Circularly polarized luminescent materials based on tetradentate cyclometallated platinum(II) or palladium(II) complexes that induce helical chirality from central chirality and their applications

Abstract

The objective of the present invention is to provide a circularly polarized luminescent material of a tetradentate cyclometallated platinum(II) and palladium(II) complex that induces helical asymmetry from central asymmetry, and applications thereof. The present invention discloses a circularly polarized luminescent material of a complex of tetradentate cyclometalated platinum(II) and palladium(II) that induces helical chirality from central chirality and its application. The helical chiral metal complex molecule is a centrally chiral fragment L in a tetradentate ligand. a The tetradentate ligand can be spontaneously induced to coordinate with the metal ion in a manner with little steric hindrance via the above reaction to form an optically pure circularly polarized luminescent material, without the need for chiral resolution. The material has high chemical and thermal stability and has important applications in circularly polarized light-emitting devices.

Description

[Technical Field]

[0001] The present invention relates to a circularly polarized luminescent material and its application, and in particular to a circularly polarized luminescent material having a central chirality. and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or Palladium(II) complex circularly polarized luminescent material and its applications. [Background technology]

[0002] Circularly polarized luminescence (CPL) is a phenomenon in which chiral luminescent materials emit left-handed or right-handed circularly polarized light upon excitation, so the design and development of chiral luminescent materials is the key to this field. With the intensive research of scientific researchers, so far, circularly polarized luminescent materials have found important applications in the fields of 3D display, data storage, quantum computing, optical anti-counterfeiting, bioimaging and asymmetric synthesis.

[0003] Phosphorescent materials based on cyclometallated platinum(II) and palladium(II) complexes can fully utilize all singlet and triplet excitons generated by electrical excitation due to the heavy atom effect, making this type of complex ideal for luminescent materials. Bidentate cyclometallated platinum(II) and palladium(II) complexes have low rigidity, and the two bidentate ligands are prone to distortion and vibration, which causes the energy of the excited state material molecules to be consumed nonradiatively, reducing their luminescence quantum efficiency (Non-Patent Document 1). However, cyclometallated platinum(II) and palladium(II) complexes based on tridentate ligands can improve luminescence quantum efficiency due to their enhanced molecular rigidity (Non-Patent Document 2), but the second monodentate ligand (Cl) - The presence of cyclometallated anions (e.g., phenoxy anions, alkyne anions, carbenes) significantly reduces the chemical and thermal stability of the complexes, making them difficult to sublimate and purify for the fabrication of OLED devices. Therefore, emissive materials based on bidentate and tridentate cyclometallated complexes are not conducive to stable and efficient OLED device applications. The central metal ions of divalent cyclometallated platinum(II) and palladium(II) complexes are both dsp2 This hybridization facilitates coordination with tetradentate ligands to form stable, rigid, square-planar molecules. This high molecular rigidity suppresses nonradiative relaxation due to molecular vibration and rotation, reducing energy loss in excited states and improving the luminescence quantum efficiency of the material molecules. The steric hindrance of the two aryl groups at the termini of the tetradentate ligands in cyclometallated platinum(II) and palladium(II) complexes results in the material molecules being distorted into a square shape (Non-Patent Document 3). While theoretically possessing helical chirality, the molecules easily racemize in solution or during thermal sublimation due to the up-and-down vibration of the two aryl groups at the termini of the ligands. This makes it impossible to separate the enantiomers, making it extremely difficult to obtain optically pure cyclometallated platinum(II) and palladium(II) complexes. Furthermore, the material molecules lack circularly polarized luminescence. Therefore, how to design and develop optically pure cyclometallated platinum(II) and palladium(II) complex molecules with high chemical and thermal stability and circularly polarized emission properties is of great significance and practical value for the application to circularly polarized light-emitting OLED devices (CP-OLEDs), and is also an urgent issue in the field of CP-OLEDs. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Inorg.Chem.2002,41,3055 [Non-patent document 2] Inorg.Chem.2010,49,11276 [Non-patent document 3] Chem.Mater.2020,32,537 Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to address the shortcomings of the prior art by providing a compound having a central chirality. and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. orThe present invention provides a circularly polarized luminescent material of palladium (II) complex and its application. The helical chiral metal complex molecule has a central chiral fragment L in a tetradentate ligand. a The tetradentate ligand can be spontaneously induced to coordinate with the metal ion in a manner with minimal steric hindrance, forming an optically pure circularly polarized luminescent material without the need for chiral resolution. The material has high chemical and thermal stability, and has important applications in circularly polarized light-emitting devices. [Means for solving the problem]

[0006] The object of the present invention is achieved by the following technical means.

[0007] Central chirality? and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or The palladium (II) complex circularly polarized luminescent material is characterized in that its chemical formula is represented by general formulas (I), (I'), (II), (II'), (III) and (III'), where (I) and (I'), (II) and (II'), and (III) and (III') are enantiomers of each other.

[0008] [ka] wherein M is Pt or Pd, and V 1 , V 2 , V 3 and V 4 are each independently N or C, L 1 , L 2 and L 3 are each independently a 5- or 6-membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring; L a and L b are each independently a 5-membered central asymmetric carbocyclic or heterocyclic ring, and L a and L 1 , L a and L b Due to the steric hindrance between the two, the entire metal complex has a non-planar configuration and central asymmetric L aA tetradentate cyclometallated platinum(II) with metal-centered helical chirality was synthesized by a method with minimal steric hindrance. or It can induce spontaneous formation of palladium(II) complexes, A 1 , A 2 , X and X 1 are independently O, S, and CR x R y , C=O, SiR x R y , GeR x R y , N.R. 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 and R 1 , R 2 and R 3 each independently represents mono-, di-, tri-, tetra- or unsubstituted, and R 1 , R 2 , R 3 , R a , R b , R c , R d , R e , R f , R g , R h , R x , R y and R zare each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; 1 , R 2 and R 3 can be optionally linked to form a fused ring, and R a , R b , R c and R d Any two groups in R can be joined to form a ring system; e , R f , R g and R h Any two groups in the formula may be joined to form a ring system.

[0009] The central chiral compounds having the above general formulae (I), (I'), (II) and (II') and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or The palladium(II) complex circularly polarized luminescent material can be one of the following general formulas (IA), (IA), (IB), (IC), (ID), (IE), (IF), (IG), (IH), (II), (II-A) and its enantiomers (I'-A), (I'-A), (I'-B), (I'-C), (I'-D), (I'-E), (I'-F), (I'-G), (I'-H), (I'-I), (II'-A), but is not limited thereto.

[0010] [ka] wherein M is Pt or Pd, and V 1 , V 2 , V 3 and V 4 are each independently N or C, L 1 , L 2 and L 3 are each independently a 5- or 6-membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring; L a is a five-membered central chiral carbocyclic or heterocyclic ring, and L a and L 1 Due to the steric hindrance between the two, the entire metal complex has a non-planar configuration and central asymmetric L a A tetradentate cyclometallated platinum(II) with metal-centered helical chirality was synthesized by a method with minimal steric hindrance. or It can induce spontaneous formation of palladium(II) complexes, A 1 , X, Z and Z 1 are independently O, S, and CR x R y , C=O, SiR x R y , GeR x R y , N.R. 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 and R 1 , R 2 , R 3 , R 4 and R 5 each independently represent mono-, di-, tri-, or tetra-substituted or unsubstituted, and R 1 , R 2 , R 3 , R 3 , R 4 , R 5 , R a , R b , R c , Rd , R x , R y and R z are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; 1 , R 2 , R 3 , R 4 and R 5 can be optionally linked to form a fused ring, and R a , R b , R c and R d Any two groups in the formula may be joined to form a ring system.

[0011] The above central chirality and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or L in the general formula structure of palladium(II) complex circularly polarized luminescent materials a and L b can be, but is not limited to, the following structures:

[0012] [ka] [In the formula, R a1 , R a2 and R a3each independently represent hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; In the formula, R b1 , R c1 and R c2 each independently represent mono-, di-, tri-, or tetra-substituted or unsubstituted, and R b1 , R c1 and R c2 are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; b1 , R c1 and R c2 can optionally be linked to form a fused ring.

[0013] The above L a and L bMore specifically, the structure may be as follows, but is not limited to these:

[0014] [ka] [ka] [ka] [In the formula, R d1 、R e2 , R e3 and R e4 each independently represent mono-, di-, tri-, tetra- or unsubstituted, and R d1 、R e2 、R e3 and R e4 are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; R d1 、R e2 、R e3 and R e4 can optionally be linked to form a fused ring.

[0015] Furthermore, from the central asymmetry and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or The palladium(II) complex circularly polarized luminescent material is preferably selected from the following:

[0016] [ka] [ka] [ka] [ka]

[0017] Furthermore, from the central asymmetry and others The tetradentate cyclometallated complex circularly polarized luminescent material that induces helical chirality can be selected from the following platinum(II) metal complexes and their corresponding isomers and their corresponding metal palladium(II) complexes:

[0018] [ka] [ka] [ka] [ka] [ka] [ka]

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[0019] Furthermore, the central chirality in organic light-emitting devices and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or The application of palladium (II), wherein the organic light-emitting device is an organic light-emitting diode, a light-emitting diode or a light-emitting electrochemical cell.

[0020] The light-emitting element includes a first electrode, a second electrode, and at least one organic layer provided between the first electrode and the second electrode, and the organic layer has a central chirality or and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or Palladium (II) complexes include circularly polarized luminescent materials.

[0021] Furthermore, the central chirality in organic light-emitting devices and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or The application of the palladium (II) complex circularly polarized luminescent material, said organic light-emitting device, is a 3D display device, a 3D imaging device, an optical information encryption device, an information storage device, a bio-imaging device, etc. [Effects of the Invention]

[0022] The advantageous effects of the present invention include: (1) Spontaneous induction of helical chirality from central chirality: Central chirality L a We designed and developed a tetradentate ligand with the other terminal ligand L 1 or L b By utilizing the steric hindrance effect between the tetradentate cyclometalated platinum(II) or Palladium(II) complex molecules are distorted into squares and have central chirality. a can spontaneously induce the entire tetradentate ligand to coordinate with the metal ion in a sterically less hindered manner, resulting in a helical asymmetric tetradentate cyclometallated platinum(II) around the metal ion, as shown in Figure 1. or Palladium (II) complexes form optically pure circularly polarized luminescent materials.

[0023] (2) Optically pure raw materials are economical and readily available: centrally chiral L a The two chiral, optically pure enantiomers required for the preparation of the tetradentate ligand having the formula (I) are commercially, economically, and readily available compounds, making it convenient for the large-scale preparation of the two chiral, optically pure tetradentate ligands.

[0024] (3) Circularly polarized luminescent materials do not require chiral resolution: Helical asymmetric tetradentate cyclometalated platinum(II) from the above two chiral optically pure tetradentate ligands orTwo chiral optically pure enantiomers of palladium(II) complexes can be easily prepared as circularly polarized luminescent materials, and separation and purification using a chiral column are not required, which significantly reduces the material preparation cost.

[0025] (4) The chemical and thermal stability of the material is high: the designed and developed tetradentate ligand is dsp 2 The central chiral ligand L can coordinate well with platinum(II) and palladium(II) metal ions during hybridization, forming stable, rigid square-shaped molecules with high chemical stability. a and the other ligand L 1 or L b Because of the large steric hindrance between the metal complex and the chiral tetradentate cyclometalated complex, the entire metal complex molecule can form a stable helical asymmetric tetradentate cyclometalated complex, and the circularly polarized luminescence property is not lost due to racemization in solution or during high-temperature sublimation. [Brief explanation of the drawings]

[0026] [Figure 1] This is a design concept diagram of an optically pure circularly polarized luminescent material based on a helical chiral tetradentate cyclometallated complex centered on a metal ion. [Figure 2] (A) is a front view of the X-ray diffraction single crystal structure of the optically pure helical asymmetric material (R,S)-M-PtLA1. (B) is a top view of the X-ray diffraction single crystal structure of the optically pure helical asymmetric material (R,S)-M-PtLA1. (C) is a front view of the molecular structure of (R,S)-M-PtLA1 after structural optimization using density functional theory (DFT) calculations. (D) is a top view of the molecular structure of (R,S)-M-PtLA1 after structural optimization using density functional theory (DFT) calculations. (E) is a front view of the molecular structure of (S,R)-P-PtLA1 after structural optimization using DFT calculations. (F) is a top view of the molecular structure of (S,R)-P-PtLA1 after structural optimization using DFT calculations. [Figure 3](A) is a front view of the molecular structure of (R,S)-M-PtLB3, whose structure was optimized by DFT calculations. (B) is a top view of the molecular structure of (R,S)--PtLB3, whose structure was optimized by DFT calculations. (C) is the molecular structural formula of (R,S)-M-PtLB3. (D) is a front view of the molecular structure of (S,R)-P-PtLB3, whose structure was optimized by DFT calculations. (E) is a top view of the molecular structure of (S,R)-P-PtLB3, whose structure was optimized by DFT calculations. (F) is the molecular structural formula of (S,R)-P-PtLB3. [Figure 4] (A) is a front view of the molecular structure of (R,S)-M-PtLH1, whose structure was optimized by DFT calculations. (B) is a top view of the molecular structure of (R,S)-M-PtLH1, whose structure was optimized by DFT calculations. (C) is the molecular structural formula of (R,S)-M-PtLH1. (D) is a front view of the molecular structure of (S,R)-P-PtL H1, whose structure was optimized by DFT calculations. (E) is a top view of the molecular structure of (S,R)-P-PtL H1, whose structure was optimized by DFT calculations. (F) is the molecular structural formula of (S,R)-P-PtL H1. [Figure 5] (A) is a front view of the molecular structure of M-PtLIII-1, whose structure was optimized by DFT calculations; (B) is the molecular structural formula of M-PtLIII-1; (C) is a front view of the molecular structure of P-PtLIII-1, whose structure was optimized by DFT calculations; and (D) is the molecular structural formula of P-PtLIII-1. [Figure 6] FIG. 1 shows the emission spectra of optically pure (R,S)-M-PtLA1 and (S,R)-P-PtLA1 in dichloromethane solution at room temperature. [Figure 7] FIG. 1 shows the emission spectra of optically pure (R,S)-M-PtLA2 and (S,R)-P-PtLA2 in dichloromethane solution at room temperature. [Figure 8] FIG. 1 shows the emission spectra of optically pure (R,S)-M-PtLA3 and (S,R)-P-PtLA3 in dichloromethane solution at room temperature. [Figure 9]FIG. 1 shows the emission spectra of optically pure (R,S)-M-PtLAN and (S,R)-P-PtLAN in dichloromethane solution at room temperature. [Figure 10] FIG. 1 shows the emission spectra of optically pure (R,S)-M-PtLH1 and (S,R)-P-PtLH1 in dichloromethane solution at room temperature. [Figure 11] FIG. 1 shows the emission spectra of optically pure (S,R)-P-PtLC3 and P-PtLIII-1 in dichloromethane solution at room temperature. [Figure 12] FIG. 1 shows the emission spectra of optically pure M-PdLA1 and P-PdLA1 in dichloromethane solution at room temperature. [Figure 13] FIG. 1 shows the emission spectra of optically pure M-PtLB1 and P-PtLB1 in dichloromethane solution at room temperature. [Figure 14] FIG. 1 shows the emission spectra of optically pure M-PtLC1 and P-PtLC1 in dichloromethane solution at room temperature. [Figure 15] FIG. 1 shows the emission spectra of optically pure M-PtLD1 and P-PtL1 in dichloromethane solution at room temperature. [Figure 16] FIG. 1 shows the emission spectra of optically pure M-PtLE1 and P-PtLE1 in dichloromethane solution at room temperature. [Figure 17] FIG. 1 shows the emission spectra of optically pure M-PtLF1 and P-PtLF1 in dichloromethane solution at room temperature. [Figure 18] FIG. 1 shows the emission spectra of optically pure (R,S)-M-PtL K1 and (S,R)-P-PtL K1 in dichloromethane solution at room temperature. [Figure 19] FIG. 1 shows the emission spectra of optically pure M-PtL1 and P-PtL1 in dichloromethane solution at room temperature. [Figure 20] FIG. 1 shows the emission spectra of optically pure M-PtL3 and P-PtL3 in dichloromethane solution at room temperature. [Figure 21]FIG. 1 shows the circular dichroism (CD) spectra of (S,R)-P-PtLA1 and (R,S)-M-PtLA1 in dichloromethane solution. [Figure 22] FIG. 1 shows the circular dichroism (CD) spectra of P-PtOO and M-PtLOO in dichloromethane solution. [Figure 23] FIG. 1 shows the circular dichroism (CD) spectra of (S,R)-P-PtLA3 and (R,S)-M-PtLA3 in dichloromethane solution. [Figure 24] FIG. 1 shows the circular dichroism (CD) spectra of (S,R)-P-PtLJ1 and (R,S)-M-PtLJ1 in dichloromethane solution. [Figure 25] FIG. 1 shows the circular dichroism (CD) spectra of P-PtLB3 and M-PtLB3 in dichloromethane solution. [Figure 26] FIG. 1 shows the circularly polarized photoluminescence (CPPL) spectra of P-PtOO, M-PtLOO, and their equivalent mixtures in dichloromethane solution. [Figure 27] FIG. 1 shows the circularly polarized photoluminescence (CPPL) spectra of (S,R)-P-PtLA1 and (R,S)-M-PtLA1 in dichloromethane solution. [Figure 28] Figure 1 shows the circularly polarized photoluminescence (CPPL) spectra of (S,R)-P-PtLA3 and (R,S)-M-PtLA3 in dichloromethane solution. [Figure 29] FIG. 1 shows the circularly polarized photoluminescence (CPPL) spectra of optically pure M-PtL1 and P-PtL1 in dichloromethane solution at room temperature. [Figure 30] Figure 1 shows the circularly polarized photoluminescence (CPPL) spectra of (S,R)-P-PtLA3 and (R,S)-M-PtLA3 in dichloromethane solution. [Figure 31] FIG. 1 shows the circularly polarized photoluminescence (CPPL) spectra of (S,R)-P-PtLJ1 and (R,S)-M-PtLJ1 in dichloromethane solution. [Figure 32] Figure 1 shows the circularly polarized photoluminescence (CPPL) spectra of P-PtLB3 and M-PtLB3 in dichloromethane solution. [Figure 33] FIG. 1 shows the circularly polarized photoluminescence (CPPL) spectra of P-PtLB9 and M-PtLB9 in dichloromethane solution. [Figure 34] From top to bottom, these figures show the HPLC spectrum of a mixture of (R,S)-M-PtLA1 and (S,R)-P-PtLA1, the HPLC spectrum of optically pure (R,S)-M-PtLA1, the HPLC spectrum of optically pure (S,R)-P-PtLA1, and the HPLC spectrum of (R,S)-M-PtLA1 after sublimation. [Figure 35] 1 is a thermogravimetric analysis curve of (R,S)-M-PtLA1. [Figure 36] FIG. 1 is a schematic diagram illustrating the configuration of an organic light-emitting element. [Figure 37] FIG. 1 is a diagram illustrating the propagation modes of sunlight. [Figure 38] FIG. 1 illustrates the propagation modes of circularly polarized light emission. DETAILED DESCRIPTION OF THE INVENTION

[0027] The present invention will be described in detail below. The following description of the components may be based on typical embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0028] Hereinafter, specific examples will be given to explain the circularly polarized light-emitting material of the present invention represented by the above general formula, but they should not be understood as limitations on the present invention.

[0029] The present disclosure may be more readily understood by reference to the following specific embodiments and the examples included therein. Before the present compounds, devices, and / or methods are disclosed and described, it is to be understood that, unless otherwise specified, they are not limited to particular synthetic methods or particular reagents, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments 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, exemplary methods and materials are described herein.

[0030] As used in this specification and the appended claims, the singular forms "a," "one," and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise. Thus, for example, reference to a "component" includes a mixture of two or more components.

[0031] As used herein, the term "optionally" or "optionally" means that the subsequently described event or circumstance may or may not occur, and thus the description includes instances where the event or circumstance occurs and instances where it does not occur.

[0032] In addition to the components used to prepare the compositions described herein, the compositions themselves used in the methods disclosed herein are also disclosed. When these and other materials are disclosed herein, and when combinations, subsets, interactions, groups, etc. of these substances are disclosed, it is understood that each is specifically contemplated and described herein, even if reference to various individual and collective combinations and permutations of these compounds is not explicitly disclosed. For example, if a particular compound is disclosed and discussed, and it is discussed that several modifications can be made to several molecules comprising that compound, then each and every possible combination and permutation of the compound and its modifications is specifically contemplated, unless otherwise indicated to the contrary. Thus, if classes of molecules A, B, and C are disclosed, as well as classes of molecules D, E, and F, and examples of the molecular combination AD, each individually and collectively encompass the meaning of the combination, even if not individually listed, and AE, AF, BD, BE, BF, CD, CE, and CF are also considered to be disclosed. Similarly, any subsets or combinations thereof are also disclosed. Thus, for example, the subgroups AE, BF, and CE are also considered to be disclosed. This concept applies to all aspects of the invention, including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, where there are various possible additional steps, it is understood that each of these additional steps can be performed with any particular embodiment or combination of embodiments of the methods of the invention.

[0033] A linking atom used in the present invention can connect two groups, for example, N and C. The linking atom can optionally have other chemical moieties attached, if valence allows. For example, when two atoms (e.g., N or C) are bonded, the valence is satisfied, so no other chemical groups are attached to the oxygen atom. Conversely, when carbon is the linking atom, two additional chemical groups can be attached to the carbon atom. Suitable chemical groups include hydrogen, hydroxy, alkyl, alkoxy, ═O, halogen, nitro, amine, amide, mercapto, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

[0034] As used herein, the term "cyclic structure" or similar terms means any cyclic chemical structure, including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

[0035] As used herein, the term "substituted" or similar terms includes all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and can be the same or different for appropriate organic compounds. For purposes of this invention, heteroatoms (e.g., nitrogen) can have hydrogen substituents and / or any permissible substituents of organic compounds described herein that satisfy the valences of the heteroatoms. This invention is not intended to be limited in any manner with respect to the permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" connote that such substitution is consistent with the permissible valences of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not undergo spontaneous transformation, such as rearrangement, cyclization, or elimination). Furthermore, in certain embodiments, it is contemplated that individual substituents may optionally be further substituted (i.e., may or may not be further substituted), unless clearly indicated to the contrary.

[0036] In the definition of various terms, "R 1 "," "R 2 "," "R 3 " and "R 4 " is used herein as a general symbol to represent various specific substituents. These symbols may be any substituent and are not limited to the substituents disclosed herein, and when defined as a certain substituent in one instance, it may be defined as a different substituent in another instance.

[0037] As used herein, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group having 1 to 30 carbon atoms, including, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 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 optionally substituted with one or more groups, including, but not limited to, substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfo-oxo, and mercapto, as described herein. A "lower alkyl" group is an alkyl group having 1 to 6 (e.g., 1 to 4) carbon atoms.

[0038] Throughout this specification, "alkyl" is used generally to refer to both unsubstituted and substituted alkyl groups. However, substituted alkyl groups are also specifically referred to in the present invention by identifying specific 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, such as those described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, such as those described below. When "alkyl" is used in one example and a specific term, such as "alkylalcohol," is used in another example, this is not meant to suggest that the term "alkyl" does not also refer to the specific term, such as "alkylalcohol."

[0039] This approach is also used for other groups described herein. Thus, for example, the term "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, and in addition, substituted moieties may be specifically designated herein. For example, a specific substituted cycloalkyl may be referred to as an "alkylcycloalkyl," etc. Similarly, a substituted alkoxy may be specifically referred to as a "halogenated alkoxy," etc., and a specific substituted alkenyl may be an "alkenylalcohol," etc. Furthermore, when a general term (e.g., "cycloalkyl") and a specific term (e.g., "alkylcycloalkyl") are used, this is not meant to imply that the general term does not include the specific term.

[0040] As used herein, the term "cycloalkyl" refers to a non-aromatic carbon ring consisting of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and the like. The term "heterocycloalkyl" is a species of cycloalkyl, as defined above, and is included within the meaning of the term "cycloalkyl," in which at least one ring carbon atom is replaced with a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. Cycloalkyl and heterocycloalkyl groups can be substituted with one or more groups, including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfo-oxo, or mercapto, as described herein.

[0041] As used herein, the term "polyalkylene group" refers to a group having two or more CH groups linked together. A polyalkylene group has the formula -(CH) a - (wherein "a" is an integer of 2 to 500).

[0042] As used herein, the terms "alkoxy" and "alkoxy" refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms attached through an ether linkage, i.e., an "alkoxy" group is defined as -OR 1 (In the formula, R 1 is alkyl or cycloalkyl as defined above. "Alkoxy" also includes polymers of this alkoxy group, i.e., alkoxy can be a polyether, e.g., -OR 1 -OR 2 -OR 1 -(OR 2 ) a -OR 3 (wherein "a" is an integer from 1 to 500, and R 1 , R 2 and R 3 are each independently an alkyl, a cycloalkyl group, or a combination thereof.

[0043] As used herein, the term "alkenyl" refers to a hydrocarbon group of 2 to 30 carbon atoms and represented by the structural formula containing at least one carbon-carbon double bond. 1 R 2 )C=C(R 3 R 4 ) is intended to include both the E and Z isomers. This can be inferred in structural formulas herein where an asymmetric alkene is present or in structural formulas designated by the bond symbol C=C. The alkenyl group can be optionally 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, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or mercapto, as described herein.

[0044] As used herein, the term "cycloalkenyl" refers to a non-aromatic carbocyclic ring of 3 to 30 carbon atoms, consisting of at least three carbon atoms and having at least one carbon-carbon double bond (i.e., C=C). Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and norbornenyl. The term "heterocycloalkenyl" refers to a type of cycloalkenyl group, as defined above, and is included within the meaning of the term "cycloalkenyl," except that at least one ring carbon atom is replaced with a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups may be optionally 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, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or mercapto, as described herein.

[0045] As used herein, the term "alkynyl" refers to a hydrocarbon group of 2 to 30 carbon atoms having at least one carbon-carbon triple bond. Alkynyl groups 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, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or mercapto, as described herein.

[0046] As used herein, the term "cycloalkynyl" refers to a non-aromatic carbon ring composed of at least seven carbon atoms and having 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 type of cycloalkenyl, as defined above, and is included within the meaning of the term "cycloalkynyl," in which at least one carbon atom 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. The cycloalkynyl and heterocycloalkynyl groups may be optionally 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, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or mercapto, as described herein.

[0047] As used herein, the term "aryl" refers to a group containing up to 60 carbon atoms and containing any carbon-based aromatic group, including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group with one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl," which is included within the term "aryl," is defined as a group containing an aromatic group that does not contain a heteroatom. Aryl groups can be substituted or unsubstituted. Aryl groups may be optionally 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, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or mercapto, as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl." Biaryl refers to two aryl groups bonded together through a fused ring structure, as in naphthalene, or through one or more carbon-carbon bonds, as in biphenyl.

[0048] As used herein, the term "aldehyde" is represented by the formula -C(O)H. Throughout this specification, "C(O)" is a shorthand notation for a carbonyl group (i.e., C=O).

[0049] As used herein, the term "amine" or "amino" refers to a group of the formula -NR 1 R 2 where R 1 and R 2 may be independently selected from hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group.

[0050] As used herein, the term "alkylamino" is represented by the formula -NH(-alkyl), wherein alkyl is as defined herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl)amino, (tert-butyl)amino, pentylamino, isopentylamino, (tert-pentyl)amino, hexylamino, and the like.

[0051] As used herein, the term "dialkylamino" is represented by the formula -N(-alkyl)2, where alkyl is as defined herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di(sec-butyl)amino, di(tert-butyl)amino, dipentylamino, diisopentylamino, di(tert-pentyl)amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, and N-ethyl-N-propylamino.

[0052] The term "carboxylic acid" as used herein is represented by the formula --C(O)OH.

[0053] As used herein, the term "ester" refers to an ester of the formula -OC(O)R 1 Or -C(O)OR 1 (In the formula, R 1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. As used herein, the term "polyester" refers to a group consisting of -(R 1 O(O)CR 2 -C(O)O) a -or-(R 1 O(O)CR 2-OC(O)) a -(In the formula, R 1 and R 2 are independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groups as described herein, and "a" is an integer from 1 to 500. The term "polyester" is used to describe groups resulting from the reaction between a compound having at least two carboxylic acid groups and a compound having at least two hydroxy groups.

[0054] As used herein, the term "ether" refers to a group of formula R 1 OR 2 (In the formula, R 1 and R 2 and R independently refer to an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. As used herein, the term "polyether" refers to a group of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groups of the formula -(R 1 OR 2 O) a -(In the formula, R 1 and R 2 and "a" are independently 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.

[0055] As used herein, the term "halogen" refers to the halogens fluorine, chlorine, bromine and iodine.

[0056] As used herein, the term "heterocyclyl" refers to monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems containing up to 60 carbon atoms, wherein at least one ring member is other than carbon. The term "heterocyclyl" includes azetidine, dioxane, furan, imidazole, isothiazole, isoxazole, morpholine, oxazole, oxazoles (e.g., 1,2,3-oxadiazole, 1,2,5-oxadiazole, and 1,3,4-oxadiazole), piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine (e.g., tetrazine ... , 1,2,4,5-tetrazine), tetrazole (e.g., 1,2,3,4-tetrazole and 1,2,4,5 tetrazole), thiadiazole (e.g., 1,2,3-thiadiazole, 1,2,5-thiadiazole and 1,3,4-thiadiazole), thiazole, thiophene, triazine (e.g., 1,3,5-triazine and 1,2,4-triazine), triazole (e.g., 1,2,3-triazole, 1,3,4-triazole), and the like.

[0057] As used herein, the term "hydroxy group" is represented by the formula --OH.

[0058] As used herein, the term “ketone” refers to a compound of formula R 1 C(O)R 2 (In the formula, R 1 and R 2 and R 1 and R 2 are each independently represented by an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

[0059] The term "azide" as used herein is represented by the formula -N3.

[0060] The term "nitro" as used herein is represented by the formula --NO.sub.2.

[0061] The term "nitrile" as used herein is represented by the formula --CN.

[0062] As used herein, the term "silyl" refers to a group of the formula -SiR 1 R 2 R 3 (In the formula, R 1 , R 2 and R 3 are represented by (which may be independently hydrogen, or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein).

[0063] As used herein, the term "sulfo-oxo" refers to a group of the formula -S(O)R 1 , -S(O)2R 1 , -OS(O)2R 1 or -OS(O)2OR 1 (In the formula, R 1 is represented by a group represented by the formula -S(O)R, which may be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout this specification, "S(O)" is a shorthand notation for S=O. As used herein, the term "sulfonyl" refers to a group of the formula -S(O)R 1 (In the formula, R 1 refers to a sulfo-oxo group represented by the formula R 1 S(O)2R 2 (In the formula, R 1 and R 2and R may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. As used herein, the term "sulfoxide" refers to a group of the formula R 1 S(O)R 2 (In the formula, R 1 and R 2 and R are independently represented by R, ...

[0064] The term "mercapto" as used herein is represented by the formula --SH.

[0065] As used herein, "R 1 "," "R 2 "," "R 3 "," "R n " (where n is an integer) may independently contain one or more groups listed above. For example, R 1 When is a straight-chain alkyl group, one of the hydrogen atoms of the alkyl group may optionally be replaced by a hydroxyl group, an alkoxy group, an alkyl group, a halogen, or the like. Depending on the group selected, the first group may be incorporated into the second group, or the first group may be pendant (i.e., attached) to the second group. For example, in the phrase "an alkyl group comprising an amino group," the amino group may be attached within the backbone of the alkyl group. Optionally, the amino group may be attached to the backbone of the alkyl group. The nature of the group selected will determine whether the first group is incorporated into or attached to the second group.

[0066] The compounds of the present invention may contain "optionally substituted" moieties. In general, the term "substituted," whether preceded by the term "optionally," means that one or more hydrogen atoms of the specified moiety have been replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group can have a suitable substituent at each substitutable position of the group, and when one or more positions in any given structure are substitutable with one or more substituents selected from a specified group, the substituents may be the same or different at all positions. Combinations of substituents envisioned by the present invention are preferably those that result in the formation of stable or chemically feasible compounds. Furthermore, in certain embodiments, it is contemplated that individual substituents may be optionally further substituted (i.e., further substituted or unsubstituted) unless clearly indicated to the contrary.

[0067] The structure of the compound can be represented by the following formula:

[0068] [ka]

[0069] This formula is understood to be the same as:

[0070] [ka] [wherein n is typically an integer, i.e., R n is a group consisting of five independent substituents R n(a) , R n(b) , R n(c) , R n(d) , R n(e) "Independent substituents" means that each R substituent can be defined independently. For example, in one example, R n(a) is a halogen, R n(b) is not necessarily a halogen in that example.

[0071] R 1 , R2 , R 3 , R 4 , R 5 , R 6 Multiple references to R, etc. are made in the chemical structures and moieties disclosed and described herein. 1 , R 2 , R 3 , R 4 , R 5 , R 6 Any statements about 1 , R 2 , R 3 , R 4 , R 5 , R 6 The present invention is applicable to any structure or part relating to the above.

[0072] As used herein, the term "fused ring" means that two adjacent substituents can be fused to form a 6-membered aromatic ring such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, an interdiazoheterocycle, a heteroaryl ring, a saturated 6- or 7-membered carbocyclic or heterocarbocyclic ring, and the like.

[0073] Unless otherwise noted, all commercially available reagents used in the following experiments were purchased and used without further purification. Both hydrogen and carbon spectra were measured in deuterated chloroform (CDCl) or deuterated dimethyl sulfoxide (DMSO-d) solutions. Hydrogen spectra were measured using a 400 or 500 MHz NMR spectrometer, while carbon spectra were measured using a 100 or 126 MHz NMR spectrometer. Chemical shifts were referenced to tetramethylsilane (TMS) or residual solvent. When CDCl was used as the solvent, TMS (δ = 0.00 ppm) and CDCl (δ = 77.00 ppm) were used as internal standards for hydrogen and carbon spectra, respectively. When DMSO-d was used as the solvent, TMS (δ = 0.00 ppm) and DMSO-d (δ = 39.52 ppm) were used as internal standards for hydrogen and carbon spectra, respectively. The following abbreviations (or combinations) are used to describe peaks in the hydrogen spectra: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad line. High-resolution mass spectra were measured on an Applied Biosystems ESI-QTOF mass spectrometer, and the ionization mode for the samples was electrospray ionization.

[0074] Example 1: Synthetic Route to Tetradentate Cyclometalated Platinum(II) Complex (S,R)-P-PtLA1 [ka]

[0075] (1) Synthesis of Intermediate 1-Br: m-Bromobenzonitrile (10 g, 54.94 mmol, 1.0 equiv.) and sodium methoxide (297 mg, 5.49 mmol, 0.1 equiv.) were sequentially added to a single-neck flask equipped with a magnetic stir bar, and the mixture was stirred at room temperature for 1 day. Acetic acid was added until no solid remained, and the solvent was removed under reduced pressure to obtain crude product A. (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol (4.10 g, 27.47 mmol, 0.5 equiv.) and absolute ethanol (30 mL) were added, and the mixture was stirred in an oil bath at 85 °C for 1.5 days. The mixture was then cooled to room temperature and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 50:1 to 10:1) to obtain product 1-Br as a white solid (5.60 g, 65% yield). 1 H NMR (500MHz, CDCl3): δ3.40(d,J=18.0Hz,1H),3.51-3.56(m,1H),5.57(t,J=7.5Hz,1H),7.79(d, J=8.0Hz,1H),7.26-7.31(m,4H),7.59-7.63(m,2H),7.96(d,J=8.0Hz,1H),8.12(t,J=2.0Hz,1H).

[0076] (2) Synthesis of Intermediate 4-OH: Chiral bromine (1.5 g, 4.77 mmol, 1.0 equiv.), cuprous chloride (24 mg, 0.24 mmol, 5 mol%), Ligand 1 (87 mg, 0.24 mmol, 5 mol%), and sodium tert-butoxide (917 mg, 9.55 mmol, 2.0 equiv.) were sequentially added to a dry, sealed tube equipped with a magnetic stir bar. After three nitrogen purges, dimethyl sulfoxide (8 mL) and deionized water (2 mL) were added under nitrogen protection. The sealed tube was placed in an oil bath at 110 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water, adjusted to neutral or slightly acidic with dilute hydrochloric acid, made slightly alkaline with sodium bicarbonate, extracted with ethyl acetate, and the aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product 4-OH as a brown solid (934 mg, yield 78%). 1 H NMR(500MHz,DMSO-d6):δ3.22(d,J=18.0Hz,1H),3.46-3.51(m,1H),5.47-5.50(m,1H),5. 68(d,J=8.0Hz,1H),6.87-6.90(m,1H),7.21-7.3(m,6H),7.43-7.44(m,1H),9.67(s,1H).

[0077] (3) Synthesis of intermediate chiral 2-Br: m-Bromobenzonitrile (10 g, 54.94 mmol, 1.0 equiv.) and sodium methoxide (297 mg, 5.49 mmol, 0.1 equiv.) were sequentially added to a single-neck flask equipped with a magnetic stir bar and stirred at room temperature for 1 day. Acetic acid was added until no solid remained, and the solvent was evaporated under reduced pressure to give crude product A. (1R,2S)-1-amino-2,3-dihydro-1H-inden-2-ol (3.28 g, 21.97 mmol, 0.4 equiv.) and absolute ethanol (30 mL) were added. The mixture was stirred in an oil bath at 85 °C for 1.5 days, then cooled to room temperature and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 50:1 to 10:1) to give product 2-Br as a white solid (5.74 g, 83% yield). 1 H NMR (500MHz, CDCl3): δ3.41(d,J=18.5Hz,1H),3.52-3.57(m,1H),5.59(s,1H),5.81(d ,J=3.0Hz,1H),7.27-7.31(m,4H),7.60-7.65(m,2H),7.98-8.00(m,1H),8.13(s,1H).

[0078] (4) Synthesis of Ligand (S,R)-LA1: 1-Br (579 mg, 1.84 mmol, 1.2 equiv.), 1-OH (400 mg, 1.54 mmol, 1.0 equiv.), cuprous iodide (29 mg, 0.15 mmol, 10 mol%), Ligand 2 (50 mg, 0.15 mmol, 10 mol%), and potassium phosphate (654 mg, 3.08 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After three nitrogen purges, dimethyl sulfoxide (10 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 90 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 533 mg (yield 70%) of the ligand (S,R)-LA1 as a white solid. 1 HNMR(500MHz,DMSO-d6):δ3.19(d,J=17.5Hz,1H),3.42-3.47(m,1H),5.46-5.49(m,1 H),5.65(d,J=7.5Hz,1H),7.03(dd,J=8.5,2.5Hz,1H),7.19-7.28(m,4H),7.35-7.40( m,3H),7.42-7.47(m,3H),7.50(d,J=2.0Hz,1H),7.57-7.59(m,1H),7.76-7.79(m,2H ),8.04-8.07(m,1H),8.23(d,J=7.5Hz,1H),8.27(d,J=8.0Hz,1H),8.65-8.66(m,1H).

[0079] (5) Synthesis of (S,R)-P-PtLA1: (S,R)-LA1 (150 mg, 0.30 mmol, 1.0 equiv.), potassium chloroplatinate (132 mg, 0.32 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (10 mg, 0.030 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (25 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then stirred at 100 °C for 2 days. The mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (114 mg, 0.6 mmol, 2.0 equiv.) and dichloromethane (30 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product (S,R)-P-PtLA1 as a pale yellow solid (126 mg, 60% yield). 1 H NMR(500MHz,DMSO-d6):δ3.49(d,J=18.5Hz,1H),3.62-3.67(m,1H),6.05(t,J=7.5Hz,1H),6.26(d ,J=7.5Hz,1H),7.01(d,J=7.5Hz,1H),7.10(t,J=7.5Hz,1H),7.12-7.18(m,3H),7.20-7.24(m,2H) ,7.35(d,J=7.5Hz,1H),7.41-7.44(m,2H),7.48-7.52(m,1H),7.88(d,J=8.0Hz,1H),8.15-8.17(m ,1H),8.20(d,J=8.5Hz,1H),8.26-8.29(m,1H),8.36(d,J=8.5Hz,1H),9.57(dd,J=6.0,1.5Hz,1H).

[0080] Example 2: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-M-PtLA1 [ka]

[0081] (1) Synthesis of Ligand (R,S)-LA1: 2-Br (53.19 g, 10.14 mmol, 1.2 equiv.), 1-OH (2.20 g, 8.45 mmol, 1.0 equiv.), cuprous iodide (29 mg, 0.84 mmol, 10 mol%), Ligand 2 (276 mg, 0.84 mmol, 10 mol%), and potassium phosphate (3.59 g, 16.90 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (40 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 100 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 2.12 g (yield 51%) of the ligand (R,S)-LA1 as a white solid. 1 H NMR(500MHz,DMSO-d6):δ3.19(d,J=18.0Hz,1H),3.42-3.47(m,1H),5.46-5.49(m,1H ),5.65(d,J=7.5Hz,1H),7.03(dd,J=7.5,2.0Hz,1H),7.19-7.28(m,4H),7.34-7.40( m,3H),7.43-7.48(m,3H),7.50(d,J=2.0Hz,1H),7.57-7.59(m,1H),7.77-7.79(m,2H ),8.04-8.08(m,1H),8.24(d,J=8.0Hz,1H),8.28(d,J=8.5Hz,1H),8.65-8.67(m,1H).

[0082] (2) Synthesis of (R,S)-M-PtLA1: (R,S)-LA1 (900 mg, 1.82 mmol, 1.0 equiv.), potassium chloroplatinate (795 mg, 1.92 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (59 mg, 0.182 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (110 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 100 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane=1:1) to obtain the product (R,S)-M-PtLA1 as a pale yellow solid (1.01 g, 81% yield). 1 H NMR(500MHz,DMSO-d6):δ3.49(d,J=18.0Hz,1H),3.62-3.67(m,1H),6.04(t,J=7.0Hz,1H),6.2 7(d,J=7.0Hz,1H),7.01(d,J=8.0Hz,1H),7.10(t,J=7.0Hz,1H),7.12-7.18(m,3H),7.21-7.24 (m,2H),7.35(d,J=7.0Hz,1H),7.41-7.44(m,2H),7.48-7.52(m,1H),7.88(d,J=8.5Hz,1H),8. 16-8.18(m,1H),8.20(d,J=8.5Hz,1H),8.26-8.30(m,1H),8.37(d,J=8.5Hz,1H),9.57(m,1H).

[0083] Example 3: Synthesis of tetradentate cyclometallated platinum(II) complex (S,R)-P-PtLA2 [ka]

[0084] (1) Synthesis of Ligand (S,R)-LA2: To a dry, sealed tube equipped with a magnetic stir bar, 1-Br (1.82 g, 5.80 mmol, 1.2 equiv.), 2-OH (1.50 g, 4.83 mmol, 1.0 equiv.), cuprous iodide (91 mg, 0.48 mmol, 10 mol%), Ligand 2 (157 mg, 0.48 mmol, 10 mol%), and potassium phosphate (2.05 g, 9.05 mmol, 2.0 equiv.) were sequentially added. After purging with nitrogen three times, dimethyl sulfoxide (30 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 100 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 20:1 to 5:1) to obtain the ligand (S,R)-LA2 as a brown solid (1.63 g, yield 62%). 1 H NMR (600MHz, CDCl3): δ3.45(d,J=18.6Hz,1H),3.53-3.56(m,1H),5.66-5.69(m,1H ),5.88(s,1H),7.01(dd,J=8.4,1.8Hz,1H),7.24-7.31(m,6H),7.35-7.40(m,2H), 7.44-7.47(m,1H),7.56-7.59(m,1H),7.63(t,J=1.8Hz,1H),7.70(d,8.4Hz,1H),7 .73-7.75(m,1H),7.77(d,J=8.0Hz,1H),7.87-7.88(m,1H),7.97(d,J=8.4Hz,1H). 8.07(d,J=8.4Hz,1H),8.08-8.10(m,2H),8.32(d,J=8.0Hz,1H).

[0085] (2) Synthesis of (S,R)-P-PtLA2: (S,R)-LA2 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (161 mg, 0.39 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (22 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 120 °C for 2 days. The mixture was then cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (30 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product (S,R)-P-PtLA2 as a pale yellow solid (101 mg, 37% yield). 1 H NMR(600MHz,DMSO-d6):δ3.47(d,J=18.0Hz,1H),3.49-3.51(m,1H),5.12(d,J=7.8Hz,1H),5.32(d,J=4.8Hz,1H),5.93-5.95(m,1H),6 .05(d,J=8.4Hz,1H),6.93(d,J=7.2Hz,1H),7.10(t,J=7.2Hz,1H),7.15(t,J=8.4Hz,1H),7.17-7.18(m,1H),7.21(d,J=7.2Hz,1H),7. 23-7.25(m,1H),7.45(t,J=7.8Hz,1H),7.53-7.56(m,1H),7.66-7.69(m,1H),7.78(d,J=8.4Hz,1H),8.04-8.06(m,1H),8.13(dd,J=7. 8,1.2Hz,1H),8.18(dd,J=7.8,1.2Hz,1H),8.36(d,J=7.8Hz,1H),8.66(d,J=9.0Hz,1H),8.82(d,J=9.0Hz,1H),9.40(d,J=8.4Hz,1H).

[0086] Example 4: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-M-PtLA2 [ka]

[0087] (1) Synthesis of Ligand (R,S)-LA2: To a dry, sealed tube equipped with a magnetic stir bar, 2-Br (1.38 g, 4.40 mmol, 1.2 equiv.), 2-OH (1.14 g, 3.67 mmol, 1.0 equiv.), cuprous iodide (70 mg, 0.37 mmol, 10 mol%), Ligand 2 (121 mg, 0.37 mmol, 10 mol%), and potassium phosphate (1.56 g, 7.34 mmol, 2.0 equiv.) were sequentially added. After purging with nitrogen three times, dimethyl sulfoxide (20 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 90 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the ligand (R,S)-LA2 as a white solid (1.23 g, yield 62%). 1 H NMR(500MHz,CDCl3):δ3.44(d,J=18.0Hz,1H),3.53-3.58(m,1H),5.66-5.70(m,1H), 5.85-5.88(m,1H),7.01(dd,J=8.0,2.0Hz,1H),7.24-7.31(m,6H),7.35-7.47(m,3H), 7.56-7.59(m,1H),7.62(t,J=2.0Hz,1H),7.70(d,J=2.0Hz,1H),7.72-7.78(m,2H),7 .88(d,J=7.5Hz,1H),7.96(d,J=8.0Hz,1H),8.06-8.10(m,3H),8.31(d,J=8.5Hz,1H).

[0088] (2) Synthesis of (R,S)-M-PtLA2: (R,S)-LA2 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (161 mg, 0.39 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (22 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 110 °C for 2 days. The mixture was then cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (30 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product (R,S)-M-PtLA2 as a pale yellow solid (119 mg, 44% yield). 1 H NMR(500MHz,DMSO-d6):δ3.29-3.34(m,1H),3.45-3.50(m,1H),5.12(d,J=7.5Hz,1H),5.94(d,J=7.0Hz,1H),6.04(d,J =8.0Hz,1H),6.94(t,J=7.5Hz,1H),7.10(t,J=7.5Hz,1H),7.15(d,J=8.0Hz,1H),7.17-7.21(m,3H),7.23-7.25(m,1H) ,7.45(t,J=7.5Hz,1H),7.53-7.56(m,1H),7.68(t,J=7.0Hz,1H),7.78(d,J=8.0Hz,1H),8.04-8.07(m,1H),8.12-8.14 (m,1H),8.17-8.19(m,1H),8.36(d,J=8.0Hz,1H),8.66(d,J=9.5Hz,1H),8.82(d,J=9.5Hz,1H),9.40(d,J=8.5Hz,1H).

[0089] Example 5: Synthesis of tetradentate cyclometallated platinum(II) complex (S,R)-P-PtLA [ka]

[0090] (1) Synthesis of Ligand (S,R)-LA3: To a dry, sealed tube equipped with a magnetic stir bar, 1-Br (477 mg, 1.52 mmol, 1.2 equiv.), 3-OH (400 mg, 1.54 mmol, 1.0 equiv.), cuprous iodide (25 mg, 0.13 mmol, 10 mol%), Ligand 2 (43 mg, 0.13 mmol, 10 mol%), and potassium phosphate (539 mg, 2.54 mmol, 2.0 equiv.) were sequentially added. After three nitrogen purges, dimethyl sulfoxide (10 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 100 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane / ethyl acetate=5:1:1) to obtain 412 mg (yield 59%) of the ligand (S,R)-LA3 as a brown solid. 1 H NMR (500MHz, CDCl3): δ1.83-1.94(m,4H),2.82(t,J=6.0Hz,2H),2.94(d,J=6.5Hz,2H),3.31-3. 35(d,J=17.5Hz,1H),3.44-3.49(m,1H),5.43-5.46(m,1H),5.71(d,J=8.0Hz,1H),6.96(dd,J=8 .5,2.5Hz,1H),7.11-7.14(m,1H),7.24-7.27(m,7H),7.28-7.30(m,2H),7.32(d,J=8.0Hz,1H), 7.37-7.41(dd,J=3.0,1.5Hz,1H),7.65-7.67(m,1H),7.77(d,J=6.0Hz,1H),8.02-8.06(m,2H).

[0091] (2) Synthesis of (S,R)-P-PtLA3: (S,R)-LA3 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (161 mg, 0.39 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (22 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 120 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1-1:2) to obtain the product (S,R)-P-PtLA3 as a pale yellow solid (134 mg, 49% yield). 1 H NMR (400MHz, CDCl3): δ1.83-1.91(m,2H),2.85-2.92(m,4H),2.94(d,J=6.5H z,2H),3.41-3.46(d,J=19.6Hz,1H),3.53-3.59(m,1H),5.61(d,J=7.6Hz,1H ),5.65-5.69(m,1H),6.96-7.00(m,1H),7.08-7.17(m,2H),7.15-7.31(m,6H ),7.36-7.40(m,2H),7.57-7.62(m1H),7.91-7.96(m,2H),8.11-8.13(m,1H).

[0092] Example 6: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-M-PtLA [ka]

[0093] (1) Synthesis of Ligand (R,S)-LA3: 2-Br (477 mg, 1.52 mmol, 1.2 equiv.), 3-OH (400 mg, 1.54 mmol, 1.0 equiv.), cuprous iodide (25 mg, 0.13 mmol, 10 mol%), Ligand 2 (43 mg, 0.13 mmol, 10 mol%), and potassium phosphate (539 mg, 2.54 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (10 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 100 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane / ethyl acetate = 5:1:1) to obtain 392 mg (yield 56%) of the ligand (R,S)-LA3 as a brown solid. 1 H NMR(500MHz, CDCl3): δ1.86-1.93(m,4H),2.84(t,J=7.5Hz,2H),2.94(d,J=6.5Hz ,2H),3.41(d,J=18.0Hz,1H),3.49-3.55(m,1H),5.61-5.66(m,1H),5.77-5.82(m ,1H),6.94-6.96(m,1H),7.24-7.27(m,7H),7.28-7.31(m,2H),7.37-7.42(m,2H) ,7.52-7.55(m,1H),7.56-7.58(m,1H),7.73(d,J=8.5Hz,1H),8.03-8.06(m,2H).

[0094] (2) Synthesis of (R,S)-PtLA3: (R,S)-LA3 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (161 mg, 0.39 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (22 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 120 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1 to 1:2) to obtain the product (R,S)-PtLA3 as a pale yellow solid (128 mg, 47% yield). δ 1.88-1.93 (m, 4H), 2.84-2.94 (m, 4H), 3.55 (d, J = 18.0 Hz, 1H), 3.56-3.61 (m, 1H), 5.62 (d, J = 7.5 Hz, 1H), 5.85-5.88 (m, 1H), 6.68 (d, J = 7.5 Hz, 1H), 6.99-7.01 (m, 1H), 7. .01-7.13(m,1H),7.18-7.24(m,5H),7.31-7.35(m,1H),7.37-7.41(m,1H),7.60(d, J=8.0Hz,1H),7.68(d,J=8.0Hz,1H),7.93-7.98(m,2H),8.13-8.14(d,J=8.5Hz,1H).

[0095] Example 7: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtLC1 [ka]

[0096] Synthesis of P-LC1: LC-OH (500 mg, 1.99 mmol, 1.0 equiv.), 1-Br (873 mg, 2.39 mmol, 1.2 equiv.), cuprous iodide (76 mg, 0.40 mmol, 20 mol%), Ligand 2 (138 mg, 0.40 mmol, 20 mol%), and potassium phosphate (845 mg, 3.98 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. The flask was purged with nitrogen three times, and then dimethyl sulfoxide (10 mL) was added. The flask was placed in an oil bath at 90 °C and reacted for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product as a white solid (758 mg, 71% yield). 1 H NMR(500MHz,DMSO-d6):δ(ppm)1.61(s,6H),3.23(d,J=18.0Hz,1H),3.48(dd,J=18.0Hz,7.0Hz,1H),5 .49-5.52(m,1H),5.68(d,J=8.0Hz,1H),6.05(d,J=2.5Hz,1H),6.36(dd,J=8.0,1.5Hz,1H),6.59(dd, J=7.5,2.5Hz,1H),6.98-7.05(m,2H),7.11(ddd,J=7.5,2.5,1.0Hz,1H),7.22-7.31(m,4H),7.35-7.4 4(m,4H),7.49-7.53(m,2H),7.55-7.57(m,1H),7.89-7.92(m,1H),8.58(ddd,J=7.5,2.0,1.0Hz,1H).

[0097] Synthesis of P-PtLC1: P-LC1 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120 °C and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator, stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added, and the mixture was stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 8:1 to 1:1) to obtain the product as a pale yellow solid, 172 m (yield 64%). 1 H NMR(500MHz,CDCl3):δ(ppm)1.34(s,3H),1.91(s,3H),3.55(s,2H),5.79-5.84(m,2H),6.76(d,J=7.5Hz,1H),6.90-6.93(m,1H),7.01(d,J= 8.5Hz,1H),7.05-7.15(m,4H),7.16-7.26(m,6H),7.37(d,J=8.5Hz,1H),7.47-7.49(m,1H),7.67-7.71(m,1H),9.11(dd,J=5.5,2.0Hz,1H).

[0098] Example 8: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtLC1 [ka]

[0099] Synthesis of M-LC1: LC-OH (550 mg, 2.19 mmol, 1.0 equiv.), 2-Br (961 mg, 2.63 mmol, 1.2 equiv.), cuprous iodide (84 mg, 0.44 mmol, 20 mol%), Ligand 2 (145 mg, 0.44 mmol, 20 mol%), and potassium phosphate (930 mg, 4.38 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. The flask was purged with nitrogen three times, and then dimethyl sulfoxide (10 mL) was added. The flask was placed in an oil bath at 90°C and reacted for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product as a white solid (525 mg, 45% yield). 1 H NMR (500 MHz, CDCl 3) :δ(ppm)1.66(s,6H),3.35(d,J=18.0Hz,1H),3.48(dd,J=18.0Hz,7.0Hz,1H),5.44-5.47(m,1H ),5.72(d,J=7.5Hz,1H),6.30(d,J=2.5Hz,1H),6.54-6.58(m,2H),6.99-7.06(m,3H),7.20(dd d,J=7.5,5.0,1.0Hz,1H),7.25-7.30(m,5H),7.36(d,J=8.5Hz,1H),7.47(dd,J=7.5,2.0Hz,1H ),7.52-7.56(m,2H),7.62-7.64(m,1H),7.71-7.74(m,1H),8.62(ddd,J=5.0,2.0,1.0Hz,1H).

[0100] Synthesis of M-PtLC1: M-LC1 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, acetic acid (22 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator, stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added, and the mixture was stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 8:1 to 1:1) to obtain the product as a pale yellow solid, 132 m (yield 49%). 1 H NMR(500MHz,CDCl3):δ(ppm)1.34(s,3H),1.91(s,3H),3.55(s,2H),5.77-5.82(m,2H),6.75(d,J=7.5Hz,1H),6.87-6.90(m,1H),7.02(d,J= 8.5Hz,1H),7.05-7.15(m,4H),7.18-7.25(m,6H),7.36(d,J=8.5Hz,1H),7.47-7.49(m,1H),7.66-7.69(m,1H),9.12(dd,J=5.5,1.5Hz,1H).

[0101] Example 9: Synthesis of tetradentate cyclometallated platinum(II) complex (S,R)-P-PtLAN [ka]

[0102] (1) Synthesis of the (S,R)-LAN ligand: 1-Br (528 mg, 1.68 mmol, 1.2 equiv.), 1-NH (548 mg, 1.40 mmol, 1.0 equiv.), tris(dibenzylideneacetone)dipalladium (39 mg, 0.042 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (13 mg, 0.032 mmol, 8 mol%), and sodium tert-butoxide (404 mg, 4.2 mmol, 3.0 equiv.) were sequentially added to a reaction tube equipped with a magnetic stir bar. After purging with nitrogen three times, toluene (10 mL) was added under nitrogen protection. The reaction mixture was then stirred in an oil bath at 110 °C for 25 h, cooled to room temperature, and the solvent was evaporated under reduced pressure to obtain the crude product. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate volume ratio 6:1 to 2:1) to obtain the product (S,R)-P-LAN as a foamy solid (599 mg, yield 68%). 1 H NMR (400MHz, DMSO-d6): δ1.27(s,9H),3.13-3.18(m,1H),3.44-3.45(m,1H),5.44(t,J=6. 0Hz,1H),5.62(d,J=7.6Hz,1H),6.95(d,J=7.6Hz,1H),7.00(d,J=7.6Hz,2H),7.10(d,J=7. 6Hz,1H),7.19-7.25(m,3H),7.29-7.38(m,7H),7.41-7.43(m,2H),7.51(s,1H),7.62(d,J =8.0Hz,1H),7.74(d,J=8.0Hz,1H),7.90(t,J=8.0Hz,1H),8.13-8.15(m,2H),8.55(s,1H).

[0103] (2) Synthesis of (S,R)-P-PtLAN: (S,R)-P-LAN (187 mg, 0.30 mmol, 1.0 equiv.) and platinum dichloride (84 mg, 0.315 mmol, 1.05 equiv.) were sequentially added to a three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, benzonitrile (18 mL) was added under nitrogen protection. The reaction mixture was then stirred in an oil bath at 180 °C for 18 h, cooled to room temperature, and the solvent was evaporated under reduced pressure to obtain the crude product. The resulting crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane in a volume ratio of 4:1 to 2:1) to obtain the product (S,R)-P-PtLAN as a red solid (91 mg, 37% yield). 1 H NMR (400MHz, DMSO-d6): δ1.39(s,9H),3.49(s,1H),3.60-3.67(m,1H),5.99(t,J=6.8Hz,1H),6.19( d,J=7.2Hz,1H),6.26(d,J=8.0Hz,1H),6.32(d,J=8.8Hz,1H),6.88-6.94(m,2H),7.00(d,J=7.2Hz, 1H),7.08(t,J=7.6Hz,1H),7.16-7.23(m,3H),7.33-7.46(m,4H),7.57(d,J=8.8Hz,1H),7.69(d,J= 8.0Hz,2H),7.99(d,J=7.6Hz,1H),8.15(d,J=8.4Hz,1H),8.22-8.30(m,2H),9.55(d,J=5.2Hz,1H).

[0104] Example 10: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-M-PtLAN [ka]

[0105] (1) Synthesis of the (R,S)-LAN ligand: 1-Br (528 mg, 1.68 mmol, 1.2 equiv.), 1-NH (548 mg, 1.40 mmol, 1.0 equiv.), tris(dibenzylideneacetone)dipalladium (39 mg, 0.042 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (13 mg, 0.032 mmol, 8 mol%), and sodium tert-butoxide (404 mg, 4.2 mmol, 3.0 equiv.) were sequentially added to a reaction tube equipped with a magnetic stir bar. After purging with nitrogen three times, toluene (10 mL) was added under nitrogen protection. The reaction mixture was then stirred in an oil bath at 110 °C for 25 h, cooled to room temperature, and the solvent was evaporated under reduced pressure to obtain the crude product. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate volume ratio 6:1 to 2:1) to obtain the product (R,S)-LAN as a foamy solid (608 mg, yield 69%). 1 H NMR(400MHz,DMSO-d6):δ1.27(s,9H),3.14-3.18(m,1H),3.44-3.46(m,1H),5.44(t,J=7.2H) z,1H),5.62(d,J=7.6Hz,1H),6.95(d,J=8.4Hz,1H),7.00(d,J=7.6Hz,2H),7.10(d,J=8.4Hz, 1H),7.18-7.27(m,3H),7.29-7.38(m,7H),7.41-7.44(m,2H),7.51(s,1H),7.62(d,J=8.0Hz ,1H),7.74(d,J=8.4Hz,1H),7.91(t,J=8.0Hz,1H),8.13-8.15(m,2H),8.56(d,J=4.8Hz,1H).

[0106] (2) Synthesis of (R,S)-M-PtLAN: (R,S)-M-LAN (250 mg, 0.40 mmol, 1.0 equiv.) and platinum dichloride (112 mg, 0.42 mmol, 1.05 equiv.) were sequentially added to a three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, benzonitrile (20 mL) was added under nitrogen protection. The reaction mixture was then stirred in an oil bath at 180 °C for 18 h, cooled to room temperature, and the solvent was evaporated under reduced pressure to obtain the crude product. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane in a volume ratio of 4:1 to 2:1) to obtain the product (R,S)-M-PtLAN as a red solid (127 mg, 39% yield). 1 H NMR (400MHz, DMSO-d6): δ1.39(s,9H),3.49(s,1H),3.60-3.67(m,1H),5.99(t,J=6.8Hz,1H),6.19( d,J=7.2Hz,1H),6.26(d,J=8.0Hz,1H),6.32(d,J=8.8Hz,1H),6.88-6.94(m,2H),7.00(d,J=7.2Hz, 1H),7.08(t,J=7.6Hz,1H),7.16-7.23(m,3H),7.33-7.46(m,4H),7.57(d,J=8.8Hz,1H),7.69(d,J= 8.0Hz,2H),7.99(d,J=7.6Hz,1H),8.15(d,J=8.4Hz,1H),8.22-8.30(m,2H),9.55(d,J=5.2Hz,1H).

[0107] Example 11: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-M-PtLH1 [ka]

[0108] (1) Synthesis of the ligand (R,S)-LH1: To a dry, sealed tube equipped with a magnetic stir bar, ACzCzH (200 mg, 0.6 mmol, 1.0 equiv.), 2-Br (245 mg, 0.78 mmol, 1.3 equiv.), tris(dibenzylideneacetone)dipalladium (22 mg, 0.024 mmol, 4 mol%), 2-(di-tert-butylphosphine)biphenyl (14 mg, 0.048 mmol, 8 mol%), and sodium tert-butoxide (115 mg, 1.2 mmol, 2.0 equiv.) were added. The mixture was purged with nitrogen three times, and then toluene (12 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (R,S)-LH1 as a white solid (214 mg, yield 63%). 1 H NMR(500MHz,DMSO-d6):δ3.21-3.24(m,1H),3.47-3.55(m,1H),5.53-5.56(m,1H),5.72(d ,J=8.5Hz,1H),7.20-7.29(m,3H),7.31-7.43(m,5H),7.47-7.54(m,3H),7.57-7.59(m,2H) ,7.72(t,J=7.5Hz,1H),7.87-7.89(m,1H),7.95(d,J=9.0Hz,1H),8.07(t,J=2.5Hz,1H),8. 30(d,J=8.5Hz,1H),8.37-8.38(m,2H),8.51(d,J=9.0Hz,1H),8.64(dd,J=8.0,1.5Hz,1H).

[0109] (2) Synthesis of (R,S)-M-PtLH1: The ligand (R,S)-LH1 (212 mg, 0.37 mmol, 1.0 equiv.) and platinum dichloride (104 mg, 0.39 mmol, 1.05 equiv.) were sequentially added to a dry three-neck flask equipped with a magnetic stir bar. After three nitrogen purges, benzonitrile (15 mL) was added under nitrogen protection. The mixture was stirred in a heating mantle at 180 °C for 3 days, then cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 2:1) to obtain the product (R,S)-M-PtLH1 as a yellow solid (207 mg, 74% yield). 1 H NMR(500MHz,DMSO-d6):δ3.51-3.61(m,2H),5.73-5.76(m,1H),5.98(t,J=6.0Hz,1H),6.22(d,J=7.0Hz,1H),6.72( t,J=7.5Hz,1H),7.11(t,J=7.5Hz,1H),7.27-7.29(m,1H),7.31-7.34(m,3H),7.47-7.51(m,1H),7.57(t,J=7.5Hz, 1H),7.63(dd,J=7.5,5.5Hz,1H),7.74-7.77(m,1H),7.85(d,J=8.5Hz,1H),8.05(d,J=8.5Hz,1H),8.18-8.20(m,1H) ),8.25-8.26(m,2H),8.32(d,J=8.5Hz,1H),8.54(d,J=7.5Hz,1H),9.11(dd,J=7.5,1.0Hz,1H),9.47-9.48(m,1H).

[0110] Example 12: Synthesis of tetradentate cyclometallated platinum(II) complex (S,R)-P-PtLH1 [ka]

[0111] (1) Synthesis of the ligand (S,R)-LH1: To a dry, sealed tube equipped with a magnetic stir bar, ACzCzH (200 mg, 0.6 mmol, 1.0 equiv.), 1-Br (245 mg, 0.78 mmol, 1.3 equiv.), tris(dibenzylideneacetone)dipalladium (22 mg, 0.024 mmol, 4 mol%), 2-(di-tert-butylphosphine)biphenyl (14 mg, 0.048 mmol, 8 mol%), and sodium tert-butoxide (115 mg, 1.2 mmol, 2.0 equiv.) were added. The mixture was purged with nitrogen three times, and then toluene (12 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (S,R)-LH1 as a white solid (203 mg, yield 60%). 1 H NMR(500MHz,DMSO-d6):δ3.21-3.24(m,1H),3.46-3.51(m,1H),5.52-5.55(m,1H),5.72(d ,J=7.5Hz,1H),7.20-7.29(m,3H),7.31-7.42(m,5H),7.47-7.53(m,3H),7.57-7.58(m,2H) ,7.72(t,J=7.5Hz,1H),7.87-7.8(m,1H),7.95(d,J=8.0Hz,1H),8.07(t,J=1.5Hz,1H),8. 29(d,J=7.5Hz,1H),8.36-8.38(m,2H),8.51(d,J=8.5Hz,1H),8.63(dd,J=8.0,2.0Hz,1H).

[0112] (2) Synthesis of (S,R)-P-PtLH1: The ligand (S,R)-LH1 (120 mg, 0.21 mmol, 1.0 equiv.) and platinum dichloride (71 mg, 0.27 mmol, 1.05 equiv.) were sequentially added to a dry three-neck flask equipped with a magnetic stir bar. After three nitrogen purges, benzonitrile (15 mL) was added under nitrogen protection. The mixture was stirred in a heating mantle at 180 °C for 3 days, then cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 2:1) to obtain the product (S,R)-P-PtLH1 as a yellow solid (83 mg, 52% yield). 1 H NMR(500MHz,DMSO-d6):δ3.51-3.61(m,2H),5.74(d,J=8.0Hz,1H),5.98(t,J=5.5Hz,1H),6.22(d,J=6.5Hz,1H),6.7 2(t,J=8.0Hz,1H),7.11(t,J=8.0Hz,1H),7.27-7.29(m,1H),7.31-7.34(m,3H),7.47-7.51(m,1H),7.58(t,J=7.5Hz, 1H),7.64(dd,J=7.5,5.5Hz,1H),7.74-7.78(m,1H),7.85(d,J=8.0Hz,1H),8.05(d,J=8.5Hz,1H),8.19(d,J=7.5Hz, 1H),8.25-8.26(m,2H),8.32(d,J=8.5Hz,1H),8.54(d,J=7.5Hz,1H),9.12(dd,J=7.5,1.0Hz,1H),9.47-9.48(m,1H).

[0113] Example 13: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtLIII-1 [ka]

[0114] (1) Synthesis of Ligand LIII-1: To a dry, sealed tube equipped with a magnetic stir bar, 1-Br (750 mg, 2.39 mmol, 1.5 equiv.), 4-OH (400 mg, 1.59 mmol, 1.0 equiv.), cuprous iodide (37 mg, 0.20 mmol, 10 mol%), Ligand 1 (65 mg, 0.20 mmol, 10 mol%), and potassium phosphate (832 mg, 3.92 mmol, 2.0 equiv.) were sequentially added. After three nitrogen purges, dimethyl sulfoxide (15 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 90 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate=10:1 to 5:1) to obtain the product, ligand LIII-1, as a white solid (431 mg, yield 56%). 1 H NMR(500MHz,DMSO-d6):δ3.22(d,J=18.5Hz,2H),3.45-3.50(m,2H),5.49-5.53(m,2H),5.69(d,J=7.5Hz, 2H),7.21-7.30(m,8H),7.38(s,2H),7.42(d,J=6.5Hz,2H),7.50(t,J=8.0Hz,2H),7.65(d,J=7.5Hz,2H).

[0115] (2) Synthesis of P-PtLIII-1: A dry 100 mL three-neck flask equipped with a magnetic stir bar and condenser was sequentially charged with L6 (200 mg, 0.41 mmol, 1.0 equiv.), potassium chloroplatinate (180 mg, 0.43 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 0.1 equiv.). After purging with nitrogen three times, acetic acid (25 mL) pre-purified with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then stirred at 100 °C for 2 days. The mixture was cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product P-PtLIII-1 as a pale yellow solid (104 mg, 36% yield). 1 H NMR(500MHz,DMSO-d6):δ3.63(d,J=18.5Hz,2H),3.67-3.72(m,2H),6.27-6.29(m,2H),6.35(d ,J=7.0Hz,2H),7.27-7.33(m,6H),7.34-7.38(m,2H),7.40-7.43(m,4H),7.87(d,J=8.0Hz,2H).

[0116] Example 14: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtLIII-1 [ka]

[0117] (1) Synthesis of M-LIII-1: 4-III-OH (500 mg, 1.99 mmol, 1.0 equiv.), 2-Br (751 mg, 2.39 mmol, 1.2 equiv.), cuprous iodide (152 mg, 0.80 mmol, 40 mol%), 2-picolinic acid (196 mg, 1.59 mmol, 80 mol%), and potassium phosphate (845 mg, 3.98 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (10 mL) was added, and the flask was placed in an oil bath at 110°C for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 30:1 to 10:1) to obtain the product as a white solid (353 mg, 37% yield). 1 H NMR (500MHz, CDCl3): δ(ppm)3.35(dd,J=17.5,1.5Hz,1H),3.48(dd,J=17.5,6.5Hz,1H),5.44-5.48(m,1H),5.72(d,J=8.0 Hz,1H),7.06(ddd,J=8.5,2.5,1.0Hz,1H),7.25-7.28(m,3H),7.32(d,J=8.0Hz,1H),7.53-7.56(m,2H),7.68-7.70(m,1H).

[0118] (2) Synthesis of M-PtLIII-1: M-LIII-1 (200 mg, 0.41 mmol, 1.0 equiv.), potassium chloroplatinate (178 mg, 0.43 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen replacement three times, acetic acid (25 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C, and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure using a rotary evaporator. Stannous chloride (155 mg, 0.82 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 4:1 to 1:1) to obtain the product as a pale yellow solid (83 mg, 30% yield). 1 H NMR(500MHz,CDCl3):δ(ppm)3.60(dd,J=18.0,5.0Hz,1H),3.65(d,J=18.0Hz,1H),5.87(d,J=7.0Hz,1H), 5.93-5.96(m,1H),7.07-7.13(m,2H),7.19(dd,J=7.0,2.0Hz,1H),7.29-7.34(m,3H),7.78-7.81(m,1H).

[0119] Example 15: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtLB1 [ka]

[0120] (1) Synthesis of P-LB1: LB-OH (500 mg, 1.92 mmol, 1.0 equiv.), 2-Br (723 mg, 2.30 mmol, 1.2 equiv.), cuprous iodide (36 mg, 0.19 mmol, 10 mol%), Ligand 2 (65 mg, 0.19 mmol, 10 mol%), and potassium phosphate (815 mg, 3.84 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (10 mL) was added, and the flask was placed in an oil bath at 90°C for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product as a white solid (678 mg, 60% yield). 1 H NMR(500MHz,CDCl3):δ(ppm)3.36(dd,J=18.0,1.5Hz1H),3.50(dd,J=18.0,7.0Hz,1H),5 .46-5.50(m,1H),5.74(d,J=8.0Hz,1H),7.06(ddd,J=8.0,2.5,1.0Hz,1H),7.21-7.24(m, 2H),7.26-7.27(m,3H),7.29-7.32(m,2H),7.35-7.45(m,3H),7.51-7.57(m,3H),7.70-7. 72(m,2H),8.10(d,J=7.5Hz,1H),8.37(dd,J=7.5,1.5Hz,1H),8.47(d,J=4.5,1.5Hz,1H).

[0121] (2) Synthesis of P-PtLB1: P-LB1 (200 mg, 0.41 mmol, 1.0 equivalent), potassium chloroplatinate (178 mg, 0.43 mmol, 1.05 equivalent), and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen replacement three times, acetic acid (25 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator. Stannous chloride (155 mg, 0.82 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 4:1 to 1:1) to obtain the product as a pale yellow solid (154 mg, 55% yield). P-PtLB1 1 H NMR(500MHz,DMSO-d6):δ(ppm)3.48(d,J=18.8Hz,1H),3.57(dd,J=18.4Hz,5.6Hz,1H),5.60(d,J=8.0Hz,1H) ,5.96(t,J=6.4Hz,1H),6.14(d,J=7.2Hz,1H),6.68(t,J=7.2Hz,1H),7.02(dd,J=7.6,0.8Hz,1H),7.07-7.19 (m,4H),7.23(t,J=8.0Hz,1H),7.30(d,J=7.6Hz,1H),7.52-7.57(m,2H),7.63(dd,J=7.6,5.6Hz,1H),7.69-7 .74(m,1H),8.19(d,J=8.4Hz,1H),8.51(d,J=7.6Hz,1H),9.08(dd,J=6.8,1.2Hz,1H),9.37(d,J=5.6Hz,1H).

[0122] Example 16: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtLB1 [ka]

[0123] (1) Synthesis of M-LB1: LB-OH (500 mg, 1.92 mmol, 1.0 equiv.), 2-Br (723 mg, 2.30 mmol, 1.2 equiv.), cuprous iodide (36 mg, 0.19 mmol, 10 mol%), Ligand 2 (65 mg, 0.19 mmol, 10 mol%), and potassium phosphate (815 mg, 3.84 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (10 mL) was added, and the flask was placed in an oil bath at 90°C for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product as a white solid (678 mg, 60% yield). 1 H NMR(500MHz,CDCl3):δ(ppm)3.36(d,J=18.0Hz1H),3.49(dd,J=18.0,7.0Hz,1H),5.46 -5.50(m,1H),5.74(d,J=8.0Hz,1H),7.06(dd,J=8.5,2.0Hz,1H),7.21-7.24(m,2H),7 .26-7.28(m,3H),7.29-7.33(m,2H),7.35-7.45(m,3H),7.51-7.57(m,3H),7.70-7.72 (m,2H),8.11(d,J=8.0Hz,1H),8.37(dd,J=7.5,1.5Hz,1H),8.47(d,J=5.0,1.5Hz,1H).

[0124] (2) Synthesis of M-PtLB1: P-LB1 (200 mg, 0.41 mmol, 1.0 equivalent), potassium chloroplatinate (178 mg, 0.43 mmol, 1.05 equivalent), and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, acetic acid (25 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C, and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure using a rotary evaporator. Stannous chloride (155 mg, 0.82 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 4:1 to 1:1) to obtain the product as a pale yellow solid (83 mg, 29% yield). 1 H NMR(500MHz,DMSO-d6):δ(ppm)3.47(d,J=18.0Hz,1H),3.57(dd,J=18.0Hz,5.5Hz,1H),5.60(d,J=8.0Hz,1H ),5.96(t,J=6.0Hz,1H),6.14(d,J=7.0Hz,1H),6.68(t,J=7.0Hz,1H),7.02(dd,J=8.0,1.5Hz,1H),7.07-7.1 8(m,4H),7.22(t,J=8.0Hz,1H),7.29(d,J=7.5Hz,1H),7.51-7.56(m,2H),7.62(dd,J=7.5,6.0Hz,1H),7.69- 7.72(m,1H),8.18(d,J=8.0Hz,1H),8.51(d,J=7.5Hz,1H),9.08(d,J=7.5,1.5Hz,1H),9.36(d,J=5.5Hz,1H).

[0125] Example 17: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtLD1 [ka]

[0126] (1) Synthesis of P-LD1: LD-OH (500 mg, 1.65 mmol, 1.0 equiv.), 1-Br (572 mg, 1.82 mmol, 1.1 equiv.), cuprous iodide (32 mg, 0.17 mmol, 10 mol%), ligand 2 (59 mg, 0.17 mmol, 10 mol%), and potassium phosphate (700 mg, 3.30 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (10 mL) was added, and the flask was placed in an oil bath at 100°C and reacted for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 20:1 to 10:1) to obtain the product as a white solid (480 mg, 54% yield). 1 H NMR (500MHz, CDCl3): δ(ppm)1.64(s,6H),3.35(dd,J=17.5,1.5Hz,1H),3.50(dd,J=18.0,7.0Hz,1H),5.46-5. 49(m,1H),5.73(d,J=8.0Hz,1H),6.37(dd,J=8.0,1.5Hz,1H),6.83(dd,J=7.5,5.0Hz,1H),6.95-7.03(m,3H), 7.07-7.12(m,2H),7.20(ddd,J=8.0,2.5,1.0Hz,1H),7.26-7.28(m,3H),7.34(t,J=8.5Hz,1H),7.42(dd,J=7. 5,1.5Hz,1H),7.52-7.57(m,2H),7.65(dd,J=7.5,1.5Hz,1H),7.67-7.69(m,2H),8.00(dd,J=5.0,2.0Hz,1H).

[0127] (2) Synthesis of P-PtLD1: P-LD1 (200 mg, 0.37 mmol, 1.0 equivalent), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equivalent), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen replacement three times, acetic acid (22 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator. Stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 1:1) to obtain the product as a pale yellow solid (135 mg, 50% yield). 1 H NMR(500MHz,DMSO-d6):δ(ppm)1.41(s,3H),1.99(s,3H),3.42(d,J=18.0Hz,1H),3.56(dd,J=18.5Hz ,6.0Hz,1H),5.92-5.98(m,3H),6.50(t,J=7.5Hz,1H),6.68(dd,J=7.5,1.0Hz,1H),6.80-6.82(m,1H ),6.88(dd,J=8.0,1.0Hz,1H),6.98(t,J=7.5Hz,1H),7.06-7.20(m,6H),7.27(d,J=7.5Hz,1H),7.34 (dd,J=7.5,5.5Hz,1H),7.57-7.59(m,1H),8.26(dd,J=7.5,1.5Hz,1H),9.06(dd,J=5.5,1.5Hz,1H).

[0128] Example 18: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtLD1 [ka]

[0129] (1) Synthesis of M-LD1: LD-OH (500 mg, 1.65 mmol, 1.0 equiv.), 2-Br (572 mg, 1.82 mmol, 1.1 equiv.), cuprous iodide (32 mg, 0.17 mmol, 10 mol%), Ligand 2 (59 mg, 0.17 mmol, 10 mol%), and potassium phosphate (700 mg, 3.30 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (10 mL) was added, and the flask was placed in an oil bath at 90°C for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 20:1 to 10:1) to obtain the product as a white solid (433 mg, 49% yield). 1 H NMR (500MHz, CDCl3): δ(ppm)1.64(s,6H),3.35(d,J=17.5Hz,1H),3.50(dd,J=17.5,6.5Hz,1H),5.46-5.49( m,1H),5.73(d,J=8.0Hz,1H),6.37(dd,J=8.0,1.5Hz,1H),6.83(dd,J=7.5,4.5Hz,1H),6.95-7.03(m,3H),7. 07-7.12(m,2H),7.20(ddd,J=7.5,2.5,1.5Hz,1H),7.26-7.28(m,3H),7.34(t,J=8.0Hz,1H),7.42(dd,J=7.5 ,2.0Hz,1H),7.52-7.57(m,2H),7.65(dd,J=8.0,1.5Hz,1H),7.67-7.69(m,2H),8.00(dd,J=4.5,1.5Hz,1H).

[0130] (2) Synthesis of M-PtLD1: P-LD1 (200 mg, 0.37 mmol, 1.0 equivalent), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equivalent), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen replacement three times, acetic acid (22 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C, and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator, stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added, stirred at room temperature for 1 day, washed with water, extracted three times, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the sample was mixed with silica gel, the sample was loaded by the dry method, and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 4:1 to 1:1) to obtain the product as a pale yellow solid (134 mg, 50% yield). 1 H NMR(500MHz,DMSO-d6):δ(ppm)1.41(s,3H),1.99(s,3H),3.43(d,J=18.5Hz,1H),3.56(dd,J=18.5H z,5.5Hz,1H),5.92-5.98(m,3H),6.50(t,J=7.5Hz,1H),6.68(dd,J=8.0,1.5Hz,1H),6.80-6.82(m,1 H),6.88(dd,J=8.0,1.5Hz,1H),6.98(t,J=7.5Hz,1H),7.06-7.20(m,6H),7.27(d,J=7.5Hz,1H),7.3 4(d,J=8.0,6.0Hz,1H),7.57-7.59(m,1H),8.26(dd,J=7.5,1.5Hz,1H),9.06(dd,J=5.5,1.5Hz,1H).

[0131] Example 19: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtLE1 [ka]

[0132] (1) Synthesis of P-LE1: LE-OH (500 mg, 1.66 mmol, 1.0 equiv.), 1-Br (575 mg, 1.83 mmol, 1.1 equiv.), cuprous iodide (32 mg, 0.17 mmol, 10 mol%), ligand 2 (59 mg, 0.17 mmol, 10 mol%), and potassium phosphate (705 mg, 3.32 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (10 mL) was added, and the flask was placed in an oil bath at 100°C for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product as a white solid (0.55 g, 62% yield). 1 H NMR(500MHz,CDCl3):δ(ppm)1.73(s,6H),3.34(dd,J=17.5,1.5Hz,1H),3.46(dd,J=18.0Hz,7.0Hz,1H),5.43-5.47(m,1H),5. 72(d,J=7.5Hz,1H),7.00(dd,J=8.5,2.0Hz,1H),7.04(dd,J=7.5,4.5Hz,1H),7.17(ddd,J=8.0,2.5,1.0Hz,1H),7.24-7.25(m ,3H),7.32-7.36(m,2H),7.39(dd,J=7.5,1.0Hz,1H),7.53-7.55(m,1H),7.63(dd,J=2.5,1.5Hz,1H),7.67-7.69(m,1H),7.80 (dd,J=7.5,1.5Hz,1H),7.84(dd,J=7.5,1.5Hz,1H),8.00(d,J=8.5Hz,1H),8.26(dd,J=5.0,2.0Hz,1H),8.82(d,J=2.0Hz,1H).

[0133] (2) Synthesis of P-PtLE1: P-LE1 (200 mg, 0.37 mmol, 1.0 equivalent), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equivalent), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen replacement three times, acetic acid (22 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C, and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator. Stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 1:1) to obtain the product as a pale yellow solid (138 mg, 51% yield). 1 H NMR(400MHz,DMSO-d6):δ(ppm)1.72(s,3H),1.94(s,3H),3.48(d,J=18.8Hz,1H),3.48(dd,J=18 .8Hz,6.4Hz,1H),5.98(t,J=6.4Hz,1H),6.21(d,J=7.2Hz,1H),6.42(d,J=8.0Hz,1H),6.95(t,J= 7.6Hz,1H),7.13-7.24(m,5H),7.32-7.37(m,2H),7.44(t,J=7.6Hz,1H),7.57(d,J=7.6Hz,1H), 7.89(d,J=8.0Hz,1H),7.95(d,J=8.0Hz,1H),8.50(dd,J=7.6,1.6Hz,1H),9.30(d,J=5.6Hz,1H).

[0134] Example 20: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtLE1 [ka]

[0135] (1) Synthesis of M-LE1: LE-OH (500 mg, 1.66 mmol, 1.0 equiv.), 2-Br (575 mg, 1.83 mmol, 1.1 equiv.), cuprous iodide (32 mg, 0.17 mmol, 10 mol%), ligand 2 (59 mg, 0.17 mmol, 10 mol%), and potassium phosphate (705 mg, 3.32 mmol, 2.0 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (8 mL) was added, and the flask was placed in an oil bath at 90°C for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product as a white solid (158 mg, 59% yield). 1 H NMR (500MHz, CDCl3): δ(ppm)1.73(s,6H),3.34(dd,J=18.0,2.0Hz,1H),3.46(dd,J=17.5,6.5Hz,1H),5.43-5.47(m,1H) ),5.71(d,J=8.0Hz,1H),7.00(dd,J=8.5,2.0Hz,1H),7.04(dd,J=7.5,4.5Hz,1H),7.17(ddd,J=8.0,2.5,1.0Hz,1H),7. 25-7.26(m,3H),7.32-7.40(m,3H),7.53-7.55(m,1H),7.63(dd,J=2.5,1.5Hz,1H),7.68(d,J=8.0Hz,1H),7.80(dd,J= 7.5,1.5Hz,1H),7.83(dd,J=7.5,1.0Hz,1H),8.00(d,J=7.5Hz,1H),8.26(dd,J=5.0,2.0Hz,1H),8.82(d,J=2.0Hz,1H).

[0136] (2) Synthesis of M-PtLE1: P-LE1 (200 mg, 0.37 mmol, 1.0 equivalent), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equivalent), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen replacement three times, acetic acid (22 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C, and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator. Stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 1:1) to obtain the product as a pale yellow solid (138 mg, 51% yield). 1 H NMR (400MHz, DMSO-d6): δ(ppm)1.72(s,3H),1.94(s,3H),3.48(d,J=18.8Hz,1H),3.48(dd,J=18. 0Hz,6.0Hz,1H),5.98(t,J=6.4Hz,1H),6.21(d,J=7.2Hz,1H),6.42(d,J=7.6Hz,1H),6.95(t,J=7. 2Hz,1H),7.13-7.24(m,5H),7.32-7.37(m,2H),7.44(t,J=7.6Hz,1H),7.57(d,J=7.6Hz,1H),7.89 (d,J=8.0Hz,1H),7.95(dd,J=7.6,0.8Hz,1H),8.50(dd,J=7.6,1.2Hz,1H),9.30(d,J=6.0Hz,1H).

[0137] Example 21: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtLF1 [ka]

[0138] (1) Synthesis of P-LF1: LF-OH (500 mg, 1.66 mmol, 1.0 equivalent), 1-Br (575 mg, 1.83 mmol, 1.1 equivalent), cuprous iodide (32 mg, 0.17 mmol, 10 mol%), ligand 2 (59 mg, 0.17 mmol, 10 mol%), and potassium phosphate (705 mg, 3.32 mmol, 2.0 equivalent) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen substitution three times, dimethyl sulfoxide (10 mL) was added, and the flask was placed in an oil bath at 90°C and reacted for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product as a white solid (455 mg, 47% yield). 1 H NMR (500MHz, CDCl3): δ(ppm)1.76(s,6H),3.35(dd,J=18.0,2.0Hz,1H),3.48(dd,J=18.0,7.0 Hz,1H),5.46-5.49(m,1H),5.73(d,J=8.0Hz,1H),6.75(dd,J=8.5,2.5Hz,1H),7.19-7.22(m,2 H),7.25-7.26(m,3H),7.35-7.40(m,2H),7.49-7.56(m,3H),7.69-7.72(m,2H),7.87(dd,J=7. 5,1.0Hz,1H),8.32(dd,J=8.0,2.0Hz,1H),8.47(dd,J=5.0,1.5Hz,1H),9.40(d,J=2.5Hz,1H).

[0139] (2) Synthesis of P-PtLF1: P-LF1 (200 mg, 0.37 mmol, 1.0 equivalent), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equivalent), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen substitution three times, acetic acid (22 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C, and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator. Stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 8:1 to 1:1) to obtain the product as a pale yellow solid (96 mg, 34% yield). 1 H NMR(500MHz,DMSO-d6):δ(ppm)1.66(s,3H),1.85(s,3H),3.49(d,J=18.5Hz,1H),3.61(dd,J=18.5Hz,6.0Hz,1H), 5.98(t,J=6.5Hz,1H),6.30(d,J=7.5Hz,1H),6.32(d,J=7.0Hz,1H),6.89(t,J=7.5Hz,1H),7.03(d,J=8.5Hz,1H), 7.07(dd,J=8.0,1.5Hz,1H),7.11-7.18(m,3H),7.32(d,J=7.5Hz,1H),7.50(d,J=8.5Hz,1H),7.55-7.59(m,2H),7 .80(dd,J=8.0,1.0Hz,1H),8.23(dd,J=8.0,1.0Hz,1H),9.04(dd,J=7.5,1.5Hz,1H),9.41(dd,J=5.5,1.0Hz,1H).

[0140] Example 22: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtLF1 [ka]

[0141] (1) Synthesis of M-LF1: LF-OH (500 mg, 1.66 mmol, 1.0 equivalent), 2-Br (625 mg, 1.99 mmol, 1.2 equivalent), cuprous iodide (32 mg, 0.17 mmol, 10 mol%), ligand 2 (59 mg, 0.17 mmol, 10 mol%), and potassium phosphate (705 mg, 3.32 mmol, 2.0 equivalent) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen substitution three times, dimethyl sulfoxide (10 mL) was added, and the flask was placed in an oil bath at 90°C and reacted for 2 days. After cooling to room temperature, the reaction mixture was washed with water and extracted three times with ethyl acetate. The combined organic phases were washed once with water, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate = 15:1 to 8:1) to obtain the product as a white solid (546 mg, 62% yield). 1 H NMR (500MHz, CDCl3): δ(ppm)1.76(s,6H),3.35(dd,J=18.0,2.0Hz,1H),3.48(dd,J=18.0,7.0 Hz,1H),5.46-5.49(m,1H),5.73(d,J=8.0Hz,1H),6.75(dd,J=8.5,2.5Hz,1H),7.19-7.22(m,2 H),7.25-7.27(m,3H),7.35-7.40(m,2H),7.49-7.56(m,3H),7.69-7.73(m,2H),7.87(dd,J=7. 5,1.0Hz,1H),8.32(dd,J=7.5,1.5Hz,1H),8.47(dd,J=5.0,1.5Hz,1H),9.40(d,J=2.5Hz,1H).

[0142] (2) Synthesis of M-PtLF1: P-LF1 (200 mg, 0.37 mmol, 1.0 equivalent), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equivalent), and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After nitrogen substitution three times, acetic acid (22 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120°C, and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure on a rotary evaporator. Stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 8:1 to 1:1) to obtain the product as a pale yellow solid (145 mg, 54% yield). 1 H NMR (400MHz, DMSO-d6): δ(ppm)1.66(s,3H),1.85(s,3H),3.49(d,J=18.4Hz,1H),3.61(dd,J=18. 5Hz,6.0Hz,1H),5.99(t,J=6.4Hz,1H),6.29(d,J=8.0Hz,1H),6.32(d,J=7.2Hz,1H),6.89(t,J=7. 2Hz,1H),7.02-7.19(m,5H),7.32(d,J=7.6Hz,1H),7.50(d,J=8.4Hz,1H),7.55-7.60(m,2H),7.81 (d,J=7.6Hz,1H),8.23(dd,J=7.6,0.8Hz,1H),9.05(dd,J=7.6,1.6Hz,1H),9.41(d,J=5.6Hz,1H).

[0143] Example 23: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtB1 [ka]

[0144] (1) Synthesis of Ligand P-B1: 1-Br (689 mg, 2.20 mmol, 1.1 equiv.), B1-OH (340 mg, 2.00 mmol, 1.0 equiv.), cuprous iodide (76 mg, 0.40 mmol, 20 mol%), Ligand 2 (69 mg, 0.20 mmol, 10 mol%), and potassium phosphate (849 mg, 4.00 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (5 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 80 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 430 mg (yield 53%) of the ligand P-B1 as a white solid. 1 H NMR(500MHz,CDCl3):δ(ppm)3.35(dd,J=18.0,1.5Hz,1H),3.48(dd,J=18.0,7.0Hz,1H),5.46(ddd,J=8.5,7.0,1.5Hz,1H),5.72(d,J=8 .0Hz,1H),7.03(ddd,J=8.0,2.5,1.0Hz,1H),7.13(ddd,J=8.5,2.5,1.0Hz,1H),7.22(ddd,J=7.5,4.5,1.0Hz,1H),7.25-7.27(m,3H),7 .34(t,J=8.0Hz,1H),7.43(t,J=8.0Hz,1H),7.53-7.56(m,1H),7.61(dd,J=2.0,1.5Hz,1H),7.62(t,J=2.0Hz,1H),7.67(dt,J=8.0,1.0 Hz,1H),7.69(dt,J=7.5,1.0Hz,1H),7.72(dd,J=7.5,2.0Hz,1H),7.75(ddd,J=7.5,1.5,1.0Hz,1H),8.66(ddd,J=5.0,2.0,1.0Hz,1H). 13CNMR(125MHz, CDCl3):δ(ppm)39.73,76.98,83.24,117.53,118.82,119.41,120.59,121.86,122.05,122.34,123.36,125.24,125.6 0,127.43,128.44,129.64,129.70,130.10,136.71,139.68,141.43,141.85,149.64,156.61,157.16,157.50,163.41.HRMS(ESI):C 27 H 21 N2O2[M+H] + Calculated value: 405.1598, measured value: 405.1581.

[0145] (2) Synthesis of P-PtB1: P-B1 (243 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinate (262 mg, 0.60 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (36 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 100 °C for 3 days. The mixture was then cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (228 mg, 1.2 mmol, 2.0 equiv.) and dichloromethane (60 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product P-PtB1 as a red solid (190 mg, 53% yield). 1H NMR (500MHz, CDCl3): δ(ppm)3.57(dd,J=18.0,5.0Hz,1H),3.63(d,J=18.0Hz,1H),5. 76(d,J=7.0Hz,1H),5.83(ddd,J=6.5,5.0,0.5Hz,1H),7.11-7.16(m,2H),7.19(dd,J= 10.5,1.0Hz,1H),7.21-7.22(m,1H),7.23-7.28(m,3H),7.29-7.33(m,2H),7.47-7.48 (m,1H),7.56(d,J=8.0Hz,1H),7.90-7.96(m,2H),9.00(d,J=5.5Hz,1H).HRMS(ESI):C 27 H 19 N2O2Pt[M+H] + Calculated value: 598.1089, measured value: 598.1090.

[0146] Example 24: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtB1 [ka]

[0147] (1) Synthesis of Ligand M-LB1: 2-Br (689 mg, 2.20 mmol, 1.1 equiv.), B1-OH (340 mg, 2.00 mmol, 1.0 equiv.), cuprous iodide (76 mg, 0.40 mmol, 20 mol%), Ligand 2 (69 mg, 0.20 mmol, 10 mol%), and potassium phosphate (849 mg, 4.00 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (5 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 80 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phases were washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 560 mg (yield 69%) of ligand M-B1 as a white solid. 1H NMR(500MHz,CDCl3):δ(ppm)3.35(dd,J=17.5,1.0Hz,1H),3.48(dd,J=18.0,7.0Hz,1H),5.46(ddd,J=8.5,7.0,1.5Hz,1H),5.72(d ,J=8.0Hz,1H),7.03(ddd,J=8.0,2.5,0.5Hz,1H),7.13(ddd,J=8.0,2.5,1.0Hz,1H),7.23(ddd,J=7.5,4.5,1.0Hz,1H),7.25-7.28( m,3H), 7.34(t,J=8.5Hz,1H),7.43(t,J=8.0Hz,1H),7.54-7.56(m,1H),7.61(dd,J=2.5,1.5Hz,1H),7.62(t,J=2.0Hz,1H),7.67(dt ,J=7.5,1.0Hz,1H),7.69(dt,J=8.0,1.0Hz,1H),7.72(dd,J=7.5,2.0Hz,1H),7.74-7.76(m,1H),8.66(ddd,J=5.0,1.5,1.0Hz,1H). 13 CNMR(125MHz,CDCl3):δ(ppm)39.73,76.97,83.24,117.52,118.81,119.40,120.59,121.86,122.05,122.34,123.36,125.23,125.6 0.127.42,128.44,129.64,129.69,130.10,136.71,139.67,141.42,141.85,149.64,156.60,157.16,157.49,163.41.HRMS(ESI):C 27 H 21 N2O2[M+H] + Enter 405.1598.

[0148] (2) Synthesis of M-PtB1: P-B1 (243 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinate (262 mg, 0.60 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (36 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 100 °C for 3 days. The mixture was then cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (228 mg, 1.2 mmol, 2.0 equiv.) and dichloromethane (60 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtB1 as a red solid (106 mg, 30% yield). 1 H NMR (500MHz, CDCl3): δ(ppm)3.58(dd,J=18.0,5.0Hz,1H),3.64(d,J=18.0Hz,1H),5. 78(d,J=7.0Hz,1H),5.85(ddd,J=6.5,5.0,1.0Hz,1H),7.11-7.17(m,2H),7.19(dd,J= 10.5,1.5Hz,1H),7.21-7.22(m,1H),7.24-7.28(m,3H),7.30-7.34(m,2H),7.47-7.49 (m,1H),7.57(d,J=7.5Hz,1H),7.91-7.97(m,2H),9.02(d,J=5.0Hz,1H).HRMS(ESI):C 27 H 19 N2O2Pt[M+H] + Calculated value: 598.1089, measured value: 598.1090.

[0149] Example 25: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtB2 [ka]

[0150] (1) Synthesis of Ligand P--B2: To a dry, sealed tube equipped with a magnetic stir bar, 1-Br (689 mg, 2.20 mmol, 1.1 equiv.), 1-OH (443 mg, 2.00 mmol, 1.0 equiv.), cuprous iodide (76 mg, 0.40 mmol, 20 mol%), Ligand 2 (69 mg, 0.20 mmol, 10 mol%), and potassium phosphate (849 mg, 4.00 mmol, 2.0 equiv.) were sequentially added. After purging with nitrogen three times, N,N-dimethylformamide (5 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 80 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phases were washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 623 mg (yield 68%) of the ligand P--B2 as a white solid. 1 H NMR (500MHz, CDCl3): δ(ppm)3.35(dd,J=13.0,1.5Hz,1H),3.49(dd,J=18.0,7.0Hz,1H),5.47(ddd,J=8.5,7. 0,1.5Hz,1H),5.73(d,J=8.0Hz,1H),7.12(ddd,J=8.0,2.5,1.5Hz,1H),7.17(ddd,J=8.0,2.5,1.0Hz,1H),7. 25-7.27(m,3H),7.30-7.31(m,1H),7.34(t,J=8.0Hz,1H),7.44-7.51(m,3H),7.53-7.56(m,1H),7.63-7.67( m,3H),7.68(dt,J=7.5,1.0Hz,1H),7.86(d,J=8.0Hz,1H),8.08(d,J=8.5,1.0Hz,1H),8.58(d,J=6.0Hz,1H). 13CNMR(125MHz, CDCl3):δ(ppm)39.72,76.95,83.26,118.91,118.92,120.12,120.33,122.10,123.48,125.01,125.23,125.62,126.55,126.9 3,127.28,127.44,128.45,129.66,129.69,129.85,130.02,136.79,139.67,141.33,141.82,142.07,157.00,159.75,163.38.HRMS(ESI):C 31 H 23 N2O2[M+H] + Calculated value: 455.1754, measured value: 455.1748.

[0151] (2) Synthesis of P-PtB2: P-B1 (182 mg, 0.40 mmol, 1.0 equiv.), potassium chloroplatinate (174 mg, 0.42 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (13 mg, 0.040 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (24 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 100 °C for 3 days. The mixture was then cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (152 mg, 0.8 mmol, 2.0 equiv.) and dichloromethane (40 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product P-PtB2 as a red solid (57 mg, 22% yield). 1H NMR(500MHz, CDCl3): δ(ppm)3.57(dd,J=18.0,4.0Hz,1H),3.63(d,J=18.0Hz,1H),5.80-5.83(m,2H ),7.09(t,J=7.5Hz,1H),7.14(t,J=8.0Hz,1H),7.20-7.24(m,3H),7.25-7.28(m,1H),7.31(t,J=6.5 Hz,2H),7.56(d,J=7.5Hz,1H),7.59(d,J=6.0Hz,1H),7.71-7.74(m,1H),7.77(t,J=7.0Hz,1H),7.8 8(d,J=8.0Hz,1H),7.98(d,J=7.5Hz,1H),8.89(d,J=6.0Hz,1H),8.94(d,J=8.5Hz,1H).HRMS(ESI):C 31 H 21 N₂O₂Pt[M+H] + The calculated value is 648.1245 and the measured value is 648.1226.

[0152] [Example 26: Synthesis of four silica platinum (II) complex M-PtB2]

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[0153] (1) Synthesis of Ligand M-B2: 2-Br (689 mg, 2.20 mmol, 1.1 equiv.), B2-OH (443 mg, 2.00 mmol, 1.0 equiv.), cuprous iodide (76 mg, 0.40 mmol, 20 mol%), Ligand 2 (69 mg, 0.20 mmol, 10 mol%), and potassium phosphate (849 mg, 4.00 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (5 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 80 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 487 mg of ligand M-B2 as a white solid (yield 54%). 1 H NMR(500MHz,CDCl3):δ(ppm)3.35(dd,J=13.0,1.5Hz,1H),3.49(dd,J=18.0,7.0Hz,1H),5.47(ddd,J=8.0, 7.0,1.5Hz,1H),5.73(d,J=8.0Hz,1H),7.12(ddd,J=8.0,2.5,1.0Hz,1H),7.18(ddd,J=8.0,2.5,1.0Hz,1H ),7.25-7.27(m,3H),7.29-7.32(m,1H),7.34(t,J=8.0Hz,1H),7.44-7.52(m,3H),7.53-7.57(m,1H),7.62 -7.67(m,3H),7.68(dt,J=7.5,1.0Hz,1H),7.86(d,J=8.0Hz,1H),8.04-8.09(m,1H),8.58(d,J=6.0Hz,1H). 13CNMR(125MHz, CDCl3):δ(ppm)39.74,76.96,83.27,118.92,118.93,120.13,120.35,122.11,123.49,125.02,125.24,125.64,126.57,126.9 4,127.30,127.45,128.46,129.68,129.70,129.86,130.03,136.80,139.68,141.34,141.83,142.09,156.98,159.77,163.39.HRMS(ESI):C 31 H 23 N2O2[M+H] + Calculated value: 455.1754, measured value: 455.1742.

[0154] (2) Synthesis of M-PtB2: A dry 100 mL three-neck flask equipped with a magnetic stir bar and condenser was charged with M-B2 (273 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinate (262 mg, 0.60 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv.), followed by nitrogen flushing three times. Acetic acid (36 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 100 °C for 3 days. The mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (228 mg, 1.2 mmol, 2.0 equiv.) and dichloromethane (60 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtB2 as a red solid (52 mg, 13% yield). 1H NMR(500MHz, CDCl3): δ(ppm)3.59(dd,J=18.0,4.0Hz,1H),3.64(d,J=18.0Hz,1H),5.82-5.85(m,2 H),7.11(t,J=7.5Hz,1H),7.16(t,J=8.0Hz,1H),7.21-7.26(m,3H),7.27-7.30(m,1H),7.33(t,J=6 .5Hz,2H),7.58(d,J=7.5Hz,1H),7.61(d,J=6.0Hz,1H),7.72-7.76(m,1H),7.78-7.81(m,1H),7.90 (d,J=8.0Hz,1H),8.00(d,J=7.5Hz,1H),8.91(d,J=6.0Hz,1H),8.96(d,J=8.5Hz,1H).HRMS(ESI):C 31 H 21 N₂O₂Pt[M+H] + The calculated value is 648.1245 and the measured value is 648.1230.

[0155] [Example 27: Synthesis of four シクロメタル platinum(II) complex P-PtB3]

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[0156] (1) Synthesis of Ligand P-B2: 1-Br (689 mg, 2.20 mmol, 1.1 equiv.), B3-OH (443 mg, 2.00 mmol, 1.0 equiv.), cuprous iodide (76 mg, 0.40 mmol, 20 mol%), Ligand 2 (69 mg, 0.20 mmol, 10 mol%), and potassium phosphate (849 mg, 4.00 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (5 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 80 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 590 mg (yield 65%) of the ligand P-B3 as a white solid. 1 H NMR(500MHz,CDCl3):δ(ppm)3.35(dd,J=18.0,1.5Hz,1H),3.49(dd,J=18.0,7.0Hz,1H),5.47(ddd,J=8.0,7.0, 1.5Hz,1H),5.72(d,J=8.0Hz,1H),7.07(ddd,J=8.0,2.5,1.0Hz,1H),7.16(ddd,J=8.0,2.5,1.0Hz,1H),7.25-7 .27(m,3H),7.36(t,J=8.0Hz,1H),7.49(t,J=8.0Hz,1H),7.51-7.56(m,2H),7.63(dd,J=2.5,1.5Hz,1H),7.70- 7.74(m,2H),7.80-7.83(m,3H),7.93(ddd,J=8.0,1.5,1.0Hz,1H),8.14(d,J=8.5Hz,1H),8.21(d,J=8.5Hz,1H). 13CNMR(125MHz, CDCl3):δ(ppm)39.69,76.94,83.22,118.20,118.70,118.85,119.77,121.81,122.72,123.34,125.22,125.57,126.38,127.22,1 27.37,127.40,128.42,129.65,129.67,129.73,130.19,136.77,139.65 ,141.67,141.81,148.14,156.38,157.17,157.45,163.38.HRMS(ESI):C 31 H 23 N2O2[M+H] + Calculated value: 455.1754, measured value: 455.1744.

[0157] (2) Synthesis of P-PtB3: P-B3 (182 mg, 0.40 mmol, 1.0 equiv.), potassium chloroplatinate (174 mg, 0.42 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (13 mg, 0.040 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (24 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 100 °C for 3 days. The mixture was then cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (152 mg, 0.8 mmol, 2.0 equiv.) and dichloromethane (40 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product P-PtB3 as a red solid (91 mg, 35% yield). 1H NMR (500MHz, CDCl3): δ (ppm) 3.55 (d, J = 3.5 Hz, 2H), 5.90-5.93 (m, 1H), 6.23 (d, J = 7.0 Hz, 1H), 6. 45(d,J=7.5Hz,1H),6.73(t,J=7.5Hz,1H),7.05(t,J=8.0Hz,1H),7.15-7.20(m,2H),7.25-7.30( m,4H),7.54-7.58(m,1H),7.65(d,J=7.5Hz,1H),7.78(ddd,J=8.5,7.0,1.5Hz,1H),7.92(dd,J=8 .0,1.0Hz,1H),8.14(d,J=8.5Hz,1H),8.42(d,J=8.5Hz,1H),9.03(d,J=8.5Hz,1H).HRMS(ESI):C 31 H 21 N₂O₂Pt[M+H] + The calculated value is 648.1245 and the measured value is 648.1242.

[0158] [Example 28: Synthesis of four silica platinum(II) complexes M-PtB3]

change

[0159] (1) Synthesis of Ligand M-B3: 2-Br (689 mg, 2.20 mmol, 1.1 equiv.), B3-OH (443 mg, 2.00 mmol, 1.0 equiv.), cuprous iodide (76 mg, 0.40 mmol, 20 mol%), Ligand 2 (69 mg, 0.20 mmol, 10 mol%), and potassium phosphate (849 mg, 4.00 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (5 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 80 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 590 mg (yield 64%) of ligand M-B3 as a white solid. 1 H NMR(500MHz,CDCl3):δ(ppm)3.35(dd,J=18.0,1.5Hz,1H),3.48(dd,J=18.0,7.0Hz,1H),5.47(ddd,J=8.0,7.0, 1.5Hz,1H),5.72(d,J=8.0Hz,1H),7.07(ddd,J=8.0,2.5,1.0Hz,1H),7.16(ddd,J=8.0,2.5,1.0Hz,1H),7.25-7 .27(m,3H),7.36(t,J=8.0Hz,1H),7.49(t,J=8.0Hz,1H),7.51-7.56(m,2H),7.63(dd,J=2.5,1.5Hz,1H),7.70- 7.74(m,2H),7.80-7.83(m,3H),7.93(ddd,J=8.0,1.5,1.0Hz,1H),8.14(d,J=8.5Hz,1H),8.21(d,J=8.5Hz,1H). 13CNMR(125MHz, CDCl3):δ(ppm)39.73,76.96,83.25,118.23,118.74,118.90,119.79,121.84,122.75,123.37,125.24,125.60,126.41,127.2 6,127.40,127.43,128.44,129.68,129.76,130.21,136.81,139.68,141.70,141.84,148.17,156.44,157.19,157.48,163.42.HRMS(ESI):C 31 H 23 N2O2[M+H] + Calculated value: 455.1754, measured value: 455.1744.

[0160] (2) Synthesis of M-PtB3: A dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser was charged with M-B3 (273 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinate (262 mg, 0.60 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv.), followed by nitrogen purge three times. Acetic acid (36 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 100 °C for 3 days. The mixture was then cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride (228 mg, 1.2 mmol, 2.0 equiv.) and dichloromethane (60 mL) were added and stirred at room temperature for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtB3 as a red solid (46 mg, 12% yield). 1H NMR(500MHz, CDCl3): δ(ppm)3.55(d,J=3.5Hz,2H),5.89-5.92(m,1H),6.23(d,J=7.0Hz,1H),6.45(d ,J=7.5Hz,1H),6.73(t,J=7.0Hz,1H),7.05(t,J=7.5Hz,1H),7.16-7.20(m,2H),7.25-7.30(m,4H),7 .56(ddd,J=8.0,7.0,1.0Hz,1H),7.65(d,J=7.0Hz,1H),7.78(ddd,J=8.5,7.0,1.5Hz,1H),7.92(dd, J=8.0,1.0Hz,1H),8.14(d,J=9.0Hz,1H),8.42(d,J=8.5Hz,1H),9.03(d,J=8.5Hz,1H).HRMS(ESI):C 31 H 21 N₂O₂Pt[M+H] + The calculated value is 648.1245 and the measured value is 648.1253.

[0161] [Example 29: Synthesis of four silica platinum(II) complexes M-PtB8]

change

[0162] (1) Synthesis of M-B8: 2-Br (1.50 g, 4.77 mmol, 1.0 equiv.), B8-OH (1.0 g, 4.77 mmol, 1.0 equiv.), cuprous iodide (91 mg, 0.48 mmol, 10 mol%), Ligand 2 (165 mg, 0.48 mmol, 10 mol%), and potassium phosphate (2.02 g, 9.54 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (30 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 80 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 1.05 g (yield 50%) of the ligand M-B8 as a white solid. 1 H NMR(400MHz,DMSO-d6)δ3.23(d,J=18.0Hz,1H),3.49(dd,J=18.0,6.8Hz,1H),5.53(t,J=7.2Hz,1H),5.71(d,J=7.6Hz,1H),7.12( d,J=8.4Hz,1H),7.21-7.35(m,6H),7.37-7.45(m,2H),7.46-7.56(m,3H),7.60-7.68(m,3H),7.77(d,J=7.6Hz,1H),8.59(s,1H).

[0163] (2) Synthesis of the ligand M-B8-Me: M-B8 (1.0 g, 2.25 mmol, 1.0 equiv.) was added to a dry sealed tube equipped with a magnetic stir bar, and the mixture was purged with nitrogen three times. Then, toluene (30 mL) and methyl iodide (384 mg, 2.71 mmol, 1.2 equiv.) were added under nitrogen protection. The sealed tube was placed in an oil bath at 100°C and stirred for 2 days, then cooled to room temperature, water was added, and the mixture was filtered. The solid was transferred to a sealed tube, and methanol (30 mL) was added to dissolve it. Ammonium hexafluorophosphate (550 mg, 3.38 mmol, 1.5 equivalents) and water (10 mL) were then added, and the mixture was reacted at 50°C for 5 days. The mixture was then cooled to room temperature, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: methanol / dichloromethane 100:1 to 5:1) to obtain 460 mg of the ligand M-B8-Me as a white solid (yield 34%). 1 H NMR(400MHz,DMSO-d6)δ3.22(d,J=18.0Hz,1H),3.49(dd,J=18.0,6.8Hz,1H),4.13(s,3H),5.53(ddd,J=8.0, 6.8,1.6Hz,1H),5.71(d,J=7.6Hz,1H),7.21-7.31(m,3H),7.35-7.39(m,2H),7.40-7.43(m,1H),7.47(t,J=2 .4Hz,1H),7.52-7.57(m,2H),7.60(ddd,J=8.0,2.0,0.8Hz,1H),7.66(ddd,J=8.4,7.2,1.2Hz,1H),7.70(dt, J=7.6,1.2Hz,1H),7.74-7.79(m,2H),7.84(dt,J=8.4,0.8Hz,1H),8.12(dt,J=8.4,0.8Hz,1H),10.08(s,1H).

[0164] (3) Synthesis of M-PtB8: A dry 100 mL three-neck flask equipped with a magnetic stir bar and condenser was charged with M-B8-Me (237 mg, 0.39 mmol, 1.0 equiv.), (1,5-cyclooctadiene)platinum dichloride (154 mg, 0.41 mmol, 1.05 equiv.), and sodium acetate (160 mg, 1.18 mmol, 3.0 equiv.). After purging with nitrogen three times, ethylene glycol dimethyl ether (25 mL) was added. The reaction mixture was bubbled with nitrogen for 30 minutes and then incubated at 120 °C for 72 hours. The mixture was cooled to room temperature, quenched with water, extracted with DCM, and evaporated under reduced pressure. The crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtB8 as a yellow solid (23 mg, 9% yield). 1 H NMR(400MHz,DMSO-d6)δ3.39(d,J=14Hz,1H),3.46-3.52(m,1H),4.36(s,3H),5.92-6.00(m,1H),6.17(d,J=6.8Hz,1H),6.93(d,J=8.0Hz,1H),7 .13-7.31(m,6H),7.39(d,J=7.6Hz,1H),7.48-7.54(m,2H),7.57(d,J=7 .6Hz,1H),7.73(d,J=7.6Hz,1H),7.81-7.86(m,1H),8.36-8.38(m,1H).

[0165] Example 30: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtB9 [ka]

[0166] (1) Synthesis of Ligand P-B9: 1-Br (500 mg, 1.60 mmol, 1.0 equiv.), B9-OH (301 mg, 1.60 mmol, 1.0 equiv.), cuprous iodide (31 mg, 0.16 mmol, 10 mol%), Ligand 2 (55 mg, 0.16 mmol, 10 mol%), and potassium phosphate (680 mg, 3.20 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (10 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phases were washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 526 mg (yield 78%) of the ligand P-B9 as a white solid. 1 H NMR(400MHz,DMSO-d6)δ2.14(s,3H),2.27(s,3H),3.21(d,J=18.0Hz,1H),3.42-3.47(m,1H),5.51(t,J=7.2Hz,1H),5.68(d,J=7.6Hz,1H), 6.05(s,1H),7.02(d,J=7.6Hz,1H),7.12-7.14(m,1H),7.21-7.32(m,5H),7.40-7.43(m,2H),7.50(t,J=8.0Hz,2H),7.64(d,J=7.6Hz,1H). 13 CNMR(125MHz,CDCl3)δ12.42,13.43,39.70,76.94,83.26,107.19,114.91,117.16,119.05,119.43,122.19,123.74,125 .24,125.56,127.42,128.45,129.72,129.74,130.08,139.35,139.64,141.19,141.78,149.08,156.49,157.51,163.25.

[0167] (2) Synthesis of P-PtB9: P-B9 (200 mg, 0.48 mmol, 1.0 equiv.), potassium chloroplatinate (208 mg, 0.50 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (15 mg, 0.048 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (30 mL) was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then reacted at 110 °C for 48 hours. The mixture was cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product P-PtB9 as a yellow solid (100 mg, 34% yield). 1 H NMR(400MHz,DMSO-d6)δ2.74(s,3H),2.78(s,3H),3.49(d,J=14Hz,1H),3.56-3.62(m,1H),5.89-5.94(m,1H),5.98(d,J=6.8Hz,1H),6.51( s,1H),6.89(dd,J=8.0,0.8Hz,1H),7.08-7.15(m,3H),7.17-7.23(m,2H),7.27-7.31(m,2H),7.39(d,J=7.6Hz,1H),7.44(d,J=7.6Hz,1H). 13 CNMR(125MHz,CDCl3)δ14.49,15.06,38.25,73.92,88.08,106.69,109.71,111.11,113.94,120.48,121.45,123.38,123 .94,125.18,125.34,125.51,128.07,129.00,133.24,139.27,140.27,141.04,147.62,149.57,150.57,152.44,180.59.

[0168] Example 31: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtB9 [ka]

[0169] (1) Synthesis of Ligand M-B9: 2-Br (500 mg, 1.60 mmol, 1.0 equiv.), B9-OH (301 mg, 1.60 mmol, 1.0 equiv.), cuprous iodide (31 mg, 0.16 mmol, 10 mol%), Ligand 2 (55 mg, 0.16 mmol, 10 mol%), and potassium phosphate (680 mg, 3.20 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (10 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phases were washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain 514 mg (yield 77%) of the ligand M-B9 as a white solid. 1 H NMR(500MHz,CDCl3)δ2.26(s,3H),2.27(s,3H),3.33-3.37(m,1H),3.49(dd,J=18.0,7.0Hz,1H),5.47(dd d,J=8.0,7.0,1.5Hz,1H),5.72(d,J=8.0Hz,1H),5.96(s,1H),6.94(ddd,J=8.0,2.5,1.0Hz,1H),7.04(t, J=2.0Hz,1H),7.13(ddd,J=8.0,2.5,1.0Hz,1H),7.19(ddd,J=8.0,2.0,1.0Hz,1H),7.26-7.29(m,3H),7. 33-7.36(m,1H),7.38(t,J=7.0Hz,1H),7.53-7.56(m,1H),7.60-7.61(m,1H),7.71(dt,J=7.5,1.0Hz,1H). 13CNMR(125MHz,CDCl3)δ12.34,13.36,39.62,76.87,83.19,107.14,114.83,117.08,118.96,119.34,122.10,123.66, 125.16,125.48,127.33,128.37,129.67,130.01,139.26,139.55,141.14,141.71,148.99,156.43,157.43,163.14.

[0170] (2) Synthesis of M-PtB9: M-B9 (200 mg, 0.48 mmol, 1.0 equiv.), potassium chloroplatinate (208 mg, 0.50 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (15 mg, 0.048 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (30 mL) was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then reacted at 110 °C for 48 hours. The mixture was then cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtB9 as a yellow solid (101 mg, 34% yield). 1 H NMR(400MHz,DMSO-d6)δ2.74(s,3H),2.78(s,3H),3.49(d,J=14Hz,1H),3.56-3.62(m,1H),5.89-5.94(m,1H),5.98(d,J=6.8Hz,1H),6. 51(s,1H),6.89(d,J=8.0Hz,1H),7.08-7.15(m,3H),7.17-7.23(m,2H),7.27-7.31(m,2H),7.39(d,J=7.6Hz,1H),7.44(d,J=7.6Hz,1H). 13CNMR(125MHz,CDCl3)δ14.53,15.08,38.28,73.95,88.10,106.71,109.74,111.06,113.99,120.55,121.47,123.43,123 .98,125.19,125.36,125.43,128.11,129.04,133.20,139.27,140.26,141.10,147.63,149.55,150.59,152.46,180.67.

[0171] Example 32: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-M-PtLI1 [ka]

[0172] (1) Synthesis of the ligand (R,S)-LI1: PyCz-NH (409 mg, 1.09 mmol, 1.0 equiv.), 2-Br (515 mg, 1.64 mmol, 1.5 equiv.), tris(dibenzylideneacetone)dipalladium (40 mg, 0.044 mmol, 4 mol%), 2-(di-tert-butylphosphine)biphenyl (26 mg, 0.088 mmol, 8 mol%), and sodium tert-butoxide (209 mg, 2.18 mmol, 2.0 equiv.) were added to a dry sealed tube equipped with a magnetic stir bar. The mixture was purged with nitrogen three times, and then toluene (15 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 °C for 2.5 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (R,S)-LI1 as a white solid (651 mg, yield 98%). 1H NMR (400MHz, CDCl3): δ1.80(s,6H),3.34-3.38(m,1H),3.47-3.52(m,1H),5.48-5.52(m,1H),5.7 7(d,J=8.0Hz,1H),6.24-6.29(m,1H),6.72(s,1H),6.95-7.00(m,3H),7.28-7.33(m,6H),7.44(t d,J=7.6,2.0Hz,1H),7.51-7.54(m,2H),7.58-7.59(m,1H),7.64(t,J=8.0Hz,1H),7.78(d,J=8.0 Hz,1H),7.98(t,J=1.6Hz,1H),8.02-8.04(m,1H),8.09-8.13(m,2H),8.35(dd,J=4.8,1.2Hz,1H).

[0173] (2) Synthesis of (R,S)-M-PtLI1: The ligand (R,S)-LI1 (304 mg, 0.50 mmol, 1.0 equiv.) and platinum dichloride (141 mg, 0.53 mmol, 1.05 equiv.) were sequentially added to a dry three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, benzonitrile (15 mL) was added under nitrogen protection. The mixture was stirred in a heating mantle at 180 °C for 3 days, then cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 2:1) to obtain the product (R,S)-M-PtLI1 as a yellow solid (112 mg, 28% yield). 1H NMR(500MHz,DMSO-d6):δ1.76(s,6H),3.25-3.29(m,1H),3.47-3.52(m,1H),5.53-5.57(m,1H),5 .74(d,J=8.0Hz,1H),6.15(dd,J=7.5,2.0Hz,1H),6.68(s,1H),6.93-7.00(m,2H),7.13-7.16(m,1 H),7.22-7.33(m,5H),7.43-7.46(m,2H),7.57(dd,J=7.5,2.0Hz,1H),7.61-7.70(m,3H),7.77(t, J=7.5Hz,1H),7.81(t,J=1.5Hz,1H),8.03(dt,J=8.0,1.5Hz,1H),8.19-8.22(m,2H),8.35(s,1H).

[0174] Example 33: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-P-PtLI1 [ka]

[0175] (1) Synthesis of the ligand (S,R)-LI1: PyCz-NH (409 mg, 1.09 mmol, 1.0 equiv.), 2-Br (515 mg, 1.64 mmol, 1.5 equiv.), tris(dibenzylideneacetone)dipalladium (40 mg, 0.044 mmol, 4 mol%), 2-(di-tert-butylphosphine)biphenyl (26 mg, 0.088 mmol, 8 mol%), and sodium tert-butoxide (209 mg, 2.18 mmol, 2.0 equiv.) were added to a dry sealed tube equipped with a magnetic stir bar. The mixture was purged with nitrogen three times, and then toluene (15 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 °C for 2.5 days, cooled to room temperature, and the solvent was removed under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (S,R)-LI1 as a white solid (511 mg, yield 77%). 1H NMR (400MHz, CDCl3): δ1.81(s,6H),3.34-3.38(m,1H),3.47-3.53(m,1H),5.48-5.52(m,1H),5.7 7(d,J=8.0Hz,1H),6.24-6.28(m,1H),6.72(s,1H),6.94-7.0(m,3H),7.27-7.33(m,6H),7.44(td ,J=7.6,2.0Hz,1H),7.51-7.56(m,2H),7.57-7.59(m,1H),7.64(t,J=8.0Hz,1H),7.78(d,J=7.6H z,1H),7.99(t,J=1.6Hz,1H),8.02-8.04(m,1H),8.09-8.13(m,2H),8.35(dd,J=4.8,1.2Hz,1H).

[0176] (2) Synthesis of (S,R)-P-PtLI1: The ligand (S,R)-LI1 (300 mg, 0.49 mmol, 1.0 equiv.) and platinum dichloride (136 mg, 0.51 mmol, 1.05 equiv.) were sequentially added to a dry three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, benzonitrile (15 mL) was added under nitrogen protection. The mixture was stirred in a heating mantle at 180 °C for 3 days, then cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 2:1) to obtain the product (S,R)-P-PtLI1 as a yellow solid (122 mg, 31% yield). 1H NMR(500MHz,DMSO-d6):δ1.76(s,6H),3.25-3.29(m,1H),3.47-3.52(m,1H),5.54-5.57(m,1H),5 .74(d,J=7.5Hz,1H),6.15(dd,J=8.0,1.5Hz,1H),6.68(s,1H),6.93-7.00(m,2H),7.13-7.16(m,1 H),7.23-7.34(m,5H),7.44-7.46(m,2H),7.57(dd,J=7.5,2.0Hz,1H),7.61-7.70(m,3H),7.77(t, J=8.0Hz,1H),7.81(t,J=2.0Hz,1H),8.03(dt,J=8.0,1.5Hz,1H),8.19-8.22(m,2H),8.35(s,1H).

[0177] Example 34: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-M-PtLK1 [ka]

[0178] (1) Synthesis of (R,S)-LJ1: To a dry three-neck flask equipped with a magnetic stir bar, ligand (R,S)-OH (512 mg, 1.23 mmol, 1.0 equiv.), 2-bromopyridine (389 mg, 2.46 mmol, 2.0 equiv.), cuprous iodide (141 mg, 0.74 mmol, 60 mol%), ligand 2 (41 mg, 0.12 mmol, 10 mol%), and potassium phosphate (522 mg, 2.46 mmol, 2.0 equiv.) were sequentially added. After three nitrogen purges, N,N-dimethylformamide (15 mL) was added under nitrogen protection. The mixture was stirred in an 80°C oil bath and reacted for 2 days, then cooled to room temperature, washed with water, and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (R,S)-LJ1 as a white solid (182 mg, 30% yield). 1H NMR (500MHz, DMSO-d6): δ3.22-3.26(m,1H),3.47-3.52(m,1H),5.56(t,J=8.0Hz,1H),5.73(d,J=8.0Hz,1H),7.01-7.12(m,4H),7.21-7. 34(m,5H),7.42(t,J=8.0Hz,2H),7.74(t,J=7.5Hz,1H),7.80-7.84(m,2H),7.95-7.98(m,2H),8.10(d,J=4.0Hz,1H),8.23-8.28(m,2H).

[0179] (2) Synthesis of (R,S)-M-PtLJ1: The ligand (R,S)-LJ1 (160 mg, 0.32 mmol, 1.0 equiv.) and platinum dichloride (90 mg, 0.34 mmol, 1.05 equiv.) were sequentially added to a dry three-neck flask equipped with a magnetic stir bar. After three nitrogen purges, benzonitrile (10 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 180 °C for 2 days, cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 2:1) to obtain the product (R,S)-M-PtLJ1 as a yellow solid (123 mg, 56% yield). 1 H NMR(400MHz,DMSO-d6):3.50-3.56(m,1H),3.60-3.66(m,1H),6.00(t,J=8.0Hz,1H),6.21(d,J=6.8Hz,1H),6.45(d,J=8.0Hz,1H),7.05(t,J=7 .6Hz,1H),7.20-7.25(m,2H),7.28-7.48(m,6H),7.69(d,J=8.0Hz,1H),7.94(d,J=8.4Hz,1H),8.20-8.31(m,4H),9.25(dd,J=4.4,1.6Hz,1H).

[0180] Example 35: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-P-PtLK1 [ka]

[0181] (1) Synthesis of (S,R)-LJ1: To a dry three-neck flask equipped with a magnetic stir bar, ligand (S,R)-OH (550 mg, 1.32 mmol, 1.0 equiv.), 2-bromopyridine (259 mg, 2.64 mmol, 2.0 equiv.), cuprous iodide (150 mg, 0.79 mmol, 60 mol%), ligand 2 (45 mg, 0.13 mmol, 10 mol%), and potassium phosphate (560 mg, 2.64 mmol, 2.0 equiv.) were sequentially added. The atmosphere was purged with nitrogen three times, and then N,N-dimethylformamide (15 mL) was added under nitrogen protection. The mixture was stirred in an 80°C oil bath and reacted for 2 days, then cooled to room temperature, washed with water, and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (S,R)-LJ1 as a white solid (150 mg, 23% yield). 1 H NMR (500MHz, DMSO-d6): δ3.22-3.26(m,1H),3.47-3.52(m,1H),5.56(t,J=8.0Hz,1H),5.73(d,J=8.0Hz,1H),7.01-7.12(m,4H),7.21-7. 34(m,5H),7.42(t,J=8.0Hz,2H),7.74(t,J=7.5Hz,1H),7.80-7.84(m,2H),7.95-7.98(m,2H),8.10(d,J=4.0Hz,1H),8.23-8.28(m,2H).

[0182] (2) Synthesis of (S,R)-P-PtLJ1: The ligand (S,R)-LJ1 (150 mg, 0.30 mmol, 1.0 equiv.) and platinum dichloride (85 mg, 0.32 mmol, 1.05 equiv.) were sequentially added to a dry three-neck flask equipped with a magnetic stir bar. After three nitrogen purges, benzonitrile (10 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 180 °C for 2 days, cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 2:1) to obtain the product (S,R)-P-PtLJ1 as a yellow solid (97 mg, 47% yield). 1 H NMR(500MHz,DMSO-d6):δ3.51-3.54(m,1H),3.60-3.65(m,1H),6.00(t,J=6.5Hz,1H),6.21(d,J=6.8Hz,1H),6.46(d,J=8.0Hz,1H),7.05(t,J =7.5Hz,1H),7.20-7.25(m,2H),7.29-7.48(m,6H),7.68-7.70(m,1H),7.93(d,J=8.0Hz,1H),8.20-8.30(m,4H),9.25(dd,J=6.0,1.5Hz,1H).

[0183] Example 36: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-M-PtLK1 [ka]

[0184] (1) Synthesis of the ligand (R,S)-LK1: PyCz (300 mg, 1.23 mmol, 1.0 equiv.), 1-Br (578 mg, 1.84 mmol, 1.5 equiv.), tris(dibenzylideneacetone)dipalladium (21 mg, 0.023 mmol, 2 mol%), 2-(di-tert-butylphosphine)biphenyl (14 mg, 0.046 mmol, 4 mol%), and sodium tert-butoxide (236 mg, 2.46 mmol, 2.0 equiv.) were added to a dry sealed tube equipped with a magnetic stir bar. After three nitrogen purges, toluene (15 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 °C for 3 days, cooled to room temperature, and the solvent was removed under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (R,S)-LK1 as a white solid (564 mg, yield 96%). 1 H NMR (400MHz, CDCl3): δ3.34-3.39(m,1H),3.47-3.53(m,1H),5.49-5.53(m,1H),5.78(d ,J=7.6Hz,1H),7.19-7.22(m,1H),7.27-7.34(m,5H),7.39-7.43(m,1H),7.54-7.57(m,1 H),7.62-7.71(m,2H),7.72-7.77(m,2H),7.91(dd,J=8.0,1.6Hz,1H),7.95(d,1H),8.08 (dt,J=7.6,1.2Hz,1H),8.15-8.17(m,2H),8.21(d,J=8.4Hz,1H),8.66(d,J=4.4Hz,1H).

[0185] (2) Synthesis of (R,S)-M-PtLI1: The ligand (R,S)-LI1 (253 mg, 0.53 mmol, 1.0 equiv.) and platinum dichloride (149 mg, 0.56 mmol, 1.05 equiv.) were sequentially added to a dry three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, benzonitrile (15 mL) was added under nitrogen protection. The mixture was stirred in a heating mantle at 180 °C for 3 days, then cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 2:1) to obtain the product (R,S)-M-PtLI1 as a yellow solid (120 mg, 34% yield). 1 H NMR(500MHz,DMSO-d6):δ3.55-3.59(m,1H),δ3.63-3.68(m,1H),6.05(t,J= 6.5Hz,1H),6.16(d,J=7.0Hz,1H),7.21-7.34(m,6H),7.42-7.47(m,3H),7. 48-7.53(m,1H),7.77(d,J=8.5Hz,1H),7.90(d,J=8.0Hz,1H),8.10(td,J=8 .0,1.0Hz,1H),8.20-8.23(m,2H),8.27-8.29(m,2H),9.14(d,J=4.5Hz,1H).

[0186] Example 37: Synthesis of tetradentate cyclometallated platinum(II) complex (R,S)-P-PtLK1 [ka]

[0187] (1) Synthesis of the ligand (S,R)-LK1: PyCz (303 mg, 1.24 mmol, 1.0 equiv.), 1-Br (584 mg, 1.86 mmol, 1.5 equiv.), tris(dibenzylideneacetone)dipalladium (23 mg, 0.025 mmol, 2 mol%), 2-(di-tert-butylphosphine)biphenyl (15 mg, 0.050 mmol, 4 mol%), and sodium tert-butoxide (238 mg, 2.48 mmol, 2.0 equiv.) were added to a dry sealed tube equipped with a magnetic stir bar. After three nitrogen purges, toluene (15 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 °C for 2.5 days, cooled to room temperature, and the solvent was removed under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (S,R)-LK1 as a white solid (425 mg, yield 72%). 1 H NMR (400MHz, CDCl3): δ3.34-3.39(m,1H),3.47-3.53(m,1H),5.49-5.53(m,1H),5.78(d ,J=7.6Hz,1H),7.19-7.22(m,1H),7.27-7.34(m,5H),7.39-7.43(m,1H),7.54-7.57(m,1 H),7.62-7.71(m,2H),7.72-7.77(m,2H),7.91(dd,J=8.0,1.6Hz,1H),7.95(d,1H),8.08 (dt,J=7.6,1.2Hz,1H),8.15-8.17(m,2H),8.21(d,J=8.4Hz,1H),8.66(d,J=4.4Hz,1H).

[0188] (2) Synthesis of (S,R)-P-PtLK1: The ligand (S,R)-LK1 (258 mg, 0.54 mmol, 1.0 equiv.) and platinum dichloride (152 mg, 0.57 mmol, 1.05 equiv.) were sequentially added to a dry three-neck flask equipped with a magnetic stir bar. After three nitrogen purges, benzonitrile (15 mL) was added under nitrogen protection. The mixture was stirred in a heating mantle at 180 °C for 3 days, then cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 3:1 to 2:1) to obtain the product (S,R)-P-PtLK1 as a yellow solid (40 mg, 11% yield). 1 H NMR(500MHz,DMSO-d6):δ3.56-3.60(m,1H),δ3.64-3.69(m,1H),6.06(t,J= 6.5Hz,1H),6.17(d,J=7.0Hz,1H),7.22-7.35(m,6H),7.43-7.50(m,3H),7. 51-7.53(m,1H),7.78(d,J=8.0Hz,1H),7.91(d,J=8.0Hz,1H),8.11(td,J=8 .0,1.5Hz,1H),8.20-8.24(m,2H),8.28-8.30(m,2H),9.15(d,J=5.5Hz,1H).

[0189] Example 38: Synthesis of tetradentate cyclometallated palladium(II) complex P-PdLA1 [ka]

[0190] Synthesis of P-PdLA1: M-LA1 (200 mg, 0.41 mmol, 1.0 equiv.), palladium acetate (101 mg, 0.45 mmol, 1.1 equiv.), and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After purging with nitrogen three times, acetic acid (25 mL) was added, nitrogen was bubbled through for 30 minutes, and the mixture was stirred at room temperature for 12 hours. The temperature was then raised to 120 °C and the mixture was allowed to react for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure using a rotary evaporator. Stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (15 mL) were added and stirred at room temperature for 1 day. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The sample was loaded by the dry method and separated and purified by column chromatography (eluent: petroleum ether / dichloromethane = 8:1 to 1:1) to obtain the product as a pale yellow solid (63 mg, 26% yield). 1 H NMR(500MHz,DMSO-d6):δ(ppm)3.46(d,J=18.5Hz,1H),3.64(dd,J=18.5Hz,6.5Hz,1H),5.97(t,J=6 .5Hz,1H),6.22(d,J=7.0Hz,1H),7.00(d,J=7.5Hz,1H),7.11(t,J=8.0Hz,1H),7.17-7.24(m,4H),7. 28(dd,J=6.5,2.0Hz,1H),7.35(d,J=7.5Hz,1H),7.39-7.42(m,1H),7.47-7.51(m,2H),7.92(d,J=8 .5Hz,1H),8.15-8.17(m,2H),8.20-8.23(m,1H),8.28(d,J=8.5Hz,1H),9.34(dd,J=6.0,2.0Hz,1H).

[0191] Example 39: Synthesis of tetradentate cyclometallated palladium(II) complex M-PdLA1 [ka]

[0192] Synthesis of M-PdLA1: M-LA1 (200 mg, 0.41 mmol, 1.0 equiv.), palladium acetate (101 mg, 0.45 mmol, 1.1 equiv.), and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 10 mol%) were sequentially added to a 50 mL three-neck flask equipped with a magnetic stir bar. After flushing with nitrogen three times, acetic acid (25 mL) was added, nitrogen was bubbled through for 30 minutes, and the temperature was raised to 120 °C for 2 days. After cooling to room temperature, the solvent was removed under reduced pressure using a rotary evaporator. The mixture was washed with water and extracted three times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the sample was mixed with silica gel. The dry sample was loaded onto the silica gel column. The product was purified by column chromatography (eluent: petroleum ether / dichloromethane = 2:1 to 1:1) to obtain 133 mg of the product as a white solid (54% yield). 1 H NMR(500MHz, CDCl3): δ(ppm)3.51-3.60(m,2H),5.78-5.81(m,1H),5.87(d,J=7.0Hz,1H ),7.04-7.08(m,2H),7.12(d,J=7.5Hz,1H),7.16-7.19(m,2H),7.24(d,J=8.0Hz,1H),7. 26-7.27(m,1H),7.29-7.31(m,2H),7.34-7.42(m,2H),7.82-7.86(m,2H),7.99(d,J=8.0 Hz,1H),8.04(dd,J=7.5,1.0Hz,1H),8.17(d,J=8.5Hz,1H),9.20(dd,J=6.0,2.0Hz,1H).

[0193] Example 40: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtL1 [ka]

[0194] (1) Synthesis of Ligand (S)-L1: (S)-IPr-Br (1.19 g, 2.99 mmol, 1.2 equiv.), 2-OH (426 g, 2.49 mmol, 1.0 equiv.), cuprous iodide (95 mg, 0.50 mmol, 20 mol%), Ligand 2 (86 mg, 0.25 mmol, 10 mol%), and potassium phosphate (1.06 g, 4.98 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (25 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate=10:1 to 5:1) to obtain 475 mg of product (S) L1 as a white solid (yield 39%). 1 H NMR (400MHz, DMSO-d6): δ0.86(d,J=6.4Hz,3H),0.94(d,J=6.4Hz,3H),1.17(s,9H),1.70-1. 78(m,1H),3.54-3.59(m,1H),3.89-3.95(m,1H),3.97-4.03(m,1H),6.70(d,J=8.8Hz,2H),6 .87-6.90(m,1H),7.00(t,J=2.0Hz,1H),7.11-7.14(m,1H),7.17-7.21(m,2H),7.27(d,J=7. 6Hz,1H),7.35-7.44(m,3H),7.69(t,J=1.6Hz,1H),7.83-7.90(m,2H),7.95(d,J=8.0Hz,1H).

[0195] (2) Synthesis of P-PtL1: (S)-L1 (431 mg, 0.88 mmol, 1.0 equiv.), potassium chloroplatinate (346 mg, 0.92 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (28 mg, 0.088 mmol, 0.1 equiv.) were sequentially added to a dry 100 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (52 mL) pre-purified with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then stirred at 120 °C for 2 days. The mixture was then cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product P-PtL1 as a red solid (102 mg, 17% yield). 1 H NMR(400MHz,DMSO-d6):δ0.86(d,J=6.8Hz,3H),1.03(d,J=6.8Hz,3H),1.33(s,9H),4.0 3-4.06(m,1H),4.30-4.36(m,1H),4.46-4.50(m,1H),6.36-6.38(m,1H),6.83(t,J=7.6 Hz,1H),6.99-7.03(m,2H),7.17(t,J=7.6Hz,1H),7.29-7.31(m,2H),7.52-7.55(m,3H) ,7.62(d,J=7.2Hz,1H),8.07-8.11(m,1H),8.20(d,J=7.6Hz,1H),8.77(d,J=4.8Hz,1H).

[0196] Example 41: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtL1 [ka]

[0197] (1) Synthesis of Ligand (R)-L1: (R)-IPr-Br (1.19 g, 2.99 mmol, 1.2 equiv.), 2-OH (426 g, 2.49 mmol, 1.0 equiv.), cuprous iodide (95 mg, 0.50 mmol, 20 mol%), Ligand 2 (86 mg, 0.25 mmol, 10 mol%), and potassium phosphate (1.06 g, 4.98 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (25 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate=10:1 to 5:1) to obtain the product (R)-L1 as a white solid (549 mg, 45% yield).

[0198] (2) Synthesis of M-PtL1: A dry 50 mL three-neck flask equipped with a magnetic stir bar and condenser was sequentially charged with L2 (150 mg, 0.31 mmol, 1.0 equiv.), potassium chloroplatinate (124 mg, 0.33 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (10 mg, 0.031 mmol, 0.1 equiv.). After purging with nitrogen three times, acetic acid (19 mL) pre-purified with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 120 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtL1 as a red solid (81 mg, 38% yield). 1H NMR(400MHz,DMSO-d6):δ0.85(d,J=6.8Hz,3H),1.03(d,J=6.8Hz,3H),1.34(s,9H),4.0 3-4.08(m,1H),4.30-4.36(m,1H),4.46-4.50(m,1H),6.36-6.38(m,1H),6.83(t,J=7.6 Hz,1H),6.99-7.03(m,2H),7.16(t,J=7.6Hz,1H),7.29-7.31(m,2H),7.52-7.55(m,3H) ,7.62(d,J=7.2Hz,1H),8.07-8.11(m,1H),8.20(d,J=7.6Hz,1H),8.78(d,J=4.8Hz,1H).

[0199] Example 42: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtL2 [ka]

[0200] (1) Synthesis of Ligand (S)-L2: (S)-IPr-Br (891 mg, 2.03 mmol, 1.2 equiv.), 1-OH (440 g, 1.69 mmol, 1.0 equiv.), cuprous iodide (65 mg, 0.34 mmol, 20 mol%), Ligand 2 (59 mg, 0.17 mmol, 10 mol%), and potassium phosphate (717 mg, 3.38 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (20 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 10:1 to 5:1) to obtain the product (S)-L2 as a white solid (450 mg, yield 46%). 1H NMR(500MHz,DMSO-d6):δ0.89-0.92(m,6H),1.18(s,9H),1.90-1.97(m,1H),3.09-3.14(m,1H),3.16-3.21(m,1H) ),3.97-4.03(m,1H),5.24(t,J=6.0Hz,1H),6.48-6.51(m,2H),7.03-7.06(m,3H),7.17-7.19(m,1H),7.33-7.36( m,1H),7.43-7.47(m,3H),7.49(d,J=2.0Hz,1H),7.52-7.53(m,1H),7.61(dt,J=8.0,1.0Hz,1H),7.77(d,J=8.0H z,2H),8.06-8.09(m,1H),8.13(d,J=9.0Hz,1H),8.23(d,J=7.5Hz,1H),8.27(d,J=8.5Hz,1H),8.67-8.68(m,1H).

[0201] (2) Synthesis of P-PtL3: (S)-L2 (249 mg, 0.43 mmol, 1.0 equiv.), potassium chloroplatinate (169 mg, 0.45 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (14 mg, 0.043 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (26 mL) pre-purified with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 120 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product P-PtL3 as a red solid (129 mg, 39% yield). 1H NMR(600MHz,DMSO-d6):δ0.76(d,J=7.2Hz,3H),0.82(d,J=7.2Hz,3H),1.30(s,9H),1.90-1.95(m,1H),3.8 3(dd,J=9.6,3.6Hz,1H),4.49-4.52(m,1H),4.60-4.63(m,1H),6.43(dd,J=7.8,1.2Hz,1H),6.85(t,J=7.8H z,1H),6.99(dd,J=7.8,0.6Hz,1H),7.12-7.25(m,3H),7.33-7.36(m,1H),7.38-7.40(m,1H),7.44-7.49(m, 3H),7.82(d,J=8.4Hz,1H),8.11-8.14(m,2H),8.17-8.20(m,1H),8.23(d,J=7.8Hz,1H),9.26-9.27(m,1H).

[0202] Example 43: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtL2 [ka]

[0203] (1) Synthesis of Ligand (R)-L2: (R)-IPr-Br (891 mg, 2.03 mmol, 1.2 equiv.), 1-OH (440 g, 1.69 mmol, 1.0 equiv.), cuprous iodide (65 mg, 0.34 mmol, 20 mol%), Ligand 2 (59 mg, 0.17 mmol, 10 mol%), and potassium phosphate (717 mg, 3.38 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (20 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate=10:1 to 5:1) to obtain the product (R)-L2 as a white solid (421 mg, 43% yield). 1H NMR(500MHz,DMSO-d6):δ0.89-0.92(m,6H),1.18(s,9H),1.90-1.97(m,1H),3.09-3.14(m,1H),3.16-3.21(m,1H) ),3.97-4.03(m,1H),5.24(t,J=6.0Hz,1H),6.48-6.51(m,2H),7.03-7.06(m,3H),7.17-7.19(m,1H),7.33-7.36( m,1H),7.43-7.47(m,3H),7.49(d,J=2.0Hz,1H),7.52-7.53(m,1H),7.61(dt,J=8.0,1.0Hz,1H),7.77(d,J=8.0H z,2H),8.06-8.09(m,1H),8.13(d,J=9.0Hz,1H),8.23(d,J=7.5Hz,1H),8.27(d,J=8.5Hz,1H),8.67-8.68(m,1H).

[0204] (2) Synthesis of M-PtL2: (R)-L2 (150 mg, 0.26 mmol, 1.0 equiv.), potassium chloroplatinate (102 mg, 0.27 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (8 mg, 0.026 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (16 mL) pre-purified with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 120 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtL2 as a red solid (48 mg, 24% yield). 1H NMR(600MHz,DMSO-d6):δ0.78(d,J=6.6Hz,3H),0.83(d,J=6.6Hz,3H),1.32(s,9H),1.92-1.95(m,1H),3.87 (dd,J=10.2,4.2Hz,1H),4.50-4.53(m,1H),4.62-4.65(m,1H),6.43(dd,J=7.8,1.2Hz,1H),6.85(t,J=7.8H z,1H),6.99(dd,J=7.8,0.6Hz,1H),7.12-7.26(m,3H),7.34-7.37(m,1H),7.38-7.41(m,1H),7.44-7.51(m, 3H),7.82(d,J=7.8Hz,1H),8.11-8.14(m,2H),8.17-8.20(m,1H),8.24(d,J=8.4Hz,1H),9.27-9.28(m,1H).

[0205] Example 44: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtL3 [ka]

[0206] (1) Synthesis of Ligand (S)-L3: Py-Ph-Br (440 mg, 1.88 mmol, 1.5 equiv.), (S)-Ph-OH (300 g, 1.25 mmol, 1.0 equiv.), cuprous iodide (48 mg, 0.25 mmol, 20 mol%), Ligand 2 (45 mg, 0.13 mmol, 10 mol%), and potassium phosphate (531 mg, 2.50 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (20 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 100 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate=10:1 to 5:1) to obtain the product (S)-L3 as a white solid (280 mg, yield 57%). 1H NMR (400MHz, DMSO-d6): δ4.18(t,J=8.4Hz,1H),4.82(t,J=9.6Hz,1H),5.37(t,J=8.8Hz,1H),7.17(d,J=8.0Hz,1H),7.26-7.38 (m,6H),7.49-7.58(m,3H),7.73(d,J=7.6Hz,1H),7.80(s,1H),7.86-7.93(m,2H),8.00(d,J=8.0Hz,1H),8.64(d,J=4.8Hz,1H).

[0207] (2) Synthesis of P-PtL3: (S)-L3 (173 mg, 0.44 mmol, 1.0 equiv.), potassium chloroplatinate (173 mg, 0.46 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (14 mg, 0.043 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (26 mL) pre-purified with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at room temperature for 12 hours. The mixture was then stirred at 120 °C for 2 days, cooled to room temperature, and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product P-PtL3 as a red solid (18 mg, 7% yield). 1 H NMR (400MHz, DMSO-d6): δ4.65(t,J=7.2Hz,1H),5.35(t,J=9.6Hz,1H),5.81(t,J=7.2Hz,1H),7.06-7.10(m,2H),7.16-7.20(m,1 H),7.25(d,J=2.4Hz,2H),7.31-7.42(m,2H),7.40(t,J=7.6Hz,2H),7.53-7.59(m,3H),7.92(t,J=8.0Hz,1H),8.05-8.09(m,2H).

[0208] Example 45: Synthesis of tetradentate cyclometallated platinum(II) complex M-PtL3 [ka]

[0209] (1) Synthesis of Ligand (R)-L3: Py-Ph-Br (735 mg, 3.14 mmol, 1.5 equiv.), (R)-Ph-OH (500 g, 2.09 mmol, 1.0 equiv.), cuprous iodide (80 mg, 0.42 mmol, 20 mol%), Ligand 2 (72 mg, 0.21 mmol, 10 mol%), and potassium phosphate (887 mg, 4.18 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (20 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 100 °C and stirred for 2 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate=10:1 to 5:1) to obtain the product (R)-L3 as a white solid (420 mg, yield 51%). 1 H NMR (400MHz, CDCl3): δ4.26(t,J=8.4Hz,1H),4.78(dd,J=10,8.4Hz,1H),5.37(dd,J=10,8.4Hz,1H),7.07-7.09(m,1H),7.20-7.25( m,2H),7.27-7.30(m,3H),7.33-7.37(m,2H),7.39-7.47(m,2H),7.68-7.77(m,5H),7.81(dt,J=8.0,1.2Hz,1H),8.67-7.69(m,1H).

[0210] (2) Synthesis of M-PtL3: (R)-L3 (200 mg, 0.51 mmol, 1.0 equiv.), potassium chloroplatinate (224 mg, 0.54 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (16 mg, 0.051 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (31 mL) pre-purified with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then stirred at 120 °C for 2 days. The mixture was then cooled to room temperature, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtL3 as a red solid (40 mg, 13% yield). 1 H NMR(500MHz,DMSO-d6):δ4.66(dd,J=8.5,6.5Hz,1H),5.35(dd,J=10,8.5Hz,1H),5.82(dd,J=10,6.0Hz,1H),7.06-7.10(m,2H), 7.23-7.27(m,2H),7.30-7.33(m,2H),7.40(t,J=8.0Hz,2H),7.54-7.60(m,3H),7.93(td,J=8.0,2.0Hz,1H),8.05-8.10(m,2H).

[0211] Example 46: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtOO [ka]

[0212] (1) Synthesis of Ligand (S,R)-L-OO: 1-Br (800 mg, 2.55 mmol, 1.2 equiv.), PyOPh-OH (512 mg, 2.12 mmol, 1.0 equiv.), cuprous iodide (40 mg, 0.21 mmol, 10 mol%), Ligand 2 (69 mg, 0.21 mmol, 10 mol%), and potassium phosphate (900 mg, 4.24 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, dimethyl sulfoxide (20 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 15:1 to 5:1) to obtain 480 mg (yield 54%) of the ligand (S,R)-L-OO as a black solid. 1 H NMR(500MHz,DMSO-d6):δ(ppm)3.22(d,J=18.0Hz,1H),3.60(dd,J=18.0,7.0Hz,1H),5.51(ddd,J=8.0,7.0,1.5H z,1H),5.69(d,J=8.0Hz,1H),6.80(t,J=2.5Hz,1H),6.85(ddd,J=8.5,2.5,0.5Hz,1H),6.93(ddd,J=8.5,2.0,0. 5Hz,1H),7.04(d,J=8.0Hz,1H),7.12(ddd,J=7.0,5.0,1.0Hz,1H),7.22-7.30(m,4H),7.40-7.44(m,3H),7.48(t ,J=8.0Hz,1H),7.62(dt,J=7.5,1.0Hz,1H),7.84(ddd,J=8.0,7.0,2.0Hz,1H),8.14(ddd,J=5.0,2.0,0.5Hz,1H). 13CNMR(125MHz, CDCl3):δ(ppm)39.73,83.27,111.61,111.72,114.53,115.77,118.72,119.16,122.26,123.66,125.25,125.6 0,127.44,128.47,129.66,130.33,139.45,139.67,141.80,147.73,155.39,156.53,158.20,163.24,163.36.HR(ESI):calcd for C 27 H 21 N2O3[M+H] + 421.15,found 421.15.

[0213] (2) Synthesis of P-PtOO: (S,R)-L-OO (200 mg, 0.48 mmol, 1.0 equiv.), potassium chloroplatinate (208 mg, 0.50 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (16 mg, 0.048 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (15 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then stirred at 120 °C for 2 days. The mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, the mixture was dissolved in dichloromethane, and the mixture was washed with water. The aqueous layer was extracted three times with dichloromethane, and the combined organic layers were evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane=3:1 to 1:1) to obtain the product P-PtOO as a pale yellow solid (140 mg, yield 48%). 1H NMR(500MHz,DMSO-d6): δ(ppm)3.48(d,J=18.5Hz,1H),3.61(dd,J=18.5,6.5Hz,1H),5.98(t,J=7.0Hz,1H),6.10(d ,J=7.0Hz,1H),6.44(d,J=7.5Hz,1H),6.89(dq,J=7.5,1.0Hz,2H),7.03-7.10(m,3H),7.12(t,J=7.5Hz,1H),7.18( dd,J=7.0,1.0Hz,1H),7.23(t,J=7.5Hz,1H),7.35(d,J=8.0Hz,1H),7.40(ddd,J=7.0,5.5,1.0Hz,1H),7.22-7.30( m,4H),7.61(dd,J=8.5,0.5Hz,1H),8.25(ddd,J=8.0,7.0,2.0Hz,1H),9.12(dd,J=5.5,1.5Hz,1H).HR(ESI):calcd for C 27 H 19 N₂O₃Pt[M+H] + 614.10, found 614.10.

[0214] [Example 47: Synthesis of four シクロメタル platinum(II) complex M-PtOO]

change

[0215] (1) Synthesis of Ligand (R,S)-L-OO: 2-Br (800 mg, 2.55 mmol, 1.2 equiv.), PyOPh-OH (512 mg, 2.12 mmol, 1.0 equiv.), cuprous iodide (40 mg, 0.21 mmol, 10 mol%), Ligand 2 (69 mg, 0.21 mmol, 10 mol%), and potassium phosphate (900 mg, 4.24 mmol, 2.0 equiv.) were sequentially added to a dry sealed tube equipped with a magnetic stir bar. After purging with nitrogen three times, N,N-dimethylformamide (15 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 15:1 to 5:1) to obtain 750 mg (yield 84%) of the ligand (R,S)-L-OO as a yellowish brown solid. 13 C NMR(125MHz,CDCl3):δ(ppm)39.74,83.28,111.61,111.73,114.53,115.77,118.73,119.19,122.28,123.68,125.26,125.62 ,127.46,128.48,129.67,130.33,139.46,139.68,141.82,147.75,155.40,156.53,158.23,163.26,163.37.HR(ESI):calcd for C 27 H 21 N2O3[M+H] + 421.15, found 421.15.

[0216] (2) Synthesis of M-PtOO: (R,S)-L-OO (210 mg, 0.50 mmol, 1.0 equiv.), potassium chloroplatinate (220 mg, 0.53 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (16 mg, 0.050 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (15 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at room temperature for 12 hours, and then stirred at 120 °C for 2 days. The mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride dihydrate (1.10 g, 5.00 mmol, 10.0 equiv.) and dichloromethane (15 mL) were added and stirred at 40 °C for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 1:1) to obtain the product M-PtOO as a pale yellow solid (185 mg, 60% yield). 1 H NMR(500MHz,DMSO-d6):δ(ppm)3.48(d,J=18.5Hz,1H),3.61(dd,J=18.5,6.5Hz,1H),5.98(t,J=7.0Hz, 1H),6.11(d,J=7.0Hz,1H),6.44(d,J=7.5Hz,1H),6.89(dq,J=7.5,1.5Hz,2H),7.03-7.14(m,4H),7.18( dd,J=7.5,1.5Hz,1H),7.22-7.25(m,1H),7.35(d,J=7.5Hz,1H),7.40(ddd,J=7.0,6.0,1.5Hz,1H),7.6 1(dd,J=8.0,0.5Hz,1H),8.26(ddd,J=8.5,7.0,1.5Hz,1H),9.13(dd,J=5.5,1.5Hz,1H).HR(ESI):calcd for C 27 H 19 N2O3Pt [M+H] + 614.10, found 614.10.

[0217] Example 48: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtOC [ka]

[0218] (1) Synthesis of the (S,R)-L-OC Ligand: To a dry, sealed tube equipped with a magnetic stir bar, 1-Br (337 mg, 1.07 mmol, 1.2 equiv.), C-OH (300 mg, 0.89 mmol, 1.0 equiv.), cuprous iodide (17 mg, 0.09 mmol, 10 mol%), Ligand 2 (29 mg, 0.09 mmol, 10 mol%), and potassium phosphate (378 mg, 1.78 mmol, 2.0 equiv.) were sequentially added. After three nitrogen purges, dimethyl sulfoxide (15 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane=3:1 to 1:1) to obtain 305 mg (yield 60%) of the ligand (S,R)-L-OC as a light brown solid. 1 H NMR(500MHz,DMSO-d6):δ(ppm)3.23(d,J=17.5Hz,1H),3.50(dd,J=18.0,6.5Hz,1H),5.52(ddd,J=8.0,7.0,1.5Hz ,1H),5.71(d,J=8.0Hz,1H),6.57(t,J=2.0Hz,1H),6.74(dq,J=8.0,1.0Hz,1H),6.84(ddd,J=8.0,2.0,0.5Hz,1H) ,7.02(d,J=8.0Hz,1H),7.13(ddd,J=8.0,2.5,1.0Hz,1H),7.18(ddd,J=7.5,5.0,1.0Hz,1H),7.22-7.31(m,5H),7 .30-7.31(m,2H),7.37-7.46(m,4H),7.51-7.60(m,4H),7.90(d,J=8.0Hz,2H),8.53(ddd,J=4.5,2.0,1.0Hz,1H). 13C NMR(125MHz,CDCl3):δ(ppm)39.74,53.38,66.98,83.24,116.52,118.59,119.0 0,120.12,121.30,121.71,121.74,122.80,123.12,125.25,125.65,126.67,127 .46,127.73,127.80,128.47,129.42,129.46,129.47,136.23,139.68,140.41,1 41.88,148.08,149.43,149.68,156.66,156.90,163.35,163.47.HR(ESI):calcd for C 40 H 29 N2O2[M+H] + 569.22, found 569.22.

[0219] (2) Synthesis of M-PtOC: (S,R)-L-OC (200 mg, 0.35 mmol, 1.0 equiv.), potassium chloroplatinate (154 mg, 0.37 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (11 mg, 0.035 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (15 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, stirred at 30 °C for 12 hours, and then stirred at 120 °C for 2 days. The mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, the mixture was dissolved in dichloromethane, and the mixture was washed with water. The aqueous layer was extracted three times with dichloromethane, and the combined organic layers were evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane=3:1 to 1:1) to obtain the product M-PtOC as a pale yellow solid (57 mg, 21% yield). 1H NMR (500MHz, DMSO-d6): δ(ppm)3.51(d,J=18.5Hz,1H),3.60(dd,J=18.5,5.5Hz,1H),5.73-5.75(m,1H),5.98-6.02(m,2H),6.26( dd,J=8.0,1.0Hz,1H),6.38(t,J=7.0Hz,1H),6.63-6.67(m,2H),6.88-6.90(m,2H),7.05(dd,J=7.5,1.0Hz,1H),7.13-7.19(m,2H) ,7.23(dd,J=7.0,1.0Hz,1H),7.27(td,J=7.5,1.0Hz,1H),7.34(d,J=7.5Hz,1H),7.39(d,J=7.5Hz,1H),7.52-7.58(m,2H),7.66(t d,J=7.5,1.0Hz,1H),7.86-7.90(m,2H),8.12(d,J=7.5Hz,1H),9.23(d,J=8.0Hz,1H),9.52(dd,J=5.5,1.5Hz,1H).HR(ESI):calcd for C 40 H 27 N₂O₂Pt [M+H] + 762.17, found 762.17.

[0220] [Example 49: Synthesis of four silica platinum (II) complex M-PtOC]

change

[0221] (1) Synthesis of the (R,S)-L-OC Ligand: To a dry, sealed tube equipped with a magnetic stir bar, 2-Br (337 mg, 1.07 mmol, 1.2 equiv.), C-OH (300 mg, 0.89 mmol, 1.0 equiv.), cuprous iodide (17 mg, 0.09 mmol, 10 mol%), Ligand 2 (29 mg, 0.09 mmol, 10 mol%), and potassium phosphate (378 mg, 1.78 mmol, 2.0 equiv.) were sequentially added. After purging with nitrogen three times, N,N-dimethylformamide (10 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane=3:1 to 1:1) to obtain the ligand (R,S)-L-OC as a pale yellow solid (278 mg, yield 55%). 13 C NMR (125MHz, CDCl3): δ(ppm)26.89,39.72,60.36,66.98,83.30,116.60,118.56,119. 02,120.12,121.34,121.75,122.86,123.11,125.23,125.71,126.67,127.47,127.74, 127.81,128.17,128.33,128.51,128.80,129.10,129.27,129.44,129.53,136.27,139 .65,140.40,141.78,149.41,149.70,156.61,156.90,163.33,163.56.HR(ESI):calcd for C 40 H 29 N2O2[M+H] + 569.22, found 569.22.

[0222] (2) Synthesis of M-PtOC: (R,S)-L-OC (200 mg, 0.35 mmol, 1.0 equiv.), potassium chloroplatinate (154 mg, 0.37 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (11 mg, 0.035 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (15 mL) pre-purged with nitrogen was added. The reaction mixture was purged with nitrogen for 30 minutes, stirred at 40 °C for 12 hours, and then stirred at 120 °C for 2 days. The mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride dihydrate (790 mg, 3.50 mmol, 10.0 equiv.) and dichloromethane (15 mL) were added and stirred at 40 °C for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 2:1 to 1:1) to obtain 80 mg of the product M-PtOC as a pale yellow solid (yield 30%). 1 H NMR(500MHz,DMSO-d6):δ(ppm)3.51(d,J=18.0Hz,1H),3.60(dd,J=18.5,5.5Hz,1H),5.74(d,J=8.0Hz,1H),5.98-6.02(m,2H),6.2 6(dd,J=8.0,1.0Hz,1H),6.38(t,J=7.5Hz,1H),6.63-6.67(m,2H),6.88-6.90(m,2H),7.05(dd,J=8.0,1.5Hz,1H),7.13-7.19(m,2H) ),7.23(dd,J=7.5,1.0Hz,1H),7.27(td,J=7.5,1.0Hz,1H),7.34(d,J=8.0Hz,1H),7.40(d,J=8.0Hz,1H),7.53-7.58(m,2H),7.66( td,J=7.5,1.0Hz,1H),7.86-7.90(m,2H),8.13(d,J=7.5Hz,1H),9.23(d,J=7.5Hz,1H),9.52(dd,J=6.0,1.5Hz,1H).HR(ESI):calcd for C 40 H 27 N2O2Pt [M+H] + 762.17, found 762.17.

[0223] Example 50: Synthesis of tetradentate cyclometallated platinum(II) complex P-PtS [ka]

[0224] (1) Synthesis of the (S,R)-LS Ligand: To a dry, sealed tube equipped with a magnetic stir bar, 1-Br (830 mg, 2.64 mmol, 1.2 equiv.), S-OH (500 mg, 2.20 mmol, 1.0 equiv.), cuprous iodide (42 mg, 0.22 mmol, 10 mol%), ligand 2 (72 mg, 0.22 mmol, 10 mol%), and potassium phosphate (934 mg, 4.40 mmol, 2.0 equiv.) were sequentially added. After three nitrogen purges, N,N-dimethylformamide (20 mL) was added under nitrogen protection. The sealed tube was placed in an oil bath at 85 °C and stirred for 3 days. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The combined organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane=3:1 to 1:1) to obtain 650 mg (yield 64%) of the ligand (S,R)-LS as a light brown solid. 1 H NMR(500MHz,DMSO-d6):δ(ppm)3.22(d,J=18Hz,1H),3.48(dd,J=18,6.5Hz,1H),5.52(td ,J=8.0,1.5Hz,1H),5.69(d,J=8.0Hz,1H),7.21-7.34(m,4H),7.32(ddd,J=8.0,2.5,1.0H z,1H),7.41-7.43(m,1H),7.50-7.49(m,2H),7.52-7.56(m,2H),7.61(t,J=8.0Hz,1H),7. 67-7.70(m,2H),7.88(ddd,J=8.0,1.5,0.5Hz,1H),8.04-8.05(m,1H),8.14-8.16(m,1H). 13C NMR(125MHz,CDCl3):δ(ppm)39.74,83.31,117.73,119.02, 121.12,121.59,122.10,122.62,123.35,123.77,125.26,125.32,125.61,126.35,127.46,128.48 ,129.8,129.83,130.43,135.09,135.43,139.68,141.80,154.02,156.69,157.69,163.35,167.10.

[0225] (2) Synthesis of P-PtS: (S,R)-LS (300 mg, 0.65 mmol, 1.0 equiv.), potassium chloroplatinate (282 mg, 0.68 mmol, 1.05 equiv.), and tetra-n-butylammonium bromide (21 mg, 0.065 mmol, 0.1 equiv.) were sequentially added to a dry 50 mL three-neck flask equipped with a magnetic stir bar and a condenser. After purging with nitrogen three times, acetic acid (20 mL) pre-purged with nitrogen was added. The reaction mixture was bubbled with nitrogen for 30 minutes, then stirred at 30 °C for 12 hours, then stirred at 120 °C for 2 days. The mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, and stannous chloride dihydrate (734 mg, 3.25 mmol, 5.0 equiv.) and dichloromethane (15 mL) were added and stirred at 40 °C for 1 day. The reaction mixture was washed with water, and the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and the solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 4:1 to 2:1) to obtain the product P-PtS as a pale yellow solid (120 mg, 28% yield). 1H NMR(500MHz,DMSO-d6):δ(ppm)3.54(d,J=18.5Hz,1H),3.66(dd,J=18.5,6.0Hz,1H),6.0 5(t,J=6.0Hz,1H),6.46(d,J=7.0Hz,1H),7.01(t,J=7.5Hz,1H),7.13(dd,J=8.0,1.0Hz, 1H),7.15-7.18(m,1H),7.19-7.25(m,4H),7.30(t,J=7.5Hz,1H),7.38(d,J=7.5Hz,1H), 7.57-7.60(m,1H),7.65-7.70(m,2H),8.33(dd,J=8.0,1.0Hz,1H),8.51(d,J=8.0Hz,1H).

[0226] (Description of electrochemical and photophysical tests and theoretical calculations) Absorption spectra were measured on an Agilent 8453 UV-Vis spectrophotometer, and steady-state emission and lifetime measurements were performed on a Horiba Jobin Yvon FluoroLog-3 spectrometer or a Shimadzu RF-6000 spectrophotometer. Low-temperature (77 K) emission spectra and lifetimes were measured in liquid nitrogen-cooled 2-methyltetrahydrofuran (2-MeTHF) solutions. Pt(II) complexes were theoretically calculated using the Gaussian 09 software package. Density functional theory (DFT) was used to optimize the ground-state (S0) molecular geometry. DFT calculations were performed with the B3LYP functional, using the 6-31G(d) basis set for C, H, O, and N atoms, and the LANL2DZ basis set for Pt atoms. The optical purity (ee value) of the enantiomers was tested using a chiral chromatography column, Enantiopak R-C (specifications: 4.6 × 250 mm, 5 μm).

[0227] (Experimental Data and Analysis) Figure 1 shows the design concept for optically pure circularly polarized luminescent materials based on helical chiral tetradentate cyclometalated complexes centered on a metal ion. Optically pure raw materials are economically available, and helical chirality is spontaneously induced from the central asymmetry. The circularly polarized luminescent materials eliminate the need for chiral resolution, significantly reducing the cost of preparing optically pure materials and allowing for large-scale production without the limitations of chiral column chromatography. As can be seen from the enantiomeric excess (ee) values ​​in Table 1, the resulting materials design concept yielded monochiral molecules with consistently high optical purity, all with ee values ​​>99%. The experimental data presented above also demonstrate the success of this material design concept.

[0228] As can be seen from the molecular structures optimized by density functional theory (DFT) calculations for a series of tetradentate cyclometalated platinum(II) complexes with different ligand structures shown in Figures 2 to 5, the occurrence of M-type helical chirality can be induced spontaneously for (R,S) ligands with central chirality, and the occurrence of P-type helical chirality can be induced spontaneously for (S,R) ligands with central chirality, and the M-type helical chiral molecules and P-type helical chiral molecules are enantiomers of each other, and the absolute configuration of the material molecules is supported by the X-ray diffraction single crystal structure of (R,S)-M-PtLA1 (Figure 1, left). Similar results were also obtained for the molecular structure of a tetradentate cyclometalated palladium(II) complex optimized by DFT calculations.

[0229] The structure of the comparative tetradentate cyclometallated platinum(II) complex of the present application is as follows. Since it is an achiral molecule, it has a specific rotation ([a] 20 D ) and chirality factor (g PL ) are both zero.

[0230] [ka]

[0231] As can be seen from the emission spectra of the synthesized optically pure helical asymmetric material molecules in dichloromethane solution at room temperature in Figures 6 to 20 and Table 2, the emission color of the cyclometallated complexes can be efficiently tuned by adjusting the tetradentate ligand structure, allowing control from the ultraviolet region of approximately 360 nm to the red region of 650 nm. Furthermore, it is believed that infrared emission can also be achieved by adjusting the tetradentate ligand structure. The emission spectra in Figures 6 to 20 essentially overlap completely, further proving that the corresponding material molecules in the figures are enantiomers.

[0232] As can be seen from the circular dichroism spectra of (S,R)-P-PtLA1 and (R,S)-M-PtLA1 in dichloromethane solution in Figure 21, CD is a circular dichroism spectrum, and the CD is a -5 The spectra have a high degree of mirror symmetry and a strong Cotton effect at approximately 248, 275, 300, and 248 nm, indicating that the enantiomers (S,R)-P-PtLA1 and (R,S)-M-PtLA1 have a strong polarizing ability for linearly polarized light. The specific rotations ([a] 20 D ) data, all of the molecules of the helical chiral tetradentate cyclometallated materials in this application exhibit a strong ability to polarize linearly polarized light. The dichroism spectra of other material molecules are shown in Figures 22 to 25, but the specific rotations ([a] 20 D ) are all zero.

[0233] From Table 2, the helical asymmetric material molecules in the present application exhibit uniformly strong circularly polarized luminescence, and the asymmetric factor (g PL ) has an absolute value of 4.0 × 10 -3 26 to 33 show the circularly polarized emission spectra of some material molecules. None of the comparative material molecules PtON1, PtON3 and PtOO3 exhibits circularly polarized emission.

[0234] The material has high chemical and thermal stability. The tetradentate ligand designed and developed is dsp 2 The central chiral ligand L can coordinate well with platinum(II) and palladium(II) metal ions during hybridization, forming stable, rigid square-shaped molecules with high chemical stability. a and the other ligand L 1 or L b Due to the large steric hindrance between the metal complex and the (R,S)-M-PtLA1, the entire metal complex molecule forms a stable helical chiral tetradentate cyclometalated complex, which does not lose its circularly polarized luminescence property due to racemization in solution or during high-temperature sublimation. Figure 34 shows the HPLC spectra of a mixture of (R,S)-M-PtLA1 and (S,R)-P-PtLA1, the HPLC spectrum of optically pure (R,S)-M-PtLA1, the HPLC spectrum of optically pure (S,R)-P-PtLA1, and the HPLC spectrum of sublimed (R,S)-M-PtLA1, respectively, demonstrating the high thermal stability of this material. Sublimation experiments also demonstrated that the (R,S)-M-PtLA1 and (S,R)-P-PtLA1 materials sublimed at 320 °C did not undergo racemization. The thermogravimetric analysis curve of (R,S)-M-PtLA1 in FIG. 35 shows that its decomposition temperature (the temperature at which the mass loss is 5%) reaches 405°C.

[0235] The specific rotation data for several chiral starting intermediates and chiral metal complexes listed in Table 1 below reveal that the sense of rotation of starting intermediates and chiral metal complexes with the same central chirality is completely different, and the specific rotation values ​​also vary significantly, indicating that the helical chirality of the metal ion-centered complex has a decisive impact on the overall optical properties of the compound. Furthermore, complexes with the same central chirality and helical chirality but different ligand structures also have very large differences in specific rotation, such as (S,R)-P-PtLA1 (+477.2) and (S,R)-P-PtLA1 (+784.6), indicating that the structure of the ligand structure has a significant impact on the optical rotation. At the same time, since stimulated emission from metal complexes is primarily related to the metal-to-ligand charge transfer state (MLCT) and the intraligand charge transfer state (ILCT), the helical chirality of the metal complex and the ligand structure also have a significant impact on its circular polarization properties.

[0236] [Table 1] NOTE: Specific rotation values ​​of all samples were measured in dichloromethane solution.

[0237] [Table 2] NOTE: The maximum emission wavelength (λ) of all samples max ) and chirality factor (g PL ) were measured in dichloromethane solution.

[0238] As can be seen from the theoretical calculations and experimental data of some chiral metal complex material molecules in Table 3 below, the molecular cores containing this type of chiral structural unit all have distorted square structures, and the coordinated heterocycles have chiral steric hindrance at adjacent positions. Therefore, the two terminal heterocycles coordinated to the central metal ion can be positioned on both sides of the plane, forming a helical asymmetric molecule centered on the central metal, which can be used as a circularly polarized luminescent material.

[0239] Furthermore, the above-mentioned large amount of theoretical calculations and experimental data also show that the importance of the steric hindrance of the neighboring groups in the chiral structural unit coordinated to the central metal, and that the central asymmetry of the chiral structural unit of the ligand is the key to inducing the generation of helical chirality around the metal in the entire material molecule. At the same time, the above-mentioned large amount of synthetic experimental examples and optical property characterization and testing also show that the molecular design method for circularly polarized luminescent materials of the present application is completely successful.

[0240] [Table 3-1] [Table 3-2] [Table 3-3] [Table 3-4] [Table 3-5] [Table 3-6] Note: The dihedral angle refers to the angle between the two terminal heterocycles coordinated to the central metal ion.

[0241] In organic light-emitting devices, carriers are injected from the positive and negative electrodes into the light-emitting material to generate an excited light-emitting material, which then emits light. The complex represented by general formula (1) of the present invention can be used as a phosphorescent material in excellent organic light-emitting devices such as organic photoluminescence devices and organic electroluminescence devices. Organic photoluminescence devices have a structure in which at least an emission layer is formed on a substrate. Organic electroluminescence devices have a structure in which at least an anode, a cathode, and an organic layer are formed between the anode and the cathode. The organic layer includes at least an emission layer, and may consist solely of an emission layer, or may have one or more organic layers in addition to the emission layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer with hole injection function, and the electron transport layer may be an electron injection transport layer with electron injection function. A specific example of the structure of an organic electroluminescence device is shown in Figure 35. In Figure 35, there are seven layers from bottom to top, which are a substrate, an anode, a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, and a cathode, in that order. The emitting layer is a mixed layer of a host material doped with a guest material.

[0242] The compounds shown in Examples 1 to 50 are used in OLED devices as phosphorescent light-emitting materials and have the structures: ITO / HATCN (10 nm) / TAPC (65 nm) / host material: emitting material (10 wt.%, 20 nm) / TmPyPB (55 nm) / LIF / Al Here, ITO is the transparent anode, HATCN is the hole injection layer, TAPC is the hole transport layer, the host materials are mCBP and 26mCPy, TmPyPB is the electron transport layer, LIF is the electron injection layer, and Al is the cathode. The number in parentheses is the film thickness in nanometers (nm).

[0243] The molecular formula of the material applied in the device is:

[0244] [ka]

[0245] Furthermore, in organic light-emitting devices, carrier injection from the positive and negative electrodes into the light-emitting material generates an excited light-emitting material, causing it to emit light. The complex represented by general formula (1) of the present invention can be used as a phosphorescent material in excellent organic light-emitting devices such as organic photoluminescence devices and organic electroluminescence devices. An organic photoluminescence device has a structure in which at least an emitting layer is formed on a substrate. An organic electroluminescence device has a structure in which at least an anode, a cathode, and an organic layer are formed between the anode and the cathode. The organic layer includes at least an emitting layer, and may consist solely of the emitting layer, or may have one or more organic layers in addition to the emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer with hole injection function, and the electron transport layer may be an electron injection transport layer with electron injection function. An example of a specific organic electroluminescence device structure is shown in Figure 35. In Figure 35, there are seven layers from bottom to top, which are a substrate, an anode, a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, and a cathode, in that order. The emitting layer is a mixed layer of a host material doped with a guest material.

[0246] Each layer of the organic light-emitting device of the present invention can be formed by a wet film-forming method such as a vacuum deposition method, a sputtering method, an ion plating method, a spin coating method, an inkjet method, or a printing method, and the solvent used is not particularly limited.

[0247] In a preferred embodiment of the present invention, the OLED device of the present invention comprises a hole transport layer, and the hole transport material can be preferably selected from known or unknown materials, and particularly preferably selected from the following structures, but it is not meant to limit the present invention to the following structures:

[0248] [ka]

[0249] In a preferred embodiment of the present invention, the hole-transporting layer included in the OLED device of the present invention comprises one or more p-type dopants. A preferred p-type dopant of the present invention has the following structure, but this does not mean that the present invention is limited to the following structure:

[0250] [ka]

[0251] In a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of compounds ET-1 to ET-13, but this does not mean that the present invention is limited to the following structure.

[0252] [ka]

[0253] The electron transport layer can be formed of an organic material and one or more n-type dopants (eg, LIQ).

[0254] The compound represented by Example 1 was used as a circularly polarized light-emitting material in an OLED device, whose structure can also be represented as follows: a hole injection layer (HIL) on glass containing ITO, consisting of HT-1:P-3 (95:5 v / v%) and having a thickness of 10 nm; a hole transport layer (HTL) on glass containing ITO, consisting of HT-1 and having a thickness of 90 nm; an electron blocking layer (EBL) on glass containing ITO, consisting of HT-10 and having a thickness of 10 nm; an emitting layer (EML) on glass containing ITO, consisting of a host material (H-1 or H-2 or H-3 or H-4 or H-5 or H-6):a platinum metal complex of the present invention (95:5 v / v%) and having a thickness of 35 nm; an electron transport layer (ETL) on glass containing ITO, consisting of ET-13:LiQ (50:50 v / v%) and having a thickness of 35 nm; and a cathode containing evaporated Al of 70 nm.

[0255] [ka]

[0256] The fabricated organic light emitting devices were subjected to a current draining test at 10 mA / cm using standard methods known in the art. 2 When tested under a current condition of 1000 Hz, the device using (S,R)-P-PtLA1 as the emitting material had a significant circularly polarized electroluminescence signal and a chirality factor (g EL ) is 1.4 × 10 -3 The maximum external quantum efficiency (EQE) reached 18%.

[0257] It should be noted that the above structure is an example of the application of the circularly polarized luminescent material of the present invention, and does not limit the specific OLED device structure of the circularly polarized luminescent material shown in the present invention, and the circularly polarized luminescent material is not limited to the compounds shown in the examples.

[0258] It should be noted that the above structure is an example of an application of the phosphorescent material of the present invention, and does not limit the specific OLED device structure of the phosphorescent material shown in the present invention, and the phosphorescent material is not limited to the compounds shown in the examples.

[0259] The above-described embodiments are specific examples for realizing the present invention, and it will be apparent to those skilled in the art that in actual applications, various changes in form and details can be made without departing from the spirit and scope of the present invention. For example, many of the substituent structures described herein can be replaced by other structures without departing from the spirit of the present invention.

[0260] (Addendum) (Appendix 1) Central chirality? and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. orA palladium (II) complex circularly polarized luminescent material, characterized in that its chemical formula is represented by general formula (I), (I'), (II), (II'), (III) and (III'), wherein (I) and (I'), (II) and (II'), and (III) and (III') are enantiomers of each other, is a centrally chiral or asymmetric material. and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or Palladium(II) complex circularly polarized luminescent material. [ka] wherein M is Pt or Pd, and V 1 , V 2 , V 3 and V 4 are each independently N or C, L 1 , L 2 and L 3 are each independently a 5- or 6-membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring; A 1 , A 2 , X and X 1 are independently O, S, and CR x R y , C=O, Si-R x R y , GeR x R y , N.R. 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 and R 1 , R 2 and R 3 each independently represent mono-, di-, tri-, or tetra-substituted or unsubstituted, and R 1 , R 2 , R 3 , R a , R b , R c , R d, R e , R f , R g , R h , R x , R y and R z are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; 1 , R 2 and R 3 can be optionally linked to form a fused ring, and R a , R b , R c and R d Any two groups in R can be joined to form a ring system; e , R f , R g and R h Any two groups in the formula may be joined to form a ring system.

[0261] (Appendix 2) The centrally chiral or asymmetric diastereomeric rings having the general formulae (I), (I'), (II) and (II') as set forth in Appendix 1 are preferably the following general formulae (IA), (IA), (IB), (IC), (ID), (IE), (IF), (IG), (IH), (II), and (II-A) and their enantiomers (I'-A), (I'-A), (I'-B), (I'-C), (I'-D), (I'-E), (I'-F), (I'-G), (I'-H), (I'-I), and (II'-A). and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or Palladium(II) complex circularly polarized luminescent material. [ka] [Z and Z 1 are independently O, S, and CR x R y , C=O, SiR x R y , GeR x R y , N.R. 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 and R 4 and R 5 each independently represents mono-, di-, tri-, tetra- or unsubstituted, and R 1 , R 2 , R 3 , R 3 , R 4 , R 5 , R a , R b , R c , R d , R x , R y and R zare each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; 1 , R 2 , R 3 , R 4 and R 5 can be optionally linked to form a fused ring, and R a , R b , R c and R d Any two groups in the formula may be joined to form a ring system.

[0262] (Appendix 3) L in the general structure a and L b The structure of the central chiral or asymmetric compound described in Appendix 1 or 2 is preferably selected from the structures shown below. and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or Palladium(II) complex circularly polarized luminescent material. [ka] [In the formula, R a1 , R a2 and R a3each independently represent hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; In the formula, R b1 , R c1 and R c2 each independently represents mono-, di-, tri-, tetra- or unsubstituted, and R b1 , R c1 and R c2 are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; b1 , R c1 and R c2 can optionally be linked to form a fused ring.

[0263] (Appendix 4) L according to Appendix 3 is preferably selected from the structures shown below a and Lb The specific structure of. [ka] [ka] [ka] [In the formula, R d1 、R e2 , R e3 and R e4 each independently represent mono-, di-, tri-, tetra- or unsubstituted, and R d1 、R e2 、R e3 and R e4 are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; R d1 、R e2 、R e3 and R e4 can optionally be linked to form a fused ring.

[0264] (Appendix 5) Shown below: [ka] [ka] [ka] [ka] The central chirality of the compound according to Supplementary Note 1 or 2 is preferably selected from and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or Palladium(II) complex circularly polarized luminescent material.

[0265] (Appendix 6) The following platinum(II) metal complexes and their enantiomers circularly polarized luminescent materials and their corresponding metal palladium(II) complex circularly polarized luminescent materials: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

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[0266] (Appendix 7) The organic light-emitting device, the 3D display device, the 3D imaging device, the optical information encryption device, the information storage device, and the bioimaging device, and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or Application of palladium(II) complexes as circularly polarized luminescent materials.

[0267] (Appendix 8) 8. The application of claim 7, wherein the organic light-emitting element is an organic light-emitting diode, a light-emitting diode, or a light-emitting electrochemical cell.

[0268] (Appendix 9) The light-emitting element includes a first electrode, a second electrode, and at least one organic layer provided between the first electrode and the second electrode, and the organic layer has a central chirality or and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or The application of claim 8, comprising a palladium(II) complex circularly polarized luminescent material.

[0269] (Appendix 10) A 3D display device including an organic light-emitting element, the organic light-emitting element including a first electrode, a second electrode, and at least one organic layer provided between the first electrode and the second electrode, the organic layer being one of the centrally asymmetric organic layers described in Supplementary Note 1 or 2. and others Tetradentate cyclometallated platinum(II) compounds inducing helical chirality. or A 3D display device containing a circularly polarized luminescent material of a palladium(II) complex.

Claims

1. A circularly polarized luminescent material of a tetradentate cyclometallated platinum(II) or palladium(II) complex in which helical asymmetry is induced from central asymmetry, characterized in that the tetradentate cyclometallated platinum(II) or palladium(II) complex in which helical asymmetry is induced from central asymmetry has a chemical formula represented by general formulas (I), (I'), (II), (II'), (III) and (III'), where (I) and (I'), (II) and (II'), and (III) and (III') are enantiomers of each other. 【Chemistry 1】 wherein M is Pt or Pd, and V １、 V ２ , V ３ and V ４ are each independently N or C; L １ , L ２ and L ３ are each independently a 5- or 6-membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring; A １ , A ２ , X and X １ are each independently O, S, or CR ｘ R ｙ , C═O, Si—R ｘ R ｙ , GeR ｘ R ｙ , N.R. ｚ , P.R. ｚ , R ｚ P=O, AsR ｚ , R ｚ As=O, S=O, SO ２ , Se, Se=O, SeO ２ , B.H., B.R. ｚ , R ｚ Bi=O or BiR ｚ and R １ , R ２ and R ３ each independently represents mono-, di-, tri-, or tetra-substituted or unsubstituted, and R １ , R ２ , R ３ , R ａ , R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ , R ｈ , R ｘ , R ｙ and R ｚ are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; １ , R ２ and R ３ can optionally be linked to form a fused ring, and R ａ , R ｂ , R ｃ and R ｄ Any two groups in R can be linked to form a ring system; ｅ , R ｆ , R ｇ and R ｈ any two groups in the formula (I) can be linked to form a ring system; L ａ and L ｂ The structure of is selected from the structures shown below: 【Chemistry 2】 In the formula, R ａ１ , R ａ２ and R ａ３ each independently represent hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; In the formula, R ｂ１ , R ｃ１ and R ｃ２ each independently represents mono-, di-, tri-, tetra- or unsubstituted, and R ｂ１ , R ｃ１ and R ｃ２ are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; ｂ１ , R ｃ１ and R ｃ２ can optionally be linked to form a fused ring.

2. The circularly polarized luminescent material of tetradentate cyclometallated platinum(II) or palladium(II) complex that induces helical chirality from central asymmetry according to claim 1, characterized in that the chemical formulas represented by the general formulas (I), (I'), (II) and (II') are the following general formulas (IA), (IB), (IC), (ID), (IE), (IF), (IG), (I-H), (II), and (II-A) and their enantiomers (I'-A), (I'-B), (I'-C), (I'-D), (I'-E), (I'-F), (I'-G), (I'-H), (I'-I), and (II'-A). 【Transformation 3】 [Z and Z １ are each independently O, S, or CR ｘ R ｙ , C═O, SiR ｘ R ｙ , GeR ｘ R ｙ , N.R. ｚ , P.R. ｚ , R ｚ P=O, AsR ｚ , R ｚ As=O, S=O, SO ２ , Se, Se=O, SeO ２ , B.H., B.R. ｚ , R ｚ Bi=O or BiR ｚ and R ４ and R ５ each independently represents mono-, di-, tri-, tetra- or unsubstituted, and R １ , R ２ , R ３ , R ３ , R ４ , R ５ , R ａ , R ｂ , R ｃ , R ｄ , R ｘ , R ｙ and R ｚ are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; １ , R ２ , R ３ , R ４ and R ５ can optionally be linked to form a fused ring, and R ａ , R ｂ , R ｃ and R ｄ any two groups in the formula (I) can be linked to form a ring system; The structure of L a is selected from the structures shown below. 【Chemistry 4】 In the formula, R a1 , R a2 and R a3 each independently represent hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl or a combination thereof; In the formula, R b1 , R c1 and R c2 each independently represent mono-, di-, tri-, or tetra-substituted or unsubstituted, and R b1 , R c1 and R c2 each independently represent hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof, and two or more adjacent R b1 , R c1 and R c2 can optionally be linked to form a fused ring.

3. Said L ａ and L ｂ Circularly polarized luminescent material of a tetradentate cyclometallated platinum (II) or palladium (II) complex inducing helical asymmetry from central asymmetry according to claim 1, characterized in that the structure of: 【Chemistry 5-1】 【Chemistry 5-2】 【Chemistry 5-3】 [In the formula, R d1 represents mono-, di-, tri-, tetra- or unsubstituted; R d1 , R ｅ２ , R ｅ３ and R ｅ４ are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, or a combination thereof; ｄ１ , R ｅ２ , R ｅ３ and R ｅ４ can optionally be linked to form a fused ring.

4. Shown below: 【Chemistry 6-1】 【Chemistry 6-2】 【Transformation 6-3】 【Chemistry 6-4】 A circularly polarized luminescent material comprising a tetradentate cyclometallated platinum(II) or palladium(II) complex in which helical chirality is induced from central chirality, characterized in that the complex is selected from the following:

5. The following platinum (II) metal complexes and their enantiomers circularly polarized luminescent materials and their corresponding metal palladium (II) complex circularly polarized luminescent materials: 【Chemistry 7-1】 【Chemistry 7-2】 【Transformation 7-3】 【Chemistry 7-4】 【Transformation 7-5】 【Transformation 7-6】 【Transformation 7-7】 [Transformation 7-8] 【Transformation 7-9】 【Chemistry 7-10】 【Chemistry 7-11】 【Chemistry 7-12】 【Chemistry 7-13】 【Chemistry 7-14】 【Chemistry 7-15】 【Chemistry 7-16】 【Chemistry 7-17】 【Chemistry 7-18】 【Chemistry 7-19】 【Chemistry 7-20】 【Chemistry 7-21】 【Chemistry 7-22】 【Chemistry 7-23】 【Chemistry 7-24】 [Chemistry 7-25] [Chemistry 7-26] 【Chemistry 7-27】 [Chemistry 7-28] [Chemistry 7-29] 【Chemistry 7-30】 【Chemistry 7-31】 【Chemistry 7-32】 【Chemistry 7-33】 【Chemistry 7-34】 【Chemistry 7-35】 【Chemistry 7-36】 【Chemistry 7-37】 【Chemistry 7-38】 【Chemistry 7-39】 【Chemistry 7-40】 【Chemistry 7-41】 【Chemistry 7-42】 【Chemistry 7-43】 [Chemistry 7-44] 【Chemistry 7-45】 [Chemistry 7-46] A circularly polarized luminescent material of a tetradentate cyclometallated platinum(II) or palladium(II) complex in which helical chirality is induced from central chirality, characterized in that the tetradentate cyclometallated platinum(II) or palladium(II) complex is further selected from the group consisting of:

6. Use of a circularly polarized light-emitting material of a tetradentate cyclometallated platinum(II) or palladium(II) complex in which helical asymmetry is induced from central asymmetry according to any one of claims 1 to 5 in an organic light-emitting device, a 3D display device, a 3D imaging device, an optical information encryption device, an information storage device, or a bioimaging device.

7. 7. The use according to claim 6, characterized in that the organic light-emitting element is an organic light-emitting diode, a light-emitting diode or a light-emitting electrochemical cell.

8. The light-emitting device according to claim 7, wherein the light-emitting device comprises a first electrode, a second electrode, and at least one organic layer provided between the first electrode and the second electrode, the organic layer comprising a circularly polarized light-emitting material of a tetradentate cyclometallated platinum(II) or palladium(II) complex that induces helical chirality from central asymmetry.

9. A 3D display device comprising an organic light-emitting element, the organic light-emitting element comprising a first electrode, a second electrode, and at least one organic layer provided between the first electrode and the second electrode, the organic layer comprising a circularly polarized light-emitting material of a tetradentate cyclometallated platinum(II) or palladium(II) complex that induces helical chirality from central asymmetry according to any one of claims 1 to 5.

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