Tetradentate cyclometalated platinum (II) complex guest phosphorescent material with spirobifluorene structure, electronic device, device and application of tetradentate cyclometalated platinum (II) complex guest phosphorescent material

Abstract

The invention belongs to the technical field of organic electroluminescence preparation, and particularly relates to a tetradentate cyclometalated platinum (II) complex guest phosphorescent material with a spirobifluorene structure, an electronic device, a device and application of the tetradentate cyclometalated platinum (II) complex guest phosphorescent material. According to the invention, a spirobifluorene structure is introduced to N-heterocyclic carbene, so that the molecule has a rigid three-dimensional structure, spirobifluorene and benzo-N-heterocyclic carbene form intramolecular pi-pi interaction, the molecular structure is stabilized, and the molecular rigidity is further enhanced. Further, the structural deformation between the ground state and the excited state is inhibited, the acromion is reduced, the spectrum is narrowed, and the luminescent color purity of the material is improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic electroluminescence preparation, and particularly relates to a tetradentate cyclometalated platinum (II) complex guest phosphorescent material with a spirobifluorene structure, an electronic device, an apparatus and application thereof. BACKGROUND

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

[0003] The core of OLED development is the design and development of light-emitting materials. In early OLED devices, the light-emitting material was mainly organic small molecule fluorescent material. However, spin statistics quantum mechanics shows that in the case of electroluminescence, the singlet exciton and triplet exciton are 25% and 75%, respectively, and because traditional fluorescent materials can only utilize singlet excitons, the maximum theoretical internal quantum efficiency is only 25%, and the remaining 75% of triplet excitons are lost through non-radiative transition. In 1998, Professor Forrest of Princeton University and Professor Thompson of the University of Southern California discovered the phenomenon of phosphorescent electroluminescence of heavy metal organic complex molecules at room temperature. Due to the strong spin-orbital coupling of heavy metal atoms, excitons can more easily undergo intersystem crossing (ISC) from singlet to triplet, so that OLED devices can fully utilize all singlet and triplet excitons generated by electrical excitation, and the theoretical internal quantum efficiency of light-emitting materials can reach 100%.

[0004] In the OLED devices currently applied, the light-emitting layer almost all uses a host-guest light-emitting system mechanism, that is, a guest light-emitting material is doped in a host material, the energy system of the host material is generally greater than that of the guest light-emitting material, 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), Pd (II) and the like. The preparation cost of the platinum (II) complex phosphorescent material is much lower than that of the iridium (III) complex phosphorescent material, and has a very high cost advantage. However, there are still some technical difficulties in the development of platinum complex materials and devices at present, such as how to improve the chemical stability and thermal stability of the material, avoid red shift or light-emitting quenching caused by molecular aggregation, and further improve the device operation life and color purity and the like. Therefore, it is urgent to develop a new type of phosphorescent metal platinum (II) complex. SUMMARY

[0005] The present application aims to provide a tetradentate ring metal platinum (II) complex guest phosphorescent material with a spirobifluorene structure, an electronic device, an apparatus and application thereof. The present application introduces a 1' substituted 9,9'-spirobifluorene structure on the nitrogen atom of the carbazole to make the molecule have a rigid three-dimensional (3D) structure, the spirofluorene and the benzocarbazole form intramolecular charge interaction, stabilize the molecular structure, further inhibit the structural deformation between the ground state and the excited state, reduce the shoulder peak and narrow the spectrum, and improve the color purity of the material. The organic electroluminescent device prepared by using the compound of the present application as the light-emitting layer has obvious improvement in current efficiency and color purity, and has great application prospect in the field of OLED display and lighting.

[0006] The purpose of the present application is achieved by the following technical solutions:

[0007] In many embodiments, the present application provides a tetradentate ring metal platinum (II) complex with a spirobifluorene structure, which has a structure shown in formula (I):

[0008]

[0009] In formula (I), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 each independently represents N or CR; R a , R b , R c , R d , R e , R f , R g , R h , R ieach independently represents mono-substitution to the maximum amount of substitution, or no substitution;

[0010] R, R a -R i each independently is selected from any one or more of: hydrogen, deuterium, halogen, CN, C1–C30alkyl, substituted or unsubstituted C3–C30cycloalkyl, substituted or unsubstituted C3–C14heterocycloalkyl, C1–C30alkoxy, substituted or unsubstituted C6–C60aryl, substituted or unsubstituted C5–C60heteroaryl, C6–C60diarylamine, C6–C60arylsilyl; when containing a heteroatom, the heteroatom is selected from N, O, S, Si; when R, R a -R i when containing substitution, the substitution is each independently selected from one or more of deuterium, halogen, -CN, C1–C12alkyl, C6–C18aryl, C5–C18heteroaryl; two adjacent substituents can form a fused ring structure.

[0011] Preferably, the hydrogen atoms in formula (I) can be partially or fully replaced by deuterium.

[0012] Preferably, in formula (I), X 1 , X 2 , X 3 , X 4 , X 5 , X 6 optionally one is selected from N, and the rest are each selected from CR; or X 1 , X 2 , X 3 , X 4 optionally one is selected from N, and the rest are each selected from CR; or X 5 , X 6 optionally one is selected from N, and the rest are each selected from CR; or X a each occurrence of R is independently selected from hydrogen, deuterium, -CN, C1–C10alkyl, C3–C12cycloalkyl, C6–C30aryl. More preferably, each occurrence of R is independently selected from hydrogen, deuterium, -CN, methyl, ethyl, isopropyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, azetidinyl, azetidinyl, azetidinyl, phenyl.

[0013] Preferably, in formula (I), R a -R eEach of the following is independently selected from one or more of hydrogen, deuterium, F, -CN, C1–C14 alkyl, substituted or unsubstituted C3–C14 cycloalkyl, substituted or unsubstituted C3–C14 heterocycloalkyl, C1–C14 alkoxy, substituted or unsubstituted C6–C30 aryl, substituted or unsubstituted C5–C30 heteroaryl, C6–C30 diarylamino, and C6–C30 arylsilyl; when substituted, each of the substituted is independently selected from one or more of deuterium, F, -CN, C1–C10 alkyl, C3–C12 cycloalkyl, and C6–C18 aryl.

[0014] Preferably, in formula (I), R f R g R h R i Each of the following is selected, either identically or differently, from hydrogen, deuterium, F, -CN, C1–C14 alkyl, substituted or unsubstituted C3–C14 cycloalkyl, substituted or unsubstituted C3–C14 heterocycloalkyl, substituted or unsubstituted C6–C30 aryl, and substituted or unsubstituted C5–C30 heteroaryl; when substituted, each substituted is independently selected from deuterium, F, -CN, C1–C10 alkyl, and C6–C18 aryl. More preferably, R f R g Whether they are the same or different, R h R i They are the same or different.

[0015] Preferably, R, R a -R i Each is independently selected from hydrogen, deuterium, CD3, F, CF3, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isohexyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, cyclobutyl, cyclopentyl, cyclo Hexyl, adamantyl, azircyclobutyl, azircyclopentyl, azircyclohexyl, phenyl, biphenyl, naphthyl, phenanthryl, tetrahydronaphthyl, pyridyl, dimethylfluorenyl, benzofuranyl, benzothiopheneyl, dibenzofuranyl, dibenzothiopheneyl, carbazolyl, N-phenylcarbazolyl, diisopropylamino, trimethylsilyl, triphenylsilyl, spirofluorenyl; the above substituents may be further substituted by deuterium, F, methyl, ethyl, propyl, tert-butyl, or phenyl.

[0016] In many embodiments, the platinum(II) complex guest phosphorescent material is selected from any of the following chemical structures: where "D" represents deuterium:

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] In many embodiments, the present invention also provides the use of tetradentate ring platinum (II) complexes having the structure shown in formula (I) above in the fabrication of electronic devices.

[0025] Furthermore, the electronic device includes one or more of the following: organic electroluminescent device, organic optoelectronic device, organic integrated circuit, organic field-effect transistor, organic thin-film transistor, organic light-emitting transistor, organic solar cell, organic optical detector, organic photoreceptor, organic field quenching device, luminescent electrochemical cell, or organic laser diode.

[0026] In many embodiments, the present invention provides an organic electroluminescent device comprising: a cathode, an anode, and an organic functional layer therebetween, the organic functional layer comprising a light-emitting layer comprising a tetradentate ring platinum(II) complex having the structure shown in formula (I) above.

[0027] Preferably, the organic functional layer further comprises a fluorescent dopant material; the fluorescent dopant material is preferably a boron-containing organic luminescent material, and more preferably a boron-containing compound.

[0028] In many embodiments, the present invention 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; and a second electrode on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises a tetradentate cyclic platinum(II) complex having the structure shown in formula (I) above. For example, the tetradentate cyclic platinum(II) complex can be included as a light-emitting material in the organic light-emitting functional layer.

[0029] Furthermore, the organic light-emitting functional layer also contains any one or more fluorescent doping materials, wherein the fluorescent doping material is preferably a boron-containing organic luminescent material, and more preferably a phosphorescently sensitizable boron-containing compound.

[0030] In this invention, organic optoelectronic devices can be fabricated by depositing metals or conductive oxides and their alloys onto a substrate using methods such as sputtering, electron beam evaporation, and vacuum deposition to form the anode. A hole injection layer, hole transport layer, light-emitting layer, air-blocking layer, and electron transport layer are then sequentially deposited onto the surface of the anode, followed by the deposition of the cathode. Alternatively, organic electroluminescent devices can be fabricated by depositing the cathode, organic functional layer, and anode onto a substrate in that order. The organic functional layer can include a multilayer structure comprising a hole injection layer, a hole transport layer, a light-emitting layer, a hole-blocking layer, and an electron transport layer. In this invention, the organic functional layer is prepared using polymer materials via solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing, or thermal imaging, etc.) instead of evaporation methods, which can reduce the number of device layers.

[0031] The present invention also provides a composition comprising a tetradentate cyclic platinum(II) complex having the structure shown in formula (I) above. Preferably, the composition further comprises a fluorescent dopant material, which is preferably a boron-containing organic luminescent material, and more preferably a phosphorescently sensitizable boron-containing compound.

[0032] The present invention also provides a formulation comprising a tetradentate cyclic platinum(II) complex having the structure shown in formula (I) as described above and at least one solvent. The solvent is not particularly limited and may be any solvent well known to those skilled in the art.

[0033] The present invention also provides a display or lighting device comprising one or more of the organic electroluminescent devices or organic optoelectronic devices as described above.

[0034] Preferably, the organic electroluminescent device of the present invention is any one of organic photovoltaic devices, organic light-emitting devices (OLEDs), organic solar cells (OSCs), electronic paper (e-paper), organic photosensitive materials (OPCs), organic thin-film transistors (OTFTs), organic memory elements, lighting and display devices.

[0035] The materials used in the organic electroluminescent devices according to the present invention can be classified as top-emitting, low-emitting, or bifacial-emitting.

[0036] The compounds of the organic electroluminescent devices according to embodiments of the present invention can be applied to electroluminescent devices such as organic solar cells, lighting OLEDs, flexible OLEDs, organic photosensitive materials, and organic thin-film transistors, based on similar principles to those of organic light-emitting devices.

[0037] Compared with the prior art, the beneficial effects of the present invention are:

[0038] By introducing a spirofluorene structure onto a benzo[a]-a]-carbene, a novel phosphorescent molecule with a rigid three-dimensional structure was successfully constructed. The spirofluorene forms an intramolecular π-π interaction with the benzo[a]-a]-carbene, stabilizing the molecular structure and further enhancing molecular rigidity, thereby suppressing the resulting emission spectral broadening. This enhanced molecular rigidity also reduces structural deformation between the ground and excited states, further lowering the shoulder peak and improving the emission color purity of the material. Furthermore, using a phosphorus-sensitized boron-containing compound system can further improve the emission color purity of the device. Attached Figure Description

[0039] Figure 1 The results show the photophysical properties of the cyclic platinum(II) complex of the present invention in toluene solution at room temperature.

[0040] Figure 2 The quantum efficiency and excited-state lifetime of the cyclic platinum(II) complex Pt1 in PMMA are presented in this invention. Detailed Implementation

[0041] As used in this invention, the terms "optional" or "optionally" mean that the event or situation described below may or may not occur, and the description includes both the case where the event or situation occurs and the case where it does not occur.

[0042] The term "substituted" as used in this invention is intended to encompass all permissible substituents of organic compounds. In a broad sense, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For a suitable organic compound, permissible substituents may be one or more, the same or different. For the purposes of this invention, heteroatoms (e.g., nitrogen) can have hydrogen substituents and / or any permissible substituent of the organic compound described herein, satisfying the valence bond of that heteroatom. This disclosure is not intended to limit in any way to permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" imply that such substitution conforms to the permissible valence bond of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformations (e.g., by rearrangement, cyclization, elimination, etc.)). It is also expected that, in some respects, unless explicitly stated otherwise, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0043] When defining various terms, R a -R i In this invention, the general symbols are used to denote various specific substituents. These symbols can be any substituent, not limited to those disclosed in this invention, and while they may be defined as certain substituents in one case, they may be defined as other substituents in other cases.

[0044] As used in this invention, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group with 1 to 30 carbon atoms. Preferred alkyl groups are alkyl groups containing 1 to 24 carbon atoms, more preferably 1 to 9 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, semi-alkyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. It may be branched or unbranched. It may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, silyl, sulfoxo, or mercapto groups described in this invention.

[0045] Throughout this specification, "alkyl" is generally used to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to in this invention by identifying the specific substituents on the alkyl group. For example, the terms "halogenated alkyl" or "halogenated alkyl" specifically refer to an alkyl group substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "deuterated alkyl" specifically refers to an alkyl group substituted with one or more deuterium atoms. The alkyl term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, etc. When "alkyl" is used in one context and a specific term such as "alkyl alcohol" is used in another context, it does not imply that the term "alkyl" does not simultaneously refer to the specific term such as "alkyl alcohol," etc.

[0046] This practice is also applied to other groups described in this invention. That is, when a term such as "cycloalkyl" refers to both an unsubstituted and a substituted cycloalkyl portion, the substituted portion may be specifically identified separately in this invention; for example, a specifically substituted cycloalkyl may be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy may be specifically referred to as, for example, "halogenated alkoxy", and a specifically substituted alkenyl may be, for example, "enol", etc. Likewise, the practice of using the general term such as "cycloalkyl" and the specific term such as "alkylcycloalkyl" is not intended to imply that the general term does not simultaneously include the specific term.

[0047] As used in this invention, the term "cycloalkyl" refers to a non-aromatic carbon-based ring consisting of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, adamantyl, etc. The term "heterocyclic alkyl" is a class of cycloalkyl groups as defined above and is included in the meaning of the term "cycloalkyl," wherein at least one ring carbon atom is substituted by a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocyclic alkyl groups may be substituted or unsubstituted. The cycloalkyl and heterocyclic alkyl groups may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, silyl, sulfo-oxo, or mercapto groups as described in this invention.

[0048] As used in this invention, the term "aryl" refers to any carbon-based aromatic group containing 6 to 60 carbon atoms, preferably aryl groups containing 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. The carbon-based aromatic groups include, but are not limited to, phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracene, phenanthrene, etc. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom introduced into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Aryl groups may be substituted or unsubstituted. Aryl groups may be substituted with one or more groups, including, but not limited to, the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azide, nitro, silyl, sulfo-oxo, or mercapto groups described in this invention. The term "biaryl" refers to a specific type of aryl group and is included in the definition of "aryl". A biaryl group is two aryl groups that are bonded together by a fused ring structure, as in naphthalene, or two aryl groups that are linked by one or more carbon-carbon bonds, as in biphenyl.

[0049] This document discloses compounds or complexes containing platinum. The terms "compound" and "complex" are used interchangeably in this invention. Additionally, the compounds disclosed herein have a neutral charge.

[0050] The compounds disclosed herein are applicable to a wide variety of optical and electro-optic devices, including but not limited to light-absorbing devices such as solar and photosensitive devices, organic light-emitting diodes, light-emitting devices or devices capable of both light absorption and emission, and as markers for biological applications.

[0051] As stated above, the disclosed compounds are platinum complexes. Furthermore, the compounds disclosed herein can be used as host materials for OLED applications, such as full-color displays.

[0052] The compounds disclosed herein can be used in a variety of applications. As luminescent materials, these compounds can be used in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

[0053] In addition, compared with traditional materials, the compounds in this invention can improve luminous efficiency and device operating time when used in light-emitting devices (such as OLEDs).

[0054] The compounds of the present invention can be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0055] The compounds disclosed in the embodiments of the present invention are applicable to a wide variety of optical and electro-optic devices, including but not limited to light-absorbing devices such as solar cells and photosensors, organic light-emitting diodes (OLEDs), light-emitting devices or devices that have both light absorption and light emission capabilities, and markers for use in biological applications.

[0056] The compounds provided by embodiments of the present invention can be used in a light-emitting device such as an OLED, the device comprising at least one cathode, at least one anode, and at least one light-emitting layer, wherein at least one of the light-emitting layers comprises a tetradentate ring platinum(II) complex of formula (I). Specifically, the light-emitting device may comprise an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode, which are sequentially deposited. The hole transport layer, the light-emitting layer, and the electron transport layer are all organic layers, and the anode and cathode are electrically connected.

[0057] It should be noted that the general instructions above and the detailed instructions below are merely illustrative and explanatory, and are not restrictive.

[0058] This disclosure can be more readily understood by referring to the following detailed description and the embodiments contained therein.

[0059] Before disclosing and describing the compounds, devices, and / or methods of the present invention, it should be understood that they are not limited to specific synthetic methods (otherwise indicated) or specific reagents (otherwise indicated), as these are, of course, subject to variation. It should also be understood that the terminology used in this invention is for descriptive purposes only and is not intended to be limiting. While any methods and materials similar to or equivalent to those described in this invention may be used in this practice or experiment, exemplary methods and materials are described below.

[0060] Synthesis Examples

[0061] 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 have striven to ensure the accuracy of data (quantities, temperatures, etc.) mentioned in the patent, some errors may still exist. Unless otherwise specified, weighings are performed separately at 25°C or room temperature, and at near-normal pressure.

[0062] 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 patent 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 protection 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.

[0063] HPLC-MS was performed on an Agilent 6210TOF LC / MS mass spectrometer; HRMS spectra were performed on an Agilent 6210TOFLC / MS liquid chromatography-time-of-flight mass spectrometer.

[0064] Synthetic route

[0065] Example 1: The synthetic route for the tetradentate cyclic platinum(II) complex Pt1 is as follows:

[0066]

[0067] Synthesis of the intermediate chiral 1-OMe: Cl (1.2 equivalents), Cz-OMe (1.0 equivalent), Pd₂(dba)₃ (3 mol%), SPhos (12 mol%), and sodium tert-butoxide (2.0 equivalents) were added sequentially to a reaction flask. Nitrogen gas was purged three times, and toluene (25 mL) was added. The reaction mixture was stirred at 110 °C for 42 hours, and the solvent was removed by vacuum distillation. The mixture was purified by silica gel column chromatography with petroleum ether / ethyl acetate as eluent (50-10:1) to give 930 mg of 1-OMe as a yellow solid (90% yield). MS: m / z 331.18 (M+H) + .

[0068] Synthesis of the intermediate chiral 1-OH: 1-OMe (1.0 equivalent), hydrobromic acid (48%) (9 mL), and acetic acid (6 mL) were added sequentially to a reaction flask. The mixture was stirred at 120 °C for 16 hours and then cooled to room temperature. The solution was neutralized with aqueous NaHCO3, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The product 1-OH was obtained by slurrying with petroleum ether / ethyl acetate, yielding 800 mg of white solid (90% yield). MS: m / z 317.16 (M+H) + .

[0069] Synthesis of the intermediate chiral 1-Cl: 1-OH (1.0 equivalent), 1-bromo-3-tert-butyl-5-chlorobenzene (1.2 equivalent), cuprous iodide (10 mol%), 2-pyridinecarboxylic acid (20 mol%), and potassium phosphate (2.0 equivalent) were added sequentially to a reaction flask. The mixture was purged with nitrogen three times, and dimethyl sulfoxide (40 mL) was added. The reaction mixture was stirred at 100 °C for 26 hours. The mixture was diluted with water, extracted three times with ethyl acetate, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The solution was purified by silica gel column chromatography with an eluent ratio of petroleum ether / ethyl acetate of 20:1–10:1, yielding 549 mg of a white solid (81% yield). MS: m / z 427.16 (M+H) + .

[0070]

[0071]

[0072] Synthesis of intermediates (1-2): 1-1 (1.0 equivalent), NO2-NH2 (1.0 equivalent), tris(2,3-benzylacetone)-palladium (3 mol%), 4,5-bis(2,3-phenylphosphine-9,9-dimethyloxanthracene) (6 mol%), and cesium carbonate (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times, and toluene (100 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 110 °C for 35 hours, then cooled to room temperature. The mixture was extracted with ethyl acetate, washed with water, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The crude product was then slurried with petroleum ether and dichloromethane to give 9.6 g of a yellow solid, with a yield of 81%. 1 H NMR (500MHz, CDCl3): δ (ppm) 6.41 (dd, J=8.5, 1.5Hz, 1H), 6.47 (ddd, J=8.5, 7.0, 1.0Hz, 1H) ,6.68(d,J=7.5Hz,1H),6.71(d,J=7.5Hz,2H),6.92–7.01(m,3H),7.07(d,J=8.0Hz,1H),7.1 2(td,J=7.5,1.0Hz,1H),7.23(td,J=7.5,1.0Hz,2H),7.38(td,J=7.5,1.0Hz,1H),7.48(t,J =7.5Hz,1H),7.64(d,J=7.5Hz,2H),7.82(d,J=7.5Hz,1H),7.84–7.89(m,2H),8.01(s,1H).

[0073] Synthesis of intermediates (1-3): 1-2 (1.0 equivalent) and palladium on carbon (4.5 mol%) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen was then purged three times. Under nitrogen protection, ethanol (70 mL), ethyl acetate (70 mL), and toluene (20 mL) were added, followed by three purgings with hydrogen. The reaction was carried out in an oil bath at 50 °C for 20 hours under a hydrogen atmosphere. After cooling to room temperature, the mixture was filtered through a silica gel-lined sintered funnel. The solvent was removed by vacuum distillation, yielding 7.9 g of a gray solid (99% yield). 1 H NMR (500MHz, CDCl3): δ (ppm) 2.81 (s, 2H), 4.11 (s, 1H), 6.43 (d, J = 8.0Hz, 1H), 6.56–6. 64(m,3H),6.68(d,J=7.5Hz,1H),6.92(td,J=8.0,1.5Hz,1H),6.97(d,J=7.5Hz,2H),7 .11(td,J=7.5,1.0Hz,1H),7.21(td,J=7.5,1.0Hz,2H),7.26(t,J=8.0Hz,1H),7.36–7 .40(m,2H),7.42(td,J=7.5,1.0Hz,2H),7.86(d,J=7.5Hz,1H),7.89(d,J=8.0Hz,2H).

[0074] Synthesis of intermediates (1-4): 1-3 (1.0 equivalent), 1-Cl (1.05 equivalent), tris(dibenzylacetone)palladium (3 mol%), 2-(di-tert-butylphosphine)biphenyl (JohnPhos) (6 mol%), and sodium tert-butoxide (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times, and toluene (50 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100 °C for 15 hours, then cooled to room temperature. The mixture was filtered, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / dichloromethane as the eluent (1:1) to give 15 g of a gray solid, yield 94%. MS: m / z 813.36 (M+H) + .

[0075] Synthesis of ligand L1: 1-4 (1.0 equivalent) and ammonium hexafluorophosphate (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times. Under nitrogen protection, triethyl orthoformate (30 mL), dichloromethane (30 mL), and toluene (30 mL) were added. The reaction was carried out in an oil bath at 75°C for 5 hours, then cooled to room temperature. The solvent was removed by vacuum distillation, and the mixture was separated by silica gel column chromatography with dichloromethane / methanol = 200:1 as the eluent, yielding 6.7 g of a white solid (83% yield). 1H NMR (500MHz, CDCl3): δ (ppm) 1.37 (s, 9H), 6.53 (d, J = 7.5Hz, 1H), 6.56 (t, J = 8.0Hz, 2H), 6.65 (t, J = 7.5Hz, 1H), 6.72 (d, J = 8.0Hz, 1H), 6.85 (t, J = 8.0 Hz,2H),6.91(t,J=7.5Hz,1H),7.00–7.06(m,2H),7.10–7.19(m,3H),7.2 5(dd,J=8.5,2.0Hz,1H),7.28–7.31(m,2H),7.32(dd,J=5.5,2.0Hz,2H),7 .33–7.38(m,2H),7.40–7.45(m,2H),7.47(ddd,J=8.5,7.0,1.0Hz,1H),7 .58(t,J=8.0Hz,1H),7.60(d,J=7.5Hz,1H),7.62(d,J=1.0Hz,1H),7.71(d ,J=8.5Hz,1H),7.75(t,J=8.0Hz,1H),7.80(d,J=2.5Hz,1H),7.93(d,J=7. 5Hz,1H),8.13–8.18(m,2H),8.26(d,J=8.5Hz,1H),8.58(d,J=5.0Hz,1H).

[0076] Synthesis of Pt1: L1 (1.0 equivalent), (1,5-cyclooctadiene)diplatinum chloride (1.0 equivalent), and sodium acetate (3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times. Diethylene glycol dimethyl ether (220 mL) was added under nitrogen protection, and the mixture was bubbled with nitrogen for 30 min to remove oxygen. The reaction was carried out in an oil bath at 150 °C for 24 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / dichloromethane as eluent (3:1-1:1), yielding 1.9 g of a yellow solid (34% yield). 1H NMR (500MHz, CDCl3): δ (ppm) 1.05 (s, 9H), 5.74 (s, 1H), 6.03 (d, J = 8.0Hz, 1H), 6.10 (d, J = 6.0Hz, 1H), 6.31 (s, 1H), 6.33 (d, J = 7. 5Hz,1H),6.38(d,J=8.0Hz,1H),6.48(d,J=7.5Hz,1H),6.63(t,J=7.5Hz,1H),6.71(t,J=7.5Hz,1H),6.77(t,J=7.0Hz,1H),6.8 4(d,J=7.5Hz,1H),6.91(d,J=7.5Hz,1H),7.00(t,J=7.5Hz,1H),7.04–7.21(m,4H),7.23(d,J=7.5Hz,1H),7.26–7.42(m,5H),7 .61(d,J=8.0Hz,1H),7.68–7.76(m,2H),7.80(t,J=8.5Hz,2H),7.83(d,J=8.0Hz,1H),7.95–8.14(m,1H),8.87(d,J=6.0Hz,1H).

[0077] Example 2: Tetradentate ring platinum(II) complex Pt2

[0078] Complex Pt2 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final result was 138 mg of a yellow solid, with a yield of 33%. MS: m / z 1128.41 (M+H) + .

[0079] Example 3: Tetradentate ring platinum(II) complex Pt9

[0080] Complex Pt9 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final result was 118 mg of a yellow solid, with a yield of 27%. MS: m / z 1066.28 (M+H) + .

[0081] Example 4: Tetradentate ring platinum(II) complex Pt10

[0082] Complex Pt10 was prepared using the same synthetic method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 160 mg of a yellow solid, with a yield of 32%. MS: m / z 1152.27 (M+H) + .

[0083] Example 5: Tetradentate ring platinum(II) complex Pt12

[0084] Complex Pt12 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 114 mg of a yellow solid, with a yield of 32%. MS: m / z 1170.35 (M+H) + .

[0085] Example 6: Tetradentate ring platinum(II) complex Pt15

[0086] Complex Pt15 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final result was 128 mg of a yellow solid, with a yield of 33%. MS: m / z 1154.41 (M+H) + .

[0087] Example 7: Tetradentate ring platinum(II) complex Pt16

[0088] Complex Pt16 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 119 mg of a yellow solid, with a yield of 32%. MS: m / z 1182.44 (M+H) + .

[0089] Example 8: Tetradentate ring platinum(II) complex Pt17

[0090] Complex Pt17 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 125 mg of a yellow solid, with a yield of 35%. MS: m / z 1066.28 (M+H) + .

[0091] Example 9: Tetradentate ring platinum(II) complex Pt18

[0092] Complex Pt18 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 123 mg of a yellow solid, with a yield of 35%. MS: m / z 1152.27 (M+H) + .

[0093] Example 10: Tetradentate ring platinum(II) complex Pt27

[0094] Complex Pt27 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 125 mg of a yellow solid, with a yield of 29%. MS: m / z 1031.38 (M+H) + .

[0095] Example 11: Tetradentate ring platinum(II) complex Pt28

[0096] Complex Pt28 was synthesized using the same method as complex Pt1 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 115 mg of a yellow solid, with a yield of 32%. MS: m / z 1025.35 (M+H) + .

[0097] Example 12: Tetradentate ring platinum(II) complex Pt30

[0098] Complex Pt30 was prepared using the same synthetic method as complex Pt1 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 128 mg of a yellow solid, with a yield of 28%. MS: m / z 1034.40 (M+H) + .

[0099] Example 13: Tetradentate ring platinum(II) complex Pt32

[0100] Complex Pt32 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 125 mg of a yellow solid, with a yield of 36%. MS: m / z 1022.33 (M+H) + .

[0101] Example 14: Tetradentate ring platinum(II) complex Pt34

[0102] Complex Pt34 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final result was 125 mg of a yellow solid, with a yield of 32%. MS: m / z 1041.44 (M+H) + .

[0103] Example 15: Tetradentate ring platinum(II) complex Pt37

[0104] Complex Pt37 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 132 mg of a yellow solid, with a yield of 36%. MS: m / z 1036.26 (M+H)+ .

[0105] Example 16: Tetradentate ring platinum(II) complex Pt38

[0106] Complex Pt38 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 127 mg of a yellow solid, with a yield of 28%. MS: m / z 1037.25 (M+H) + .

[0107] Example 17: Tetradentate ring platinum(II) complex Pt40

[0108] Complex Pt40 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 125 mg of a yellow solid, with a yield of 32%. MS: m / z 985.22 (M+H) + .

[0109] Example 18: Tetradentate ring platinum(II) complex Pt41

[0110] Complex Pt41 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 133 mg of a yellow solid, with a yield of 33%. MS: m / z 1094.34 (M+H) + .

[0111] Example 19: Tetradentate ring platinum(II) complex Pt42

[0112] Complex Pt42 was synthesized using the same method as complex Pt1 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 105 mg of a yellow solid, with a yield of 29%. MS: m / z 1072.35 (M+H) + .

[0113] Example 20: Tetradentate ring platinum(II) complex Pt46

[0114] Complex Pt46 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 122 mg of a yellow solid, with a yield of 40%. MS: m / z 1106.30 (M+H) + .

[0115] Example 21: Tetradentate ring platinum(II) complex Pt49

[0116] Complex Pt49 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 123 mg of a yellow solid, with a yield of 31%. MS: m / z 1254.37 (M+H) + .

[0117] Example 22: Tetradentate ring platinum(II) complex Pt53

[0118] Complex Pt53 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 136 mg of a yellow solid, with a yield of 36%. MS: m / z 1030.30 (M+H) + .

[0119] Example 23: Tetradentate ring platinum(II) complex Pt54

[0120] Complex Pt54 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 126 mg of a yellow solid, with a yield of 39%. MS: m / z 1072.35 (M+H) + .

[0121] Example 24: Tetradentate ring platinum(II) complex Pt56

[0122] Complex Pt56 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 122 mg of a yellow solid, with a yield of 41%. MS: m / z 1041.29 (M+H) + .

[0123] Example 25: Tetradentate ring platinum(II) complex Pt57

[0124] Complex Pt57 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 118 mg of a yellow solid, with a yield of 30%. MS: m / z 1084.28 (M+H) + .

[0125] Example 26: Tetradentate ring platinum(II) complex Pt61

[0126] Complex Pt61 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final result was 142 mg of a yellow solid, with a yield of 29%. MS: m / z 1084.28 (M+H)+ .

[0127] Example 27: Tetradentate ring platinum(II) complex Pt62

[0128] Complex Pt62 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 138 mg of a yellow solid, with a yield of 37%. MS: m / z 1184.48 (M+H) + .

[0129] Example 28: Tetradentate ring platinum(II) complex Pt68

[0130] Complex Pt68 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 117 mg of a yellow solid, with a yield of 31%. MS: m / z 1100.38 (M+H) + .

[0131] Example 29: Tetradentate ring platinum(II) complex Pt71

[0132] Complex Pt71 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final result was 115 mg of a yellow solid, with a yield of 31%. MS: m / z 1224.41 (M+H) + .

[0133] Example 30: Tetradentate ring platinum(II) complex Pt76

[0134] Complex Pt76 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 122 mg of a yellow solid, with a yield of 37%. MS: m / z 1238.50 (M+H) + .

[0135] Example 31: Tetradentate ring platinum(II) complex Pt84

[0136] Complex Pt84 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 133 mg of a yellow solid, with a yield of 35%. MS: m / z 1340.57 (M+H) + .

[0137] Example 32: Tetradentate ring platinum(II) complex Pt86

[0138] Complex Pt86 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 122 mg of a yellow solid, with a yield of 44%. MS: m / z 1099.37 (M+H) + .

[0139] Example 33: Tetradentate ring platinum(II) complex Pt96

[0140] Complex Pt96 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 127 mg of a yellow solid, with a yield of 31%. MS: m / z 1195.37 (M+H) + .

[0141] Example 34: Tetradentate ring platinum(II) complex Pt104

[0142] Complex Pt104 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 123 mg of a yellow solid, with a yield of 27%. MS: m / z 1068.30 (M+H) + .

[0143] Example 35: Tetradentate ring platinum(II) complex Pt109

[0144] Complex Pt109 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 124 mg of a yellow solid, with a yield of 30%. MS: m / z 1311.52 (M+H) + .

[0145] Example 36: Tetradentate ring platinum(II) complex Pt111

[0146] Complex Pt111 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 123 mg of a yellow solid, with a yield of 38%. MS: m / z 1030.30 (M+H) + .

[0147] Example 37: Tetradentate ring platinum(II) complex Pt112

[0148] Complex Pt112 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 101 mg of a yellow solid, with a yield of 41%. MS: m / z 1142.43 (M+H)+ .

[0149] Example 38: Tetradentate ring platinum(II) complex Pt113

[0150] Complex Pt113 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 153 mg of a yellow solid, with a yield of 31%. MS: m / z 1058.33 (M+H) + .

[0151] Example 39: Tetradentate ring platinum(II) complex Pt131

[0152] Complex Pt131 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 101 mg of a yellow solid, with a yield of 31%. MS: m / z 1055.30 (M+H) + .

[0153] Example 40: Tetradentate ring platinum(II) complex Pt136

[0154] Complex Pt136 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 121 mg of a yellow solid, with a yield of 21%. MS: m / z 1017.29 (M+H) + .

[0155] Example 41: Tetradentate ring platinum(II) complex Pt141

[0156] Complex Pt141 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 112 mg of a yellow solid, with a yield of 27%. MS: m / z 1126.37 (M+H) + .

[0157] Example 42: Tetradentate ring platinum(II) complex Pt142

[0158] Complex Pt142 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 109 mg of a yellow solid, with a yield of 23%. MS: m / z 1237.51 (M+H) + .

[0159] Example 43: Tetradentate ring platinum(II) complex Pt143

[0160] Complex Pt143 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 126 mg of a yellow solid, with a yield of 31%. MS: m / z 1164.27 (M+H) + .

[0161] Example 44: Tetradentate ring platinum(II) complex Pt144

[0162] Complex Pt144 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 105 mg of a yellow solid, with a yield of 20%. MS: m / z 1206.44 (M+H) + .

[0163] Example 45: Tetradentate ring platinum(II) complex Pt145

[0164] Complex Pt145 was prepared using the same synthetic method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 126 mg of a yellow solid, with a yield of 31%. MS: m / z 1091.28 (M+H) + .

[0165] Example 46: Tetradentate ring platinum(II) complex Pt146

[0166] Complex Pt146 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 105 mg of a yellow solid, with a yield of 20%. MS: m / z 1295.46 (M+H) + .

[0167] Photophysical properties:

[0168] Figure 1 The results show the photophysical properties of the cyclic platinum(II) complex of the present invention in toluene solution at room temperature. Figure 2 The quantum efficiency and excited-state lifetime of the cyclic platinum(II) complex Pt1 (5% by mass) of the present invention in polymethyl methacrylate (PMMA) are presented. Figure 1 Data shows that the emission wavelength of the Pt1 platinum metal complex phosphorescent material is in the blue light emission region around 456 nm, with a small full width at half maximum (FWHM), as low as 22 nm. Its CIE (0.146, 0.182) indicates blue emission and high color purity. Figure 2 It is known that Pt1 has a quantum efficiency of up to 92% in polymethyl methacrylate (PMMA) and an excited state lifetime of 3.14 microseconds.

[0169] Fabrication of OLED devices:

[0170] An OLED device is fabricated by depositing p-doped material onto the surface or anode of an ITO glass with a light-emitting area of ​​2.5 mm × 2.5 mm, or by co-evaporating p-doped material with hole injection material at a concentration of 1% to 50% to form a 5-100 nm hole injection layer (HIL) and a 5-200 nm hole transport layer (HTL). Subsequently, a 10-100 nm light-emitting layer (EML) (which may contain the compound described in this invention) is formed on the hole transport layer, followed by 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 EML layers, and an electron injection layer (EIL) is added between the ETL and the cathode. The OLED is then tested using standard methods. Unless otherwise specified, the device materials involved in this invention can be obtained using known synthesis methods.

[0171] In a preferred embodiment, the structure of the device Example 1 provided by the present invention is: ITO / P-4 (10nm) / HT1 (60nm) / HTH-85 (5nm) / platinum (II) complex:HTH-85:ETH-45 (25nm) (Pt1:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0172] Device Examples 2-26 and Comparative Example 1 were fabricated using structures similar to those in Device Example 1, the only difference being that Pt1 in Device Example 1 was replaced with platinum(II) complexes as shown in Table 1. The luminescence properties of the comparative examples and each device example prepared above were tested using standard methods and are shown in Table 1. The device structural formulas involved are as follows: where P-4 is HATCN and ET-14 is BPyTP.

[0173]

[0174] Table 1. Luminescence properties of some compounds after fabrication into devices

[0175]

[0176]

[0177]

[0178] As shown in Table 1, compared with Comparative Example 1, Device Examples 1-29 prepared in this application exhibit excellent device performance in terms of driving voltage and current efficiency. The performance improvement of each device example is based on the high chemical stability and better electron transport capability of the specific compound material of this invention. Furthermore, all devices prepared in this invention are deep blue light devices. It is evident that using this material as a light-emitting layer material to prepare electronic devices results in higher current efficiency and color purity while reducing the driving voltage. This indicates that the compound provided by this invention has certain commercial application value.

[0179] In a preferred embodiment, the structure of device example 30 provided by the present invention is as follows: ITO / P-4 (10nm) / HT1 (60nm) / HTH-85 (5nm) / platinum (II) complex: boron-containing compound: HTH-85:ETH-45 (25nm) (Pt1:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0180] Device Examples 31-36 were fabricated using structures similar to those in Device Example 30, the only difference being that the platinum(II) complex and boron-containing compound in Device Example 30 were replaced with platinum(II) complexes and boron-containing compounds as listed in Table 2. The device structural formulas are as follows, and the device structure and luminescence characteristic data are shown in Table 2.

[0181]

[0182] Table 2. Device Structure and Luminescent Properties Data

[0183]

[0184]

[0185] As shown in Table 2, when the compounds of this invention are used as sensitizing materials, together with boron-containing compounds as luminescent materials in devices, the performance of each device is significantly improved. This further demonstrates that the compounds provided by this invention have certain commercial application value. Adding boron-containing compounds to sensitize the device structure can further reduce the CIEy value, thereby improving the purity of the emitted color.

[0186] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A tetradentate ring platinum(II) complex having a spirodifluorene structure, characterized in that, It has the structure shown in equation (I): In formula (I), X 1 X 2 X 3 X 4 X 5 X 6 Each can be represented independently as N or CR; R a R b R c R d R e R f R g R h R i Each can be used independently to represent single substitution to the maximum amount of substitution, or no substitution. R, R a -R i Each is independently selected from any one or more of the following: hydrogen, deuterium, halogen, CN, C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, substituted or unsubstituted C3–C14 heterocycloalkyl, C1–C30 alkoxy, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C5–C60 heteroaryl, C6–C60 diarylamino, and C6–C60 arylsilyl; when containing heteroatoms, the heteroatoms are selected from N, O, S, and Si; when R, R a -R i When substituted, each substituted group is independently selected from one or more of deuterium, halogen, -CN, C1–C12 alkyl, C6–C18 aryl, and C5–C18 heteroaryl; two adjacent substituents may form a fused ring structure.

2. The tetradentate ring platinum(II) complex according to claim 1, characterized in that, In formula (I) R a -R e Each is independently selected from any one or more of hydrogen, deuterium, F, -CN, C1–C14 alkyl, substituted or unsubstituted C3–C14 cycloalkyl, substituted or unsubstituted C3–C14 heterocycloalkyl, C1–C14 alkoxy, substituted or unsubstituted C6–C30 aryl, substituted or unsubstituted C5–C30 heteroaryl, C6–C30 diarylamino, and C6–C30 arylsilyl; when R a -R e When substituted, each substituted substance is independently selected from one or more of deuterium, F, -CN, C1–C10 alkyl, C3–C12 cycloalkyl, and C6–C18 aryl; R f R g R h R i Each is selected, either identically or differently, from hydrogen, deuterium, F, -CN, C1–C14 alkyl, substituted or unsubstituted C3–C14 cycloalkyl, substituted or unsubstituted C3–C14 heterocycloalkyl, substituted or unsubstituted C6–C30 aryl, and substituted or unsubstituted C5–C30 heteroaryl; when R f R g R h R i When substituted, each substituted element is independently selected from one or more of deuterium, F, -CN, C1–C10 alkyl, and C6–C18 aryl.

3. The tetradentate ring platinum(II) complex according to claim 1, characterized in that, R, R a -R i Each is independently selected from hydrogen, deuterium, CD3, F, CF3, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isohexyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, cyclobutyl, cyclopentyl, cyclo Hexyl, adamantyl, azircyclobutyl, azircyclopentyl, azircyclohexyl, phenyl, biphenyl, naphthyl, phenanthryl, tetrahydronaphthyl, pyridyl, dimethylfluorenyl, benzofuranyl, benzothiopheneyl, dibenzofuranyl, dibenzothiopheneyl, carbazolyl, N-phenylcarbazolyl, diisopropylamino, trimethylsilyl, triphenylsilyl, spirofluorenyl; the above substituents may be further substituted by deuterium, F, methyl, ethyl, propyl, tert-butyl, or phenyl.

4. The tetradentate ring platinum(II) complex according to claim 1, characterized in that, It is selected from any of the chemical structures shown below, where "D" represents deuterium:

5. The use of the tetradentate ring platinum(II) complex according to any one of claims 1-4 in the preparation of electronic devices.

6. The application according to claim 4, characterized in that, The electronic devices include one or more of the following: organic electroluminescent devices, organic optoelectronic devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photosensors, organic field quenching devices, luminescent electrochemical cells, or organic laser diodes.

7. An organic electroluminescent device, characterized in that, The organic electroluminescent device comprises a cathode, an anode, and an organic functional layer between the two; the organic functional layer further comprises a light-emitting layer, wherein the light-emitting layer contains the tetradentate ring platinum(II) complex according to any one of claims 1-4.

8. The organic electroluminescent device according to claim 7, characterized in that, The light-emitting layer also contains a fluorescent dopant material, which is a boron-containing compound.

9. An organic optoelectronic device, characterized in that, The organic optoelectronic device comprises: 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; wherein the organic light-emitting functional layer comprises the tetradentate ring platinum(II) complex according to any one of claims 1-4.

10. A composition, characterized in that, The composition comprises the tetradentate cyclic platinum(II) complex according to any one of claims 1-4.

11. A formulation, characterized in that, The formulation comprises the tetradentate cyclic platinum(II) complex according to any one of claims 1-4.

12. A display or lighting device, characterized in that, The device comprises one or more of the organic electroluminescent device of claim 7 or the organic optoelectronic device of claim 9.

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