Spiro chiral tetradentate cyclometalated platinum (II) and / or palladium (II) complex circularly polarized luminescence material and use thereof

Abstract

Provided are a spiro chiral tetradentate cyclometalated platinum (II) and / or palladium (II) complex circularly polarized luminescence material and the use thereof. For the formation of the spiro chiral metal complex molecule, a central chiral fragment in a ligand can autonomously induce the coordination of the entire tetradentate ligand with metal ions in a small steric hindrance manner, so as to form an optically-pure spiro chiral metal complex circularly polarized luminescence material. The induced reaction has stereospecificity, such that the spiro chiral metal complex does not require chiral resolution. The spiro chiral metal complex has significant application value in circularly polarized luminescence elements and related fields.

Description

Screw chiral tetradentate cyclometalated platinum (II) and / or palladium (II) complex circularly polarized light emitting material and application TECHNICAL FIELD

[0001] The present application relates to the circularly polarized light emitting material preparation technical field, and particularly relates to a screw chiral tetradentate cyclometalated platinum (II) and / or palladium (II) complex circularly polarized light emitting material and application. BACKGROUND

[0002] Circularly polarized light (CPL) is a completely different form of light from the straight light of the sun. Circularly polarized light is a phenomenon that the chiral light emitting material emits left-handed or right-handed circularly polarized light after being excited. Therefore, the design and development of chiral light emitting materials are the key in this field. With the in-depth research of researchers, so far, circularly polarized light materials have important applications in 3D display, data storage, quantum computing, optical anti-counterfeiting, biological imaging and asymmetric synthesis.

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

[0004] Therefore, in view of the deficiencies in the prior art, the present application provides a helical chirality four-tooth ring metal platinum (II) and / or palladium (II) complex circularly polarized light emitting material and application. The circularly polarized light emitting material provided has a triazole carbene and its derivative structure group, which can independently induce the entire four-tooth ligand to coordinate with the metal ion in a small steric hindrance manner through the central chiral fragment in the four-tooth ligand, to form an optically pure helical chirality metal platinum (II) or palladium (II) complex circularly polarized light emitting material without the need for chiral separation. The circularly polarized light emitting material has high chemical stability and thermal stability, and has important application prospects in circularly polarized luminescence elements.

[0005] The object of the present application is achieved by the following technical solutions.

[0006] In many embodiments, the present application provides a helical chirality four-tooth ring metal platinum (II) and / or palladium (II) complex circularly polarized light emitting material, which has a chemical formula as shown in general formula (I) and / or (I'), wherein (I) and (I') are enantiomers of each other:

[0007] wherein M is Pt or Pd; V 1 , V 2 and V 3 are each independently N or C;

[0008] L 1 , L 2 , L 3 and L 4 are each independently a five- or six-membered carbocyclic ring, a heterocyclic ring, an aromatic ring or a heteroaromatic ring; L5 is a six- to ten-membered carbocyclic or heterocyclic ring with a central chirality, "*" indicates the carbon atom with central chirality, i.e. R a and R b are different substituents;

[0009] A is selected from O, S, CR x R y , C=O, SiR x R y , GeR x R y , NR z , PR z , R z P=O, AsR z , R z As=O, S=O, SO2, Se, Se=O, SeO2, BH, BR z , R z Bi=O or BiR z ;

[0010] X 1 and X 2 may be present or absent, if present, X 1 and X 2 are each independently selected from a single bond, O, S, CR x R y , C=O, SiR x R y , GeR x R y , NR z , PR z , R z P=O, AsR z , R z As=O, S=O, SO2, Se, Se=O, SeO2, BH, BR z , R z Bi=O or BiR z ;

[0011] Z is N, CR x , SiR x , GeR x , B, P, P=O, As, As=O, Bi=O or Bi;

[0012] R 1 , R 2 , R 3 , R 4 , and R 5 each independently represent mono-, di-, tri-, tetra-, penta-, or hexa-substitution or no substitution, while R 1R 2 R 3 R 4 R 5 R a R b R x R y R z each independently is selected from any one or a combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, halo heteroaryl, deuterated alkyl, haloaryl, halo heteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylheteroarylsilyl, alkylarylsilyl, arylsilyloxy, heteroarylsilyloxy, alkylheteroarylsilyloxy, alkylarylsilyloxy, alkenyl, cycloalkenyl, alkynyl, hydroxy, thiohydroxy, nitro, -CN, amino, mono- or di- alkylamino, mono- or di- arylamino, ester, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramidate, imine, sulfo, carboxyl, hydrazine.

[0013] Preferably, two or more adjacent R 1 R 2 R 3 R 4 R 5 may optionally be joined to form a fused ring; and any two of R a R b and R 5 may be joined to form a ring system.

[0014] In many embodiments, L 3 is preferably selected from the following structures:

[0015] wherein X a , X b , X c and X d may each independently be selected from a single bond, O, S, CR x R y , C=O, SiR x R y , GeR x R y , NR z , PR z , R z P=O, AsR z , R zAs=O, S=O, SO2, Se, Se=O, SeO2, BH, BR z , R z Bi=O or BiR z ; M, V 3 , R x , R y , R z are each independently defined as in general formula (I) and / or (I').

[0016] In many embodiments, the helical tetradentate ring metal platinum(II) and / or palladium(II) complex circularly polarized luminescent material of general formula (I) and / or (I') is preferably selected from the following general formulae (I-A), (I-B), (I-C), (I-D), (I-E), (I-F), (I-G), (I-H), (I-I) and / or their enantiomers (I'-A), (I'-B), (I'-C), (I'-D), (I'-E), (I'-F), (I'-G), (I'-H), (I-I):

[0017] wherein Y 4 , Y 5 , Y 6 are each independently N, CR 3 , Y 7 , Y 8 , Y 18 are each independently N, CR 2 , Y 9 , Y 10 , Y 11 , Y 16 are each independently N, CR 1 , Y 12 , Y 13 , Y 14 , Y 15 and Y 17 are each independently N, CR 4 ; the R 1 -R 5 are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, haloaryl, haloheteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylheteroarylsilyl, alkylarylsilyl, arylsilyloxy, heteroarylsilyloxy, alkylheteroarylsilyloxy, alkylarylsilyloxy, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, nitro, -CN, or combinations thereof, and A, M, X 1 , X 2 , R a , Rb and L 5 as defined in general formula (I) and / or (I').

[0018] In many embodiments, L 5 in the circularly polarized luminescent material of general formula (I) and / or (I') is preferably selected from the following structures, and corresponding isomers thereof, but is not limited thereto:

[0019] wherein X 3 , X 4 , X 5 , X 6 and X 7 are each independently selected from O, S, CR x R y , C=O, SiR x R y , GeR x R y , NR z , PR z , R z P=O, AsR z , R z As=O, S=O, SO2, Se, Se=O, SeO2, BH, BR z , R z Bi=O or BiR z ; R x , R y , R z , M, R 5 , R a and R b are as defined in general formula (I) and / or (I').

[0020] In many embodiments, L 5 in the circularly polarized luminescent material of general formula (I) and / or (I') is more preferably selected from the following structures, and corresponding isomers thereof, but is not limited thereto:

[0021] wherein R 1‘ , R 2’ , R 3‘ , R 4‘ , R 5‘ and R 6‘Each time it appears, it is independently selected from any one or combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylarylsilyl, alkylheteroarylsilyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, nitro, -CN, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, aminosulfonyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfonyl, carboxyl, and hydrazine; M, R a and R b As defined in general formulas (I) and / or (I'); two or more adjacent R a R b R 1’ R 2’ R 3‘ R 4‘ R 5‘ and R 6‘ They can be selectively linked to form fused rings or other cyclic systems.

[0022] In many embodiments, L in the circularly polarized luminescent materials represented by general formula (I) and / or (I') 5 The structure is further preferably derived from the following structures and their corresponding isomers, but is not limited to these:

[0023] Among them, R 7 and R 8 Each occurrence independently represents single, double, triple, quadruple, or penta-substitution or no substitution, while R 7 and R 8 Each is independently selected from any one or combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteraryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkyl(hetero)arylsilyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, nitro, -CN, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, aminosulfonyl, carbamoyl, alkylthio, sulfinyl, ureyl, phosphoramido, imino, sulfonyl, carboxyl, and hydrazyl; two or more adjacent R 7 and R 8 Selective linkage can be used to form fused rings; R 1‘ To R6‘ each occurrence is selected independently from any one or combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylarylsilyl, alkylheteroarylsilyl, -CN; M is Pt or Pd.

[0024] In many embodiments, the present application also provides a spirochiral tetradentate cyclometalated platinum(II) and / or palladium(II) complex circularly polarized luminescent material, whose chemical formula is preferably selected from the P-type structure (M = Pt or Pd) shown below, and its corresponding M-type isomer, but not limited thereto, "D" represents deuterium:

[0025] In many embodiments, the present application also provides a spirochiral tetradentate cyclometalated platinum(II) and / or palladium(II) complex circularly polarized luminescent material, whose chemical formula is preferably selected from the P-type structure (M = Pt or Pd) shown below, and its corresponding M-type isomer, but not limited thereto:

[0026] wherein X 4 is selected from O, S, CR x R y , C=O, SiR x R y , GeR x R y , NR z , PR z , R z P=O, AsR z , R z As=O, S=O, SO2, Se, Se=O, SeO2, BH, BR z , R z Bi=O or BiR z ; R x, R y , and R z each independently is selected from any one of, or a combination of, hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, halo heteroaryl, deuterated alkyl, haloaryl, halo heteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylheteroarylsilyl, alkylarylsilyl, arylsilyloxy, heteroarylsilyloxy, alkylheteroarylsilyloxy, alkylarylsilyloxy, alkenyl, cycloalkenyl, -CN;

[0027] R 1 , R 2 , R 3 , R 4 , and R 7 each independently represents mono, di, tri, tetra, penta, or hexa- substitution or no substitution, while R 1 , R 2 , R 3 , R 4 and R 7 each independently is selected from any one of, or a combination of, hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, halo heteroaryl, deuterated alkyl, haloaryl, halo heteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylheteroarylsilyl, alkylarylsilyl, arylsilyloxy, heteroarylsilyloxy, alkylheteroarylsilyloxy, alkylarylsilyloxy, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, nitro, -CN, amino, mono- or di- alkylamino, mono- or di- arylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramidate, imine, sulfo, carboxyl, hydrazine; 1 , R 2 , R 3 and R 4 may optionally be linked to form a fused ring; R 1‘ , R 2’ , R 3‘ and R 4‘each independently selected from any one or combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, halo heteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylarylsilyl, alkylheteroarylsilyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, nitro, -CN, amino, mono- or di-alkylamino, mono- or di-aryl amino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, alkylthio, sulfinyl, urea, phosphoramide, imine, sulfo, carboxyl, hydrazine; two or more adjacent R 1’ , R 2’ , R 3‘ , and R 4‘ may optionally be linked to form a fused ring or other cyclic system.

[0028] The present application also provides the use of the chiral spiro tetradentate platinum(II) and / or palladium(II) complex circularly polarized luminescent material based on the triazole carbene and its derivative structural unit in the preparation of electronic devices. Preferably, the electronic device is a light-emitting element, a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device, or a biological imaging device. Further, the light-emitting element is an organic electroluminescent device or an organic optoelectronic device.

[0029] The present application also provides an organic electroluminescent device, which comprises a cathode, an anode, and an organic functional layer between the two; the organic functional layer comprises at least one chiral spiro tetradentate platinum(II) and / or palladium(II) complex circularly polarized luminescent material having the structure shown in general formula (I) and / or (I').

[0030] The present application also provides an organic optoelectronic device, which comprises a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer comprises a chiral spiro tetradentate platinum(II) and / or palladium(II) complex circularly polarized luminescent material having the structure shown in general formula (I) and / or (I').

[0031] In many embodiments, the present application also provides a light-emitting display device comprising one or more of the organic electroluminescent device or the organic optoelectronic device as described above.

[0032] In many embodiments, the present application also provides a display or lighting device comprising one or more of the organic electroluminescent device or the organic optoelectronic device as described above.

[0033] A composition comprising a helical tetradentate chiral ring metal platinum(II) and / or palladium(II) complex circularly polarized luminescent material having a structure represented by general formula (I) and / or (I').

[0034] A formulation comprising a helical tetradentate chiral ring metal platinum(II) and / or palladium(II) complex circularly polarized luminescent material having a structure represented by general formula (I) and / or (I') and at least one solvent.

[0035] Compared with the prior art, the present application has the following advantages:

[0036] (1) Generation of central chiral self-induced helicity: the present application designs and develops a central chiral triazole carbene and its derivative structural fragment L 5 , utilizes the steric hindrance effect between the fragment and another terminal ligand L 1 , and makes the whole tetradentate chiral ring metal platinum(II) and / or palladium(II) complex molecule into a twisted quadrilateral configuration; at the same time, the central chiral triazole carbene and its derivative structural fragment L 5 can self-induce the whole tetradentate ligand to coordinate with a metal ion in a small steric hindrance manner, and form an optically pure metal ion-centered helical tetradentate chiral ring metal platinum(II) and / or palladium(II) complex circularly polarized luminescent material, and the induction reaction has stereospecificity.

[0037] (2) Economical and easy-to-obtain optically pure raw materials: the two chiral optically pure corresponding isomers of the tetradentate ligand containing the central chiral L 5 are commercially available and easy-to-obtain compounds, which facilitate the preparation of the two chiral optically pure tetradentate ligands.

[0038] (3) Circularly polarized luminescent material without chiral separation: the two chiral optically pure corresponding isomer circularly polarized luminescent materials of the helical tetradentate chiral ring metal platinum(II) and / or palladium(II) complex can be conveniently prepared from the two chiral optically pure tetradentate ligands, without the need for separation and purification by a chiral column, which greatly reduces the preparation cost of the material.

[0039] (4) Chiral fragment of aromatic system: the central chiral fragment in the material molecule provided by the present application is a triazole carbene and its derivative, both of which are aromatic systems and have high chemical stability; the triazole carbene chiral fragment has a great contribution to the charge distribution in the frontier orbital and has a great contribution to the excited triplet state of the material molecule, and can participate in the charge transfer process of the excited state, which is beneficial to the improvement of the optical physical properties of the material molecule, such as quantum efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 is a diagram of light propagation mode; wherein (a) is sunlight, and (b) is circularly polarized luminescent light;

[0041] Figure 2 is a diagram of the design idea of optically pure metal ion-centered helical chiral tetradentate ring metal complex circularly polarized light emitting material;

[0042] Figure 3 is a graph of M-Pt1 and its enantiomer P-Pt1 in dichloromethane solution; wherein (a) is a circularly polarized luminescence spectrum CPPL, (b) is a graph of the asymmetry factor (g PL ) at different wavelengths;

[0043] Figure 4 is an emission spectrum of optically pure M-Pt1 and its enantiomer P-Pt1 in dichloromethane solution at room temperature;

[0044] Figure 5 is a schematic diagram of the structure of an organic light emitting element. Wherein 110 represents a substrate, 120 represents an anode, 130 represents a hole injection layer, 140 represents a hole transport layer, 150 represents a light emitting layer, 160 represents a hole blocking layer, 170 represents an electron transport layer, 180 represents an electron injection layer, and 190 represents a cathode. DETAILED DESCRIPTION

[0045] The following describes the content of the present application in detail. The description of the constituent elements described below is sometimes based on representative embodiments or specific examples of the present application, but the present application is not limited to such embodiments or specific examples.

[0046] The present disclosure can be understood more readily by reference to the following detailed description and examples contained therein. Before the present compounds, devices, and / or methods are disclosed and described, it is to be understood that the aspects described herein are not limited to specific synthetic methods or specific reagents, as such may, vary. It is to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, example methods and materials are now described.

[0047] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" can include mixtures comprising two or more components.

[0048] The term "optional" or "optionally" as used herein means that the subsequent occurrence described can or can not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0049] Disclosed are components that can be used to prepare compositions described herein, as well as compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be specifically enumerated, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules containing the compound are discussed, then each and every combination and permutation of the compound is specifically contemplated unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then each and every combination and permutation of the compounds A, B, C, D, E, and F is specifically contemplated unless specifically indicated to the contrary. Likewise, any subset or combination of these is also specifically contemplated. For example, subgroups of A-E, B-F, and C-E are also specifically contemplated. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions. Thus, if there are a variety of additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods.

[0050] The linking atom used herein is capable of linking two groups, e.g., linking N and C. The linking atom can optionally have other chemical groups attached (if the valence allows). For example, an oxygen atom will not have any other chemical groups attached because the valence is already satisfied upon bonding two atoms (e.g., N or C). In contrast, when carbon is the linking atom, two additional chemical groups can be attached to the carbon atom. Suitable chemical groups include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, =0, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

[0051] The term "cyclic structure" or similar terms used herein refer to any cyclic chemical structure, including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

[0052] The term "substituted" or a similar term as used herein encompasses all permissible substituents of an organic compound. Broadly speaking, permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Exemplary substituents are described below. Permissible substituents can be one or more, and the same or different for each organic compound. For organic compounds, a heteroatom (e.g., nitrogen) can have a hydrogen substituent and / or any permissible substituents described herein for the organic compound to which this heteroatom is attached. The present application is not intended to be limited in any way by the permissible substituents of organic compounds. Also, the term "substitution" or "substituted with" includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). In certain aspects, unless explicitly otherwise stated, an individual substituent can be further optionally substituted (i.e., further substituted or unsubstituted).

[0053] In defining various terms, "R 1 ", "R 2 ", "R 3 ", and "R 4 " are used herein as generic symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when defined as certain substituents in one instance, can be defined as some other substituents in another instance.

[0054] The term "alkyl" as used herein, unless otherwise indicated, means a branched or unbranched, saturated hydrocarbon group having from one to sixty carbon atoms, preferably one to thirty carbon atoms, more preferably one to fourteen carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, sulfenyl, thiol, and the like, as described herein.

[0055] Throughout the specification, "alkyl" generally refers to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to in the application by specifying the particular substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, and the like. When "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another instance, it is not meant to imply that the term "alkyl" does not also refer to the specific term such as "alkyl alcohol" and the like.

[0056] This approach is also used for other groups described in the application. That is, when a general term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moieties can additionally be specifically identified in the application; for example, a specifically substituted cycloalkyl group can be referred to as, for example, "alkylcycloalkyl." Similarly, a substituted alkoxy group can be specifically referred to as, for example, "haloalkoxy," a specific substituted alkenyl group can be, for example, "enol," and the like. Likewise, the use of a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" is not meant to imply that the general term does not also encompass the specific term.

[0057] Unless otherwise indicated, the term "cycloalkyl" as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms, preferably 3 to 12 carbon atoms, composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, cyclooctyl, adamantyl, norbornane, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is included within the meaning of the term "cycloalkyl," wherein at least one ring carbon atom is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, silicon, or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, thio-oxo groups, and thiol groups as described herein.

[0058] The terms "alkoxy" and "alkoxy group" as used herein refer to an alkyl or cycloalkyl group of 1 to 60 carbon atoms bonded through an ether linkage, preferably 1 to 30 carbon atoms, more preferably 1 to 14 carbon atoms; that is, "alkoxy" can be defined as — OR 1 where R 1 is an alkyl or cycloalkyl group as defined above. "Alkoxy" also includes the alkoxylated polymers just described; that is, the alkoxy group can be a polyether such as — OR 1 — OR 2 or — 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 alkyl, cycloalkyl, or a combination thereof.

[0059] The term "alkenyl" as used herein is a hydrocarbon group of 2 to 60 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 14 carbon atoms, whose structural formula contains at least one carbon-carbon double bond. Asymmetric structures such as (R 1 R 2 )C=C(R 3 R 4 ) include both the E and Z isomers. This can be inferred in the structural formulae of the present application where an asymmetric alkene is present or it can be explicitly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0060] The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring of 3 to 60 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 14 carbon atoms, which is composed of at least 3 carbon atoms and contains at least one carbon-carbon double bond, i.e., C=C. Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, and the like. The term "heterocycloalkenyl" is a class of cycloalkenyl as defined above and is included in the meaning of the term "cycloalkenyl" wherein at least one carbon atom of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, silicon, or phosphorus. The cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0061] The term "alkynyl" as used herein is a hydrocarbon group of 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, whose structural formula contains at least one carbon-carbon triple bond. The alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0062] The term "cycloalkynyl" as used herein is a non-aromatic carbocyclic ring containing at least 7 carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a cycloalkenyl as defined above and is included within the meaning of the term "cycloalkynyl," wherein at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, silicon, or phosphorus. Cycloalkynyl and heterocycloalkynyl groups can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo, or thiol groups as described herein.

[0063] The term "aryl" as used herein refers to any carbocyclic aromatic group containing 60 carbon atoms and less, preferably 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, including, but not limited to, phenyl, naphthyl, phenylnaphthyl, biphenyl, phenoxyphenyl, anthryl, phenanthryl, and the like. The term "aryl" also includes "heteroaryl," which is defined as an aromatic group containing at least one heteroatom within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, silicon, or phosphorus. Also, the term "non-heteroaryl" (which is also included within the term "aryl") defines an aromatic group containing no heteroatoms. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo, or thiol groups as described herein. The term "biaryl" is a specific type of aryl and is included within the definition of "aryl." Biaryl refers to two aryl groups joined together via a fused ring structure, as in naphthalene, or joined by one or more carbon-carbon bonds, as in biphenyl.

[0064] The term "aldehyde" as used herein is represented by the formula— C(O)H. Throughout the specification, "C(O)" is a shorthand form for carbonyl (i.e., C=O).

[0065] The term "amine" or "amino" as used herein is represented by the formula— NR 1 R 2 wherein R 1 and R 2 may be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.

[0066] The term "alkylamino" as used herein is represented by the formula— NH(-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, t-butylamino, pentylamino, isopentylamino, t-pentylamino, hexylamino, and the like.

[0067] The term "dialkylamino" as used herein is represented by the formula— N(-alkyl)2, wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-t-butylamino, dipentylamino, diisopentylamino, di-t-pentylamino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.

[0068] The term "carboxylic acid" as used herein is represented by the formula— C(O)OH.

[0069] The term "ester" as used herein is represented by the formula— OC(O)R 1 or— C(O)OR 1 wherein R 1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyester" as used herein is represented by the formula— (R 1 O(O)C-R 2 -C(O)O) a or— (R 1 O(O)C-R 2 -OC(O)) a — wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein and "a" is an integer from 1 to 500. The term "polyester" is used to describe a group that results from a reaction between a compound having at least two carboxylic acid groups and a compound having at least two hydroxyl groups.

[0070] The term "ether" as used herein is represented by the formula R 1 OR 2 wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyether" as used herein is represented by the formula— (R 1 O-R 2 O) a — wherein R 1 and R 2may be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

[0071] As used herein, the term "halogen" means fluorine (F), chlorine (CI), bromine (Br), or iodine (I).

[0072] As used herein, the term "heterocyclyl" means 3- to 60- membered monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein means monocyclic and polycyclic aromatic ring systems of not more than 60 carbon atoms, preferably 6-30 carbon atoms, more preferably 6-18 carbon atoms: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including oxazolyl of 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, and 1,3,4-oxadiazolyl), piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, tetrazolyl including 1,2,3,4-tetrazolyl and 1,2,4,5-tetrazolyl, thiadiazolyl including 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, and 1,3,4-thiadiazolyl, thiazolyl, thienyl, triazinyl including 1,3,5-triazinyl and 1,2,4-triazinyl, triazolyl including 1,2,3-triazolyl and 1,3,4-triazolyl, and the like.

[0073] As used herein, the term "hydroxyl" is represented by the formula— OH.

[0074] As used herein, the term "ketone" is represented by the formula— C(O)R 1 C(O)R 2 wherein R 1 and R 2 may be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described herein.

[0075] As used herein, the term "azido" is represented by the formula— N3.

[0076] As used herein, the term "nitro" is represented by the formula— NO2.

[0077] As used herein, the term "nitrile" is represented by the formula— CN.

[0078] As used herein, the term "silyl" is represented by the formula— SiR 1 R 2 R 3 wherein R 1R 2 and R 3 may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group, as described herein.

[0079] The term "thio-oxo group" as used herein is represented by the formula— S(O)R 1 , —S(O)2R 1 , —OS(O)2R 1 , or— OS(O)2OR 1 , wherein R 1 may be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group, as described herein. Throughout the specification, "S(O)" is a shorthand notation for S=O. The term "sulfonyl" as used herein refers to a thio-oxo group represented by the formula— S(O)2R 1 , wherein R 1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group. The term "sulfone" as used herein is represented by the formula R 1 S(O)2R 2 , wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group, as described herein. The term "sulfoxide" as used herein is represented by the formula R 1 S(O)R 2 , wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group, as described herein.

[0080] The term "mercapto" as used herein is represented by the formula— SH.

[0081] The "R 1 ", "R 2 ", "R 3 ",... "R n " (wherein n is an integer) as used herein can independently have one or more of the groups listed above. For example, if R 1 is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be replaced with a hydroxyl group, an alkoxy group, an alkyl group, a halogen, etc. Depending on the group selected, the first group can be embedded within the second group, or the first group can be pendant (i.e., attached) to the second group. For example, for the phrase "alkyl group comprising an amino group", the amino group can be embedded within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the groups selected will determine whether the first group is embedded or attached to the second group.

[0082] The compounds described herein can contain "optionally substituted" moieties. In general, the term "substituted" whether preceded by the term "optionally" or not, means that the indicated moiety is either substituted or unsubstituted. An "optionally substituted" group can have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted with more than one substituent, the substituent can be either the same or different at every position. Combinations of substituents envisioned are those that result in the formation of stable or chemically feasible compounds. It is also contemplated that, in certain aspects, each substituent can further optionally be substituted (i.e., further substituted or unsubstituted) unless specifically indicated otherwise.

[0083] The structure of a compound can be represented by the formula which is understood to be equivalent to the formula where n is typically an integer. That is, R n is understood to represent five separate substituents R n(a) , R n(b) , R n(c) , R n(d) , and R n(e) . "Separate substituents" means that each R substituent can be defined independently. For example, if in one instance R n(a) is halogen, then in that instance R n(b) is not necessarily halogen.

[0084] The R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ...etc. are mentioned several times in the chemical structures and units disclosed and described herein. Any description of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ...etc. in the specification applies to any structure or unit that refers to R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ...etc. respectively, unless otherwise indicated.

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

[0086] Disclosed herein are compounds or complex complexes comprising platinum. The terms compound or complex are used interchangeably in the present invention. Additionally, the compounds disclosed herein have a neutral charge.

[0087] The compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices, such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices or devices capable of both light absorption and emission, and as labels for biological applications.

[0088] As described above, the disclosed compounds are platinum or palladium complexes. Also, the compounds disclosed herein can be used as host materials for OLED applications, such as full color displays.

[0089] The compounds disclosed herein can be used in a variety of applications. As light emitting materials, the compounds can be used in organic light emitting diodes (OLEDs), light emitting devices and displays, and other light emitting devices.

[0090] The compounds of the present invention can be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0091] In the present invention, an organic optoelectronic device is prepared by a method in which a metal or an oxide having conductivity and an alloy thereof are evaporated on a substrate using a sputtering coating method, an electron beam evaporation, a vacuum evaporation, etc. to form an anode; a hole injection layer, a hole transport layer, a light emitting layer, an air barrier layer, and an electron transport layer are sequentially evaporated on the surface of the prepared anode, and then a cathode is evaporated. The above method is a method in which an organic electroluminescent device is prepared by sequentially evaporating a cathode, an organic layer, and an anode on a substrate. The organic layer can also include a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole barrier layer, and an electron transport layer. In the present invention, the organic layer is prepared by a solvent engineering method (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing, or thermal imaging, etc.) using a polymer material instead of an evaporation method, which can reduce the number of layers of the device.

[0092] The materials used in the organic electroluminescent device according to the present invention can be classified as top emission, low emission, or double-sided emission. The compounds of the organic electroluminescent device according to the embodiments of the present invention can be applied to organic solar cells, lighting OLEDs, flexible OLEDs, organic photosensitive bodies, organic thin film transistors, etc. in a similar manner to the principles of organic light emitting devices.

[0093] Unless otherwise indicated, all commercial reagents used in the following experiments were used as received without further purification. NMR spectra of hydrogen and carbon were measured in deuterated chloroform (CDCI3) or deuterated dimethyl sulfoxide (DMSO-d6) solution, hydrogen spectrum was measured using 400 or 500 megahertz nuclear magnetic resonance spectrometer, carbon spectrum was measured using 100 or 126 megahertz nuclear magnetic resonance spectrometer, chemical shifts were referenced to tetramethylsilane (TMS) or residual solvent. If CDCI3 was used as solvent, hydrogen spectrum and carbon spectrum were referenced to TMS (δ = 0.00 ppm) and CDCI3 (δ = 77.00 ppm) as internal standard, respectively. If DMSO-d6 was used as solvent, hydrogen spectrum and carbon spectrum were referenced to TMS (δ = 0.00 ppm) and DMSO-d6 (δ = 39.52 ppm) as internal standard, respectively. The following abbreviations (or combinations) were used to interpret hydrogen spectrum: s = singlet, d = doublet, t = triplet, q = quartet, p = pentuplet, m = multiplet, br = broad. High resolution mass spectrum was measured on an ESI-QTOF mass spectrometer of Applied Biosystems, and sample ionization mode was electrospray ionization.

[0094] Example 1: Tetradentate cyclometalated platinum (II) complex P-Pt1

[0095] The synthetic route is as follows:

[0096] Synthesis of intermediate NH2: Into a reaction flask was added 1-OH (2.0 g, 6.32 mmol, 1.0 eq), 3-bromoaniline (1.41 g, 8.22 mmol, 1.3 eq), cuprous iodide (120 mg, 0.63 mmol, 10 mol%), 2-picolinic acid (155 mg, 1.26 mmol, 20 mol%), potassium phosphate (2.68 g, 12.64 mmol, 3.0 eq), and dimethyl sulfoxide (20 mL) successively, and the flask was purged with nitrogen three times. The reaction was stirred at 120 °C for 3 days, cooled to room temperature, diluted with water, extracted with ethyl acetate three times, combined organic phase was washed with brine once, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1-10:1, to give 2.49 g of white solid, yield 97%. 1H NMR (500 MHz, CDC13) δ 1.36 (s, 9H), 2.63 (br, 2H), 6.36 (t, J = 2.0 Hz, 1H), 6.40 (ddd, J = 8.0, 2.0, 1.0 Hz, 1H), 6.46 (ddd, J = 8.0, 2.5, 1.0 Hz, 1H), 7.03 (dd, J = 8.5, 2.0 Hz, 1H), 7.08 (t, J = 8.0 Hz, 1H), 7.27 (dd, J = 5.5, 1.5 Hz, 1H), 7.30 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.40 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.43 (d, J = 2.0 Hz, 1H), 7.55 (dd, J = 2.0, 1.0 Hz, 1H), 7.76 (dt, J = 8.5, 1.0 Hz, 1H), 8.02 - 8.08 (m, 2H), 8.58 (dd, J = 5.5, 0.5 Hz, 1H).

[0097] Synthesis of intermediate Hydrazine: Into a reaction flask was added NH2(2.40 g, 5.89 mmoL, 1.0 eq), ethanol (22 mL), concentrated hydrochloric acid (22 mL), cooled to -5 °C, dropwise added sodium nitrite (427 mg, 6.18 mmoL, 1.05 eq) aqueous solution (5 mL water), reacted for 1 hour, then dropwise added stannous chloride hydrochloride (6.91 g, 30.63 mmoL, 5.2 eq, 6 mL concentrated hydrochloric acid), reacted for 2 hours, then filtered, the filter cake was moved to a beaker, diluted with water, neutralized with NaOH, extracted with DCM, dried over anhydrous sodium sulfate, and stirred. Purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1-3:1, to obtain 1.65 g of white solid, yield 66%.

[0098] Synthesis of intermediate (S,R)-CONH: Into a reaction flask was added (S,R)-NH2(5.0 g, 33.51 mmoL, 1.0 eq), tetrahydrofuran (120 mL), triethylamine (6.06 mL, 43.56 mmoL, 1.3 eq), cooled to 0 °C, dropwise added acyl chloride (3.2 mL, 40.22 mmoL, 1.2 eq), stirred at room temperature for 3 hours, quenched with water, extracted with ethyl acetate, concentrated after drying, placed in a three-necked flask, added tetrahydrofuran, cooled to -5 °C, slowly added NaH (4.02 g, 100.53 mmoL, 3.0 eq, 60 wt%), stirred at room temperature, quenched with ice water, extracted with ethyl acetate, concentrated after drying, and slurried with PE:EA:EtOH to obtain 6.05 g of brown solid, total yield 95%. 1H NMR (500 MHz, CDC13) δ 3.10 (d, J = 16.5 Hz, 1H), 3.22 (dd, J = 16.5, 5.0 Hz, 1H), 4.16 (d, J = 1.0 Hz, 2H), 4.49 - 4.56 (m, 1H), 4.74 - 4.81 (m, 1H), 7.26 - 7.29 (m, 3H), 7.32 - 7.36 (m, 1H), 8.02 (s, 1H).

[0099] Synthesis of Ligand P-L1 : A reaction flask was charged with (S, R)-CONH (358 mg, 1.9 mmol, 1.0 equiv), DCM (9 mL), trimethyl oxonium tetrafluoroborate (336 mg, 2.27 mmol, 1.2 equiv), stirred at room temperature for 12 hours, hydrazine was added, stirred for 12 hours overnight. The reaction was dried by rotary evaporation, dried under reduced pressure, chlorobenzene (8 mL) was added, heated to 130 °C for 14 hours, cooled to room temperature, the solvent was removed by distillation under reduced pressure. The obtained crude product was purified by silica gel column chromatography, eluent: dichloromethane: methanol = 100: 1, to get brown solid 677 mg, yield 52%.

[0100] Synthesis of P-Pt1 : A dry Schlenk flask with magnetic stirrer was charged with P-L1 (400 mg, 0.58 mmol, 1.0 equiv), (1,5-cyclooctadiene) dichloroplatinum (216 mg, 0.58 mmol, 1.0 equiv) and sodium acetate (143 mg, 1.74 mmol, 3.0 equiv) sequentially, then replaced with nitrogen three times, diethyleneglycol dimethyl ether (8 mL) was added under nitrogen protection, bubbled with nitrogen for 30 minutes, then the mixture was placed in an oil bath at 120 °C and stirred for 2 days, cooled to room temperature, the solvent was removed by distillation under reduced pressure. The obtained crude product was purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 2: 1, to get yellow-green solid 70 mg, yield 15%. 1H NMR (500 MHz, DMSO-d6) δ 1.22 (s, 9 H), 3.07 (d, J = 16.5 Hz, 1 H), 3.41 (d, J = 4.5 Hz, 1 H), 4.99 (d, J = 15.5 Hz, 1 H), 5.02 (t, J = 4.0 Hz, 1 H), 5.16 (d, J = 15.5 Hz, 1 H), 6.09 (d, J = 4.0 Hz, 1 H), 6.81 (t, J = 7.5 Hz, 1 H), 7.01 - 7.06 (m, 1 H), 7.12 (t, J = 7.5 Hz, 1 H), 7.16 (dd, J = 6.5, 2.0 Hz, 1 H), 7.24 (d, J = 2.0 Hz, 1 H), 7.25 (s, 1 H), 7.27 (d, J = 7.5 Hz, 1 H), 7.30 (d, J = 8.5 Hz, 1 H), 7.40 (t, J = 7.5 Hz, 1 H), 7.46 (ddd, J = 8.5, 7.0, 1.5 Hz, 1 H), 7.90 (d, J = 8.0 Hz, 1 H), 7.94 (d, J = 8.0 Hz, 1 H), 7.98 (d, J = 2.0 Hz, 1 H), 8.13 (d, J = 7.5 Hz, 1 H), 8.18 (dd, J = 7.5, 1.0 Hz, 1 H), 9.73 (d, J = 6.5 Hz, 1 H).

[0101] Example 2: Tetradentate cyclometalated platinum(II) complex M-Pt1

[0102] The synthesis route is as follows:

[0103] Synthesis of intermediate (R,S)-CONH: To a reaction flask was added (R,S)-NH2(5.0 g, 33.51 mmol, 1.0 eq), tetrahydrofuran (130 mL), triethylamine (6.06 mL, 43.56 mmol, 1.3 eq), cooled to 0 °C, acyl chloride (3.2 mL, 40.22 mmol, 1.2 eq) was added dropwise, stirred at room temperature for 3 hours, quenched with water, extracted with ethyl acetate, dried and concentrated, placed in a three-necked flask, added tetrahydrofuran, cooled to -5 °C, slowly added NaH (4.02 g, 100.53 mmol, 3.0 eq, 60 wt%), stirred at room temperature, quenched with ice water, extracted with ethyl acetate, dried and concentrated, slurried with PE:EA:EtOH to give brown solid 5.2 g, total yield 82%. 1H NMR (500 MHz, CDC13) δ 3.10 (d, J = 16.5 Hz, 1H), 3.22 (dd, J = 16.5, 5.0 Hz, 1H), 4.16 (s, 2H), 4.51 - 4.56 (m, 1H), 4.76 - 4.79 (m, 1H), 7.26 - 7.29 (m, 3H), 7.31 - 7.34 (m, 1H), 7.55 (s, 1H).

[0104] Synthesis of Ligand M-L1 : A flask was charged with (R,S)-CONH (400 mg, 2.11 mmol, 1.0 equiv), DCM (9 mL), trimethyl oxonium tetrafluoroborate (375 mg, 2.54 mmol, 1.2 equiv), stirred at room temperature for 12 h, hydrazine (660 mg) was added, stirred for 12 h overnight. The reaction was concentrated, dried under reduced pressure, chlorobenzene (8 mL) was added, heated to 130 °C for 14 h, cooled to room temperature, the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography, eluent: dichloromethane:methanol = 100:1, to give 444 mg of brown solid, yield 41%.

[0105] Synthesis of M-Pt1 : To a dry Schlenk tube with a magnetic bar was added L1 (400 mg, 0.58 mmol, 1.0 equiv), (1,5-cyclooctadiene) dichloroplatinum (216 mg, 0.58 mmol, 1.0 equiv) and sodium acetate (143 mg, 1.74 mmol, 3.0 equiv) sequentially, then purged with nitrogen three times, diethyleneglycol dimethyl ether (8 mL) was added under nitrogen protection, the mixture was stirred at 120 °C for 2 days, cooled to room temperature, the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 2:1, to give 64 mg of yellow-green solid, yield 14%. 1H NMR (500 MHz, DMSO-d6) δ 1.21 (s, 9 H), 3.07 (d, J = 16.5 Hz, 1 H), 3.47 - 3.52 (m, 1 H), 4.99 (d, J = 15.5 Hz, 1 H), 5.02 (t, J = 4.0 Hz, 1 H), 5.15 (d, J = 15.5 Hz, 1 H), 6.09 (d, J = 4.0 Hz, 1 H), 6.80 (t, J = 7.5 Hz, 1 H), 7.00 - 7.06 (m, 1 H), 7.12 (t, J = 7.5 Hz, 1 H), 7.16 (dd, J = 6.5, 2.0 Hz, 1 H), 7.23 (d, J = 1.5 Hz, 1 H), 7.24 (s, 1 H), 7.27 (d, J = 7.5 Hz, 1 H), 7.30 (d, J = 8.5 Hz, 1 H), 7.40 (td, J = 7.5, 1.0 Hz, 1 H), 7.45 (ddd, J = 8.5, 7.0, 1.5 Hz, 1 H), 7.90 (d, J = 8.0 Hz, 1 H), 7.94 (d, J = 8.5 Hz, 1 H), 7.98 (d, J = 2.0 Hz, 1 H), 8.12 (d, J = 7.5 Hz, 1 H), 8.16 - 8.19 (m, 1 H), 9.73 (d, J = 6.5 Hz, 1 H).

[0106] Example 3: Tetradentate cyclometalated platinum(II) complex M-Pt2

[0107] The synthesis route is as follows:

[0108] Synthesis of intermediate (S)-CONH-2: To a dry three-necked flask with magnetic stirrer was added D-phenylglycinol (5.0 g, 36.44 mmol, 1.0 eq), chloroacetyl chloride (4.94 g, 43.73 mmol, 1.2 eq), tetrahydrofuran (120 mL), the flask was placed in an ethanol bath at 0 °C, triethylamine (4.79 g, 47.37 mmol, 1.3 eq) was added slowly, then the reaction was allowed to proceed at room temperature. After the reaction was completed, water was added to quench, extracted with ethyl acetate, the water layer was extracted with ethyl acetate three times, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a brown oily liquid. The product was used directly in the next step.

[0109] Synthesis of Ligand L2: To a dry three-necked flask with magnetic stirring bar was added (S)-CONH-2 (36.44 mmol, 1.0 eq), tetrahydrofuran (150 mL), and the flask was placed in an ethanol bath at 0 °C. Sodium hydride (4.36 g, 109.32 mmol, 3.0 eq) was added slowly, and the reaction was allowed to warm to room temperature. After the reaction was completed, water was added to quench the reaction, and the mixture was extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate three times, and the combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was recrystallized from PE / EA / EtOH to give (S)-CONH-2 as a white solid. The product was used directly in the next step. To a dry three-necked flask with magnetic stirring bar was added (S)-CONH-2 (500 mg, 2.82 mmol, 1.0 eq), Me3OBF4 (501 mg, 3.38 mmol, 1.2 eq), and dichloromethane (11 mL). The reaction was stirred at room temperature for 12 h, and then hydrazine (1.19 g, 2.82 mmol, 1.0 eq) was added. The mixture was stirred overnight. The solvent was removed, chlorobenzene (8 mL) and triethyl orthoformate (1.25 g, 8.46 mmol, 3.0 eq) were added, and the mixture was stirred at 110 °C for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography using dichloromethane / ethyl acetate (10:1-2:1-1:1) as the eluent to give L2 as a brown solid (934 mg, 48% yield). The product contained a small amount of impurities and was used directly in the next step.

[0110] Synthesis of M-Pt2: To a dry Schlenk tube with magnetic stirring bar was added L2 (500 mg, 0.73 mmol, 1.0 eq), (1,5-cyclooctadiene) dichloroplatinum (284 mg, 0.76 mmol, 1.05 eq), and sodium acetate (180 mg, 2.19 mmol, 3.0 eq). The tube was purged with nitrogen three times, and then diethyleneglycol dimethyl ether (15 mL) was added under nitrogen. The mixture was stirred at 120 °C for 3 days. After the reaction was completed, the mixture was cooled to room temperature, and then quenched by stirring with water for 5-10 min. The mixture was extracted with dichloromethane, and the aqueous layer was extracted with dichloromethane three times. The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using petroleum ether / dichloromethane (1:1-dichloromethane) as the eluent to give M-Pt2 as a yellow solid (68 mg, 11% yield).

[0111] Example 4: Tetradentate cyclometalated platinum (II) complex P-Pt2

[0112] Reference Example 3 was synthesized in the same manner as Example 3, except that the starting material in Example 3 was replaced with the enantiomer to produce complex P-Pt2.

[0113] Example 5: Tetradentate cyclometalated platinum(II) complex M-Pt3

[0114] The synthetic route is as follows:

[0115] M-Pt3 was synthesized in the same manner as Reference Example 2, except that the hydrazine starting material in the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt3, a yellow solid. MS: m / z 853.28 (M+H) + .

[0116] Example 6: Tetradentate cyclometalated platinum(II) complex P-Pt3

[0117] Reference Example 5 was synthesized in the same manner as Example 5, except that the starting material in Example 5 was replaced with the enantiomer to produce complex P-Pt3.

[0118] Example 7: Tetradentate cyclometalated platinum(II) complex M-Pt4 The synthetic route is as follows:

[0119] M-Pt4 was synthesized in the same manner as Reference Example 2, except that the hydrazine starting material in the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt4, a yellow solid. MS: m / z 839.27 (M+H) + .

[0120] Example 8: Platinum(II) complex P-Pt4

[0121] Reference Example 7 was synthesized in the same manner as Example 7, except that the starting material in Example 7 was replaced with the enantiomer to produce complex P-Pt4.

[0122] Example 9: Tetradentate cyclometalated platinum(II) complex M-Pt5

[0123] The synthetic route is as follows:

[0124] M-Pt5 was synthesized in the same manner as Reference Example 2, except that the hydrazine starting material in the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt5, a yellow solid. MS: m / z 957.34 (M+H) + .

[0125] Example 10: Platinum(II) complex P-Pt5

[0126] Reference Example 9 was synthesized in the same manner as Example 9, except that the starting material in Example 9 was replaced with the enantiomer to produce complex P-Pt5.

[0127] Example 11 : Tetradentate cyclometalated platinum (II) complex M-Pt6

[0128] The synthesis route is as follows:

[0129] M-Pt6 was synthesized in the same manner as Reference Example 2, except that the starting tetrafluoroborate salt and hydrazine in the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt6, yellow solid. MS: m / z 807.30 (M+H) + .

[0130] Example 12: Platinum (II) complex P-Pt6

[0131] Reference Example 11 was synthesized in the same manner as Example 11, except that the starting material in Example 11 was replaced with the enantiomer to produce complex P-Pt6.

[0132] Example 13: Tetradentate cyclometalated platinum (II) complex M-Pt7 The synthesis route is as follows:

[0133] M-Pt7 was synthesized in the same manner as Reference Example 2, except that the starting tetrafluoroborate salt in the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt7, yellow solid. MS: m / z 751.24 (M+H) + .

[0134] Example 14: Platinum (II) complex P-Pt7

[0135] Reference Example 13 was synthesized in the same manner as Example 13, except that the starting material in Example 13 was replaced with the enantiomer to produce complex P-Pt7.

[0136] Example 15: Tetradentate cyclometalated platinum (II) complex M-Pt8 The synthesis route is as follows:

[0137] M-Pt8 was synthesized in the same manner as Reference Example 2, except that the starting tetrafluoroborate salt and hydrazine in the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt8, yellow solid. MS: m / z 807.30 (M+H) + .

[0138] Example 16: Platinum (II) complex P-Pt8

[0139] Reference Example 15 was synthesized in the same manner as Example 15, except that the starting material in Example 15 was replaced with the enantiomer to produce complex P-Pt8.

[0140] Example 17: Tetradentate cyclometalated platinum (II) complex M-Pt9 The synthesis route is as follows:

[0141] M-Pt9 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt9, yellow solid. MS: m / z 835.32 (M+H) + .

[0142] Example 18: Platinum (II) complex P-Pt9

[0143] Complex P-Pt9 was prepared according to the synthetic procedure of Reference Example 17, with the difference that the starting materials in Example 17 were replaced by the enantiomers.

[0144] Example 19: Tetradentate cyclometalated platinum (II) complex M-Pt10

[0145] The synthesis route is as follows:

[0146] M-Pt10 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt10, yellow solid. MS: m / z 779.27 (M+H) + .

[0147] Example 20: Platinum (II) complex P-Pt10

[0148] Complex P-Pt10 was prepared according to the synthetic procedure of Reference Example 19, with the difference that the starting materials in Example 19 were replaced by the enantiomers.

[0149] Example 21: Tetradentate cyclometalated platinum (II) complex M-Pt11

[0150] The synthesis route is as follows:

[0151] M-Pt11 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt11, yellow solid. MS: m / z 765.25 (M+H) + .

[0152] Example 22: Platinum (II) complex P-Pt11

[0153] Complex P-Pt11 was prepared according to the synthetic procedure of Reference Example 21, with the difference that the starting materials in Example 21 were replaced by the enantiomers.

[0154] Example 23: Tetradentate cyclometalated platinum(II) complex M-Pt12

[0155] The synthetic route is as follows:

[0156] M-Pt12 was synthesized in the same manner as Example 2, except that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt12, yellow solid. MS: m / z 821.31 (M+H) + .

[0157] Example 24: Platinum(II) complex P-Pt12

[0158] M-Pt12 was synthesized in the same manner as Example 23, except that the enantiomer of the starting materials in Example 23 was used.

[0159] Example 25: Tetradentate cyclometalated platinum(II) complex M-Pt13

[0160] The synthetic route is as follows:

[0161] M-Pt13 was synthesized in the same manner as Example 2, except that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt13, yellow solid. MS: m / z 793.28 (M+H) + .

[0162] Example 26: Platinum(II) complex P-Pt13

[0163] M-Pt13 was synthesized in the same manner as Example 25, except that the enantiomer of the starting materials in Example 25 was used.

[0164] Example 27: Tetradentate cyclometalated platinum(II) complex M-Pt14

[0165] The synthetic route is as follows:

[0166] M-Pt14 was synthesized in the same manner as Example 2, except that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt14, yellow solid. MS: m / z 799.27 (M+H) + .

[0167] Example 28: Platinum(II) complex P-Pt14

[0168] M-Pt14 was synthesized in the same manner as Example 27, except that the enantiomer of the starting materials in Example 27 was used.

[0169] Example 29: Tetradentate cyclometalated platinum(II) complex M-Pt15

[0170] The synthetic route is as follows:

[0171] M-Pt15 was synthesized in the same manner as in Reference Example 2, except that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt15, a yellow solid. MS: m / z 855.30 (M+H) + .

[0172] Example 30: Platinum(II) complex P-Pt15

[0173] M-Pt15 was synthesized in the same manner as in Reference Example 29, except that the starting materials in Example 29 were replaced with the enantiomer.

[0174] Example 31: Tetradentate cyclometalated platinum(II) complex M-Pt16

[0175] The synthetic route is as follows:

[0176] M-Pt16 was synthesized in the same manner as in Reference Example 2, except that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt16, a yellow solid. MS: m / z 827.27 (M+H) + .

[0177] Example 32: Platinum(II) complex P-Pt16

[0178] M-Pt16 was synthesized in the same manner as in Reference Example 31, except that the starting materials in Example 31 were replaced with the enantiomer.

[0179] Example 33: Tetradentate cyclometalated platinum(II) complex M-Pt17

[0180] The synthetic route is as follows:

[0181] M-Pt17 was synthesized in the same manner as in Reference Example 2, except that the tetrafluoroborate salt and hydrazine starting materials of the corresponding segment in Example 2 were replaced to synthesize the target compound M-Pt17, a yellow solid. MS: m / z 883.33 (M+H) + .

[0182] Example 34: Platinum(II) complex P-Pt17

[0183] M-Pt17 was synthesized in the same manner as in Reference Example 33, except that the starting materials in Example 33 were replaced with the enantiomer.

[0184] Example 35: Tetradentate cyclometalated platinum(II) complex M-Pt18

[0185] The synthetic route is as follows:

[0186] M-Pt18 was synthesized in the same manner as Example 2, except that the tetrafluoroborate salt starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt18, yellow solid. MS: m / z 861.25 (M+H) + .

[0187] Example 36: Platinum(II) complex P-Pt18

[0188] M-Pt18 was synthesized in the same manner as Example 35, except that the starting material in Example 35 was replaced with the enantiomer.

[0189] Example 37: Tetradentate cyclometalated platinum(II) complex M-Pt19

[0190] The synthetic route is as follows:

[0191] M-Pt19 was synthesized in the same manner as Example 2, except that the tetrafluoroborate salt starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt19, yellow solid. MS: m / z 917.31 (M+H) + .

[0192] Example 38: Platinum(II) complex P-Pt19

[0193] M-Pt19 was synthesized in the same manner as Example 37, except that the starting material in Example 37 was replaced with the enantiomer.

[0194] Example 39: Tetradentate cyclometalated platinum(II) complex M-Pt20

[0195] The synthetic route is as follows:

[0196] M-Pt20 was synthesized in the same manner as Example 2, except that the hydrazine starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt20, yellow solid. MS: m / z 839.27 (M+H) + .

[0197] Example 40: Platinum(II) complex P-Pt20

[0198] M-Pt20 was synthesized in the same manner as Example 39, except that the starting material in Example 39 was replaced with the enantiomer.

[0199] Example 41: Tetradentate cyclometalated platinum(II) complex M-Pt21

[0200] The synthetic route is as follows:

[0201] M-Pt21 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the hydrazine starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt21, yellow solid. MS: m / z 813.22 (M+H) + .

[0202] Example 42: Platinum(II) complex P-Pt21

[0203] M-Pt21 was synthesized according to the synthetic procedure of Reference Example 41, with the difference that the starting material in Example 41 was replaced by the enantiomer.

[0204] Example 43: Tetradentate cyclometalated platinum(II) complex M-Pt22

[0205] The synthetic route is as follows:

[0206] M-Pt22 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the hydrazine starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt22, yellow solid. MS: m / z 741.16 (M+H) + .

[0207] Example 44: Platinum(II) complex P-Pt22

[0208] M-Pt22 was synthesized according to the synthetic procedure of Reference Example 43, with the difference that the starting material in Example 43 was replaced by the enantiomer.

[0209] Example 45: Tetradentate cyclometalated platinum(II) complex M-Pt23

[0210] M-Pt23 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the hydrazine starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt23, yellow solid. MS: m / z 729.19 (M+H) + .

[0211] Example 46: Platinum(II) complex P-Pt23

[0212] M-Pt23 was synthesized according to the synthetic procedure of Reference Example 45, with the difference that the starting material in Example 45 was replaced by the enantiomer.

[0213] Example 47: Tetradentate cyclometalated platinum (II) complex M-Pt24 The synthesis route is as follows:

[0214] M-Pt24 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the hydrazine starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt24, yellow solid. MS: m / z 743.17 (M+H) + .

[0215] Example 48: Platinum (II) complex P-Pt24

[0216] According to the synthetic procedure of Reference Example 47, the starting material in Example 47 was replaced by the enantiomer.

[0217] Example 49: Tetradentate cyclometalated platinum (II) complex M-Pt25 The synthesis route is as follows:

[0218] M-Pt25 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the hydrazine starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt25, yellow solid. MS: m / z 738.14 (M+H) + .

[0219] Example 50: Platinum (II) complex P-Pt25

[0220] According to the synthetic procedure of Reference Example 49, the starting material in Example 49 was replaced by the enantiomer.

[0221] Example 51: Tetradentate cyclometalated platinum (II) complex M-Pt26 The synthesis route is as follows:

[0222] M-Pt26 was synthesized according to the synthetic procedure of Reference Example 2, with the difference that the hydrazine starting material of the corresponding segment in Example 2 was replaced to synthesize the target compound M-Pt26, yellow solid. MS: m / z 781.19 (M+H) + .

[0223] Example 52: Platinum (II) complex P-Pt26

[0224] According to the synthetic procedure of Reference Example 51, the starting material in Example 51 was replaced by the enantiomer.

[0225] Example 53: Tetradentate cyclometalated platinum (II) complex M-Pt27

[0226] The synthesis route is as follows:

[0227] M-Pt27 was synthesized using the same method as in Example 2. The only difference from Example 2 was the replacement of the corresponding fragment of the hydrazine starting material. The target compound M-Pt27 was a yellow solid. MS: m / z 781.19 (M+H) + .

[0228] Example 54: Platinum(II) complex P-Pt27

[0229] The synthesis method of Example 53 can be referenced by replacing the raw materials in Example 53 with enantiomers.

[0230] Example 55: The synthetic route for the tetradentate cyclic platinum(II) complex M-Pt28 is as follows:

[0231] M-Pt28 was synthesized using the same method as in Example 2. The only difference from Example 2 was the substitution of the corresponding fragment of the hydrazine starting material. The target compound M-Pt28 was synthesized as a yellow solid. MS: m / z 823.24 (M+H) + .

[0232] Example 56: Platinum(II) complex P-Pt28

[0233] The synthesis method of Example 55 can be referenced by replacing the raw materials in Example 55 with enantiomers.

[0234] Example 57: Synthesis of palladium(II) complex M-Pd1:

[0235] Synthesis of M-Pd1: L1 (1.0 equivalent), palladium acetate (1.05 equivalent), and potassium carbonate (3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times. 1,4-Dioxane (14 mL) was added under nitrogen protection, and the mixture was bubbled with nitrogen for 30 min to remove oxygen. The flask was then placed in an oil bath with a magnetic stirrer and the reaction was carried out at 110 °C for 72 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography to obtain a yellow solid, with a yield of 6%. MS: m / z 708.16 (M+H) + .

[0236] Experimental data and analysis:

[0237] Figure 1 is a diagram of light propagation mode; wherein (a) is sunlight light ray, (b) is circularly polarized luminescent light ray. Figure 2 is a diagram of the design idea of optically pure metal ion-centered helical chiral tetradentate ring metal complex circularly polarized luminescent material; from Figure 2 and Examples 1 to 57, it can be known that the formation of helical chiral metal complex molecules can be induced by the central chiral fragment in the ligand to coordinate with metal ions in a small steric hindrance way to form optically pure helical chiral metal complex circularly polarized luminescent material, and the induction reaction has stereospecificity. For example, in Example 1, the ligand P-L1 stereospecifically induces the generation of P-configuration helical chiral metal complex P-Pt1; and in Example 2, the ligand M-L1 stereospecifically induces the generation of M-configuration helical chiral metal complex M-Pt1, and the like. In addition, the helical chiral metal complex can be prepared in large quantities from the corresponding chiral raw materials without chiral separation. The present application designs and develops a tetradentate ligand with a central chiral triazole carbene and its derivative structural fragment L 5 , utilizes the steric hindrance effect between L 1 and another end ligand L 5 , so that the entire tetradentate ring metal platinum(II) and / or palladium(II) complex molecule is in a twisted quadrilateral configuration; at the same time, the central chiral triazole carbene and its derivative structural fragment L 20 can autonomously induce the entire tetradentate ligand to coordinate with metal ions in a small steric hindrance way to form optically pure metal ion-centered helical chiral tetradentate ring metal platinum(II) and / or palladium(II) complex circularly polarized luminescent material. The optically pure raw material is economical and easy to obtain; the central chiral autonomous induction generates chirality; the circularly polarized luminescent material does not need to be separated by chiral, which greatly saves the economic cost and time cost of optically pure material, can be prepared in large quantities, and is not limited by chiral preparation chromatographic column separation.

[0238] Table 1. Specific optical rotation of some chiral ligands and chiral metal complexes ([a 20 D )

[0239] Note: The specific optical rotation values of all samples are measured in dichloromethane solution.

[0240] Table 1 is a specific optical rotation table of some chiral ligands and chiral metal complexes ([a 20 D ) From the enantiomeric excess value (ee value) in Table 1, it can be known that the complexes obtained based on the design idea provided by the present application are single chiral material molecules with extremely high optical purity, and the ee values are all > 99%; the above experimental data also show that the material design idea is successful.

[0241] Comparing the specific optical rotation data of some chiral ligands and chiral metal complexes in Table 1, it can be seen that even if the chiral ligands and chiral metal complexes contain the same central chiral center, the specific optical rotation values are quite different, and even the optical rotation directions are completely opposite, indicating that the helical chiral center in the metal complex has a decisive influence on the optical rotation properties of the entire compound. Since the luminescence of the metal complex under excitation radiation mainly involves the metal-to-ligand charge transfer state (MLCT) and the intraligand charge transfer state (ILCT), the helical chiral center of the metal complex has a significant influence on its circularly polarized light properties. In contrast, the control molecules PtON7-dtb and PdON7-dtb without a central chiral center have no optical rotation, and the specific optical rotation ([a] 20 D ) is zero, indicating that they are achiral molecules.

[0242] Table 2. Maximum emission wavelength (λ max ) and half-peak width (FWHM) and asymmetry factor (g PL ) of chiral metal complexes

[0243] Note: The maximum emission wavelength (λ max ) and asymmetry factor (g PL ) of all samples were measured in dichloromethane solution.

[0244] Figure 3 is the spectrum of M-Pt1 and its enantiomer P-Pt1 in dichloromethane solution; wherein (a) is the circularly polarized luminescence spectrum CPPL, and (b) is the asymmetry factor (g PL ) curve at different wavelengths; Figure 4 is the emission spectrum of optically pure M-Pt1 and its enantiomer P-Pt1 in dichloromethane solution at room temperature;

[0245] As can be seen from Table 2 and Figures 3 and 4, the representative helical chiral material molecules of the present application all exhibit strong circularly polarized luminescence, and the absolute value of the asymmetry factor (g PL ) can be as high as 8.73 x 10 -4 Such helical chiral metal complexes have important applications in circularly polarized luminescence elements and related fields. In contrast, the control molecules PtON7-dtb and PdON7-dtb have no circularly polarized luminescence, and the asymmetry factor (g PL ) is zero. Most of the helical chiral material molecules provided by the present application emit narrow-band deep blue light (about 455 nm), have small half-peak width, and high color purity; in addition, tests show that their quantum efficiency is also very high, most of which is between 80% and 98%. Such material molecules are currently urgently needed high-color-purity blue light emitting materials in the field of OLEDs.

[0246] Furthermore, the numerous synthetic experimental examples and their photophysical property characterization and testing also demonstrate that the method for designing circularly polarized luminescent material molecules in this application is completely successful; such helical metal complex material molecules all possess strong helical molecular properties, such as specific rotation values ​​and strong circularly polarized luminescence signals.

[0247] In organic light-emitting elements, carriers are injected into the light-emitting material from the positive and negative electrodes to generate an excited state of the light-emitting material and make it emit light.

[0248] The circularly polarized luminescent material of the chiral tetradentate ring platinum (II) and / or palladium (II) complex with the structure shown in general formula (I) and / or (I') of this invention can be used as a phosphorescent material in excellent organic light-emitting devices such as organic photoluminescent devices or organic electroluminescent devices. The organic photoluminescent device has a structure in which at least a light-emitting layer is formed on a substrate. Furthermore, the organic electroluminescent device has a structure in which at least an anode, a cathode, and an organic layer between the anode and cathode are formed. The organic layer at least includes a light-emitting layer, which may consist only of the light-emitting layer, or may have one or more other organic layers besides the light-emitting layer. Examples of such other organic layers include hole transport layers, hole injection layers, electron blocking layers, hole blocking layers, electron injection layers, electron transport layers, exciton blocking layers, etc. The hole transport layer may also be a hole injection transport layer with hole injection function, and the electron transport layer may also be an electron injection transport layer with electron injection function. Figure 5 is a schematic diagram of a reference organic light-emitting device structure. In Figure 5, 110 represents the substrate, 120 represents the anode, 130 represents the hole injection layer, 140 represents the hole transport layer, 150 represents the light-emitting layer, 160 represents the hole blocking layer, 170 represents the electron transport layer, 180 represents the electron injection layer, and 190 represents the cathode. The light-emitting layer is a hybrid layer in which the guest material is doped into the host material.

[0249] The organic light-emitting device of the present invention can be formed by vacuum evaporation, sputtering, ion electroplating, or wet film formation methods such as spin coating, printing, etc., and there are no particular restrictions on the solvents used.

[0250] In a preferred embodiment of the present invention, the OLED device of the present invention includes a hole transport layer. The hole transport material can preferably be selected from known or unknown materials, and is particularly preferably selected from the following structures, but this does not mean that the present invention is limited to the following structures:

[0251] In a preferred embodiment of the present application, the hole transport layer contained in the OLED device of the present application comprises one or more p-type dopants. Preferred p-type dopants of the present application are the following structures, but the present application is not limited to the following structures:

[0252] In a preferred embodiment of the present application, the electron transport layer can be selected from at least one of compounds ET-1 to ET-77, but the present application is not limited to the following structures:

[0253] Preferably, the electron transport layer can be formed together with one or more n-type dopants (such as LiQ, LiTHPh, etc.).

[0254] In a preferred embodiment of the present application, the host material can be selected from at least one of compounds H-1 to H-32, preferably at least one of compounds H-1 to H-6, but the present application is not limited to the following structures:

[0255] As a reference embodiment, the complexes represented in the examples are applied to OLED devices as circularly polarized light emitting materials, and the structure can be represented as: on ITO-containing glass, the hole injection layer (HIL) is HT-1:P-3 (95:5 v / v%), with a thickness of 10 nm; the hole transport layer (HTL) is HT-1, with a thickness of 90 nm; the electron blocking layer (EBL) is HT-10, with a thickness of 10 nm; the light emitting layer (EML) is the host material:dopant (H-5:P-Pt1, 95:5 v / v%), with a thickness of 35 nm; the electron transport layer (ETL) is ET-13:LiQ (50:50 v / v%), with a thickness of 35 nm; and then an Al cathode is evaporated to a thickness of 70 nm. This is denoted as device 1. Referring to the device structure provided by device 1, the dopants listed in Table 3 are respectively selected as the implementation object to replace P-Pt1, which is co-evaporated with the host compound at a volume ratio of 5:95 to form a light emitting layer, and an organic electroluminescent diode is prepared, denoted as device 2 to device 28. The luminescent properties of the above-prepared device examples are tested by a standard method, and the data is shown in Table 3.

[0256] Table 3. Luminescent performance table of part of electroluminescent devices

[0257] Note: λ max is the maximum emission wavelength; EQE max is the maximum external quantum efficiency; g EL is the electroluminescent asymmetry factor.

[0258] As can be seen from the electroluminescent devices of some materials in Table 3, the chiral material molecules in the application can be used as dopants for the preparation of circularly polarized light emitting devices, and a higher external quantum efficiency can be achieved, and a stronger circularly polarized light signal is obtained.

[0259] It should be noted that the device structure described in the application is only an example of one of the many applications of the circularly polarized light emitting material of the application, and should not be construed as a limitation of the specific OLED device structure of the circularly polarized light emitting material of the application. The circularly polarized light emitting material is not limited to the compounds represented in the examples.

[0260] Those skilled in the art can understand that the above-mentioned embodiments are specific examples for implementing the application, and in actual application, various changes can be made in form and details without departing from the spirit and scope of the application. For example, many substituent structures described herein can be replaced by other structures without departing from the spirit of the application.

Claims

1. A chiral tetradentate cyclometalated platinum(II) and / or palladium(II) complex circularly polarized luminescent material, characterized in that, of the formula (I) and / or (I'), wherein (I) and (I') are enantiomers of each other: wherein M is Pt or Pd; V 1 , V 2 and V 3 are each independently N or C; L 1 , L 2 , L 3 and L 4 are each independently five- or six-membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring; L 5 is a six- to ten-membered carbocyclic or heterocyclic ring containing a central chiral center; A is selected from O, S, CR x R y , C=0, SiR x R y , GeR x R y , NR z , PR z , R z P=0, AsR z , R z As=0, S=0, S02, Se, Se=0, Se02, BH, BR z , R z Bi=0 or BiR z ; X 1 and X 2 may be present or absent, and if present, X 1 and X 2 are each independently selected from a single bond, O, S, CR x R y , C=0, SiR x R y , GeR x R y , NR z , PR z , R z P=0, AsR z , R z As=0, S=0, S02, Se, Se=0, Se02, BH, BR z , R z Bi=0, or BiR z ; Z is N, CR x , SiR x , GeR x , B, P, P=0, As, As=0, Bi=0, or Bi; R 1 , R 2 , R 3 , R 4 , and R 5 each independently represents mono-, di-, tri-, tetra-, penta-, or hexa-substituted or unsubstituted, while R 1 , R 2 , R 3 , R 4 , R 5 , R a , R b , R x , R y and R z each independently is selected from any one of or a combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, haloaryl, haloheteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylheteroarylsilyl, alkylarylsilyl, arylsiloxy, heteroarylsiloxy, alkylheteroarylsiloxy, alkylarylsiloxy, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, nitro, -CN, amino, mono- or di-alkylamino, mono- or di-arylamino, ester, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramidate, imine, sulfo, carboxyl, hydrazine.

2. The circularly polarized luminescent material of claim 1, wherein, L in the structure of general formula (I) and / or (I') 3 selected from any one of the following structures: wherein X a , X b , X c and X d may each independently be a single bond, O, S, CR x R y , C=O, SiR x R y , GeR x R y , NR z , PR z , R z P=O, AsR z , R z As=O, S=O, SO2, Se, Se=O, SeO2, BH, BR z , R z Bi=O or BiR z ; M, V 3 , R x , R y and R z are each as defined in claim 1.

3. The circularly polarized light emitting material of claim 1, wherein, The circularly polarized luminescent material is selected from the following general formulae (I-A), (I-B), (I-C), (I-D), (I-E), (I-F), (I-G), (I-H), (I-I) and / or its enantiomers (I'-A), (I'-B), (I'-C), (I'-D), (I'-E), (I'-F), (I'-G), (I'-H), (I'-I): Among them, Y 4 Y 5 Y 6 Each is independent as N or CR 3 Y 7 Y 8 Y 18 Each is independent as N or CR 2 Y 9 Y 10 Y 11 Y 16 Each is independent as N or CR 1 Y 12 Y 13 Y 14 Y 15 and Y 17 Each is independent as N or CR 4 The R 1 -R 5 Each of the following is independently selected from any one or a combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteralkyl, haloaryl, haloheteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylheteroarylsilyl, alkylarylsilyl, arylsiloxy, heteroarylsiloxy, alkylheteroarylsiloxy, alkylarylsiloxy, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, nitro, -CN; The A, M, X 1 X 2 R a R b and L 5 As defined in claim 1.

4. The circularly polarized luminescent material according to any one of claims 1-3, characterized in that, L in the general structure 5 selected from the following structures, and corresponding isomers thereof: wherein X 3 , X 4 , X 5 , X 6 , and X 7 are each independently O, S, CR x R y , C=0, SiR x R y , GeR x R y , NR z , PR z , R z P=0, AsR z , R z As=0, S=0, S02, Se, Se=0, Se02, BH, BR z , R z Bi=0 or BiR z ; R x , R y , R z , M, R 5 , R a and R b are as defined in claim 1.

5. The circularly polarized luminescent material according to any one of claims 1-3, characterized in that, L in the general structure 5 selected from the following structures, and corresponding isomers thereof: wherein R 1‘ , R 2’ , R 3‘ , R 4‘ , R 5‘ , R 6‘ are each independently selected from any one or combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, halo heteroaryl, alkylaryl, alkylheteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylarylsilyl, alkylheteroarylsilyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, nitro, -CN, amino, mono- or di-alkylamino, mono- or di-aryl amino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, alkylthio, sulfinyl, ureido, phosphonamidate, imine, sulfo, carboxyl, hydrazine; two or more adjacent R a , R b , R 1’ , R 2’ , R 3‘ , R 4‘ , R 5‘ and R 6‘ may optionally be linked to form a fused ring or other cyclic system; and R a , R b and M are as defined in claim 1.

6. The circularly polarized luminescent material according to any one of claims 1-3, characterized in that, L in the general structure 5 the structure of Formula (I) is selected from the following structures, and corresponding isomers thereof: wherein R 7 and R 8 each independently represents mono-, di-, tri-, tetra-, or penta-substitution or no substitution, while R 7 and R 8 each independently is selected from any one or combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, halo-heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkyl( hetero)arylsilyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, nitro, -CN, amino, mono- or di-alkylamino, mono- or di-arylaminos, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfonamide, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramidate, imine, sulfo, carboxyl, hydrazine; two or more adjacent R 7 and R 8 may optionally be linked to form a fused ring; R 1‘ to R 6‘ each independently is selected from any one or combination of hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, halo-heteroaryl, alkoxy, aryloxy, alkylsilyl, arylsilyl, heteroarylsilyl, alkylaryl silyl, alkylheteroaryl silyl, -CN; M is Pt or Pd.

7. The circularly polarized luminescent material according to any one of claims 1-3, characterized in that, of the formula selected from the group consisting of P-type isomers wherein M = Pt or Pd, and their corresponding M-type isomers:

8. The circularly polarized luminescent material according to any one of claims 1-3, characterized in that, having the chemical formula selected from the group consisting of P-type isomers as shown below, wherein M = Pt or Pd, and their corresponding M-type isomers:

9. Use of the circularly polarized luminescent material according to claim 1 in the preparation of an electronic device.

10. An organic electroluminescent device, characterized by The organic electroluminescent device comprises a cathode, an anode and an organic functional layer interposed therebetween; the organic functional layer comprises the complex circularly polarized luminescent material according to claim 1.

11. The organic electroluminescent device according to claim 10, wherein The organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the complex circularly polarized luminescent material according to claim 1.

12. An organic optoelectronic device, characterized in that The organic optoelectronic device comprises a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer comprises the complex circularly polarized luminescent material according to claim 1.

13. A display or illumination device, characterized in that The display or lighting device comprises the organic electroluminescent device according to claim 10, and / or the organic optoelectronic device according to claim 12.

14. A composition characterized in that, The composition comprises the complex circularly polarized luminescent material according to claim 1.

15. A formulation characterized in that, The preparation comprises the complex circularly polarized luminescent material according to claim 1 and at least one solvent.

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