Central chirality remotely induced spiro-chiral tetradentate cyclometalated platinum(II) and / or palladium(II) complex-based circularly polarized luminescent material, and use thereof

Abstract

Disclosed in the present invention are a central chirality remotely induced spiro-chiral tetradentate cyclometalated platinum(II) and / or palladium(II) complex-based circularly polarized luminescent material, and a use thereof. The provided spiro-chiral tetradentate cyclometalated complex molecule can autonomously induce the entire tetradentate ligand to coordinate with metal ions in a low-steric-hindrance manner by means of a remote central chiral fragment in a chiral-substituted pyridine, thereby forming an optically pure spiro-chiral metal complex-based circularly polarized luminescent material. The spiro-chiral metal complex-based circularly polarized luminescent material requires no chiral resolution, has a high molecular thermodynamic stability, and is of significant practical value in circularly polarized luminescent elements.

Description

Circularly polarized luminescent material of chiral remote induction helical tetradentate ring metal platinum (II) and / or palladium (II) complex and application thereof TECHNICAL FIELD

[0001] The present application relates to the field of circularly polarized luminescent material preparation, and particularly relates to a circularly polarized luminescent material of chiral remote induction helical tetradentate ring metal platinum (II) and / or palladium (II) complex and application thereof. BACKGROUND

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

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

[0004] The purpose of the present application is to solve the problem of the lack of development of circularly polarized luminescent materials at present, and to provide a center chirality induced remote helical chirality four-tooth ring metal platinum (II) and / or palladium (II) complex circularly polarized luminescent material and application. The circularly polarized luminescent material has a chiral substituted pyridine-carbazole-phenyl carbene and its derivative structure based on chirality, which is self-induced by a remote center chirality fragment in a chiral substituted pyridine to coordinate with a metal ion in a small steric hindrance manner, forming an optically pure helical chirality metal complex circularly polarized light emitting material. Such helical chirality metal complex circularly polarized luminescent material does not need to be chiral split, and has high molecular thermodynamic stability, which has important application in circularly polarized luminescent elements.

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

[0006] The present application provides a center chirality remote induced helical chirality four-tooth ring metal platinum (II) and / or palladium (II) complex circularly polarized luminescent material, which has a chemical formula as shown in general formula (I) and / or (I'):

[0007] Wherein, M is Pt or Pd;

[0008] L is O, S, CR x R y , C=O, SiR x R y , GeR x R y , NR z , PRz , R z P = O, AsR z , R z As = O, S = O, SO2, Se, Se = O, SeO2, BR z , R z Bi = O or BiR z ; wherein R x , R y and R z are each independently selected from one or more of hydrogen, deuterium, halogen, -CN, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl, R x and R y may optionally be linked to form a cyclic system;

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

[0010] R 1 is at least one of substituted or unsubstituted alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl; when containing a substitution, the substituent is selected from one or more of deuterium, halogen, cycloalkyl, aryl;

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

[0012] R 2 - R 4 represents a poly-substituted group, which can be non-substituted, mono-substituted or poly-substituted; R 2 - R 4each occurrence is independently selected from one or more of hydrogen, deuterium, halogen, -CN, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, haloalkyl, deuterated alkyl, aryl, heteroaryl, deuterated aryl, haloaryl, halo heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl;

[0013] R a and R b each occurrence is independently selected from one or more of hydrogen, deuterium, halogen, alkyl, haloalkyl, deuterated alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloaryl, halo heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, nitrile, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl; m and R n each occurrence is independently selected from one or more of hydrogen, deuterium, halogen, alkyl, haloalkyl, deuterated alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloaryl, halo heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, nitrile, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl.

[0014] each occurrence is independently selected from one or more of hydrogen, deuterium, halogen, -CN, alkyl, aryl. R 2 each occurrence is independently selected from one or more of hydrogen, deuterium, halogen, -CN, alkyl, aryl. R 3 each occurrence is independently selected from one or more of hydrogen, deuterium, halogen, -CN, alkyl, heteroalkyl, alkoxy, haloalkyl, deuterated alkyl, aryl, haloaryl, alkenyl, cycloalkenyl, carboxyl, alkynyl, ester, alkylsilyl, arylsilyl, heteroarylsilyl; R 4 each occurrence is independently selected from one or more of hydrogen, deuterium.

[0015] In many embodiments, two or more adjacent R 2 , R 3 and R 4 may optionally be linked to form a fused ring or unsaturated ring system; said R a , R b , R m , R n , R 2 -R 4 at least one hydrogen of R

[0016] In many embodiments, the chiral center-remote induced helical tetradentate ring metal platinum (II) or palladium (II) complex circularly polarized luminescent material described in the present application can be as follows, but not limited to, the structure, wherein "D" represents deuterium:

[0017] According to one or more embodiments, the present application also provides the use of the circularly polarized luminescent material having the structure of general formula (I) and / or (I') as described above in the preparation of electronic devices.

[0018] Further, the electronic device is a light-emitting device, a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device, or a biological imaging device. The light-emitting device is preferably an organic electroluminescent device or an organic optoelectronic device.

[0019] According to one or more embodiments, the present application also provides an organic electroluminescent device, comprising a cathode, an anode, and an organic functional layer between the two; the organic functional layer comprises the circularly polarized luminescent material having the structure of general formula (I) and / or (I') as described above.

[0020] Further, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the circularly polarized luminescent material having the structure of general formula (I) and / or (I'). The mass percentage of the circularly polarized luminescent material is 0.01% to 50%.

[0021] According to one or more embodiments, the present application also provides an organic optoelectronic device, comprising a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer comprises the circularly polarized luminescent material having the structure of general formula (I) and / or (I'). For example, the circularly polarized luminescent material can be included in the light-emitting material layer as a guest material or a dopant.

[0022] According to one or more embodiments, the present application also provides a display or lighting device, including but not limited to a full-color display, a light-emitting display device, etc.; comprising the organic electroluminescent device and / or the organic optoelectronic device described above.

[0023] The present application also provides a composition comprising the circularly polarized luminescent material having the structure of general formula (I) and / or (I').

[0024] The present application also provides a preparation comprising the circularly polarized luminescent material having the structure of general formula (I) and / or (I') or the composition described above and at least one solvent. The solvent is not particularly limited, and solvents known to those skilled in the art, such as unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents, halogenated unsaturated hydrocarbon solvents, ether solvents or ester solvents, can be used; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetralin, n-butylbenzene, sec-butylbenzene or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; and the ester solvent is benzoic acid alkyl ester.

[0025] The present application also provides a display or lighting device comprising one or more of the organic electroluminescent devices described above.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] (1) Generation of central chiral remote autonomous induction of helicity: by designing and developing a tetradentate ligand containing a chiral substituted pyridine central chiral fragment, using the steric hindrance effect between the terminal ligand chiral substituted pyridine and the substituted carbine, the whole tetradentate ring metal platinum(II) and / or palladium(II) complex molecule is in a twisted quadrilateral configuration; at the same time, the chiral substituted pyridine central chiral fragment can autonomously and remotely induce the whole tetradentate ligand to coordinate with the metal ion in a small steric hindrance manner, forming an optically pure helical tetradentate ring metal platinum(II) and / or palladium(II) complex circularly polarized light emitting material with the metal ion as the center.

[0028] (2) Economical and easy to obtain optically pure raw materials: the chiral optically pure isomer required for preparing the tetradentate ligand containing a chiral substituted pyridine is a commercially available and economically easy-to-obtain compound, which facilitates the preparation of chiral optically pure tetradentate ligands.

[0029] (3) Circularly polarized light emitting material does not need to be chiral separated: the chiral optically pure circularly polarized light emitting material of the helical tetradentate ring metal platinum(II) and / or palladium(II) complex can be conveniently prepared from the above chiral optically pure tetradentate ligand, without the need for separation and purification by a chiral column, and is not limited by high-cost chiral separation, greatly reducing the preparation cost of the material.

[0030] (4) High chemical stability and thermal stability of the material: the designed and developed tetradentate ligand can form a stable complex with dsp2 The hybrid platinum (II) and / or palladium (II) metal ion is well coordinated to form a thermodynamically stable and rigid square planar configuration molecule, which has high chemical stability and does not racemize to lose the circularly polarized luminescent property in either solution or solid state. BRIEF DESCRIPTION OF DRAWINGS

[0031] Fig. 1 is a diagram of the design idea of optically pure metal ion-centered helical chiral tetradentate ring metal complex circularly polarized light luminescent material;

[0032] Fig. 2 is a circularly polarized luminescence spectrum diagram of optically pure Pt1 in dichloromethane solution at room temperature under oxygen-free conditions; in the diagram, (a) is a circularly polarized luminescence spectrum (CPPL), and (b) is a plot of the dissymmetry factor (g PL ) at different wavelengths;

[0033] Fig. 3 is a circularly polarized luminescence spectrum diagram of optically pure Pt2 in dichloromethane solution at room temperature under oxygen-free conditions; in the diagram, (a) is a circularly polarized luminescence spectrum (CPPL), and (b) is a plot of the dissymmetry factor (g PL ) at different wavelengths;

[0034] Fig. 4 is a single crystal diffraction diagram of optically pure Pt2;

[0035] Fig. 5 is an emission spectrum diagram of some helical chiral material molecules in a 5% PMMA film at room temperature under oxygen-free conditions; in the diagram, (a) is an emission spectrum diagram of optically pure Pt1 and Pt2, and (b) is an emission spectrum diagram of optically pure Pt4 and Pt6;

[0036] Fig. 6 is a structural schematic diagram of a specific organic light-emitting element that can be referred to; in the diagram, 110 represents a substrate, 120 represents an anode, 130 represents a hole injection layer, 140 represents a hole transport layer, 150 represents a light-emitting layer, 160 represents a hole blocking layer, 170 represents an electron transport layer, 180 represents an electron injection layer, and 190 represents a cathode. DETAILED DESCRIPTION

[0037] The content of the present application will be described in detail below. The description of the constituent elements described below is sometimes based on a representative embodiment or a specific example of the present application, but the present application is not limited to such an embodiment or a specific example.

[0038] The specific examples of the circularly polarized light luminescent material of the present application represented by the above general formula will be illustrated below, but are not construed as limiting the present application.

[0039] The present disclosure can be understood more readily by reference to the following detailed description and examples contained therein. Before the present compounds, devices, and / or methods are disclosed and described, it is to be understood that the aspects described herein are not limited to specific synthetic methods or specific reagents, as such may, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure.

[0040] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" can include mixtures comprising two or more components.

[0041] As used herein the term "optional" or "optionally" means that the subsequently described event or circumstance can or can not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0042] Disclosed are components that can be used to prepare compositions described herein, as well as compositions themselves to be used in disclosed methods of the application. These and other materials are disclosed herein, and it is understood that the disclosure extends to combinations, subsets, interactions, groups, etc. of the disclosed materials, even if each and every specific combination and permutation of the various compounds and arrangements is not specifically disclosed, but is instead specifically contemplated. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules containing the compound are discussed, then each and every combination and permutation of the compound is specifically contemplated, unless specifically indicated to the contrary. Thus, if a set of three molecules A, B, and C is disclosed, and a set of three molecules D, E, and F is disclosed, and an example of a combination molecule A-D is disclosed, then even if each and every specification of the molecules did not include the A- D combination, it is understood that each and every combination and permutation of the individual set is specifically contemplated herein, even if specifically recited. Likewise, any subset or combination of these is also specifically contemplated. For example, subsets of A-E, B-F, and C-E are also specifically contemplated. This concept applies to all aspects of the present application, including but not limited to steps in methods of making and using the compositions. Thus, if there are a variety of additional steps that can be performed, it is understood that each of these additional steps can be performed with any specific aspect of the methods of the application, or in combination with aspects of the methods of the application.

[0043] The linking atom used herein is capable of linking two groups, e.g., linking N and C. The linking atom can optionally be attached to other chemical groups, if valence allows. For example, an oxygen atom will not have any other chemical groups attached because the valence is already satisfied upon bonding two atoms (e.g., N or C). In contrast, when carbon is the linking atom, two additional chemical groups can be attached to the carbon atom. Suitable chemical groups include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, =0, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

[0044] The term "cyclic structure" or like terms used herein refer to any cyclic chemical structure, including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

[0045] The term "substituted" or like terms used herein encompass all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. For example, illustrative substituents are described below. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For the purposes of this application, a heteroatom (e.g., nitrogen) can have hydrogen substituents and / or any permissible substituents of organic compounds described herein that satisfy the valencies of the heteroatom. This application is not intended to be limited in any manner by the permissible substituents of organic compounds. Also, the term "substitution" or "substituted with" encompasses the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). In certain aspects, unless explicitly stated otherwise, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0046] The term "alkyl" used herein refers to a branched or unbranched saturated hydrocarbon group of 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms. For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, thio-oxo, and thiol groups described herein. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.

[0047] Throughout the specification, "alkyl" generally refers to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to in the application by specifying the particular substituents on the alkyl group. For example, the terms "halogenated alkyl" or "haloalkyl" specifically refer to alkyl groups substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine).

[0048] This practice is also used for other groups described in the application. That is, when a general term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moieties can be specifically identified in the application; for example, a specifically substituted cycloalkyl group can be referred to as, for example, "alkylcycloalkyl." Similarly, a substituted alkoxy group can be specifically referred to as, for example, "haloalkoxy," a specifically substituted alkenyl group can be, for example, "enol," and the like. Likewise, the use of a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" is not meant to imply that the general term does not also include the specific term.

[0049] The term "cycloalkyl" as used in the application is a non-aromatic carbon-based ring of 3 to 30 carbon atoms, preferably 3 to 14 carbon atoms, composed of at least three carbon atoms, which can be optionally substituted with 1 to 6 alkyl groups. Examples of cycloalkyl groups include, but are not limited to, cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, adamantane, and the like. The term "heterocycloalkyl" 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 replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, thio-oxo, and thiol groups as described in the application.

[0050] The term "polyalkylene group" as used in the application refers to a group containing two or more CH2groups linked to each other. The "polyalkylene group" can be represented as— (CH2)a—, where "a" is an integer between 2 and 500. a —, where "a" is an integer between 2 and 500.

[0051] The terms "alkoxy" and "alkoxy group" as used in the application refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms bonded through an ether linkage; that is, "alkoxy" can be defined as— OR 1 , where R 1 is an alkyl or cycloalkyl group as defined above. "Alkoxy" also includes alkoxylated polymers just described; that is, the alkoxy group can be a polyether such as— OR 1 — OR 2 , or— OR 1 — (OR 2 )a -OR 3 where "a" is an integer from 1 to 500 and R 1 , R 2 , and R 3 are each independently alkyl, cycloalkyl, or a combination thereof.

[0052] The term "alkenyl" as used herein is a hydrocarbon group of 2 to 30 carbon atoms having at least one carbon-carbon double bond in its structure. Asymmetric structures such as (R 1 R 2 )C=C(R 3 R 4 ) include both E and Z isomers. This can be inferred in the structural formulae of the present application where an asymmetric alkene is present or it can be explicitly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0053] The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms that is composed of at least 3 carbon atoms and contains at least one carbon-carbon double bond, i.e., C=C. Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, and the like. The term "heterocycloalkenyl" is a class of cycloalkenyl as defined above and is included in the meaning of the term "cycloalkenyl" wherein at least one carbon atom of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0054] The term "alkynyl" as used herein is a hydrocarbon group of 2 to 30 carbon atoms having at least one carbon-carbon triple bond in its structure. The alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfo-oxo group, or thiol as described herein.

[0055] The term "cycloalkynyl" as used herein is a non-aromatic carbocyclic ring containing at least 7 carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a cycloalkenyl as defined above and is included within the meaning of the term "cycloalkynyl," wherein at least one of the carbon atoms of the ring is replaced with a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl groups can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo, or thiol groups as described herein.

[0056] The term "aryl" as used herein refers to any carbocyclic aromatic group containing 60 carbon atoms and less, preferably 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. Included, but not limited to, are phenyl, naphthyl, phenanthryl, biphenyl, phenoxyphenyl, anthryl, phenanthryl, and the like. The term "aryl" also includes "heteroaryl," which is defined as an aromatic group containing at least one heteroatom within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, or phosphorus. Also, the term "non-heteroaryl" (which is also included within the term "aryl") defines an aromatic group containing no heteroatoms. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo, or thiol groups as described herein. The term "biaryl" is a specific type of aryl and is included within the definition of "aryl." Biaryl refers to two aryl groups joined together via a fused ring structure, as in naphthalene, or joined by one or more carbon-carbon bonds, as in biphenyl.

[0057] The term "aldehyde" as used herein is represented by the formula— C(O)H. Throughout the specification, "C(O)" is a shorthand form for carbonyl (i.e., C=O).

[0058] The term "amine" or "amino" as used herein is represented by the formula— NR 1 R 2 wherein R 1 and R 2 may be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.

[0059] The term "alkylamino" as used herein is represented by the formula— NH(-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, t-butylamino, pentylamino, isopentylamino, t-pentylamino, hexylamino, and the like.

[0060] The term "dialkylamino" as used herein is represented by the formula— N(-alkyl)2, wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-t-butylamino, dipentylamino, diisopentylamino, di-t-pentylamino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.

[0061] The term "carboxylic acid" as used herein is represented by the formula— C(O)OH.

[0062] The term "ester" as used herein is represented by the formula— OC(O)R 1 or— C(O)OR 1 wherein R 1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyester" as used herein is represented by the formula— (R 1 O(O)C-R 2 -C(O)O) a or— (R 1 O(O)C-R 2 -OC(O)) a — wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein and "a" is an integer from 1 to 500. The term "polyester" is used to describe a group resulting from a reaction between a compound having at least two carboxylic groups and a compound having at least two hydroxyl groups.

[0063] The term "ether" as used herein is represented by the formula R 1 OR 2 wherein R 1 and R 2 may independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyether" as used herein is represented by the formula— (R 1 O-R 2 O) a — wherein R 1 and R 2may be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

[0064] As used herein, the term "halogen" means the halogens fluorine, chlorine, bromine, and iodine.

[0065] As used herein, the term "heterocyclyl" means 3- to 30- membered monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein means monocyclic and polycyclic aromatic ring systems of up to 60 carbon atoms: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including oxazolyl of 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, and 1,3,4-oxadiazolyl), piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, tetrazolyl including 1,2,3,4-tetrazolyl and 1,2,4,5-tetrazolyl, thiadiazolyl including 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, and 1,3,4-thiadiazolyl, thiazolyl, thienyl, triazinyl including 1,3,5-triazinyl and 1,2,4-triazinyl, triazolyl including 1,2,3-triazolyl and 1,3,4-triazolyl, and the like.

[0066] As used herein, the term "hydroxyl" is represented by the formula—OH.

[0067] As used herein, the term "nitro" is represented by the formula—NO2.

[0068] As used herein, the term "nitrile" is represented by the formula—CN.

[0069] As used herein, the term "silyl" is represented by the formula—SiR 1 R 2 R 3 wherein R 1 , R 2 , and R 3 may be independently hydrogen or alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described herein.

[0070] As used herein, the term "sulfur-oxy group" is represented by the formula—S(O)R 1 , —S(O)2R 1 , —OS(O)2R 1 , or—OS(O)2OR 1 wherein R 1may be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout the specification the notation "S(O)" is a shorthand for S=O. The term "sulfonyl" as used herein refers to a sulfoxy group represented by the formula — S(O)2R 1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group. The term "sulfone" as used herein refers to a group represented by the formula R 1 S(O)2R 1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group. The term "sulfone" as used herein refers to a group represented by the formula R 2 S(O)2R 1 and R 2 may be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfoxide" as used herein refers to a group represented by the formula R 1 S(O)R 2 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group. The term "sulfone" as used herein refers to a group represented by the formula R 1 and R 2 may be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group.

[0071] The term "mercapto" as used herein refers to a group represented by the formula — SH.

[0072] The "R 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 is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be replaced with a hydroxyl, alkoxy, alkyl, halogen, etc. Depending on the group selected, the first group can be embedded within the second group, or the first group can be pendant (i.e., attached) to the second group. For example, for the phrase "alkyl group comprising an amino group", the amino group can be embedded within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is embedded or attached to the second group.

[0073] The compounds described herein can contain "optionally substituted" moieties. In general, the term "substituted" whether preceded by the term "optionally" or not, means that the indicated moiety is either substituted or unsubstituted. An "optionally substituted" group can have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted with more than one substituent, the substituent can be either the same or different at every position. Combinations of substituents envisioned are those that result in the formation of stable or chemically feasible compounds. It is also contemplated that, in certain aspects, each substituent can further optionally be substituted (i.e., further substituted or unsubstituted) unless specifically indicated otherwise.

[0074] The structure of a compound can be represented by the following formula:

[0075] which is understood to be equivalent to the following formula:

[0076] where n is typically an integer. That is, R n is understood to represent five separate substituents R n(a) , R n(b) , R n(c) , R n(d) , and R n(e) . "Separate substituents" means that each R substituent can be defined independently. For example, if in one instance R n(a) is halogen, then in that instance R n(b) is not necessarily halogen.

[0077] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. are mentioned several times in the chemical structures and units disclosed and described herein. Any description of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. in the specification applies to any structure or unit that refers to R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. respectively, unless otherwise stated.

[0078] The term "fused ring" as used herein means that two adjacent substituents can be fused five- or six-membered aromatic, heteroaromatic, e.g. benzene, pyridine, pyrazine, pyridazine, pyrimidine, etc., and saturated six- or seven-membered carbocyclic or heterocyclic rings, etc.

[0079] Opto-electronic devices that make use of organic materials are becoming increasingly important for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential to be lower cost than other technology options. Organic light emitting devices make use of thin films of organic semiconductors. Organic light emitting devices are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination devices, and backlights. In addition, the inherent properties of organic materials, such as their flexibility and their ability to be deposited from solution into thin films, make them well suited for the manufacture of organic opto-electronic devices over large areas on flexible substrates.

[0080] Excitons decay from singlet excited states to the ground state to produce prompt emission, which is fluorescence. If excitons decay from triplet excited states to the ground state to produce emission, this is phosphorescence. Phosphorescent metal complexes, such as platinum complexes, have demonstrated the potential to utilize both singlet and triplet excitons due to the strong spin-orbit coupling of heavy metal atoms between singlet and triplet excited states, which effectively enhances the intersystem crossing (ISC). As a result, phosphorescent metal complexes are good candidates for dopants in the emissive layer of organic light emitting devices (OLEDs) and have received great attention in both academic and industrial fields. In the past decade, many achievements have been made, leading to the profitable commercialization of this technology, for example, OLEDs have been used in advanced displays of smartphones, televisions, and digital cameras.

[0081] However, to date, blue electroluminescent devices remain the most challenging area in this technology, and the stability of blue devices is one of the major issues. It has been proven that the selection of host materials is very important for the stability of blue devices. However, the triplet excited state (T1) of blue light emitting materials is very high in energy, which means that the triplet excited state (T1) of host materials for blue devices should be higher. This leads to the difficulty of developing host materials for blue devices.

[0082] The metal complexes of the present invention can be tailored or tuned to specific applications that are desired to have specific emission or absorption properties. The optical properties of the metal complexes in the present disclosure can be adjusted by changing the structure of the ligand around the metal center or changing the structure of the fluorescent emitters on the ligand. For example, metal complexes with ligands having electron donating substituents or electron withdrawing substituents can generally exhibit different optical properties in the emission and absorption spectra. The color of the metal complex can be adjusted by modifying the conjugated groups on the fluorescent emitters and the ligand.

[0083] The emission of such complexes of the present invention can be adjusted, for example, from the ultraviolet to the near infrared, by changing the ligand or fluorescent emitter structure. A fluorescent emitter is a group of atoms in an organic molecule that can absorb energy to create a singlet excited state, which rapidly decays to produce immediate luminescence. In one aspect, the complexes of the present invention can provide emission across a large portion of the visible spectrum. In particular examples, the complexes of the present invention can emit light in the range of about 400 nm to about 700 nm. In another aspect, the complexes of the present invention have improved stability and efficiency relative to conventional emissive complexes. Additionally, the complexes of the present invention can be used as emitters in, for example, organic light emitting diodes (OLEDs) or luminescent markers for combinations thereof. In another aspect, the complexes of the present invention can be used in light emitting devices, such as compact fluorescent lamps (CFLs), light emitting diodes (LEDs), incandescent lamps, and combinations thereof.

[0084] Disclosed herein are compounds or complex complexes comprising platinum or palladium. The terms compound or complex are used interchangeably in the present invention. Additionally, the compounds disclosed herein have a neutral charge.

[0085] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be adjusted by selecting appropriate ligands. In another aspect, the present invention can exclude any one or more of the compounds, structures, or portions thereof specifically recited herein.

[0086] The compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices, such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices, or devices capable of both light absorption and emission, and as markers for biological applications.

[0087] As noted above, the disclosed compounds are platinum or palladium complexes. Also, the compounds disclosed herein can be used as host materials for OLED applications, such as full color displays.

[0088] The compounds disclosed herein can be used in a variety of applications. As light emitting materials, the compounds can be used in organic light emitting diodes (OLEDs), light emitting devices and displays, and other light emitting devices.

[0089] The compounds of the present application can be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0090] The compounds disclosed herein can be delayed fluorescent and / or phosphorescent emitters. In one aspect, the compounds disclosed herein can be delayed fluorescent emitters. In one aspect, the compounds disclosed herein can be phosphorescent emitters. In another aspect, the compounds disclosed herein can be both delayed fluorescent and phosphorescent emitters.

[0091] The present disclosure relates to polychelated dinuclear cyclometalated platinum complexes which are useful as light-emitting and host materials in OLED devices.

[0092] Unless otherwise indicated, all commercial reagents used in the following experiments were used as received without further purification. NMR spectra of hydrogen and carbon were measured in deuterated chloroform (CDCI3) or deuterated dimethyl sulfoxide (DMSO-d6) solution, hydrogen spectrum was measured using a 400 or 500 megahertz nuclear magnetic resonance spectrometer, carbon spectrum was measured using a 100 or 126 megahertz nuclear magnetic resonance spectrometer, and chemical shifts were referenced to tetramethylsilane (TMS) or residual solvents. If CDCI3 was used as a solvent, hydrogen and carbon spectra were measured using TMS (δ = 0.00 ppm) and CDCI3 (δ = 77.00 ppm) as internal standards, respectively. If DMSO-d6 was used as a solvent, hydrogen and carbon spectra were measured using TMS (δ = 0.00 ppm) and DMSO-d6 (δ = 39.52 ppm) as internal standards, respectively. The following abbreviations (or combinations) were used to interpret the hydrogen spectrum: s = singlet, d = doublet, t = triplet, q = quartet, p = pentuplet, m = multiplet, br = broad. High resolution mass spectrometry was measured on an ESI-QTOF mass spectrometer of Applied Biosystems, and the sample ionization mode was electrospray ionization.

[0093] Synthetic route of intermediate chiral OTf:

[0094] The compound pyridine was dissolved in ethyl acetate (400 mL), and ethyl bromoacetate was added dropwise, and then the reaction was stirred at 50°C for lh, and after cooling, the filter cake was collected and dried to obtain 20.84 g of the product PyBr, with a yield of 84%.

[0095] The prepared compound PyBr was dissolved in formamide, and myrtenal and 10 equivalents of ammonium acetate were added, and then the reaction was stirred at 40°C for 3 days, at 80°C for 3 days, and at 150°C for 6 h. The system was cooled to room temperature, water and ethyl acetate were added, the organic phase was separated, washed with water and saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography to obtain 5.2 g of NHO, with a yield of 43%.

[0096] NHO and triethylamine were dissolved in dichloromethane, cooled to -40 °C, slowly added triflic anhydride, stirred at room temperature for 18 h. The reaction was quenched with water, extracted with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography to give OTf 6.29 g, yield 71%. 1 H NMR (500 MHz, CDC13) δ 0.62 (s, 3H), 1.20 (d, J = 10.0 Hz, 1H), 1.42 (s, 3H), 2.30 - 2.34 (m, 1H), 2.72 (dt, J = 10.0, 5.5 Hz, 1H), 2.88 (t, J = 5.5 Hz, 1H), 3.03 (d, J = 3.0 Hz, 2H), 6.95 (s, 1H), 7.89 (s, 1H).

[0097] Synthetic route of intermediate chiral 1-Cl:

[0098] Synthesis of intermediate chiral 1-OMe: To a reaction flask was added OTf (1.0 g, 3.11 mmol, 1.2 equiv), Cz-OMe (512 mg, 2.59 mmol, 1.0 equiv), Pd2(dba)3 (71 mg, 0.08 mmol, 3 mol%), XPhos (148 mg, 0.31 mmol, 12 mol%) and potassium phosphate (1.65 g, 7.77 mmol, 3.0 equiv) in sequence, and the flask was purged with nitrogen three times. Toluene (25 mL) was added. The reaction was stirred at 110 °C for 42 h, and the solvent was removed by distillation under reduced pressure. Purification by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 50-10:1 gave 1-OMe as a yellow solid 930 mg, yield 98%. 1 H NMR (500 MHz, CDC13) δ 0.62 (s, 3H), 1.20 (d, J = 10.0 Hz, 1H), 1.42 (s, 3H), 2.30 - 2.34 (m, 1H), 2.72 (dt, J = 10.0, 5.5 Hz, 1H), 2.88 (t, J = 5.5 Hz, 1H), 3.03 (d, J = 3.0 Hz, 2H), 6.95 (s, 1H), 7.89 (s, 1H).

[0099] Synthesis of intermediate chiral 1-Cl: To a reaction flask was added 1-OH (4.60 g, 12.98 mmol, 1.0 equiv), 1-bromo-3-tert-butyl-5-chlorobenzene (3.86 g, 15.57 mmol, 1.2 equiv), cuprous iodide (248 mg, 1.30 mmol, 10 mol%), 2-picolinic acid (320 mg, 2.60 mmol, 20 mol%) and potassium phosphate (5.51 g, 25.96 mmol, 2.0 equiv) sequentially, and the reaction was stirred at 100 °C for 26 h. The reaction was diluted with water and extracted with ethyl acetate three times. The organic layer was washed with brine once, dried over anhydrous sodium sulfate, filtered and the solvent was removed under reduced pressure. The product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 20:1-10:1 to give 5.49 g of white solid in 81% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.70 (s, 3H), 1.24 (d, J = 9.5 Hz, 1H), 1.44 (s, 3H), 2.26 - 2.35 (m, 1H), 2.76 (dt, J = 9.5, 5.5 Hz, 1H), 2.96 (t, J = 5.5 Hz, 1H), 3.03 - 3.18 (m, 2H), 6.76 (dd, J = 8.5, 2.0 Hz, 1H), 7.13 (d, J = 2.0 Hz, 1H), 7.23 (ddd, J = 7.5, 7.0, 1.0 Hz, 1H), 7.31 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.51 (s, 1H), 7.65 (dt, J = 8.5, 1.0 Hz, 1H), 7.97 (d, J = 8.5 Hz, 1H), 8.04 (dq, J = 7.5, 1.0 Hz, 1H), 8.26 (s, 1H), 9.56 (s, 1H).

[0100] Synthesis of intermediate chiral 1-Cl: To a reaction flask was added 1-OH (4.60 g, 12.98 mmol, 1.0 equiv), 1-bromo-3-tert-butyl-5-chlorobenzene (3.86 g, 15.57 mmol, 1.2 equiv), cuprous iodide (248 mg, 1.30 mmol, 10 mol%), 2-picolinic acid (320 mg, 2.60 mmol, 20 mol%) and potassium phosphate (5.51 g, 25.96 mmol, 2.0 equiv) sequentially, and the reaction was stirred at 100 °C for 26 h. The reaction was diluted with water and extracted with ethyl acetate three times. The organic layer was washed with brine once, dried over anhydrous sodium sulfate, filtered and the solvent was removed under reduced pressure. The product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 20:1-10:1 to give 5.49 g of white solid in 81% yield. 1HNMR (500 MHz, CDC13) δ 0.73 (s, 3H), 1.27 (s, 9H), 1.32 (d, J = 10.0 Hz, 1H), 1.46 (s, 3H), 2.34 - 2.38 (m, 1H), 2.77 (dt, J = 10.0, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.07 (d, J = 2.5 Hz, 2H), 6.78 (t, J = 2.0 Hz, 1H), 6.98 (dd, J = 8.5, 2.0 Hz, 1H), 7.01 (t, J = 2.0 Hz, 1H), 7.06 (t, J = 1.5 Hz, 1H), 7.30 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.37 (s, 1H), 7.41 (ddd, J = 8.5, 7.0, 1.0 Hz, 1H), 7.48 (d, J = 2.0 Hz, 1H), 7.75 (dt, J = 8.0, 1.0 Hz, 1H), 8.05 - 8.08 (m, 2H), 8.20 (s, 1H).

[0101] Example 1: Tetradentate cyclometalated platinum(II) complex Pt1

[0102] Synthetic route:

[0103] Synthesis of intermediate tBu-NO2: Into a reaction flask was added tert-butylamine (5.18 g, 70.87 mmol, 2.0 equiv), o-fluoronitrobenzene (5 g, 35.44 mmol, 1.0 equiv), potassium fluoride (4.12 g, 70.87 mmol, 2.0 equiv), N,N-dimethylformamide (30 mL), and the flask was purged with nitrogen three times. The reaction was stirred at 100 °C for 40 h. Silica gel column chromatography afforded 6.80 g of yellow liquid in 98% yield. Directly used in the following reaction.

[0104] Synthesis of intermediate tBu-NH2: Into a reaction flask was added tBu-NO2 (6.80 g, 35 mmol, 1.0 equiv), palladium on carbon (1.0 g, 10%), ethyl acetate (20 mL), and ethanol (20 mL). The flask was purged with hydrogen three times and the reaction was stirred at 35 °C for 20 h under a hydrogen atmosphere. Concentration and silica gel column chromatography afforded 5.12 g of brown-red liquid in 89% yield. Directly used in the following reaction.

[0105] 1-NH2Synthesis: To a reaction flask was added 1-Cl (300 mg, 0.58 mmol, 1.0 equiv), tBu-NH2(123 mg, 0.75 mmol, 1.3 equiv), Pd2(dba)3(16 mg, 0.017 mmol, 3 mol%), John Phos (21 mg, 0.069 mmol, 12 mol%), and sodium tert-butoxide (111 mg, 1.15 mmol, 2.0 equiv) sequentially, and the flask was purged with nitrogen three times. Toluene (3 mL) was added, and the reaction was stirred at 100 °C for 16 h. The solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography to give 356 mg of brown solid in 95% yield. The compound was easily oxidized, and was used directly in the next step without characterization.

[0106] Ligand 1-L Synthesis: To a schlenk tube was added 1-NH2(350 g, 0.54 mmol, 1.0 equiv), ammonium hexafluorophosphate (176 mg, 1.08 mmol, 2.0 equiv) sequentially, and the flask was purged with nitrogen three times. Triethyl orthoformate (3 mL) was added sequentially, and the reaction was stirred at 75 °C for 10 h. The solvent was removed under reduced pressure. Purification was performed by silica gel column chromatography to give 423 mg of ligand foam in 97% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.18 (d, J = 9.5 Hz, 1H), 1.35 (s, 9H), 1.41 (s, 3H), 1.81 (s, 9H), 2.27 - 2.31 (m, 1H), 2.73 (dt, J = 9.5, 5.5 Hz, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.01 - 3.11 (m, 2H), 7.16 (dd, J = 8.5, 2.0 Hz, 1H), 7.27 (t, J = 2.0 Hz, 1H), 7.30 - 7.34 (m, 1H), 7.44 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.48 (t, J = 2.0 Hz, 1H), 7.55 - 7.59 (m, 3H), 7.63 - 7.76 (m, 4H), 8.18 - 8.22 (m, 2H), 8.29 (d, J = 8.5 Hz, 1H), 8.37 (d, J = 7.5 Hz, 1H), 9.86 (s, 1H).

[0107] Synthesis of complex Pt1 : Into a sealed tube was added ligand 1-L (360 mg, 0.45 mmol, 1.0 equiv), Pt(COD)Cl2(167 mg, 0.45 mmol, 1.0 equiv) and sodium acetate (111 mg, 1.35 mmol, 3.0 equiv) sequentially, and the mixture was purged with nitrogen three times. Diethyleneglycol dimethyl ether (7 mL) was added and the mixture was purged with nitrogen for 30 min. The mixture was stirred at 120 °C for 72 h. The solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography to give yellow solid 96 mg in 25% yield. MS: 852.32 [M+H] + .

[0108] Example 2: Tetradentate cyclometalated platinum(II) complex Pt2

[0109] Synthesis route:

[0110] Synthesis of intermediate Ada-NO2: Into a reaction flask was added adamantylamine (9.08 g, 60 mmol, 1.4 equiv), o-fluoronitrobenzene (6.20 g, 43.94 mmol, 1.0 equiv), cesium carbonate (28.63 g, 87.88 mmol, 2.0 equiv), dimethyl sulfoxide (130 mL), and the mixture was purged with nitrogen three times. The mixture was stirred at 45 °C for 40 h. The residue was purified by silica gel column chromatography to give yellow liquid 9.27 g in 77% yield. It was used directly in the next reaction.

[0111] Synthesis of intermediate Ada-NH2: Into a reaction flask was added Ada-NO2 (9.26 g, 34 mmol, 1.0 equiv), palladium on carbon (2.0 g, 10%), tetrahydrofuran (130 mL) and ethanol (15 mL), and the mixture was purged with hydrogen three times. The mixture was stirred at 35 °C for 45 h under hydrogen atmosphere. The residue was purified by silica gel column chromatography to give off-white solid 7.06 g in 93% yield. It was used directly in the next reaction.

[0112] Synthesis of 2-NH2: Into a reaction flask was added 1-Cl (400 mg, 0.77 mmol, 1.0 equiv), Ada-NH2 (223 mg, 0.92 mmol, 1.2 equiv), Pd2(dba)3(21 mg, 0.023 mmol, 3 mol%), JohnPhos (28 mg, 0.093 mmol, 12 mol%) and sodium tert-butoxide (148 mg, 1.54 mmol, 2.0 equiv) sequentially, and the mixture was purged with nitrogen three times. Toluene (5 mL) was added. The mixture was stirred at 100 °C for 14 h. The solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography to give brown solid 540 mg in 96% yield.

[0113] Synthesis of Ligand 2-L: Ligand 2-L was prepared following the synthesis procedure of Ligand 1-L in Reference Example 1, with the modification that the reaction feed was modified to: 2-NH2(540 mg, 0.74 mmol, 1.0 equiv), ammonium hexafluorophosphate (242 mg, 1.49 mmol, 2.0 equiv), triethyl orthoformate (3 mL), resulting in 630 mg of a solid, 96% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.65 (s, 3H), 1.19 (d, J = 9.5 Hz, 1H), 1.35 (s, 9H), 1.42 (s, 3H), 1.77 (d, J = 12.5 Hz, 3H), 1.84 (d, J = 12.0 Hz, 3H), 2.27 - 2.30 (m, 4H), 2.40 (s, 6H), 2.71 - 2.76 (m, 1H), 2.93 (t, J = 5.5 Hz, 1H), 3.02 - 3.11 (m, 2H), 7.16 (dd, J = 8.0, 2.0 Hz, 1H), 7.27 (t, J = 2.0 Hz, 1H), 7.30 - 7.34 (m, 1H), 7.44 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.48 (t, J = 2.0 Hz, 1H), 7.56 (s, 1H), 7.56 - 7.58 (m, 2H), 7.62 - 7.69 (m, 2H), 7.71 - 7.74 (m, 1H), 7.75 (dt, J = 8.0, 1.0 Hz, 1H), 8.21 - 8.23 (m, 2H), 8.29 (d, J = 8.5 Hz, 1H), 8.45 - 8.48 (m, 1H), 9.85 (s, 1H).

[0114] Synthesis of Complex Pt2: Complex Pt2 was prepared following the synthesis procedure of Complex Pt1 in Reference Example 1, with the modification that the reaction feed was modified to: Ligand 2-L (500 mg, 0.57 mmol, 1.0 equiv), Pt(COD)Cl2(212 mg, 0.57 mmol, 1.0 equiv), sodium acetate (139 mg, 1.70 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (5 mL), resulting in 73 mg of a yellow solid, 14% yield. MS: 930.37 [M+H] + .

[0115] Example 3: Tetradentate cyclometalated platinum(II) complex Pt4

[0116] Synthesis route:

[0117] Synthesis of intermediate chiral 4-NH2: Into a reaction vial was added 1-Cl (500 mg, 0.96 mmol, 1.0 equiv), PNBNH2 (228 mg, 0.1.15 mmol, 1.2 equiv), Pd2(dba)3 (26 mg, 0.029 mmol, 3 mol%), John Phos (34 mg, 0.12 mmol, 12 mol%), and sodium tert-butoxide (184 mg, 1.92 mmol, 2.0 equiv) sequentially, and the reaction vial was flushed with nitrogen three times. Toluene (6 mL) was added. The reaction was stirred at 85 °C for 12 h. The reaction mixture was separated by silica gel column to give 680 mg of white solid in 99% yield. The compound was oxidized easily and used directly for the next step without characterization.

[0118] Synthesis of ligand 4-L: Ligand 4-L was prepared following the procedure for the synthesis of ligand 1-L in Reference Example 1, except that the reaction charge was modified to: 4-NH2 (650 mg, 0.95 mmol, 1.0 equiv), ammonium hexafluorophosphate (310 mg, 1.90 mmol, 2.0 equiv), triethyl orthoformate (3 mL) to give 474 mg of solid in 60% yield.

[0119] Synthesis of complex Pt4: The synthesis was performed following the procedure for the synthesis of complex Pt1 in Reference Example 1, except that the reaction charge was modified to: ligand 4-L (450 mg, 0.54 mmol, 1.0 equiv), Pt(COD)Cl2 (211 mg, 0.56 mmol, 1.05 equiv), sodium acetate (132 mg, 1.61 mmol, 3.0 equiv), diethyleneglycol dimethyl ether (5 mL) to give 310 mg of yellow solid in 65% yield. MS: 886.31 [M+H] + .

[0120] Example 4: Tetradentate cyclometalated platinum(II) complex Pt5

[0121] Complex Pt5 was synthesized following the procedure for the synthesis of complex Pt1 in Reference Example 1 to give 110 mg of yellow solid in 45% yield. MS: m / z 829.35 (M+H) + .

[0122] Example 5: Tetradentate cyclometalated platinum(II) complex Pt6

[0123] Complex Pt6 was synthesized following the procedure for the synthesis of complex Pt1 in Reference Example 1 to give 104 mg of yellow solid in 32% yield. MS: m / z 810.28 (M+H) + .

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

[0125] Complex Pt7 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 98 mg, 36% yield. MS: m / z 838.31 (M+H) + .

[0126] Example 7: Tetradentate cyclometalated platinum(II) complex Pt8

[0127] Complex Pt8 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 135 mg, 41% yield. MS: m / z 852.32 (M+H) + .

[0128] Example 8: Tetradentate cyclometalated platinum(II) complex Pt10

[0129] Complex Pt10 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 124 mg, 42% yield. MS: m / z 810.28 (M+H) + .

[0130] Example 9: Tetradentate cyclometalated platinum(II) complex Pt11

[0131] Complex Pt11 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 125 mg, 38% yield. MS: m / z 824.29 (M+H) + .

[0132] Example 10: Tetradentate cyclometalated platinum(II) complex Pt31

[0133] Complex Pt31 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 136 mg, 39% yield. MS: m / z 836.29 (M+H) + .

[0134] Example 11: Tetradentate cyclometalated platinum(II) complex Pt32

[0135] Complex Pt32 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 137 mg, 35% yield. MS: m / z 850.31 (M+H) + .

[0136] Example 12: Tetradentate cyclometalated platinum(II) complex Pt33

[0137] Complex Pt33 was prepared in the same way as complex Pt1 in Reference Example 1. Finally, yellow solid 128 mg was obtained in 45% yield. MS: m / z 864.32 (M+H) + .

[0138] Example 13: Tetradentate cyclometalated platinum(II) complex Pt34

[0139] Complex Pt34 was prepared in the same way as complex Pt1 in Reference Example 1. Finally, yellow solid 125 mg was obtained in 26% yield. MS: m / z 890.35 (M+H) + .

[0140] Example 14: Tetradentate cyclometalated platinum(II) complex Pt37

[0141] Complex Pt37 was prepared in the same way as complex Pt1 in Reference Example 1. Finally, yellow solid 136 mg was obtained in 42% yield. MS: m / z 892.35 (M+H) + .

[0142] Example 15: Tetradentate cyclometalated platinum(II) complex Pt41

[0143] Complex Pt41 was prepared in the same way as complex Pt1 in Reference Example 1. Finally, yellow solid 132 mg was obtained in 36% yield. MS: m / z 866.34 (M+H) + .

[0144] Example 16: Tetradentate cyclometalated platinum(II) complex Pt91

[0145] Complex Pt91 was prepared in the same way as complex Pt1 in Reference Example 1. Finally, yellow solid 127 mg was obtained in 38% yield. MS: m / z 872.29 (M+H) + .

[0146] Example 17: Tetradentate cyclometalated platinum(II) complex Pt92

[0147] Complex Pt92 was prepared in the same way as complex Pt1 in Reference Example 1. Finally, yellow solid 145 mg was obtained in 42% yield. MS: m / z 950.34 (M+H) + .

[0148] Example 18: Tetradentate cyclometalated platinum(II) complex Pt94

[0149] Complex Pt94 was prepared following the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 153 mg, 47% yield. MS: m / z 906.28 (M+H) + .

[0150] Example 19: Tetradentate cyclometalated platinum(II) complex Pt95

[0151] Complex Pt95 was prepared following the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 142 mg, 51% yield. MS: m / z 914.34 (M+H) + .

[0152] Example 20: Tetradentate cyclometalated platinum(II) complex Pt96

[0153] Complex Pt96 was prepared following the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 136 mg, 36% yield. MS: m / z 830.25 (M+H) + .

[0154] Example 21: Tetradentate cyclometalated platinum(II) complex Pt97

[0155] Complex Pt97 was prepared following the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 126 mg, 39% yield. MS: m / z 858.28 (M+H) + .

[0156] Example 22: Tetradentate cyclometalated platinum(II) complex Pt101

[0157] Complex Pt101 was prepared following the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 112 mg, 31% yield. MS: m / z 844.26 (M+H) + .

[0158] Example 23: Tetradentate cyclometalated platinum(II) complex Pt116

[0159] Complex Pt116 was prepared following the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 128 mg, 32% yield. MS: m / z 864.25 (M+H) + .

[0160] Example 24: Tetradentate cyclometalated platinum(II) complex Pt117

[0161] Complex Pt1 17 was prepared in the same manner as complex Pt1 in Reference Example 1, and finally yellow solid 102 mg was obtained in 29% yield. MS: m / z 942.30 (M+H) + .

[0162] Example 25: Tetradentate cyclometalated platinum (II) complex Pt1 19

[0163] Complex Pt1 19 was prepared in the same manner as complex Pt1 in Reference Example 1, and finally yellow solid 138 mg was obtained in 37% yield. MS: m / z 898.23 (M+H) + .

[0164] Example 26: Tetradentate cyclometalated platinum (II) complex Pt1 26

[0165] Complex Pt1 26 was prepared in the same manner as complex Pt1 in Reference Example 1, and finally yellow solid 107 mg was obtained in 31% yield. MS: m / z 793.22 (M+H) + .

[0166] Example 27: Tetradentate cyclometalated platinum (II) complex Pt1 35

[0167] Complex Pt1 35 was prepared in the same manner as complex Pt1 in Reference Example 1, and finally yellow solid 115 mg was obtained in 33% yield. MS: m / z 880.30 (M+H) + .

[0168] Example 28: Tetradentate cyclometalated platinum (II) complex Pt1 36

[0169] Complex Pt1 36 was prepared in the same manner as complex Pt1 in Reference Example 1, and finally yellow solid 172 mg was obtained in 47% yield. MS: m / z 873.29 (M+H) + .

[0170] Example 29: Tetradentate cyclometalated platinum (II) complex Pt1 37

[0171] Complex Pt1 37 was prepared in the same manner as complex Pt1 in Reference Example 1, and finally yellow solid 163 mg was obtained in 46% yield. MS: m / z 951.33 (M+H) + .

[0172] Example 30: Tetradentate cyclometalated platinum (II) complex Pt1 41

[0173] Complex Pt 141 was prepared in the same way as complex Pt 1 in Reference Example 1. Finally, yellow solid 142 mg was obtained in 43% yield. MS: m / z 831.24 (M+H) + .

[0174] Example 31 : Tetradentate cyclometalated platinum (II) complex Pt 181

[0175] Complex Pt 181 was prepared in the same way as complex Pt 1 in Reference Example 1. Finally, yellow solid 127 mg was obtained in 31% yield. MS: m / z 876.32 (M+H) + .

[0176] Example 32: Tetradentate cyclometalated platinum (II) complex Pt 182

[0177] Complex Pt 182 was prepared in the same way as complex Pt 1 in Reference Example 1. Finally, yellow solid 153 mg was obtained in 37% yield. MS: m / z 954.36 (M+H) + .

[0178] Example 33: Tetradentate cyclometalated platinum (II) complex Pt 186

[0179] Complex Pt 186 was prepared in the same way as complex Pt 1 in Reference Example 1. Finally, yellow solid 124 mg was obtained in 42% yield. MS: m / z 836.28 (M+H) + .

[0180] Example 34: Tetradentate cyclometalated platinum (II) complex Pt 207

[0181] Complex Pt 207 was prepared in the same way as complex Pt 1 in Reference Example 1. Finally, yellow solid 113 mg was obtained in 48% yield. MS: m / z 891.34 (M+H) + .

[0182] Example 35: Tetradentate cyclometalated platinum (II) complex Pt 211

[0183] Complex Pt 211 was prepared in the same way as complex Pt 1 in Reference Example 1. Finally, yellow solid 121 mg was obtained in 51% yield. MS: m / z 825.22 (M+H) + .

[0184] Example 36: Tetradentate cyclometalated platinum (II) complex Pt 226

[0185] Complex Pt226 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 131 mg, 30% yield. MS: m / z 868.30 (M+H) + .

[0186] Example 37: Tetradentate cyclometalated platinum(II) complex Pt234

[0187] Complex Pt234 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 134 mg, 43% yield. MS: m / z 885.32 (M+H) + .

[0188] Example 38: Tetradentate cyclometalated platinum(II) complex Pt237

[0189] Complex Pt237 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 155 mg, 35% yield. MS: m / z 946.32 (M+H) + .

[0190] Example 39: Tetradentate cyclometalated platinum(II) complex Pt244

[0191] Complex Pt244 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 137 mg, 37% yield. MS: m / z 884.29 (M+H) + .

[0192] Example 40: Tetradentate cyclometalated platinum(II) complex Pt249

[0193] Complex Pt249 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 125 mg, 37% yield. MS: m / z 950.23 (M+H) + .

[0194] Example 41: Tetradentate cyclometalated platinum(II) complex Pt256

[0195] Complex Pt256 was prepared according to the synthetic procedure of complex Pt1 in Reference Example 1, resulting in a yellow solid 147 mg, 30% yield. MS: m / z 910.36 (M+H) + .

[0196] Example 42: Tetradentate cyclometalated platinum(II) complex Pt266

[0197] Complex Pt266 was prepared in the same manner as complex Pt1 in Reference Example 1, resulting in a yellow solid 122 mg in 39% yield. MS: m / z 850.31 (M+H) + .

[0198] Example 43: Tetradentate cyclometalated platinum(II) complex Pt275

[0199] Complex Pt275 was prepared in the same manner as complex Pt1 in Reference Example 1, resulting in a yellow solid 131 mg in 31% yield. MS: m / z 858.25 (M+H) + .

[0200] Example 44: Tetradentate cyclometalated platinum(II) complex Pt280

[0201] Complex Pt280 was prepared in the same manner as complex Pt1 in Reference Example 1, resulting in a yellow solid 128 mg in 34% yield. MS: m / z 840.91 (M+H) + .

[0202] Example 45: Tetradentate cyclometalated platinum(II) complex Pt291

[0203] Complex Pt291 was prepared in the same manner as complex Pt1 in Reference Example 1, resulting in a yellow solid 123 mg in 50% yield. MS: m / z 962.34 (M+H) + .

[0204] Example 46: Tetradentate cyclometalated platinum(II) complex Pt299

[0205] Complex Pt299 was prepared in the same manner as complex Pt1 in Reference Example 1, resulting in a yellow solid 133 mg in 46% yield. MS: m / z 802.30 (M+H) + .

[0206] Example 47: Tetradentate cyclometalated platinum(II) complex Pt303

[0207] Complex Pt303 was prepared in the same manner as complex Pt1 in Reference Example 1, resulting in a yellow solid 120 mg in 50% yield. MS: m / z 785.26 (M+H) + .

[0208] Example 48: Tetradentate cyclometalated platinum(II) complex Pd1

[0209] Synthetic route:

[0210] Synthesis of complex Pd1 was prepared according to the synthetic route and the synthesis procedure of complex Pt1 in Example 1, except that ligand 1-L (1.0 eq), palladium acetate (1.0 eq) and potassium carbonate (3.0 eq) were added to the sealed tube, the tube was purged with nitrogen three times, 1,4-dioxane was added, and the mixture was bubbled with nitrogen for 30 min, and then the mixture was heated at 110 °C for 2 days. The solvent was removed by distillation under reduced pressure. The obtained crude product was purified by silica gel column chromatography to give a white solid in 10% yield. MS: m / z 763.26 (M+H) + .

[0211] Example 49: Synthesis of tetradentate cyclometalated platinum(II) complex Pd2

[0212] Synthesis of complex Pd2 was prepared according to the synthetic route and the synthesis procedure of complex Pt1 in Example 1, except that ligand 2-L (1.0 eq), palladium acetate (1.0 eq) and potassium carbonate (3.0 eq) were added to the sealed tube, the tube was purged with nitrogen three times, 1,4-dioxane was added, and the mixture was bubbled with nitrogen for 30 min, and then the mixture was heated at 110 °C for 2 days. The solvent was removed by distillation under reduced pressure. The obtained crude product was purified by silica gel column chromatography to give a white solid in 11% yield. MS: m / z 841.39 (M+H) + .

[0213] Example 50: Tetradentate cyclometalated platinum(II) complex Pd4

[0214] Synthesis of complex Pd4 was prepared according to the synthesis procedure of complex Pd1 in Example 48, and finally white solid 120 mg was obtained in 15% yield. MS: m / z 797.25 (M+H) + .

[0215] Example 51: Tetradentate cyclometalated platinum(II) complex Pd5

[0216] Synthesis of complex Pd5 was prepared according to the synthesis procedure of complex Pd1 in Example 48, and finally white solid 105 mg was obtained in 11% yield. MS: m / z 803.29 (M+H) + .

[0217] Example 52: Tetradentate cyclometalated platinum(II) complex Pd6

[0218] Synthesis of complex Pd6 was prepared according to the synthesis procedure of complex Pd1 in Example 48, and finally white solid 133 mg was obtained in 12% yield. MS: m / z 721.22 (M+H) + .

[0219] Example 53: Tetradentate cyclometalated platinum(II) complex Pd7

[0220] Complex Pd7 was prepared in the same manner as complex Pd1 in Reference Example 48. Final white solid 210 mg, yield 14%. MS: m / z 749.25 (M+H) + .

[0221] Example 54: Tetradentate cyclometalated platinum(II) complex Pd8

[0222] Complex Pd8 was prepared in the same manner as complex Pd1 in Reference Example 48. MS: m / z 763.26 (M+H) + .

[0223] Example 55: Tetradentate cyclometalated platinum(II) complex Pd10

[0224] Complex Pd10 was prepared in the same manner as complex Pd1 in Reference Example 48. MS: m / z 721.22 (M+H) + .

[0225] Example 56: Tetradentate cyclometalated platinum(II) complex Pd11

[0226] Complex Pd11 was prepared in the same manner as complex Pd1 in Reference Example 48. MS: m / z 735.23 (M+H) + .

[0227] Example 57: Tetradentate cyclometalated platinum(II) complex Pd12

[0228] Complex Pd12 was prepared in the same manner as complex Pd1 in Reference Example 48. MS: m / z 749.25 (M+H) + .

[0229] Example 58: Tetradentate cyclometalated platinum(II) complex Pd20

[0230] Complex Pd20 was prepared in the same manner as complex Pd1 in Reference Example 48. MS: m / z 805.31 (M+H) + .

[0231] Example 59: Tetradentate cyclometalated platinum(II) complex Pd31

[0232] Complex Pd31 was prepared in the same manner as complex Pd1 in Reference Example 48. MS: m / z 747.23 (M+H) + .

[0233] Example 60: Tetradentate cyclometalated platinum(II) complex Pd32

[0234] Complex Pd32 was prepared according to the synthetic procedure of complex Pd1 in Reference Example 48. MS: m / z 761.25 (M+H) + .

[0235] Example 61: Tetradentate cyclometalated platinum (II) complex Pd33

[0236] Complex Pd33 was prepared according to the synthetic procedure of complex Pd1 in Reference Example 48. MS: m / z 775.26 (M+H) + .

[0237] Example 62: Tetradentate cyclometalated platinum (II) complex Pd34

[0238] Complex Pd34 was prepared according to the synthetic procedure of complex Pd1 in Reference Example 48. MS: m / z 803.29 (M+H) + .

[0239] Optical physics test and theoretical calculation:

[0240] Steady-state emission experiments and lifetime measurements were performed on a Horiba Jobin Yvon FluoroLog-3 spectrometer, or steady-state emission spectra were tested on a SHIMADZU RF-6000 spectrometer. Circularly polarized light tests were completed on a JASCO CPL-300, and the test conditions were all dichloromethane solutions at room temperature.

[0241] Experimental data and analysis:

[0242] Figure 1 is a diagram of the design idea of optically pure metal ion-centered helical chiral tetradentate cyclometalated complex circularly polarized light emitting material: the optically pure raw material of the present application is economically and easily obtained; the generation of helical chirality is self-induced by central chirality; the circularly polarized light emitting material does not need to be chiral, which greatly saves the preparation cost of optically pure material, and can be prepared in large quantities, and is not limited by chiral preparation column separation.

[0243] Figure 2 is a circularly polarized luminescence spectrum of optically pure Pt1 in dichloromethane solution at room temperature under oxygen-free conditions; in the figure, (a) is a circularly polarized luminescence spectrum (CPPL), and (b) is a plot of the dissymmetry factor (g PL ) at different wavelengths. Figure 3 is a circularly polarized luminescence spectrum of optically pure Pt2 in dichloromethane solution at room temperature under oxygen-free conditions; in the figure, (a) is a circularly polarized luminescence spectrum (CPPL), and (b) is a plot of the dissymmetry factor (g PL ) at different wavelengths. As can be seen from Figure 2 and Figure 3, the representative helical chiral material molecules of the present application all exhibit strong circularly polarized luminescence.

[0244] Figure 4 is a single crystal structure diagram of optically pure Pt2. As can be seen from Figure 4, the structure of Pt2 is confirmed by X-ray single crystal diffraction analysis, and the plan view shows that Pt2 presents a helical structure with a helical chirality. At the same time, only a single P configuration is present in the unit cell, and no diastereoisomer and enantiomer is found, which also indicates that the enantiomeric purity is greater than 99%. The series of helical chiral tetradentate ring metal complexes have very high isomer purity, and the spatial steric hindrance of the helical chirality inducing segment is large enough to ensure that the platinum complex does not racemize and the configuration is stable.

[0245] Figure 5 is an emission spectrum diagram of part of the helical material molecules in a 5% PMMA film under room temperature deoxygenated conditions. In the figure, (a) is an emission spectrum diagram of optically pure Pt1 and Pt2, and (b) is an emission spectrum diagram of optically pure Pt4 and Pt6. As can be seen from Figure 5, the fine adjustment of the luminescent color can be realized by structure adjustment, and the blue light range of 450-470 nm can be realized.

[0246] It is worth noting that the material has high chemical stability and thermal stability. The designed and developed tetradentate ligand can be combined with dsp 2 hybrid platinum (II) and / or palladium (II) metal ions to form stable and rigid square planar molecules with high chemical stability. At the same time, due to the large spatial steric hindrance effect between the designed central chiral ligand L a and the other end ligand L 1 or L b , the entire metal complex molecule can form a stable helical tetradentate ring metal complex, so that it will not racemize and lose circularly polarized luminescent properties in solution or high-temperature sublimation process.

[0247] Table 1 is the specific optical rotation of part of the chiral ligand and chiral metal complex ([a] 20 D ). As can be seen from the specific optical rotation data of part of the chiral metal complex and its ligand in Table 1, even if the same central chiral ligand and chiral metal complex have completely different optical rotation directions, and the specific optical rotation values are also greatly different, which indicates that the helical chirality of the metal ion as the center of the complex has a decisive influence on the optical properties of the entire compound.

[0248] Table 2 is the maximum emission wavelength (λ max ) and the asymmetric factor (g PL ) of the chiral metal complex. As can be seen from the data in Table 2, the absolute value of the asymmetric factor (g PL ) can be as high as 0.84 x 10 -3Such a helical metal complex has important applications in circularly polarized light emitting elements and related fields. In contrast, the reference molecule BD-02 does not emit circularly polarized light, and its g PL ) are both zero.

[0249] Table 1. Specific optical rotations ([a] 20 D )

[0250] Note: All samples were measured in dichloromethane solution.

[0251] Table 2. Maximum emission wavelengths (λ max ) and asymmetric factors (g PL )

[0252] Note: Maximum emission wavelengths (λ max ) were measured in PMMA films, and asymmetric factors (g PL ) were measured in dichloromethane solution.

[0253] In an organic light emitting element, carriers are injected from both the positive and negative electrodes into the light emitting material, generating an excited state of the light emitting material and causing it to emit light. The circularly polarized light emitting material represented by general formula (I) or (I') of the present application can be used as a phosphorescent light emitting material in an organic photoluminescent element or an organic electroluminescent element, and the like, as an excellent organic light emitting element. An organic photoluminescent element has a structure in which at least a light emitting layer is formed on a substrate. In addition, an organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer contains at least a light emitting layer, and can be composed of only the light emitting layer, or can have one or more other organic layers in addition to the light emitting layer. As such other organic layers, a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, an exciton blocking layer, and the like can be cited. The hole transport layer can also be a hole injection transport layer having a hole injection function, and the electron transport layer can also be an electron injection transport layer having an electron injection function. FIG. 6 is a structural schematic diagram of a specific organic light emitting element that can be referenced. In FIG. 6, 110 represents a substrate, 120 represents an anode, 130 represents a hole injection layer, 140 represents a hole transport layer, 150 represents a light emitting layer, 160 represents a hole blocking layer, 170 represents an electron transport layer, 180 represents an electron injection layer, and 190 represents a cathode, wherein the light emitting layer is a mixed layer in which a guest material is doped into a host material.

[0254] The layers of the organic light-emitting device of the present application can be formed by vacuum evaporation, sputtering, ion plating, etc., or wet film formation such as spin coating, printing, printing, etc., and the solvent used is not particularly limited.

[0255] In a preferred embodiment of the present application, the OLED device of the present application contains a hole transport layer, and the hole transport material can be preferably selected from known or unknown materials, and is particularly preferably selected from the following structures, but the present application is not limited to the following structures:

[0256] In a preferred embodiment of the present application, the hole transport layer contained in the OLED device of the present application comprises one or more p-type dopants. The preferred p-type dopant of the present application is the following structure, but the present application is not limited to the following structure:

[0257] In a preferred embodiment of the present application, the electron transport layer can be selected from at least one of compounds ET-1 to ET-77, but the present application is not limited to the following structures:

[0258] In a preferred embodiment of the present application, the electron transport layer can be formed by an organic material and one or more n-type dopants (such as LiQ, LiThPh, etc.).

[0259] In a preferred embodiment of the present application, the host material can be selected from known or unknown materials, and the preferred host material can be selected from at least one of compounds H-1 to H-6, but the present application is not limited to the following structures:

[0260] The compounds represented in the examples are applied to the OLED device as a circularly polarized light-emitting material, and in a preferred embodiment, the structure can be represented as:

[0261] On the ITO-containing glass, a hole injection layer (HIL) of HT-1:P-3 (95:5 v / v%) was evaporated in sequence, with a thickness of 10 nm; a hole transport layer (HTL) of HT-1, with a thickness of 90 nm; an electron blocking layer (EBL) of HT-10, with a thickness of 10 nm, a light-emitting layer (EML) of a host material (H-3): the metal complex Pt1 (95:5 v / v%) of the application, with a thickness of 35 nm, an electron transport layer (ETL) of ET-13:LiQ (50:50 v / v%), with a thickness of 35 nm, and an Al cathode with a thickness of 70 nm were evaporated to prepare an organic electroluminescent diode, which was denoted as device 1.

[0262] Referring to the device structure provided by device 1, the metal complexes listed in Table 3 were selected as the implementation objects to replace Pt1, and were co-evaporated with the host compound at a volume ratio of 5:95 to form a light-emitting layer, to prepare organic electroluminescent diodes, which were denoted as devices 2-62. The luminescent properties of the above-prepared device examples were tested by a standard method, and the data are shown in Table 3.

[0263] Table 3. Performance of OLED devices doped with some helical metal complexes

[0264] Note: g EL is the electroluminescent asymmetry factor.

[0265] As can be seen from Table 3, the device prepared with Pt1 as a representative luminescent material has a significant circularly polarized photoluminescence signal, which indicates that the OLED devices doped with the helical tetradentate metal complex circularly polarized photoluminescent material can all exhibit a strong circularly polarized luminescence signal, and have great application prospects in circularly polarized luminescence.

[0266] It should be noted that the structure is an example of an application of the circularly polarized photoluminescent material of the application, and does not limit the specific OLED device structure of the circularly polarized photoluminescent material of the application, and the circularly polarized photoluminescent material is not limited to the compounds represented in the examples.

[0267] Those skilled in the art can understand that the above embodiments are specific examples of implementing the application, and in actual applications, various changes can be made in form and details without departing from the spirit and scope of the application. For example, many substituent structures described herein can be replaced by other structures without departing from the spirit of the application.

Claims

1. A centrosymmetric telechiral distal induction helical tetradentate cyclometalated platinum(II) and / or palladium(II) complex circularly polarized luminescent material, characterized in that, of the formula (I) and / or (I'), wherein (I) and (I') are enantiomers of each other: wherein M is Pt or Pd; L is O, S, CR x R y , C=0, SiR x R y , GeR x R y , NR z , PR z , R z P=0, AsR z , R z As=0, S=0, S02, Se, Se = O, SeO2, BR z , R z Bi = O or BiR z ; wherein R x , R y and R z are each independently selected from one or more of hydrogen, deuterium, halogen, -CN, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, halo heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl, R x and R y may optionally be linked to form a cyclic system; "*" is a carbon atom with a central chirality; R 1 at least one of substituted or unsubstituted alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl; when containing substitution, the substituent is selected from one or more of deuterium, halogen, cycloalkyl, aryl; X 1 , X 2 , X 3 , X 4 each independently CR 2 or N; Y 1 , Y 2 , Y 3 each independently CR 3 or N; Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 each independently CR 4 or N; R 2 -R 4 represents a mono- or poly- substituent group, and can be unsubstituted, mono- or poly- substituted; R 2 -R 4 each occurrence is selected independently from one or more of hydrogen, deuterium, halogen, -CN, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, haloalkyl, deuterated alkyl, aryl, heteroaryl, deuterated aryl, haloaryl, halo heteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, alkylsilyl, alkoxysilyl, arylsilyl, heteroarylsilyl, aryloxysilyl; R a and R b each independently is selected from one or more of hydrogen, deuterium, halogen, alkyl, haloalkyl, deuterated alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloaryl, haloheteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, nitrile, alkylsilicon, alkoxy silicon, arylsilicon, heteroarylsilicon, aryloxy silicon groups; R m and R n each independently is selected from one or more of hydrogen, deuterium, halogen, alkyl, haloalkyl, deuterated alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloaryl, haloheteroaryl, aryloxy, alkenyl, cycloalkenyl, alkynyl, mono- or di- alkylamino, mono- or di- arylamino, ester, nitrile, alkylsilicon, alkoxy silicon, arylsilicon, heteroarylsilicon, aryloxy silicon groups.

2. The complex circularly polarized luminescent material of claim 1, wherein, R in formula (I) and / or (I') is 2 each occurrence is independently selected from one or more of hydrogen, deuterium, halogen, -CN, alkyl, aryl; R 3 each occurrence is independently selected from one or more of hydrogen, deuterium, halogen, -CN, alkyl, heteroalkyl, alkoxy, haloalkyl, deuterioalkyl, aryl, haloaryl, alkenyl, cycloalkenyl, carboxyl, alkynyl, ester, alkylsilyl, arylsilyl, heteroarylsilyl; R 4 each occurrence is independently selected from hydrogen, deuterium.

3. The complex circularly polarized luminescent material of claim 1, wherein, two or more adjacent R 2 , R 3 and R 4 may optionally be joined to form a fused ring or an unsaturated ring system, said R a , R b , R m , R n , R 2 - R 4 at least one hydrogen of R may be replaced by deuterium.

4. The complex circularly polarized luminescent material of claim 1, wherein, The complex circularly polarized luminescent material can be, but is not limited to, the following structure, wherein "D" represents deuterium:

5. Use of the complex circularly polarized luminescent material according to any one of claims 1-4 in the preparation of an electronic device.

6. Use according to claim 5, characterized in that, The electronic device is a light-emitting device, a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device, or a biological imaging device.

7. An organic electroluminescent device, characterized by comprising The organic electroluminescent device comprises a cathode, an anode, and an organic functional layer interposed therebetween; the organic functional layer comprises the complex circularly polarized luminescent material according to any one of claims 1-4.

8. The organic electroluminescent device according to claim 7, characterized in that, The organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the complex circularly polarized luminescent material according to any one of claims 1-4.

9. An organic optoelectronic device, characterized in that The organic optoelectronic device comprises a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer comprises the complex circularly polarized luminescent material according to any one of claims 1-4.

10. A display or illumination device, characterized in that The display or lighting device comprises the organic electroluminescent device according to claim 7, and / or the organic optoelectronic device according to claim 9.

11. A composition characterized in that, The composition comprises the complex circularly polarized luminescent material according to any one of claims 1-4.

12. A formulation characterized in that, The preparation comprises the complex circularly polarized luminescent material according to any one of claims 1-4 and at least one solvent.

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