, 128.11, 128.24, 128.48, 128.77, 129.20, 129.27, 130.09, 132.31, 132.40, 134.98, 136.54, 140.23, 140.82, 140.97, 141.12, 142.07, 143.54, 145.32, 153.96, 156.54, 159.58, 164.13. HRMS (ESI): C. 65 H 54 FN4O + [M] + Calcd 925.4276, Found 925.4227.

[0172] Synthesis of complex Pt14: Into a sealed tube, ligand 14-L (650 mg, 0.61 mmol, 1.0 equiv), (1,5-cyclooctadiene) dichloroplatinum (238 mg, 0.64 mmol, 1.05 equiv) and sodium acetate (149 mg, 1.82 mmol, 3.0 equiv) were added successively, and the tube was purged with nitrogen three times. Diethyleneglycol dimethyl ether (15 mL) was added, and the mixture was purged with nitrogen for 30 min. The mixture was heated at 120 °C for 72 h. After cooling, the solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 10:1 as eluent to give complex Pt14 as a yellow-green solid 571 mg in 84% yield. 1 H NMR (500 MHz, CDC13) δ 0.21 (s, 3H), 0.61 (d, J = 9.5 Hz, 1H), 1.03 (s, 3H), 1.46 (s, 9H), 1.96 - 2.03 (m, 2H), 2.2318 - 2.28 (m, 1H), 2.62 (d, J = 17.5 Hz, 1H), 2.73 (d, J = 17.5 Hz, 1H), 6.27 - 6.33 (m, 2H), 6.52 - 6.57 (m, 1H), 6.68 (d, J = 7.5 Hz, 2H), 6.91 (d, J = 8.0 Hz, 1H), 7.03 - 7.08 (m, 1H), 7.11 (d, J = 1.5 Hz, 1H), 7.19 - 7.23 (m, 1H), 7.23 - 7.25 (m, 1H), 7.27 - 7.30 (m, 3H), 7.32 (d, J = 8.0 Hz, 1H), 7.41 - 7.45 (m, 1H), 7.50 - 7.52 (m, 2H), 7.53 (m, 1H), 7.58 - 7.62 (m, 2H), 7.63 - 7.69 (m, 3H), 7.74 (d, J = 2.5 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.83 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 8.10 - 8.13 (m, 1H), 8.83 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.20, 25.69, 29.67, 31.58, 32.97, 34.76, 39.34, 39.36, 43.27, 105.76, 107.45, 110.99, 111.36, 112.15, 112.21, 113.39, 114.57, 115.22, 116.01, 116.06, 116.23, 116.58, 120.20, 122.20, 122.73, 123.64, 124.10, 127.58, 127.71, 128.01, 128.05, 128.09, 128.62, 128.68, 128.85, 129.10, 131.14, 131.57, 135.55, 136.26, 136.75, 137.79, 138.18, 138.73, 140.05, 141.14, 143.22, 146.99, 147.86, 147.95, 149.50, 150.23, 152.55, 154.81, 193.29. HRMS (ESI): C 65 H 51 FN4OPt[M+H] + Calcd 1118.3767, Found 1118.3760.

[0173] Example 14: Synthesis route of tetradentate cyclometalated platinum (II) complex Pt15

[0174] (1) Synthesis of intermediate chiral 15-NH2: Into a reaction vial was added 2-Cl (231 mg, 0.81 mmol, 1.4 equiv), NH-NH2 (300 mg, 0.58 mmol, 1.0 equiv), Pd2(dba)3 (16 mg, 0.017 mmol, 3 mol%), John Phos (21 mg, 0.069 mmol, 12 mol%) and NaOt-Bu (111 mg, 1.15 mmol, 2.0 equiv) successively, and the vial was purged with nitrogen three times. Toluene (4 mL) was added. The mixture was heated at 90 °C for 12 h. The mixture was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 388 mg of white solid in 87% yield. The compound was easily oxidized and used directly for the next step without characterization.

[0175] (2) Synthesis of Ligand 15-L: The synthesis was performed according to the procedure described for the synthesis of 1-L in Example 1, with 15-NH2(388 mg, 0.5 mmol, 1.0 equiv), ammonium hexafluorophosphate (164 mg, 1.01 mmol, 2.0 equiv), triethyl orthoformate (4 mL) as the reaction feed. The final product was obtained as a solid 257 mg in 56% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.18 (d, J = 9.5 Hz, 1H), 1.39 (s, 9H), 1.41 (s, 3H), 2.47 - 2.28 (m, 1H), 2.70 - 2.74 (m, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.01 - 3.09 (m, 2H), 7.20 (d, J = 8.5 Hz, 1H), 7.24 (dd, J = 8.5, 2.0 Hz, 1H), 7.31 - 7.35 (m, 1H), 7.45 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.55 (t, J = 2.0 Hz, 1H), 7.57 - 7.64 (m, 6H), 7.68 - 7.71 (m, 2H), 7.74 - 7.79 (m, 4H), 7.88 (t, J = 2.0 Hz, 1H), 8.06 (d, J = 9.0 Hz, 1H), 8.22 - 8.24 (m, 2H), 8.33 (d, J = 8.5 Hz, 1H), 8.37 (d, J = 8.5 Hz, 2H), 9.16 (s, 1H), 10.78 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.49, 25.87, 30.94, 31.72, 32.95, 35.53, 39.27, 39.81, 44.21, 103.23, 110.67, 110.84, 113.16, 113.91, 114.41, 116.73, 117.97, 118.38, 119.93, 120.54, 120.89, 120.98, 121.42, 121.63, 123.56, 125.78, 126.39, 127.99, 128.76, 128.89, 128.95, 129.60, 131.03, 131.44, 131.90, 133.03, 133.34, 140.15, 140.76, 141.15, 141.52, 145.22, 147.88, 149.36, 154.08, 157.04, 159.73. HRMS (ESI): C 55 H 47 N4O[M] + Calcd 779.3744, Found 779.3740.

[0176] (3) Synthesis of complex Pt15: The synthesis was performed according to the procedure described for the synthesis of Pt1 in Example 1, with ligand 15-L (200 mg, 0.22 mmol, 1.0 equiv), Pt(COD)Cl2(85 mg, 0.23 mmol, 1.05 equiv), sodium acetate (53 mg, 0.65 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (13 mL). The final product was obtained as a yellow solid 197 mg, 94% yield. 1 H NMR (500 MHz, CDC13) δ 0.57 (t, J = 5.0 Hz, 1H), 0.92 (d, J = 9.5 Hz, 1H), 1.01 (s, 3H), 1.54 (s, 9H), 1.55 (s, 3H), 1.97 - 2.01 (m, 1H), 2.39 - 2.45 (m, 2H), 2.69 (dd, J = 18.0, 3.0 Hz, 1H), 6.73 (d, J = 8.0 Hz, 1H), 7.00 (ddd, J = 8.5, 6.5, 1.0 Hz, 1H), 7.18 (t, J = 7.5 Hz, 1H), 7.24 - 7.31 (m, 4H), 7.33 - 7.37 (m, 1H), 7.38 (d, J = 8.0 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 7.49 (ddd, J = 8.5, 7.5, 1.0 Hz, 1H), 7.56 - 7.63 (m, 3H), 7.71 (d, J = 8.5 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 1.5 Hz, 1H), 7.88 (d, J = 8.5 Hz, 1H), 7.97 (d, J = 7.0 Hz, 1H), 8.13 (d, J = 7.5 Hz, 1H), 8.28 (d, J = 8.5 Hz, 2H), 8.48 (s, 1H). HRMS (ESI): C 55 H 45 N4OPt[M+H] + Calcd 972.3236,Found 972.3241.

[0177] Example 15: Tetradentate cyclometalated platinum(II) complex Pt16 synthesis route:

[0178] (1) Synthesis of intermediate chiral 16-NH2: Into a reaction vial was added 2-Cl (350 mg, 0.67 mmol, 1.0 equiv), 16NH-NH2(349 mg, 0.74 mmol, 1.1 equiv), Pd2(dba)3(19 mg, 0.02 mmol, 3 mol%), SPhos (33 mg, 0.08 mmol, 12 mol%), and sodium tert-butoxide (129 mg, 1.34 mmol, 2.0 equiv) sequentially, and the vial was flushed with nitrogen three times and toluene (4 mL) was added. The reaction was stirred at 110 °C for 27 h, and the product was isolated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 568 mg of white solid in 87% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0179] (2) Synthesis of ligand 16-L: The synthesis was performed according to the procedure for 1-L in Example 1 with 16-NH2(568 mg, 0.59 mmol, 1.0 equiv), ammonium hexafluorophosphate (193 mg, 1.19 mmol, 2.0 equiv), and triethyl orthoformate (3 mL) as the reactants. The final product was obtained as a solid in 85% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.18 (d, J = 9.5 Hz, 1H), 1.38 (s, 9H), 1.39 (s, 9H), 1.40 (s, 3H), 1.41 (s, 9H), 2.24 - 2.27 (m, 1H), 2.69 - 2.74 (m, 1H), 2.92 (t, J = 5.5 Hz, 1H), 2.99 - 3.10 (m, 2H), 7.24 - 7.26 (m, 2H), 7.29 (d, J = 8.5 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.36 (t, J = 1.5 Hz, 1H), 7.45 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.56 - 7.61 (m, 6H), 7.62 - 7.65 (m, 3H), 7.69 (t, J = 2.0 Hz, 1H), 7.73 - 7.81 (m, 6H), 7.91 (t, J = 2.0 Hz, 1H), 8.07 (d, J = 8.5 Hz, 1H), 8.22 - 8.24 (m, 2H), 8.33 (d, J = 8.5 Hz, 1H), 10.79 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.49, 25.87, 30.96, 31.53, 31.72, 32.96, 35.01, 35.03, 35.55, 39.27, 39.82, 44.22, 103.31, 110.59, 110.86, 113.27, 114.06, 114.46, 116.78, 118.04, 118.42, 119.92, 120.49, 120.88, 121.04, 121.26, 121.44, 121.83, 123.59, 124.99, 125.27, 125.78, 126.12, 127.88, 128.10, 128.78, 128.94, 129.28, 130.09, 131.55, 133.05, 133.52, 136.21, 140.20, 140.82, 141.16, 141.65, 144.41, 145.30, 147.87, 149.40, 150.86, 151.10, 154.08, 157.06, 159.83.

[0180] (3) Synthesis of complex Pt16: The synthetic procedure was identical to that of Pt1 in Example 1. The reaction was fed with ligand 16-L (350 mg, 0.31 mmol, 1.0 equiv), Pt(COD)Cl2(118 mg, 0.31 mmol, 1.0 equiv), sodium acetate (77 mg, 0.94 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (15 mL). The final product was obtained as a yellow solid 345 mg in 95% yield. HRMS (ESI): C 69 H 64 N4OPt[M + H] + Calcd 1159.4728, Found 1159.4724.

[0181] Example 16: Tetradentate cyclometalated platinum(II) complex Pt17 synthesis route:

[0182] (1) Synthesis of intermediate chiral 17-NH2: Into a reaction vial was added 2-Cl (210 mg, 0.40 mmol, 1.0 equiv), MedPhNH2 (180 mg, 0.44 mmol, 1.1 equiv), Pd2(dba)3 (11 mg, 0.012 mmol, 3 mol%), JohnPhos (14 mg, 0.48 mmol, 12 mol%) and NaOtBu (77 mg, 0.80 mmol, 2.0 equiv) successively, and the vial was purged with nitrogen three times and toluene (5 mL) was added. The reaction was stirred at 85 °C for 18 h, and the product was isolated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 327 mg of white solid in 92% yield. The compound was easily oxidized and used directly for the next step without characterization.

[0183] (2) Synthesis of ligand 17-L: The synthesis was performed according to the procedure described in Example 1 for the synthesis of 1-L, using 17-NH2 (327 mg, 0.37 mmol, 1.0 equiv), ammonium hexafluorophosphate (120 mg, 0.73 mmol, 2.0 equiv) and triethyl orthoformate (3 mL) as the starting materials to give 280 mg of solid in 72% yield. 1 H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.31 (s, 9H), 1.32 (d, J = 9.5 Hz, 1H), 1.45 (s, 3H), 1.46 (s, 9H), 2.34 - 2.36 (m, 1H), 2.37 (s, 3H), 2.76 (dt, J = 9.5, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.07 - 3.14 (m, 2H), 6.46 (t, J = 2.0 Hz, 1H), 6.67 (t, J = 2.0 Hz, 1H), 6.98 (s, 1H), 7.02 - 7.19 (m, 11H), 7.23 - 7.26 (m, 1H), 7.30 (t, J = 2.0 Hz, 1H), 7.31 - 7.34 (m, 1H), 7.36 (d, J = 8.5 Hz, 1H), 7.38 - 7.47 (m, 2H), 7.59 (s, 2H), 7.60 (d, J = 2.0 Hz, 1H), 7.75 (d, J = 8.5 Hz, 1H), 8.11 (d, J = 7.5 Hz, 1H), 8.14 (d, J = 8.5 Hz, 1H), 8.21 (s, 1H), 9.02 (s, 1H).

[0184] (3) Synthesis of complex Pt17: The synthetic procedure was referred to the synthesis of Pt1 in Example 1. The reaction was carried out with ligand 17-L (171 mg, 0.16 mmol, 1.0 equiv), Pt(COD)Cl2 (64 mg, 0.17 mmol, 1.0 equiv), sodium acetate (40 mg, 0.49 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (5 mL). The final product was obtained as yellow solid 56 mg in 41% yield. 1 H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.31 (s, 9H), 1.32 (d, J = 9.5 Hz, 1H), 1.45 (s, 3H), 1.46 (s, 9H), 2.34 - 2.36 (m, 1H), 2.37 (s, 3H), 2.76 (dt, J = 9.5, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.07 - 3.14 (m, 2H), 6.46 (t, J = 2.0 Hz, 1H), 6.67 (t, J = 2.0 Hz, 1H), 6.98 (s, 1H), 7.02 - 7.19 (m, 11H), 7.23 - 7.26 (m, 1H), 7.30 (t, J = 2.0 Hz, 1H), 7.31 - 7.34 (m, 1H), 7.36 (d, J = 8.5 Hz, 1H), 7.38 - 7.47 (m, 2H), 7.59 (s, 2H), 7.60 (d, J = 2.0 Hz, 1H), 7.75 (d, J = 8.5 Hz, 1H), 8.11 (d, J = 7.5 Hz, 1H), 8.14 (d, J = 8.5 Hz, 1H), 8.21 (s, 1H), 9.02 (s, 1H). MS: 1094.43 [M+H] + .

[0185] Example 17: Synthetic route of tetradentate cyclometalated platinum (II) complex Pt18:

[0186] (1) Synthesis of intermediate chiral 18-NH2: Into a reaction vial was added 2-Cl (350 mg, 0.67 mmol, 1.0 equiv), PhdPhNH2 (378 mg, 0.81 mmol, 1.2 equiv), Pd2(dba)3 (18 mg, 0.02 mmol, 3 mol%), JohnPhos (24 mg, 0.08 mmol, 12 mol%), and sodium tert-butoxide (129 mg, 1.34 mmol, 2.0 equiv) successively, and the vial was purged with nitrogen for 3 times. Toluene (5 mL) was added. The reaction was carried out at 85 °C for 18 h. The product was isolated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 615 mg of white solid in 96% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0187] (2) Synthesis of Ligand 18-L: The synthetic procedure was consistent with 1-L in Example 1, with reaction feed of 18-NH2(615 mg, 0.65 mmol, 1.0 equiv), ammonium hexafluorophosphate (210 mg, 1.29 mmol, 2.0 equiv), triethyl orthoformate (3 mL) to give 382 mg of solid, 53% yield. 1 H NMR (500 MHz, CDC13) δ 0.75 (s, 3H), 1.33 (d, J = 9.0 Hz, 1H), 1.34 (s, 9H), 1.47 (s, 3H), 1.47 (s, 9H), 2.36 - 2.39 (m, 1H), 2.78 (dt, J = 9.5, 5.5 Hz, 1H), 2.95 (t, J = 5.5 Hz, 1H), 3.08 - 3.16 (m, 2H), 6.52 (t, J = 2.0 Hz, 1H), 6.74 (t, J = 2.0 Hz, 1H), 7.07 - 7.14 (m, 3H), 7.14 - 7.20 (m, 4H), 7.21 - 7.25 (m, 4H), 7.31 - 7.36 (m, 3H), 7.37 - 7.50 (m, 7H), 7.56 (d, J = 8.5 Hz, 1H), 7.60 - 7.68 (m, 4H), 7.77 (d, J = 8.5 Hz, 1H), 8.13 (dt, J = 7.5, 1.0 Hz, 1H), 8.17 (d, J = 8.5 Hz, 1H), 8.23 (s, 1H), 9.14 (s, 1H).

[0188] (3) Synthesis of Complex Pt18: The synthetic procedure was consistent with Pt1 in Example 1, with reaction feed of Ligand 18-L (360 mg, 0.32 mmol, 1.0 equiv), Pt(COD)Cl2(128 mg, 0.34 mmol, 1.05 equiv), sodium acetate (80 mg, 0.97 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (5 mL) to give 225 mg of yellow solid, 61% yield. 1H NMR (500 MHz, CDC13) δ 0.25 (s, 3H), 1.09 (s, 3H), 1.22 (d, J = 9.5 Hz, 1H), 1.42 (s, 9H), 1.46 (s, 9H), 2.09 (t, J = 5.5 Hz, 1H), 2.13 - 2.19 (m, 1H), 2.52 (dt, J = 10.5, 5.5 Hz, 1H), 2.70 (d, J = 18.0 Hz, 1H), 2.83 - 2.92 (m, 1H), 6.17 (t, J = 7.5 Hz, 2H), 6.49 (t, J = 7.5 Hz, 1H), 6.55 (s, 2H), 6.98 (d, J = 1.5 Hz, 1H), 7.09 (d, J = 1.5 Hz, 1H), 7.20 - 7.25 (m, 1H), 7.27 - 7.38 (m, 7H), 7.41 (t, J = 7.5 Hz, 3H), 7.45 - 7.52 (m, 3H), 7.53 (d, J = 2.0 Hz, 1H), 7.69 (d, J = 7.5 Hz, 2H), 7.75 (s, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 8.01 (d, J = 8.5 Hz, 1H), 8.11 (d, J = 7.0 Hz, 1H), 8.93 (s, 1H). MS: 1156.45 [M+H] + .

[0189] Example 18: Synthesis route of tetradentate cyclometalated platinum (II) complex Pt19

[0190] (1) Synthesis of intermediate chiral 19-NH2: Into a reaction flask was added 2-Cl (350 mg, 0.67 mmol, 1.0 equiv), mPhdPhNH2 (378 mg, 0.81 mmol, 1.2 equiv), Pd2(dba)3 (18 mg, 0.02 mmol, 3 mol%), JohnPhos (24 mg, 0.08 mmol, 12 mol%) and sodium tert-butoxide (129 mg, 1.34 mmol, 2.0 equiv) successively, and the flask was purged with nitrogen three times, and toluene (5 mL) was added. The mixture was stirred at 85 °C for 18 h, and separated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 608 mg of white solid in 94% yield. The compound was easily oxidized and used directly in the next step without characterization.

[0191] (2) Synthesis of Ligand 19-L: The synthesis was performed according to the procedure described in the synthesis of 1-L in Example 1 with 19-NH2(624 mg, 0.65 mmol, 1.0 equiv), ammonium hexafluorophosphate (213 mg, 1.31 mmol, 2.0 equiv), triethyl orthoformate (3 mL) to give 260 mg of a solid in 36% yield. 1 H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.31 (d, J = 9.5 Hz, 1H), 1.32 (s, 9H), 1.45 (s, 3H), 1.46 (s, 9H), 2.33 - 2.37 (m, 1H), 2.76 (dt, J = 9.5, 5.5 Hz, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.05 - 3.13 (m, 2H), 6.56 (t, J = 2.0 Hz, 1H), 6.69 (t, J = 2.0 Hz, 1H), 7.05 (dd, J = 8.5, 2.0 Hz, 1H), 7.08 - 7.17 (m, 6H), 7.18 - 7.22 (m, 4H), 7.30 (t, J = 8.0 Hz, 2H), 7.32 - 7.33 (m, 1H), 7.37 - 7.46 (m, 7H), 7.56 (d, J = 1.0 Hz, 1H), 7.58 - 7.62 (m, 3H), 7.63 (d, J = 2.0 Hz, 1H), 7.75 (dt, J = 8.5, 1.0 Hz, 1H), 8.06 - 8.12 (m, 2H), 8.20 (s, 1H), 9.17 (s, 1H).

[0192] (3) Synthesis of Complex Pt19: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1 with ligand 19-L (240 mg, 0.22 mmol, 1.0 equiv), Pt(COD)Cl2(85 mg, 0.23 mmol, 1.05 equiv), sodium acetate (53 mg, 0.65 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (5 mL) to give 210 mg of a yellow solid in 82% yield. 1H NMR (500 MHz, CDC13) δ 0.25 (s, 3H), 1.09 (s, 3H), 1.21 (d, J = 9.5 Hz, 1H), 1.43 (s, 9H), 1.45 (s, 9H), 2.05 (t, J = 5.5 Hz, 1H), 2.15 - 2.17 (m, 1H), 2.50 (dt, J = 10, 5.5 Hz, 1H), 2.69 (d, J = 17.5 Hz, 1H), 2.80 - 2.93 (m, 1H), 6.18 (t, J = 7.5 Hz, 2H), 6.49 (d, J = 7.5 Hz, 1H), 6.57 (d, J = 7.0 Hz, 2H), 6.88 (d, J = 8.5 Hz, 1H), 7.10 (d, J = 1.5 Hz, 1H), 7.19 - 7.33 (m, 5H), 7.35 - 7.44 (m, 3H), 7.48 (t, J = 7.5 Hz, 3H), 7.52 (d, J = 2.5 Hz, 1H), 7.56 (d, J = 1.5 Hz, 1H), 7.62 - 7.66 (m, 4H), 7.75 (s, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 8.11 (d, J = 7.0 Hz, 1H), 8.18 (s, 1H), 8.93 (s, 1H). MS: 1156.45 [M+H] + .

[0193] Example 19: Synthesis route of tetradentate cyclometalated platinum (II) complex Pt20:

[0194] (1) Synthesis of intermediate chiral 20-NH2: Into a reaction flask was added 2-Cl (350 mg, 0.67 mmol, 1.0 equiv), iPrdPhNH2 (446 mg, 0.81 mmol, 1.2 equiv), Pd2(dba)3 (18 mg, 0.02 mmol, 3 mol%), JohnPhos (24 mg, 0.08 mmol, 12 mol%) and sodium tert-butoxide (129 mg, 1.34 mmol, 2.0 equiv) successively, and the flask was purged with nitrogen three times, and toluene (5 mL) was added. The mixture was stirred at 85 °C for 18 h, and separated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 687 mg of white solid in 99% yield. The compound was easily oxidized and used directly in the next step without characterization.

[0195] (2) Synthesis of Ligand 20-L: The synthesis was performed according to the procedure described in the synthesis of 1-L in Example 1 with 20-NH2(687 mg, 0.66 mmol, 1.0 equiv), ammonium hexafluorophosphate (216 mg, 1.32 mmol, 2.0 equiv), triethyl orthoformate (3 mL) to give 510 mg of a solid in 65% yield. 1 H NMR (500 MHz, CDC13) δ 0.75 (s, 3H), 0.91 (d, J = 7.0 Hz, 6H), 0.99 (d, J = 7.0 Hz, 6H), 1.30 (s, 9H), 1.33 (d, J = 10.0 Hz, 1H), 1.47 (s, 3H), 1.48 (s, 9H), 2.05 - 2.16 (m, 2H), 2.35 - 2.39 (m, 1H), 2.77 (dt, J = 9.5, 5.5 Hz, 1H), 2.94 (t, J = 5.5 Hz, 1H), 3.07 - 3.15 (m, 2H), 6.47 (t, J = 2.0 Hz, 1H), 6.78 (t, J = 2.0 Hz, 1H), 7.01 (dd, J = 8.5, 2.0 Hz, 1H), 7.07 - 7.23 (m, 11H), 7.24 - 7.30 (m, 5H), 7.33 - 7.36 (m, 1H), 7.38 (t, J = 7.5 Hz, 1H), 7.41 (s, 1H), 7.45 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.60 (d, J = 2.0 Hz, 1H), 7.62 (s, 2H), 7.78 (d, J = 8.0 Hz, 1H), 8.04 (d, J = 8.5 Hz, 1H), 8.09 (dt, J = 7.5, 1.0 Hz, 1H), 8.22 (s, 1H), 9.26 (s, 1H).

[0196] (3) Synthesis of Complex Pt20: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1 with Ligand 20-L (490 mg, 0.41 mmol, 1.0 equiv), Pt(COD)Cl2(161 mg, 0.43 mmol, 1.05 equiv), sodium acetate (101 mg, 1.23 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (5 mL) to give 241 mg of a yellow solid in 47% yield. 1H NMR (500 MHz, CDC13) δ 0.27 (s, 3H), 1.05 (d, J = 2.5 Hz, 3H), 1.06 (d, J = 2.5 Hz, 3H), 1.08 - 1.18 (m, 9H), 1.24 (d, J = 9.5 Hz, 1H), 1.37 (s, 9H), 1.44 (s, 9H), 2.10 (t, J = 5.5 Hz, 1H), 2.16 - 2.20 (m, 1H), 2.25 (p, J = 6.5 Hz, 1H), 2.54 (dt, J = 10.0, 5.5 Hz, 1H), 2.66 (p, J = 6.5 Hz, 1H), 2.72 (d, J = 18.5 Hz, 1H), 2.85 - 2.95 (m, 1H), 6.26 (t, J = 7.5 Hz, 2H), 6.55 (t, J = 7.5 Hz, 1H), 6.69 (d, J = 7.5 Hz, 2H), 6.77 (d, J = 8.0 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H), 7.08 (d, J = 1.5 Hz, 1H), 7.21 - 7.25 (m, 3H), 7.28 - 7.33 (m, 3H), 7.37 - 7.45 (m, 4H), 7.48 - 7.53 (m, 1H), 7.56 (d, J = 2.5 Hz, 1H), 7.60 (d, J = 7.5 Hz, 2H), 7.72 (s, 1H), 7.77 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 8.13 (dd, J = 7.5, 1.5 Hz, 1H), 8.93 (s, 1H). MS: 1240.54 [M+H] + .

[0197] Example 20: Synthesis route of tetradentate cyclometalated platinum (II) complex Pt21

[0198] (1) Synthesis of intermediate chiral 3-Cl: Into a reaction flask was added 1-OH (360 mg, 1.02 mmol, 1.0 eq), Ph-Br (299 mg, 1.12 mmol, 1.1 eq), cuprous iodide (19 mg, 0.1 mmol, 10 mol%), 2-picolinic acid (25 mg, 0.2 mmol, 20 mol%), and potassium phosphate (433 mg, 2.04 mmol, 2.0 eq) successively, and the flask was purged with nitrogen three times. Dimethyl sulfoxide (5 mL) was added. The reaction was stirred at 100 °C for 60 h, diluted with water, extracted with ethyl acetate three times, washed with brine once, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1-10:1, to give 300 mg of a white solid, yield 54%.1 H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.31 (d, J = 10.0 Hz, 1H), 1.45 (s, 3H), 2.32 - 2.36 (m, 1H), 2.76 (dt, J = 10.0, 6.0 Hz, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.06 (d, J = 2.5 Hz, 2H), 6.98 (t, J = 2.0 Hz, 1H), 7.03 (dd, J = 8.5, 2.0 Hz, 1H), 7.15 (dd, J = 2.5, 1.5 Hz, 1H), 7.27 (t, J = 1.5 Hz, 1H), 7.29 - 7.36 (m, 2H), 7.38 - 7.44 (m, 4H), 7.49 - 7.52 (m, 2H), 7.55 (d, J = 2.0 Hz, 1H), 7.76 (dt, J = 8.5, 1.0 Hz, 1H), 8.07 - 8.09 (m, 2H), 8.20 (s, 1H).

[0199] (2) Synthesis of intermediate chiral 21-NH2: Into a reaction vial was added 3-Cl (300 mg, 0.55 mmol, 1.0 equiv), dPhNH2 (261 mg, 0.67 mmol, 1.2 equiv), Pd2(dba)3 (15 mg, 0.017 mmol, 3 mol%), JohnPhos (20 mg, 0.067 mmol, 12 mol%), and sodium tert-butoxide (106 mg, 1.1 mmol, 2.0 equiv) sequentially, and the vial was flushed with nitrogen three times and toluene (3 mL) was added. The reaction was stirred at 85 °C for 18 h, and the product was isolated by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 50:1 to 10:1 to give 313 mg of white solid in 63% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0200] (3) Synthesis of ligand 21-L: The synthesis was performed according to the procedure described in Example 1 for the synthesis of 1-L, using 21-NH2 (313 mg, 0.35 mmol, 1.0 equiv), ammonium hexafluorophosphate (114 mg, 0.7 mmol, 2.0 equiv), and triethyl orthoformate (3 mL). The final product was obtained as a solid in 64% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.64 (s, 3H), 1.19 (d, J = 9.5 Hz, 1H), 1.41 (s, 3H), 1.45 (s, 9H), 2.26 - 2.30 (m, 1H), 2.70 - 2.75 (m, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.01 - 3.11 (m, 2H), 6.91 (t, J = 2.0 Hz, 1H), 7.09 - 7.18 (m, 10H), 7.20 (dd, J = 8.5, 2.0 Hz, 1H), 7.28 (t, J = 1.5 Hz, 1H), 7.33 - 7.37 (m, 1H), 7.46 - 7.50 (m, 3H), 7.51 - 7.58 (m, 4H), 7.60 (s, 1H), 7.66 (d, J = 2.0 Hz, 1H), 7.70 (t, J = 2.0 Hz, 1H), 7.71 - 7.74 (m, 4H), 7.80 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.5 Hz, 1H), 8.21 (s, 1H), 8.26 - 8.31 (m, 1H), 8.37 (d, J = 8.5 Hz, 1H), 10.26 (s, 1H). HRMS (ESI): C 65 H 55 N4O[M] + Calcd 907.4370, Found 907.4370.

[0201] (4) Synthesis of complex Pt21: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1, with ligand 21-L (181 mg, 0.17 mmol, 1.0 equiv), Pt(COD)Cl2(64 mg, 0.17 mmol, 1.0 equiv), sodium acetate (42 mg, 0.51 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (4 mL). The final product was obtained as a yellow solid 155 mg in 83% yield. 1H NMR (500 MHz, CDC13) δ 0.26 (s, 3H), 1.08 (s, 3H), 1.21 (d, J = 9.5 Hz, 1H), 1.43 (s, 9H), 2.05 (t, J = 5.5 Hz, 1H), 2.15 - 2.18 (dt, J = 5.9, 2.4 Hz, 1H), 2.45 - 2.54 (m, 1H), 2.71 (d, J = 18.0 Hz, 1H), 2.88 (d, J = 18.1 Hz, 1H), 6.16 (t, J = 7.6 Hz, 2H), 6.43 - 6.59 (m, 3H), 6.84 (d, J = 8.1 Hz, 1H), 7.03 (t, J = 7.7 Hz, 1H), 7.20 - 7.24 (m, 1H), 7.27 - 7.38 (m, 6H), 7.42 (t, J = 7.4 Hz, 1H), 7.45 - 7.55 (m, 4H), 7.62 (d, J = 7.6 Hz, 2H), 7.68 (s, 1H), 7.72 - 7.80 (m, 3H), 7.82 (d, J = 8.2 Hz, 1H), 7.90 (d, J = 8.1 Hz, 1H), 8.06 (d, J = 8.3 Hz, 1H), 8.12 (d, J = 7.5 Hz, 1H), 8.93 (s, 1H). HRMS (ESI): C 65 H 53 N4OPt[M+H] + Calcd 1100.3862, Found 1100.3862.

[0202] Example 21: Tetradentate cyclometalated platinum(II) complex Pt22synthesis route:

[0203] 1) Synthesis of intermediate chiral 4-Cl: Into a reaction flask was added 1-OH (300 mg, 0.85 mmol, 1.0 eq), 3-chloro-5-bromobenzotrifluoride (264 mg, 1.02 mmol, 1.2 eq), cuprous iodide (16 mg, 0.085 mmol, 10 mol%), 2-picolinic acid (21 mg, 0.17 mmol, 20 mol%), and potassium phosphate (359 mg, 1.69 mmol, 2.0 eq), and the flask was purged with nitrogen three times. Dimethyl sulfoxide (5 mL) was added. The reaction was stirred at 100 °C for 60 h, diluted with water, extracted with ethyl acetate three times, washed with brine once, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. Purification was performed on a silica gel column eluting with petroleum ether / ethyl acetate = 20:1-10:1 to give 230 mg of white solid in 51% yield. 1H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.32 (d, J = 10 Hz, 1H), 1.46 (s, 3H), 2.34 - 2.38 (m, 1H), 2.77 (dt, J = 10.0, 5.5 Hz, 1H), 2.94 (t, J = 5.5 Hz, 1H), 3.08 (d, J = 2.5 Hz, 2H), 6.99 (dd, J = 8.5, 2.5 Hz, 1H), 7.13 (t, J = 2.0 Hz, 1H), 7.17 (t, J = 2.0 Hz, 1H), 7.28 (t, J = 2.0 Hz, 1H), 7.30 - 7.35 (m, 1H), 7.39 (s, 1H), 7.45 (ddd, J = 8.4, 7.0, 1.5 Hz, 1H), 7.54 (d, J = 2.0 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 8.08 - 8.12 (m, 2H), 8.22 (s, 1H).

[0204] (2) Synthesis of intermediate chiral 22-NH2: Into a reaction vial was added 4-Cl (210 mg, 0.39 mmol, 1.0 equiv), dPhNH2 (155 mg, 0.394 mmol, 1.0 equiv), Pd2(dba)3 (11 mg, 0.012 mmol, 3 mol%), JohnPhos (7 mg, 0.24 mmol, 6 mol%), and sodium tert-butoxide (76 mg, 0.79 mmol, 2.0 equiv), and the vial was flushed with nitrogen three times. Toluene (5 mL) was added. The reaction was heated at 110 °C for 18 h. The reaction mixture was separated by silica gel column chromatography, eluting with petroleum ether / ethyl acetate = 50:1 to 10:1, to give 180 mg of white solid in 51% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0205] (3) Synthesis of ligand 22-L: The procedure was the same as that for 1-L in Example 1. The reaction was carried out using 22-NH2 (180 mg, 0.20 mmol, 1.0 equiv), ammonium hexafluorophosphate (66 mg, 0.40 mmol, 2.0 equiv), and triethyl orthoformate (2 mL) to give 205 mg of solid in 98% yield.

[0206] (4) Synthesis of complex Pt22: The procedure was the same as that for Pt1 in Example 1. The reaction was carried out using ligand 22-L (200 mg, 0.19 mmol, 1.0 equiv), Pt(COD)Cl2 (75 mg, 0.20 mmol, 1.05 equiv), sodium acetate (47 mg, 0.57 mmol, 3.0 equiv), and diethyleneglycol dimethyl ether (5 mL) to give 45 mg of yellow solid in 22% yield. 1H NMR (500 MHz, CDC13) δ 0.26 (s, 3H), 1.08 (s, 3H), 1.20 (d, J = 9.5 Hz, 1H), 1.42 (s, 9H), 2.05 (t, J = 5.0 Hz, 1H), 2.16 (s, 1H), 2.50 (dt, J = 9.5, 5.5 Hz, 1H), 2.72 (d, J = 18.0 Hz, 1H), 2.89 (d, J = 18.0 Hz, 1H), 6.13 (t, J = 7.5 Hz, 2H), 6.48 (t, J = 7.5 Hz, 2H), 6.84 (d, J = 8.0 Hz, 1H), 7.02 - 7.07 (m, 2H), 7.23 - 7.37 (m, 6H), 7.39 - 7.45 (m, 2H), 7.48 - 7.53 (m, 2H), 7.60 (d, J = 7.5 Hz, 3H), 7.77 (d, J = 4.5 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 8.13 (d, J = 7.5 Hz, 1H), 8.90 (s, 1H). MS: 1092.34 [M+H] + .

[0207] Example 22: Synthesis route of tetradentate cyclometalated platinum(II) complex Pt23:

[0208] (1) Synthesis of intermediate chiral MeCz-OMe: Into a reaction flask was added OTf (675 mg, 2.1 mmol, 1.05 equiv), MeCz (423 mg, 2.0 mmol, 1.0 equiv), Pd2(dba)3(55 mg, 0.06 mmol, 3 mol%), XPhos (114 mg, 0.24 mmol, 12 mol%) and potassium phosphate (1.27 g, 6.0 mmol, 3.0 equiv) successively, and the flask was replaced with nitrogen three times, and then toluene (6 mL) was added. The stirred reaction was carried out at 110 °C for 18 h, and then the solvent was removed by distillation under reduced pressure. Purification was performed by silica gel column chromatography, and elution was performed using petroleum ether / ethyl acetate = 50:1-10:1 to obtain 742 mg of yellow solid, with a yield of 97%. 1H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.32 (d, J = 9.5 Hz, 1H), 1.45 (s, 3H), 2.33 - 2.37 (m, 1H), 2.52 (s, 3H), 2.77 (dt, J = 9.5, 5.5 Hz, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.08 (d, J = 2.5 Hz, 2H), 5.54 (br, 1H), 6.77 (dd, J = 8.5, 2.0 Hz, 1H), 7.16 (dd, J = 8.5, 1.5 Hz, 1H), 7.31 (d, J = 2.0 Hz, 1H), 7.38 (s, 1H), 7.57 (d, J = 8.5 Hz, 1H), 7.78 (s, 1H), 7.87 (d, J = 8.5 Hz, 1H), 8.20 (s, 1H).

[0209] (2) Synthesis of intermediate chiral MeCz-OH: MeCz-OMe (742 mg, 1.94 mmol, 1.0 equiv), hydrobromic acid (48%) (8 mL), acetic acid (3 mL) were added into a reaction flask sequentially, stirred at 120 °C for 16 h, cooled to room temperature. Neutralized with aqueous NaHC03, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product MeCz-OH was obtained as a white solid 657 mg, yield 92% by slurry in petroleum ether / ethyl acetate. 1 H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.32 (d, J = 9.5 Hz, 1H), 1.45 (s, 3H), 2.33 - 2.37 (m, 1H), 2.52 (s, 3H), 2.77 (dt, J = 9.5, 5.5 Hz, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.08 (d, J = 2.5 Hz, 2H), 5.54 (br, 1H), 6.77 (dd, J = 8.5, 2.0 Hz, 1H), 7.16 (dd, J = 8.5, 1.5 Hz, 1H), 7.31 (d, J = 2.0 Hz, 1H), 7.38 (s, 1H), 7.57 (d, J = 8.5 Hz, 1H), 7.78 (s, 1H), 7.87 (d, J = 8.5 Hz, 1H), 8.20 (s, 1H).

[0210] (3) Synthesis of intermediate chiral 5-Cl: Into a reaction flask was added MeCz-OH (600 mg, 1.63 mmol, 1.0 eq), 1-bromo-3-tert-butyl-5-chlorobenzene (484 mg, 1.95 mmol, 1.2 eq), copper(I) iodide (31 mg, 0.16 mmol, 10 mol%), 2-picolinic acid (40 mg, 0.33 mmol, 20 mol%) and potassium phosphate (692 mg, 3.26 mmol, 2.0 eq) successively, and the flask was purged with nitrogen for three times. Dimethyl sulfoxide (5 mL) was added. The reaction was stirred at 100 °C for 48 h, diluted with water, extracted with ethyl acetate for three times, the organic phase was washed with brine once, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. Purification was performed on a silica gel column eluted with petroleum ether / ethyl acetate = 20:1-10:1 to give 375 mg of white solid in 43% yield. 1 H NMR (500 MHz, CDC13) δ 0.72 (s, 3H), 1.27 (s, 9H), 1.31 (d, J = 9.5 Hz, 1H), 1.45 (s, 3H), 2.33 - 2.37 (m, 1H), 2.54 (s, 3H), 2.76 (dt, J = 9.5, 5.5 Hz, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.06 (d, J = 2.5 Hz, 2H), 6.77 (t, J = 2.0 Hz, 1H), 6.95 (dd, J = 8.5, 2.0 Hz, 1H), 7.01 (t, J = 2.0 Hz, 1H), 7.05 (t, J = 1.5 Hz, 1H), 7.23 (dd, J = 8.0, 1.5 Hz, 1H), 7.36 (s, 1H), 7.50 (d, J = 2.0 Hz, 1H), 7.64 (d, J = 8.5 Hz, 1H), 7.85 (s, 1H), 8.01 (d, J = 8.5 Hz, 1H), 8.18 (s, 1H).

[0211] (4) Synthesis of intermediate chiral 23-NH2: Into a reaction flask was added 5-Cl (370 mg, 0.69 mmol, 1.0 eq), dPhNH2 (353 mg, 0.90 mmol, 1.3 eq), Pd2(dba)3 (19 mg, 0.02 mmol, 3 mol%), JohnPhos (25 mg, 0.083 mmol, 12 mol%) and sodium tert-butoxide (133 mg, 1.38 mmol, 2.0 eq) successively, and the flask was purged with nitrogen for three times. Toluene (3 mL) was added. The reaction was stirred at 85 °C for 18 h, and purification was performed on a silica gel column eluted with petroleum ether / ethyl acetate = 50:1-10:1 to give 345 mg of white solid in 57% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0212] (5) Synthesis of Ligand 23-L: The synthetic procedure was consistent with 1-L in Example 1, with reaction charge of 23-NH2(345 mg, 0.39 mmol, 1.0 eq), ammonium hexafluorophosphate (126 mg, 0.77 mmol, 2.0 eq), triethyl orthoformate (3 mL), and finally 329 mg of solid was obtained in 81% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.63 (s, 3H), 1.18 (d, J = 8.5 Hz, 1H), 1.30 (s, 9H), 1.41 (s, 3H), 1.44 (s, 9H), 2.27 - 2.30 (m, 1H), 2.73 (dt, J = 9.5, 5.5 Hz, 1H), 2.91 (t, J = 5.5 Hz, 1H), 2.99 - 3.10 (m, 2H), 6.74 (t, J = 2.0 Hz, 1H), 6.96 (t, J = 2.0 Hz, 1H), 7.08 - 7.17 (m, 11H), 7.29 (dd, J = 8.5, 1.5 Hz, 1H), 7.45 (t, J = 2.0 Hz, 1H), 7.46 - 7.49 (m, 1H), 7.51 - 7.58 (m, 3H), 7.59 (d, J = 2.0 Hz, 1H), 7.68 - 7.74 (m, 4H), 8.06 (s, 1H), 8.19 (s, 1H), 8.29 (d, J = 8.5 Hz, 1H), 10.23 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 25.89, 30.89, 31.14, 31.75, 32.94, 35.25, 35.28, 39.30, 39.84, 44.24, 103.28, 110.03, 110.71, 113.01, 113.29, 114.17, 115.84, 117.84, 118.05, 119.92, 120.93, 121.31, 123.83, 125.36, 127.02, 127.97, 128.01, 128.04, 128.23, 128.67, 130.08, 130.33, 132.31, 132.40, 137.08, 138.42, 139.92, 140.76, 140.93, 141.78, 145.23, 147.65, 149.73, 153.86, 155.13, 156.37, 159.56. HRMS (ESI): C 64 H 61 N4O[M] + Calcd 901.4840, Found 901.4839.

[0213] (6) Synthesis of complex Pt23: The synthetic procedure was consistent with Pt1 in Example 1, with ligand 23-L (200 mg, 0.19 mmol, 1.0 equiv), Pt(COD)Cl2(75 mg, 0.02 mmol, 1.0 equiv), sodium acetate (47 mg, 0.57 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (4 mL) as the reaction feed. The final product was obtained as a yellow solid 200 mg in 96% yield. 1 H NMR (500 MHz, CDC13) δ 0.24 (s, 3H), 1.07 (s, 3H), 1.19 (d, J = 9.5 Hz, 1H), 1.41 (s, 9H), 1.44 (s, 9H), 2.02 (t, J = 5.5 Hz, 1H), 2.13 - 2.15 (m, 1H), 2.46 - 2.51 (m, 1H), 2.61 (s, 3H), 2.67 (d, J = 18.0 Hz, 1H), 2.83 - 2.88 (m, 1H), 6.16 (t, J = 7.5 Hz, 2H), 6.45 - 6.53 (m, 3H), 6.83 (d, J = 8.0 Hz, 1H), 7.01 (t, J = 7.5 Hz, 1H), 7.08 (d, J = 1.5 Hz, 1H), 7.18 - 7.29 (m, 6H), 7.34 (d, J = 2.0 Hz, 1H), 7.49 (dd, J = 11.0, 2.0 Hz, 2H), 7.60 (d, J = 7.5 Hz, 2H), 7.71 (s, 1H), 7.76 (t, J = 8.5 Hz, 2H), 7.90 (s, 1H), 7.97 (d, J = 8.0 Hz, 1H), 8.89 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.25, 21.60, 25.76, 31.33, 31.65, 32.15, 33.09, 34.80, 35.02, 39.48, 39.69, 42.93, 105.76, 107.64, 110.71, 111.29, 111.90, 112.35, 113.00, 114.50, 115.10, 115.88, 116.83, 120.36, 122.66, 123.95, 124.75, 125.58, 127.11, 127.49, 127.73, 128.14, 128.32, 128.72, 129.21, 129.51, 129.68, 131.59, 131.86, 136.47, 136.50, 136.87, 138.04, 138.74, 138.77, 142.38, 144.70, 147.02, 147.56, 147.64, 149.67, 150.28, 152.32, 152.47, 154.62, 194.10. HRMS (ESI): C 64 H 59 N4OPt[M+H] + Calcd 1094.4331, Found 1094.4337.

[0214] Example 23: Synthesis route of tetradentate cyclometalated platinum(II) complex Pt24:

[0215] (1) Synthesis of intermediate chiral PhCz-OMe: Into a reaction flask was added OTf (675 mg, 2.10 mmol, 1.05 equiv), PhCz (547 mg, 2.0 mmol, 1.0 equiv), Pd2(dba)3(55 mg, 0.06 mmol, 3 mol%), XPhos (114 mg, 0.24 mmol, 12 mol%) and potassium phosphate (1.27 g, 6.0 mmol, 3.0 equiv) successively, and the flask was purged with nitrogen three times. Toluene (6 mL) was added. The reaction was stirred at 110 °C for 18 h, and the solvent was removed by distillation under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 859 mg of yellow solid, yield 97%. 1H NMR (500 MHz, CDC13) δ 0.74 (s, 3 H), 1.32 (d, J = 10.0 Hz, 1 H), 1.46 (s, 3 H), 2.34 - 2.38 (m, 1 H), 2.77 (dt, J = 10.0, 5.5 Hz, 1 H), 2.92 (t, J = 5.5 Hz, 1 H), 3.10 (d, J = 3.0 Hz, 2 H), 6.47 (br, 1 H), 6.76 (dd, J = 8.5, 2.0 Hz, 1 H), 7.30 - 7.37 (m, 2 H), 7.43 (s, 1 H), 7.47 (t, J = 7.5 Hz, 2 H), 7.59 (dd, J = 8.5, 1.5 Hz, 1 H), 7.67 - 7.77 (m, 3 H), 7.91 (d, J = 8.0 Hz, 1 H), 8.18 (d, J = 1.5 Hz, 1 H), 8.21 (s, 1 H).

[0216] (2) Synthesis of intermediate chiral PhCz-OH: To a reaction flask was added PhCz-OMe (859 mg, 1.93 mmol, 1.0 equiv), hydrobromic acid (48%) (15 mL), acetic acid (5 mL), stirred at 120 °C for 16 h, cooled to room temperature. Neutralized with aqueous NaHC03, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product PhCz-OH was obtained as a white solid 780 mg, 94% yield, by trituration with petroleum ether / ethyl acetate. 1 H NMR (500 MHz, CDC13) δ 0.74 (s, 3 H), 1.32 (d, J = 10.0 Hz, 1 H), 1.46 (s, 3 H), 2.34 - 2.38 (m, 1 H), 2.77 (dt, J = 10.0, 5.5 Hz, 1 H), 2.92 (t, J = 5.5 Hz, 1 H), 3.10 (d, J = 3.0 Hz, 2 H), 6.47 (br, 1 H), 6.76 (dd, J = 8.5, 2.0 Hz, 1 H), 7.30 - 7.37 (m, 2 H), 7.43 (s, 1 H), 7.47 (t, J = 7.5 Hz, 2 H), 7.59 (dd, J = 8.5, 1.5 Hz, 1 H), 7.67 - 7.77 (m, 3 H), 7.91 (d, J = 8.0 Hz, 1 H), 8.18 (d, J = 1.5 Hz, 1 H), 8.21 (s, 1 H).

[0217] (3) Synthesis of intermediate chiral 6-Cl: The synthesis was performed according to the procedure described in the synthesis of 1-Cl in Example 1 with PhCz-OH (750 mg, 1.74 mmol, 1.0 equiv), 1-bromo-3-tert-butyl-5-chlorobenzene (518 mg, 2.09 mmol, 1.2 equiv), copper(I) iodide (33 mg, 0.17 mmol, 10 mol%), 2-picolinic acid (43 mg, 0.35 mmol, 20 mol%), potassium phosphate (1.11 g, 5.22 mmol, 3.0 equiv), and dimethyl sulfoxide (6 mL). White solid was obtained in 758 mg, 73% yield. 1 H NMR (500 MHz, CDC13) δ 0.74 (s, 3H), 1.28 (s, 9H), 1.33 (d, J = 10.0 Hz, 1H), 1.46 (s, 3H), 2.34 - 2.38 (m, 1H), 2.78 (dt, J = 10.0, 5.5 Hz, 1H), 2.94 (t, J = 5.5 Hz, 1H), 3.09 (d, J = 3.0 Hz, 2H), 6.79 (t, J = 2.0 Hz, 1H), 7.00 (dd, J = 8.5, 2.0 Hz, 1H), 7.02 (t, J = 2.0 Hz, 1H), 7.07 (t, J = 1.5 Hz, 1H), 7.33 - 7.37 (m, 1H), 7.40 (s, 1H), 7.46 - 7.52 (m, 3H), 7.66 (dd, J = 8.5, 2.0 Hz, 1H), 7.70 - 7.75 (m, 2H), 7.82 (d, J = 8.5 Hz, 1H), 8.10 (d, J = 8.5 Hz, 1H), 8.21 (s, 1H), 8.27 (d, J = 2.0 Hz, 1H).

[0218] (4) Synthesis of intermediate chiral 24-NH2: Into a reaction vial was added 6-Cl (400 mg, 0.67 mmol, 1.0 equiv), dPhNH2 (316 mg, 0.8 mmol, 1.2 equiv), Pd2(dba)3 (18 mg, 0.02 mmol, 3 mol%), JohnPhos (24 mg, 0.08 mmol, 12 mol%), and sodium tert-butoxide (161 mg, 1.68 mmol, 2.0 equiv) sequentially, and the vial was purged with nitrogen three times and toluene (4 mL) was added. The reaction was stirred at 85 °C for 18 h, and the mixture was separated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent to give 319 mg of white solid in 49% yield. The compound was oxidized easily and used directly in the next step without characterization.

[0219] (5) Synthesis of Ligand 24-L: The synthesis was performed according to the procedure described for the synthesis of 1-L in Example 1, with 24-NH2(319 mg, 0.33 mmol, 1.0 equiv), ammonium hexafluorophosphate (109 mg, 0.67 mmol, 2.0 equiv), triethyl orthoformate (3 mL) as the reactants. The final product was obtained as a solid 310 mg in 85% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.20 (d, J = 9.5 Hz, 1H), 1.31 (s, 9H), 1.42 (s, 3H), 1.44 (s, 9H), 2.28 - 2.32 (m, 1H), 2.74 (dt, J = 10.5, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.04 - 3.13 (m, 2H), 6.77 (t, J = 2.0 Hz, 1H), 6.96 (t, J = 2.0 Hz, 1H), 7.10 - 7.18 (m, 11H), 7.37 (t, J = 7.5 Hz, 1H), 7.45 - 7.59 (m, 6H), 7.62 (d, J = 2.5 Hz, 2H), 7.71 - 7.73 (m, 3H), 7.77 - 7.82 (m, 3H), 7.87 (d, J = 9.0 Hz, 1H), 8.22 (s, 1H), 8.46 (d, J = 8.5 Hz, 1H), 8.61 (d, J = 2.0 Hz, 1H), 10.24 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.53, 25.90, 30.91, 31.16, 31.75, 32.99, 35.27, 35.32, 39.32, 39.86, 44.28, 103.35, 110.23, 111.32, 113.29, 113.30, 114.19, 116.00, 117.93, 118.23, 118.39, 121.07, 121.52, 124.22, 125.24, 125.37, 126.67, 127.24, 127.96, 128.00, 128.23, 128.28, 128.70, 128.76, 130.13, 132.34, 132.44, 134.37, 137.12, 139.69, 139.94, 141.11, 141.25, 141.70, 141.94, 145.39, 147.84, 149.49, 154.24, 155.17, 156.44, 159.45. HRMS (ESI): C 69 H 63 N4O[M] + Calcd 963.4996, Found 963.4998.

[0220] (6) Synthesis of complex Pt24: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1, with ligand 24-L (200 mg, 0.18 mmol, 1.0 equiv), Pt(COD)Cl2(71 mg, 0.19 mmol, 1.0 equiv), sodium acetate (44 mg, 0.54 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (6 mL). The final product was obtained as a yellow solid 117 mg in 56% yield. 1 H NMR (500 MHz, CDC13) δ 0.25 (s, 3H), 1.08 (s, 3H), 1.21 (d, J = 9.5 Hz, 1H), 1.43 (s, 9H), 1.45 (s, 9H), 2.04 (t, J = 5.5 Hz, 1H), 2.14 - 2.18 (m, 1H), 2.48 - 2.52 (m, 1H), 2.71 (d, J = 18.0 Hz, 1H), 2.87 - 2.91 (m, 1H), 6.19 (t, J = 7.5 Hz, 2H), 6.48 - 6.55 (m, 3H), 6.84 (d, J = 8.0 Hz, 1H), 7.02 (t, J = 7.5 Hz, 1H), 7.09 (d, J = 1.5 Hz, 1H), 7.19 - 7.29 (m, 4H), 7.32 (d, J = 8.0 Hz, 1H), 7.37 (d, J = 2.0 Hz, 1H), 7.40 (tt, J = 7.0, 1.5 Hz, 1H), 7.49 - 7.55 (m, 4H), 7.61 (d, J = 7.5 Hz, 2H), 7.72 (dd, J = 8.5, 2.0 Hz, 1H), 7.76 (s, 1H), 7.80 - 7.85 (m, 3H), 7.96 (dd, J = 17.0, 8.5 Hz, 2H), 8.31 (d, J = 1.5 Hz, 1H), 8.92 (s, 1H). HRMS (ESI): C 69 H 61 N4OPt [M+H] + Calcd 1156.4488, Found 1156.4478.

[0221] Example 24: Tetradentate cyclometalated platinum(II) complex Pt25 synthesis route:

[0222] (1) Synthesis of intermediate chiral NCz-OMe: Into a reaction flask was added OTf (675 mg, 2.10 mmol, 1.05 equiv), NCz (397 mg, 2.0 mmol, 1.0 equiv), Pd2(dba)3(55 mg, 0.06 mmol, 3 mol%), XPhos (114 mg, 0.24 mmol, 12 mol%) and potassium phosphate (1.06 g, 5.0 mmol, 2.5 equiv) successively, and the flask was purged with nitrogen three times. Toluene (6 mL) was added. The reaction was stirred at 110 °C for 18 h, and the solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 430 mg of a yellow solid, yield 58%. 1 H NMR (500 MHz, CDC13) δ 0.75 (s, 3H), 1.34 (d, J = 9.5 Hz, 1H), 1.47 (s, 3H), 2.36 - 2.40 (m, 1H), 2.79 (dt, J = 10.0, 6.0 Hz, 1H), 2.95 (t, J = 5.5 Hz, 1H), 3.10 (d, J = 2.5 Hz, 2H), 3.92 (s, 3H), 7.01 (dd, J = 8.5, 2.0 Hz, 1H), 7.26 - 7.30 (m, 1H), 7.33 (d, J = 2.0 Hz, 1H), 7.38 (s, 1H), 8.04 (dd, J = 8.5, 1.5 Hz, 1H), 8.23 (s, 1H), 8.30 (d, J = 8.5 Hz, 1H), 8.55 (dd, J = 5.0, 1.5 Hz, 1H).

[0223] (2) Synthesis of intermediate chiral NCz-OH: Into a reaction flask was added NCz-OMe (430 mg, 1.16 mmol, 1.0 equiv), hydrobromic acid (48%) (20 mL), acetic acid (2 mL) successively, and the reaction was stirred at 120 °C for 24 h, and cooled to room temperature. Neutralized with aqueous NaHC03solution, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product NCz-OH was obtained as a white solid by slurrying with petroleum ether / ethyl acetate, 325 mg, yield 84%.

[0224] (3) Synthesis of intermediate chiral 7-Cl: The synthesis was performed according to the procedure described in the synthesis of 1-Cl in Example 1 with NCz-OH (325 mg, 0.91 mmol, 1.0 equiv), 1-bromo-3-tert-butyl-5-chlorobenzene (294 mg, 1.19 mmol, 1.2 equiv), copper(I) iodide (35 mg, 0.18 mmol, 10 mol%), 2-picolinic acid (45 mg, 0.36 mmol, 20 mol%), potassium phosphate (483 mg, 2.28 mmol, 2.0 equiv), and dimethyl sulfoxide (5 mL). White solid 445 mg was obtained in 94% yield. 1 H NMR (500 MHz, CDC13) δ 0.72 (s, 3H), 1.28 (s, 9H), 1.31 (d, J = 9.5 Hz, 1H), 1.46 (s, 3H), 2.34 - 2.38 (m, 1H), 2.77 (dt, J = 9.5, 5.5 Hz, 1H), 2.94 (t, J = 5.5 Hz, 1H), 3.08 (d, J = 2.5 Hz, 2H), 6.83 (t, J = 2.0 Hz, 1H), 7.03 (t, J = 2.0 Hz, 1H), 7.06 (dd, J = 8.5, 2.0 Hz, 1H), 7.10 (t, J = 2.0 Hz, 1H), 7.31 - 7.35 (m, 2H), 7.50 (d, J = 2.0 Hz, 1H), 8.11 (dd, J = 8.0, 1.5 Hz, 1H), 8.20 (s, 1H), 8.37 (d, J = 8.5 Hz, 1H), 8.60 (dd, J = 5.0, 1.5 Hz, 1H).

[0225] (4) Synthesis of intermediate chiral 25-NH2: Into a reaction vial was added 7-Cl (435 mg, 0.83 mmol, 1.0 equiv), dPhNH2 (360 mg, 0.92 mmol, 1.1 equiv), Pd2(dba)3 (23 mg, 0.025 mmol, 3 mol%), SPhos (41 mg, 0.1 mmol, 12 mol%), and sodium tert-butoxide (200 mg, 2.08 mmol, 2.0 equiv), and the vial was purged with nitrogen three times and toluene (6 mL) was added. The reaction was stirred at 85 °C for 18 h, and the product was isolated by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 50:1 to 10:1 to give 701 mg of white solid in 96% yield. The compound was oxidized easily and used directly in the next step without characterization.

[0226] (5) Synthesis of Ligand 25-L: The synthesis was performed according to the procedure described for the synthesis of 1-L in Example 1, with 25-NH2(700 mg, 0.8 mmol, 1.0 equiv), ammonium hexafluorophosphate (261 mg, 1.6 mmol, 2.0 equiv), triethyl orthoformate (3 mL) as the reaction feed. The final product was obtained as a solid 730 mg, 88% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.63 (s, 3H), 1.17 (d, J = 9.5 Hz, 1H), 1.31 (s, 9H), 1.41 (s, 3H), 1.44 (s, 9H), 2.27 - 2.31 (m, 1H), 2.71 - 2.75 (m, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.06 - 3.12 (m, 2H), 6.82 (t, J = 2.0 Hz, 1H), 6.97 (t, J = 2.0 Hz, 1H), 7.09 - 7.17 (m, 10H), 7.21 (dd, J = 8.5, 2.0 Hz, 1H), 7.46 - 7.50 (m, 3H), 7.51 - 7.59 (m, 2H), 7.61 (s, 1H), 7.70 (d, J = 2.0 Hz, 1H), 7.70 - 7.73 (m, 3H), 8.20 (s, 1H), 8.22 (dd, J = 8.5, 1.5 Hz, 1H), 8.39 (d, J = 8.5 Hz, 1H), 8.60 (dd, J = 5.0, 1.5 Hz, 1H), 10.24 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.48, 25.84, 30.86, 31.13, 31.66, 32.96, 35.25, 35.31, 39.23, 39.78, 44.23, 103.22, 110.60, 113.22, 113.78, 114.20, 116.31, 117.87, 117.99, 118.56, 119.93, 120.05, 122.07, 125.33, 127.99, 128.04, 128.22, 128.25, 128.68, 130.08, 132.29, 132.47, 133.79, 137.08, 139.90, 141.42, 141.47, 141.84, 142.31, 143.24, 145.38, 148.25, 148.74, 155.16, 155.75, 156.52, 159.03. HRMS (ESI): C 62 H 58 N5O[M] + Calcd 888.4636, Found 888.4643.

[0227] (6) Synthesis of complex Pt25: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1, with ligand 25-L (500 mg, 0.48 mmol, 1.0 equiv), Pt(COD)Cl2(181 mg, 0.48 mmol, 1.0 equiv), sodium acetate (119 mg, 1.45 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (20 mL). The final product was obtained as a yellow solid, 96 mg, 17% yield. 1 H NMR (500 MHz, CDC13) δ 0.25 (s, 3H), 1.08 (s, 3H), 1.19 (d, J = 9.5 Hz, 1H), 1.41 (s, 9H), 1.45 (s, 9H), 2.04 (t, J = 5.0 Hz, 1H), 2.15 - 2.18 (m, 1H), 2.48 - 2.53 (m, 1H), 2.71 (d, J = 18.0 Hz, 1H), 2.87 (d, J = 18.0 Hz, 1H), 6.17 (t, J = 7.5 Hz, 2H), 6.47 - 6.50 (m, 3H), 6.83 (d, J = 8.0 Hz, 1H), 7.02 (t, J = 7.5 Hz, 1H), 7.10 (d, J = 1.5 Hz, 1H), 7.19 - 7.29 (m, 4H), 7.33 (s, 1H), 7.38 (d, J = 8.0 Hz, 1H), 7.41 (dd, J = 8.0, 5.0 Hz, 1H), 7.49 - 7.61 (m, 5H), 7.98 (d, J = 8.5 Hz, 1H), 8.14 (t, J = 9.0 Hz, 2H), 8.68 (dd, J = 5.0, 1.5 Hz, 1H), 8.94 (s, 1H). HRMS (ESI): C 62 H 56 N5OPt [M+H] + Calcd 1081.4127, Found 1081.4131.

[0228] Example 25: Synthesis route of tetradentate cyclometalated platinum(II) complex Pt40:

[0229] (1) Synthesis of intermediate chiral 40-NH2: Into a reaction flask was added 2-Cl (600 mg, 1.15 mmol, 1.0 eq), diPrPhFNH2(500 mg, 1.38 mmol, 1.2 eq), Pd2(dba)3(32 mg, 0.035 mmol, 3 mol%), JohnPhos (41 mg, 0.14 mmol, 12 mol%), and NaOtBu (221 mg, 2.3 mmol, 2.0 eq) successively, and the flask was purged with nitrogen three times, and toluene (6 mL) was added. The reaction was carried out at 105 °C for 24 h, and the product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 873 mg of a white solid, in 90% yield. The compound was easily oxidized and was used directly in the next step without characterization.

[0230] (2) Synthesis of ligand 40-L: The synthesis was performed according to the procedure described in Example 1 for the synthesis of 1-L, with 40-NH2(873 mg, 1.03 mmol, 1.0 eq), ammonium hexafluorophosphate (336 mg, 2.06 mmol, 2.0 eq), and triethyl orthoformate (3 mL) as the starting materials. The final product was obtained as a solid in 73% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.64 (s, 3H), 1.08 (d, J = 6.5 Hz, 6H), 1.16 (d, J = 7.0 Hz, 1H), 1.17 (d, J = 6.5 Hz, 6H), 1.36 (s, 9H), 1.41 (s, 3H), 2.28 - 2.30 (m, 1H), 2.35 - 2.40 (m, 2H), 2.71 - 2.75 (m, 1H), 2.92 (t, J = 5.5 Hz, 1H), 3.03 - 3.12 (m, 2H), 7.21 (dd, J = 8.5, 2.0 Hz, 1H), 7.30 - 7.40 (m, 3H), 7.43 - 7.47 (m, 2H), 7.51 (t, J = 2.0 Hz, 1H), 7.57 (s, 1H), 7.60 - 7.64 (m, 2H), 7.66 (t, J = 2.0 Hz, 1H), 7.71 - 7.79 (m, 5H), 7.88 - 7.91 (m, 2H), 7.99 (dt, J = 8.5, 1.0 Hz, 1H), 8.20 (s, 1H), 8.23 (dt, J = 8.0, 1.0 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H), 10.63 (s, 1H).

[0231] (3) Synthesis of complex Pt40: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1, with ligand 40-L (600 mg, 0.60 mmol, 1.1 equiv), Pt(COD)Cl2(204 mg, 0.54 mmol, 1.0 equiv), sodium acetate (134 mg, 1.63 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (6 mL). The final product was obtained as a yellow solid 529 mg, 93% yield. 1 H NMR (500 MHz, CDC13) δ 0.24 (s, 3H), 0.59 (d, J = 9.5 Hz, 1H), 0.62 (d, J = 6.5 Hz, 3H), 1.03 (d, J = 6.5 Hz, 3H), 1.18 (s, 3H), 1.25 (d, J = 6.5 Hz, 3H), 1.37 (d, J = 7.0 Hz, 3H), 1.50 (s, 9H), 2.00 - 2.03 (m, 1H), 2.16 - 2.21 (m, 1H), 2.33 (t, J = 5.5 Hz, 1H), 2.58 - 2.67 (m, 2H), 2.72 - 2.78 (m, 1H), 3.81 - 3.87 (m, 1H), 6.93 (d, J = 8.0 Hz, 1H), 7.21 - 7.27 (m, 4H), 7.30 - 7.40 (m, 4H), 7.44 (t, J = 7.5 Hz, 1H), 7.57 (d, J = 2.0 Hz, 1H), 7.62 - 7.69 (m, 4H), 7.74 - 7.77 (m, 2H), 8.01 (d, J = 7.0 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.31 (s, 1H).

[0232] Example 26: Tetradentate cyclometalated platinum(II) complex Pt47:

[0233] Pt47 was synthesized according to the procedure described in Example 1, with the corresponding ligand as starting material. After metallation, the target compound was synthesized. MS: m / z 1094.14 (M+H) + .

[0234] Example 27: Tetradentate cyclometalated platinum(II) complex Pt78:

[0235] Pt78 was synthesized according to the procedure described in Example 1, with the corresponding ligand as starting material. After metallation, the target compound was synthesized. MS: m / z 1058.36 (M+H) + .

[0236] Example 28: Tetradentate cyclometalated platinum(II) complex Pt82:

[0237] Pt82was synthesized by the same way as in Reference Example 1, replacing the corresponding ligand starting material. After re- metallization, the target compound was synthesized. MS: m / z 1094.42 (M+H) + .

[0238] Example 29: Tetradentate cyclometalated platinum (II) complex Pt88:

[0239] Pt88was synthesized by the same way as in Reference Example 1, replacing the corresponding ligand starting material. After re- metallization, the target compound was synthesized. MS: m / z 1102.29 (M+H) + .

[0240] Example 30: Tetradentate cyclometalated platinum (II) complex Pt95:

[0241] Pt95was synthesized by the same way as in Reference Example 1, replacing the corresponding ligand starting material. After re- metallization, the target compound was synthesized. MS: m / z 907.37 (M+H) + .

[0242] Example 31: Tetradentate cyclometalated platinum (II) complex Pt113:

[0243] Pt113was synthesized by the same way as in Reference Example 1, replacing the corresponding ligand starting material. After re- metallization, the target compound was synthesized. MS: m / z 1024.36 (M+H) + .

[0244] Example 32: Tetradentate cyclometalated platinum (II) complex Pt132:

[0245] Pt132was synthesized by the same way as in Reference Example 1, replacing the corresponding ligand starting material. After re- metallization, the target compound was synthesized. MS: m / z 1064.33 (M+H) + .

[0246] Example 33: Tetradentate cyclometalated platinum (II) complex Pt135:

[0247] Pt135was synthesized by the same way as in Reference Example 1, replacing the corresponding ligand starting material. After re- metallization, the target compound was synthesized. MS: m / z 943.37 (M+H) + .

[0248] Example 34: Tetradentate cyclometalated platinum (II) complex Pt151:

[0249] (1) Synthesis of intermediate chiral oNPCz-OMe: Into a reaction flask was added OTf (675 mg, 2.10 mmol, 1.05 equiv), oNPCz (495 mg, 2.0 mmol, 1.0 equiv), Pd2(dba)3(55 mg, 0.06 mmol, 3 mol%), XPhos (114 mg, 0.24 mmol, 12 mol%) and potassium phosphate (1.06 g, 5.0 mmol, 3.0 equiv) successively, and the flask was purged with nitrogen three times. Toluene (6 mL) was added, and the reaction was stirred at 100 °C for 23 h. The solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 787 mg of a yellow solid, yield 94%. 1 H NMR (500 MHz, CDC13) δ 0.78 (s, 3H), 1.37 (d, J = 10.0 Hz, 1H), 1.49 (s, 3H), 2.37 - 2.41 (m, 1H), 2.81 (dt, J = 9.5, 5.5 Hz, 1H), 2.98 (t, J = 5.5 Hz, 1H), 3.12 (d, J = 3.0 Hz, 2H), 3.92 (s, 3H), 7.07 (dd, J = 8.5, 2.0 Hz, 1H), 7.35 (d, J = 2.0 Hz, 1H), 7.42 (s, 1H), 7.48 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.70 (ddd, J = 8.0, 7.0, 1.5 Hz, 1H), 7.79 (d, J = 9.0 Hz, 1H), 7.85 (d, J = 9.0 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 8.29 (s, 1H), 8.49 (d, J = 9.0 Hz, 1H), 8.78 (d, J = 8.5 Hz, 1H).

[0250] (2) Synthesis of intermediate chiral oNPCz-OH: Into a reaction flask was added oNPCz-OMe (787 mg, 1.88 mmol, 1.0 equiv), hydrobromic acid (48%) (20 mL), acetic acid (4 mL) successively, and the reaction was stirred at 120 °C for 24 h. The reaction was cooled to room temperature. Neutralization was performed with aqueous NaHC03solution, and extraction was performed with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product oNPCz-OH was obtained as a white solid by slurrying with petroleum ether / ethyl acetate, 731 mg, yield 96%.

[0251] (3) Synthesis of intermediate chiral 8-Cl: The synthesis was performed according to the procedure described in the synthesis of 1-Cl in Example 1 with oNPCz-OH (700 mg, 1.73 mmol, 1.0 equiv), 1-bromo-3-tert-butyl-5-chlorobenzene (514 mg, 2.08 mmol, 1.2 equiv), copper(I) iodide (33 mg, 0.17 mmol, 10 mol%), 2-picolinic acid (43 mg, 0.35 mmol, 20 mol%), potassium phosphate (919 mg, 4.33 mmol, 2.5 equiv), and dimethyl sulfoxide (5 mL). White solid was obtained 401 mg in 41% yield. 1 H NMR (500 MHz, CDC13) δ 0.75 (s, 3H), 1.28 (s, 9H), 1.34 (d, J = 10.0 Hz, 1H), 1.47 (s, 3H), 2.36 - 2.39 (m, 1H), 2.79 (dt, J = 10.0, 5.5 Hz, 1H), 2.96 (t, J = 5.5 Hz, 1H), 3.10 (d, J = 3.5 Hz, 2H), 6.81 (t, J = 2.0 Hz, 1H), 7.04 (t, J = 2.0 Hz, 1H), 7.07 (t, J = 2.0 Hz, 1H), 7.13 (dd, J = 8.5, 2.0 Hz, 1H), 7.39 (s, 1H), 7.49 - 7.53 (m, 2H), 7.72 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.85 (d, J = 9.0 Hz, 1H), 7.89 (d, J = 9.0 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 8.25 (s, 1H), 8.58 (d, J = 8.5 Hz, 1H), 8.80 (d, J = 8.0 Hz, 1H).

[0252] (4) Synthesis of intermediate chiral 151-NH2: Into a reaction vial was added 8-Cl (400 mg, 0.70 mmol, 1.0 equiv), dPhNH2 (330 mg, 0.84 mmol, 1.2 equiv), Pd2(dba)3 (19 mg, 0.021 mmol, 3 mol%), JohnPhos (34 mg, 0.084 mmol, 12 mol%), sodium tert-butoxide (168 mg, 1.75 mmol, 2.5 equiv), and toluene (4 mL) successively. The reaction vial was purged with nitrogen for 3 times. The reaction was stirred at 85 °C for 18 h. The mixture was separated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-10:1 as eluent. White solid was obtained 640 mg in 98% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0253] (5) Synthesis of Ligand 151-L: The synthesis was performed according to the procedure described for the synthesis of 1-L in Example 1, with 151-NH2(640 mg, 0.69 mmol, 1.0 equiv), ammonium hexafluorophosphate (225 mg, 1.38 mmol, 2.0 equiv), triethyl orthoformate (4 mL) as the reactants. The final product was obtained as a solid 631 mg, 84% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.61 (s, 3H), 1.17 (d, J = 10.0 Hz, 1H), 1.28 (s, 9H), 1.39 (s, 3H), 1.39 (s, 9H), 2.25 - 2.29 (m, 1H), 2.69 - 2.74 (m, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.00 - 3.11 (m, 2H), 6.69 (t, J = 2.0 Hz, 1H), 6.93 (t, J = 2.0 Hz, 1H), 7.05 - 7.11 (m, 10H), 7.27 (dd, J = 8.5, 2.0 Hz, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7.45 (t, J = 2.0 Hz, 1H), 7.49 - 7.59 (m, 5H), 7.62 - 7.66 (m, 3H), 7.78 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.87 (d, J = 9.0 Hz, 1H), 7.98 (d, J = 9.0 Hz, 1H), 8.10 (dd, J = 8.0, 1.5 Hz, 1H), 8.23 (s, 1H), 8.81 (d, J = 9.0 Hz, 1H), 8.88 (d, J = 8.5 Hz, 1H), 10.17 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.55, 25.89, 30.91, 31.15, 31.70, 32.97, 35.26, 35.31, 39.28, 39.84, 44.30, 103.27, 110.11, 112.37, 113.30, 113.87, 114.16, 115.94, 116.04, 117.81, 119.43, 121.59, 123.25, 123.48, 125.34, 127.07, 127.17, 128.00, 128.24, 128.69, 129.17, 129.37, 129.78, 130.13, 132.32, 132.45, 137.08, 138.19, 139.93, 140.15, 141.78, 141.89, 145.61, 148.04, 149.03, 152.78, 155.17, 156.40, 159.62. HRMS (ESI): C 67 H 61N4O[M] + Calcd 937.4840, Found 937.4852.

[0254] (6) Synthesis of complex Pt151: The synthesis was performed according to the procedure described in the synthesis of Pt1 in Example 1, with ligand 151-L (350 mg, 0.32 mmol, 1.0 equiv), Pt(COD)Cl2(121 mg, 0.32 mmol, 1.0 equiv), sodium acetate (80 mg, 0.97 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (6 mL). The final product was obtained as a yellow solid 231 mg, 84% yield. 1 H NMR (500 MHz, CDC13) δ 0.24 (s, 3H), 1.09 (s, 3H), 1.23 (d, J = 9.5 Hz, 1H), 1.44 (s, 9H), 1.46 (s, 9H), 2.06 (t, J = 5.5 Hz, 1H), 2.14 - 2.18 (m, 1H), 2.50 - 2.55 (m, 1H), 2.68 (d, J = 17.5 Hz, 1H), 2.89 (dd, J = 18.0, 2.5 Hz, 1H), 6.12 (t, J = 7.5 Hz, 2H), 6.44 (t, J = 7.5 Hz, 1H), 6.55 (d, J = 6.5 Hz, 2H), 6.85 (d, J = 8.0 Hz, 1H), 7.02 (t, J = 7.5 Hz, 1H), 7.12 (d, J = 1.5 Hz, 1H), 7.19 - 7.29 (m, 4H), 7.38 (d, J = 2.5 Hz, 1H), 7.45 (d, J = 8.5 Hz, 1H), 7.50 (d, J = 1.5 Hz, 1H), 7.53 (d, J = 2.0 Hz, 1H), 7.56 - 7.63 (m, 3H), 7.66 (s, 1H), 7.76 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.94 (d, J = 9.0 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 8.07 - 8.10 (m, 2H), 8.32 (d, J = 8.5 Hz, 1H), 8.94 (s, 1H), 8.95 (d, J = 8.0 Hz, 1H). HRMS (ESI): C 67 H 59 N4OPt[M+H] + Calcd 1130.4331, Found 1130.4315.

[0255] Example 35: Tetradentate cyclometalated platinum(II) complex Pt152synthesis route:

[0256] (1) Synthesis of intermediate chiral mNPCz-OMe: Into a reaction flask was added OTf (675 mg, 2.1 mmol, 1.05 equiv), mNPCz (495 mg, 2.0 mmol, 1.0 equiv), Pd2(dba)3(55 mg, 0.06 mmol, 3 mol%), XPhos (114 mg, 0.24 mmol, 12 mol%) and potassium phosphate (1.06 g, 5.0 mmol, 2.5 equiv) successively, and the flask was purged with nitrogen three times. Toluene (6 mL) was added. The reaction was stirred at 100 °C for 23 h, and the solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to give 291 mg of a yellow solid, yield 35%. 1 H NMR (500 MHz, CDC13) δ 0.81 (s, 3H), 1.40 (d, J = 10.0 Hz, 1H), 1.50 (s, 3H), 2.35 - 2.39 (m, 1H), 2.83 (dt, J = 10.0, 6.0 Hz, 1H), 2.98 - 3.07 (m, 3H), 3.86 (s, 3H), 6.93 (d, J = 2.5 Hz, 1H), 6.97 (dd, J = 8.5, 2.5 Hz, 1H), 7.15 - 7.21 (m, 3H), 7.38 (ddd, J = 8.0, 6.0, 2.0 Hz, 1H), 7.71 (d, J = 8.5 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 8.03 (d, J = 8.5 Hz, 1H), 8.13 (d, J = 8.5 Hz, 1H), 8.35 (s, 1H).

[0257] (2) Synthesis of intermediate chiral mNPCz-OH: Into a reaction flask was added mNPCz-OMe (291 mg, 0.70 mmol, 1.0 equiv), hydrobromic acid (48%) (15 mL), acetic acid (2 mL) successively, and the reaction was stirred at 120 °C for 24 h, and cooled to room temperature. Neutralized with aqueous NaHC03solution, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The product mNPCz-OH was obtained as a white solid by slurrying with petroleum ether / ethyl acetate, 230 mg, yield 79%.

[0258] (3) Synthesis of intermediate chiral 9-Cl: The synthesis was performed according to the procedure described in the synthesis of 1-Cl in Example 1 with mNPCz-OH (230 mg, 0.57 mmol, 1.0 equiv), 1-bromo-3-tert-butyl-5-chlorobenzene (169 mg, 0.68 mmol, 1.2 equiv), copper(I) iodide (11 mg, 0.057 mmol, 10 mol%), 2-picolinic acid (14 mg, 0.11 mmol, 20 mol%), potassium phosphate (302 mg, 1.43 mmol, 2.0 equiv), and dimethyl sulfoxide (5 mL). White solid, 201 mg, 62% yield was obtained. 1 H NMR (500 MHz, CDC13) δ 0.79 (s, 3H), 1.26 (s, 9H), 1.38 (d, J = 10.0 Hz, 1H), 1.49 (s, 3H), 2.35 - 2.39 (m, 1H), 2.82 (dt, J = 10.0, 6.0 Hz, 1H), 2.99 - 3.04 (m, 3H), 6.76 (t, J = 2.0 Hz, 1H), 6.99 (t, J = 2.0 Hz, 1H), 7.02 - 7.05 (m, 2H), 7.11 (d, J = 2.0 Hz, 1H), 7.16 - 7.24 (m, 3H), 7.42 (ddd, J = 8.0, 6.0, 2.0 Hz, 1H), 7.74 (d, J = 8.5 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 8.5 Hz, 1H), 8.16 (d, J = 8.5 Hz, 1H), 8.30 (s, 1H).

[0259] (4) Synthesis of intermediate chiral 152-NH2: Into a reaction vial was added 9-Cl (200 mg, 0.35 mmol, 1.0 equiv), dPhNH2 (165 mg, 0.42 mmol, 1.2 equiv), Pd2(dba)3 (10 mg, 0.011 mmol, 3 mol%), SPhos (17 mg, 0.042 mmol, 12 mol%), and sodium tert-butoxide (84 mg, 0.88 mmol, 2.5 equiv), and the vial was purged with nitrogen three times and toluene (3 mL) was added. The reaction was stirred at 85 °C for 18 h, and the mixture was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 50:1 to 10:1 to give 310 mg of white solid in 94% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0260] (5) Synthesis of Ligand 152-L: The synthetic procedure was referred to the synthesis of 1-L in Example 1. The reaction was carried out using 152-NH2(310 mg, 0.33 mmol, 1.0 equiv), ammonium hexafluorophosphate (109 mg, 0.67 mmol, 2.0 equiv), triethyl orthoformate (3 mL). The final product was obtained as a solid 285 mg in 80% yield. 1 H NMR (500 MHz, CDC13) δ 0.80 (s, 3H), 1.31 (s, 9H), 1.39 (d, J = 10.0 Hz, 1H), 1.45 (s, 9H), 1.49 (s, 3H), 2.35 - 2.39 (m, 1H), 2.79 - 2.84 (m, 1H), 3.01 (t, J = 5.5 Hz, 1H), 3.05 - 3.10 (m, 2H), 6.43 (t, J = 2.0 Hz, 1H), 6.70 (t, J = 1.5 Hz, 1H), 7.05 - 7.25 (m, 15H), 7.28 (s, 1H), 7.30 (t, J = 2.0 Hz, 1H), 7.39 - 7.44 (m, 2H), 7.46 - 7.49 (m, 2H), 7.58 (s, 2H), 7.76 (d, J = 8.5 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 8.21 (dd, J = 8.5, 2.0 Hz, 2H), 8.31 (s, 1H), 9.17 (s, 1H). HRMS (ESI): C 67 H 61 N4O[M] + Calcd 937.4840, Found 937.4852.

[0261] (6) Synthesis of Complex Pt152: The synthetic procedure was referred to the synthesis of Pt1 in Example 1. The reaction was carried out using Ligand 152-L (200 mg, 0.18 mmol, 1.0 equiv), Pt(COD)Cl2(69 mg, 0.18 mmol, 1.0 equiv), sodium acetate (45 mg, 0.54 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (6 mL). The final product was obtained as a yellow solid 137 mg in 67% yield. 1H NMR (500 MHz, CDC13) δ 0.21 (s, 3H), 1.05 (s, 3H), 1.19 (d, J = 9.0 Hz, 1H), 1.46 (s, 9H), 1.53 (s, 9H), 2.04 - 2.08 (m, 2H), 2.46 - 2.55 (m, 2H), 2.62 - 2.66 (m, 1H), 6.28 (t, J = 7.5 Hz, 2H), 6.53 - 6.56 (m, 1H), 6.80 - 6.85 (m, 2H), 6.91 (d, J = 8.0 Hz, 1H), 7.03 - 7.06 (m, 2H), 7.12 (d, J = 1.5 Hz, 1H), 7.20 - 7.24 (m, 1H), 7.27 - 7.32 (m, 3H), 7.38 (d, J = 8.5 Hz, 1H), 7.43 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.48 - 7.54 (m, 3H), 7.59 (d, J = 2.5 Hz, 1H), 7.62 - 7.66 (m, 2H), 7.86 (d, J = 8.0 Hz, 1H), 7.90 - 7.93 (m, 2H), 8.00 (d, J = 8.5 Hz, 1H), 8.11 (d, J = 8.0 Hz, 1H), 8.23 (d, J = 8.5 Hz, 1H), 8.90 (s, 1H). HRMS (ESI): C 67 H 59 N4OPt[M+H] + Calcd 1130.4331,Found 1130.4313.

[0262] Example 36: Synthesis route of tetradentate cyclometalated platinum(II) complex Pt155:

[0263] (1) Synthesis of intermediate M1Cz-NO2: Into a reaction flask was placed M1-B(OH)2(5.8 g, 25.4 mmol, 1.2 equiv), B (4.5 g, 21.2 mmol, 1.0 equiv), tetrakis(triphenylphosphine)palladium (734 g, 0.64 mmol, 3 mol%), and potassium carbonate (5.86 g, 85.2 mmol, 2.0 equiv), dioxane (40 mL) and water (10 mL). The reaction was stopped after 24 h at 90 °C, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give yellow solid 4.5 g in 68% yield. 1H NMR (500 MHz, DMSO-d6) δ 3.95 (s, 3H), 7.42 (td, J = 7.5, 1.0 Hz, 1H), 7.47 (dd, J = 8.5, 2.5 Hz, 1H), 7.49 - 7.54 (m, 3H), 7.59 (d, J = 8.5 Hz, 1H), 7.67 (d, J = 8.65 Hz, 1H), 7.71 (d, J = 3.0 Hz, 1H), 8.18 (dd, J = 6.5, 2.0 Hz, 2H).

[0264] (2) Synthesis of intermediate M1Cz: To a reaction flask was added M1Cz-NO2(4.5 g, 14.1 mmol, 1.0 eq) and triphenylphosphine (11.1 g, 42.3 mmol, 3.0 eq), o-dichlorobenzene (60 mL). The reaction was stopped after 24 h at 180 °C, cooled to room temperature, concentrated, and silica gel column chromatography to give brown solid 2.61 g, yield 65%. 1 H NMR (500 MHz, CDCl3) δ 3.93 (s, 3H), 6.97 - 7.02 (m, 2H), 7.35 - 7.39 (m, 2H), 7.43 (td, J = 7.0, 1.5 Hz, 1H), 7.70 (d, J = 8.5 Hz, 1H), 7.88 (d, J = 8.5 Hz, 1H), 7.97 (dd, J = 7.5, 1.0 Hz, 1H), 8.22 (s, 1H), 8.35 (d, J = 8.0 Hz, 1H).

[0265] (3) Synthesis of intermediate otf-1OMe: To a schlenk tube was added M1Cz (1.0 g, 3.5 mmol, 1.0 eq), potassium phosphate (1.49 g, 7 mmol, 3.0 eq), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (667 mg, 1.4 mmol, 0.4 eq), tris(dibenzylideneacetone)dipalladium (320 mg, 3.9 mmol, 0.1 eq), and the reaction was purged with nitrogen three times, Py-otf (1.23 g, 3.9 mmol, 1.1 eq), toluene (52 mL), and the reaction was run at 100 °C for 17 h. Concentration and silica gel column chromatography to give yellow solid 850 mg, yield 67%. 1H NMR (500 MHz, DMSO-d6) δ 0.74 (s, 3 H), 1.29 (d, J = 10.0 Hz, 1 H), 1.46 (s, 3 H), 2.33 - 2.37 (m, 1 H), 2.77 - 2.81 (m, 1 H), 3.01 (t, J = 5.5 Hz, 1 H), 3.12 - 3.221 (m, 2 H), 3.87 (s, 3 H), 7.11 (dd, J = 8.5, 2.0 Hz, 1 H), 7.31 (d, J = 2.5 Hz, 1 H), 7.45 (td, J = 8.0, 1.0 Hz, 1 H), 7.52 (td, J = 7.5, 1.5 Hz, 1 H), 7.66 (s, 1 H), 7.75 (d, J = 9.0 Hz, 1 H), 7.86 (d, J = 8.0 Hz, 1 H), 8.10 (d, J = 8.5 Hz, 1 H), 8.18 (dd, J = 7.5, 1.0 Hz, 1 H), 8.30 (d, J = 8.5 Hz, 1 H), 8.34 (s, 1 H).

[0266] (4) Synthesis of intermediate otf-1OH: To a single-neck flask was added otf-1OMe (900 mg, 1.96 mmol, 1.0 equiv), dissolved with DCM (14 mL), and boron tribromide (981 mg, 3.92 mmol, 2.0 equiv) was added at low temperature, and the reaction was allowed to proceed at room temperature for 4 hours. Concentration and silica gel column chromatography gave 590 mg of yellow solid in a yield of 72%. 1 H NMR (500 MHz, DMSO-d6) δ 0.72 (s, 3 H), 0.91 (t, J = 7.5 Hz, 1 H), 1.27 (d, J = 10.0 Hz, 1 H), 1.45 (s, 3 H), 2.34 - 2.35 (m, 1 H), 2.76 - 2.80 (m, 1 H), 3.00 (t, J = 5.5 Hz, 1 H), 3.09 - 3.19 (m, 2 H), 6.93 (dd, J = 8.0, 2.0 Hz, 1 H), 7.17 (d, J = 2.0 Hz, 1 H), 7.43 (td, J = 7.5, 1.0 Hz, 1 H), 7.50 (td, J = 7.0, 1.0 Hz, 1 H), 7.61 (s, 1 H), 7.69 (d, J = 8.5 Hz, 1 H), 7.83 (d, J = 8.0 Hz, 1 H), 8.04 (d, J = 8.5 Hz, 1 H), 8.15 (d, J = 6.0 Hz, 1 H), 8.19 (d, J = 8.0 Hz, 1 H), 8.32 (s, 1 H), 9.74 (s, 1 H).

[0267] (5) Synthesis of intermediate otf-1CI: Into a schlenk tube was added otf-1OH (400 mg, 0.9 mmol, 1.0 eq), 1-bromo-3-tert-butyl-5-chlorobenzene (334 mg, 1.35 mmol, 1.5 eq), 2-picolinic acid (110 mg, 0.9 mmol, 1.0 eq), cuprous iodide (85 mg, 0.45 mmol, 0.5 eq), potassium phosphate (382 mg, 1.8 mmol, 2.0 eq) successively, and the atmosphere was replaced with nitrogen three times, dimethyl sulfoxide (5 mL) was added, and the mixture was stirred at 110 °C for 12 hours. Concentration, and column chromatography on silica gel gave 333 mg of a white solid, and the yield was 60%. 1 H NMR (500 MHz, DMSO-d6) δ 0.68 (s, 3H), 1.22 (s, 1H), 1.24 (s, 9H), 1.43 (s, 3H), 2.31 - 2.33 (m, 1H), 2.73 - 2.77 (m, 1H), 2.96 (t, J = 5.5 Hz, 1H), 3.06 - 3.15 (m, 2H), 6.90 (t, J = 2.0 Hz, 1H), 7.12 (t, J = 2.0 Hz, 1H), 7.18 - 7.20 (m, 2H), 7.44 - 7.47 (m, 2H), 7.52 (td, J = 7.5, 1.5 Hz, 1H), 7.62 (s, 1H), 7.77 (d, J = 8.5 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 8.17 (d, J = 11.5 Hz, 1H), 8.19 (d, J = 7.0 Hz, 1H), 8.26 (s, 1H), 8.42 (d, J = 8.5 Hz, 1H). 13 C NMR (126 MHz, CDC13) δ 21.58, 25.95, 31.09, 31.77, 33.01, 35.04, 39.37, 39.92, 44.35, 102.49, 106.69, 109.12, 111.67, 113.54, 113.96, 115.20, 117.24, 117.53, 118.13, 118.83, 119.83, 120.22, 122.85, 123.59, 125.03, 125.45, 134.50, 140.63, 140.78, 141.38, 145.56, 147.73, 149.55, 150.77, 154.72, 154.84, 156.33, 158.64.

[0268] (6) Synthesis of intermediate 155-NH2: To a schlenk tube was added otf-1Cl (300 mg, 0.49 mmol, 1.0 equiv), dPhNH2 (227 mg, 0.58 mmol, 1.2 equiv), tris(dibenzylideneacetone)dipalladium (13 mg, 0.015 mmol, 0.03 equiv), 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl (12 mg, 0.03 mmol, 0.06 equiv), sodium tert-butoxide (95 mg, 0.98 mmol, 2.0 equiv), and the flask was purged with nitrogen three times, then toluene (5 mL) was added, and the reaction was stirred at 90 °C for 3 h. Concentration and silica gel column chromatography gave 393 mg of white solid in 83% yield. Directly used in the following reaction.

[0269] (7) Synthesis of ligand 155-L: To a schlenk tube was added 155-NH2 (393 mg, 0.41 mmol, 1.0 equiv), ammonium hexafluorophosphate (134 mg, 0.82 mmol, 2.0 equiv), and the flask was purged with nitrogen three times, then triethyl orthoformate (4 mL) was added, and the reaction was stirred at 70 °C for 1 h. Concentration and silica gel column chromatography gave 283 mg of white solid in 63% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.67 (s, 3H), 1.22 (d, J = 9.5 Hz, 1H), 1.31 (s, 9H), 1.43 (s, 12H), 2.23 - 2.32 (m, 1H), 2.73 - 2.78 (m, 1H), 2.96 (t, J = 6.0 Hz, 1H), 3.06 - 3.16 (m, 2H), 6.81 (t, J = 2.5 Hz, 1H), 6.95 (t, J = 2.0 Hz, 1H), 7.11 - 7.13 (m, 6H), 7.13 - 7.17 (m, 4H), 7.29 (dd, J = 9.0, 2.0 Hz, 1H), 7.45 - 7.50 (m, 3H), 7.52 - 7.55 (m, 2H), 7.57 - 7.60 (m, 1H), 7.62 (d, J = 2.0 Hz, 1H), 7.67 (s, 1H), 7.71 - 7.73 (m, 3H), 7.81 (d, J = 8.5 Hz, 1H), 7.87 (d, J = 8.5 Hz, 1H), 8.19 - 8.21 (m, 2H), 8.27 (s, 1H), 8.51 (d, J = 8.5 Hz, 1H), 10.24 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.61, 25.96, 30.97, 31.22, 31.77, 33.05, 35.33, 35.40, 39.36, 39.91, 44.37, 103.34, 106.73, 109.05, 110.24, 111.76, 113.37, 113.85, 114.25, 116.13, 117.35, 117.82, 117.87, 118.65, 118.89, 119.88, 122.95, 123.89, 124.98, 125.42, 125.57, 128.00, 128.07, 128.30, 128.34, 128.77, 130.21, 132.39, 132.51, 137.17, 140.00, 140.69, 140.81, 141.67, 142.03, 145.60, 148.10, 149.43, 150.82, 153.96, 155.23, 156.37, 156.54, 159.55.

[0270] (8) Synthesis of Pt155: To a sealed tube was added 155-L (200 mg, 0.18 mmol, 1.0 equiv), (1,5-cyclooctadiene) dichloroplatinum (71 mg, 0.19 mmol, 1.05 equiv) and sodium acetate (44 mg, 0.54 mmol, 3.0 equiv) sequentially, and the tube was purged with nitrogen three times. Diethyleneglycol dimethyl ether (4 mL) was added and the mixture was purged with nitrogen for 30 min. The mixture was heated at 120 °C for 72 h. The mixture was concentrated and purified by silica gel column to give yellow solid 119 mg in 57% yield. 1 H NMR (400 MHz, DMSO-d6) δ 0.26 (s, 3H), 1.07 (s, 3H), 1.18 - 1.24 (m, 4H), 1.43 (s, 18H), 2.02 (t, J = 5.2 Hz, 1H), 2.16 (s, 1H), 2.80 (d, J = 17.6 Hz, 1H), 2.96 (d, J = 17.6 Hz, 1H), 6.09 (t, J = 7.6 Hz, 2H), 6.43 - 6.50 (m, 3H), 6.87 - 6.93 (m, 2H), 7.12 (t, J = 8.0 Hz, 1H), 7.23 - 7.29 (m, 2H), 7.32 - 7.41 (m, 4H), 7.49 - 7.63 (m, 6H), 7.90 - 7.94 (m, 2H), 8.06 (d, J = 8.4 Hz, 2H), 8.15 (d, J = 8.5 Hz, 1H), 8.26 (d, J = 7.6 Hz, 1H), 8.32 (d, J = 8.4 Hz, 1H), 8.82 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.24, 25.71, 31.31, 31.60, 32.09, 33.11, 34.78, 35.01, 39.43, 39.62, 42.92, 105.81, 107.39, 108.76, 110.77, 111.28, 111.89, 112.33, 112.65, 112.83, 114.10, 115.03, 115.42, 116.84, 118.40, 118.55, 119.89, 122.67, 122.85, 123.97, 124.95, 125.58, 125.88, 127.14, 127.46, 127.73, 128.07, 128.26, 128.71, 129.49, 129.58, 131.78, 136.37, 137.21, 138.09, 138.64, 138.72, 138.84, 142.29, 144.45, 146.95, 147.79, 149.58, 150.26, 150.97, 152.27, 152.54, 154.59, 156.66, 193.78.

[0271] Example 37: Tetradentate cyclometalated platinum (II) complex Pt156 synthesis route:

[0272] (1) Synthesis of intermediate M5Cz-NO2: Into a reaction flask was placed M5Cz-B(OH)2(13.55 g, 63.9 mmol, 1.5 equiv), B (8 g, 42.6 mmol, 1.0 equiv), tetrakis(triphenylphosphine)palladium (1.47 g, 1.28 mmol, 3 mol%), and potassium carbonate (11.78 g, 85.2 mmol, 2.0 equiv), dioxane (80 mL) and water (20 mL). The reaction was stopped after 24 h at 90 °C, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give yellow solid 10 g in 74% yield. 1 H NMR (400 MHz, DMSO-d6) δ 3.97 (s, 3H), 6.97 (d, J = 7.2 Hz, 1H), 7.20 (td, J = 7.6, 0.8 Hz, 2H), 7.46 - 7.51 (m, 2H), 7.56 - 7.60 (m, 2H), 7.72 - 7.77 (m, 3H).

[0273] (2) Synthesis of intermediate M5Cz: To a reaction flask was added M5Cz-NO2 10 g, 31.3 mmol, 1.0 eq) and triphenylphosphine (32.84 g, 125.2 mmol, 3.0 eq), o-dichlorobenzene (60 mL) was added and heated at 180 °C for 24 h. The reaction was cooled to room temperature, concentrated and purified by silica gel column chromatography to give brown solid 6.89 g, yield 78%. 1 H NMR (500 MHz, CDC13) δ 3.95 (s, 3H), 7.02 (s, 1H), 7.48 (s, 1H), 7.51-7.54 (m, 2H), 7.61 (d, J = 8.5 Hz, 1H), 7.67 (d, J = 8.0 Hz, 2H), 8.42 (s, 1H), 8.51 (d, J = 8.5 Hz, 1H), 8.57 (d, J = 7.5 Hz, 1H).

[0274] (3) Synthesis of intermediate otf-5OMe: To a schlenk tube was added M5Cz (1.0 g, 3.5 mmol, 1.0 eq), potassium phosphate (1.49 g, 7.0 mmol, 3.0 eq), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (667 mg, 1.4 mmol, 0.4 eq), tris(dibenzylideneacetone)dipalladium (320 mg, 0.35 mmol, 0.1 eq), and the reaction was purged with nitrogen three times, Py-otf (1.23 g, 3.85 mmol, 1.2 eq), toluene (5 mL) was added and heated at 100 °C for 22 h. The reaction was concentrated and purified by silica gel column chromatography to give yellow solid 1.55 g, yield 87%. 1 H NMR (500 MHz, CDC13) δ 0.78 (s, 3H), 1.37 (d, J = 9.9 Hz, 1H), 1.49 (s, 3H), 2.37-2.41 (m, 1H), 2.79-2.83 (m, 1H), 2.98 (t, J = 5.5 Hz, 1H), 3.12 (d, J = 2.5 Hz, 2H), 3.94 (s, 3H), 7.08 (dd, J = 9.0 2.5 Hz, 1H), 7.32 (d, J = 2.0 Hz, 1H), 7.44 (s, 1H), 7.49-7.55 (m, 2H), 7.61 (d, J = 9.0 Hz, 1H), 7.68-7.70 (m, 1H), 7.80 (d, J = 9.0 Hz, 1H), 8.29 (s, 1H), 8.59 (d, J = 8.5 Hz, 1H), 8.62 (dd, J = 7.5 1.0 Hz, 1H).

[0275] (4) Synthesis of intermediate otf-5OH: Into a single-necked flask was added otf-5OMe (1.48 g, 3.2 mmol, 1.0 eq), dissolved with dichloromethane (10 mL), and boron tribromide (1.60 g, 6.4 mmol, 2.0 eq) was added at low temperature. The reaction was allowed to proceed at room temperature for 11 hours. Concentration and silica gel column chromatography gave 1.19 g of brownish red solid in 83% yield. 1 H NMR (500 MHz, CDC13) δ 0.76 (s, 3H), 1.34 (d, J = 10.0 Hz, 1H), 1.47 (s, 3H), 1.72 (s, 1H), 2.36 - 2.39 (m, 1H), 2.77 - 2.81 (m, 1H), 2.96 (t, J = 5.5 Hz, 1H), 3.11 (d, J = 3.0 Hz, 2H), 6.92 (dd, J = 8.5, 2.5 Hz, 1H), 7.29 (d, J = 2.0 Hz, 1H), 7.43 (s, 1H), 7.46 - 7.54 (m, 1H), 7.59 (d, J = 9.0 Hz, 1H), 7.67 (d, J = 7.5 Hz, 1H), 7.76 (d, J = 8.5 Hz, 1H), 8.27 (s, 1H), 8.47 (d, J = 8.5 Hz, 1H), 8.55 (dd, J = 8.0, 1.0 Hz, 1H).

[0276] (5) Synthesis of intermediate otf-5Cl: Into a schlenk tube was added otf-5OH (1.10 g, 2.47 mmol, 1.0 eq), 1-bromo-3-tert-butyl-5-chlorobenzene (918 mg, 3.71 mmol, 1.5 eq), 2-picolinic acid (304 mg, 2.47 mmol, 1.0 eq), cuprous iodide (235 mg, 1.24 mmol, 0.5 eq), potassium phosphate (1.05 g, 4.94 mmol, 2.0 eq) sequentially, and the nitrogen gas was exchanged three times. Dimethyl sulfoxide (6 mL) was added, and the reaction was allowed to proceed at 110 °C for 12 hours. Concentration and silica gel column chromatography gave 1.14 g of white solid in 76% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.68 (s, 3H), 0.75 - 0.85 (m, 1H), 1.25 (s, 9H), 1.43 (s, 3H), 2.30 - 2.35 (m, 1H), 2.74 - 2.78 (m, 1H), 2.97 (t, J = 5.5 Hz, 1H), 3.04 - 3.16 (m, 2H), 6.94 (t, J = 2.0 Hz, 1H), 7.15 (t, J = 2.0 Hz, 1H), 7.19 - 7.22 (m, 2H), 7.41 (d, J = 2.0 Hz, 1H), 7.57 - 7.60 (m, 2H), 7.65 (t, J = 7.5 Hz, 1H), 7.83 - 7.86 (m, 2H), 7.90 (d, J = 9.0 Hz, 1H), 8.27 (s, 1H), 8.74 (d, J = 7.5 Hz, 1H), 8.80 (d, J = 9.0 Hz, 1H). 13 C NMR (126 MHz, CDC13) δ 21.58, 25.94, 31.10, 31.76, 32.99, 35.05, 39.36, 39.91, 44.35, 101.98, 109.24, 110.43, 111.78, 112.65, 114.17, 115.41, 117.45, 117.55, 119.36, 119.80, 120.38, 122.51, 123.12, 124.01, 124.47, 126.59, 134.51, 137.10, 141.37, 141.46, 145.65, 147.75, 149.49, 152.25, 154.77, 154.90, 156.52, 158.41.

[0277] (6) Synthesis of intermediate 156-NH2: Into a schlenk tube was added tf-5Cl (580 mg, 0.95 mmol, 1.0 equiv), dPhNH2 (412 mg, 1.05 mmol, 1.1 equiv), tris(dibenzylideneacetone)dipalladium (26 mg, 0.03 mmol, 0.03 equiv), 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl (23 mg, 0.06 mmol, 0.06 equiv), sodium tert-butoxide (183 mg, 1.90 mmol, 2.0 equiv), and the system was purged with nitrogen three times, toluene (5 mL) was added, and the reaction was stirred at 90 °C for 6 h. Concentration and silica gel column chromatography afforded 832 mg of white solid in 91% yield.

[0278] (7) Synthesis of Ligand 156-L: Into a schlenk tube was added 156-NH2(832 mg, 0.86 mmol, 1.0 eq), ammonium hexafluorophosphate (280 mg, 1.72 mmol, 2.0 eq) successively, and the substitution of nitrogen was performed for three times, then triethyl orthoformate (4 mL) was added, and the reaction was performed at 70 °C for 1 h. Concentration and silica gel column chromatography gave 761 mg of white solid with a yield of 79%. 1 H NMR (500 MHz, DMSO-d6) δ 0.66 (s, 3H), 1.22 (d, J = 9.5 Hz, 1H), 1.32 (s, 9H), 1.43 (s, 12H), 2.27 - 2.33 (m, 1H), 2.73 - 2.77 (m, 1H), 2.96 (t, J = 5.5 Hz, 1H), 3.04 - 3.13 (m, 2H), 6.83 (t, J = 2.0 Hz, 1H), 6.98 (s, 1H), 7.11 - 7.16 (m, 10H), 7.30 (dd, J = 8.5, 2.5 Hz, 1H), 7.47 (d, J = 8.5 Hz, 1H), 7.51 - 7.55 (m, 2H), 7.57 - 7.62 (m, 3H), 7.65 - 7.68 (m, 2H), 7.93 (d, J = 8.0 Hz, 3H), 7.86 - 7.88 (m, 2H), 7.93 (d, J = 9.0 Hz, 1H), 8.27 (s, 1H), 8.76 (d, J = 9.0 Hz, 1H), 8.87 (d, J = 8.5 Hz, 1H), 10.25 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.56, 25.91, 30.94, 31.17, 31.73, 32.99, 35.28, 35.35, 39.30, 39.87, 44.33, 102.71, 109.46, 110.35, 110.46, 111.69, 112.97, 113.32, 114.21, 116.18, 117.47, 117.59, 118.05, 119.38, 120.29, 122.81, 123.27, 124.35, 124.42, 125.36, 126.70, 127.93, 128.03, 128.22, 128.29, 128.70, 130.18, 132.36, 132.48, 137.12, 139.94, 141.35, 141.67, 142.06, 145.62, 148.04, 149.38, 152.23, 153.96, 155.20, 156.49, 159.33.

[0279] (8) Synthesis of Pt156: To a sealed tube was added 156-L (670 mg, 0.60 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum dichloride (236 mg, 0.63 mmol, 1.05 equiv), and sodium acetate (147 mg, 1.80 mmol, 3.0 equiv) sequentially, purged with nitrogen three times, added diethyleneglycol dimethyl ether (5 mL), and bubbled with nitrogen for 30 min, and reacted at 120 °C for 72 h. Concentrated and purified by silica gel column chromatography to give yellow solid 283 mg, 40% yield. 1 H NMR (500 MHz, CDC13) δ 0.25 (s, 3H), 1.09 (s, 3H), 1.23 (d, J = 9.5 Hz, 1H), 1.46 (s, 18H), 2.06 (d, J = 5.0 Hz, 1H), 2.16 (d, J = 6.0 Hz, 1H), 2.48 - 2.56 (m, 1H), 2.69 (d, J = 17.5 Hz, 1H), 2.89 (dd, J = 18.5, 3.0 Hz, 1H), 6.14 (t, J = 7.5 Hz, 2H), 6.45 (t, J = 7.5 Hz, 1H), 6.57 (d, J = 6.0 Hz, 2H), 6.85 (d, J = 7.5 Hz, 1H), 7.03 (d, J = 8.0 Hz, 1H), 7.13 (d, J = 1.5 Hz, 1H), 7.19 - 7.26 (m, 2H), 7.29 (d, J = 7.0 Hz, 2H), 7.40 (d, J = 2.0 Hz, 1H), 7.47 (d, J = 8.5 Hz, 1H), 7.52 (d, J = 1.7 Hz, 1H), 7.53 (d, J = 2.5 Hz, 1H), 7.56 - 7.59 (m, 2H), 7.59 - 7.64 (m, 2H), 7.70 - 7.76 (m, 3H), 7.98 (d, J = 8.0 Hz, 1H), 8.03 (d, J = 9.0 Hz, 1H), 8.42 (d, J = 8.5 Hz, 1H), 8.73 - 8.81 (m, 1H), 8.94 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.24, 25.72, 31.34, 31.61, 32.11, 33.11, 34.79, 35.02, 39.44, 39.62, 42.92, 105.86, 106.91, 107.71, 110.76, 111.27, 111.59, 112.28, 112.33, 115.11, 115.31, 117.06, 118.06, 119.01, 122.70, 123.46, 123.71, 123.98, 124.68, 125.58, 126.70, 127.16, 127.46, 127.72, 128.10, 128.26, 128.72, 129.49, 129.57, 131.74, 135.08, 136.37, 137.03, 138.11, 138.65, 138.73, 142.32, 145.38, 146.98, 147.70, 147.79, 149.61, 150.10, 152.17, 152.58, 152.89, 154.59, 156.65, 193.62.

[0280] Example 38: Synthesis route of tetradentate cyclometalated platinum (II) complex Pt157:

[0281] (1) Synthesis of intermediate M4Cz-NO2: Into a reaction flask was added M4-B(OH)2(10 g, 43.8 mmol, 1.5 equiv), B (6.2 g, 29.2 mmol, 1.0 equiv), tetrakis(triphenylphosphine)palladium (1.01 g, 0.88 mmol, 3 mol%), and potassium carbonate (8.07 g, 58.4 mmol, 2.0 equiv), dioxane (60 mL) and water (15 mL). The reaction was stopped after 24 h at 90 °C, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give yellow solid 7.34 g, 79% yield. 1 H NMR (500 MHz, DMSO-d6) δ 3.91 (s, 3H), 7.30 (dd, J = 7.5, 1.5 Hz, 1H), 7.38 (dd, J = 8.5, 2.5 Hz, 1H), 7.44 (td, J = 7.5, 0.5 Hz, 1H), 7.59 - 7.61 (m, 2H), 7.56 (m, 1H), 7.69 (d, J = 1.0 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 8.18 - 8.20 (m, 2H).

[0282] (2) Synthesis of intermediate M4Cz: Into a reaction flask was placed M4Cz-NO2 (7.3 g, 30.6 mmol, 1.0 equiv) and triphenylphosphine (24.1 g, 91.8 mmol, 3.0 equiv), o-dichlorobenzene (60 mL) was added. The reaction was stopped after 24 h at 180 °C, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 6.03 g of brown solid in 69% yield. Used directly in the following reaction. 1 H NMR (500 MHz, CDC13) δ 3.94 (s, 3H), 6.93 (dd, J = 8.5, 2.0 Hz, 1H), 7.03 (d, J = 2.0 Hz, 1H), 7.38 (td, J = 7.5, 1.5 Hz, 1H), 7.45 (td, J = 7.1, 1.5 Hz, 1H), 7.63 (d, J = 8.5 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.98 - 8.03 (m, 2H), 8.44 (s, 1H).

[0283] (3) Synthesis of intermediate otf-4OMe: Into a schlenk tube was placed M4Cz (1.0 g, 3.5 mmol, 1.0 equiv), potassium phosphate (1.49 g, 7.0 mmol, 3.0 equiv), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (667 mg, 1.4 mmol, 0.4 equiv), tris(dibenzylideneacetone)dipalladium (320 mg, 0.35 mmol, 0.1 equiv), and the reaction was purged with nitrogen three times, Py-otf (1.23 g, 3.85 mmol, 1.2 equiv), toluene (5 mL) was added, and the reaction was run at 100 °C for 32 h. Concentrated, and purified by silica gel column chromatography to give 1.25 g of yellow solid in 87% yield.1H NMR (500 MHz, CDC13) δ 0.88 (s, 3H), 1.44 (d, J = 9.8 Hz, 1H), 1.51 (s, 3H), 2.37 - 2.43 (m, 1H), 2.79 - 2.87 (m, 1H), 3.02 (t, J = 5.6 Hz, 1H), 3.13 (s, 2H), 3.91 (s, 3H), 6.97 (dd, J = 8.5, 2.3 Hz, 1H), 7.32 - 7.39 (m, 3H), 7.43 - 7.45 (m, 2H), 7.85 (d, J = 8.1 Hz, 1H), 7.98 - 8.05 (m, 3H), 8.28 (s, 1H).

[0284] (4) Synthesis of intermediate otf-4OH: To a single-neck flask was added otf-4OMe (1.10 g, 2.4 mmol, 1.0 equiv), dissolved with dichloromethane (10 mL), and boron tribromide (1.20 g, 4.8 mmol, 2.0 equiv) was added at low temperature, which was moved to room temperature for 12 hours of reaction. Concentration, silica gel column chromatography gave 983 mg of brownish red solid, with a yield of 90%. 1 H NMR (500 MHz, CDC13) δ 0.85 (s, 3H), 1.40 (d, J = 9.5 Hz, 1H), 1.49 (s, 3H), 1.80 (s, 1H), 2.37 - 2.41 (m, 1H), 2.77 - 2.83 (m, 1H), 2.98 (t, J = 5.5 Hz, 1H), 3.09 - 3.16 (m, 2H), 6.83 (dd, J = 8.5, 2.0 Hz, 1H), 7.34 - 7.41 (m, 3H), 7.45 (s, 1H), 7.49 (d, J = 2.0 Hz, 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.92 (d, J = 8.5 Hz, 2H), 7.99 - 8.01 (m, 1H), 8.25 (s, 1H).

[0285] (5) Synthesis of intermediate otf-4Cl: To a schlenk tube was added otf-4OH (910 mg, 2.05 mmol, 1.0 equiv), 1-bromo-3-tert-butyl-5-chlorobenzene (762 mg, 3.08 mmol, 1.5 equiv), 2-picolinic acid (252 mg, 2.05 mmol, 1.0 equiv), cuprous iodide (195 mg, 1.025 mmol, 0.5 equiv), potassium phosphate (870 mg, 4.1 mmol, 2.0 equiv) sequentially, and nitrogen was exchanged for three times, dimethyl sulfoxide (6 mL) was added, and reaction was carried out at 120°C for 12 hours. Concentration, silica gel column chromatography gave 792 mg of white solid, with a yield of 63%. 1 H NMR (500 MHz, DMSO-d6) δ 0.76 (s, 3H), 1.24 (s, 9H), 1.31 (d, J = 9.5 Hz, 1H), 1.46 (s, 3H), 2.34 - 2.36 (m, 1H), 2.77 - 2.81 (m, 1H), 2.99 (t, J = 5.5 Hz, 1H), 3.07 - 3.15 (m, 2H), 6.86 (t, J = 2.0 Hz, 1H), 7.10 - 7.13 (m, 2H), 7.19 (t, J = 1.5 Hz, 1H), 7.42 - 7.51 (m, 4H), 7.61 (s, 1H), 8.09 (d, J = 8.5 Hz, 1H), 8.22 (d, J = 7.5 Hz, 2H), 8.27 (d, J = 8.0 Hz, 1H), 8.37 (d, J = 8.5 Hz, 1H).13 C NMR (126 MHz, CDC13) δ 21.40, 26.01, 31.08, 31.89, 33.15, 35.03, 39.42, 40.00, 44.36, 103.11, 111.43, 112.96, 113.44, 114.01, 114.94, 115.20, 120.15, 120.30, 120.49, 120.92, 121.16, 122.56, 122.88, 124.28, 124.91, 125.59, 126.21, 134.45, 141.37, 141.50, 141.83, 144.61, 146.92, 149.56, 154.62, 155.06, 155.75, 158.64.

[0286] (6) Synthesis of intermediate 157-NH2: Into a schlenk tube was added tf-4Cl (580 mg, 0.95 mmol, 1.0 equiv), dPhNH2 (412 mg, 1.05 mmol, 1.1 equiv), tris(dibenzylideneacetone)dipalladium (26 mg, 0.03 mmol, 0.03 equiv), 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl (23 mg, 0.06 mmol, 0.06 equiv), sodium tert-butoxide (183 mg, 1.90 mmol, 2.0 equiv), and the system was purged with nitrogen three times, then toluene (5 mL) was added, and the reaction mixture was stirred at 90 °C for 7 h. The mixture was concentrated and purified by silica gel column chromatography to give 823 mg of white solid in 90% yield. It was used directly in the next reaction.

[0287] (7) Synthesis of ligand 157-L: Into a schlenk tube was added 157-NH2 (823 mg, 0.85 mmol, 1.0 equiv), ammonium hexafluorophosphate (277 mg, 1.70 mmol, 2.0 equiv), and the system was purged with nitrogen three times, then triethyl orthoformate (4 mL) was added, and the reaction mixture was stirred at 70 °C for 3 h. The mixture was concentrated and purified by silica gel column chromatography to give 776 mg of white solid in 81% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.74 (s, 3H), 1.28 (d, J = 9.5 Hz, 1H), 1.31 (s, 9H), 1.43 (s, 9H), 1.45 (s, 3H), 2.33 - 2.35 (m, 1H), 2.76 - 2.81 (m, 1H), 2.99 (t, J = 5.5 Hz, 1H), 3.07 - 3.16 (m, 2H), 6.80 (t, J = 2.0 Hz, 1H), 6.94 (t, J = 2.0 Hz, 1H), 7.12 - 7.14 (m, 6H), 7.14 - 7.17 (m, 4H), 7.22 (dd, J = 8.5, 2.0 Hz, 1H), 7.43 - 7.48 (m, 3H), 7.50 - 7.54 (m, 3H), 7.57 - 7.61 (m, 1H), 7.63 (d, J = 2.0 Hz, 1H), 7.66 (s, 1H), 7.72 - 7.75 (m, 3H), 8.11 (d, J = 8.0 Hz, 1H), 8.21 - 8.24 (m, 2H), 8.33 (d, J = 8.0 Hz, 1H), 8.45 (d, J = 8.5 Hz, 1H), 10.24 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.36, 25.96, 30.92, 31.16, 31.86, 33.15, 35.28, 35.34, 39.37, 39.94, 44.31, 103.55, 110.17, 111.39, 113.15, 113.83, 114.18, 115.10, 115.99, 118.04, 120.34, 120.46, 121.44, 121.69, 122.75, 122.96, 124.16, 124.80, 125.38, 125.57, 126.33, 127.96, 128.24, 128.28, 128.70, 130.14, 132.37, 132.45, 137.13, 139.95, 141.36, 141.49, 141.73, 141.95, 144.51, 147.12, 149.48, 154.21, 155.17, 155.71, 156.47, 159.43.

[0288] (8) Synthesis of Pt157: To a sealed tube was added 157-L (700 mg, 0.62 mmol, 1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (243 mg, 0.65 mmol, 1.05 equiv), and sodium acetate (152 mg, 1.86 mmol, 3.0 equiv) sequentially, and the mixture was purged with nitrogen three times, diethyleneglycol dimethyl ether (5 mL) was added, and the mixture was purged with nitrogen for 30 min, and then heated at 120 °C for 72 h. The mixture was concentrated and purified by silica gel column chromatography to give yellow solid 356 mg, 49% yield. 1 H NMR (500 MHz, CDC13) δ 0.24 (s, 3H), 1.09 (s, 3H), 1.31 (d, J = 9.5 Hz, 1H), 1.46 (s, 9H), 1.55 (s, 9H), 2.09 (d, J = 5.0 Hz, 1H), 2.11 - 2.18 (m, 1H), 2.51 - 2.59 (m, 1H), 2.64 (d, J = 18.0 Hz, 1H), 2.80 - 2.90 (m, 1H), 6.16 (d, J = 7.5 Hz, 2H), 6.47 (d, J = 7.5 Hz, 1H), 6.66 (s, 2H), 6.88 (d, J = 6.5 Hz, 1H), 7.03 (d, J = 7.5 Hz, 1H), 7.10 (d, J = 1.5 Hz, 1H), 7.19 - 7.26 (m, 2H), 7.26 - 7.31 (m, 3H), 7.36 (d, J = 8.5 Hz, 1H), 7.41 - 7.56 (m, 6H), 7.63 (s, 2H), 7.87 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 8.5 Hz, 1H), 8.04 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 2H), 8.90 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.22, 25.76, 31.52, 31.61, 32.21, 33.20, 34.78, 35.09, 39.50, 39.67, 42.93, 77.20, 105.85, 107.38, 110.76, 111.20, 111.26, 112.38, 112.48, 114.79, 115.26, 115.94, 116.34, 117.28, 120.41, 121.43, 122.64, 123.22, 123.32, 123.95, 125.49, 126.20, 127.07, 127.48, 127.67, 128.31, 128.71, 129.51, 129.59, 129.85, 131.78, 136.35, 136.89, 137.98, 138.77, 138.86, 142.21, 142.98, 145.57, 146.26, 147.07, 147.69, 149.10, 149.64, 152.18, 152.46, 154.60, 155.86, 193.97.

[0289] Example 39: Synthesis route of tetradentate cyclometalated platinum (II) complex Pt159:

[0290] (1) Synthesis of intermediate M2Cz-NO2: Into a reaction flask was added M2-B(OH)2(8.76 g, 38.4 mmol, 1.2 equiv), B (6 g, 32 mmol, 1.0 equiv), tetrakis(triphenylphosphine)palladium (1.11 g, 0.96 mmol, 3 mmol%), and potassium carbonate (8.86, 64 mmol, 2.0 equiv), dioxane (80 mL) and water (20 mL). The reaction was stopped after 24 h at 90 °C, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give yellow solid 9.23 g in 80% yield. 1 H NMR (500 MHz, CDC13) δ 3.96 (s, 3H), 7.22 - 7.28 (m, 2H), 7.30 (dd, J = 7.5, 1.0 Hz, 1H), 7.42 - 7.49 (m, 2H), 7.53 (d, J = 7.0 Hz, 1H), 7.60 (d, J = 2.5 Hz, 1H), 7.76 - 7.80 (m, 1H), 8.15 - 8.20 (m, 2H).

[0291] (2) Synthesis of intermediate M2Cz: Into a reaction flask was added M2Cz-NO2(6 g, 17.9 mmol, 1.0 eq) and triphenylphosphine (14.08 g, 53.7 mmol, 3.0 eq), o-dichlorobenzene (60 mL) was added. The reaction was stopped after 24 h at 180 °C, cooled to room temperature, concentrated, and silica gel column chromatography to give brown solid 4.45 g, yield 82%.

[0292] (3) Synthesis of intermediate otf-2OMe: Into a schlenk tube was added M2Cz (1.0 g, 3.3 mmol, 1.0 eq), potassium phosphate (1.40 g, 6.6 mmol, 3.0 eq), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (630 mg, 1.32 mmol, 0.4 eq), tris(dibenzylideneacetone)dipalladium (302 mg, 0.33 mmol, 0.1 eq), and the reaction was purged with nitrogen three times, Py-otf (1.20 g, 3.63 mmol, 1.1 eq), toluene (5 mL) was added, and the reaction was carried out at 100 °C for 12 h. Concentration and silica gel column chromatography gave yellow solid 867 mg, yield 56%. 1 H NMR (400 MHz, DMSO-d6) δ 0.74 (s, 3H), 1.28 (d, J = 10.0 Hz, 1H), 1.45 (s, 3H), 2.32 (s, 1H), 2.77 - 2.81 (m, 1H), 3.00 (t, J = 5.6 Hz, 1H), 3.16 (s, 2H), 3.87 (s, 3H), 7.14 - 7.26 (m, 2H), 7.36 (s, 1H), 7.50 - 7.58 (m, 2H), 7.67 (s, 1H), 7.84 - 7.88 (m, 1H), 8.08 (d, J = 8.4 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.34 - 8.42 (m, 2H).

[0293] (4) Synthesis of intermediate otf-2OH: Into a single-neck flask was added otf-2OMe (800 mg, 1.69 mmol, 1.0 eq) and dissolved with dichloromethane (10 mL), and boron tribromide (846 mg, 3.38 mmol, 2.0 eq) was added at low temperature, and the reaction was carried out at room temperature for 2 h. Concentration and silica gel column chromatography gave brownish red solid 552 mg, yield 72%. 1H NMR (500 MHz, DMSO-d6) δ 0.73 (s, 3 H), 1.27 (d, J = 10.0 Hz, 1 H), 1.45 (s, 3 H), 2.34 - 2.36 (m, 1 H), 2.76 - 2.80 (m, 1 H), 3.00 (t, J = 5.5 Hz, 1 H), 3.08 - 3.19 (m, 2 H), 6.97 (dd, J = 8.5, 2.0 Hz, 1 H), 7.22 (d, J = 2.0 Hz, 1 H), 7.49 - 7.57 (m, 2 H), 7.62 (s, 1 H), 7.83 (d, J = 8.5 Hz, 1 H), 7.97 (d, J = 8.5 Hz, 1 H), 8.14 (d, J = 7.0 Hz, 1 H), 8.30 - 8.32 (m, 2 H), 8.39 (d, J = 7.0 Hz, 1 H), 9.78 (s, 1 H).

[0294] (5) Synthesis of intermediate otf-2Cl: Into a schlenk tube was added otf-2OH (520 mg, 1.23 mmol, 1.0 eq), 1-bromo-3-tert-butyl-5-chlorobenzene (458 mg, 1.85 mmol, 1.5 eq), 2-picolinic acid (151 mg, 1.23 mmol, 1.0 eq), cuprous iodide (117 mg, 0.615 mmol, 0.5 eq), potassium phosphate (522 mg, 2.46 mmol, 2.0 eq) and dimethyl sulfoxide (5 mL) successively, and the mixture was replaced with nitrogen three times. The mixture was stirred at 110 °C for 12 h. Concentration and silica gel column chromatography gave white solid 606 mg in 76% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.73 (s, 3 H), 1.27 (d, J = 10.0 Hz, 1 H), 1.45 (s, 3 H), 2.34 - 2.36 (m, 1 H), 2.76 - 2.80 (m, 1 H), 3.00 (t, J = 5.5 Hz, 1 H), 3.08 - 3.19 (m, 2 H), 6.97 (dd, J = 8.5, 2.0 Hz, 1 H), 7.22 (d, J = 2.0 Hz, 1 H), 7.49 - 7.57 (m, 2 H), 7.62 (s, 1 H), 7.83 (d, J = 8.5 Hz, 1 H), 7.97 (d, J = 8.5 Hz, 1 H), 8.14 (d, J = 7.0 Hz, 1 H), 8.30 - 8.32 (m, 2 H), 8.39 (d, J = 7.0 Hz, 1 H), 9.78 (s, 1 H). 13C NMR (126 MHz, CDC13) δ 21.58, 25.95, 31.09, 31.77, 33.01, 35.04, 39.37, 39.92, 44.35, 102.61, 108.79, 113.45, 114.04, 115.23, 117.57, 118.75, 118.84, 119.64, 120.30, 121.03, 122.50, 122.98, 124.59, 125.41, 129.72, 132.19, 134.51, 135.95, 138.75, 139.41, 140.77, 141.37, 145.57, 147.72, 149.46, 154.75, 154.86, 158.59.

[0295] (6) Synthesis of intermediate 159-NH2: Into a schlenk tube was added otf-2Cl (500 mg, 0.83 mmol, 1.0 equiv), dPhNH2 (393 mg, 1.0 mmol, 1.2 equiv), tris(dibenzylideneacetone)dipalladium (45 mg, 0.05 mmol, 0.03 equiv), 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl (41 mg, 0.10 mmol, 0.06 equiv), sodium tert-butoxide (160 mg, 1.66 mmol, 2.0 equiv), and the flask was purged with nitrogen three times, toluene (5 mL) was added, and the reaction mixture was heated at 90 °C for 6 h. Concentration and silica gel column chromatography afforded 736 mg of white solid in 90% yield. Directly used in the following reaction.

[0296] (7) Synthesis of ligand 159-L: Into a schlenk tube was added 159-NH2 (736 mg, 0.75 mmol, 1.0 equiv), ammonium hexafluorophosphate (245 mg, 1.5 mmol, 2.0 equiv), and the flask was purged with nitrogen three times, triethyl orthoformate (4 mL) was added, and the reaction mixture was heated at 70 °C for 1 h. Concentration and silica gel column chromatography afforded 713 mg of white solid in 83% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.67 (s, 3 H), 1.23 (d, J = 10.0 Hz, 1 H), 1.32 (s, 9 H), 1.43 (d, J = 3.5 Hz, 12 H), 2.28 - 2.34 (m, 1 H), 2.74 - 2.78 (m, 1 H), 2.97 (t, J = 5.5 Hz, 1 H), 3.07 - 3.15 (m, 2 H), 6.79 (t, J = 2.5 Hz, 1 H), 6.98 (t, J = 2.0 Hz, 1 H), 7.10 - 7.12 (m, 6 H), 7.13 - 7.16 (m, 4 H), 7.34 (dd, J = 8.5, 2.0 Hz, 1 H), 7.48 (d, J = 8.5 Hz, 1 H), 7.50 - 7.61 (m, 5 H), 7.67 - 7.73 (m, 5 H), 7.95 (d, J = 8.5 Hz, 1 H), 8.18 (d, J = 8.0 Hz, 1 H), 8.28 - 8.31 (m, 2 H), 8.45 (t, J = 9.0 Hz, 2 H), 10.25 (s, 1 H). 13 C NMR (101 MHz, CDC13) δ 21.56, 25.89, 30.91, 31.15, 31.70, 32.98, 35.27, 35.34, 39.29, 39.81, 44.27, 103.40, 108.76, 110.14, 113.32, 113.76, 114.17, 116.09, 117.39, 117.83, 118.75, 119.05, 120.08, 121.03, 122.73, 122.98, 124.62, 125.32, 125.47, 127.93, 128.02, 128.23, 128.26, 128.70, 129.75, 130.12, 132.26, 132.31, 132.43, 135.84, 137.09, 138.68, 139.38, 139.91, 140.73, 141.59, 141.92, 145.53, 148.05, 149.25, 153.84, 155.14, 156.47, 159.45.

[0297] (8) Synthesis of Pt159: To a sealed tube was added 159-L (570 mg, 0.50 mmol, 1.0 equiv), (1,5-cyclooctadiene) dichloroplatinum (198 mg, 0.53 mmol, 1.05 equiv), and sodium acetate (123 mg, 1.50 mmol, 3.0 equiv) sequentially, flushed with nitrogen three times, added diethyleneglycol dimethyl ether (5 mL), and bubbled with nitrogen for 30 min, and reacted at 120 °C for 72 h. Concentrated and purified by silica gel column chromatography to give yellow solid 450 mg in 76% yield. 13C NMR (126 MHz, CDC13) δ 21.22, 25.70, 31.32, 31.60, 32.09, 33.12, 34.78, 35.02, 39.43, 39.62, 42.92, 105.83, 107.36, 110.68, 110.79, 111.29, 112.34, 112.57, 114.49, 115.00, 116.81, 116.99, 117.41, 121.05, 122.70, 122.85, 123.13, 123.99, 124.60, 125.58, 125.71, 127.17, 127.49, 127.74, 128.07, 128.25, 128.72, 129.50, 129.58, 130.74, 131.77, 132.32, 135.86, 136.37, 137.27, 138.08, 138.64, 138.71, 139.39, 142.33, 144.69, 146.85, 147.77, 147.85, 149.59, 150.28, 152.23, 152.55, 154.61, 193.75.

[0298] Example 40: Tetradentate cyclometalated platinum(II) complex Pt160 synthesis route:

[0299] (1) Synthesis of intermediate M3Cz-Br: Into a reaction flask was added 1-bromo- carbazole (8 g, 32.5 mmol, 1.0 equiv) dissolved in N,N-dimethylformamide, sodium hydride (1.43 g, 35.8 mmol, 1.10 equiv) was added at low temperature, stirred for 30 minutes, then deuterated methyl iodide (4.9 g, 34.1 mmol, 1.05 equiv) was added. The reaction was stopped after 14 hours of reaction at room temperature, cooled to room temperature, concentrated, and column chromatography on silica gel to obtain a yellow solid 8.35 g, yield 97%.

[0300] (2) Synthesis of intermediate M3Cz-Bpin: Into a reaction flask was added M3Cz-Br (7.9 g, 30.0 mmol, 1.0 equiv), bis(pinacolato)diboron (15.2 g, 60 mmol, 2.0 equiv), DPPF palladium dichloride (878 mg, 1.2 mmol, 4 mol%), potassium acetate (8.83 g, 90 mmol, 3.0 equiv) was added after three times of nitrogen replacement, dimethyl sulfoxide (60 mL) was added. The reaction was stopped after 12 hours of reaction at 80 °C, cooled to room temperature, concentrated, and column chromatography on silica gel to obtain a white solid 7.2 g, yield 77%. 1H NMR (500 MHz, CDC13) δ 1.44 (s, 12 H), 7.21 - 7.25 (m, 2 H), 7.41 (d, J = 8.5 Hz, 1 H), 7.45 - 7.50 (m, 1 H), 7.90 (dd, J = 7.0, 1.0 Hz, 1 H), 8.09 (d, J = 7.5 Hz, 1 H), 8.21 (dd, J = 7.5, 1.0 Hz, 1 H).

[0301] (3) Synthesis of intermediate M3Cz-NO2: Into a reaction flask was placed M3Cz-Bpin (6.4 g, 20.6 mmol, 1.2 equiv), 4-chloro-3-nitroanisole (3.23 g, 17.2 mmol, 1.0 equiv), tetrakis(triphenylphosphine)palladium (596 mg, 0.52 mmol, 3 mol%), and potassium carbonate (4.75 g, 34.4 mmol, 2.0 equiv), dioxane (40 mL) and water (10 mL). The reaction was stopped after 11 h at 100 °C, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give yellow solid 4.6 g in 80% yield. 1 H NMR (500 MHz, CDC13) δ 1.44 (s, 12 H), 7.21 - 7.25 (m, 2 H), 7.41 (d, J = 8.5 Hz, 1 H), 7.45 - 7.50 (m, 1 H), 7.90 (dd, J = 7.0, 1.0 Hz, 1 H), 8.09 (d, J = 7.5 Hz, 1 H), 8.21 (dd, J = 7.5, 1.0 Hz, 1 H).

[0302] (4) Synthesis of intermediate M3Cz: Into a reaction flask was placed M3Cz-NO2 (4.6 g, 14.4 mmol, 1.0 equiv) and triphenylphosphine (11.3 g, 43.2 mmol, 3.0 equiv), and o-dichlorobenzene (50 mL). The reaction was stopped after 15 h at 180 °C, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give brown solid 3.4 g in 79% yield. 1 H NMR (500 MHz, CDC13) δ 1.44 (s, 12 H), 7.21 - 7.25 (m, 2 H), 7.41 (d, J = 8.5 Hz, 1 H), 7.45 - 7.50 (m, 1 H), 7.90 (dd, J = 7.0, 1.0 Hz, 1 H), 8.09 (d, J = 7.5 Hz, 1 H), 8.21 (dd, J = 7.5, 1.0 Hz, 1 H).

[0303] (5) Synthesis of intermediate otf-3OMe: Into a schlenk tube was added M3Cz (1.12 g, 3.3 mmol, 1.0 equiv), potassium phosphate (2.1 g, 9.9 mmol, 3.0 equiv), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (629 mg, 1.32 mmol, 0.4 equiv), tris(dibenzylideneacetone)dipalladium (302 mg, 0.33 mmol, 0.1 equiv), and the system was purged with nitrogen three times, then Py-otf (1.12 g, 3.47 mmol, 1.05 equiv), toluene (5 mL) was added, and the reaction was carried out at 100 °C for 24 h. Concentration and silica gel column chromatography gave yellow solid 1.29 g in 82% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.74 (s, 3H), 1.30 (d, J = 9.5 Hz, 1H), 1.46 (s, 3H), 2.34-2.35 (m, 1H), 2.76-2.81 (m, 1H), 3.01 (t, J = 5.5 Hz, 1H), 3.10-3.20 (m, 2H), 3.32 (s, 3H), 3.82 (s, 3H), 7.00 (dd, J = 9.0, 2.5 Hz, 1H), 7.13 (d, J = 2.5 Hz, 1H), 7.24 (t, J = 8.0 Hz, 1H), 7.40-7.46 (m, 2H), 7.58 (s, 1H), 7.69 (d, J = 8.0 Hz, 1H), 8.11-8.14 (m, 2H), 8.34 (s, 1H), 8.58 (d, J = 9.0 Hz, 1H).

[0304] (6) Synthesis of intermediate otf-3OH: Into a single-neck flask was added otf-3OMe (1.29 g, 2.7 mmol, 1.0 equiv) and dissolved with dichloromethane (5 mL), and boron tribromide (1.35 g, 5.4 mmol, 2.0 equiv) was added at low temperature, and the reaction was carried out at room temperature for 4 h. Concentration and silica gel column chromatography gave brown-red solid 870 mg in 72% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.74 (s, 3 H), 1.28 (d, J = 10.0 Hz, 1 H), 1.46 (s, 3 H), 2.35 - 2.37 (m, 1 H), 2.77 - 2.81 (m, 1 H), 3.01 (t, J = 6.0 Hz, 1 H), 3.12 - 3.14 (m, 2 H), 6.84 (dd, J = 8.5, 2.0 Hz, 1 H), 7.00 (d, J = 2.0 Hz, 1 H), 7.21 - 7.24 (m, 1 H), 7.36 (d, J = 8.5 Hz, 1 H), 7.41 - 7.44 (m, 1 H), 7.55 (s, 1 H), 7.67 (d, J = 9.5 Hz, 1 H), 8.06 - 8.13 (m, 2 H), 8.33 (s, 1 H), 8.46 (d, J = 9.0 Hz, 1 H), 9.56 (s, 1 H).

[0305] (7) Synthesis of intermediate otf-3Cl: Into a schlenk tube was added otf-3OH (2.44 g, 5.3 mmol, 1.0 eq), 1-bromo-3-tert-butyl-5-chlorobenzene (1.97 g, 7.95 mmol, 1.5 eq), 2-picolinic acid (653 mg, 5.3 mmol, 1.0 eq), cuprous iodide (505 mg, 2.65 mmol, 0.5 eq), potassium phosphate (2.25 g, 10.6 mmol, 2.0 eq) and dimethyl sulfoxide (10 mL) successively, and the mixture was replaced with nitrogen three times. The mixture was stirred at 110 °C for 24 h. Concentration and silica gel column chromatography gave 659 mg of white solid in 68% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.68 (s, 3 H), 1.24 (s, 11 H), 1.43 (s, 3 H), 2.31 - 2.33 (m, 1 H), 2.73 - 2.77 (m, 2 H), 2.96 (t, J = 5.5 Hz, 1 H), 3.05 - 3.14 (m, 2 H), 6.87 (t, J = 2.0 Hz, 1 H), 7.08 - 7.12 (m, 2 H), 7.18 (t, J = 2.0 Hz, 1 H), 7.24 - 7.27 (m, 2 H), 7.42 - 7.47 (m, 2 H), 7.55 (s, 1 H), 7.71 (d, J = 8.0 Hz, 1 H), 8.15 (d, J = 7.5 Hz, 1 H), 8.19 (d, J = 8.5 Hz, 1 H), 8.27 (s, 1 H), 8.73 (d, J = 9.0 Hz, 1 H). 13C NMR (126 MHz, CDC13) δ 21.58, 25.95, 31.09, 31.73, 32.95, 35.03, 39.34, 39.91, 44.36, 102.05, 103.52, 108.09, 108.93, 112.49, 114.06, 115.19, 117.53, 118.29, 118.65, 119.00, 119.42, 120.12, 120.21, 123.44, 124.17, 134.45, 137.08, 140.85, 141.16, 141.32, 141.71, 145.76, 147.70, 149.48, 153.77, 154.70, 158.55.

[0306] (8) Synthesis of intermediate 160-NH2: Into a schlenk tube was added otf-3Cl (400 mg, 0.64 mmol, 1.0 equiv), dPhNH2 (279 mg, 0.71 mmol, 1.1 equiv), tris(dibenzylideneacetone)dipalladium (18 mg, 0.019 mmol, 0.03 equiv), 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl (16 mg, 0.038 mmol, 0.06 equiv), sodium tert-butoxide (123 mg, 1.28 mmol, 2.0 equiv), and the flask was purged with nitrogen three times, then toluene (5 mL) was added and the reaction was heated at 90 °C for 3 h. Concentration and silica gel column chromatography afforded 600 mg of white solid in 95% yield. Used directly in the following reaction.

[0307] (9) Synthesis of ligand 160-L: Into a schlenk tube was added 160-NH2 (600 mg, 0.61 mmol, 1.0 equiv), ammonium hexafluorophosphate (199 mg, 1.22 mmol, 2.0 equiv), and the flask was purged with nitrogen three times, then triethyl orthoformate (5 mL) was added and the reaction was heated at 70 °C for 2 h. Concentration and silica gel column chromatography afforded 622 mg of white solid in 87% yield. 1H NMR (400 MHz, DMSO-d6) δ 0.67 (s, 3 H), 1.23 (d, J = 9.6 Hz, 1 H), 1.32 (s, 9 H), 1.44 (s, 12 H), 2.28 - 2.33 (m, 1 H), 2.73 - 2.78 (m, 1 H), 2.97 (t, J = 5.2 Hz, 1 H), 3.04 - 3.15 (m, 2 H), 6.81 (t, J = 2.0 Hz, 1 H), 6.95 (s, 1 H), 7.12 - 7.21 (m, 11 H), 7.27 (t, J = 7.6 Hz, 1 H), 7.43 (d, J = 2.4 Hz, 1 H), 7.45 - 7.49 (m, 3 H), 7.52 - 7.62 (m, 3 H), 7.71 (t, J = 7.6 Hz, 4 H), 8.17 (d, J = 7.6 Hz, 1 H), 8.23 (d, J = 8.8 Hz, 1 H), 8.28 (s, 1 H), 8.81 (d, J = 8.8 Hz, 1 H), 10.25 (s, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.57, 25.92, 30.96, 31.16, 31.73, 32.96, 35.28, 35.32, 39.31, 39.87, 44.35, 102.45, 103.35, 108.13, 109.10, 110.29, 112.94, 113.33, 114.21, 115.83, 117.57, 118.14, 118.42, 118.91, 119.22, 119.35, 120.09, 124.01, 124.22, 125.35, 127.92, 128.00, 128.21, 128.26, 128.66, 130.14, 132.42, 132.46, 137.13, 139.92, 140.76, 141.10, 141.33, 141.80, 142.04, 145.70, 147.86, 149.51, 152.89, 155.19, 156.35, 159.54.

[0308] (10) Synthesis of Pt160: To a sealed tube was added 160-L (530 mg, 0.47 mmol, 1.0 equiv), (1,5-cyclooctadiene) dichloroplatinum (183 mg, 0.49 mmol, 1.05 equiv), and sodium acetate (116 mg, 1.41 mmol, 3.0 equiv) sequentially, purged with nitrogen three times, added diethyleneglycol dimethyl ether (5 mL), and bubbled with nitrogen for 30 min, and reacted at 120 °C for 72 h. Concentrated and purified by silica gel column chromatography to give yellow solid 269 mg in 48% yield. 1H NMR (500 MHz, CDC13) δ 0.25 (s, 3H), 1.09 (s, 3H), 1.23 (d, J = 9.5 Hz, 1H), 1.46 (s, 18H), 2.05 (d, J = 5.0 Hz, 1H), 2.12 - 2.19 (m, 1H), 2.49 - 2.55 (m, 1H), 2.66 (d, J = 18.5 Hz, 1H), 2.87 (d, J = 16.0 Hz, 1H), 6.13 (d, J = 8.0 Hz, 2H), 6.43 (d, J = 7.5 Hz, 1H), 6.58 (d, J = 6.0 Hz, 2H), 6.85 (d, J = 8.5 Hz, 1H), 7.03 (d, J = 7.5 Hz, 1H), 7.11 (d, J = 1.5 Hz, 1H), 7.18 - 7.26 (m, 2H), 7.28 (d, J = 7.0 Hz, 2H), 7.31 - 7.38 (m, 2H), 7.42 (d, J = 2.5 Hz, 1H), 7.49 - 7.59 (m, 4H), 7.59 - 7.65 (m, 2H), 7.78 - 7.84 (m, 2H), 7.98 (d, J = 8.0 Hz, 1H), 8.16 (d, J = 7.5 Hz, 1H), 8.19 (d, J = 8.5 Hz, 1H), 8.29 (d, J = 8.5 Hz, 1H), 8.91 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.21, 25.73, 31.33, 31.62, 32.07, 33.03, 34.79, 35.02, 39.44, 39.63, 42.94, 105.77, 106.12, 107.96, 109.26, 110.70, 111.25, 111.97, 112.32, 113.46, 113.97, 115.85, 116.21, 117.38, 118.74, 119.03, 119.42, 122.66, 123.94, 124.04, 124.61, 125.52, 127.05, 127.42, 127.69, 128.09, 128.27, 128.70, 129.55, 131.76, 136.40, 137.17, 137.35, 138.11, 138.62, 138.76, 139.04, 141.95, 142.33, 144.40, 147.19, 147.49, 147.82, 149.65, 149.86, 152.34, 152.57, 153.81, 193.58.

[0309] Example 41: Tetradentate cyclometalated platinum (II) complex Pt161 synthesis route:

[0310] Synthesis of intermediate (2NO): Into a three-necked flask was placed 4-chloro-3-nitroanisole (7.0 g, 37.32 mmol, 1.0 eq), 9,9-dimethyl-2-fluorenylboronic acid (13.32 g, 55.98 mmol, 1.5 eq), potassium carbonate (10.32 g, 74.64 mmol, 2.0 eq), tetrakis(triphenylphosphine)palladium (870 mg, 0.75 mmol, 2 mol%). After purging with nitrogen three times, 1,4-dioxane / water = 4:1 (80 mL:20 mL) was added. The reaction was carried out at 90 °C for 10 h, extracted with water and ethyl acetate, and then separated by silica gel column after removing the solvent under reduced pressure, eluent: petroleum ether / ethyl acetate = 50:1-15:1, to give yellow solid 11.96 g, yield 93%. 1 H NMR (500 MHz, DMSO-d6) δ 1.45 (s, 6 H), 3.90 (s, 3 H), 7.26 (dd, J = 8.0, 2.0 Hz, 1 H), 7.32-7.40 (m, 3 H), 7.50 (dd, J = 1.5, 0.5 Hz, 1 H), 7.54-7.60 (m, 3 H), 7.84-7.90 (m, 2 H).

[0311] Synthesis of intermediate (2NH): Into a three-necked flask was placed 2NO (6.59 g, 19.08 mmol, 1.0 eq), triphenylphosphine (15.01 g, 57.24 mmol, 3.0 eq). After purging with nitrogen three times, o-dichlorobenzene (50 mL) was added. The reaction was carried out at 180 °C for 10 h, and then separated by silica gel column after removing the solvent under reduced pressure, eluent: petroleum ether / dichloromethane = 20:1, to give white solid 1.90 g, yield 32%. 1 H NMR (500 MHz, DMSO-d6) δ 1.65 (s, 6 H), 3.86 (s, 3 H), 6.80 (dd, J = 8.0, 2.0 Hz, 1 H), 7.05 (d, J = 2.0 Hz, 1 H), 7.29 (td, J = 7.5, 1.5 Hz, 1 H), 7.34 (td, J = 7.5, 1.5 Hz, 1 H), 7.59 (d, J = 7.0 Hz, 1 H), 7.63 (d, J = 8.0 Hz, 1 H), 7.83 (d, J = 7.0 Hz, 1 H), 8.00 (dd, J = 8.0, 2.5 Hz, 2 H), 11.16 (s, 1 H).

[0312] Synthesis of intermediate (2OMe): Into a three-necked flask was added 2NH (700 mg, 2.2 mmol, 1.0 eq), potassium phosphate (1.4 g, 6.6 mmol, 3.0 eq), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (420 mg, 0.88 mmol, 0.4 eq), tris(dibenzylideneacetone)dipalladium (201 mg, 0.22 mmol, 0.1 eq), and the flask was purged with nitrogen three times. Py-OTF (754 mg, 2.34 mmol, 1.05 eq) and toluene (10 mL) were added, and the mixture was stirred at 100 °C for 12 h. After removing the solvent under reduced pressure, the residue was separated by silica gel column chromatography using petroleum ether / ethyl acetate (20:1) as eluent to give 1.05 g of a solid in 98% yield.

[0313] Synthesis of intermediate (2OH): Into a single-necked flask was added 2OMe (1.05 g, 2.17 mmol, 1.0 eq), hydrobromic acid (15 mL, 21.7 mmol, 10.0 eq), and acetic acid (3 mL). The mixture was stirred at 120 °C for 11 h. The reaction was quenched with saturated sodium bicarbonate solution and extracted with water and ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography using petroleum ether / ethyl acetate (5:1) as eluent to give 955 mg of a solid in 94% yield. 1 H NMR (500 MHz, CDC13) δ 0.77 (s, 3H), 1.37 (d, J = 10.0 Hz, 1H), 1.48 (s, 3H), 1.59 (s, 6H), 2.38 (t, J = 3.0 Hz, 1H), 2.80 (d, J = 10.0 Hz, 1H), 2.95 (t, J = 5.5 Hz, 1H), 3.12 (d, J = 1.5 Hz, 2H), 5.94 (s, 1H), 6.78 (dd, J = 8.5, 2.5 Hz, 1H), 7.27 (d, J = 2.0 Hz, 1H), 7.31 (td, J = 6.5, 1.5 Hz, 2H), 7.44-7.47 (m, 2H), 7.73-7.76 (m, 1H), 7.91 (d, J = 8.5 Hz, 1H), 7.98 (dd, J = 10.0, 0.8 Hz, 2H), 8.25 (s, 1H).

[0314] Synthesis of intermediate (2Cl): Into a three-neck flask was added 2OH (955 mg, 2.03 mmol, 1.0 eq), 1-bromo-3-tert-butyl-5-chlorobenzene (754 mg, 3.04 mmol, 1.5 eq), 2-picolinic acid (250 mg, 2.03 mmol, 1.0 eq), cuprous iodide (193 mg, 1.02 mmol, 0.5 eq), potassium phosphate (862 mg, 4.06 mmol, 2.0 eq) and dimethyl sulfoxide (15 mL) successively, and the mixture was stirred at 120 °C for 12 h under nitrogen. The mixture was concentrated, and the residue was purified by column chromatography on silica gel to give 932 mg of a white solid, in 72% yield. 1 H NMR (500 MHz, CDC13) δ 0.77 (s, 3H), 1.28 (s, 9H), 1.37 (d, J = 9.5 Hz, 1H), 1.48 (s, 3H), 1.58 (s, 1H), 1.61 (s, 6H), 2.37-2.39 (m, 1H), 2.79 (dt, J = 11.5 Hz, 6.0 Hz, 1H), 2.97 (t, J = 5.5 Hz, 1H), 3.10 (d, J = 2.5 Hz, 2H), 6.79 (t, J = 2.0 Hz, 1H), 6.99 (dd, J = 8.5 Hz, 2.0 Hz, 1H), 7.02 (t, J = 2.0 Hz, 1H), 7.07 (t, J = 1.5 Hz, 1H), 7.32 (tt, J = 7.2 Hz, 5.8 Hz, 2H), 7.42 (s, 1H), 7.45 (d, J = 2.1 Hz, 1H), 7.47 (dd, J = 6.9, 1.6 Hz, 1H), 7.78 (dd, J = 6.0, 2.0 Hz, 1H), 8.06 (d, J = 8.0 Hz, 2H), 8.08 (d, J = 8.5 Hz, 1H), 8.26 (s, 1H).

[0315] Synthesis of intermediate (161-NH2): Into a three-neck flask was added dPhNH2 (610 mg, 1.6 mmol, 1.1 eq), 2Cl (900 mg, 1.4 mmol, 1.0 eq), tris-dibenzylideneacetone palladium (38 mg, 0.04 mmol, 3 mol%), 2-bis(cyclohexyl)phosphino-2',6'-dimethoxybiphenyl (33 mg, 0.08 mmol, 6 mol%) and sodium tert-butoxide (269 mg, 2.8 mmol, 2.0 eq). The mixture was stirred at 90 °C for 8 h, then the temperature was raised to 120 °C for 10 h. The mixture was extracted with water and ethyl acetate, and the solvent was removed by distillation under reduced pressure. The residue was separated by column chromatography on silica gel to give 1.06 g of a solid, in 76% yield.

[0316] Synthesis of Ligand 161-L: Into a three-neck flask was added 161-NH2(1.06 g, 1.07 mmol, 1.0 eq), ammonium hexafluorophosphate (348 mg, 2.13 mmol, 2.0 eq), and the flask was purged with nitrogen three times, and then triethyl orthoformate (10 mL) was added. The reaction was stirred at 75 °C for 40 min, and then the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography with dichloromethane-dichloromethane / ethyl acetate = 40:1 as eluent to give 944 mg of a solid in 76% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.67 (s, 3H), 1.24 (d, J = 9.5 Hz, 1H), 1.30 (s, 9H), 1.43 (s, 3H), 1.44 (s, 9H), 1.56 (s, 6H), 2.30-2.32 (m, 1H), 2.73-2.78 (m, 1H), 2.95 (t, J = 5.5 Hz, 1H), 3.04-3.20 (m, 2H), 6.79 (t, J = 2.0 Hz, 1H), 6.94 (t, J = 1.5 Hz, 1H), 7.12-7.17 (m, 11H), 7.33-7.35 (m, 2H), 7.44 (dd, J = 2.0, 1.5 Hz, 1H), 7.47-7.49 (m, 1H), 7.53 (td, J = 8.5 Hz, 1.5 Hz, 1H), 7.56-7.59 (m, 3H), 7.65 (s, 1H), 7.71 (t, J = 1.0 Hz, 1H), 7.72 (s, 2H), 7.93-7.95 (m, 1H), 8.14 (d, J = 1.0 Hz, 1H), 8.25 (s, 1H), 8.35 (d, J = 8.5 Hz, 1H), 8.41 (d, J = 1.0 Hz, 1H), 10.24 (s, 1H).

[0317] Synthesis of Pt161: Into a sealed tube was added 161-L (850 mg, 0.73 mmol, 1.0 eq), (1,5-cyclooctadiene) dichloroplatinum (288 mg, 0.79 mmol, 1.05 eq), and sodium acetate (180 mg, 2.18 mmol, 3.0 eq), and the tube was purged with nitrogen three times, and then diethyleneglycol dimethyl ether (40 mL) was added and the mixture was bubbled with nitrogen for 30 min to remove oxygen. The reaction was stirred at 120 °C for 72 h, and then the solvent was removed by distillation under reduced pressure after the reaction was cooled to room temperature. The residue was separated by silica gel column chromatography with petroleum ether / dichloromethane = 2:1-1:1 as eluent to give 659 mg of a yellow solid in 74% yield. 1H NMR (400 MHz, DMSO-d6) δ 0.26 (s, 3H), 1.06 (s, 3H), 1.22 (d, J = 9.2 Hz, 1H), 1.42 (s, 10H), 1.45 (s, 9H), 1.62 (d, J = 3.2 Hz, 6H), 1.99 (t, J = 5.2 Hz, 1H), 2.15 (s, 1H), 2.80 (d, J = 18.4 Hz, 1H), 2.98 (d, J = 18.2 Hz, 1H), 5.75 (s, 1H), 6.07 (t, J = 7.6 Hz, 2H), 6.42 - 6.54 (m, 3H), 6.85 - 6.91 (m, 2H), 7.12 (dd, J = 10.8 Hz, 8.4 Hz, 2H), 7.26 (t, J = 7.2 Hz, 1H), 7.32 - 7.39 (m, 5H), 7.43 - 7.48 (m, 2H), 7.51 (dd, J = 6.4 Hz, 2.4 Hz, 2H), 7.62 - 7.64 (m, 3H), 7.82 (d, J = 7.2 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.96 (s, 1H), 8.14 (d, J = 8.4 Hz, 1H), 8.24 (s, 1H), 8.35 (s, 1H), 8.78 (s, 1H).

[0318] Example 42: Tetradentate cyclometalated platinum(II) complex Pt165:

[0319] Pt165 was synthesized according to the synthetic procedure of Reference Example 1, replacing the corresponding ligand starting material. After metallation, the target compound was synthesized. MS: m / z 1124.39 (M+H) + .

[0320] Example 43: Tetradentate cyclometalated platinum(II) complex Pt174:

[0321] Pt174 was synthesized according to the synthetic procedure of Reference Example 1, replacing the corresponding ligand starting material. After metallation, the target compound was synthesized. MS: m / z 1262.43 (M+H) + .

[0322] Example 44: Tetradentate cyclometalated platinum(II) complex Pt183:

[0323] Pt183 was synthesized according to the synthetic procedure of Reference Example 1, replacing the corresponding ligand starting material. After metallation, the target compound was synthesized. MS: m / z 1130.42 (M+H) + .

[0324] Example 45: Tetradentate cyclometalated platinum(II) complex Pt193:

[0325] Reference to the synthesis of Example 1, replace the corresponding ligand raw material to prepare synthesis of Pt193, after remetallization can synthesize the target compound. MS: m / z 1278.41 (M+H) + .

[0326] Example 46: Tetradentate cyclometalated platinum (II) complex Pt196:

[0327] Reference to the synthesis of Example 1, replace the corresponding ligand raw material to prepare synthesis of Pt196, after remetallization can synthesize the target compound. MS: m / z 1156.39 (M+H) + .

[0328] Example 47: Tetradentate cyclometalated platinum (II) complex Pt203 synthesis route:

[0329] Synthesis of intermediate i-Pr-Br: Add intermediate 2,6-diisopropylaniline (5 g, 28.2 mmol, 1.0 equivalent) to a 200 mL single-neck flask, add dichloromethane (100 mL), cool to 0°C, slowly add NBS (N-bromosuccinimide) (5.52 g, 31 mmol, 1.1 equivalent), and move to room temperature to stir the reaction for 17 hours. Quench the reaction mixture with sodium thiosulfate solution, extract with dichloromethane and water three times, and dry with anhydrous sodium sulfate. Remove the solvent under reduced pressure, separate and purify with a silica gel column, and elute with petroleum ether / ethyl acetate = 50:1-20:1 to obtain the intermediate i-Pr-Br as a brownish red liquid, 6.5 g, with a yield of 90%. 1 H NMR (500 MHz, CDCl3) δ 1.26 (d, J = 7.0 Hz, 12H), 2.85-2.94 (m, 2H), 3.70 (s, 2H), 7.13 (s, 2H).

[0330] Synthesis of intermediate i-Pr-Br-NO2: Add intermediate i-Pr-Br (3 g, 11.7 mmol, 1.1 equivalent), o-bromonitrobenzene (2.15 g, 10.6 mmol, 1.0 equivalent), Pd2(dba)3 (292 mg, 0.32 mmol, 0.03 equivalent), BINAP (1,1'-binaphthalene-2,2'-diphenylphosphine) (397 mg, 0.64 mmol, 0.06 equivalent), cesium carbonate (6.9 g, 21.2 mmol, 2.0 equivalent) to a 100 mL three-neck flask, replace nitrogen three times, add toluene (30 mL), and stir the reaction at 100°C for 48 hours. Remove the solvent under reduced pressure, separate and purify with a silica gel column, and elute with petroleum ether / ethyl acetate = 100:1-50:1 to obtain the intermediate i-Pr-Br-NO2 as an orange solid, 3.1 g, with a yield of 70%.1 H NMR (500 MHz, CDC13) δ 1.10 (d, J = 6.5 Hz, 6H), 1.16 (d, J = 7.0 Hz, 6H), 2.95 - 3.07 (m, 2H), 6.36 (dd, J = 8.5, 1.5 Hz, 1H), 6.72 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.29 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.37 (s, 2H), 8.23 (dd, J = 8.5, 1.5 Hz, 1H), 9.09 (s, 1H).

[0331] Synthesis of intermediate i-Pr-Cz-NO2: Into a 100 mL three-necked flask was placed intermediate i-Pr-Br-NO2(2.78 g, 7.36 mmol, 1.0 eq), 3,6-di-tert-butylcarbazole (4.11 g, 14.7 mmol, 2.0 eq), Pd2(dba)3(202 mg, 0.22 mmol, 0.03 eq), SPhos (2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl) (182 mg, 0.44 mmol, 0.06 eq), cesium carbonate (4.8 g, 14.7 mmol, 2.0 eq), and the flask was purged with nitrogen three times, then toluene (30 mL) was added, and the reaction was stirred at 100 °C for 36 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether ~ petroleum ether / ethyl acetate = 100:1 to give intermediate i-Pr-Cz-NO2 as a brownish red liquid 2.93 g in 69% yield. 1 H NMR (500 MHz, CDC13) δ 1.10 (d, J = 6.5 Hz, 6H), 1.16 (d, J = 7.0 Hz, 6H), 2.95 - 3.07 (m, 2H), 6.36 (dd, J = 8.5, 1.5 Hz, 1H), 6.72 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.29 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.37 (s, 2H), 8.23 (dd, J = 8.5, 1.5 Hz, 1H), 9.09 (s, 1H).

[0332] Synthesis of intermediate i-Pr-Cz-NH2: Into a 50 mL three-necked flask was placed intermediate i-Pr-Cz-NO2 (1.5 g, 2.6 mmol, 1.0 eq), stannous chloride dihydrate (2.4 g, 10.4 mmol, 4.0 eq), and the flask was purged with nitrogen three times, then ethyl acetate and ethanol (10 + 10 mL) were added, and the reaction was stirred at 78 °C for 48 h. The reaction was neutralized with aqueous sodium bicarbonate solution, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The product was purified by silica gel column chromatography, eluting with petroleum ether / ethyl acetate = 20:1 to 5:1, to give intermediate i-Pr-Cz-NH2 as a gray-brown foamy solid, 1.4 g, 98% yield. 1 H NMR (500 MHz, CDC13) δ 1.14 (s, 6H), 1.21 (s, 6H), 1.49 (s, 18H), 3.11-3.23 (m, 2H), 3.92 (s, 2H), 5.03 (s, 1H), 6.31-6.37 (m, 1H), 6.73-6.79 (m, 2H), 6.82-6.90 (m, 1H), 7.40 (s, 2H), 7.41-7.45 (m, 2H), 7.48-7.53 (m, 2H), 8.17 (d, J = 2.0 Hz, 2H).

[0333] Synthesis of intermediate i-Pr-Cz-NH: Into a schlenk tube was placed intermediate i-Pr-Cz-NH2 (565 mg, 1.03 mmol, 1.2 eq), intermediate 2-Cl (450 mg, 0.96 mmol, 1.0 eq), Pd2(dba)3 (26 mg, 0.027 mmol, 0.03 eq), SPhos (2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl) (23 mg, 0.055 mmol, 0.06 eq), sodium tert-butoxide (177 mg, 1.84 mmol, 2.0 eq), and the flask was purged with nitrogen three times, then toluene (5 mL) was added, and the reaction was stirred at 90 °C for 9 h. The solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography, eluting with petroleum ether / ethyl acetate = 50:1, to give intermediate i-Pr-Cz-NH as a foamy solid, 825 mg, 93% yield. It was used directly in the following reaction.

[0334] Synthesis of ligand LDB1 : i-Pr-Cz-NH (825 mg, 0.8 mmol, 1.0 eq), ammonium hexafluorophosphate (261 mg, 1.6 mmol, 2.0 eq) were added into a schlenk tube successively, and the tube was replaced with nitrogen for three times. Then triethyl orthoformate (5 mL) was added successively, and the mixture was stirred at 70 °C for 30 min. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / ethyl acetate = 20:1 ~ dichloromethane / methanol = 500:1 as eluent. Finally, ligand LDB1 was obtained as a foamy solid 829 mg in 87% yield. 1 H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.08 (d, J = 7.0 Hz, 6H), 1.29 (dd, J = 6.5, 1.0 Hz, 6H), 1.32 (d, J = 9.5 Hz, 1H), 1.42 (s, 9H), 1.45 (s, 3H), 1.48 (s, 18H), 2.26 - 2.34 (m, 2H), 2.34 - 2.40 (m, 1H), 2.72 - 2.82 (m, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.08 - 3.13 (m, 2H), 7.09 (t, J = 2.0 Hz, 1H), 7.18 (dd, J = 8.5, 2.0 Hz, 1H), 7.30 - 7.34 (m, 1H), 7.40 - 7.46 (m, 2H), 7.46 - 7.51 (m, 5H), 7.54 (dd, J = 8.5, 2.0 Hz, 2H), 7.63 (s, 2H), 7.69 (d, J = 2.0 Hz, 1H), 7.69 - 7.77 (m, 3H), 7.94 - 7.98 (m, 1H), 8.10 (d, J = 8.0 Hz, 1H), 8.14 - 8.18 (m, 3H), 8.20 (s, 1H), 9.83 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.50, 23.71, 24.36, 25.88, 29.25, 30.91, 31.73, 31.95, 32.98, 34.73, 35.50, 39.30, 39.84, 44.26, 53.39, 103.43, 109.24, 110.01, 110.86, 113.38, 113.61, 114.48, 116.11, 116.31, 117.99, 118.43, 119.96, 120.92, 121.12, 121.44, 122.89, 123.59, 123.77, 124.07, 124.72, 125.83, 128.85, 128.94, 130.93, 132.73, 133.45, 138.60, 140.22, 140.84, 141.18, 141.24, 142.07, 143.47, 145.34, 147.87, 148.35, 149.45, 153.93, 157.18, 159.91. HRMS (ESI): C 73 H 78 N5O + [M] + Calcd 1040.6201, Found 1040.6161.

[0335] Synthesis of complex Pt203: Ligand LDB1 (720 mg, 0.61 mmol, 1.0 eq), Pt(COD)Cl2((1,5-cyclooctadiene) dichloroplatinum) (238 mg, 0.637 mmol, 1.05 eq) and sodium acetate (149 mg, 1.82 mmol, 3.0 eq) were added into a sealed tube successively, and the tube was purged with nitrogen for three times. Then DEDM (diethyleneglycol dimethyl ether) (8 mL) was added, and the tube was purged with nitrogen for 30 min. The tube was heated at 120 °C for 72 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 2:1 as eluent. Finally, complex Pt203 was obtained as yellow-green solid, 460 mg, yield 61%. 1H NMR (500 MHz, CDC13) δ 0.22 (s, 3H), 0.24 (d, J = 9.5 Hz, 1H), 0.61 (d, J = 7.0 Hz, 3H), 1.07 (s, 3H), 1.11 (d, J = 7.0 Hz, 3H), 1.44 (dd, J = 11, 6.5 Hz, 6H), 1.54 (s, 9H), 1.58 (s, 18H), 1.70 - 1.75 (m, 1H), 1.92 - 2.0 (m, 1H), 2.33 (dd, J = 18.5, 3.0 Hz, 1H), 2.45 (t, J = 5.0 Hz, 1H), 2.48 - 2.54 (m, 1H), 2.97 - 3.05 (m, 1H), 3.63 - 3.71 (m, 1H), 7.20 (d, J = 8.0 Hz, 1H), 7.25 - 7.28 (m, 1H), 7.36 - 7.40 (m, 1H), 7.40 - 7.45 (m, 2H), 7.46 (d, J = 2.5 Hz, 1H), 7.49 - 7.52 (m, 2H), 7.52 - 7.56 (m, 2H), 7.63 - 7.69 (m, 3H), 7.72 (d, J = 2.0 Hz, 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.87 (s, 1H), 8.07 (t, J = 7.5 Hz 2H), 8.20 - 8.25 (m, 3H), 8.43 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.09, 21.38, 24.61, 25.00, 25.59, 25.62, 28.85, 29.06, 29.60, 31.64, 32.01, 32.72, 34.79, 34.88, 39.04, 39.18, 42.89, 106.26, 107.55, 109.44, 111.50, 111.96, 112.77, 113.83, 114.71, 115.85, 116.19, 116.48, 116.63, 120.27, 120.38, 121.61, 122.28, 123.21, 123.56, 123.60, 124.01, 124.68, 129.41, 129.91, 137.14, 138.05, 139.18, 139.70, 143.61, 144.89, 147.37, 148.02, 148.85, 149.24, 149.35, 149.61, 150.06, 153.56, 155.23, 192.89. HRMS (ESI): C 73 H 75 N5OPt[M+H] + Calcd 1233.5692, Found 1233.5702.

[0336] Example 48: Tetradentate cyclometalated platinum(II) complex Pt204synthesis route:

[0337] Synthesis of intermediate Cz-NO2-F-2: A 250 mL three-necked flask was charged with potassium phosphate (7.6 g, 35.78 mmol, 2.0 eq), the water vapor was blown out by air gun, and 2-fluoro-4-bromonitrobenzene (4.72 g, 21.47 mmol, 1.2 eq), 3,6-di-tert-butylcarbazole (5 g, 17.8 mmol, 1.0 eq), Pd2(dba)3(491 mg, 0.54 mmol, 0.03 eq), XPhos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) (511 mg, 1.07 mmol, 0.06 eq) were added under nitrogen protection, and the nitrogen was replaced for three times, then toluene (70 mL) was added, and the reaction was stirred at 110 °C for 16 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 100:1 as the eluent to give intermediate Cz-NO2-F-2 as an orange solid (6.9 g, 92% yield). 1 H NMR (500 MHz, CDC13) δ 1.47 (s, 18H), 7.48-7.50 (m, 2H), 7.50-7.53 (m, 2H), 7.56-7.61 (m, 2H), 8.13 (dd, J = 2.0, 1.0 Hz, 2H), 8.34 (t, J = 8.5 Hz, 1H).

[0338] Synthesis of intermediate Cz-NO2-Br-2: A 250 mL three-necked flask was charged with 2,6-dibromo-4-tert-butylaniline (2.13 g, 6.95 mmol, 1.0 eq), N,N-dimethylformamide (100 mL) was added, and the temperature was lowered to -10 °C, sodium hydride (500 mg, 20.85 mmol, 3.0 eq) was slowly added, and the temperature was kept low for 1 h, then intermediate Cz-NO2-F-2 (3.2 g, 7.64 mmol, 1.1 eq) was added, and the reaction was stirred at room temperature for 20 h. The reaction was quenched with water, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 50:1 as the eluent to give intermediate Cz-NO2-Br-2 as a liquid (4.84 g, 99% yield). 1H NMR (500 MHz, CDC13) δ 1.29 (s, 9H), 1.44 (s, 18H), 6.60 (d, J = 2.0 Hz, 1H), 7.10 (dd, J = 9.0, 2.5 Hz, 1H), 7.41 - 7.44 (m, 2H), 7.45 - 7.48 (m, 2H), 7.65 (s, 2H), 8.06 (d, J = 2.0 Hz, 2H), 8.47 (d, J = 9.0 Hz, 1H), 9.38 (s, 1H).

[0339] Synthesis of intermediate Cz-NH2-Br-2: Into a 100 mL three-necked flask was placed intermediate Cz-NO2-Br-2 (2 g, 2.88 mmol, 1.0 eq), stannous chloride (2.13 g, 11.28 mmol, 4.0 eq), and the flask was purged with nitrogen three times, then ethyl acetate and ethanol (25 + 25 mL) were added, and the reaction was stirred at 78 °C for 18 h. Neutralized with aqueous sodium bicarbonate solution, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. Purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 20:1-5:1, to give intermediate Cz-NH2-Br-2 as a solid, 1.42 g, 74% yield. Used directly in the following reaction.

[0340] Synthesis of intermediate Cz-NH2-Ph-2: Into a 100 mL three-necked flask with a magnetic rotor was placed intermediate Cz-NH2-Br-2 (1.42 g, 2.1 mmol, 1.0 eq), phenylboronic acid (769 mg, 6.3 mmol, 3.0 eq), tetrakis(triphenylphosphine)palladium (100 mg, 0.084 mmol, 0.04 eq), potassium carbonate (1.45 g, 10.5 mmol, 5.0 eq), and the flask was purged with nitrogen three times, then 1,4-dioxane and water (24 mL / 6 mL) were added, and the reaction was stirred at 100 °C for 10 h under nitrogen bubbling for 30 min. Extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. Purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1, to give intermediate Cz-NH2-Ph-2 as a solid, 1.16 g, 83% yield. 1H NMR (500 MHz, DMSO-d6) δ 1.24 (s, 9H), 1.39 (s, 18H), 4.85 (s, 2H), 6.02 (s, 1H), 6.04 (d, J = 2.5 Hz, 1H), 6.35 (dd, J = 8.0, 2.5 Hz, 1H), 6.52 (d, J = 8.0 Hz, 1H), 6.81 - 6.86 (m, 2H), 7.24 (s, 2H), 7.28 - 7.32 (m, 2H), 7.33 - 7.38 (m, 4H), 7.41 (dd, J = 8.5, 2.0 Hz, 2H), 7.44 - 7.48 (m, 4H), 8.15 (dd, J = 2.0, 1.0 Hz, 2H).

[0341] Synthesis of intermediate Cz-NH-Ph-2: Into a schlenk tube was added intermediate Cz-NH2-Ph-2 (617 mg, 0.92 mmol, 1.2 equiv), intermediate OTf-Cl (400 mg, 0.76 mmol, 1.0 equiv), Pd2(dba)3(42 mg, 0.046 mmol, 0.06 equiv), SPhos (38 mg, 0.092 mmol, 0.12 equiv), sodium tert-butoxide (148 mg, 1.53 mmol, 2.0 equiv), and the flask was purged with nitrogen three times, then toluene (5 mL) was added, and the reaction was stirred at 90 °C for 4 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 40: 1-20: 1 to give intermediate Cz-NH-Ph-2 as a yellow foamy solid 834 mg in 94% yield. Used directly in the next reaction.

[0342] Synthesis of ligand LDB2: Into a schlenk tube was added intermediate Cz-NH-Ph-2 (834 mg, 0.72 mmol, 1.0 equiv), ammonium hexafluorophosphate (235 mg, 1.44 mmol, 2.0 equiv), and the flask was purged with nitrogen three times, then triethyl orthoformate (5 mL) was added, and the reaction was stirred at 70 °C for 30 min. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 20: 1- dichloromethane:methanol = 500: 1 to give ligand LDB2 as a green foamy solid 627 mg in 66% yield. 1H NMR (500 MHz, CDC13) δ 0.72 (s, 3 H), 1.30 (d, J = 9.5 Hz, 1 H), 1.36 (s, 9 H), 1.40 (s, 9 H), 1.45 (s, 3 H), 1.46 (s, 18 H), 2.35 (dt, J = 5.5, 3.0 Hz, 1 H), 2.71 - 2.79 (m, 1 H), 2.93 (t, J = 5.5 Hz, 1 H), 3.09 (d, J = 3.0 Hz, 2 H), 6.58 (t, J = 2.0 Hz, 1 H), 6.78 (t, J = 2.0 Hz, 1 H), 6.95 (d, J = 9.0 Hz, 2 H), 7.11 (dd, J = 8.5, 2.5 Hz, 1 H), 7.16 - 7.22 (m, 3 H), 7.22 - 7.23 (m, 5 H), 7.23 - 7.24 (m, 2 H), 7.30 - 7.34 (m, 1 H), 7.37 (t, J = 2.0 Hz, 1 H), 7.41 - 7.46 (m, 5 H), 7.55 (s, 2 H), 7.62 - 7.67 (m, 2 H), 7.72 (dd, J = 8.0, 2.5 Hz, 2 H), 8.09 - 8.13 (m, 3 H), 8.17 (d, J = 8.5 Hz, 1 H), 8.21 (s, 1 H), 9.38 (s, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.52, 25.91, 30.93, 31.10, 31.75, 31.92, 32.96, 34.76, 35.28, 35.40, 39.31, 39.86, 44.28, 103.34, 108.54, 109.93, 110.97, 111.97, 113.32, 115.02, 116.02, 116.62, 118.18, 118.40, 119.98, 120.94, 121.07, 121.51, 123.64, 123.74, 123.77, 125.06, 125.81, 127.18, 128.17, 128.41, 128.49, 128.66, 128.86, 132.25, 133.69, 137.09, 138.44, 138.76, 139.89, 140.23, 140.83, 141.11, 143.37, 144.08, 145.34, 147.83, 149.52, 154.01, 155.42, 156.69, 159.67. HRMS (ESI): C 83 H 82 N5O + [M] + Calcd 1164.6514, Found 1164.6481.

[0343] Synthesis of complex Pt2O4: Ligand LDB2 (543 mg, 0.41 mmol, 1.0 equivalent), Pt(COD)Cl2 (163 mg, 0.435 mmol, 1.05 equivalent), and sodium acetate (102 mg, 1.24 mmol, 3.0 equivalent) were added sequentially to a sealed tube. Nitrogen gas was purged three times. DEDM (20 mL) was added, and the mixture was bubbled with nitrogen for 30 minutes. The reaction was carried out at 120 °C for 72 hours. The solvent was removed by vacuum distillation, and the mixture was purified by silica gel chromatography with petroleum ether / dichloromethane as the eluent at a ratio of 4:1. The final product was complex Pt2O4, a yellow-green solid, 527 mg, in 93% yield. 1 H NMR(500MHz, CDCl3)δ0.25(s,3H),1.08(s,3H),1.19(d,J=9.5Hz,1H),1.35(s,9H),1.47(s,27H),1.97(t,J=5.5Hz,1H),2.12–2.18(m,1H),2.44– 2.51(m,1H),2.69(d,J=18.0Hz,1H),2.82–2.90(m,1H),6.22(t,J=7.5Hz ,2H),6.53(t,J=7.5Hz,1H),6.55–6.62(m,2H),6.83(s,1H),7.02(d,J=2 .0Hz,1H),7.13(d,J=1.5Hz,1H),7.30(d,J=2.0Hz,1H),7.33(d,J=8.0Hz ,1H),7.39–7.41(m,2H),7.41–7.44(m,5H),7.44–7.49(m,3H),7.54(d,J =1.5Hz,1H),7.64–7.70(m,2H),7.74(s,1H),7.81(d,J=8.0Hz,1H),7.87 (d,J=8.0Hz,1H),8.08–8.13(m,3H),8.16(d,J=8.5Hz,1H),8.93(s,1H). 13C NMR (126 MHz, CDC13) δ 21.20, 25.70, 31.18, 31.63, 32.02, 33.07, 34.71, 34.81, 34.96, 39.39, 39.64, 42.87, 105.76, 107.66, 109.07, 111.04, 111.20, 112.07, 113.23, 114.57, 115.20, 116.11, 116.19, 120.18, 122.15, 123.14, 123.39, 123.48, 123.68, 125.74, 127.22, 127.51, 127.98, 128.12, 128.33, 128.96, 129.06, 129.14, 129.67, 133.19, 136.80, 137.39, 137.74, 138.44, 138.59, 138.70, 139.54, 142.47, 142.87, 146.89, 147.73, 147.85, 149.31, 150.27, 152.36, 152.66, 154.64. HRMS (ESI): C 83 H 79 N5OPt[M+H] + Calcd 1357.6005, Found 1357.5972.

[0344] Example 49: Synthesis route of tetradentate cyclometalated platinum (II) complex Pt205:

[0345] Synthesis of intermediate Cz-NO2-F-3: A 250 mL three-necked flask was charged with potassium phosphate (7.6 g, 35.78 mmol, 2.0 eq), the water vapor was removed by blowing the side with a hot air gun, and then 2-fluoro-5-bromonitrobenzene (4.72 g, 21.47 mmol, 1.2 eq), 3,6-di-tert-butylcarbazole (5 g, 17.8 mmol, 1.0 eq), Pd2(dba)3(491 mg, 0.54 mmol, 0.03 eq), XPhos (511 mg, 1.07 mmol, 0.06 eq) were added under nitrogen protection, the nitrogen was replaced for three times, and then toluene (70 mL) was added. The reaction was stirred at 100 °C for 24 h. The solvent was removed by distillation under reduced pressure, and then the product was separated and purified by silica gel column chromatography with petroleum ether / dichloromethane = 100:1-50:1 as eluent. Finally, intermediate Cz-NO2-F-3 was obtained as a yellow solid in 7 g with a yield of 94%. 1H NMR (500 MHz, CDC13) δ 1.48 (s, 18 H), 7.30 (d, J = 1.0 Hz, 1 H), 7.32 (d, J = 1.0 Hz, 1 H), 7.50 (d, J = 2.0 Hz, 1 H), 7.50 - 7.55 (m, 2 H), 7.84 - 7.88 (m, 1 H), 8.15 (dd, J = 2.0, 0.5 Hz, 2 H), 8.30 (dd, J = 6.5, 2.5 Hz, 1 H).

[0346] Synthesis of intermediate Cz-NO2-Br-3: Into a 250 mL three-necked flask was placed 2,6-dibromo-4-tert-butylaniline (3.33 g, 10.9 mmol, 1.0 eq), N,N-dimethylformamide (100 mL), cooled to -10 °C, sodium hydride (1.3 g, 32.6 mmol, 3.0 eq) was added slowly, keep low temperature for 1 hour, intermediate Cz-NO2-F-3 (5 g, 11.9 mmol, 1.1 eq) was added, stirred at room temperature for 60 hours. The reaction was quenched with water, extracted with ethyl acetate for three times, dried over anhydrous sodium sulfate, removed the solvent under reduced pressure, purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 50:1, finally intermediate Cz-NO2-Br-3 was obtained as a liquid, 7.34 g, yield 96%. 1 H NMR (500 MHz, CDC13) δ 1.48 (s, 18 H), 7.30 (d, J = 1.0 Hz, 1 H), 7.32 (d, J = 1.0 Hz, 1 H), 7.50 (d, J = 2.0 Hz, 1 H), 7.50 - 7.55 (m, 2 H), 7.84 - 7.88 (m, 1 H), 8.15 (dd, J = 2.0, 0.5 Hz, 2 H), 8.30 (dd, J = 6.5, 2.5 Hz, 1 H).

[0347] Synthesis of intermediate Cz-NH2-Br-3: Into a 100 mL three-necked flask was placed intermediate Cz-NO2-Br-3 (2 g, 2.83 mmol, 1.0 eq), stannous chloride (2.15 g, 11.33 mmol, 4.0 eq), replaced with nitrogen for three times, added ethyl acetate and ethanol (20 + 20 mL), stirred at 78 °C for 13 hours. Neutralized with aqueous sodium bicarbonate solution, extracted with ethyl acetate for three times, dried over anhydrous sodium sulfate, removed the solvent under reduced pressure, purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 50:1-10:1 ~ petroleum ether / dichloromethane / ethyl acetate = 5:1:1, finally intermediate Cz-NH2-Br-3 was obtained as a solid, 1.58 g, yield 83%. Used directly for the following reaction.

[0348] Synthesis of intermediate Cz-NH2-Ph-3: Into a 100 mL three-necked flask with a magnetic rotor was added intermediate Cz-NH2-Br-3 (1.58 g, 2.33 mmol, 1.0 eq), phenylboronic acid (855 mg, 7 mmol, 3.0 eq), tetrakis(triphenylphosphine)palladium (108 mg, 0.093 mmol, 0.04 eq), potassium carbonate (1.62 g, 11.69 mmol, 5.0 eq), and the flask was purged with nitrogen three times, 1,4-dioxane and water (24 mL / 6 mL) were added, and the mixture was bubbled with nitrogen for 30 min. The reaction was stirred at 100 °C for 11 h. The reaction mixture was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 50:1 as eluent to give intermediate Cz-NH2-Ph-3 as a white solid 1.42 g in 90% yield. 1 H NMR (500 MHz, DMSO-d6) δ 1.36 (s, 9H), 1.40 (s, 18H), 4.84 (s, 2H), 5.85 (s, 1H), 6.20-6.24 (m, 1H), 6.26-6.29 (m, 1H), 6.38 (d, J = 2.5 Hz, 1H), 6.98 (d, J = 8.5 Hz, 2H), 7.25-7.29 (m, 2H), 7.31 (s, 2H), 7.33-7.38 (m, 4H), 7.42 (dd, J = 8.5, 2.0 Hz, 2H), 7.46-7.51 (m, 4H), 8.17 (d, J = 2.0 Hz, 2H).

[0349] Synthesis of intermediate Cz-NH-Ph-3: Into a schlenk tube was added intermediate Cz-NH2-Ph-2 (617 mg, 0.92 mmol, 1.2 eq), intermediate OTf-Cl (400 mg, 0.76 mmol, 1.0 eq), Pd2(dba)3 (42 mg, 0.046 mmol, 0.06 eq), SPhos (38 mg, 0.092 mmol, 0.12 eq), sodium tert-butoxide (148 mg, 1.53 mmol, 2.0 eq), and the flask was purged with nitrogen three times, toluene (5 mL) was added, and the reaction was stirred at 90 °C for 3 h. The solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / ethyl acetate = 40:1-20:1 as eluent to give intermediate Cz-NH-Ph-3 as a yellow foamy solid 818 mg in 92% yield. Used directly in the following reaction.

[0350] Synthesis of ligand LDB3: Cz-NH-Ph-3 (818 mg, 0.71 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (231 mg, 1.42 mmol, 2.0 equivalent) were added sequentially to a Scklenk tube. Nitrogen gas was purged three times. Triethyl orthoformate (15 mL) was then added sequentially, and the reaction was carried out at 70 °C for 30 minutes. The solvent was removed by vacuum distillation, and the mixture was purified by silica gel chromatography with eluents of petroleum ether / ethyl acetate = 20:1 to dichloromethane / methanol = 500:1. The final product was ligand LDB3, a green, foamy solid, 702 mg, in yield (76%). 1 H NMR (500MHz, CDCl3) δ0.70 (s, 3H), 1.29 (d, J = 10.0Hz, 1H), 1.31 (s, 9H), 1.43 ( s,3H),1.45(s,18H),1.47(s,9H),2.29–2.36(m,1H),2.73(dt,J=9.5,6.0Hz, 1H),2.89(t,J=5.5Hz,1H),3.06(s,2H),6.43(t,J=2.0Hz,1H),6.82(t,J=2.0 Hz,1H),6.97(dd,J=8.5,2.0Hz,1H),7.10–7.15(m,2H),7.16(s,1H),7.16–7. 20(m,5H),7.24–7.25(m,2H),7.25–7.26(m,2H),7.27–7.32(m,2H),7.37(s,1 H),7.39–7.43(m,2H),7.44(d,J=2.0Hz,1H),7.46(d,J=1.5Hz,1H),7.56(d,J =2.0Hz,1H),7.61–7.65(m,4H),7.72(d,J=8.0Hz,1H),7.88(d,J=8.0Hz,1H), 8.03(dt,J=7.5,1.0Hz,1H),8.13(d,J=2.0Hz,2H),8.16(s,1H),9.27(s,1H). 13C NMR (126 MHz, CDC13) δ 21.49, 25.90, 30.89, 31.19, 31.71, 31.89, 32.94, 34.76, 35.34, 39.29, 39.85, 44.25, 103.35, 108.48, 110.28, 110.47, 111.01, 112.95, 115.66, 115.91, 116.61, 118.00, 118.28, 119.89, 120.85, 120.96, 121.33, 123.61, 123.94, 124.03, 125.36, 125.71, 126.44, 128.12, 128.42, 128.83, 130.36, 131.31, 132.15, 137.13, 138.33, 138.48, 139.90, 140.24, 140.80, 141.03, 143.31, 144.25, 145.41, 147.71, 149.42, 153.94, 155.40, 156.50, 159.67. HRMS (ESI): C 83 H 82 N5O + [M] + Calcd 1164.6514, Found 1164.6464.

[0351] Synthesis of complex Pt205: Ligand LDB3 (550 mg, 0.42 mmol, 1.0 eq), Pt(COD)Cl2(165 mg, 0.44 mmol, 1.05 eq) and sodium acetate (104 mg, 1.29 mmol, 3.0 eq) were added into a sealed tube successively, and the tube was purged with nitrogen for three times. DEDM (15 mL) was added and the mixture was bubbled with nitrogen for 30 min. The mixture was heated at 120 °C for 72 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 4:1 as eluent. Complex Pt205 was obtained as a yellow-green solid, 298 mg, yield 52%. 1H NMR (500 MHz, CDC13) δ 0.27 (s, 3 H), 1.11 (s, 3 H), 1.23 (d, J = 9.5 Hz, 1 H), 1.31 (s, 9 H), 1.44 (s, 9 H), 1.47 (s, 18 H), 2.09 (t, J = 5.5 Hz, 1 H), 2.18 (s, 1 H), 2.50 - 2.58 (m, 1 H), 2.71 (d, J = 17.5 Hz, 1 H), 2.89 (d, J = 17.5 Hz, 1 H), 6.26 (t, J = 7.5 Hz, 2 H), 6.55 (t, J = 7.5 Hz, 1 H), 6.65 (d, J = 7.5 Hz, 2 H), 6.98 (d, J = 8.5 Hz, 1 H), 7.08 (d, J = 1.5 Hz, 1 H), 7.21 (dd, J = 9.0, 2.0 Hz, 1 H), 7.28 - 7.34 (m, 3 H), 7.34 - 7.38 (m, 4 H), 7.40 (d, J = 2.0 Hz, 1 H), 7.42 (td, J = 8.0, 1.0 Hz, 1 H), 7.47 (d, J = 2.0 Hz, 1 H), 7.48 - 7.52 (m, 2 H), 7.56 (d, J = 2.5 Hz, 1 H), 7.65 (d, J = 7.5 Hz, 2 H), 7.77 (s, 1 H), 7.81 (d, J = 8.0 Hz, 1 H), 7.92 (d, J = 8.0 Hz, 1 H), 8.12 (dd, J = 7.5, 1.5 Hz, 1 H), 8.15 - 8.16 (m, 2 H), 8.19 (d, J = 2.0 Hz, 1 H), 8.94 (s, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.24, 25.73, 31.30, 31.44, 31.97, 32.14, 33.09, 34.70, 34.74, 35.04, 39.47, 39.63, 42.94, 105.54, 107.50, 109.03, 109.32, 110.90, 112.03, 113.00, 113.21, 114.68, 115.14, 116.07, 116.27, 120.17, 121.02, 122.13, 123.49, 123.66, 123.75, 125.58, 127.25, 127.61, 127.90, 128.17, 128.35, 128.87, 128.96, 129.43, 129.60, 134.53, 134.90, 136.84, 138.07, 138.70, 139.30, 142.26, 143.23, 146.90, 147.76, 147.89, 149.21, 150.23, 152.29, 152.73, 154.61. HRMS (ESI): C83 H 79 N5OPt[M+H] + Calcd 1357.6005,Found 1357.5957.

[0352] Example 50: Synthesis route of tetradentate cyclometalated platinum(II) complex Pt206:

[0353] Synthesis of intermediate Cz-Cl-Br-4: Into a sealed tube was added 3,6-di-tert- butylcarbazole (1 g, 3.57 mmol, 1.0 eq), 1-bromo-3-chloro-5-fluorobenzene (1.49 g, 7.15 mmol, 2.0 eq), cesium carbonate (3.5 g, 10.74 mmol, 3.0 eq), the tube was purged with nitrogen three times, N,N-dimethylformamide (8 mL) was added, and the reaction was stirred at 150 °C for 12 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate / dichloromethane = 100:1:1 to give intermediate Cz-Cl-Br-4 as a white solid 1.6 g in 96% yield. 1 H NMR (500 MHz, CDC13) δ 1.46 (s, 18H), 7.37 (dd, J = 8.5, 0.5 Hz, 2H), 7.49 (dd, J = 8.5, 2.0 Hz, 2H), 7.54 (t, J = 2.0 Hz, 1H), 7.57 (t, J = 2.0 Hz, 1H), 7.65 (t, J = 2.0 Hz, 1H), 8.12 (dd, J = 2.0, 0.5 Hz, 2H).

[0354] Synthesis of intermediate Cz-OTf-Cl-4: Into a 50 mL three-necked flask was added potassium phosphate (850 mg, 4 mmol, 2.0 eq), the flask was purged with nitrogen and the water vapor was blown off by a heat gun, Cz-Cl-Br-4 (1.03 g, 2.2 mmol, 1.1 eq), OTf-OH (709 mg, 2 mmol, 1.0 eq), cuprous iodide (58 mg, 0.3 mmol, 0.15 eq), 2-picolinic acid (74 mg, 0.6 mmol, 0.3 eq) were added successively, the flask was purged with nitrogen three times, dimethyl sulfoxide (10 mL) was added, and the reaction was stirred at 110 °C for 10 h. The reaction was quenched with water, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 60:1 to give intermediate Cz-OTf-Cl-4 as a white foamy solid 1.1 g in 74% yield. 1H NMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.32 (d, J = 10 Hz, 1H), 1.45 (s, 18H), 1.46 (s, 3H), 2.30 - 2.39 (m, 1H), 2.76 (dt, J = 10, 6.0 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.07 (d, J = 3.0 Hz, 2H), 7.03 (t, J = 2.0 Hz, 1H), 7.09 (dd, J = 8.5, 2.0 Hz, 1H), 7.18 (t, J = 2.5 Hz, 1H), 7.27 (t, J = 2.0 Hz, 1H), 7.31 (td, J = 8.0, 1.0 Hz, 1H), 7.38 - 7.42 (m, 3H), 7.42 - 7.47 (m, 3H), 7.60 (d, J = 2.5 Hz, 1H), 7.73 - 7.78 (m, 1H), 8.07 - 8.10 (m, 3H), 8.11 (d, J = 8.5 Hz, 1H), 8.22 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.56, 25.95, 31.78, 31.95, 32.99, 34.70, 39.37, 39.91, 44.30, 103.16, 109.19, 111.03, 113.09, 114.17, 116.22, 116.28, 118.29, 119.90, 120.45, 120.88, 121.06, 121.29, 123.62, 123.67, 123.79, 125.77, 135.89, 138.58, 140.25, 140.30, 140.83, 140.92, 143.36, 145.44, 147.56, 149.59, 154.24, 160.20.

[0355] Synthesis of intermediate Cz-NH-4: Into a schlenk tube was added intermediate dPhNH2 (380 mg, 0.967 mmol, 1.2 equiv), intermediate Cz-OTf-Cl-4 (600 mg, 0.81 mmol, 1.0 equiv), Pd2(dba)3 (22 mg, 0.024 mmol, 0.03 equiv), Johnphos (2-(di-tert-butylphosphino)biphenyl) (15 mg, 0.048 mmol, 0.06 equiv), sodium tert-butoxide (155 mg, 1.61 mmol, 2.0 equiv), replaced with nitrogen gas for three times, added toluene (8 mL), stirred at 90-100 °C for 24 hours. The solvent was removed by distillation under reduced pressure, and purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 40: 1-20: 1, finally obtained intermediate Cz-NH-4, 430 mg, yield 49% as a foamy solid. Used directly for the following reaction.

[0356] Synthesis of Ligand LDB4: Into a schlenk tube was added sequentially Cz-NH-4 (430 mg, 0.39 mmol, 1.0 eq), ammonium hexafluorophosphate (127 mg, 0.78 mmol, 2.0 eq), and the system was purged with nitrogen three times, then triethyl orthoformate (5 mL) was added, and the reaction was carried out at 70 °C for 30 min. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1 ~ dichloromethane / methanol = 500:1, to give the ligand LDB4, 330 mg of green foamy solid, yield 67%. 1 H NMR (500 MHz, CDC13) δ 0.74 (s, 3H), 1.33 (d, J = 10 Hz, 1H), 1.45 (s, 3H), 1.46 (s, 9H), 1.47 (s, 18H), 2.34 - 2.36 (m, 1H), 2.75 (dt, J = 15, 5.0 Hz, 1H), 2.93 (t, J = 5.0 Hz, 1H), 3.03 - 3.16 (m, 2H), 6.69 (t, J = 5.0 Hz, 1H), 6.74 (t, J = 5.0 Hz, 1H), 6.85 - 6.90 (m, 2H), 6.96 - 7.01 (m, 4H), 7.14 (d, J = 10 Hz, 4H), 7.22 (dd, J = 10, 5.0 Hz, 1H), 7.24 - 7.26 (m, 1H), 7.30 - 7.35 (m, 1H), 7.39 - 7.46 (m, 3H), 7.46 - 7.50 (m, 4H), 7.51 - 7.57 (m, 3H), 7.60 (s, 2H), 7.72 (d, J = 0.5 Hz, 1H), 7.77 (d, J = 10 Hz, 1H), 8.10 (d, J = 5.0 Hz, 2H), 8.13 (d, J = 10 Hz, 1H), 8.21 (d, J = 5.0 Hz, 1H), 8.23 (s, 1H), 9.23 (s, 1H). 13C NMR (500 MHz, CDC13) δ 21.56, 25.94, 31.19, 31.74, 31.95, 32.96, 34.75, 35.33, 39.33, 39.89, 44.31, 103.67, 109.43, 111.09, 111.66, 113.10, 113.45, 114.32, 116.19, 117.81, 118.34, 120.05, 120.93, 121.47, 121.73, 123.63, 123.81, 124.22, 125.37, 125.88, 127.96, 128.01, 128.06, 128.21, 128.29, 128.84, 130.14, 132.12, 133.88, 137.02, 138.46, 139.90, 140.32, 140.81, 141.06, 141.45, 142.53, 143.80, 145.42, 147.83, 149.52, 153.51, 155.29, 161.37. HRMS (ESI): C 79 H 74 N5O + [M] + Calcd 1108.5888, Found 1108.5862.

[0357] Synthesis of complex Pt206: Ligand LDB4 (300 mg, 0.238 mmol, 1.0 eq), Pt(COD)Cl2(94 mg, 0.25 mmol, 1.05 eq) and sodium acetate (59 mg, 0.716 mmol, 3.0 eq) were added into a sealed tube successively, and the tube was purged with nitrogen for three times. DEDM (6 mL) was added and the mixture was bubbled with nitrogen for 30 min. The mixture was heated at 120 °C for 72 h. The solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 4:1 as eluent. Complex Pt206 was obtained as yellow-green solid, 173 mg, yield 56%. 1H NMR (500 MHz, CDC13) δ 0.28 (s, 3 H), 1.10 (s, 3 H), 1.22 (d, J = 9.5 Hz, 1 H), 1.44 (s, 9 H), 1.49 (s, 18 H), 2.04 - 2.10 (m, 1 H), 2.17 (s, 1 H), 2.46 - 2.55 (m, 1 H), 2.73 (d, J = 18 Hz, 1 H), 2.90 (d, J = 18 Hz, 1 H), 6.23 (t, J = 7.5 Hz, 2 H), 6.49 - 6.62 (m, 3 H), 6.84 (d, J = 8.0 Hz, 1 H), 6.99 (t, J = 8.0 Hz, 1 H), 7.15 (t, J = 7.5 Hz, 1 H), 7.20 - 7.24 (m, 2 H), 7.27 - 7.30 (m, 2 H), 7.32 (d, J = 8.0 Hz, 1 H), 7.36 - 7.40 (m, 1 H), 7.43 (t, J = 7.5 Hz, 1 H), 7.50 (dd, J = 8.5, 2.0 Hz, 3 H), 7.51 - 7.55 (m, 3 H), 7.57 (d, J = 2.0 Hz, 1 H), 7.63 (d, J = 7.5 Hz, 2 H), 7.73 - 7.80 (m, 2 H), 7.83 (d, J = 8.5 Hz, 1 H), 7.92 (d, J = 8.0 Hz, 1 H), 8.12 - 8.15 (m, 1 H), 8.18 (d, J = 2.0 Hz, 2 H), 8.97 (s, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.26, 25.72, 31.30, 32.09, 33.10, 34.73, 35.03, 39.42, 39.62, 42.91, 106.88, 109.70, 110.37, 111.24, 112.09, 112.46, 112.72, 113.27, 114.60, 115.46, 116.04, 116.25, 116.52, 120.28, 122.25, 122.99, 123.06, 123.57, 123.84, 124.29, 125.67, 127.25, 127.53, 127.85, 128.12, 128.25, 128.78, 128.92, 129.51, 131.61, 134.04, 136.95, 137.98, 138.56, 138.70, 139.75, 142.30, 146.85, 147.99, 150.32, 150.38, 152.64, 153.11, 154.31. HRMS (ESI): C 79 H 71 N5OPt[M+H] +Calcd 1301.5379, Found 1301.5340.

[0358] Example 51: Tetradentate cyclometalated platinum(II) complex Pt207 synthesis route:

[0359] Synthesis of intermediate OTf-Br-Cl-5: Into a sealed tube was added 1-bromo-4-chloro-2-fluorobenzene (628 mg, 3 mmol, 1.3 eq), intermediate OTf-OH (818 mg, 2.3 mmol, 1.0 eq), cesium carbonate (2.25 g, 6.9 mmol, 3.0 eq), the tube was purged with nitrogen three times, N,N-dimethylformamide (17 mL) was added, the reaction was stirred at 150 °C for 10 h. The solvent was removed under reduced pressure, the product was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1, to give intermediate OTf-Br-Cl-5 as a white solid 516 mg, yield 41%. 1 H NMR (500 MHz, CDC13) δ 0.75 (s, 3H), 1.33 (d, J = 9.5 Hz, 1H), 1.46 (s, 3H), 2.34 - 2.39 (m, 1H), 2.77 (dt, J = 10.0, 6.0 Hz, 1H), 2.94 (t, J = 5.5 Hz, 1H), 3.08 (d, J = 2.5 Hz, 2H), 6.87 (d, J = 2.5 Hz, 1H), 6.95 (td, J = 8.5, 2.5 Hz, 2H), 7.32 (td, J = 8.0, 1.0 Hz, 1H), 7.39 (s, 1H), 7.41 - 7.46 (m, 1H), 7.53 (d, J = 8.5 Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H), 7.77 (dt, J = 8.0, 1.0 Hz, 1H), 8.06 - 8.10 (m, 2H), 8.23 (s, 1H).

[0360] Synthesis of Intermediate Cz-OTf-Cl-5: Into a three-neck flask was placed potassium phosphate (402 mg, 1.89 mmol, 2.0 eq), the water vapor was removed by blowing hot air, and under nitrogen protection, OTf-Br-Cl-5 (516 mg, 0.95 mmol, 1.0 eq), 3,6-di-tert-butylcarbazole (292 mg, 1.04 mmol, 1.1 eq), cuprous iodide (90 mg, 0.47 mmol, 0.5 eq), (1R,2R)-(-)-1,2-Diaminocyclohexane (trans-1,2-diaminocyclohexane) (108 mg, 0.95 mmol, 1.0 eq) were added successively, and the nitrogen was replaced three times, 1,4-dioxane (15 mL) was added, and the reaction was stirred at 100 °C for 11 h. The solvent was removed by distillation under reduced pressure, and the product was separated and purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 100:1, to give Intermediate Cz-OTf-Cl-5, 397 mg of crude product, which was used directly in the subsequent reaction. The separated part of the clean product was characterized by nuclear magnetic resonance spectroscopy, 1 H NMR (500 MHz, CDC13) δ 0.74 (s, 3H), 1.32 (d, J = 9.5 Hz, 1H), 1.45 (s, 18H), 1.46 (s, 3H), 2.31 - 2.40 (m, 1H), 2.73 - 2.81 (m, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.06 (d, J = 3.0 Hz, 2H), 6.93 (dd, J = 8.5, 2.0 Hz, 1H), 7.11 (d, J = 2.5 Hz, 1H), 7.18 - 7.23 (m, 3H), 7.27 - 7.30 (m, 2H), 7.34 (d, J = 2.0 Hz, 1H), 7.38 - 7.42 (m, 1H), 7.43 (d, J = 4.5 Hz, 1H), 7.44 (d, J = 2.0 Hz, 1H), 7.45 (d, J = 2.0 Hz, 1H), 7.73 (d, J = 8.5 Hz, 1H), 7.99 (d, J = 8.5 Hz, 1H), 8.01 - 8.04 (m, 1H), 8.10 (d, J = 2.0 Hz, 2H), 8.20 (s, 1H).

[0361] Synthesis of intermediate Cz-NH-5: Into a schlenk tube was added intermediate dPhNH2(630 mg, 1.6 mmol, 3.0 eq), intermediate Cz-OTf-Cl-5 (397 mg, 0.53 mmol, 1.0 eq), Pd2(dba)3(50 mg, 0.053 mmol, 0.1 eq), SPhos (44 mg, 0.107 mmol, 0.2 eq), sodium tert-butoxide (155 mg, 1.6 mmol, 3.0 eq), and the reaction vessel was purged with nitrogen three times, then toluene (10 mL) was added, and the reaction was stirred at 90 °C for 8 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 100:1 to give intermediate Cz-NH-5 as a solid 316 mg in 54% yield. Used directly in the next reaction.

[0362] Synthesis of ligand LDB5: Into a schlenk tube was added intermediate Cz-NH-5 (316 mg, 0.29 mmol, 1.0 eq), ammonium hexafluorophosphate (94 mg, 0.58 mmol, 2.0 eq), and the reaction vessel was purged with nitrogen three times, then triethyl orthoformate (8 mL) was added, and the reaction was stirred at 70 °C for 20 min. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether / dichloromethane = 5:1-2:1 ~ dichloromethane / methanol = 500:1 to give ligand LDB5 as a white foamy solid 314 mg in 87% yield. 1 H NMR (400 MHz, CDC13) δ 0.71 (s, 3H), 1.30 (d, J = 10.0 Hz, 1H), 1.44 (s, 21H), 1.45 (s, 9H), 2.34 (s, 1H), 2.72 - 2.80 (m, 1H), 2.93 (t, J = 5.2 Hz, 1H), 3.09 (s, 2H), 6.70 (s, 1H), 6.92 - 6.99 (m, 3H), 7.00 - 7.04 (m, 3H), 7.06 - 7.14 (m, 5H), 7.17 (d, J = 8.0 Hz, 1H), 7.23 - 7.26 (m, 1H), 7.29 - 7.39 (m, 4H), 7.40 - 7.46 (m, 3H), 7.46 - 7.50 (m, 2H), 7.50 - 7.54 (m, 1H), 7.58 (s, 2H), 7.63 (d, J = 8.4 Hz, 1H), 7.73 (t, J = 7.6 Hz, 2H), 8.07 - 8.12 (m, 3H), 8.15 (d, J = 8.4 Hz, 1H), 8.20 (s, 1H), 9.32 (s, 1H). HRMS (ESI): C 79 H 74 N5O + [M] +Calcd 1108.5888, Found 1108.5837.

[0363] Synthesis of complex Pt207: Ligand LDB5 (264 mg, 0.21 mmol, 1.0 eq), Pt(COD)Cl2(83 mg, 0.22 mmol, 1.05 eq) and sodium acetate (52 mg, 0.63 mmol, 3.0 eq) were added into a sealed tube successively, and the tube was purged with nitrogen for three times. DEDM (12 mL) was added and the tube was purged with nitrogen for 30 min. The tube was heated at 120 °C for 72 h. The solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 4:1 as eluent. Complex Pt207 was obtained as yellow-green solid, 43 mg, yield 16%. 1 H NMR (500 MHz, DMSO-d6) δ 0.24 (s, 3H), 1.06 (s, 3H), 1.17 (d, J = 9.5 Hz, 1H), 1.39 (s, 9H), 1.40 (s, 9H), 1.47 (s, 9H), 2.02 (t, J = 5.0 Hz, 1H), 2.13 (s, 1H), 2.5 (s, 1H), 2.74 - 2.81 (m, 1H), 2.88 - 2.94 (m, 1H), 6.14 (t, J = 8.0 Hz, 2H), 6.18 (d, J = 8.5 Hz, 1H), 6.47 - 6.57 (m, 3H), 6.90 (d, J = 8.0 Hz, 1H), 7.07 (dd, J = 10.5, 8.5 Hz, 2H), 7.15 (t, J = 8.0 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H), 7.32 - 7.36 (m, 3H), 7.36 - 7.38 (m, 3H), 7.40 (dd, J = 6.5, 2.0 Hz, 1H), 7.45 (dd, J = 8.5, 2.0 Hz, 1H), 7.53 - 7.58 (m, 3H), 7.64 (d, J = 7.5 Hz, 2H), 7.81 (s, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.98 (d, J = 8.5 Hz, 1H), 8.08 (d, J = 8.0 Hz, 1H), 8.27 - 8.32 (m, 3H), 8.83 (s, 1H). (One hydrogen is buried in the solvent peak DMSO at 2.5). 13C NMR (126 MHz, CDC13) δ 21.58, 25.90, 31.09, 31.62, 32.03, 32.93, 34.72, 35.05, 39.33, 39.86, 44.27, 102.69, 109.34, 110.14, 113.32, 113.93, 115.19, 116.16, 118.31, 120.16, 120.25, 120.70, 121.23, 122.89, 123.15, 123.51, 134.51, 135.60, 139.89, 141.04, 141.27, 141.63, 142.59, 145.61, 147.77, 149.24, 154.73, 155.15, 158.62. HRMS (ESI): C 79 H 71 N5OPt[M+H] + Calcd 1301.5379, Found 1301.5342.

[0364] Example 52: Synthesis route of tetradentate cyclometalated platinum(II) complex Pt208:

[0365] Synthesis of intermediate Cz-Br-6: Into a three-necked flask was added potassium phosphate (3.8 g, 17.9 mmol, 2.0 eq), the water vapor was removed by blowing the edge with a heat gun, and 2-iodo-4-bromoanisole (3.64 g, 11.63 mmol, 1.3 eq), 3,6-di-tert-butylcarbazole (2.5 g, 8.9 mmol, 1.0 eq), cuprous iodide (171 mg, 0.89 mmol, 0.1 eq), trans-cyclohexanediamine (204 mg, 1.79 mmol, 0.2 eq) were added under nitrogen protection, the nitrogen was replaced for three times, 1,4-dioxane (15 mL) was added, and the reaction was stirred at 100 °C for 34 h. The solvent was removed by distillation under reduced pressure, and the product was separated and purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 100:1, to give 3.4 g of solid, yield 76%.

[0366] Synthesis of intermediate Cz-Bpin-6: Into a 100 mL three-necked flask was placed Cz-Br-6 (2 g, 4.3 mmol, 1.0 eq), purged and maintained with nitrogen three times, tetrahydrofuran (30 mL) was added under nitrogen, the temperature was gradually decreased to -78 °C, 2.5 M n-butyllithium (2.1 mL, 5.16 mmol, 1.2 eq) was added gradually at low temperature, the reaction was kept at low temperature for 1 h, isopropyl alcohol pinacolboronate (1.2 g, 6.5 mmol, 1.5 eq) was added gradually at low temperature, the temperature was gradually increased to room temperature, the reaction was stirred for another 10 h. The reaction mixture was quenched with saturated aqueous ammonium chloride solution, extracted with ethyl acetate and water for three times, dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 100:1, finally gave intermediate Cz-Bpin-6 as white solid 1.74 g, yield 79%. 1 H NMR (500 MHz, CDC13) δ 1.31 (s, 12H), 1.46 (s, 18H), 3.73 (s, 3H), 7.02 (dd, J = 8.5, 0.5 Hz, 2H), 7.14 (d, J = 8.5 Hz, 1H), 7.41 (dd, J = 8.5, 2.0 Hz, 2H), 7.84 (d, J = 2.0 Hz, 1H), 7.91 (dd, J = 8.5, 1.5 Hz, 1H), 8.11 - 8.13 (m, 2H).

[0367] Synthesis of intermediate Cz-NO2-6: Into a 100 mL three-necked flask with magnetic rotor was placed intermediate Cz-Bpin-6 (2.14 g, 4.18 mmol, 1.0 eq), o-bromonitrobenzene (929 mg, 4.6 mmol, 1.1 eq), tetrakis(triphenylphosphine)palladium (97 mg, 0.084 mmol, 0.02 eq), potassium carbonate (1.45 g, 10.4 mmol, 2.5 eq), purged and maintained with nitrogen three times, tetrahydrofuran and water (24 mL / 6 mL) was added, bubbled with nitrogen for 30 min, stirred at 60 °C for 34 h, increased the temperature to 80 °C for 14 h. Extracted with ethyl acetate for three times, dried over anhydrous sodium sulfate, removed the solvent by distillation under reduced pressure, purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 100:1, finally gave intermediate Cz-NO2-6 as yellow solid 1.83 g, yield 83%. 1H NMR (500 MHz, CDC13) δ 1.46 (s, 18 H), 3.77 (s, 3 H), 7.13 (d, J = 8.5 Hz, 2 H), 7.21 (d, J = 8.5 Hz, 1 H), 7.38 - 7.40 (m, 1 H), 7.41 - 7.42 (m, 1 H), 7.44 (d, J = 2.0 Hz, 1 H), 7.45 - 7.46 (m, 1 H), 7.46 - 7.49 (m, 2 H), 7.57 - 7.62 (m, 1 H), 7.87 (dd, J = 8.5, 1.5 Hz, 1 H), 8.12 (d, J = 2.0 Hz, 2 H).

[0368] Synthesis of intermediate Cz-6: Into a 50 mL three-necked flask with a magnetic rotor, intermediate Cz-NO2-6 (1.73 g, 3.41 mmol, 1.0 eq), PPh3 (triphenylphosphine) (2.68 g, 10.24 mmol, 3.0 eq) were added, replaced with nitrogen for three times, o-dichlorobenzene (10 mL) was added, stirred at 180 °C for 24 hours. The solvent was removed by distillation under reduced pressure, separated and purified by silica gel column, eluent: petroleum ether / ethyl acetate = 20:1-5:1, finally obtained intermediate Cz-6, solid 812 mg, yield 50%. 1 H NMR (500 MHz, CDC13) δ 1.46 (s, 18 H), 3.77 (s, 3 H), 7.13 (d, J = 8.5 Hz, 2 H), 7.21 (d, J = 8.5 Hz, 1 H), 7.38 - 7.40 (m, 1 H), 7.41 - 7.42 (m, 1 H), 7.44 (d, J = 2.0 Hz, 1 H), 7.45 - 7.46 (m, 1 H), 7.46 - 7.49 (m, 2 H), 7.57 - 7.62 (m, 1 H), 7.87 (dd, J = 8.5, 1.5 Hz, 1 H), 8.12 (d, J = 2.0 Hz, 2 H).

[0369] Synthesis of intermediate Cz-OTf-6: Into a schlenk tube was added potassium phosphate (1.2 g, 5.44 mmol, 3.0 eq), the water vapor was removed by blowing the edge with a heat gun, and nitrogen was protected. Then intermediate Cz-6 (862 mg, 1.82 mmol, 1.0 eq), intermediate OTf (713 mg, 1.99 mmol, 1.1 eq), Pd2(dba)3(167 mg, 0.18 mmol, 0.1 eq), XPhos (346 mg, 0.73 mmol, 0.4 eq) were added in turn, and the nitrogen was replaced three times. Toluene (10 mL) was added, and the reaction was stirred at 100 °C for 8 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / ethyl acetate = 40:1-20:1 as eluent. Finally, intermediate Cz-OTf-6 was obtained as a yellow foamy solid 1.16 g in 99% yield. 1 H NMR (500 MHz, CDC13) δ 0.80 (s, 3H), 1.26 (s, 3H), 1.39 (d, J = 10.0 Hz, 1H), 1.47 (s, 18H), 2.38 - 2.42 (m, 1H), 2.82 (dt, J = 9.5, 6.0 Hz, 1H), 2.99 (t, J = 5.5 Hz, 1H), 3.15 (d, J = 2.5 Hz, 2H), 3.73 (s, 3H), 7.07 - 7.10 (m, 2H), 7.26 - 7.30 (m, 1H), 7.39 - 7.41 (m, 1H), 7.41 - 7.44 (m, 2H), 7.51 (s, 1H), 7.61 (s, 1H), 7.70 (dt, J = 8.5, 1.0 Hz, 1H), 7.93 (dt, J = 7.5, 1.0 Hz, 1H), 8.08 (s, 1H), 8.17 (d, J = 2.0 Hz, 2H), 8.31 (s, 1H).

[0370] Synthesis of intermediate Cz-OH-6: Into a 50 mL single bottle with a magnetic rotor was added intermediate Cz-OTf-6 (1.16 g, 1.79 mmol, 1.0 eq), hydrobromic acid (15 mL) and acetic acid (1 mL), and the reaction was stirred at 120 °C for 22 h. Neutralization with sodium bicarbonate solution, extraction with ethyl acetate three times, drying with anhydrous sodium sulfate, removing the solvent by distillation under reduced pressure, and purifying by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-20:1 as eluent. Finally, intermediate Cz-OH-6 was obtained as a solid 615 mg in 51% yield. 1H NMR (500 MHz, CDC13) δ 0.78 (s, 3H), 1.36 (d, J = 9.5 Hz, 1H), 1.48 (s, 18H), 1.49 (s, 3H), 2.36 - 2.43 (m, 1H), 2.81 (dt, J = 10, 6.0 Hz, 1H), 2.98 (t, J = 5.5 Hz, 1H), 3.14 (d, J = 3.0 Hz, 2H), 7.13 (dd, J = 8.5, 1.5 Hz, 2H), 7.23 - 7.26 (m, 1H), 7.27 (d, J = 0.5 Hz, 1H), 7.40 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.47 (dd, J = 2.0, 1.0 Hz, 1H), 7.48 - 7.50 (m, 2H), 7.61 (s, 1H), 7.72 - 7.76 (m, 1H), 7.87 - 7.91 (m, 1H), 7.98 (s, 1H), 8.19 (d, J = 2.0 Hz, 2H), 8.28 (s, 1H).

[0371] Synthesis of Intermediate Cz-Cl-6: Into a 25 mL three-necked flask was placed potassium phosphate (846 mg, 3.98 mmol, 2.5 eq), hot air gun to blow off water vapor, under nitrogen protection, 1-bromo-3-tert-butyl-5-chlorobenzene (592 mg, 2.39 mmol, 1.5 eq), Cz-OH-6 (565 mg, 1.59 mmol, 1.0 eq), cuprous iodide (304 mg, 1.59 mmol, 1.0 eq), 2-picolinic acid (393 mg, 3.18 mmol, 2.0 eq) were added successively, nitrogen was replaced for three times, dimethyl sulfoxide (6 mL) was added, and the reaction was stirred at 110 °C for 15 hours. Water was added for quenching, and the reaction was extracted with ethyl acetate for three times, dried over anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation. The product was separated and purified by silica gel column chromatography, and eluent was petroleum ether / ethyl acetate = 60: 1. Finally, intermediate Cz-Cl-6 was obtained as white foamy solid 508 mg, yield 40%. 1H NMR (500 MHz, CDC13) δ 0.77 (s, 3 H), 0.90 (s, 9 H), 1.36 (d, J = 9.5 Hz, 1 H), 1.44 (s, 18 H), 1.48 (s, 3 H), 2.37 - 2.42 (m, 1 H), 2.80 (dt, J = 10, 5.5 Hz, 1 H), 2.97 (t, J = 5.5 Hz, 1 H), 3.13 (d, J = 2.5 Hz, 2 H), 5.96 (dd, J = 2.5, 1.0 Hz, 1 H), 6.23 (t, J = 2.0 Hz, 1 H), 6.43 (t, J = 1.5 Hz, 1 H), 7.09 (ddd, J = 8.5, 1.0, 0.5 Hz, 2 H), 7.33 (ddd, J = 8.0, 7.0, 1.0 Hz, 1 H), 7.40 (dd, J = 8.5, 2.0 Hz, 2 H), 7.46 - 7.51 (m, 2 H), 7.80 - 7.84 (m, 2 H), 7.91 - 7.96 (m, 2 H), 8.02 (dt, J = 8.0, 1.0 Hz, 1 H), 8.24 (s, 1 H), 8.27 (d, J = 0.5 Hz, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.57, 25.96, 30.63, 31.81, 32.03, 33.06, 34.37, 34.63, 39.40, 39.94, 44.36, 105.12, 109.42, 111.24, 112.30, 114.26, 115.86, 118.44, 119.86, 120.12, 121.18, 122.02, 122.66, 122.81, 123.18, 123.48, 126.23, 133.31, 139.54, 139.77, 140.54, 141.24, 142.11, 145.55, 147.78, 149.48, 151.87, 153.03, 157.66.

[0372] Synthesis of intermediate Cz-NH-6: Into a schlenk tube was added intermediate dPhNH2(297 mg, 0.72 mmol, 1.2 equiv), intermediate Cz-Cl-6 (480 mg, 0.6 mmol, 1.0 equiv), Pd2(dba)3(17 mg, 0.018 mmol, 0.03 equiv), SPhos (15 mg, 0.036 mmol, 0.06 equiv), sodium tert-butoxide (116 mg, 1.2 mmol, 2.0 equiv), and the reaction vessel was purged with nitrogen three times. Toluene (6 mL) was added and the reaction was stirred at 90 °C for 10 h. The solvent was removed under reduced pressure and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 100:1 to give intermediate Cz-NH-6 as a solid 675 mg, 97% yield. Used directly in the next reaction.

[0373] Synthesis of ligand LDB6: Into a schlenk tube was added intermediate Cz-NH-6 (675 mg, 0.58 mmol, 1.0 equiv), ammonium hexafluorophosphate (191 mg, 1.17 mmol, 2.0 equiv) and the reaction vessel was purged with nitrogen three times. Triethyl orthoformate (4 mL) was added and the reaction was stirred at 70 °C for 30 min. The solvent was removed under reduced pressure and the product was purified by silica gel column chromatography eluting with petroleum ether / dichloromethane = 5:1-2:1 ~ dichloromethane / methanol = 500:1 to give ligand LDB6 as a white foamy solid 647 mg, 84% yield. 1H NMR (500 MHz, CDC13) δ 0.79 (s, 3H), 0.94 (s, 9H), 1.39 (d, J = 1.0 Hz, 18H), 1.41 (s, 1H), 1.44 (s, 9H), 1.47 (s, 3H), 2.37 - 2.42 (m, 1H), 2.75 - 2.82 (m, 1H), 2.99 (t, J = 5.5 Hz, 1H), 3.16 - 3.27 (m, 2H), 5.95 (t, J = 2.0 Hz, 1H), 6.27 (t, J = 2.0 Hz, 1H), 6.42 (t, J = 2.0 Hz, 1H), 6.84 - 6.87 (m, 1H), 6.92 - 6.99 (m, 2H), 7.02 - 7.05 (m, 3H), 7.06 - 7.07 (m, 4H), 7.08 - 7.11 (m, 3H), 7.20 - 7.23 (m, 1H), 7.28 - 7.32 (m, 2H), 7.32 - 7.36 (m, 1H), 7.41 - 7.48 (m, 2H), 7.51 (ddd, J = 8.0, 7.5, 1.5 Hz, 1H), 7.57 (s, 2H), 7.61 (s, 1H), 7.86 (d, J = 8.5 Hz, 1H), 8.00 (t, J = 2.0 Hz, 2H), 8.02 - 8.06 (m, 2H), 8.19 (s, 1H), 8.32 (s, 1H), 8.70 (s, 1H). 13 C NMR (126 MHz, CDC13) δ 21.58, 25.93, 30.49, 31.15, 31.69, 31.98, 33.01, 34.59, 34.71, 35.28, 39.29, 39.90, 44.35, 106.27, 109.42, 109.68, 111.58, 113.36, 114.04, 115.80, 116.03, 116.31, 118.55, 120.01, 121.22, 121.75, 122.49, 122.93, 123.05, 123.16, 125.20, 126.57, 127.79, 128.04, 128.15, 128.26, 128.69, 130.06, 131.31, 132.14, 136.98, 139.30, 139.77, 139.82, 139.85, 140.74, 141.35, 141.66, 142.40, 145.66, 148.36, 149.10, 150.45, 154.89, 155.32, 158.87. HRMS (ESI): C 83 H 82 N5O + [M] +Calcd 1164.6514, Found 1164.6468.

[0374] Synthesis of complex Pt208: Ligand LDB6 (547 mg, 0.41 mmol, 1.0 eq), Pt(COD)Cl2(164 mg, 0.44 mmol, 1.05 eq) and sodium acetate (103 mg, 1.25 mmol, 3.0 eq) were added into a sealed tube successively, and the tube was purged with nitrogen for three times. DEDM (5 mL) was added and the tube was purged with nitrogen for 30 min. The tube was heated at 120 °C for 72 h. The solvent was removed by distillation under reduced pressure. The product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 6:1 as eluent. Complex Pt208 was obtained as yellow-green solid, 358 mg, yield 61%. 1 H NMR (500 MHz, CDC13) δ 0.29 (s, 3H), 1.10 (s, 3H), 1.21 (s, 9H), 1.23 (s, 1H), 1.44 (s, 9H), 1.46 (s, 9H), 1.50 (s, 9H), 2.06 (t, J = 5.5 Hz, 1H), 2.15 - 2.22 (m, 1H), 2.48 - 2.56 (m, 1H), 2.75 (d, J = 18.0 Hz, 1H), 2.92 (d, J = 18 Hz, 1H), 6.18 (d, J = 1.5 Hz, 1H), 6.25 (t, J = 7.5 Hz, 2H), 6.55 (d, J = 7.5 Hz, 2H), 6.59 (t, J = 7.5 Hz, 1H), 6.86 (dd, J = 14, 9.0 Hz, 2H), 7.02 (t, J = 7.5 Hz, 1H), 7.19 - 7.23 (m, 1H), 7.23 - 7.25 (m, 1H), 7.26 - 7.29 (m, 2H), 7.29 - 7.33 (m, 1H), 7.38 (d, J = 2.0 Hz, 1H), 7.39 - 7.42 (m, 1H), 7.42 - 7.44 (m, 3H), 7.49 - 7.56 (m, 2H), 7.62 (d, J = 8.0 Hz, 2H), 7.82 (s, 1H), 7.93 - 7.99 (m, 3H), 8.04 (d, J = 8.0 Hz, 1H), 8.20 (d, J = 2.0 Hz, 1H), 8.21 - 8.25 (m, 1H), 8.95 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.31, 25.71, 31.32, 31.42, 32.16, 33.13, 34.54, 34.67, 34.70, 35.01, 39.41, 39.64, 42.94, 105.61, 107.81, 109.88, 111.22, 111.34, 111.86, 112.33, 113.16, 114.66, 115.27, 115.52, 115.72, 120.43, 121.09, 122.32, 122.74, 122.93, 123.12, 123.25, 123.97, 124.25, 125.59, 126.91, 127.63, 127.75, 128.13, 128.28, 128.51, 128.72, 129.43, 129.66, 136.40, 137.07, 138.08, 138.67, 138.78, 138.89, 140.40, 140.53, 141.39, 141.60, 142.35, 146.65, 147.31, 147.86, 149.06, 149.83, 150.32, 151.92, 152.54, 193.33. HRMS (ESI): C 83 H 79 N5OPt[M+H] + Calcd 1357.6005, Found 1357.5971.

[0375] Example 53: Synthesis of tetradentate cyclometalated platinum(II) complex Pt209

[0376] Synthesis of intermediate Cz-Br-7: Into a three-neck flask was added potassium phosphate (3.8 g, 17.9 mmol, 2.0 eq), hot air gun to blow off water vapor, under nitrogen protection, 3-iodo-4-bromo anisole (3.64 g, 11.63 mmol, 1.3 eq), 3,6-di-tert-butylcarbazole (2.5 g, 8.9 mmol, 1.0 eq), cuprous iodide (171 mg, 0.89 mmol, 0.1 eq), trans-cyclohexanediamine (204 mg, 1.79 mmol, 0.2 eq) were added in turn, nitrogen was replaced for three times, 1,4-dioxane (25 mL) was added, and the reaction was stirred at 100 °C for 16 h. The solvent was removed by distillation under reduced pressure, and the product was separated and purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 100:1, to give 1.5 g of solid, yield 33%. 1H NMR (400 MHz, CDC13) δ 1.46 (s, 18H), 3.78 (s, 3H), 6.94 - 7.00 (m, 2H), 7.03 (d, J = 7.6 Hz, 2H), 7.45 (dd, J = 8.4, 2.0 Hz, 2H), 7.68 - 7.74 (m, 1H), 8.14 (d, J = 2.0 Hz, 2H).

[0377] Synthesis of intermediate Cz-Bpin-7: Into a 100 mL three-necked flask was placed Cz-Br-6 (2.9 g, 6.24 mmol, 1.0 eq), purged and maintained with nitrogen, tetrahydrofuran (30 mL) was added by drop wise, the reaction mixture was gradually cooled to -78 °C, 2.5 M n-butyllithium (3 mL, 7.5 mmol, 1.2 eq) was added drop wise at low temperature, the reaction mixture was kept at low temperature for 1 h, isopropyl alcohol pinacolboronate (1.74 g, 9.36 mmol, 1.5 eq) was added drop wise at low temperature, the reaction mixture was gradually warmed to room temperature and stirred for 15 h. The reaction mixture was quenched with saturated aqueous ammonium chloride solution, extracted with ethyl acetate and water for three times, dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, the residue was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 100:1, to give intermediate Cz-Bpin-7 as white solid 1.92 g, yield 60%.

[0378] Synthesis of intermediate Cz-NO2-7: Into a 100 mL three-necked flask was placed intermediate Cz-Bpin-7 (1.5 g, 2.93 mmol, 1.0 eq), o-bromonitrobenzene (513 mg, 2.5 mmol, 1.0 eq), Pd2(dba)3 (139 mg, 0.15 mmol, 0.06 eq), Pcy3 (tricyclohexylphosphine) (85 mg, 0.3 mmol, 0.12 eq), cesium carbonate (1.65 g, 5.08 mmol, 2.0 eq), purged and maintained with nitrogen, 1,4-dioxane (15 mL) was added, the reaction mixture was stirred at 100 °C for 10 h. The solvent was removed by distillation under reduced pressure, the residue was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 100:1, to give intermediate Cz-NO2-7 as yellow solid 1.7 g, yield 81%.

[0379] Synthesis of intermediate Cz-OTf-7: Into a 50 mL three-necked flask with a magnetic rotor, intermediate Cz-NO2-7 (1.7 g, 3.35 mmol, 1.0 eq), triphenylphosphine (2.64 g, 10.06 mmol, 3.0 eq), nitrogen was replaced for three times, o-dichlorobenzene (15 mL) was added, the reaction was stirred at 180 °C for 29 h. The solvent was removed by distillation under reduced pressure, and then purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1 ~ petroleum ether / dichloromethane = 1:1, finally intermediate Cz-OTf-7 was obtained as yellow foamy solid 1.15 g, yield 98%. 1 H NMR (500 MHz, CDC13) δ 1.48 (s, 18H), 3.90 (s, 3H), 6.53 (dd, J = 8.0, 1.0 Hz, 1H), 6.74 (ddd, J = 8.0, 7.5, 1.5 Hz, 1H), 6.93 (d, J = 2.0 Hz, 1H), 7.04 (d, J = 2.0 Hz, 1H), 7.07 (s, 1H), 7.09 (s, 1H), 7.19 - 7.24 (m, 1H), 7.34 (dt, J = 8.0, 1.0 Hz, 1H), 7.37 (d, J = 2.0 Hz, 1H), 7.38 (d, J = 2.0 Hz, 1H), 8.16 (s, 1H), 8.24 (d, J = 1.5 Hz, 2H).

[0380] Synthesis of intermediate Cz-OTf-7: Into a 50 mL three-necked flask with a magnetic rotor, intermediate Cz-NO2-7 (1.7 g, 3.35 mmol, 1.0 eq), triphenylphosphine (2.64 g, 10.06 mmol, 3.0 eq), nitrogen was replaced for three times, o-dichlorobenzene (15 mL) was added, the reaction was stirred at 180 °C for 29 h. The solvent was removed by distillation under reduced pressure, and then purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1 ~ petroleum ether / dichloromethane = 1:1, finally intermediate Cz-OTf-7 was obtained as yellow foamy solid 1.15 g, yield 98%. 1H NMR (500 MHz, CDC13) δ 0.79 (s, 3H), 1.38 (d, J = 10.0 Hz, 1H), 1.48 (s, 18H), 2.37 - 2.42 (m, 1H), 2.81 (dt, J = 10.0, 6.0 Hz, 1H), 2.99 (t, J = 5.5 Hz, 1H), 3.13 (d, J = 3.0 Hz, 2H), 3.88 (s, 3H), 6.56 (dt, J = 8.0, 1.0 Hz, 1H), 6.76 - 6.81 (m, 1H), 6.96 (d, J = 2.5 Hz, 1H), 7.06 - 7.08 (m, 1H), 7.08 - 7.10 (m, 1H), 7.20 - 7.24 (m, 1H), 7.37 (dd, J = 2.0, 1.0 Hz, 1H), 7.39 (dd, J = 2.0, 0.5 Hz, 1H), 7.45 (d, J = 2.0 Hz, 1H), 7.47 (s, 1H), 7.59 (dt, J = 8.5, 1.0 Hz, 1H), 8.23 (dd, J = 2.0, 0.5 Hz, 2H), 8.29 (s, 1H).

[0381] Synthesis of intermediate Cz-OH-7: Into a schlenk tube with a magnetic rotor was added intermediate Cz-OTf-7 (200 mg, 0.31 mmol, 1.0 eq), Py-HCl (pyridine hydrochloride) (537 mg, 4.65 mmol, 15 eq) and DMI (1,3-dimethyl-2-imidazolidinone) (1 mL), stirred at 170 °C for 21 hours. Neutralized with sodium bicarbonate solution, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, removed the solvent under reduced pressure, separated and purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1-5:1, finally obtained intermediate Cz-OH-7, solid 170 mg, yield 87%. 1H NMR (500 MHz, CDC13) δ 0.78 (s, 3H), 1.36 (d, J = 9.5 Hz, 1H), 1.46 (s, 18H), 1.49 (s, 3H), 2.35 - 2.42 (m, 1H), 2.81 (dt, J = 10.0, 5.5 Hz, 1H), 2.98 (t, J = 5.5 Hz, 1H), 3.13 (d, J = 3.0 Hz, 2H), 5.65 (s, 1H), 6.55 (d, J = 8.0 Hz, 1H), 6.79 (td, J = 8.0, 7.0, 1.0 Hz, 1H), 6.85 (d, J = 2.0 Hz, 1H), 7.07 (dd, J = 8.5, 2.5 Hz, 2H), 7.19 - 7.24 (m, 1H), 7.36 (dt, J = 9.0, 2.0 Hz, 2H), 7.42 (d, J = 2.0 Hz, 1H), 7.47 (s, 1H), 7.57 (d, J = 8.0 Hz, 1H), 8.22 (d, J = 2.0 Hz, 2H), 8.28 (s, 1H).

[0382] Synthesis of Intermediate Cz-Cl-7: Into a schlenk tube was added potassium phosphate (170 mg, 0.8 mmol, 2.0 eq), the water vapor was removed by blowing air with a hot air gun, 1-bromo-3-tert-butyl-5-chlorobenzene (147 mg, 0.59 mmol, 1.5 eq), Cz-OH-7 (250 mg, 0.4 mmol, 1.0 eq), cuprous iodide (8 mg, 0.04 mmol, 0.1 eq), 2-picolinic acid (10 mg, 0.08 mmol, 0.2 eq) were added under nitrogen protection, the nitrogen was replaced for three times, dimethyl sulfoxide (2 mL) was added, and the reaction was stirred at 100 °C for 21.5 h. Quench with water, extract with ethyl acetate for three times, dry over anhydrous sodium sulfate, remove the solvent under reduced pressure, and purify by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-20:1, to give finally intermediate Cz-Cl-7, brown solid 239 mg, yield 75%. 1H NMR (500 MHz, CDC13) δ 0.77 (s, 3H), 1.27 (s, 9H), 1.36 (d, J = 10.0 Hz, 1H), 1.46 (s, 18H), 1.48 (s, 3H), 2.35 - 2.42 (m, 1H), 2.80 (dt, J = 10.0, 6.0 Hz, 1H), 2.97 (t, J = 5.5 Hz, 1H), 3.12 (d, J = 2.5 Hz, 2H), 6.67 (dt, J = 8.0, 1.0 Hz, 1H), 6.83 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 6.88 (t, J = 2.5 Hz, 1H), 6.99 (d, J = 2.0 Hz, 1H), 7.03 - 7.06 (m, 2H), 7.07 (ddd, J = 9.0, 2.0, 0.5 Hz, 2H), 7.28 (ddd, J = 8.5, 7.0, 1.0 Hz, 1H), 7.37 (dd, J = 8.5, 2.0 Hz, 2H), 7.46 (t, J = 1.0 Hz, 1H), 7.61 (d, J = 2.0 Hz, 1H), 7.64 (dt, J = 8.5, 1.0 Hz, 1H), 8.17 - 8.23 (m, 2H), 8.23 - 8.28 (m, 1H).

[0383] Synthesis of intermediate Cz-NH-7: Into a schlenk tube was added intermediate dPhNH2 (148 mg, 0.38 mmol, 1.3 equiv), intermediate Cz-Cl-7 (230 mg, 0.29 mmol, 1.0 equiv), Pd2(dba)3 (16 mg, 0.017 mmol, 0.06 equiv), SPhos (14 mg, 0.035 mmol, 0.12 equiv), sodium tert-butoxide (56 mg, 0.58 mmol, 2.0 equiv), and the reaction vessel was purged with nitrogen three times, toluene (2 mL) was added, and the reaction was stirred at 90 °C for 15 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 50:1-20:1 to give intermediate Cz-NH-7 as a brown solid 320 mg in 95% yield. Used directly in the next reaction.

[0384] Synthesis of ligand LDB7: Into a schlenk tube was added intermediate Cz-NH-7 (320 mg, 0.28 mmol, 1.0 equiv), ammonium hexafluorophosphate (90 mg, 0.55 mmol, 2.0 equiv), and the reaction vessel was purged with nitrogen three times, triethyl orthoformate (4 mL) was added, and the reaction was stirred at 75 °C for 1.5 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with dichloromethane / methanol = 200:1-100:1 to give ligand LDB7 as a white foamy solid 310 mg in 85% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.67 (s, 3 H), 1.22 (d, J = 9.5 Hz, 1 H), 1.29 (s, 9 H), 1.40 (s, 18 H), 1.43 (s, 3 H), 1.44 (s, 9 H), 2.27 - 2.35 (m, 1 H), 2.69 - 2.83 (m, 1 H), 2.97 (t, J = 5.5 Hz, 1 H), 3.04 - 3.17 (m, 2 H), 6.31 - 6.40 (m, 1 H), 6.81 (t, J = 1.5 Hz, 1 H), 6.84 (t, J = 8.0 Hz, 1 H), 6.99 (d, J = 8.5 Hz, 2 H), 7.10 - 7.14 (m, 4 H), 7.15 (s, 2 H), 7.16 - 7.18 (m, 5 H), 7.18 - 7.20 (m, 1 H), 7.29 - 7.34 (m, 3 H), 7.38 (ddd, J = 8.5, 7.0, 1.5 Hz, 1 H), 7.45 - 7.52 (m, 2 H), 7.55 (t, J = 2.0 Hz, 1 H), 7.64 (d, J = 8.5 Hz, 1 H), 7.67 (s, 1 H), 7.70 - 7.77 (m, 4 H), 8.27 (s, 1 H), 8.40 (d, J = 2.0 Hz, 2 H), 10.22 (s, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.57, 25.91, 30.87, 31.17, 31.70, 32.01, 33.03, 34.73, 35.29, 35.37, 39.31, 39.85, 44.33, 102.88, 109.94, 110.35, 110.72, 112.03, 113.12, 114.16, 116.29, 116.49, 118.04, 118.43, 119.03, 120.97, 121.42, 122.85, 123.40, 123.76, 125.36, 126.04, 127.74, 127.93, 128.01, 128.25, 128.32, 128.72, 129.97, 132.31, 132.47, 132.69, 137.16, 139.22, 139.92, 140.50, 141.81, 141.90, 142.42, 142.94, 145.62, 148.25, 148.96, 154.60, 155.20, 156.76, 158.86. HRMS (ESI): C 83 H 82 N5O + [M] + Calcd 1164.6514, Found 1164.6473.

[0385] Synthesis of complex Pt209: Ligand LDB7 (200 mg, 0.15 mmol, 1.0 equivalent), Pt(COD)Cl2 (57 mg, 0.15 mmol, 1.0 equivalent), and sodium acetate (37 mg, 0.45 mmol, 3.0 equivalent) were added sequentially to a sealed tube. Nitrogen gas was purged three times, and DEDM (8 mL) was added. The mixture was bubbled with nitrogen for 30 minutes and reacted at 120 °C for 72 hours. The solvent was removed by vacuum distillation, and the mixture was purified by silica gel column chromatography with petroleum ether / dichloromethane at a ratio of 5:1 to 3:1 as the eluent. The final product was complex Pt209, a yellow-green solid, 115 mg, in yield (56%). 1 H NMR (500MHz, CDCl3) δ0.32(s,3H),1.11(s,3H),1.22(d,J=9.5Hz,1H),1.42(s,9H),1.44(s,9H),1.48(s,9H),1.50(s,9H),2.08(t,J=5.0Hz ,1H),2.15–2.22(m,1H),2.48–2.57(m,1H),2.73(d,J=18.0Hz,1H),2. 83–2.95(m,1H),6.21(t,J=7.5Hz,2H),6.49–6.65(m,4H),6.84–6.95( m,2H),7.00–7.10(m,2H),7.17(dd,J=13.0,8.5Hz,2H),7.23(t,J=7.5Hz,1H),7.27–7.36(m,5H),7.36–7.40(m,2H),7.44(dd,J=8.5,2.0Hz, 1H),7.53(t,J=2.5Hz,2H),7.60–7.67(m,2H),7.78(s,1H),7.85(d,J=8.0Hz,1H),8.00(d,J=8.5Hz,1H),8.26(d,J=2.0Hz,2H),8.97(s,1H). 13C NMR (126 MHz, CDC13) δ 21.36, 25.73, 31.30, 31.58, 32.09, 32.11, 33.09, 34.74, 34.78, 35.00, 39.42, 39.61, 42.93, 105.98, 110.01, 110.45, 110.71, 111.29, 112.23, 112.38, 113.04, 115.13, 115.93, 115.98, 122.16, 122.75, 122.92, 123.05, 123.53, 123.61, 123.90, 124.06, 125.61, 126.44, 127.18, 127.48, 127.70, 127.76, 128.15, 128.28, 128.74, 129.53, 131.80, 136.35, 137.25, 138.09, 138.70, 139.76, 139.90, 142.11, 142.19, 145.33, 146.67, 147.82, 147.88, 149.57, 150.22, 152.46, 152.57, 154.84. HRMS (ESI): C 83 H 79 N5OPt[M+H] + Calcd 1357.6005, Found 1357.5957.

[0386] Example 54: Tetradentate cyclometalated platinum (II) complex Pt210 synthesis route:

[0387] Synthesis of intermediate NO2-F-8: A three-necked flask was charged with 2-bromo-3-fluoronitrobenzene (4 g, 18.1 mmol, 1.0 eq), p-methoxyphenylboronic acid (3.6 g, 23.5 mmol, 1.3 eq), tetrakis(triphenylphosphine)palladium (420 mg, 0.36 mmol, 0.02 eq), potassium carbonate (6.28 g, 45.5 mmol, 2.5 eq), and the flask was purged with nitrogen three times, 1,4-dioxane and water (40 mL / 10 mL) were added, nitrogen was bubbled for 30 minutes, the reaction was stirred at 80 °C for 8 hours, the temperature was raised to 85 °C, and the reaction was continued for 12 hours. The reaction was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The product was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate / dichloromethane = 200:2:1-100:2:1, and finally intermediate NO2-F-8 was obtained as a yellow solid, 3.6 g, yield 81%. 1H NMR (500 MHz, CDC13) δ 1.48 (s, 18H), 3.77 (s, 3H), 6.37 (dd, J = 9.0, 2.0 Hz, 1H), 6.46 (d, J = 8.5 Hz, 1H), 6.84 (d, J = 2.5 Hz, 1H), 7.04 (d, J = 8.5 Hz, 2H), 7.26 - 7.29 (m, 1H), 7.38 (dd, J = 8.5, 2.0 Hz, 2H), 7.46 - 7.49 (m, 2H), 8.14 (s, 1H), 8.25 (d, J = 2.0 Hz, 2H).

[0388] Synthesis of intermediate Cz-NO2-8: Into a sealed tube was placed NO2-F-8 (4.2 g, 16.98 mmol, 1.0 eq), 3,6-di-tert-butylcarbazole (5.7 g, 20.4 mmol, 1.2 eq), cesium carbonate (16.6 g, 50.9 mmol, 3.0 eq), and the tube was purged with nitrogen three times. N,N-dimethylformamide (40 mL) was added and the reaction was stirred at 150 °C for 10 h. The solvent was removed by distillation under reduced pressure and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate / dichloromethane = 200:1:1 to give intermediate Cz-NO2-8 as a yellow solid 8.23 g in 95% yield.

[0389] Synthesis of intermediate Cz-8: Into a 50 mL three-necked flask with a magnetic rotor was placed intermediate Cz-NO2-8 (8.23 g, 16.2 mmol, 1.0 eq), triphenylphosphine (12.7 g, 48.7 mmol, 3.0 eq), and the flask was purged with nitrogen three times. O-dichlorobenzene (40 mL) was added and the reaction was stirred at 180 °C for 10 h. The solvent was removed by distillation under reduced pressure and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 20:1 to petroleum ether / dichloromethane = 1:1 to give intermediate Cz-8 as a solid 6.7 g in 87% yield. 1 H NMR (500 MHz, CDC13) δ 1.48 (s, 18H), 3.77 (s, 3H), 6.37 (dd, J = 9.0, 2.0 Hz, 1H), 6.46 (d, J = 8.5 Hz, 1H), 6.84 (d, J = 2.5 Hz, 1H), 7.04 (d, J = 8.5 Hz, 2H), 7.26 - 7.29 (m, 1H), 7.38 (dd, J = 8.5, 2.0 Hz, 2H), 7.46 - 7.49 (m, 2H), 8.14 (s, 1H), 8.25 (d, J = 2.0 Hz, 2H).

[0390] Synthesis of Intermediate Cz-OTf-8: A schlenk tube was charged with potassium phosphate (1.27 g, 6 mmol, 3.0 equiv), the water vapor was removed by blowing air with a heat gun, and nitrogen was bubbled through the solution for three times. Then Intermediate Cz-8 (996 mg, 2.1 mmol, 1.05 equiv), Intermediate OTf (642 mg, 2.0 mmol, 1.0 equiv), Pd2(dba)3(55 mg, 0.06 mmol, 0.03 equiv), and XPhos (115 mg, 0.24 mmol, 0.12 equiv) were added successively. Toluene (10 mL) was added, and the reaction was stirred at 100 °C for 11 h. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography eluted with petroleum ether / ethyl acetate = 50:1 to give Intermediate Cz-OTf-8 as a yellow foamy solid 820 mg in 64% yield.

[0391] Synthesis of Intermediate Cz-OH-8: A 50 mL single-neck flask with a magnetic rotor was charged with Intermediate Cz-OTf-8 (820 mg, 1.27 mmol, 1.0 equiv), and hydrobromic acid (15 mL) was added. The reaction was stirred at 120 °C for 40 h. The reaction was neutralized with sodium bicarbonate solution, and extracted with ethyl acetate three times. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography eluted with petroleum ether / ethyl acetate = 50:1-20:1 to give Intermediate Cz-OH-8 as a solid 457 mg in 57% yield. 1 H NMR (500 MHz, CDC13) δ 0.76 (s, 3H), 1.35 (d, J = 9.5 Hz, 1H), 1.47 (s, 18H), 1.48 (s, 3H), 2.37 - 2.41 (m, 1H), 2.80 (dt, J = 10.0, 6.0 Hz, 1H), 2.96 (t, J = 5.5 Hz, 1H), 3.12 (d, J = 2.5 Hz, 2H), 5.62 (s, 1H), 6.27 (dd, J = 8.5, 2.5 Hz, 1H), 6.41 (d, J = 8.5 Hz, 1H), 7.01 (dd, J = 8.5, 2.0 Hz, 2H), 7.16 (d, J = 2.0 Hz, 1H), 7.26 - 7.29 (m, 1H), 7.35 (dd, J = 8.5, 1.5 Hz, 2H), 7.44 - 7.49 (m, 2H), 7.79 (dd, J = 8.0, 1.0 Hz, 1H), 8.23 (d, J = 2.0 Hz, 2H), 8.25 (s, 1H).

[0392] Synthesis of Intermediate Cz-Cl-8: A schlenk was charged with potassium phosphate (287 mg, 1.35 mmol, 2.0 eq), the water vapor was blown out by a heat gun, 1-bromo-3-tert-butyl-5-chlorobenzene (184 mg, 0.74 mmol, 1.1 eq), Cz-OH-8 (427 mg, 0.68 mmol, 1.0 eq), cuprous iodide (65 mg, 0.34 mmol, 0.5 eq), 2-picolinic acid (83 mg, 0.68 mmol, 1.0 eq) were added under nitrogen protection, the nitrogen was replaced for three times, dimethyl sulfoxide (5 mL) was added, the reaction was stirred at 110 °C for 10 hours, the unreacted raw material 1-bromo-3-tert-butyl-5-chlorobenzene 160 mg was added, and the reaction was continued to stir for 7 hours. Quench with water, extract with ethyl acetate three times, dry over anhydrous sodium sulfate, remove the solvent under reduced pressure, separate and purify by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1, finally obtain intermediate Cz-Cl-8, white foamy solid 347 mg, yield 64%. 1 H NMR (500 MHz, CDC13) δ 0.76 (s, 3H), 1.21 (s, 9H), 1.35 (d, J = 10 Hz, 1H), 1.47 (s, 18H), 1.48 (s, 3H), 2.34 - 2.41 (m, 1H), 2.80 (dt, J = 11.5, 6.0 Hz, 1H), 2.97 (t, J = 5.5 Hz, 1H), 3.11 (d, J = 2.5 Hz, 2H), 6.47 (dd, J = 9.0, 2.5 Hz, 1H), 6.56 (d, J = 9.0 Hz, 1H), 6.70 (t, J = 2.0 Hz, 1H), 6.90 (t, J = 2.0 Hz, 1H), 7.01 (t, J = 2.0 Hz, 1H), 7.06 (dd, J = 9.0, 1.5 Hz, 2H), 7.32 - 7.35 (m, 2H), 7.39 (dd, J = 8.5, 2.0 Hz, 2H), 7.44 (s, 1H), 7.55 (dd, J = 8.0, 7.5 Hz, 1H), 7.86 (dd, J = 8.5, 1.0 Hz, 1H), 8.21 - 8.24 (m, 2H), 8.26 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.58, 25.96, 31.03, 31.78, 32.05, 33.04, 34.74, 34.97, 39.39, 39.93, 44.37, 101.18, 109.95, 110.68, 112.55, 114.21, 115.57, 116.20, 118.04, 118.96, 120.37, 120.98, 121.45, 123.26, 123.64, 124.24, 126.09, 131.49, 134.38, 139.50, 141.16, 141.45, 142.00, 142.61, 145.63, 147.81, 149.34, 154.64, 155.32, 158.02.

[0393] Synthesis of intermediate Cz-NH-8: Into a schlenk tube was added intermediate dPhNH2 (193 mg, 0.49 mmol, 1.2 equiv), intermediate Cz-Cl-8 (327 mg, 0.41 mmol, 1.0 equiv), Pd2(dba)3 (38 mg, 0.041 mmol, 0.1 equiv), SPhos (25 mg, 0.082 mmol, 0.2 equiv), sodium tert-butoxide (79 mg, 0.82 mmol, 2.0 equiv), and the reaction vessel was purged with nitrogen three times. Toluene (4 mL) was added, and the reaction was stirred at 90 °C for 6 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 100:1 to give intermediate Cz-NH-8 as a solid 278 mg in 59% yield. It was used directly in the next reaction.

[0394] Synthesis of ligand LDB8: Into a schlenk tube was added intermediate Cz-NH-8 (278 mg, 0.24 mmol, 1.0 equiv), ammonium hexafluorophosphate (79 mg, 0.48 mmol, 2.0 equiv), and the reaction vessel was purged with nitrogen three times. Triethyl orthoformate (4 mL) was added, and the reaction was stirred at 75 °C for 30 min. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography eluting with petroleum ether / dichloromethane = 1:1-1:5 ~ dichloromethane / methanol = 1000:1 to give ligand LDB8 as a white foamy solid 176 mg in 56% yield. 1H NMR (500 MHz, CDC13) δ 0.77 (s, 3 H), 1.25 (s, 9 H), 1.37 (d, J = 10 Hz, 1 H), 1.42 - 1.46 (m, 27 H), 1.47 (s, 3 H), 2.34 - 2.44 (m, 1 H), 2.79 (dt, J = 10, 6.0 Hz, 1 H), 2.98 (t, J = 5.5 Hz, 1 H), 3.10 - 3.24 (m, 2 H), 6.36 (t, J = 2.0 Hz, 1 H), 6.48 (dd, J = 8.5, 2.0 Hz, 1 H), 6.59 (d, J = 8.5 Hz, 1 H), 6.64 - 6.68 (m, 1 H), 6.94 - 7.00 (m, 2 H), 7.03 - 7.05 (m, 2 H), 7.06 (d, J = 4.0 Hz, 3 H), 7.07 (d, J = 3.0 Hz, 1 H), 7.09 - 7.15 (m, 4 H), 7.20 (t, J = 2.0 Hz, 1 H), 7.23 (d, J = 8.0 Hz, 1 H), 7.31 - 7.35 (m, 3 H), 7.35 - 7.37 (m, 2 H), 7.37 - 7.40 (m, 1 H), 7.50 (d, J = 2.5 Hz, 1 H), 7.52 (s, 1 H), 7.58 (t, J = 8.5 Hz, 3 H), 7.85 - 7.92 (m, 1 H), 8.22 (d, J = 2.0 Hz, 2 H), 8.27 (s, 1 H), 9.06 (s, 1 H). 13 C NMR (126 MHz, CDC13) δ 21.57, 25.92, 30.85, 31.18, 31.71, 32.02, 33.02, 34.71, 35.29, 39.31, 39.87, 44.34, 102.33, 109.86, 110.53, 110.92, 112.76, 113.30, 114.17, 116.24, 117.93, 118.49, 119.00, 121.13, 121.31, 123.21, 123.64, 124.12, 125.38, 126.38, 127.82, 128.01, 128.25, 128.68, 130.12, 131.48, 132.30, 137.10, 139.49, 139.92, 141.23, 141.77, 141.95, 142.06, 142.62, 145.65, 148.24, 149.07, 154.39, 155.16, 156.46, 158.98. HRMS (ESI): C 83 H 82 N5O + [M] +Calcd 1164.6514, Found 1164.6476.

[0395] Synthesis of complex Pt210: Ligand LDB8 (134 mg, 0.102 mmol, 1.0 eq), Pt(COD)Cl2(40 mg, 0.107 mmol, 1.05 eq) and sodium acetate (26 mg, 0.306 mmol, 3.0 eq) were added into a sealed tube successively, and the tube was purged with nitrogen for three times. Diethyleneglycol dimethyl ether (2 mL) was added and the tube was purged with nitrogen for 30 min. The tube was heated at 120 °C for 72 h. The solvent was removed by distillation under reduced pressure, and the product was purified by silica gel column chromatography with petroleum ether / dichloromethane = 4:1 as eluent. Complex Pt210 was obtained as yellow-green solid, 65 mg, yield 47%. 1 H NMR (500 MHz, CDC13) δ 0.28 (s, 3H), 1.10 (s, 3H), 1.23 (s, 1H), 1.40 (s, 9H), 1.45 (s, 9H), 1.49 (d, J = 4.0 Hz, 18H), 2.04 - 2.09 (m, 1H), 2.17 - 2.22 (m, 1H), 2.49 - 2.57 (m, 1H), 2.77 (d, J = 18.0 Hz, 1H), 2.93 (d, J = 18.0 Hz, 1H), 6.21 (t, J = 7.5 Hz, 2H), 6.34 (d, J = 8.5 Hz, 1H), 6.51 - 6.61 (m, 3H), 6.81 (d, J = 8.5 Hz, 1H), 6.85 (d, J = 8.0 Hz, 1H), 6.98 (d, J = 1.5 Hz, 1H), 7.02 (t, J = 7.5 Hz, 1H), 7.10 (d, J = 8.5 Hz, 1H), 7.18 - 7.26 (m, 4H), 7.26 - 7.30 (m, 2H), 7.39 (dd, J = 4.0, 2.0 Hz, 1H), 7.40 - 7.42 (m, 2H), 7.44 - 7.48 (m, 2H), 7.53 (d, J = 2.5 Hz, 1H), 7.59 - 7.65 (m, 3H), 7.83 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 8.27 (d, J = 2.0 Hz, 2H), 8.94 (s, 1H). 13C NMR (126 MHz, CDC13) δ 21.24, 25.72, 29.69, 31.34, 31.55, 32.06, 32.09, 33.16, 34.72, 34.76, 35.03, 39.45, 39.66, 42.93, 105.76, 107.36, 109.90, 110.36, 110.72, 111.29, 112.20, 112.30, 112.39, 113.01, 115.20, 116.17, 116.28, 119.41, 122.12, 122.68, 123.25, 123.48, 123.72, 123.96, 124.10, 125.59, 126.46, 127.26, 127.44, 127.75, 128.14, 128.27, 128.72, 129.46, 129.63, 131.69, 131.78, 136.36, 137.23, 138.09, 138.71, 139.44, 139.61, 140.50, 142.32, 142.58, 146.69, 147.70, 147.78, 149.48, 150.31, 152.15, 152.55, 154.69, 193.70. HRMS (ESI): C 83 H 79 N5OPt[M+H] + Calcd 1357.6005, Found 1357.5958.

[0396] Example 55: Synthesis of tetradentate cyclometalated platinum(II) complex Pt211

[0397] Synthesis of intermediate Cl-NO2-9: Into a 50 mL three-necked flask was added 2-bromo-4-chloro-1-nitrobenzene (2 g, 8.46 mmol, 1.0 eq), p-methoxyphenylboronic acid (1.54 g, 10.15 mmol, 1.2 eq), tetrakis(triphenylphosphine)palladium (195 mg, 0.17 mmol, 0.02 eq), potassium carbonate (2.34 g, 16.92 mmol, 2.0 eq), and the flask was flushed with nitrogen three times, 1,4-dioxane and water (20 mL / 5 mL) were added, and the mixture was bubbled with nitrogen for 30 min. The reaction was stirred at 80 °C for 23.5 h. The reaction mixture was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation. The product was purified by silica gel column chromatography with petroleum ether / ethyl acetate (100:1-20:1) as eluent to give intermediate Cl-NO2-9 as a yellow solid, 1.95 g, in 87% yield.

[0398] Synthesis of intermediate Cz-NO2-9: Into a 50 mL three-necked flask, Cl-NO2-9 (1.75 g, 6.64 mmol, 1.0 eq), 3,6-di-tert-butylcarbazole (2.23 g, 7.96 mmol, 1.2 eq), Pd2(dba)3 (182 mg, 0.2 mmol, 0.03 eq), XPhos (190 mg, 0.399 mmol, 0.06 eq), cesium carbonate (4.33 g, 13.28 mmol, 2.0 eq), was purged with nitrogen for three times, then toluene (20 mL) was added, the reaction was stirred at 90 °C for 20.5 h. The solvent was removed by distillation under reduced pressure, the product was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, finally the crude product Cz-NO2-9 was obtained as yellow solid 1.75 g, which was used for the next reaction directly. Since the product was difficult to separate from the raw material, the crude product was used for the next reaction directly.

[0399] Synthesis of intermediate Cz-9: Into a 100 mL three-necked flask with a magnetic rotor, intermediate Cz-NO2-9 (1.75 g, 6.6 mmol, 1.0 eq), PPh3 (5.19 g, 19.8 mmol, 3.0 eq) were added, the reaction was purged with nitrogen for three times, then o-dichlorobenzene (30 mL) was added, the reaction was stirred at 180 °C for 20 h. The solvent was removed by distillation under reduced pressure, the product was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 15:1-5:1, finally intermediate Cz-9 was obtained as solid 1.57 g, 50% yield for two steps. 1 H NMR (500 MHz, CDC13) δ 1.48 (s, 18H), 3.93 (s, 3H), 6.88 (dd, J = 8.5, 2.0 Hz, 1H), 6.97 (d, J = 2.5 Hz, 1H), 7.31 (dd, J = 8.5, 0.5 Hz, 2H), 7.46 (dt, J = 9.0, 2.5 Hz, 3H), 7.53 (dd, J = 8.0, 0.5 Hz, 1H), 7.88 (d, J = 9.0 Hz, 1H), 8.06 - 8.14 (m, 2H), 8.18 (dd, J = 2.0, 0.5 Hz, 2H).

[0400] Synthesis of intermediate Cz-OTf-9: A schlenk tube was charged with potassium phosphate (637 mg, 3 mmol, 2.5 equiv), the water vapor was removed by blowing the side of the tube with a heat gun, and nitrogen was bubbled through the solution three times. Intermediate Cz-9 (570 mg, 1.2 mmol, 1.0 equiv), intermediate OTf (405 mg, 1.25 mmol, 1.05 equiv), Pd2(dba)3(33 mg, 0.036 mmol, 0.03 equiv), and XPhos (69 mg, 0.14 mmol, 0.12 equiv) were added sequentially, and the mixture was stirred at 100 °C for 17 h. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 20:1-10:1 to give intermediate Cz-OTf-9 as a brown-yellow solid (729 mg, 94% yield). 1 H NMR (500 MHz, CDC13) δ 0.78 (s, 3H), 1.37 (d, J = 9.5 Hz, 1H), 1.48 (s, 18H), 1.49 (s, 3H), 2.36 - 2.43 (m, 1H), 2.81 (dt, J = 10.0, 6.0 Hz, 1H), 2.98 (t, J = 5.5 Hz, 1H), 3.14 (d, J = 3.0 Hz, 2H), 3.92 (s, 3H), 6.93 (dd, J = 8.5, 2.0 Hz, 1H), 7.30 - 7.34 (m, 2H), 7.35 (s, 1H), 7.45 (d, J = 2.0 Hz, 1H), 7.46 - 7.51 (m, 3H), 7.89 (d, J = 8.5 Hz, 1H), 7.93 (d, J = 8.5 Hz, 1H), 8.12 (d, J = 2.0 Hz, 1H), 8.17 (d, J = 2.0 Hz, 2H), 8.28 (s, 1H).

[0401] Synthesis of intermediate Cz-OH-9: A 50 mL single-neck flask with a magnetic rotor was charged with intermediate Cz-OTf-9 (720 mg, 1.12 mmol, 1.0 equiv), hydrobromic acid (20 mL), and acetic acid (2 mL), and the mixture was stirred at 120 °C for 47 h. The reaction mixture was neutralized with sodium bicarbonate solution, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 10:1-5:1 to give intermediate Cz-OH-9 as a brown foam (640 mg, 90% yield).

[0402] Synthesis of Intermediate Cz-Cl-9: A schlenk was charged with potassium phosphate (536 mg, 2.53 mmol, 2.5 equiv), the water vapor was blown out by a heat gun, 1-bromo-3-tert-butyl-5-chlorobenzene (326 mg, 1.32 mmol, 1.3 equiv), Cz-OH-9 (640 mg, 1.01 mmol, 1.0 equiv), cuprous iodide (19 mg, 0.1 mmol, 0.1 equiv), 2-picolinic acid (25 mg, 0.2 mmol, 0.2 equiv) were added under nitrogen protection, the nitrogen was replaced for three times, dimethyl sulfoxide (8 mL) was added, the reaction was stirred at 90 °C for 40 h. Quenched with water, extracted with ethyl acetate for three times, dried over anhydrous sodium sulfate, removed the solvent under reduced pressure, separated and purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-20:1, finally obtained intermediate Cz-Cl-9, brown foamy solid 519 mg, yield 64%. 1 H NMR (500 MHz, CDC13) δ 0.76 (s, 3H), 1.29 (s, 9H), 1.34 (d, J = 10.0 Hz, 1H), 1.48 (s, 3H), 1.48 (s, 18H), 2.36 - 2.41 (m, 1H), 2.79 (dt, J = 10.0, 6.0 Hz, 1H), 2.96 (t, J = 5.5 Hz, 1H), 3.12 (d, J = 3.0 Hz, 2H), 6.81 (t, J = 2.0 Hz, 1H), 7.00 (dd, J = 8.5, 2.5 Hz, 1H), 7.03 (dd, J = 2.5, 1.5 Hz, 1H), 7.08 (t, J = 1.5 Hz, 1H), 7.34 (dd, J = 8.5, 0.5 Hz, 2H), 7.45 (s, 1H), 7.46 (d, J = 2.0 Hz, 1H), 7.48 (d, J = 2.0 Hz, 1H), 7.50 (d, J = 2.0 Hz, 1H), 7.55 (dd, J = 8.5, 2.5 Hz, 1H), 7.94 - 7.96 (m, 1H), 8.02 (d, J = 8.5 Hz, 1H), 8.17 - 8.20 (m, 3H), 8.25 (s, 1H).

[0403] Synthesis of intermediate Cz-NH-9: Into a schlenk tube was added intermediate dPhNH2(306 mg, 0.78 mmol, 1.2 equiv), intermediate Cz-Cl-9 (519 mg, 0.65 mmol, 1.0 equiv), Pd2(dba)3(18 mg, 0.02 mmol, 0.03 equiv), SPhos (32 mg, 0.078 mmol, 0.12 equiv), sodium tert-butoxide (156 mg, 1.63 mmol, 2.5 equiv), and the reaction vessel was purged with nitrogen three times. Toluene (6 mL) was added and the reaction was stirred at 85 °C for 24 h. The solvent was removed under reduced pressure and the product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 20:1-10:1 to give intermediate Cz-NH-9 as a yellow solid 705 mg, 94% yield. Used directly in the next reaction.

[0404] Synthesis of ligand LDB9: Into a schlenk tube was added intermediate Cz-NH-9 (705 mg, 0.61 mmol, 1.0 equiv), ammonium hexafluorophosphate (199 mg, 1.22 mmol, 2.0 equiv) and the reaction vessel was purged with nitrogen three times. Triethyl orthoformate (4 mL) was added and the reaction was stirred at 75 °C for 3 h. The solvent was removed under reduced pressure and the product was purified by silica gel column chromatography eluting with petroleum ether / dichloromethane = 1:1-1:5 to dichloromethane / methanol = 500:1 to give ligand LDB9 as a yellow foamy solid 681 mg, 85% yield. 1H NMR (500 MHz, CDC13) δ 0.76 (s, 3 H), 1.11 (s, 3 H), 1.32 (s, 9 H), 1.35 (d, J = 9.5 Hz, 1 H), 1.46 (s, 9 H), 1.48 (s, 18...

Claims

A chiral tetradentate platinum(II) and / or palladium(II) complex circularly polarized luminescent material based on a pyridine-carbazole-phenyl carbene and derivatives thereof, characterized in that of the formula (I) and / or (I'), (II) and / or (II'), wherein (I) and (I'), (II) and (II') are enantiomers of each other: wherein M is Pt or Pd; L is O, S, CR x R y , C=0, SiR x R y , GeR x R y , NR z , PR z , R z P=0, AsR z , R z As=0, S=0, S02, Se, Se=0, Se02, BH, BR z , R z Bi=0 or BiR z ; R x , R y and R z are each independently one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl; "*" is a carbon atom with a central chirality; X 1 , X 2 , X 3 , X 4 each independently CR 2 or N; Y 1 , Y 2 , Y 3 each independently CR 3 or N; Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 each independently is CR 4 or N; R 1 , R 2 , R 3 , R 4 each independently represents mono-, di-, tri-, tetra-, penta-substitution or no substitution; R 1 - R 4 each independently is one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl; R a , R b , R m and R n are each independently one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl. The circularly polarized luminescent material according to claim 1, characterized in that R1is independently at each occurrence selected from the group consisting of hydrogen, deuterium, -CN, F, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, deuterated tert-butyl, substituted or unsubstituted aryl, substituted or unsubstituted carbazolyl; when containing substitution, the substituents are selected from the group consisting of hydrogen, deuterium, F, -CN, C1-C10alkyl; when R1is selected from aryl, it can be linked to the substituted group to form a fused ring. The circularly polarized luminescent material according to claim 1, characterized in that R2is independently at each occurrence selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24alkyl, substituted or unsubstituted C3-C24cycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C6-C30arylamino; when containing substitution, the substituents are selected from the group consisting of hydrogen, deuterium, F, -CN, C1-C10alkyl, phenyl, carbazolyl. The circularly polarized luminescent material according to claim 1, characterized in that R3is independently at each occurrence selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24alkyl, substituted or unsubstituted C3-C24cycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C1-C30silyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted C6-C30arylamino, substituted or unsubstituted C6-C30indenyl, substituted or unsubstituted C6-C30heteroindenyl; when containing substitution, the substituents are selected from the group consisting of hydrogen, deuterium, F, -CN, C1-C10alkyl, phenyl, carbazolyl, adjacent substituents can be linked to form a ring. The circularly polarized luminescent material according to claim 1, characterized in that R4is independently at each occurrence selected from the group consisting of hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24alkyl, substituted or unsubstituted C3-C30cycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C5-C30heteroanthracenyl, substituted or unsubstituted C1-C30silyl, substituted or unsubstituted C6-C30arylamino, substituted or unsubstituted carbazolyl, substituted or unsubstituted C6-C30heteroindenyl; when containing substitution, the substituents are selected from the group consisting of hydrogen, deuterium, F, -CN, C1-C10alkyl, phenyl, carbazolyl. The circularly polarized luminescent material according to claim 1, characterized in that Two or more adjacent substituents can optionally be linked to form a fused ring or an unsaturated ring system. The circularly polarized luminescent material according to claim 1, characterized in that The complex circularly polarized luminescent material can be, but is not limited to, the following structure and its enantiomers, wherein "D" represents deuterium: Use of the complex circularly polarized luminescent material according to any one of claims 1-7 in the preparation of an electronic device. The use according to claim 8, characterized in that The electronic device is a light-emitting device, a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device, or a biological imaging device. An organic electroluminescence device is characterized by comprising: The organic electroluminescent device comprises a cathode, an anode, and an organic functional layer between the two; the organic functional layer comprises the complex circularly polarized luminescent material according to any one of claims 1-7. The organic electroluminescence device according to claim 10, characterized in that The organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the complex circularly polarized luminescent material according to any one of claims 1-7. An organic optoelectronic component, characterized in that The organic optoelectronic device comprises a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer comprises the complex circularly polarized luminescent material according to any one of claims 1-7. A display or illumination device, characterized in that The display or lighting device comprises the organic electroluminescent device according to claim 10, and / or the organic optoelectronic device according to claim 12. A composition characterized in that, The composition comprises the complex circularly polarized luminescent material according to any one of claims 1-7. A formulation characterized in that, The preparation comprises the complex circularly polarized luminescent material according to any one of claims 1-7 and at least one solvent. The organic optoelectronic device comprises a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer comprises the complex circularly polarized luminescent material according to any one of claims 1-7. The display or lighting device comprises the organic electroluminescent device according to claim 10, and / or the organic optoelectronic device according to claim 12. The composition comprises the complex circularly polarized luminescent material according to any one of claims 1-7. The preparation comprises the complex circularly polarized luminescent material according to any one of claims 1-7 and at least one solvent.

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