Arylamine-substituted benzocarbene tetradentate platinum (II) complex with large steric hinderance, and electronic device, apparatus and use thereof

Abstract

Provided are an arylamine-substituted benzocarbene tetradentate platinum (II) complex with large steric hindrance, and an electronic device, an apparatus and the use thereof. A new tetradentate platinum (II) complex is constructed by introducing a donor with large steric hindrance to a position of benzocarbene, and the complex is found to emit blue light. All the materials involved can effectively inhibit intermolecular stacking and interactions, have good chemical stability and thermal stability, and are well-suited to the preparation of an evaporation OLED device. An organic electroluminescent device fabricated by using the complex as a light-emitting layer has significantly improved current efficiency, a significantly prolonged service life and a substantially reduced turn-on voltage. In particular, the use of the complex in combination with a phosphorescence-sensitized boron-containing compound can improve the color purity of a device. The complex has good application prospects in the fields of OLED display and illumination.

Description

Hindered benzocarbene tetradentate platinum (II) complexes based on arylamine substitution, electronic devices, apparatuses and applications thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic electroluminescent material preparation, and particularly relates to a hindered benzocarbene tetradentate platinum (II) complex based on arylamine substitution, an electronic device, an apparatus and applications thereof. BACKGROUND

[0002] An organic light-emitting diode (OLED) is a new generation of full-color display and lighting technology. Compared with the liquid crystal display, the OLED has the advantages of slow response speed, small viewing angle, need for a backlight source, high energy consumption and the like. As a kind of self-luminous device, the OLED does not need a backlight source and is energy-saving. Moreover, the OLED has low driving voltage, fast response speed, high resolution and contrast, wide viewing angle, outstanding low-temperature performance, and can be made thinner and into a flexible structure. In addition, the OLED has the advantages of low production cost, simple production process, large-area production and the like. Therefore, the OLED has a wide and huge application prospect in high-end electronic products and aerospace. With the gradual increase of investment, further in-depth research and development, and upgrading and reconstruction of production equipment, the OLED has a very wide application scene and development prospect in the future.

[0003] The core of OLED development is the design and development of light-emitting materials. In the currently applied OLED devices, the light-emitting layer almost entirely uses a host-guest light-emitting system mechanism, that is, a guest light-emitting material is doped in a host material, the energy level of the host material is generally higher than that of the guest light-emitting material, and the energy is transferred from the host material to the guest material, so that the guest material is excited to emit light. Common organic phosphorescent guest materials are generally heavy metal atoms such as iridium (III), platinum (II), palladium (II), etc. Common phosphorescent organic materials mCBP (3,3'-bis(9-carbazolyl)-biphenyl) and 2,6-mCPy (2,6-bis(9-carbazolyl)-pyridine) have high efficiency and high triplet energy level, and when they are used as organic materials, the triplet energy can be effectively transferred from the light-emitting organic material to the guest phosphorescent light-emitting material. However, due to the characteristics of mCBP that the holes are easy to transport and the electrons are difficult to flow, and 2,6-mCPy has poor hole transport, the charge balance of the light-emitting layer is poor, which results in the reduction of the current efficiency of the device. Moreover, the currently applied heavy metal phosphorescent organic complex molecules are iridium (III) complex molecules, and the number is limited. The content of metal platinum element in the earth's crust and the annual production worldwide are about ten times of that of metal iridium element, and the price of IrCl3·H2O used for preparing iridium (III) complex phosphorescent materials is also much higher than that of PtCl2 used for preparing platinum (II) complex phosphorescent materials. In addition, the preparation of iridium (III) complex phosphorescent materials involves four steps of reactions, including iridium (III) dimer, iridium (III) intermediate ligand exchange, synthesis of mer-iridium (III) complex, and mer-to-fac-iridium (III) complex isomer conversion, which greatly reduces the total yield and the utilization rate of raw material IrCl3·H2O, and increases the preparation cost of iridium (III) complex phosphorescent materials. In contrast, the preparation of platinum (II) complex phosphorescent materials only has the last step of ligand metallization reaction, and the utilization rate of platinum element is high, which can further reduce the preparation cost of platinum (II) complex phosphorescent materials. In summary, the preparation cost of platinum (II) complex phosphorescent materials is much lower than that of iridium (III) complex phosphorescent materials. However, there are still some technical difficulties in the development of platinum complex materials and devices at present, for example, Chinese patent application CN201910978759.X discloses the introduction of methylpyridine imidazole type carbene into divalent platinum complex ligand, but the problem of how to reduce the height of the shoulder peak in the emission spectrum to improve the color purity of the material molecule light emission has not been solved, which has a great influence on the efficiency and energy utilization rate of the commercialized top emission device. Therefore, it is urgent to develop new phosphorescent metal platinum (II) complexes. SUMMARY

[0004] In view of the above, the present application aims to provide one or more guest phosphorescent materials for use in organic electroluminescent devices. Specifically, a novel tetradentate platinum(II) complex is provided. They all exhibit blue light emission, have good chemical and thermal stability, and are easy to prepare into an evaporation-type OLED device. After being prepared into a device, the current efficiency and lifetime can be improved, the turn-on voltage can be reduced, the device lifetime can be prolonged, and a higher color purity can be obtained.

[0005] In many embodiments, the present application provides a tetradentate platinum(II) complex having the structure shown in the following formula (I):

[0006] wherein, in formula (I), R 1 -R 9 each independently represents mono-substitution, di-substitution, tri-substitution, tetra-substitution, or no substitution; R 1 -R 9 each independently represents any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C1–C30 heteroalkyl, substituted or unsubstituted C3–C30 cycloalkyl, substituted or unsubstituted C3–C30 heterocycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C5–C60 heteroaryl, substituted or unsubstituted amino, substituted or unsubstituted C1–C30 silyl, substituted or unsubstituted C1–C30 heterosilyl;

[0007] R a , R b each independently is selected from hydrogen, C1–C3 alkyl; the L is a single bond or substituted or unsubstituted C6–C30 aryl, and when the L is a single bond, R a may be connected to form a ring with R b .

[0008] In many embodiments, the formula (I) has the structure shown in any one of the following formula (I-i) or formula (I-ii):

[0009] In formula (I-i), formula (I-ii), R 1 -R 9 is substituted as in formula (I); R 10 represents mono-substitution, di-substitution, tri-substitution, tetra-substitution, or no substitution, R 10 each independently is selected from hydrogen, deuterium, C1–C30 alkyl.

[0010] In many embodiments, in formula (I), formula (I-i), formula (I-ii), R 1Each time it appears, it is independently selected from hydrogen, deuterium, halogen, -CN, C1–C24 alkyl, C1–C24 haloalkyl, C1–C24 deuteralkyl, substituted or unsubstituted C1–C24 heteroalkyl, C3–C24 cycloalkyl, substituted or unsubstituted C1–C24 heterocycloalkyl, substituted or unsubstituted C1–C24 silyl, substituted or unsubstituted C6–C30 aryl, and amino.

[0011] Preferred, R 1 Each time it appears, it is independently selected from hydrogen, deuterium, F, -CN, methyl, ethyl, isopropyl, tert-butyl, deuterated isopropyl, deuterated tert-butyl, halogenated tert-butyl, cyclopropyl, methoxy, phenoxy, methylthio, phenylthio, methylsilyl, trimethylsilyl, diphenoxymethylsilyl, dimethoxymethylsilyl, cyclopentylmethylsilyl, amino-substituted phenyl, amino.

[0012] In many implementations, R 2 Each time it appears, it is independently selected from hydrogen, deuterium, -CN, halogen, C1–C24 alkyl, C1–C24 haloalkyl, C3–C24 cycloalkyl, C3–C24 heterocycloalkyl, substituted or unsubstituted C1–C24 alkoxy, substituted or unsubstituted C1–C30 alkylthio, C1–C24 aryloxy, substituted or unsubstituted C1–C30 silyl, substituted or unsubstituted C6–C30 aryl, substituted or unsubstituted C3–C30 heteroaryl.

[0013] Preferred, R 2 Each time it appears, it is independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, deuterated tert-butyl, methoxy, oxacyclopentane, azircyclopentane, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, trimethylsiloxane, dimethoxymethylsiloxane, xylyldimethylsiloxane, cyclopentyldimethylsiloxane, and diphenylsiloxane.

[0014] In many implementations, R 3 R 4 Each time it appears, it is independently selected from hydrogen, deuterium, C1–C24 alkyl, C1–C24 deuterated alkyl, C3–C24 heterocyclic alkyl, substituted or unsubstituted C1–C30 siloxane, substituted or unsubstituted C6–C30 aryl.

[0015] Preferred, R 3 R 4 Each time it appears, it is independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, deuterated tert-butyl, oxacyclopentane, phenyl, trimethylsiloxane, cyclopentyldimethylsiloxane, and diphenylsiloxane.

[0016] In many embodiments, R 5 each occurrence is independently selected from hydrogen, deuterium, C1-C24alkyl, C1-C24deuterated alkyl, C3-C24cycloalkyl, substituted or unsubstituted C1-C24alkoxy, C1-C24aryloxy, substituted or unsubstituted C1-C24silyl, substituted or unsubstituted C6-C30aryl.

[0017] In many embodiments, R 5 each occurrence is independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, deuterated tert-butyl, cyclopropane, phenyloxy, phenyl, trimethylsilyl, phenyldimethylsilyl.

[0018] In many embodiments, R 6 each occurrence is independently selected from hydrogen, C1-C24alkyl, C6-C30aryl.

[0019] In many embodiments, R 6 each occurrence is independently selected from hydrogen, ethyl, isopropyl, tert-butyl, phenyl.

[0020] In many embodiments, R 7 , R 8 each occurrence is independently selected from hydrogen, deuterium, C1-C24alkyl, C1-C24deuterated alkyl, C3-C24cycloalkyl, substituted or unsubstituted C1-C24alkoxy, substituted or unsubstituted C1-C24silyl, C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl.

[0021] In many embodiments, R 7 , R 8 each occurrence is independently selected from hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, phenyl, pyridyl, phenyldimethylsilyl, pyridyldimethylsilyl, pyridyldimethylsiloxy.

[0022] In many embodiments, R 9 each occurrence is independently selected from hydrogen, deuterium, -CN, halogen, C1-C24alkyl, C1-C24deuterated alkyl, C1-C24halogenated alkyl, C1-C24alkoxy, C3-C24cycloalkyl, substituted or unsubstituted C3-C30heteroaryl, aminyl, silyl, arylsiloxy, heteroarylsilyl.

[0023] In many embodiments, R 9each occurrence is independently selected from the group consisting of hydrogen, deuterium, -CN, F, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, pyridyl, methoxy, NH2, trimethylsilyl, pyridyldimethylsilyl, pyridyl.

[0024] In many embodiments, R 10 each occurrence is independently selected from the group consisting of hydrogen, deuterium, C1-C3 alkyl.

[0025] The substituents for the substituent group are optionally selected from any one or more of deuterium, tritium, a halogen atom, a cyano group, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with deuterium or tritium, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a C3-C10 cycloalkyl group, a C6-C30 aryl group, a C6-C30 aryl group substituted with deuterium or tritium, a C6-C30 aryl group substituted with a methyl group or a tert-butyl group, a C5-C30 heteroaryl group, a C2-C30 heteroaryl group substituted with deuterium or tritium, and an amino group.

[0026] Preferably, the substituents for the substituent group are optionally selected from any one or more of deuterium, tritium, F, a cyano group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isopropyl group substituted with deuterium or tritium, a tert-butyl group substituted with deuterium or tritium, a cyclopropyl group, a cyclopentyl group, an oxolane group, an azolane group, a phenyl group, a carbazolyl group, and an amino group.

[0027] Further, the tetradentate platinum(II) complex can be selected from one of the following structures:

[0028] Further, the present application also provides a use of the tetradentate platinum(II) complex having the structure of formula (I) as above in the preparation of an electronic device.

[0029] Further, the electronic device includes an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field quench device (O-FQD), a light emitting electrochemical cell (LEC), and an organic laser diode (O-laser).

[0030] In another aspect, the present application also provides an organic electroluminescent device comprising the tetradentate platinum(II) complex having the structure of formula (I) as described above.

[0031] Further, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer interposed therebetween; the organic functional layer comprises the tetradentate platinum(II) complex having the structure of formula (I) as described above.

[0032] Preferably, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the tetradentate platinum(II) complex having the structure of formula (I) as described above.

[0033] Further, the light-emitting layer further comprises a fluorescent dopant material. The present application does not make specific limitation to the structure of the fluorescent dopant material, and any conventional fluorescent dopant material in the art can be used; preferably, the fluorescent dopant material is selected from any one or more of the compounds represented by formula (BN1) to formula (BN5):

[0034] wherein X is O, S, Se or NR 300 ;

[0035] X 1 , X 2 , X 3 , X 4 each independently represents O, S, Se or N;

[0036] R b -R e each independently represents mono-substitution, di-substitution, tri-substitution, tetra-substitution or no substitution; R b -R e each independently is selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, C6-C60 aryl; the R4-R 11 each independently represents the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, C6-C60 aryl.

[0037] Preferably, the R4, R5, R6, R9 each independently is selected from substituted or unsubstituted diphenylamine group, substituted or unsubstituted carbazolyl group; the substitution can be multiple substitution, and when containing a substituent, the substituent is selected from deuterium, C1-C30 alkyl, C6-C30 aryl.

[0038] Preferably, the R7-R8, R 10 -R 11 each independently is selected from the group consisting of hydrogen, C1-C30 alkyl, C6-C60 aryl.

[0039] Further preferably, the R4-R11 at least one hydrogen can be replaced by deuterium.

[0040] Further, the fluorescent dopant material is selected from any one of the following chemical structures, wherein Ph represents a phenyl group, and D4 and D5 mean substituted by 4 and 5 deuterium atoms, respectively:

[0041] In another aspect, the present application also provides an organic optoelectronic device, comprising: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; a second electrode on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises a tetradentate cyclometalated platinum (II) complex having the structure of formula (I) or formula (II) as described above. For example, the platinum (II) complex can be included in the organic light-emitting functional layer as a light-emitting material.

[0042] Further, the organic light-emitting functional layer further comprises a fluorescent dopant material of any one or more of the compounds represented by formula (BN1) to formula (BN5) as described above.

[0043] The present application also provides a composition comprising a tetradentate cyclometalated platinum (II) complex having the structure of formula (I) or formula (II) as described above. Preferably, the composition further comprises a fluorescent dopant material of any one or more of the compounds represented by formula (BN1) to formula (BN5) as described above.

[0044] The present application also provides a formulation comprising a tetradentate cyclometalated platinum (II) complex having the structure of formula (I) or formula (II) as described above or a composition as described above and at least one solvent. The solvent is not particularly limited, and any of the solvents well known to those skilled in the art can be used, such as unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, dicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran, tetrahydropyran, ester solvents such as benzoic acid alkyl ester.

[0045] Preferably, the composition further comprises a fluorescent dopant material having any one or more of the compounds represented by formula (BN1) - (BN5) as described above.

[0046] The present application also provides a display or lighting device comprising one or more of the organic optoelectronic devices described above.

[0047] Compared with the prior art, the present application has the following advantages:

[0048] The present application provides a new type of tetradentate platinum (II) complex by introducing a large steric hindrance donor at one position of the benzocarbene. It is found that the complexes all exhibit blue light emission. It is verified that the representative complex of the present application not only has the smallest maximum emission wavelength, but also has a bluer light emission color, which makes the color purity of the prepared device higher. The material involved in the present application can effectively inhibit the stacking and interaction between molecules, and has good chemical stability and thermal stability, and is easy to prepare an evaporation type OLED device. After being combined with a fluorescent dopant material, the transmission of holes and electrons can be balanced, and the energy transfer between the host and the guest is more efficient. The organic electroluminescent device prepared by using the complex of the present application as a light-emitting layer has obvious improvement in current efficiency and lifetime, and significantly reduces the turn-on voltage. Especially when used together with a phosphorescent sensitized boron-containing compound, the light color purity of the device can be improved, and the present application has great application prospect in the field of OLED display and lighting. BRIEF DESCRIPTION OF DRAWINGS

[0049] Fig. 1 is a room temperature emission spectrum diagram of platinum complex Pt1 in dichloromethane solution;

[0050] Fig. 2 is a room temperature emission spectrum diagram of platinum complex Pt2 in dichloromethane solution;

[0051] Fig. 3 is a room temperature emission spectrum diagram of platinum complex Pt3 in dichloromethane solution;

[0052] Fig. 4 is a HOMO and LUMO orbital distribution diagram of part of the complexes Pt1-Pt3. DETAILED DESCRIPTION

[0053] The content of the present application is described in detail below. The description of the constituent elements described below is sometimes based on the representative embodiment or specific example of the present application, but the present application is not limited to such an embodiment or specific example.

[0054] The term "substituted" as used herein is intended to encompass all permissible substituents of the organic compounds. In broad aspect, permissible substituents include noncyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of the organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more, and the same or different for each organic compound. For the purposes of this application, heteroatoms such as nitrogen can have hydrogen substituents and / or any permissible substituents of the organic compounds described herein which satisfy the valencies of the heteroatoms. This application is not intended to be limited in any manner by the permissible substituents of the organic compounds. Also, the term "substitution" or "substituted with" includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the resultant compound is stable (e.g., is not inappreciably transformed by virtue of the substitution). It is also contemplated that, in certain aspects, unless expressly

[0055] In defining various terms, "R 1 "-"R 10 " are used in this application as general designations for various specific substituents. These symbols can be any substituents, not limited to those disclosed herein, and when they are defined in one instance as certain substituents, they can be defined in other instances as some other substituents.

[0056] As used herein, "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 group, an alkoxy group, an alkyl group, a halogen, etc. Depending on the group selected, the first group can be incorporated within the second group, or alternatively, 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 incorporated within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the groups selected will determine whether the first group is incorporated or attached to the second group.

[0057] The term "alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group of 1 to 30 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted.

[0058] The term "cycloalkyl" as used herein refers to a cyclic alkyl group. The cycloalkyl group can be a cyclic alkyl group having 3 to 30 ring carbon atoms, preferably a cyclic alkyl group having 3 to 14 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl are preferred. In addition, the cycloalkyl group can be optionally substituted.

[0059] The term "heteroalkyl" as used herein refers to a group in which one or more carbons of an alkyl group is replaced by a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a silicon atom, a germanium atom, and a boron atom. The heteroalkyl group can be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of the heteroalkyl group include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxy methyl, ethoxymethoxy methyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, t-butyldimethylsilyl, triethylsilyl, triisopropylsilyl, trimethylsilylmethyl, trimethylsilyl ethyl, trimethylsilylisopropyl. In addition, the heteroalkyl group can be optionally substituted.

[0060] In the present application, "alkylthio" refers to the recited alkyl group bonded through a sulfur bond (-S-).

[0061] In the present application, "alkoxy" refers to the recited alkyl group bonded through an oxygen bond (-O-).

[0062] The term "aryl" as used herein refers to any carbon-based aromatic group having 6 to 60 carbon atoms, both non-fused and fused systems are contemplated. The carbon-based aromatic groups include, but are not limited to, phenyl, naphthyl, phenylnaphthyl, biphenyl, phenoxyphenyl, anthryl, phenanthryl, and the like. The aryl group can be substituted or unsubstituted. The aryl 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, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, sulfo-oxo, or mercapto groups as described herein.

[0063] In the present application, the term "heteroaryl" refers to a monoheterocyclic or polyheterocyclic aromatic hydrocarbon monovalent substituent having 6 to 60 carbon atoms, preferably a heteroaryl group having 6 to 30 carbon atoms, more preferably a heteroaryl group having 6 to 18 carbon atoms. In this case, one or more carbons, preferably 1 to 3 carbons, in the ring are substituted with a heteroatom such as N, O, S, P, or Se. Examples of the heteroatom include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. In addition, a form in which two or more rings are pendant or fused to each other, and a form in which an aryl group is fused can also be included. As examples of such heteroaryl groups, there can be mentioned, for example, dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridinoindole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazol, indolizine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthridine, phtalazine, pteridine, xanthene, acridine, phenoxazine, phenothiazine, benzofuro[3,2-g]pyridine, furo[3,2-g]dipyridine, thieno[3,2-g]pyridine, thieno[2,3-g]dipyridine, seleno[3,2-g]pyridine, seleno[2,3-g]dipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazole, and nitrogen analogs thereof, but are not limited thereto.

[0064] The term "heterocyclyl" as used herein refers to at least one carbon atom constituting an aryl group, a cycloalkyl group, or an alkylaryl group (arylalkyl group) is substituted with a heteroatom such as oxygen (O), nitrogen (N), sulfur (S), or the like. In addition, the heterocyclyl group can be optionally substituted.

[0065] The term "silyl" as used herein is intended to encompass alkyl substituted silyl groups. The silyl group can be a silyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Examples of silyl groups include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-t-butylsilyl, triisobutylsilyl, dimethyl-t-butylsilyl, methyldi-t-butylsilyl. Additionally, the silyl group can be optionally substituted.

[0066] In the present disclosure, unless otherwise defined, when any one of the terms from the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted aryl, substituted heteroaryl, substituted silyl, substituted arylsilyl, substituted amino is used, it means that any one of the alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, aryl, heteroaryl, silyl, arylsilyl and amino groups can be substituted with one or more selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 24 carbon atoms, unsubstituted cycloalkyl having 3 to 24 ring carbon atoms, unsubstituted heteroalkyl having 1 to 24 carbon atoms, unsubstituted heterocyclyl having 3 to 24 ring atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 24 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted silyl having 3 to 24 carbon atoms, unsubstituted arylsilyl having 6 to 24 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, cyano, isocyano, hydroxyl, mercapto and combinations thereof.

[0067] Examples of the term "halogen" or "halo" as used herein include, but are not limited to, fluorine, chlorine, bromine and iodine.

[0068] In the compounds mentioned in the present application, hydrogen atoms can be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. The replacement of other stable isotopes in the compounds can be preferred due to its enhanced efficiency and stability of the device.

[0069] The compounds described herein can contain "optionally substituted" moieties. In general, the term "substituted" means that one or more hydrogens of the designated moiety is replaced with a suitable substituent. Unless otherwise indicated, "optionally substituted" groups can have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted with more than one substituent, the substituent can be either the same or different at every position. Combinations of substituents envisioned by this application are preferably those that result in the formation of stable or chemically feasible compounds. In certain aspects, further optionally substituted (i.e., further substituted or unsubstituted) individual substituents are also encompassed, unless specifically indicated to the contrary.

[0070] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be modulated by selection of appropriate ligands. In another aspect, the present application can exclude any one or more of the compounds, structures, or moieties specifically recited herein.

[0071] 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.

[0072] It should be noted that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.

[0073] The present application can be more easily understood with reference to the following detailed description and examples included therein.

[0074] Before the present compounds, devices and / or methods are disclosed and described, it is to be understood that the compounds, devices and / or methods are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, exemplary methods and materials are described below. All patents and publications mentioned herein are incorporated by reference.

[0075] The substrate described in this invention can be any substrate typically used in organic optoelectronic devices. It can be a glass or transparent plastic substrate, an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance, and their applications vary depending on their properties. As materials for the hole injection layer, hole transport layer, and electron injection layer, any known materials used in OLED devices can be selected, and this invention does not impose specific limitations.

[0076] Synthesis Examples

[0077] The examples of compound synthesis, composition, devices, or methods below are intended to provide a general approach to the industry and are not intended to limit the scope of this patent. While we strive for accuracy in the data (quantities, temperatures, etc.) mentioned in the patent, some errors may still exist. Unless otherwise specified, weighings are performed separately, temperatures are in °C or room temperature, and pressures are close to atmospheric pressure.

[0078] The examples below provide methods for preparing novel compounds, but the preparation of such compounds is not limited to these methods. In this field of expertise, since the compounds protected in this invention are easily modified and prepared, their preparation can be carried out using the methods listed below or other methods. The examples below are merely illustrative and are not intended to limit the scope of this patent. Temperature, catalyst, concentration, reactants, and reaction process can all be varied to select different conditions for preparing the compounds with different reactants.

[0079] 1 H NMR (500MHz), 1 H NMR (400MHz), 13 C10 NMR (126 MHz) spectra were measured on an ANANCE III (500 M) NMR spectrometer; unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR measurements. 1 When using CDCl3 as the solvent in ¹H NMR spectroscopy, TMS (δ = 0.00 ppm) is used as the internal standard; when using DMSO-d6 as the solvent, TMS (δ = 0.00 ppm), residual DMSO peak (δ = 2.50 ppm), or residual water peak (δ = 3.33 ppm) are used as the internal standard. 13C NMR spectra in CDCh (δ = 77.00 ppm) or DMSO-d6(δ = 39.52 ppm) as internal standard. HPLC-MS Agilent 6210 TOF LC / MS type mass spectrometer; HRMS spectra were determined on an Agilent 6210 TOF LC / MS type liquid chromatography-time of flight mass spectrometer. 1 H NMR spectral data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0080] Synthesis route

[0081] Example 1 : Complex Pt1

[0082] The synthesis route is as follows

[0083] Synthesis of intermediate NO2-1 : Into a Schlenk tube with magnetic stirring was added SA-1 (1.0 g, 2.4 mmol, 1.0 eq), Br-NO2 (1.1 g, 2.9 mmol, 1.2 eq), Pd2(dba)3 (67 mg, 0.073 mmol, 0.03 eq), XPhos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) (44 mg, 0.146 mmol, 0.06 eq) and sodium tert-butoxide (468 mg, 4.78 mmol, 2.0 eq). After three times of nitrogen replacement, toluene (15 mL) was added under nitrogen protection. After reaction in 110 °C oil bath for 8 h, it was cooled to room temperature, extracted with water and ethyl acetate, and the organic phase was collected. After removing the solvent by reduced pressure distillation, the crude product was separated by silica gel column, eluent: petroleum ether / ethyl acetate = 100:1 ~ petroleum ether / dichloromethane = 50:1, to obtain 1.22 g of product, yield 71%. 1H NMR (400 MHz, DMSO-d6) d (ppm) 0.86 (d, J = 7.2 Hz, 6H), 1.03 (d, J = 7.2 Hz, 6H), 2.80 - 2.94 (m, 2H), 5.48 (d, J = 2.4 Hz, 1H), 6.36 (dd, J = 9.6, 2.4 Hz, 1H), 7.02 (d, J = 7.6 Hz, 2H), 7.15 (t, J = 8.0 Hz, 1H), 7.19 - 7.25 (m, 4H), 7.26 - 7.27 (m, 2H), 7.27 - 7.32 (m, 2H), 7.34 - 7.40 (m, 1H), 7.41 - 7.46 (m, 3H), 7.46 - 7.51 (m, 2H), 7.56 - 7.60 (m, 2H), 7.60 - 7.66 (m, 3H), 8.07 (d, J = 9.6 Hz, 1H), 8.23 (dt, J = 7.6, 0.8 Hz, 2H), 9.38 (s, 1H).

[0084] Synthesis of intermediate NH2-1: Into a three-necked flask was placed NO2-1 (951 mg, 1.34 mmoL, 1.0 eq), stannous chloride (1.02 g, 5.38 mmoL, 4.0 eq), ethanol (20 mL) and ethyl acetate (20 mL). After reaction at 78 °C for 16 h, it was cooled to room temperature, quenched by NaHCO3 solution, extracted by EA, the organic phase was concentrated by reduced pressure distillation, and then the product was separated by silica gel column, eluent: petroleum ether / dichloromethane = 5:1-2:1, 489 mg of raw material was recovered, and 280 mg of product was obtained with a yield of 63% (based on conversion). The product obtained in this step was unstable and inconvenient to characterize, so it was directly used in the subsequent reaction.

[0085] Synthesis of intermediate NH-1: Into a Schlenk tube with magnetic stirring was placed NH2-1 (855 mg, 1.26 mmoL, 1.0 eq), t-Bu-Cl (610 mg, 1.26 mmoL, 1.0 eq), Pd2(dba)3 (35 mg, 0.038 mmoL, 0.03 eq), Johnphos (2-(di-tert-butylphosphino)biphenyl) (23 mg, 0.076 mmoL, 0.06 eq) and sodium tert-butoxide (243 mg, 2.53 mmoL, 2.0 eq). After three times of nitrogen replacement, toluene (15 mL) was added under nitrogen protection. After reaction in a 100 °C oil bath for 19 h, it was cooled to room temperature, extracted by water and ethyl acetate, and then the organic phase was concentrated by reduced pressure distillation. After removing the solvent, the crude product was separated by silica gel column, eluent: petroleum ether / ethyl acetate = 50:1-25:1, 740 mg of green foamy solid was obtained with a yield of 52%. The product obtained in this step was unstable and inconvenient to characterize, so it was directly used in the subsequent reaction.

[0086] Synthesis of Ligand L1 : Into a Schlenk tube with magnetic stirring bar was added NH-1 (740 mg, 0.66 mmol, 1.0 equiv), ammonium hexafluorophosphate (215 mg, 1.32 mmol, 2.0 equiv), and the flask was purged with nitrogen three times. Under nitrogen protection, triethyl orthoformate (5 mL) was added. After reaction in 80 °C oil bath for 9 h, the mixture was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 2:1 to dichloromethane / ethyl acetate = 10:1 to give 382 mg of solid with a yield of 47%. 1 H NMR (400 MHz, DMSO-d6) d (ppm): 0.79 (d, J = 6.8 Hz, 6H), 1.03 (d, J = 6.8 Hz, 6H), 1.25 (s, 9H), 1.34 (s, 9H), 2.25 - 2.35 (m, 2H), 6.93 (d, J = 2.0 Hz, 1 H), 7.09 (t, J = 2.4 Hz, 1 H), 7.12 - 7.16 (m, 1 H), 7.18 - 7.22 (m, 3H), 7.25 (td, J = 5.2, 2.8 Hz, 2H), 7.32 - 7.35 (m, 2H), 7.36 - 7.38 (m, 4H), 7.39 - 7.42 (m, 2H), 7.41 - 7.44 (m, 3H), 7.45 - 7.48 (m, 3H), 7.50 (t, J = 2.0 Hz, 1 H), 7.54 - 7.59 (m, 2H), 7.59 - 7.63 (m, 4H), 7.63 - 7.68 (m, 4H), 7.74 (d, J = 8.4 Hz, 1 H), 7.89 (d, J = 9.2 Hz, 1 H), 8.19 (dt, J = 8.0, 1.2 Hz, 2H), 8.23 (d, J = 8.0 Hz, 1 H), 8.32 (d, J = 8.4 Hz, 1 H), 8.51 (d, J = 5.2 Hz, 1 H), 10.51 (s, 1 H).

[0087] Synthesis of Pt1 : Into a sealed tube with magnetic stirring bar was added L1 (382 mg, 0.298 mmol, 1.0 equiv), Pt(COD)Cl2((1,5-cyclooctadiene) dichloroplatinum) (117 mg, 0.31 mmol, 1.05 equiv), and sodium acetate (73 mg, 0.89 mmol, 3.0 equiv). The flask was purged with nitrogen three times, and diethyleneglycol dimethyl ether (8 mL) was added under nitrogen protection. The mixture was bubbled with nitrogen for 30 min to remove oxygen. The reaction was carried out in 120 °C oil bath for 72 h. After the reaction was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted with DCM. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 4:1 to 2:1 to give 360 mg of yellow solid with a yield of 91 %. 1HNMR (500 MHz, DMSO-d6) δ (ppm): 0.68 (s, 6H), 1.00 (s, 6H), 1.21 (s, 9H), 1.45 (s, 9H), 2.86 (s, 1H), 6.22 (dd, J = 6.5, 2.0 Hz, 1H), 6.60 (d, J = 2.0 Hz, 1H), 7.03 (d, J = 1.5 Hz, 1H), 7.06 - 7.11 (m, 2H), 7.14 - 7.18 (m, 3H), 7.21 - 7.25 (m, 4H), 7.25 - 7.28 (m, 1H), 7.28 - 7.33 (m, 2H), 7.33 - 7.37 (m, 4H), 7.37 - 7.43 (m, 4H), 7.44 - 7.49 (m, 2H), 7.53 - 7.60 (m, 5H), 7.66 (d, J = 1.5 Hz, 1H), 7.78 - 7.88 (m, 3H), 8.10 (d, J = 7.5 Hz, 1H), 8.17 (d, J = 8.0 Hz, 2H), 8.36 - 8.44 (m, 2H). HRMS [M+H] + : 1326.6.

[0088] Example 2: Complex Pt2

[0089] The synthesis route is as follows

[0090] Synthesis of intermediate NO2-1 : Into a Schlenk tube with magnetic stirring was added SA-1 (907 mg, 2.2 mmoL, 1.0 eq), Br-NO2 (1 g, 2.65 mmoL, 1.2 eq), Pd2(dba)3 (61 mg, 0.063 mmoL, 0.03 eq), XPhos (40 mg, 0.133 mmoL, 0.06 eq) and sodium tert-butoxide (425 mg, 4.4 mmoL, 2.0 eq). The flask was purged with nitrogen three times and toluene (10 mL) was added under nitrogen protection. After 10 hours of reaction in an oil bath at 110 °C, it was cooled to room temperature, extracted with water and ethyl acetate, the organic phase was collected and the solvent was removed by distillation under reduced pressure, then the crude product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 100:1 ~ petroleum ether / dichloromethane = 50:1, to obtain 1.4 g of product with a yield of 90%. It has been characterized on the hydrogen spectrum.

[0091] Synthesis of intermediate NH2-1 : A three-neck flask was charged with NO2-1 (1.4 g, 1.98 mmol, 1.0 eq), stannous chloride (1.5 g, 7.92 mmol, 4.0 eq), ethanol (10 mL) and ethyl acetate (10 mL). The reaction was monitored by TLC and more ethanol (10 mL) was added when necessary. After the reaction was completed at 78 °C for 37 h, the reaction mixture was cooled to room temperature and quenched with NaHCO3 solution. The organic phase was extracted with EA and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography with petroleum ether / dichloromethane = 5:1-2:1 as eluent. The product was recovered as 220 mg and the yield was 61% (based on conversion). The product obtained from this step was unstable and was used directly in the subsequent reaction.

[0092] Synthesis of intermediate NH-2: A Schlenk tube with magnetic stirring was charged with NH2-1 (820 mg, 1.33 mmol, 1.0 eq), Cl (567 mg, 1.33 mmol, 1.0 eq), Pd2(dba)3 (37 mg, 0.040 mmol, 0.03 eq), XPhos (38 mg, 0.079 mmol, 0.06 eq) and sodium tert-butoxide (255 mg, 2.6 mmol, 2.0 eq). The tube was purged with nitrogen three times and toluene (12 mL) was added under nitrogen protection. After the reaction was completed at 100 °C for 7 h, the reaction mixture was cooled to room temperature and extracted with water and ethyl acetate. The organic phase was collected and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography with petroleum ether / ethyl acetate = 50:1-25:1 as eluent. The product was obtained as a green foam solid with a yield of 813 mg, 57%. The product obtained from this step was unstable and was used directly in the subsequent reaction.

[0093] Synthesis of ligand L2: A Schlenk tube with magnetic stirring was charged with NH-2 (813 mg, 0.76 mmol, 1.0 eq), ammonium hexafluorophosphate (248 mg, 1.52 mmol, 2.0 eq). The tube was purged with nitrogen three times and triethyl orthoformate (5 mL) was added under nitrogen protection. After the reaction was completed at 75 °C for 6 h, the reaction mixture was cooled to room temperature and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography with petroleum ether / dichloromethane = 2:1~ dichloromethane / ethyl acetate = 10:1 as eluent. The product was obtained as a solid with a yield of 530 mg, 57%. 1H NMR (400 MHz, DMSO-d6) d (ppm) 0.78 (d, J = 6.8 Hz, 6H), 1.03 (d, J = 6.4 Hz, 6H), 1.27 (s, 9H), 2.26 - 2.38 (m, 2H), 6.91 (d, J = 2.0 Hz, 1H), 7.10 (t, J = 2.4 Hz, 1H), 7.15 (dd, J = 8.0, 2.4 Hz, 1H), 7.18 - 7.24 (m, 4H), 7.24 - 7.27 (m, 2H), 7.34 (d, J = 2.4 Hz, 1H), 7.35 - 7.37 (m, 4H), 7.37 - 7.38 (m, 1H), 7.39 - 7.42 (m, 2H), 7.42 - 7.44 (m, 3H), 7.44 - 7.46 (m, 2H), 7.46 - 7.48 (m, 1H), 7.49 (d, J = 2.0 Hz, 1H), 7.55 - 7.58 (m, 1H), 7.58 - 7.60 (m, 2H), 7.61 - 7.62 (m, 1H), 7.62 - 7.65 (m, 2H), 7.65 - 7.66 (m, 2H), 7.67 - 7.69 (m, 1H), 7.71 - 7.79 (m, 2H), 7.93 (d, J = 8.8 Hz, 1H), 8.19 (d, J = 8.0 Hz, 2H), 8.24 (d, J = 7.6 Hz, 1H), 8.33 (d, J = 8.8 Hz, 1H), 8.53 (d, J = 5.6 Hz, 1H), 10.48 (s, 1H).

[0094] Synthesis of Pt2: To a sealed tube with magnetic stirring was added L2 (530 mg, 0.43 mmoL, 1.0 eq), Pt(COD)Cl2 (170 mg, 0.45 mmoL, 1.05 eq) and sodium acetate (107 mg, 1.3 mmoL, 3.0 eq), replaced with nitrogen three times, added diethylene glycol dimethyl ether (10 mL) under nitrogen protection, nitrogen bubbling for 30 min to remove oxygen. Reaction in 120 °C oil bath for 72 h, after the reaction was cooled to room temperature, quenched with water, extracted with DCM, dried over anhydrous sodium sulfate, removed the solvent under reduced pressure, the obtained crude product was separated by silica gel column, eluent: petroleum ether / dichloromethane = 4:1-2:1, obtained 223 mg of yellow solid, yield 41%. 1H NMR (500 MHz, CDCI3-d) δ (ppm): 1.11 (s, 6H), 1.24 (s, 9H), 1.25-1.31 (m, 6H), 3.07 (s, 2H), 6.01 (dd, J = 6.5, 2.0 Hz, 1 H), 6.74 (d, J = 2.0 Hz, 1 H), 7.04-7.08 (m, 1 H), 7.11-7.15 (m, 3H), 7.17-7.20 (m, 2H), 7.23 (t, J = 2.5 Hz, 1 H), 7.24-7.26 (m, 1 H), 7.26-7.28 (m, 1 H), 7.28-7.31 (m, 1 H), 7.31-7.34 (m, 2H), 7.35 (d, J = 2.0 Hz, 2H), 7.36-7.38 (m, 5H), 7.40 (dd, J = 8.5, 3.0 Hz, 4H), 7.41-7.43 (m, 2H), 7.44-7.46 (m, 1 H), 7.48-7.51 (m, 2H), 7.57 (d, J = 7.5 Hz, 1 H), 7.74 (d, J = 7.5 Hz, 1 H), 7.76 (d, J = 8.5 Hz, 1 H), 7.92 (d, J = 2.0 Hz, 1 H), 8.00 (dd, J = 7.0, 2.0 Hz, 1 H), 8.09 (dt, J = 8.0, 1.0 Hz, 2H), 8.13 (d, J = 9.0 Hz, 1 H), 8.55 (d, J = 6.5 Hz, 1 H). HRMS [M+H] + : 1270.5.

[0095] Example 3: Complex Pt3

[0096] The synthetic route is as follows

[0097] Synthesis of intermediate NO2-2: Into a Schlenk tube with magnetic stirring was added SA-2 (1 g, 3 mmol, 1.0 eq), Br-NO2 (1.47 g, 3.9 mmol, 1.3 eq), Pd2(dba)3 (83 mg, 0.09 mmol, 0.03 eq), XPhos (54 mg, 0.18 mmol, 0.06 eq) and sodium tert-butoxide (578 mg, 6 mmol, 2.0 eq). The flask was purged with nitrogen three times and toluene (15 mL) was added under nitrogen protection. After reaction for 10 h in a 110 °C oil bath, it was cooled to room temperature, extracted with water and ethyl acetate, and the organic phase was collected. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel column chromatography with eluent: petroleum ether / ethyl acetate = 100:1 ~ petroleum ether / dichloromethane = 50:1, to give the product 986 mg, yield 52%. 1H NMR (500 MHz, CDCI3-d) d (ppm): 1.23 (dd, J = 11.0, 7.0 Hz, 12H), 3.18 (m, 2H), 6.67 (d, J = 2.0 Hz, 1 H), 7.01 (dd, J = 9.0, 2.5 Hz, 1 H), 7.24 (d, J = 7.5 Hz, 2H), 7.27 - 7.31 (m, 3H), 7.32 - 7.36 (m, 3H), 7.37 - 7.44 (m, 4H), 7.48 - 7.54 (m, 2H), 8.04 (d, J = 8.0 Hz, 1 H), 8.18 (dt, J = 8.0, 1.0 Hz, 2H), 8.21 (d, J = 1.5 Hz, 1 H), 8.53 (d, J = 9.0 Hz, 1 H), 9.45 (s, 1 H).

[0098] Synthesis of intermediate NH2-2: Into a three-necked flask was added NO2-1 (1.64 g, 2.6 mmoL, 1.0 eq), stannous chloride (1.98 g, 10.43 mmoL, 4.0 eq), ethanol (30 mL) and ethyl acetate (30 mL). After reaction at 80 °C for 43 h, it was cooled to room temperature, quenched by sodium bicarbonate solution, extracted by ethyl acetate, the organic phase was collected and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 5:1-2:1, 457 mg of raw material was recovered and 1.06 g of product was obtained with a yield of 94% (based on conversion). The product obtained in this step was unstable and inconvenient to characterize, so it was directly used in the subsequent reaction.

[0099] Synthesis of intermediate NH-3: Into a Schlenk tube with magnetic stirring was added NH2-2 (480 mg, 0.8 mmoL, 1.0 eq), Cl (360 mg, 0.84 mmoL, 1.05 eq), Pd2(dba)3(22 mg, 0.024 mmoL, 0.03 eq), XPhos (14 mg, 0.048 mmoL, 0.06 eq) and sodium tert-butoxide (154 mg, 1.6 mmoL, 2.0 eq). After three times of nitrogen replacement, toluene (10 mL) was added under nitrogen protection. After reaction in 100 °C oil bath for 10 h, it was cooled to room temperature, extracted by water and ethyl acetate, the organic phase was collected and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 50:1-25:1, 759 mg of green foamy solid was obtained with a yield of 96%. The product obtained in this step was unstable and inconvenient to characterize, so it was directly used in the subsequent reaction.

[0100] Synthesis of Ligand L3: Into a Schlenk tube with magnetic stirring bar was added NH-3 (759 mg, 0.77 mmol, 1.0 eq), ammonium hexafluorophosphate (250 mg, 1.52 mmol, 2.0 eq), and triethyl orthoformate (5 mL) was added under nitrogen protection after three times of nitrogen exchange. After 10 hours of reaction in 80 °C oil bath, it was cooled to room temperature, the solvent was removed by distillation under reduced pressure, and the product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 2:1 ~ dichloromethane / ethyl acetate = 10:1 to obtain 191 mg of solid with a yield of 22%. 1 H NMR (400 MHz, DMSO-d6) d (ppm): 1.14 (d, J = 6.8 Hz, 6H), 1.17 - 1.20 (m, 6H), 1.31 (s, 9H), 2.54 - 2.61 (m, 2H), 7.25 - 7.29 (m, 2H), 7.29 - 7.33 (m, 3H), 7.33 - 7.36 (m, 3H), 7.41 - 7.46 (m, 3H), 7.46 - 7.51 (m, 4H), 7.56 (d, J = 8.0 Hz, 2H), 7.60 (d, J = 2.4 Hz, 1H), 7.68 - 7.74 (m, 2H), 7.74 - 7.82 (m, 2H), 7.82 - 7.89 (m, 2H), 8.11 - 8.18 (m, 2H), 8.25 - 8.32 (m, 4H), 8.33 - 8.41 (m, 3H), 8.58 (d, J = 2.0 Hz, 1H), 8.61 (d, J = 5.6 Hz, 1H), 10.82 (s, 1H).

[0101] Synthesis of Pt3: Into a sealed tube with magnetic stirring bar was added L3 (191 mg, 0.167 mmol, 1.0 eq), Pt(COD)Cl2 (66 mg, 0.175 mmol, 1.05 eq), and sodium acetate (41 mg, 0.5 mmol, 3.0 eq), and diethyleneglycol dimethyl ether (5 mL) was added under nitrogen protection after three times of nitrogen exchange. After 72 hours of reaction in 120 °C oil bath, the reaction was cooled to room temperature, quenched by water, extracted by dichloromethane, dried by anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 4:1 - 2:1 to obtain 30 mg of yellow solid with a yield of 15%. 1H NMR (400 MHz, CDCI3-d) d (ppm): 0.90 - 1.07 (m, 6H), 1.08 - 1.23 (m, 6H), 1.26 (s, 9H), 3.23 (s, 2H), 6.06 (dd, J = 6.4, 2.0 Hz, 1H), 7.19 (d, J = 2.0 Hz, 1H), 7.27 - 7.30 (m, 3H), 7.30 - 7.32 (m, 2H), 7.33 - 7.36 (m, 2H), 7.36 - 7.37 (m, 3H), 7.37 - 7.41 (m, 4H), 7.41 - 7.46 (m, 3H), 7.49 (d, J = 8.0 Hz, 2H), 7.69 (dd, J = 8.4, 2.0 Hz, 1H), 7.72 (d, J = 7.6 Hz, 1H), 7.77 (d, J = 7.6 Hz, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.97 (d, J = 2.0 Hz, 1H), 8.00 - 8.04 (m, 1H), 8.09 (d, J = 8.0 Hz, 1H), 8.17 (d, J = 7.6 Hz, 2H), 8.26 (d, J = 2.0 Hz, 1H), 8.44 (d, J = 8.4 Hz, 1H), 8.65 (d, J = 6.4 Hz, 1H). HRMS [M + H] + : 1192.3.

[0102] Example 4: Complex Pt4

[0103] The synthetic route is as follows

[0104] Synthesis of intermediate NH-4: Into a Schlenk tube with magnetic stirring bar was added NH2-1 (500 mg, 0.74 mmol, 1.0 eq), CI-4 (326 mg, 0.74 mmol, 1.0 eq), Pd2(dba)3 (20 mg, 0.022 mmol, 0.03 eq), XPhos (21 mg, 0.044 mmol, 0.06 eq) and sodium tert-butoxide (142 mg, 1.48 mmol, 2.0 eq). The flask was purged with nitrogen three times and toluene (10 mL) was added under nitrogen protection. After reaction in 100 °C oil bath for 7 h, it was cooled to room temperature, extracted with water and ethyl acetate, the organic phase was collected and the solvent was removed by reduced pressure distillation, then the crude product was separated by silica gel column, eluent: petroleum ether / ethyl acetate = 50:1-25:1, 687 mg of green foam solid was obtained with a yield of 86%. The product obtained in this step was unstable and inconvenient to characterize, so it was directly used in the subsequent reaction.

[0105] Synthesis of ligand L4: To a Schlenk tube with magnetic stirring was added NH-4 (687 mg, 0.64 mmoL, 1.0 eq), ammonium hexafluorophosphate (207 mg, 1.27 mmoL, 2.0 eq), and the flask was purged with nitrogen three times. Under nitrogen protection, triethyl orthoformate (6 mL) was added. After 3 h of reaction in a 75 °C oil bath, the mixture was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography with eluents of petroleum ether / dichloromethane = 2:1 to dichloromethane / ethyl acetate = 10:1 to give 338 mg of a solid with a yield of 43%.

[0106] Synthesis of Pt4: To a sealed tube with magnetic stirring was added L4 (338 mg, 0.27 mmoL, 1.0 eq), Pt(COD)Cl2 (107 mg, 0.28 mmoL, 1.05 eq), and sodium acetate (67 mg, 0.82 mmoL, 3.0 eq), and the flask was purged with nitrogen three times. Under nitrogen protection, diethyleneglycol dimethyl ether (5 mL) was added, and the mixture was bubbled with nitrogen for 30 min to remove oxygen. After 72 h of reaction in a 120 °C oil bath, the mixture was cooled to room temperature, and water was added to quench the reaction. The mixture was extracted with DCM, and the organic phase was dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and the residue was separated by silica gel column chromatography with eluents of petroleum ether / dichloromethane = 4:1 to 2:1 to give 133 mg of a yellow solid with a yield of 38%. HRMS [M+H]: 1284.4. + :1284.4.

[0107] Example 5: Complex Pt13

[0108] The synthetic route is as follows

[0109] Synthesis of intermediate NH-13: To a Schlenk tube with magnetic stirring was added NH2-13 (430 mg, 0.61 mmoL, 1.0 eq), Cl-13 (358 mg, 0.61 mmoL, 1.0 eq), Pd2(dba)3 (17 mg, 0.018 mmoL, 0.03 eq), XPhos (17 mg, 0.037 mmoL, 0.06 eq), and sodium tert-butoxide (117 mg, 1.22 mmoL, 2.0 eq). The flask was purged with nitrogen three times, and toluene (7 mL) was added under nitrogen protection. After 7 h of reaction in a 100 °C oil bath, the mixture was cooled to room temperature, and water and ethyl acetate were added to extract the mixture. The organic phase was collected, and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography with eluents of petroleum ether / ethyl acetate = 50:1 to 25:1 to give 590 mg of a green foamy solid with a yield of 77%. The product obtained in this step was unstable and was not characterized. It was used directly in the subsequent reaction.

[0110] Synthesis of ligand L13: To a Schlenk tube with magnetic stirring was added NH-13 (590 mg, 0.47 mmol, 1.0 equiv), ammonium hexafluorophosphate (153 mg, 0.94 mmol, 2.0 equiv), and triethyl orthoformate (6 mL) was added under nitrogen protection. After 3 hours of reaction in 75 °C oil bath, it was cooled to room temperature, the solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 2:1 ~ dichloromethane / ethyl acetate = 10:1 to give 365 mg of solid with a yield of 55%.

[0111] Synthesis of Pt13: To a sealed tube with magnetic stirring was added L13 (365 mg, 0.26 mmol, 1.0 equiv), Pt(COD)Cl2(102 mg, 0.27 mmol, 1.05 equiv), and sodium acetate (64 mg, 0.78 mmol, 3.0 equiv), and diethyleneglycol dimethyl ether (5 mL) was added under nitrogen protection. After 30 min of oxygen removal by nitrogen bubbling, it was reacted for 72 hours in 120 °C oil bath. After the reaction was cooled to room temperature, it was quenched by water, extracted by DCM, dried by anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 4:1 ~ 2:1 to give 173 mg of yellow solid with a yield of 46%. HRMS [M+H]: 1458.5. + : 1458.5.

[0112] Example 6: Complex Pt17

[0113] The synthetic route is as follows

[0114] Synthesis of intermediate NH-17: To a Schlenk tube with magnetic stirring was added NH2-17 (430 mg, 0.70 mmol, 1.0 equiv), Cl-17 (430 mg, 0.70 mmol, 1.0 equiv), Pd2(dba)3(19 mg, 0.021 mmol, 0.03 equiv), XPhos (20 mg, 0.042 mmol, 0.06 equiv), and sodium tert-butoxide (134 mg, 1.4 mmol, 2.0 equiv). After three times of nitrogen replacement, toluene (7 mL) was added under nitrogen protection. After 7 hours of reaction in 100 °C oil bath, it was cooled to room temperature, extracted by water and ethyl acetate, and the organic phase was collected to remove the solvent by distillation under reduced pressure. The crude product was separated by silica gel column chromatography with eluent of petroleum ether / ethyl acetate = 50:1 ~ 25:1 to give 626 mg of green foamy solid with a yield of 73%. Since the product obtained from this step is unstable and inconvenient to characterize, it was directly used in the subsequent reaction.

[0115] Synthesis of ligand L17: To a Schlenk tube with magnetic stirring was added NH-17 (626 mg, 0.51 mmol, 1.0 equiv), ammonium hexafluorophosphate (166 mg, 1.02 mmol, 2.0 equiv), and the flask was purged with nitrogen three times. Trifluoroacetic acid triethyl ester (6 mL) was added under nitrogen protection. After 3 hours of reaction in 75 °C oil bath, the reaction was cooled to room temperature, the solvent was removed by distillation under reduced pressure, and the product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 2:1 to dichloromethane / ethyl acetate = 10:1, to give 458 mg of solid, with a yield of 65%.

[0116] Synthesis of Pt17: To a sealed tube with magnetic stirring was added L17 (458 mg, 0.33 mmol, 1.0 equiv), Pt(COD)Cl2(130 mg, 0.35 mmol, 1.05 equiv), and sodium acetate (82 mg, 0.99 mmol, 3.0 equiv), and the flask was purged with nitrogen three times. Diethyleneglycol dimethyl ether (5 mL) was added under nitrogen protection, and the flask was bubbled with nitrogen for 30 min to remove oxygen. The reaction was carried out in 120 °C oil bath for 72 hours, and the reaction was quenched with water after being cooled to room temperature. The product was extracted with DCM, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 4:1 to 2:1, to give 213 mg of yellow solid, with a yield of 45%. HRMS [M+H]: 1430.6. + :1430.6.

[0117] Example 7: Complex Pt102

[0118] The synthetic route is as follows

[0119] Synthesis of intermediate NH-102: To a Schlenk tube with magnetic stirring was added NH2-102 (552 mg, 0.75 mmol, 1.0 equiv), Cl-102 (341 mg, 0.75 mmol, 1.0 equiv), Pd2(dba)3(21 mg, 0.022 mmol, 0.03 equiv), XPhos (21 mg, 0.045 mmol, 0.06 equiv), and sodium tert-butoxide (144 mg, 1.5 mmol, 2.0 equiv). The flask was purged with nitrogen three times, and toluene (7 mL) was added under nitrogen protection. The reaction was carried out in 100 °C oil bath for 7 hours, and the reaction was quenched with water and ethyl acetate after being cooled to room temperature. The organic phase was collected and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography with eluent of petroleum ether / ethyl acetate = 25-50 / 1, to give intermediate NH-102 as green foamy solid, with a yield of 571 mg, 66%. The product obtained from this step was unstable and not convenient to characterize, and was directly used in the subsequent reaction.

[0120] Synthesis of ligand L102: Into a Schlenk tube with magnetic stirring bar was added NH-102 (571 mg, 0.49 mmol, 1.0 equiv), ammonium hexafluorophosphate (161 mg, 0.99 mmol, 2.0 equiv), and triethyl orthoformate (6 mL) was added under nitrogen protection. After reaction in 75 °C oil bath for 3 h, the reaction was cooled to room temperature, the solvent was removed by distillation under reduced pressure, and the product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 2:1 ~ dichloromethane / ethyl acetate = 10:1 to give ligand L102 as a solid, 363 mg, 56% yield.

[0121] Synthesis of Pt102: Into a sealed tube with magnetic stirring bar was added L102 (363 mg, 0.28 mmol, 1.0 equiv), Pt(COD)Cl2(109 mg, 0.29 mmol, 1.05 equiv), and sodium acetate (68 mg, 0.83 mmol, 3.0 equiv), and diethyleneglycol dimethyl ether (4 mL) was added under nitrogen protection. After reaction in 120 °C oil bath for 72 h, the reaction was cooled to room temperature, quenched by water, extracted by DCM, dried by anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane (V:V = 2-4:1) to give yellow solid, 147 mg, 39% yield. HRMS [M+H]: 1358.6. + :1358.6.

[0122] Example 8: Complex Pt293

[0123] The synthetic route is as follows

[0124] Synthesis of intermediate NH-293: Into a Schlenk tube with magnetic stirring bar was added NH2-2 (536 mg, 0.89 mmol, 1.0 equiv), Cl-293 (370 mg, 0.89 mmol, 1.0 equiv), Pd2(dba)3(25 mg, 0.027 mmol, 0.03 equiv), XPhos (26 mg, 0.054 mmol, 0.06 equiv), and sodium tert-butoxide (172 mg, 1.79 mmol, 2.0 equiv). After three times of nitrogen replacement, toluene (7 mL) was added under nitrogen protection. After reaction in 100 °C oil bath for 7 h, the reaction was cooled to room temperature, extracted by water and ethyl acetate, and the organic phase was collected and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography with eluent of petroleum ether / ethyl acetate = 50:1 ~ 25:1 to give green foamy solid, 506 mg, 58% yield. The product obtained from this step was unstable and not convenient to characterize, so it was directly used in the subsequent reaction.

[0125] Synthesis of ligand L293: Into a Schlenk tube with magnetic stirring bar was added NH-293 (506 mg, 0.52 mmol, 1.0 equiv), ammonium hexafluorophosphate (169 mg, 1.04 mmol, 2.0 equiv), and the flask was purged with nitrogen three times. Into the flask was added triethyl orthoformate (6 mL) under nitrogen. After the reaction was stirred at 75 °C for 3 h, the reaction was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography using petroleum ether / dichloromethane = 2:1 to dichloromethane / ethyl acetate = 10:1 as eluent to give ligand L293 as a solid (364 mg, 62% yield).

[0126] Synthesis of Pt293: Into a sealed tube with magnetic stirring bar was added L293 (364 mg, 0.32 mmol, 1.0 equiv), Pt(COD)Cl2(126 mg, 0.34 mmol, 1.05 equiv), and sodium acetate (79 mg, 0.96 mmol, 3.0 equiv), and the flask was purged with nitrogen three times. Into the flask was added diethyleneglycol dimethyl ether (4 mL) under nitrogen, and the flask was purged with nitrogen for 30 min to remove oxygen. After the reaction was stirred at 120 °C for 72 h, the reaction was cooled to room temperature, and water was added to quench the reaction. The mixture was extracted with DCM, and the organic phase was dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and the residue was separated by silica gel column chromatography using petroleum ether / dichloromethane = 4:1 to 2:1 as eluent to give Pt293 as a yellow solid (197 mg, 52% yield). HRMS [M+H]: 1178.5. +

[0127] Example 9: Complex Pt301

[0128] The synthesis route is as follows

[0129] Synthesis of intermediate NH-301: Into a Schlenk tube with magnetic stirring bar was added NH2-301 (482 mg, 0.77 mmol, 1.0 equiv), Cl-301 (408 mg, 0.77 mmol, 1.0 equiv), Pd2(dba)3(21 mg, 0.023 mmol, 0.03 equiv), XPhos (22 mg, 0.046 mmol, 0.06 equiv), and sodium tert-butoxide (148 mg, 1.54 mmol, 2.0 equiv). The flask was purged with nitrogen three times, and toluene (7 mL) was added under nitrogen. After the reaction was stirred at 100 °C for 7 h, the reaction was cooled to room temperature, and the mixture was extracted with water and ethyl acetate. The organic phase was collected, and the solvent was removed by distillation under reduced pressure. The residue was separated by silica gel column chromatography using petroleum ether / ethyl acetate = 50:1 to 25:1 as eluent to give NH-301 as a green foamy solid (742 mg, 73% yield). The product was unstable and was used directly in the next reaction without characterization.

[0130] ​Synthesis of ligand L301 : To a Schlenk tube with magnetic stirring was added NH-301 (742 mg, 0.66 mmol, 1.0 eq), ammonium hexafluorophosphate (216 mg, 1.32 mmol, 2.0 eq), and triethyl orthoformate (6 mL) was added under nitrogen protection after three times of nitrogen exchange. After 3 hours of reaction in 75 °C oil bath, it was cooled to room temperature, the solvent was removed by distillation under reduced pressure, and the product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 2:1 ~ dichloromethane / ethyl acetate = 10:1 to obtain 532 mg of solid with a yield of 63%.

[0131] Synthesis of Pt301 : To a sealed tube with magnetic stirring was added L301 (532 mg, 0.42 mmol, 1.0 eq), Pt(COD)Cl2(164 mg, 0.44 mmol, 1.05 eq) and sodium acetate (103 mg, 1.25 mmol, 3.0 eq), and diethyleneglycol dimethyl ether (4 mL) was added under nitrogen protection after three times of nitrogen exchange. After 72 hours of reaction in 120 °C oil bath, the reaction was cooled to room temperature and quenched with water, extracted with DCM, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated by silica gel column chromatography with eluent of petroleum ether / dichloromethane = 4:1-2:1 to obtain 303 mg of yellow solid with a yield of 55%. HRMS [M+H] + : 1324.6.

[0132] Example 10: Synthesis of complex Pt42

[0133] According to the synthesis method of Example 1-Example 9, the corresponding complex was prepared by replacing the diamine and chloride with the corresponding fragments, yellow solid 332 mg, yield 35%. HRMS [M+H] + : 1489.7.

[0134] Example 11 : Synthesis of complex Pt71

[0135] According to the synthesis method of Example 1-Example 9, the corresponding complex was prepared by replacing the diamine and chloride with the corresponding fragments, yellow solid 550 mg, yield 42%. HRMS [M+H] + : 1402.5.

[0136] Example 12: Synthesis of complex Pt93

[0137] According to the synthesis method of Example 1-Example 9, the corresponding complex was prepared by replacing the diamine and chloride with the corresponding fragments, yellow solid 183 mg, yield 39%. HRMS [M+H] + : 1459.6.

[0138] Example 13: Synthesis of complex Pt142

[0139] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of example 1 - example 9, yellow solid 258 mg, yield 60%. HRMS [M+H] + : 1425.5.

[0140] Example 14: Synthesis of complex Pt175

[0141] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of example 1 - example 9, yellow solid 177 mg, yield 48%. HRMS [M+H] + : 1402.5.

[0142] Example 15: Synthesis of complex Pt193

[0143] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of example 1 - example 9, yellow solid 330 mg, yield 55%. HRMS [M+H] + : 1329.5.

[0144] Example 16: Synthesis of complex Pt235

[0145] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of example 1 - example 9, yellow solid 352 mg, yield 52%. HRMS [M+H] + : 1464.7.

[0146] Example 17: Synthesis of complex Pt343

[0147] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of example 1 - example 9, yellow solid 378 mg, yield 42%. HRMS [M+H] + : 1319.6.

[0148] Example 18: Synthesis of complex Pt350

[0149] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of example 1 - example 9, yellow solid 309 mg, yield 41%. HRMS [M+H] + : 1134.3.

[0150] Example 19: Synthesis of complex P352

[0151] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride with the corresponding fragments, yellow solid 333 mg, 37% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1166.4 Found: 1166.4. + : 1166.4.

[0152] Example 20: Synthesis of complex Pt357

[0153] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride with the corresponding fragments, yellow solid 430 mg, 67% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1280.4 Found: 1280.4. + : 1280.4.

[0154] Example 21 : Synthesis of complex Pt358

[0155] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride with the corresponding fragments, yellow solid 419 mg, 41% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1282.4 Found: 1282.4. + : 1282.4.

[0156] Example 22: Synthesis of complex Pt363

[0157] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride with the corresponding fragments, yellow solid 271 mg, 37% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1274.3 Found: 1274.3. + : 1274.3.

[0158] Example 23: Synthesis of complex Pt364

[0159] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride with the corresponding fragments, yellow solid 382 mg, 43% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1348.4 Found: 1348.4. + : 1348.4.

[0160] Example 24: Synthesis of complex Pt368

[0161] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride with the corresponding fragments, yellow solid 198 mg, 32% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1461.5 Found: 1461.5. + : 1461.5.

[0162] Example 25: Synthesis of complex Pt371

[0163] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 460 mg, 51% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1438.5 Found: 1438.5. + : 1438.5.

[0164] Example 26: Synthesis of complex Pt372

[0165] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 247 mg, 43% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1446.5 Found: 1446.5. + : 1446.5.

[0166] Example 27: Synthesis of complex Pt378

[0167] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 278 mg, 40% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1338.5 Found: 1338.5. + : 1338.5.

[0168] Example 28: Synthesis of complex Pt380

[0169] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 431 mg, 52% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1474.6 Found: 1474.6. + : 1474.6.

[0170] Example 29: Synthesis of complex P382

[0171] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 382 mg, 39% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1531.6 Found: 1531.6. + : 1531.6.

[0172] Example 30: Synthesis of complex Pt388

[0173] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 410 mg, 44% yield. HRMS [M+H] Calcd for C64H76N8P2Pt 1527.6 Found: 1527.6. + : 1527.6.

[0174] Example 31: Synthesis of complex Pt393

[0175] The corresponding complex was prepared following the synthetic procedure of Example 1 - Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 431 mg, 40% yield. HRMS [M+H]+ :1377.4.

[0176] Example 32: Synthesis of complex Pt394

[0177] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of Example 1 - Example 9, yellow solid 283 mg, 43% yield. HRMS [M+H] + :1473.6.

[0178] Example 33: Synthesis of complex Pt398

[0179] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of Example 1 - Example 9, yellow solid 280 mg, 46% yield. HRMS [M+H] + :1320.4.

[0180] Example 34: Synthesis of complex Pt402

[0181] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of Example 1 - Example 9, yellow solid 271 mg, 43% yield. HRMS [M+H] + :1377.5.

[0182] Example 35: Synthesis of complex Pt403

[0183] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of Example 1 - Example 9, yellow solid 349 mg, 50% yield. HRMS [M+H] + :1342.5.

[0184] Example 36: Synthesis of complex Pt404

[0185] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of Example 1 - Example 9, yellow solid 267 mg, 49% yield. HRMS [M+H] + :1254.4.

[0186] Example 37: Synthesis of complex Pt405

[0187] The corresponding complex was prepared by replacing the diamine and chloride by the corresponding fragments following the synthesis method of Example 1 - Example 9, yellow solid 199 mg, 32% yield. HRMS [M+H] + :1288.5.

[0188] Example 38: Synthesis of complex Pt406

[0189] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 280 mg, 47% yield. HRMS [M+H] + : 1361.5.

[0190] Example 39: Synthesis of complex P407

[0191] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 302 mg, 32% yield. HRMS [M+H] + : 1342.4.

[0192] Example 40: Synthesis of complex Pt408

[0193] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 384 mg, 47% yield. HRMS [M+H] + : 1353.5.

[0194] Example 31 : Synthesis of complex Pt409

[0195] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 265 mg, 39% yield. HRMS [M+H] + : 1439.5.

[0196] Example 32: Synthesis of complex Pt410

[0197] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 238 mg, 36% yield. HRMS [M+H] + : 1260.4.

[0198] Example 33: Synthesis of complex Pt411

[0199] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 318 mg, 48% yield. HRMS [M+H] + : 1290.4.

[0200] Example 34: Synthesis of complex Pt412

[0201] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 274 mg, 46% yield. HRMS [M+H] : 1434.6. + : 1434.6.

[0202] Example 35: Synthesis of complex Pt413

[0203] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 310 mg, 51% yield. HRMS [M+H] : 1728.6. + : 1728.6.

[0204] Example 36: Synthesis of complex Pt414

[0205] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 321 mg, 46% yield. HRMS [M+H] : 1339.4. + : 1339.4.

[0206] Example 37: Synthesis of complex Pt415

[0207] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 223 mg, 45% yield. HRMS [M+H] : 1387.5. + : 1387.5.

[0208] Example 48: Synthesis of complex Pt416

[0209] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 230 mg, 51% yield. HRMS [M+H] : 1322.4. + : 1322.4.

[0210] Example 49: Synthesis of complex P417

[0211] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 323 mg, 62% yield. HRMS [M+H] : 1386.4. + : 1386.4.

[0212] Example 50: Synthesis of complex Pt418

[0213] The corresponding complex was prepared following the synthetic procedure of Example 1-Example 9, replacing the diamine and chloride by the corresponding fragments, yellow solid 430 mg, 67% yield. HRMS [M+H] : 1386.4.+ :1368.5.

[0214] Example 51: Synthesis of complex P419

[0215] Referring to the synthesis method of Example 1-Example 9, the diamine and chloride are replaced with the corresponding fragments to prepare the corresponding complex, yellow solid 149 mg, yield 54%. HRMS [M+H] + :1490.5.

[0216] Example 52: Synthesis of complex Pt420

[0217] Referring to the synthesis method of Example 1-Example 9, the diamine and chloride are replaced with the corresponding fragments to prepare the corresponding complex, yellow solid 118 mg, yield 43%. HRMS [M+H] + :1446.5.

[0218] Theoretical calculation description

[0219] The geometry of the ground state (S0) molecule was optimized using density functional theory (DFT). DFT calculations were performed using the B3LYP functional, with 6-31G(d) basis sets for C, H, O, and N atoms and LANL2DZ basis sets for Pt atoms. Figure 1 is a diagram of the HOMO and LUMO orbital distribution of some complexes Pt1-Pt3 of the application.

[0220] As can be seen from Figure 1, the three complexes have similar mother nuclei, and their HOMO and LUMO distribution is similar. These calculation results show that the introduction of different substituents in the key structure can effectively change the frontier molecular orbitals of the Pt(II) complex, and can regulate the luminescence performance and corresponding optical properties of the Pt(II) complex. The large steric hindrance of the carbazole substituent part in the Pt(II) complex does not contribute to the frontier orbitals, and does not have a significant impact on the luminescence color, which can effectively inhibit the stacking between molecules, and is beneficial to the improvement of device performance.

[0221] Optical properties:

[0222] Table 1. Optical property data of some metal complexes in dichloromethane solution

[0223] Figure 2 is a room temperature emission spectrum of platinum complex Pt1 in dichloromethane solution; Figure 3 is a room temperature emission spectrum of platinum complex Pt2 in dichloromethane solution; Figure 4 is a room temperature emission spectrum of platinum complex Pt3 in dichloromethane solution; from Figures 2-4 and Table 1 above, by introducing donor structures with greater steric hindrance, the influence of such substituents on the photophysical properties of the complexes is studied, it is found that the complexes Pt1-Pt3 all exhibit blue light emission, different substituents have certain influence on the photophysical properties, Pt3 containing a superior donor not only has the smallest maximum emission wavelength, the light emission color is bluer, and its half-peak width is only 21 nm, which makes the color purity of the prepared device also higher.

[0224] Manufacture of OLED device:

[0225] As a reference preparation mode of a device embodiment, the present application evaporates p-doped material on the surface of ITO glass or anode with a size of 2 mm x 2 mm or co-evaporates p-doped material with a concentration of 1% to 50% with hole injection material to form a 5-100 nm hole injection layer (HIL), a 5-200 nm hole transport layer (HTL), then forms a 10-100 nm light emitting layer (EML) (which can contain the compound described in the present application) on the hole transport layer, forms a 20-200 nm electron transport layer (ETL) and a 50-200 nm cathode; if necessary, an electron blocking layer (EBL) is added between the HTL and the EML layer, and an electron injection layer (EIL) is added between the ETL and the cathode, thereby manufacturing an OLED device. The device materials involved in the present application can be obtained by known synthesis methods if not specially mentioned.

[0226] In a preferred embodiment, the structure of device example 1 provided by the present application is: ITO / P-4 (10 nm) / NPD (60 nm) / HTH-85 (5 nm) / platinum (II) complex: HTH-85: ETH-45 (25 nm) (mass ratio of Pt1: HTH-85: ETH-45 is 10:60:30) / ETH-5 (5 nm) / ET110: LiQ (40 nm, 50:50) / LiQ (1 nm) / Yb (100 nm).

[0227] Device examples 2-device examples 52 and comparative example 1 are prepared by using similar structures as device example 1, the only difference is that the platinum (II) complexes in Table 2 are used to replace Pt-1 in device example 1. The light emission properties of the above-prepared comparative examples and device examples are tested by standard methods, and the data is shown in Table 2. The device structure formula is as follows: wherein P-4 is HATCN.

[0228] Table 2. Device light emitting characteristics data table

[0229] As can be seen from Table 2, compared with Comparative Example 1, the device examples 1-52 prepared by the present application all exhibit good device performance in driving voltage, current efficiency and device lifetime, and in addition, the color purity of the device is also greatly improved. The performance improvement of each device example is based on the specific compound material of the present application having a small emission shoulder peak, while having better electron transport ability. It can be seen that, as a light emitting layer material, it has higher current efficiency, device lifetime and color purity while reducing the driving voltage. It shows that the compound provided by the present application has certain commercial application value. In addition, the devices prepared by the present application are all deep blue light devices.

[0230] In a preferred embodiment, the structure of Comparative Example 2 provided by the present application is: ITO / P-4(10nm) / NPD(60nm) / HTH-85(5nm) / platinum(II) complex:boron-containing compound:HTH-85:ETH-45(25nm)(mass ratio of R1:BN1-8:HTH-85:ETH-45 is 10:1:59:30) / ETH-5(5nm) / ET110:LiQ(40nm,50:50) / LiQ(1nm) / Yb(100nm).

[0231] Device examples 53-60 and Comparative Example 2 are prepared using a structure similar to Comparative Example 2, the only difference being that the compounds listed in Table 3 are used to replace the platinum(II) complex:boron-containing compound in Comparative Example 2. The device structure and light emitting characteristics data are shown in Table 4.

[0232] Table 3. Device structure and light emitting characteristics data table

[0233] As can be seen from Table 3, the compounds of the present application are used as sensitizing materials, together with boron-containing compounds as light emitting materials applied to the device, and the performance of each device is also significantly improved. Further indicating that the compound provided by the present application has certain commercial application value. The sensitized device structure after adding the boron-containing compound can further reduce the CIEy value, thereby improving the color purity of the device light emission.

[0234] The applicant declares that the above description is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and those skilled in the art should understand that any changes or replacements within the technical scope disclosed by the present application can be easily thought of by those skilled in the art, and all fall within the protection scope and disclosure range of the present application.

Claims

1. A tetra dentate platinum (II) complex characterized in that, The tetradentate platinum (II) complex has the following structure of formula (I): wherein R 1 -R 9 each independently represents mono-, di-, tri-, tetra- or non-substitution; R 1 -R 9 each independently represents any of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted amino, substituted or unsubstituted C1-C30 silyl, substituted or unsubstituted C1-C30 heterosilyl; R a , R b are each independently selected from the group consisting of hydrogen, C1–C3alkyl; said L is a single bond or a substituted or unsubstituted C6–C30aryl, and when L is a single bond, R a may be linked to form a ring with R b .

2. The tetradentate platinum (II) complex according to claim 1, characterized in that, The tetradentate platinum (II) complex has a structure according to either of formula (I-i) or formula (I-ii): wherein: R 1 -R 9 substituted as in claim 1 ; R 10 denotes mono-, di-, tri-, tetra- or unsubstituted, R 10 each occurrence is independently selected from the group consisting of hydrogen, deuterium, C1–C30alkyl.

3. The tetradentate platinum (II) complex according to any one of claims 1 or 2, characterized in that, R 1 each occurrence is independently selected from hydrogen, deuterium, halogen, -CN, C1–C24alkyl, C1–C24haloalkyl, C1–C24deuteroalkyl, substituted or unsubstituted C1–C24heteroalkyl, C3–C24cycloalkyl, substituted or unsubstituted C1–C24heterocycloalkyl, substituted or unsubstituted C1–C24silyl, substituted or unsubstituted C6–C30aryl, amino.

4. The tetradentate platinum (II) complex according to any one of claims 1 or 2, characterized in that, R 2 each occurrence is independently selected from hydrogen, deuterium, -CN, halogen, C1–C24alkyl, C1–C24haloalkyl, C3–C24cycloalkyl, C3–C24heterocycloalkyl, substituted or unsubstituted C1–C24alkoxy, substituted or unsubstituted C1–C30alkylthio, C1–C24aryloxy, substituted or unsubstituted C1–C30silyl, substituted or unsubstituted C6–C30aryl, substituted or unsubstituted C3–C30heteroaryl.

5. The tetradentate platinum (II) complex according to any one of claims 1 or 2, characterized in that, R 3 , R 4 each occurrence is independently selected from hydrogen, deuterium, C1–C24alkyl, C1–C24deuterated alkyl, C3–C24heterocycloalkyl, substituted or unsubstituted C1–C30siloxanyl, substituted or unsubstituted C6–C30aryl.

6. The tetradentate platinum (II) complex according to any one of claims 1 or 2, characterized in that, R 5 each occurrence is independently selected from hydrogen, deuterium, Ci-6alkyl, C2-6alkenyl, C2-6alkynyl, C3-6cycloalkyl, haloalkyl, hydro alkyl of C1-C24, deuterated alkyl of C1-C24, cycloalkyl of C3-C24, substituted or unsubstituted alkoxy of C1-C24, aryloxy of C1-C24, substituted or unsubstituted silyl of C1-C24, substituted or unsubstituted aryl of C6-C30.

7. The tetradentate platinum (II) complex according to any one of claims 1 or 2, characterized in that, R 6 each occurrence is independently selected from hydrogen, C1-C24alkyl, C6-C30aryl; R 7 , R 8 each occurrence is independently selected from hydrogen, deuterium, C1-C24alkyl, C1-C24deuterated alkyl, C3-C24cycloalkyl, substituted or unsubstituted C1-C24alkoxy, substituted or unsubstituted C1-C24silyl, C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl.

8. The tetradentate platinum (II) complex according to any one of claims 1 or 2, characterized in that, R 9 each occurrence is independently selected from hydrogen, deuterium, -CN, halogen, C1–C24alkyl, C1–C24deuterated alkyl, C1–C24halogenated alkyl, C1–C24alkoxy, C3–C24cycloalkyl, substituted or unsubstituted C3–C30heteroaryl, aminyl, silyl, arylsiloxy, heteroarylsilyl; R 10 each occurrence is independently selected from hydrogen, deuterium, C1–C3alkyl.

9. The tetradentate platinum (II) complex according to any one of claims 1 or 2, characterized in that, The tetradentate platinum (II) complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

10. Use of the tetradentate platinum (II) complex according to any one of claims 1-9 for the preparation of an electronic device.

11. Use according to claim 10, characterized in that, The electronic device includes an organic electroluminescence device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell, and an organic laser diode.

12. An organic electroluminescent device, characterized by The organic electroluminescence device includes a cathode, an anode, and an organic functional layer between the two; the organic functional layer contains the tetradentate platinum (II) complex according to any one of claims 1-9.

13. The organic electroluminescent device according to claim 12, characterized in that The organic functional layer contains a light-emitting layer, and the light-emitting layer contains the tetradentate platinum (II) complex according to any one of claims 1-9.

14. The organic electroluminescent device according to claim 13, characterized in that, The light-emitting layer further contains a fluorescent dopant material.

15. An organic optoelectronic device, characterized in that The organic optoelectronic device includes a substrate layer, a first electrode on the substrate, an organic light-emitting functional layer on the first electrode, and a second electrode on the organic light-emitting functional layer; the organic light-emitting functional layer contains the tetradentate platinum (II) complex according to any one of claims 1-9.

16. The organic optoelectronic device of claim 15, wherein, The organic light-emitting functional layer further contains a fluorescent dopant material.

17. A composition characterized in that, The composition contains the tetradentate platinum (II) complex according to any one of claims 1-9.

18. A formulation characterized in that, The preparation contains the tetradentate platinum (II) complex according to any one of claims 1-9.

19. A display or illumination device, characterized in that The device contains one or more of the organic electroluminescence devices according to any one of claims 12-14.

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