Spirochiral tetradentate platinum(II) complex-based circularly polarized luminescent material and application thereof

Abstract

The present invention relates to the technical field of circularly polarized luminescent material preparation, and in particular to a spirochiral tetradentate platinum(II) complex-based circularly polarized luminescent material based on pyridine-carbazole-phenylcarbene and a derivative structure thereof, and an application thereof. The provided complex molecule autonomously induces, by means of a remote stereocenter-containing fragment in chirally substituted pyridine, an entire tetradentate ligand to coordinate with a metal ion in a less sterically hindered manner, so as to form an optically pure spirochiral metal complex-based circularly polarized luminescent material. Such spirochiral metal complex-based circularly polarized luminescent material does not require chiral resolution, has high molecular thermodynamic stability, and has important applications in circularly polarized light-emitting components.

Description

Spiral chiral tetradentate platinum(II) complex circularly polarized luminescent materials and their applications Technical Field

[0001] This invention relates to the field of circularly polarized luminescent material preparation technology, and in particular to a spiral-chiral tetradentate platinum(II) complex circularly polarized luminescent material based on pyridine-carbazole-phenylcarbene and its derivative structures and its applications. Background Technology

[0002] Circularly polarized luminescence (CPL) is the phenomenon where chiral luminescent materials emit left- or right-handed circularly polarized light upon excitation. Therefore, the design and development of chiral luminescent materials is crucial in this field. With in-depth research, circularly polarized luminescent materials have now found important applications in 3D displays, data storage, quantum computing, optical anti-counterfeiting, bioimaging, and asymmetric synthesis.

[0003] Phosphorescent materials composed of cyclic platinum(II) and palladium(II) complexes can fully utilize all singlet and triplet excitons generated by electro-excitation due to the heavy atom effect, achieving a maximum theoretical quantum efficiency of up to 100%. Therefore, these complexes are ideal luminescent materials. Bidentate cyclic platinum(II) and palladium(II) complexes have low rigidity. The two bidentate ligands are prone to twisting and vibration, causing the energy of the excited-state molecules to be consumed non-radiatively, thus reducing their luminescence quantum efficiency. Although cyclic platinum(II) and palladium(II) complexes based on tridentate ligands can improve luminescence quantum efficiency due to increased molecular rigidity, the presence of a second monodentate ligand (such as Cl, phenoxy anion, alkyne anion, carbene, etc.) significantly reduces the chemical and thermal stability of the complexes, making sublimation and purification difficult for use in OLED device fabrication. Therefore, luminescent materials based on bidentate and tridentate ligand cyclic metal complexes are not suitable for stable and efficient OLED device applications. The central metal ion in divalent cyclic platinum(II) and palladium(II) complexes is dsp. 2Hybridization facilitates coordination with tetradentate ligands to form stable and rigid planar quadrilateral molecular configurations. High molecular rigidity suppresses nonradiative relaxation caused by molecular vibrations and rotations, reducing energy loss in excited-state molecules and thus improving the quantum efficiency of luminescence. However, due to the steric hindrance of the two terminal aryl groups of the tetradentate ligands in cyclic platinum(II) and palladium(II) complexes, the molecules exhibit a distorted quadrilateral configuration, theoretically possessing helical chirality. However, in solution or during sublimation, the molecules easily race through the up-and-down vibrations of the two terminal aryl groups, making it impossible to separate their enantiomers. This makes it extremely difficult to obtain optically pure cyclic platinum(II) and palladium(II) complex molecules, thus preventing them from exhibiting circularly polarized luminescence. Therefore, designing and developing optically pure cyclic platinum(II) complex molecules with high chemical and thermodynamic stability, while also possessing circularly polarized luminescence properties, is of great significance and practical value for their application in circularly polarized OLED devices (CP-OLED), and is a problem urgently needing to be solved in the CP-OLED field. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings in current research and development of circularly polarized light-emitting materials by providing a helical tetradentate platinum(II) complex circularly polarized light-emitting material and its applications. The provided complex has a pyridine-carbazole-phenylcarbene structure and its derivatives. The complex molecule can autonomously induce the entire tetradentate ligand to coordinate with metal ions in a sterically unhindered manner by chirally substituting the long-range central chiral segment in pyridine, forming an optically pure helical chiral metal complex circularly polarized light-emitting material. This complex circularly polarized light-emitting material does not require chiral resolution and possesses high molecular thermodynamic stability, making it important for applications in circularly polarized light-emitting elements.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] According to one or more embodiments, the present invention provides a helical tetradentate platinum(II) complex circularly polarized luminescent material having a structure as shown in general formula (I) or (I'), wherein (I) and (I') are enantiomers of each other:

[0007] L represents O, S, and 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 ;R x R y and R z Each of the following is independently one or more of the following: hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteralkyl, deuteroaryl, deuteroheteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or dialkylamino, mono- or diarylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, and aryloxysilyl.

[0008] * indicates a carbon atom with central chirality;

[0009] Y 1 Y 2 Y 3 Each is independent as CR 3 Or N; Z 1 Z 2 Z 3 Z 4 Z 5 Z 6 Z 7 Z 8 Each is independent as CR 4 Or N;

[0010] R 1 R 2 R 3 R 4 Each can be used independently to indicate monosubstituted, polysubstituted, or unsubstituted substances;

[0011] R 1 R 3 R 4 R a R b R m and R n Each of the following is independently one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, haloalkyl, aryl, heteroaryl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or dialkylamino, mono- or diarylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, and aryloxysilyl;

[0012] R 2Each of the following is independently hydrogen, deuterium, alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted azaaryl, substituted or unsubstituted fused-ring aryl, substituted or unsubstituted fused-ring heteroaryl; when substituted, the substituent is selected from one or more of deuterium, alkyl, aryl, heteroaryl, mono- or dialkylamino, mono- or diarylamino, and -CN.

[0013] Preferred, R 2 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, F, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, deuterated tert-butyl, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, substituted or unsubstituted phenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted triphenylamino; when substituted, the substituent is selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, and carbazolyl; R 2 It can connect with the substituted group to form a fused ring.

[0014] According to one or more embodiments, the circularly polarized luminescent material of the chiral tetradentate platinum(II) complex represented by formula (I) or (I') provided by the present invention has the chemical formula as shown in general formula (Ii) or (I'-i), (I-ii) or (I'-ii), wherein (Ii) and (I'-i), (I-ii) and (I'-ii) are enantiomers of each other:

[0015] Among them, L, Y 1 -Y 3 Z 1 -Z 8 R 1 R 3 R 4 R a R b R m and R n The substitution cases are all as defined in general formula (I) or (I');

[0016] In formula (Ii) or (I'-i), X 1 X 2 X 3 X 4 Each is independent as CR 7 Or N; R 7Each time it appears, it is independently one or more of the following: hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or dialkylamino, mono- or diarylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, and aryloxysilyl.

[0017] In formula (I-ii) or (I'-ii), R 5 R 6 Each time it appears, it independently represents one or more of the following: hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteralkyl, deuteroaryl, deuteroheteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or dialkylamino, mono- or diarylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, and aryloxysilyl. R 5 R 6 They can be fused together to form rings.

[0018] Preferred, R 7 Each time it appears, it is independently selected from hydrogen, deuterium, halogen, alkyl, substituted or unsubstituted aryl, substituted or unsubstituted carbazole, substituted or unsubstituted diphenylamino; when it contains a substituted group, the substituent is selected from hydrogen, deuterium, fluorine, methyl, ethyl, propyl, butyl, tert-butyl, phenyl, biphenyl, naphthyl, carbazole.

[0019] Preferred, R 5 R 6 Each time it appears, it is independently represented by hydrogen, deuterium, fluorine, methyl, ethyl, propyl, butyl, tert-butyl, phenyl, or R. 5 R 6 They can be linked together to form cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, or cyclooctane.

[0020] Preferably, R in formula (I) or (I') a R b R m and R n Each of the following is independently one or more of hydrogen, deuterium, fluorine atom, substituted or unsubstituted C1-C24 alkyl, C3-C24 cycloalkyl, substituted or unsubstituted C6-C18 aryl, C1-C24 heteroalkyl, C3-C24 heterocycloalkyl, and C6-C18 heteroaryl; when a substituent is present, the substituent is selected from hydrogen, deuterium, fluorine atom, and C1-C14 alkyl.

[0021] Preferably, R in formula (I) or (I') x Ry and R z Each is independently selected from one or more of hydrogen, deuterium, fluorine atom, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C6-C18 aryl, C1-C24 heteroalkyl, C6-C18 heteroaryl; when a substituent is present, the substituent is selected from hydrogen, deuterium, fluorine atom, and C1-C14 alkyl.

[0022] Preferred, R 1 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, F, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, deuterated tert-butyl, substituted or unsubstituted aryl, substituted or unsubstituted carbazole; when substituted, the substituent is selected from hydrogen, deuterium, F, -CN, C1-C10 alkyl; when R 1 When selected from aryl groups, it can connect with the substituted group to form a fused ring.

[0023] Preferred, R 3 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 silyl, substituted or unsubstituted carbazole, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C6-C30 indene, substituted or unsubstituted C6-C30 heteroindene; when it contains substitution, the substituent is selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, carbazole, and adjacent substituents may be linked to form a ring.

[0024] Preferred, R 4 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 xanthyl, substituted or unsubstituted C1-C30 silyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted carbazole, substituted or unsubstituted C6-C30 xenodanyl; when it contains a substitution, the substituent is selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, and carbazole.

[0025] In many embodiments, two or more adjacent substituents may selectively connect to form a fused ring or unsaturated cyclic system.

[0026] In many embodiments, the helical tetradentate platinum(II) complex circularly polarized luminescent material provided by the present invention can have the following structure, but is not limited thereto, where "D" represents deuterium:

[0027] According to one or more embodiments, the present invention also provides the use of chiral tetradentate platinum (II) complex circularly polarized luminescent materials having the structures shown in formula (I) and / or (I') in the fabrication of electronic devices.

[0028] Furthermore, the electronic device is a light-emitting device, a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device, or a biological imaging device. The light-emitting device is preferably an organic electroluminescent device or an organic optoelectronic device.

[0029] According to one or more embodiments, the present invention also provides an organic electroluminescent device comprising a cathode, an anode, and an organic functional layer therebetween; said organic functional layer comprising a circularly polarized light-emitting material having the structure shown in formula (I) and / or (I') as above.

[0030] Furthermore, the organic functional layer includes a light-emitting layer, which contains a circularly polarized light-emitting material having the structure shown in formula (I) and / or (I'). The mass percentage of the circularly polarized light-emitting material is between 0.01% and 50%.

[0031] According to one or more embodiments, the present invention also provides an organic optoelectronic device, including 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 circularly polarized light-emitting material having a structure shown in formula (I) and / or (I'). For example, the circularly polarized light-emitting material may be included in the light-emitting material layer as a guest material or a dopant.

[0032] According to one or more embodiments, the present invention also provides a display or lighting device, including but not limited to a full-color display, a light-emitting display device, etc.; the display or lighting device comprises one or more of the organic electroluminescent devices and / or organic optoelectronic devices.

[0033] The present invention also provides a composition comprising a circularly polarized luminescent material having the structure shown in formula (I) and / or (I') above.

[0034] The present invention also provides a formulation comprising a circularly polarized luminescent material with the structure shown in formula (I) and / or (I') above, or a composition as described above, and at least one solvent. The solvent is not particularly limited and may be any solvent well known to those skilled in the art, such as unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents, halogenated unsaturated hydrocarbon solvents, ether solvents, or ester solvents; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetrahydronaphthalene, n-butylbenzene, sec-butylbenzene, or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene, or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; and the ester solvent is an alkyl benzoate ester.

[0035] The beneficial effects of this invention are:

[0036] (1) Central chirality remotely autonomously induces the generation of spirochetal chirality: This invention designs and develops a tetradentate ligand containing a central chiral segment of chiral substituted pyridine. Utilizing the steric hindrance effect between the terminal ligand chiral substituted pyridine and the substituted carbene, the entire tetradentate ring metal platinum (II) and palladium (II) complex molecule is distorted into a quadrilateral configuration. Simultaneously, the central chiral segment of chiral substituted pyridine can autonomously and remotely induce the entire tetradentate ligand to coordinate with metal ions in a manner with low steric hindrance, diastereoselectively forming optically pure P-configuration spirochetal tetradentate ring metal platinum (II) or palladium (II) complex circularly polarized light luminescent material centered on metal ions. In contrast, the M-configuration spirochetal tetradentate platinum (II) complex is thermodynamically unstable due to the large steric hindrance at the ligand end and is therefore undetectable.

[0037] (2) Low preparation cost without chiral separation: The materials used in this invention can be purchased commercially and are readily available, which facilitates the large-scale preparation of chiral optically pure tetradentate ligands. Furthermore, the circularly polarized light luminescent material of the prepared helical tetradentate ring metal platinum(II) complex does not need to be separated and purified by chiral columns, and is not limited by high-cost chiral separation, which greatly reduces the preparation cost of the material.

[0038] (3) High chemical stability of the material: The designed and developed tetradentate ligand can react with dsp. 2 Hybridized platinum(II) metal ions coordinate well to form chemically stable and rigid tetragonal molecules, which prevents them from racemizing and losing their circularly polarized luminescence properties in solution or solid form.

[0039] (4) High thermal stability of the material: The platinum (II) complex material molecules designed and developed do not contain four-membered rings, which can avoid the [2+2] reverse ring-opening reaction of four-membered rings at high temperatures and avoid the ring-opening decomposition of material molecules; such molecules can be well sublimated and purified at high temperatures (>250℃) and used for the preparation of thermally deposited devices. Attached Figure Description

[0040] Figure 1 is a schematic diagram of the design concept of optically pure spiral chiral tetradentate ring metal complex circularly polarized light luminescent material centered on metal ions.

[0041] Figure 2 is a schematic diagram of a specific organic light-emitting element for reference; in the figure, 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. Detailed Implementation

[0042] The present invention will now be described in detail. The descriptions of the constituent elements described below are sometimes based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0043] The following examples illustrate specific instances of the circularly polarized light-emitting materials of the present invention represented by the above general formula; however, they are not intended to limit the present invention.

[0044] This disclosure can be more readily understood by referring to the following detailed description and the examples contained therein. Before disclosing and describing the compounds, devices, and / or methods of the present invention, it should be understood that, unless otherwise stated, they are not limited to specific synthetic methods or specific reagents, as these can vary. It should also be understood that the terminology used in this invention is for describing particular aspects only and is not intended to be limiting. Although any similar or equivalent methods and materials described in this invention can be used in this practice or experiment, exemplary methods and materials are now described.

[0045] The singular forms of the terms “a,” “an,” and “the” used in the specification and appended claims include plural references unless otherwise explicitly indicated by the context. Thus, for example, reference to “component” includes a mixture of two or more components.

[0046] The terms “optional” or “optionally” as used in this invention mean that the event or situation described below may or may not occur, and the description includes instances where the event or situation occurs and instances where it does not occur.

[0047] The present invention discloses components that can be used to prepare the compositions described herein, as well as the compositions themselves to be used in the methods disclosed herein. The present invention discloses these and other materials, and it should be understood that combinations, subsets, interactions, groups, etc., of these substances are disclosed. While specific references to every particular individual and total combination and arrangement of these compounds cannot be specifically disclosed, each has its own specific conception and description. For example, if a specific compound is disclosed and discussed, and many modifications that can be made to a number of molecules containing that compound are discussed, then every combination and arrangement of that compound and possible modifications are specifically considered, unless the opposite possible modifications are specifically indicated. Thus, if an example of a class of molecules A, B, and C and a class of molecules D, E, and F, and examples of the combination molecule AD are disclosed, then even if each is not individually described, the individual and total meaning of each combination is considered to be disclosed, AE, AF, BD, BE, BF, CD, CE, and CF. Similarly, any subsets or combinations of these are also disclosed. For example, subgroups of AE, BF, and CE are also disclosed. This concept applies to all aspects of the present invention, including but not limited to the steps in methods for preparing and using the compositions. Therefore, if various additional steps are possible, it should be understood that each of these additional steps can be performed in a specific embodiment of the method or a combination of embodiments.

[0048] The linking atom used in this invention is capable of connecting two groups, for example, connecting N and C. This linking atom can optionally (if the valence bond allows) attach other chemical groups. For example, an oxygen atom will not have any other chemical groups attached because the valence bond is already satisfied once the two atoms (e.g., N or C) are bonded. Conversely, when carbon is the linking atom, two additional chemical groups can attach to that carbon atom. Suitable chemical groups include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, =O, halogen, nitro, amine, amide, mercapto, aryl, heteroaryl, cycloalkyl, and heterocyclic groups.

[0049] The term "cyclic structure" or similar term used in this invention refers to any cyclic chemical structure, including but not limited to aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic, carbene, and N-heterocyclic carbene.

[0050] The term "substituted" or similar terms used in this invention encompass all permissible substituents in organic compounds. In a broad sense, permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents in organic compounds. Exemplary substituents include those described below. For suitable organic compounds, permissible substituents may be one or more, identical or different. For the purposes of this invention, heteroatoms (e.g., nitrogen, oxygen, sulfur, silicon, germanium, etc.) can have hydrogen substituents and / or any permissible substituent in organic compounds satisfying the heteroatom valence as described in this invention. This invention is not intended to limit in any way to permissible substituents in organic compounds. Similarly, the terms "substituted" or "substituted with" implicitly include the condition that such substitution conforms to the permissible 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 transformations (e.g., by rearrangement, cyclization, elimination, etc.)). In some aspects, unless explicitly stated otherwise, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0051] When defining various terms, "R" 1 “R” 2 “R” 3 "~"R n "n" is selected from integers from 1 to 10; in this invention, it is used as a general symbol to represent various specific substituents. These symbols can be any substituents, not limited to those disclosed in this invention, and when they are defined as certain substituents in one instance, they can also be defined as some other substituents in another instance.

[0052] As used in this invention, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group with 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may substitute one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, thio-oxo, and mercapto groups described in this invention. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.

[0053] Throughout this specification, "alkyl" generally refers to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to in this invention by identifying the specific substituents on the alkyl group. For example, the terms "halogenated alkyl" or "halogenated alkyl" specifically refer 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 so on. When "alkyl" is used in one context and a specific term such as "alkyl alcohol" is used in another context, it does not imply that the term "alkyl" does not simultaneously refer to the specific term such as "alkyl alcohol," etc.

[0054] This approach is also applied to other groups described in this invention. That is, when a term such as "cycloalkyl" refers to both an unsubstituted and a substituted cycloalkyl moiety, the substituted moiety may be specifically identified separately in this invention; for example, a specifically substituted cycloalkyl may be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy may be specifically referred to as, for example, "haloalkoxy", and a specifically substituted alkenyl may be, for example, "enol", etc. Likewise, the use of a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" does not imply that the general term does not simultaneously include the specific term.

[0055] As used in this invention, the term "cycloalkyl" refers to a non-aromatic carbonyl ring consisting of 3 to 30 carbon atoms, preferably 3 to 14 carbon atoms, which may be substituted by 1 to 6 alkyl groups. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclononyl. The term "heterocyclic alkyl" is a class of cycloalkyl groups as defined above and is included in the meaning of the term "cycloalkyl," wherein at least one ring carbon atom is substituted by a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocyclic alkyl groups may be substituted or unsubstituted. The cycloalkyl and heterocyclic alkyl groups may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, thio-oxo, and mercapto groups as described in this invention.

[0056] As used in this invention, the terms "alkoxy" and "alkoxy group" refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms bonded by an ether bond; that is, "alkoxy" can be defined as -OR 1 , where R 1 It is an alkyl or cycloalkyl group as defined above. "Alkoxy" also includes alkoxy polymers just described; that is, the alkoxy group can be a polyether, such as —OR 1 -OR 2 OR 1 -(OR 2 ) a -OR 3Where "a" is an integer from 1 to 500, and R 1 R 2 and R 3 Each is independently an alkyl, cycloalkyl, or combination thereof.

[0057] The term "alkenyl" as used in this invention refers to a hydrocarbon group with 2 to 30 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 It contains E and Z isomers. This presumes that an asymmetric olefin is present in the structural formula of the invention, or that it can be explicitly represented by the bond symbol C=C. The alkenyl group may 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, azide, nitro, silyl, thio-oxo group, or mercapto.

[0058] As used in this invention, the term "cycloalkenyl" refers to a non-aromatic carbonyl ring of 3 to 30 carbon atoms, consisting of at least 3 carbon atoms and containing 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, etc. The term "heterocyclic alkenyl" is a class of cycloalkenyl groups as defined above and is included in the meaning of the term "cycloalkenyl," wherein at least one carbon atom of the ring is substituted with a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocyclic alkenyl groups may be substituted or unsubstituted. These cycloalkenyl and heterocyclic alkenyl groups may 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, azide, nitro, silyl, sulfoxy, or mercapto groups.

[0059] As used in this invention, the term "alkynyl" refers to a hydrocarbon group having 2 to 30 carbon atoms, with a structural formula containing at least one carbon-carbon triple bond. The alkynyl group may 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, azide, nitro, silyl, thio-oxo, or mercapto groups as described in this invention.

[0060] As used in this invention, the term "cycloalkynyl" refers to a non-aromatic carbonyl ring containing at least seven carbon atoms and at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, and cyclononynyl. The term "heterocyclic alkynyl" is a cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkynyl," wherein at least one carbon atom of the ring is replaced by a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocyclic alkynyl groups may be substituted or unsubstituted. Cycloalkynyl and heterocyclic alkynyl groups may 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, azide, nitro, silyl, sulfoxy, or mercapto groups as described in this invention.

[0061] As used in this invention, the term "aryl" refers to a group containing 60 or fewer carbon atoms of any carbon-based aromatic group, preferably 6-30 carbon atoms, and more preferably 6-18 carbon atoms. This includes, but is not limited to, phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracene, phenanthrene, etc. The term "aryl" also includes "heteroaryl," which is defined as an aromatic group containing at least one heteroatom within its ring. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, silicon, or germanium. Similarly, the term "non-heteroaryl" (which is also included in the term "aryl") defines an aromatic group that does not contain a heteroatom. 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, azide, nitro, silyl, sulfoxy, or mercapto groups as described in this invention. The term "biaryl" refers to a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups that are linked together by a fused ring structure, as in naphthalene, or two aryl groups that are linked by one or more carbon-carbon bonds, as in biphenyl.

[0062] The term "aldehyde" as used in this invention is represented by the formula —C(O)H. Throughout the specification, "C(O)" is the abbreviation for carbonyl (i.e., C=O).

[0063] The term "amine" or "amino" used in this invention is derived from the formula —NR 1 R 2 It means that R 1 and R 2 It can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl or heteroaryl.

[0064] The term "alkylamino" as used in this invention is represented by the formula —NH(-alkyl), wherein the alkyl group is as described in this invention. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, tert-butylamino, pentylamino, isopentylamino, tert-pentylamino, hexylamino, etc.

[0065] The term "ester" used in this invention is derived from the formula —OC(O)R 1 Or —C(O)OR 1 It means that R 1 It can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl as described in this invention. The term "polyester" as used in this invention is derived from the formula —(R 1 O(O)CR 2 -C(O)O) a —or—(R) 1 O(O)CR 2 -OC(O)) a — indicates that R 1 and R 2 The group can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl group as described in this invention, and "a" is an integer from 1 to 500. The term "polyester" is used to describe a group produced by the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.

[0066] The term "ether" used in this invention is derived from formula R 1 OR 2 It means that R 1 and R 2 It can be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described in this invention. The term "polyether" as used in this invention is derived from the formula —(R 1 OR 2 O) a — indicates that R 1 and R 2 The group can be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl as described in this invention, and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutene oxide.

[0067] The term "halogen" as used in this invention refers to the halogens fluorine, chlorine, bromine, and iodine.

[0068] The term "heterocyclic group" as used in this invention refers to a monocyclic or polycyclic non-aromatic ring system with 3 to 30 carbon atoms, and the term "heteroaryl group" as used in this invention refers to an aromatic ring system with no more than 60 carbon atoms, both monocyclic and polycyclic, wherein at least one of the ring members is not a carbon atom. This term includes nitrogen-containing heterocyclic butyl, dioxyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including oxazolyl groups of 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, and 1,3,4-oxadiazolyl), piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, including 1,2,4, Tetraazinyl of 5-tetraazinyl, 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, thiophene, triazinyl including 1,3,5-triazinyl and 1,2,4-triazinyl, triazolyl including 1,2,3-triazolyl and 1,3,4-triazolyl, etc.

[0069] The term "hydroxyl group" used in this invention is represented by the formula —OH.

[0070] The term "ketone" used in this invention is derived from formula R. 1 C(O)R 2 It means that R 1 and R 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described in this invention.

[0071] The term "nitrile" used in this invention is represented by the formula -CN.

[0072] The term "silyl methyl" used in this invention is derived from the formula —SiR 1 R 2 R 3 It means that R 1 R 2 and R 3 It can be hydrogen or the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, aryl or heteroaryl groups described in this invention.

[0073] The term "sulfide-oxo group" used in this invention is derived from the formula —S(O)R 1 —S(O)2R 1 —OS(O)2R 1 Or —OS(O)2OR 1 It means that R 1It can be hydrogen or the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groups described in this invention. Throughout the specification, "S(O)" is the abbreviation for S=O. The term "sulfonyl" as used in this invention refers to a group derived from the formula —S(O)2R 1 The sulfide-oxo group represents R. 1 It can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, ynyl, cycloynyl, aryl, or heteroaryl. The term "sulfone" as used in this invention is derived from formula R. 1 S(O)2R 2 It means that R 1 and R 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described in this invention. The term "sulfoxide" as used in this invention is derived from the formula R. 1 S(O)R 2 It means that R 1 and R 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described in this invention.

[0074] The term "thiol" used in this invention is represented by the formula -SH.

[0075] The “R” used in this invention 1 “R” 2 “R” 3 "...R" n (where n is an integer) can independently have one or more of the groups listed above. For example, if R 1 If the alkyl group is a straight-chain alkyl group, then one hydrogen atom of the alkyl group may be optionally substituted with a hydroxyl, alkoxy, alkyl, halogen, etc. Depending on the chosen group, the first group may be incorporated into the second group, or the first group may be side-attached (i.e., connected) to the second group. For example, for the phrase "alkyl group containing an amino group," the amino group may be incorporated into the backbone of the alkyl group. Alternatively, the amino group may be connected to the backbone of the alkyl group. The nature of the chosen group will determine whether the first group is inserted into or connected to the second group.

[0076] The compounds described in this invention may contain an "optionally substituted" portion. Generally, the term "substituted" (regardless of whether the preceding term "optional") means that one or more hydrogens of the specified portion are substituted by a suitable substituent. Unless otherwise stated, the "optionally substituted" group may have a suitable substituent at each substituted position of the group, and the substituents may be the same or different at each position when more than one position in any given structure can be substituted by more than one substituent selected from the specified group. The combinations of substituents contemplated in this invention are preferably combinations that form stable or chemically viable compounds. It is also contemplated that, in some aspects, unless explicitly stated otherwise, the individual substituents may be further optionally substituted (i.e., further substituted or unsubstituted).

[0077] The term "fused ring" as used in this invention refers to the fact that two adjacent substituents can be fused together to form a five- or six-membered aromatic ring or heteroaromatic ring, such as a benzene ring, pyridine ring, pyrazine ring, pyridazine ring, m-diazide ring, etc., as well as a saturated six- or seven-membered carbon ring or carbon heterocycle.

[0078] The use of organic materials in optoelectronic devices is becoming increasingly urgent for several reasons. Many materials used to fabricate such devices are relatively inexpensive, thus organic optoelectronic devices have the potential to offer cost advantages over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, make them well-suited for specialized applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may offer performance advantages over conventional materials. For instance, the wavelength of light emitted by an organic light-emitting layer can often be easily tuned with appropriate dopants.

[0079] Excitons decay from a singlet excited state to the ground state to produce instantaneous luminescence, which is fluorescence. If excitons decay from a triplet excited state to the ground state to produce luminescence, this is phosphorescence. Due to the strong spin-orbit coupling between singlet and triplet excited states of heavy metal atoms, which effectively enhances intersystem crossing (ISC), phosphorescent metal complexes (such as platinum complexes) have shown the potential to utilize both singlet and triplet excitons simultaneously, achieving 100% internal quantum efficiency. Therefore, phosphorescent metal complexes are excellent candidates for dopants in the emitter layer of organic light-emitting devices (OLEDs) and have gained considerable attention in both academic and industrial fields. Numerous achievements have been made in the past decade, leading to the lucrative commercialization of this technology; for example, OLEDs have been used in advanced displays for smartphones, televisions, and digital cameras.

[0080] However, blue electroluminescent devices remain the most challenging area of ​​this technology to date, with stability being a major concern. The choice of host material has been shown to be crucial to the stability of blue devices. However, the minimum energy of the triplet excited state (T1) of blue luminescent materials is very high, meaning that the minimum energy of the triplet excited state (T1) of the host material for blue devices should also be even higher. This significantly increases the difficulty in developing host materials for blue devices.

[0081] The metal complexes of this invention can be tailored or tuned to specific applications where particular emission or absorption properties are desired. The optical properties of the metal complexes disclosed herein can be tuned by altering the structure of the ligand surrounding the metal center or by changing the structure of the fluorescent emitter on the ligand. For example, metal complexes with electron-donating or electron-withdrawing substituents in their emission and absorption spectra can typically exhibit different optical properties. The color of the metal complexes can be tuned by modifying the fluorescent emitter and the conjugated groups on the ligand.

[0082] The emission of the complexes of this invention can be tuned, for example, by altering the structure of the ligands or phosphors, from ultraviolet to near-infrared. A phosphor is a group of atoms in an organic molecule that can absorb energy to generate a singlet excited state; the singlet exciton decays rapidly to produce instantaneous luminescence. On one hand, the complexes of this invention can provide emission across most of the visible spectrum. In specific examples, the complexes of this invention can emit light in the range of about 400 nm to about 700 nm. On the other hand, the complexes of this invention exhibit improved stability and efficiency compared to conventional emitting complexes. Furthermore, the complexes of this invention can be used as luminescent markers, for example, in biological applications, anticancer agents, and as emitters or combinations thereof in organic light-emitting diodes (OLEDs). On another hand, the complexes of this invention can be used in light-emitting devices, such as compact fluorescent lamps (CFLs), light-emitting diodes (LEDs), incandescent lamps, and combinations thereof.

[0083] This document discloses compounds or complexes containing platinum. The terms "compound" and "complex" are used interchangeably in this invention. Additionally, the compounds disclosed herein have a neutral charge.

[0084] The compounds disclosed herein can exhibit desired properties and have emission and / or absorption spectra that can be tuned by selecting suitable ligands. On the other hand, the invention excludes any one or more compounds, structures, or portions thereof specifically described herein.

[0085] The compounds disclosed herein are applicable to a wide variety of optical and electro-optic devices, including but not limited to light-absorbing devices such as solar and photosensitive devices, organic light-emitting diodes (OLEDs), light-emitting devices or devices capable of both light absorption and emission, and as markers for biological applications.

[0086] As stated above, the disclosed compounds are platinum complexes. Furthermore, the compounds disclosed herein can be used as host materials for OLED applications, such as full-color displays.

[0087] The compounds disclosed herein can be used in a variety of applications. As luminescent materials, these compounds can be used in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

[0088] 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.

[0089] The compounds disclosed herein can be delayed fluorescent and / or phosphorescent emitters. On one hand, the compounds disclosed herein can be delayed fluorescent emitters. On the other hand, the compounds disclosed herein can be phosphorescent emitters. Furthermore, the compounds disclosed herein can be both delayed fluorescent emitters and phosphorescent emitters.

[0090] This disclosure relates to multidentate binuclear cyclic platinum metal or platinum complexes, which can be used as luminescent materials and host materials in OLED devices.

[0091] Unless otherwise stated, all commercial reagents used in the following experiments were used directly after purchase without further purification. Both 1H and 1C NMR spectra were obtained in deuterated chloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO-d6) solutions. 1H NMR spectra were obtained using a 400 or 500 MHz NMR spectrometer, and 1C NMR spectra were obtained using a 100 or 126 MHz NMR spectrometer. Chemical shifts were based on tetramethylsilane (TMS) or the residual solvent. If CDCl3 was used as the solvent, TMS (δ = 0.00 ppm) and CDCl3 (δ = 77.00 ppm) were used as internal standards for both 1H and 1C NMR spectra, respectively. If DMSO-d6 was used as the solvent, TMS (δ = 0.00 ppm) and DMSO-d6 (δ = 39.52 ppm) were used as internal standards for both 1H and 1C NMR spectra, respectively. The following abbreviations (or combinations) are used to interpret proton spectrum peaks: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad peak. High-resolution mass spectrometry was performed on an Applied Biosystems ESI-QTOF mass spectrometer, with the sample ionization mode being electrospray ionization.

[0092] Example 1: Tetradentate ring platinum(II) complex Pt1

[0093] Synthesis route:

[0094] (1) Synthesis of intermediate chiral 1: D-camphor (300 g, 1971 mmol, 1.0 equivalent) and sodium amide (150 g, 3941 mmol, 2.0 equivalent) were added sequentially to a reaction flask. Nitrogen gas was purged three times. Toluene (3000 mL) was added, and the mixture was stirred at room temperature for 15 hours. Isoamyl formate (266 mL, 1971 mmol, 1.0 equivalent) was then added, and the mixture was stirred at room temperature for 12 hours. The solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography with an eluent of petroleum ether / ethyl acetate at a ratio of 50:1 to 10:1, yielding 149 g of solid product (42% yield). 1 H NMR (500MHz, DMSO-d6): δ (ppm) 0.72 (s, 3H), 0.80 (s, 3H), 0.88 (s, 3H), 1.19–1.27 (m, 2H), 1. 58–1.63(m,1H),1.89–1.93(m,1H),2.75(d,J=4.0Hz,1H),7.2(s,1H),9.75–10.14(br,1H).

[0095] (2) Synthesis of intermediate chiral 2: 1 (149 g, 827 mmol, 1.0 equivalent), n-butanethiol (111 mL, 1033 mmol, 1.25 equivalent), and p-toluenesulfonic acid (1.4 g, 0.83 mmol, 0.1 mol%) were added sequentially to a reaction flask. Nitrogen gas was purged three times, and toluene (1500 mL) was added. The reaction mixture was stirred at 120 °C for 12 hours, and the solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography with an eluent of petroleum ether / ethyl acetate at a ratio of 120:1 to 100:1, yielding 193 g of liquid product (92% yield). 1 H NMR (500MHz, CDCl3): δ (ppm) 0.81 (s, 3H), 0.92 (d, J = 7.5Hz, 3H), 0.95 (s, 3H), 0.96 (s, 3H), 1.36–1.46 (m, 4H ),1.63–1.72(m,3H),1.94–2.00(m,1H),2.62(d,J=4.0Hz,1H),2.80(t,J=7.5Hz,2H),7.11(d,J=1.0Hz,1H).

[0096] (3) Synthesis of intermediate chiral 3: 2 (193 g, 759 mmol, 1.0 equivalent) and sodium borohydride (100 g, 2655 mmol, 3.5 equivalent) were added sequentially to a reaction flask. Nitrogen gas was purged three times, and isopropanol (1500 mL) was added. The mixture was refluxed and stirred for 24 hours. The mixture was washed with sodium hydroxide aqueous solution, extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent. The product was purified by silica gel column chromatography with an eluent of petroleum ether / ethyl acetate at a ratio of 80:1 to 60:1, yielding 100 g of product (52% yield). 1 H NMR (500MHz, CDCl3): δ (ppm) 0.85 (s, 3H), 0.92 (t, J = 7.5Hz, 3H), 0.94 (s, 3H), 0. 96(s,3H),1.03–1.09(m,1H),1.14–1.20(m,1H),1.38–1.45(m,2H),1.52(d,J=6 .5Hz,1H),1.56–1.64(m,3H),1.75–1.82(m,1H),2.54(d,J=4.5Hz,1H),2.67(dd ,J=14.5,3.0Hz,1H),2.68(d,J=4.0Hz,1H),3.79(d,J=5.5Hz,1H),6.02(s,1H).

[0097] (4) Synthesis of intermediate chiral 4: 3 (100 g, 393 mmol, 1.0 equivalent) was added sequentially to the reaction flask, and the mixture was purged with nitrogen three times. Hydrochloric acid (1000 mL) and ethanol (500 mL) were then added. The mixture was refluxed and stirred for 24 hours. After washing with NaHCO3, the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography with an eluent of petroleum ether / ethyl acetate at a ratio of 120:1 to 100:1, yielding 22 g of liquid product (34% yield). 1 H NMR (500MHz, CDCl3): δ (ppm) 0.80 (s, 3H), 0.84 (s, 3H), 0.92–0.97 (m, 1H), 1 .14(s,3H),1.71–1.76(m,2H),1.90–1.94(m,2H),6.76(s,1H),9.58(s,1H).

[0098] (5) Synthesis of intermediate chiral 5: 4 (22 g, 134 mmol, 1.0 equivalent), A (36 g, 147 mmol, 1.1 equivalent), and ammonium acetate (103 g, 1339 mmol, 10.0 equivalent) were added sequentially to a reaction flask. Nitrogen gas was purged three times, and formamide (200 mL) was added. The reaction mixture was stirred at 40°C for three days, at 80°C for three days, and at 150°C for six hours. The mixture was washed with water, extracted five times with dichloromethane, and the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography with an eluent of ethyl acetate / methanol = 10:1, yielding 3.8 g of product (14% yield). MS: m / z 203.11 (M+H) + .

[0099] (6) Synthesis of the intermediate chiral OTf: 5 g (3.8 g, 18 mmol, 1.0 equivalent) was added sequentially to a reaction flask, and the mixture was purged with nitrogen three times. Triethylamine (16 mL, 112 mmol, 6.0 equivalent) and dichloromethane were added, and the mixture was cooled to -40°C. Trifluoromethanesulfonic anhydride (6.3 mL, 37 mmol, 2.0 equivalent) was added, and the mixture was stirred at room temperature for 12 hours. The mixture was washed with water, extracted three times with dichloromethane, and the organic phases were combined. The mixture was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography with a petroleum ether / ethyl acetate ratio of 10:1, yielding 125 mg of product (2% yield). 1 H NMR (500MHz, CDCl3): δ (ppm) 0.54 (s, 3H), 1.00 (s, 3H), 1.08–1.15 (m, 1H), 1.16–1.22 (m, 1H), 1.27 (s, 3H), 1.87–1.94(m,1H),2.11–2.19(m,1H),2.91(d,J=5.0Hz,1H),6.85(d,J=10.0Hz,1H),7.50(d,J=9.5Hz,1H).

[0100] (7) Synthesis of the intermediate chiral 1-OMe: OTf (1.25 g, 3.7 mmol, 1.0 equivalent), Cz-OMe (1.07 g, 3.7 mmol, 1.0 equivalent), Pd2(dba)3 (205 mg, 0.22 mmol, 3 mol%), XPhos (213 mg, 0.44 mmol, 12 mol%), and potassium phosphate (2.77 g, 13.05 mmol, 3.0 equivalent) were added sequentially to a reaction flask. Nitrogen gas was purged three times, and toluene (20 mL) was added. The reaction mixture was stirred at 110 °C for 12 hours, and the solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography with petroleum ether / ethyl acetate as eluent at a ratio of 50:1 to 10:1, yielding 1.66 g of solid product (94% yield). MS: m / z 383.20 (M+H)+ .

[0101] (8) Synthesis of the intermediate chiral 1-OH: 1-OMe (1.66 g, 4.34 mmol, 1.0 equivalent), hydrobromic acid (48%) (5 mL), and acetic acid (2 mL) were added sequentially to a reaction flask. The mixture was stirred at 120 °C for 16 hours and then cooled to room temperature. The solution was neutralized with aqueous NaHCO3, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The product 1-OH was obtained by slurrying with petroleum ether / ethyl acetate, yielding 1.15 g of a white solid (75% yield). MS: m / z 369.19 (M+H) + .

[0102] (9) Synthesis of the intermediate chiral 1-Cl: 1-OH (1.15 g, 3.12 mmol, 1.0 equivalence), m-chlorobromobenzene (718 mg, 3.75 mmol, 1.2 equivalence), cuprous iodide (119 mg, 0.62 mmol, 20 mol%), 2-pyridinecarboxylic acid (154 mg, 1.24 mmol, 40 mol%), and potassium phosphate (1.33 g, 6.25 mmol, 2.0 equivalence) were added sequentially to a reaction flask. Nitrogen gas was purged three times, and dimethyl sulfoxide (10 mL) was added. The reaction mixture was stirred at 100 °C for 12 hours. The mixture was diluted with water, extracted three times with ethyl acetate, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The mixture was purified by silica gel column chromatography with an eluent of petroleum ether / ethyl acetate at a ratio of 20:1 to 10:1, yielding 1.27 g of a white solid (85% yield). MS: m / z 479.15 (M+H) + .

[0103] (10) Synthesis of the intermediate chiral 1-NH2: 1-Cl (1.27 g, 2.66 mmol, 1.0 equivalent), tBuNH2 (1.96 mg, 3.19 mmol, 1.2 equivalent), tris(dibenzylacetone)palladium (61 mg, 0.07 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (40 mg, 0.13 mmol, 6 mol%), and sodium tert-butoxide (425 mg, 4.4 mmol, 2.0 equivalent) were added sequentially to a reaction flask. Nitrogen gas was purged three times, and toluene (20 mL) was added. The reaction mixture was stirred at 110 °C for 12 hours, and the solvent was removed by vacuum distillation. The product was purified by silica gel column chromatography with petroleum ether / ethyl acetate as eluent at a ratio of 30:1 to 10:1, yielding 2.6 g of solid product (92% yield). The compound was easily oxidized and was used directly in the next step without characterization.

[0104] (11) Synthesis of ligand 1-L: 1-NH₂ (2.6 g, 2.4 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (789 mg, 4.8 mmol, 2.0 equivalent) were added sequentially to a Schlenk tube. Nitrogen gas was purged three times, and triethyl orthoformate (10 mL) was added sequentially. The reaction was carried out at 75 °C for 4 hours. The solvent was removed by vacuum distillation, and the mixture was purified by silica gel chromatography with eluents of petroleum ether / ethyl acetate = 20:1 to dichloromethane / methanol = 200:1. 1.85 g of the ligand in a foamy solid was obtained, with a yield of 62%. MS: m / z 1215.63 (M+H) + .

[0105] (12) Synthesis of complex Pt1: Ligand 1-L (1.85 g, 1.5 mmol, 1.0 equivalent), Pt(COD)Cl2 (562 mg, 1.5 mmol, 1.0 equivalent), and sodium acetate (370 mg, 4.5 mmol, 3.0 equivalent) were added sequentially to a sealed tube. Nitrogen gas was purged three times. Diethylene glycol dimethyl ether (20 mL) was added, and the mixture was bubbled under nitrogen for 30 minutes. The reaction was carried out at 120 °C for 36 hours. The solvent was removed by vacuum distillation, and the mixture was purified by silica gel chromatography with petroleum ether / dichloromethane as eluent at a ratio of 4:1–1:1. Complex Pt1 was finally obtained as a yellow solid, 882 mg, in a yield of 46%. MS: m / z 1293.67 (M+H) + .

[0106] Example 2: Tetradentate ring platinum(II) complex Pt2

[0107] Following the synthesis methods described in Example 1, Pt2 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1012.44 (M+H) + .

[0108] Example 3: Tetradentate ring platinum(II) complex Pt3

[0109] Following the synthesis methods described in Example 1, Pt3 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 984.41 (M+H) + .

[0110] Example 4: Tetradentate ring platinum(II) complex Pt4

[0111] Following the synthesis methods described in Example 1 and Example 2, Pt4 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1013.43 (M+H) + .

[0112] Example 5: Tetradentate ring platinum(II) complex Pt5

[0113] Following the synthesis methods described in Example 1, Pt5 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 999.42 (M+H) + .

[0114] Example 6: Tetradentate ring platinum(II) complex Pt6

[0115] Following the synthesis methods described in Example 1, Pt6 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1052.38 (M+H) + .

[0116] Example 7: Tetradentate ring platinum(II) complex Pt7

[0117] Following the synthesis methods described in Example 1, Pt7 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1108.44 (M+H) + .

[0118] Example 8: Tetradentate ring platinum(II) complex Pt8

[0119] Following the synthesis methods described in Example 1, Pt8 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1077.37 (M+H) + .

[0120] Example 9: Tetradentate ring platinum(II) complex Pt9

[0121] Following the synthesis methods described in Example 1, Pt9 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1144.42 (M+H) + .

[0122] Example 10: Tetradentate ring platinum(II) complex Pt10

[0123] Following the synthesis methods described in Example 1, Pt10 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1276.63 (M+H) + .

[0124] Example 11: Tetradentate ring platinum(II) complex Pt11

[0125] Following the synthesis methods described in Example 1 and Example 2, Pt11 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1060.44 (M+H) + .

[0126] Example 12: Tetradentate ring platinum(II) complex Pt12

[0127] Following the synthesis methods described in Example 1, Pt12 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1085.43 (M+H) + .

[0128] Example 13: Tetradentate ring platinum(II) complex Pt13

[0129] Following the synthesis methods described in Example 1, Pt13 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1240.53 (M+H) + .

[0130] Example 14: Tetradentate ring platinum(II) complex Pt14

[0131] Following the synthesis methods described in Example 1 and Example 2, Pt14 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1146.40 (M+H) + .

[0132] Example 15: Tetradentate ring platinum(II) complex Pt15

[0133] Following the synthesis methods described in Example 1, Pt15 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1000.34 (M+H) + .

[0134] Example 16: Tetradentate ring platinum(II) complex Pt16

[0135] Following the synthesis methods described in Example 1 and Example 2, Pt16 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1188.50 (M+H) + .

[0136] Example 17: Tetradentate ring platinum(II) complex Pt17

[0137] Following the synthesis methods described in Example 1, Pt17 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1122.45 (M+H) + .

[0138] Example 18: Tetradentate ring platinum(II) complex Pt18

[0139] Following the synthesis methods described in Example 1, Pt18 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1184.47 (M+H) + .

[0140] Example 19: Tetradentate ring platinum(II) complex Pt19

[0141] Following the synthesis methods described in Example 1, Pt19 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1187.46 (M+H) + .

[0142] Example 20: Tetradentate ring platinum(II) complex Pt20

[0143] Following the synthesis methods described in Example 1, Pt₂O was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1268.56 (M+H) + .

[0144] Example 21: Tetradentate ring platinum(II) complex Pt21

[0145] Following the synthesis methods described in Example 1, Pt21 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1128.41 (M+H) + .

[0146] Example 22: Tetradentate ring platinum(II) complex Pt22

[0147] Following the synthesis methods described in Example 1, Pt22 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1120.36 (M+H) + .

[0148] Example 23: Tetradentate ring platinum(II) complex Pt23

[0149] Following the synthesis methods described in Example 1, Pt23 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1122.45 (M+H) + .

[0150] Example 24: Tetradentate ring platinum(II) complex Pt24

[0151] Following the synthesis methods described in Example 1 and Example 2, Pt24 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1184.47 (M+H) + .

[0152] Example 25: Tetradentate ring platinum(II) complex Pt25

[0153] Following the synthesis methods described in Example 1, Pt25 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1109.43 (M+H) + .

[0154] Example 26: Tetradentate ring platinum(II) complex Pt40

[0155] Following the synthesis methods described in Example 1 and Example 2, Pt40 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 944.28 (M+H) + .

[0156] Example 27: Tetradentate ring platinum(II) complex Pt77

[0157] Following the synthesis methods described in Example 1, Pt77 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1068.34 (M+H) + .

[0158] Example 28: Tetradentate ring platinum(II) complex Pt78

[0159] Following the synthesis methods described in Example 1, Pt78 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1086.37 (M+H) + .

[0160] Example 29: Tetradentate ring platinum(II) complex Pt83

[0161] Following the synthesis methods described in Example 1, Pt83 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 940.33 (M+H) + .

[0162] Example 30: Tetradentate ring platinum(II) complex Pt89

[0163] Following the synthesis methods described in Example 1, Pt89 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1156.41 (M+H) + .

[0164] Example 31: Tetradentate ring platinum(II) complex Pt108

[0165] Following the synthesis methods described in Example 1, Pt108 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1035.31 (M+H) + .

[0166] Example 32: Tetradentate ring platinum(II) complex Pt151

[0167] Following the synthesis methods described in Example 1, Pt151 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1157.42 (M+H) + .

[0168] Example 33: Tetradentate ring platinum(II) complex Pt152

[0169] Following the synthesis methods described in Example 1, Pt152 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1158.44 (M+H) + .

[0170] Example 34: Tetradentate ring platinum(II) complex Pt155

[0171] Following the synthesis methods described in Example 1, Pt155 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1197.43 (M+H) + .

[0172] Example 35: Tetradentate ring platinum(II) complex Pt156

[0173] Following the synthesis methods described in Example 1, Pt156 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1197.40 (M+H) + .

[0174] Example 36: Tetradentate ring platinum(II) complex Pt157

[0175] Following the synthesis methods described in Example 1, Pt157 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1197.41 (M+H) + .

[0176] Example 37: Tetradentate ring platinum(II) complex Pt159

[0177] Following the synthesis methods described in Example 1, Pt159 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1213.40 (M+H) + .

[0178] Example 38: Tetradentate ring platinum(II) complex Pt160

[0179] Following the synthesis methods described in Example 1, Pt160 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1213.48 (M+H) + .

[0180] Example 39: Tetradentate ring platinum(II) complex Pt161

[0181] Following the synthesis methods described in Example 1 and Example 2, Pt161 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1223.48 (M+H) + .

[0182] Example 40: Tetradentate ring platinum(II) complex Pt189

[0183] Following the synthesis methods described in Example 1, Pt189 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1292.46 (M+H) + .

[0184] Example 41: Tetradentate ring platinum(II) complex Pt191

[0185] Following the synthesis methods described in Example 1 and Example 2, Pt191 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1290.44 (M+H) + .

[0186] Example 42: Tetradentate ring platinum(II) complex Pt197

[0187] Following the synthesis methods described in Example 1, Pt197 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1308.44 (M+H) + .

[0188] Example 43: Tetradentate ring platinum(II) complex Pt2O1

[0189] Following the synthesis methods described in Example 1 and Example 2, Pt₂O₁ was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1300.46 (M+H) + .

[0190] Example 44: Tetradentate ring platinum(II) complex Pt2O3

[0191] Following the synthesis methods described in Example 1, Pt₂O₃ was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1261.59 (M+H) + .

[0192] Example 45: Tetradentate ring platinum(II) complex Pt2O4

[0193] Following the synthesis methods described in Example 1, Pt₂O₄ was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1385.62 (M+H) + .

[0194] Example 46: Tetradentate ring platinum(II) complex Pt2O5

[0195] Following the synthesis methods described in Example 1, Pt₂O₅ was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1385.61 (M+H) + .

[0196] Example 47: Tetradentate ring platinum(II) complex Pt2O6

[0197] Following the synthesis methods described in Example 1, Pt₂O₆ was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1329.55 (M+H) + .

[0198] Example 48: Tetradentate ring platinum(II) complex Pt2O7

[0199] Following the synthesis methods described in Example 1, Pt₂O₇ was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1329.54 (M+H) + .

[0200] Example 49: Tetradentate ring platinum(II) complex Pt2O8

[0201] Following the synthesis methods described in Example 1, Pt₂O₈ was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1385.60 (M+H) + .

[0202] Example 50: Tetradentate ring platinum(II) complex Pt2O9

[0203] Following the synthesis methods described in Example 1, Pt₂O₉ was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1385.61 (M+H) + .

[0204] Example 51: Tetradentate ring platinum(II) complex Pt210

[0205] Following the synthesis methods described in Example 1, Pt210 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1385.62 (M+H) + .

[0206] Example 52: Tetradentate ring platinum(II) complex Pt211

[0207] Following the synthesis methods described in Example 1, Pt211 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1385.59 (M+H) + .

[0208] Example 53: Tetradentate ring platinum(II) complex Pt212

[0209] Following the synthesis methods described in Example 1, Pt₂₁₂ was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1385.63 (M+H) + .

[0210] Example 54: Tetradentate ring platinum(II) complex Pt214

[0211] Following the synthesis methods described in Example 1, Pt214 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1319.56 (M+H) + .

[0212] Example 55: Tetradentate ring platinum(II) complex Pt225

[0213] Following the synthesis methods described in Example 1, Pt225 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1366.52 (M+H) + .

[0214] Example 56: Tetradentate ring platinum(II) complex Pt226

[0215] Following the synthesis methods described in Example 1, Pt226 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1288.45 (M+H) + .

[0216] Example 57: Tetradentate ring platinum(II) complex Pt229

[0217] Following the synthesis methods described in Example 1, Pt229 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1335.52 (M+H) + .

[0218] Example 58: Tetradentate ring platinum(II) complex Pt230

[0219] Following the synthesis methods described in Example 1, Pt230 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1314.52 (M+H) + .

[0220] Example 59: Tetradentate ring platinum(II) complex Pt234

[0221] Following the synthesis methods described in Example 1, Pt234 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1304.45 (M+H) + .

[0222] Example 60: Tetradentate ring platinum(II) complex Pt238

[0223] Following the synthesis methods described in Example 1, Pt238 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1283.48 (M+H) + .

[0224] Example 61: Tetradentate ring platinum(II) complex Pt240

[0225] Following the synthesis methods described in Example 1, Pt240 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1308.47 (M+H) + .

[0226] Example 62: Tetradentate ring platinum(II) complex Pt256

[0227] Following the synthesis methods described in Example 1, Pt256 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1391.55 (M+H) + .

[0228] Example 63: Tetradentate ring platinum(II) complex Pt268

[0229] Following the synthesis methods described in Example 1, Pt268 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1606.72 (M+H) + .

[0230] Example 64: Tetradentate ring platinum(II) complex Pt288

[0231] Following the synthesis methods described in Example 1, Pt288 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 878.32 (M+H) + .

[0232] Example 65: Tetradentate ring platinum(II) complex Pt294

[0233] Following the synthesis methods described in Example 1, Pt294 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1038.33 (M+H) + .

[0234] Example 66: Tetradentate ring platinum(II) complex Pt3O3

[0235] Following the synthesis methods described in Example 1, Pt3O3 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1086.44 (M+H) + .

[0236] Example 67: Tetradentate ring platinum(II) complex Pt3O7

[0237] Following the synthesis methods described in Example 1, Pt240 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1111.36 (M+H) + .

[0238] Example 68: Tetradentate ring platinum(II) complex Pt311

[0239] Following the synthesis methods described in Example 1, Pt311 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1120.52 (M+H) + .

[0240] Example 69: Tetradentate ring platinum(II) complex Pt332

[0241] Following the synthesis methods described in Example 1, Pt240 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1072.52 (M+H) + .

[0242] Example 70: Tetradentate ring platinum(II) complex Pt346

[0243] Following the synthesis methods described in Example 1, Pt346 was prepared by replacing the corresponding ligand raw materials. After metallization, the target compound was synthesized. MS: m / z 1246.57 (M+H) + .

[0244] Example 71: Tetradentate ring platinum(II) complex Pt359

[0245] Following the synthesis methods described in Example 1, Pt359 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1076.43 (M+H) + .

[0246] Example 72: Tetradentate ring platinum(II) complex Pt367

[0247] Following the synthesis methods described in Example 1, Pt367 was prepared by replacing the corresponding ligand raw materials, and then metallized to synthesize the target compound. MS: m / z 1142.51 (M+H) + .

[0248] Explanation of photophysical tests and theoretical calculations:

[0249] Steady-state emission experiments and lifetime measurements were performed using a Horiba Jobin Yvon FluoroLog-3 spectrometer, or steady-state emission spectroscopy was performed using a SHIMADZU RF-6000 spectrometer. Circularly polarized light measurements were performed using a JASCO CPL-300 spectrophotometer, all under room temperature conditions with dichloromethane solution.

[0250] Experimental data and analysis:

[0251] Figure 1 is a schematic diagram of the design concept for an optically pure, spiky-chiral, tetradentate ring metal complex circularly polarized light-emitting material centered on a metal ion. As can be seen from Figure 1, the optically pure raw materials provided by this invention are economical and readily available; the central chirality autonomously induces the generation of spiky chirality; the circularly polarized light-emitting material does not require chiral separation, greatly saving the preparation cost of optically pure materials, and can be prepared in large quantities without being limited by chiral preparation chromatographic column separation.

[0252] The material provided by this invention exhibits high chemical and thermal stability. The designed and developed tetradentate ligand can interact with dsp. 2 Hybridized platinum(II) ions coordinate well to form a stable and rigid tetragonal molecular configuration with high chemical stability. Simultaneously, due to the significant steric hindrance between the designed central chiral ligands, the entire metal complex molecule can form a stable helical tetradentate ring metal complex, preventing derotation and loss of circularly polarized luminescence properties during solution or high-temperature sublimation. Table 1 shows the quantum efficiency (PLQY) and asymmetry factor (g) of some chiral metal complexes. PL Data table.

[0253] Table 1. Quantum efficiency (PLQY) and asymmetry factor (g) of some chiral metal complexes PL )

[0254] Note: Quantum efficiency (PLQY) was measured in PMMA thin films, g PL Determined in dichloromethane solution.

[0255] As shown in Table 1, some of the listed chiral metal complexes exhibit circularly polarized luminescence and an asymmetry factor (g) PL The absolute value can be as high as 1.97 × 10⁻⁶. -3 This demonstrates the important applications of such chiral metal complexes in circularly polarized light-emitting elements and related fields. In contrast, the control molecule PtR1 exhibits no circularly polarized luminescence, and its g... PL All are zero.

[0256] In organic light-emitting devices (OLEDs), carriers are injected into the luminescent material from both positive and negative electrodes, generating an excited-state luminescent material that emits light. The circularly polarized luminescent material of this invention, represented by general formula (I) or (I'), can be used as a phosphorescent material in excellent organic light-emitting devices such as organic photoluminescent devices or organic electroluminescent devices. Organic photoluminescent devices have a structure in which at least a luminescent layer is formed on a substrate. Furthermore, organic electroluminescent devices have 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 luminescent layer, and may consist of only a luminescent layer, or may have one or more organic layers in addition to the luminescent 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 2 is a schematic diagram of a specific organic light-emitting element for reference; in the figure, 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.

[0257] 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.

[0258] 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:

[0259] In a preferred embodiment of the present invention, the hole transport layer in the OLED device of the present invention comprises one or more p-type dopants. The preferred p-type dopants of the present invention have the following structures, but this does not mean that the present invention is limited to these structures:

[0260] In a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of compounds ET-1 to ET-77, but this does not mean that the present invention is limited to the following structures:

[0261] The electron transport layer can be formed by organic materials together with one or more n-type dopants (such as LiQ, LiThPh, etc.).

[0262] In a preferred embodiment of the present invention, the host material may be selected from known or unknown materials, and the preferred host material may be selected from at least one of compounds H-1 to H-6, but this does not mean that the present invention is limited to the following structures:

[0263] The compounds shown in some embodiments are used as circularly polarized light-emitting materials in OLED devices. In a preferred embodiment, the structure can be represented as follows: On a glass containing ITO, the hole injection layer (HIL) is HT-1:P-3 (95:5v / 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 (H-1): the metal complex Pt1 of the present invention (95:5v / v%) with a thickness of 35 nm; the electron transport layer (ETL) is ET-13:LiQ (50:50v / v%) with a thickness of 35 nm; and then a cathode Al of 70 nm is deposited by evaporation. This is referred to as device 1. Referring to the device structure provided in Device 1, metal complexes listed in Table 2 were selected as the subjects to replace Pt1 in Device 1. These complexes were co-evaporated with the host compound to form a light-emitting layer, thus preparing organic light-emitting diodes (OLEDs), denoted as Control Device, Devices 2 through 55, respectively. The light-emitting characteristics of the prepared devices were tested using standard methods, and the data are shown in Table 2.

[0264] Table 2. Performance of OLED devices doped with some chiral metal complexes Note: g EL It represents the electroluminescence asymmetry factor.

[0265] As shown in Table 2, the devices made from Pt1-based luminescent materials all exhibit significant circularly polarized light emission signals, with a significant increase in their relative external quantum efficiency. This indicates that this series of spiral-chiral tetradentate ring metal complex circularly polarized light emission materials has a promising application prospect.

[0266] It should be noted that the structure described is an example of an application of the circularly polarized light-emitting material of the present invention, and does not constitute a limitation on the specific OLED device structure of the circularly polarized light-emitting material shown in the present invention. The circularly polarized light-emitting material is also not limited to the compounds represented in the embodiments.

[0267] Those skilled in the art will understand that the above embodiments are specific examples of implementing the present invention, and in practical applications, various changes in form and detail may be made without departing from the spirit and scope of the invention. For example, many of the substituent structures described herein can be replaced with other structures without departing from the spirit of the invention.

Claims

1. A spirally chiral tetradentate platinum(II) complex circularly polarized luminescent material, characterized in that, Having a structure as shown in general formula (I) or (I'), where (I) and (I') are enantiomers of each other: In formula (I) or (I'), L represents O, S, and 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 of the following is independently one or more of the following: hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteralkyl, deuteroaryl, deuteroheteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or dialkylamino, mono- or diarylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, and aryloxysilyl. * indicates a carbon atom with central chirality; Y 1 Y 2 Y 3 Each is independent as CR 3 Or N; Z 1 Z 2 Z 3 Z 4 Z 5 Z 6 Z 7 Z 8 Each is independent as CR 4 Or N; R 1 R 2 R 3 R 4 Each can be used independently to indicate monosubstituted, polysubstituted, or unsubstituted substances; R 1 R 3 R 4 R a R b R m and R n Each of the following is independently one or more of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, haloalkyl, aryl, heteroaryl, haloaryl, haloheteroaryl, deuterated alkyl, deuterated aryl, deuterated heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or dialkylamino, mono- or diarylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, and aryloxysilyl; R 2 Each of the following is independently hydrogen, deuterium, alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted azaaryl, substituted or unsubstituted fused-ring aryl, substituted or unsubstituted fused-ring heteroaryl; when substituted, the substituent is selected from one or more of deuterium, alkyl, aryl, heteroaryl, mono- or dialkylamino, mono- or diarylamino, and -CN.

2. The circularly polarized luminescent material of a chiral tetradentate platinum(II) complex according to claim 1, characterized in that, R 2 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, F, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, deuterated tert-butyl, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, substituted or unsubstituted phenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted triphenylamino; when substituted, the substituent is selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, and carbazolyl; R 2 It can connect with the substituted group to form a fused ring.

3. The circularly polarized luminescent material of a helical tetradentate platinum(II) complex according to claim 1, characterized in that, The chemical formulas of helical tetradentate platinum(II) complex circularly polarized luminescent materials are shown in general formulas (Ii) or (I'-i), (I-ii) or (I'-ii), where (Ii) and (I'-i), and (I-ii) and (I'-ii) are enantiomers: Among them, L, Y 1 -Y 3 Z 1 -Z 8 R 1 R 3 R 4 R a R b R m and R n The substitution scenarios are all as defined in claim 1; In formula (Ii) or (I'-i), X 1 X 2 X 3 X 4 Each is independent as CR 7 Or N; R 7 Each time it appears, it is independently one or more of the following: hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteralkyl, deuteroaryl, deuteroheteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or dialkylamino, mono- or diarylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, and aryloxysilyl. In formula (I-ii) or (I'-ii), R 5 R 6 Each time it appears, it independently represents one or more of the following: hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, deuteralkyl, deuteroaryl, deuteroheteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or dialkylamino, mono- or diarylamino, ester, -CN, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, and aryloxysilyl. R 5 R 6 They can be fused together to form rings.

4. The circularly polarized luminescent material of a helical tetradentate platinum(II) complex according to claim 1, characterized in that, R a R b R m and R n Each of the following is independently one or more of hydrogen, deuterium, fluorine atom, substituted or unsubstituted C1-C24 alkyl, C3-C24 cycloalkyl, substituted or unsubstituted C6-C18 aryl, C1-C24 heteroalkyl, C3-C24 heterocycloalkyl, and C6-C18 heteroaryl; when a substituent is present, the substituent is selected from hydrogen, deuterium, fluorine atom, and C1-C14 alkyl; R x R y and R z Each is independently selected from one or more of hydrogen, deuterium, fluorine atom, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C6-C18 aryl, C1-C24 heteroalkyl, and C6-C18 heteroaryl; when a substituent is present, the substituent is selected from hydrogen, deuterium, fluorine atom, and C1-C14 alkyl.

5. The circularly polarized luminescent material of a helical tetradentate platinum(II) complex according to claim 1, characterized in that, R 1 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, F, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, deuterated tert-butyl, substituted or unsubstituted aryl, substituted or unsubstituted carbazole; when substituted, the substituent is selected from hydrogen, deuterium, F, -CN, C1-C10 alkyl; when R 1 When selected from aryl groups, it can connect with the substituted group to form a fused ring.

6. The circularly polarized luminescent material of a helical tetradentate platinum(II) complex according to claim 1, characterized in that, R 3 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 silyl, substituted or unsubstituted carbazole, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C6-C30 indenyl, substituted or unsubstituted C6-C30 heteroindenyl; when substituted, the substituent is selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, and carbazole, and adjacent substituents may be linked to form a ring; R 4 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, F, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 xanthyl, substituted or unsubstituted C1-C30 silyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted carbazole, substituted or unsubstituted C6-C30 xenodanyl; when it contains a substitution, the substituent is selected from one or more of hydrogen, deuterium, F, -CN, C1-C10 alkyl, phenyl, and carbazole.

7. The circularly polarized luminescent material of a chiral tetradentate platinum(II) complex according to claim 3, characterized in that, R 7 Each time it appears, it is independently selected from hydrogen, deuterium, halogen, alkyl, substituted or unsubstituted aryl, substituted or unsubstituted carbazole, substituted or unsubstituted diphenylamino; when it contains a substitution, the substituent is selected from hydrogen, deuterium, fluorine, methyl, ethyl, propyl, butyl, tert-butyl, phenyl, biphenyl, naphthyl, carbazole; R 5 R 6 Each time it appears, it is independently represented by hydrogen, deuterium, fluorine, methyl, ethyl, propyl, butyl, tert-butyl, phenyl, or R. 5 R 6 They can be linked together to form cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, or cyclooctane.

8. The circularly polarized luminescent material of a helical tetradentate platinum(II) complex according to claim 1, characterized in that, The circularly polarized luminescent material of the complex is selected from the following structures and their enantiomers, but is not limited thereto, where "D" represents deuterium:

9. The application of the spiral-chiral tetradentate platinum(II) complex circularly polarized luminescent material according to any one of claims 1-8 in the fabrication of electronic devices.

10. The application according to claim 9, characterized in that, The electronic devices mentioned are light-emitting devices, 3D display devices, three-dimensional imaging devices, optical information encryption devices, information storage devices, or biological imaging devices.

11. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a cathode, an anode, and an organic functional layer between them; the organic functional layer includes the circularly polarized light-emitting material of the chiral tetradentate platinum(II) complex according to any one of claims 1-8.

12. An organic optoelectronic device, characterized in that, The organic optoelectronic device includes 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 spiral-chiral tetradentate platinum(II) complex circularly polarized light-emitting material as described in any one of claims 1-8.

13. A display or lighting device, characterized in that, The display or lighting device comprises the organic electroluminescent device of claim 11, and / or the organic optoelectronic device of claim 12.

14. A composition, characterized in that, The composition comprises the spiral-chiral tetradentate platinum(II) complex circularly polarized luminescent material according to any one of claims 1-8.

15. A formulation, characterized in that, The formulation comprises the chiral tetradentate platinum(II) complex circularly polarized luminescent material according to any one of claims 1-8 and at least one solvent.

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