Tetradentate cyclometalated platinum (II) complex guest phosphorescent material with substituted phenyl 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 narrow-band tetradentate platinum (II) complex guest phosphorescent material with a substituted phenyl structure, an electronic device, a device and application of the narrow-band tetradentate platinum (II) complex guest phosphorescent material. A large-steric-hindrance group is introduced to the ortho-position of N-heterocyclic carbene substituted phenyl, so that steric hindrance is increased, molecular resonance is reduced, and red shift or luminescence quenching caused by molecular aggregation can be avoided; the photophysical properties of the material can be regulated and controlled by regulating the peripheral substituted functional groups of the ligands, so that fine regulation and control of light-emitting colors are realized; the chemical stability and the thermal stability can be improved by deuteration on the periphery of the ring metal ligand, and an evaporation type OLED device is easy to prepare. The current efficiency and the service life of an organic light-emitting device manufactured by taking the complex as a light-emitting layer material are obviously improved, and the organic light-emitting device has a great application prospect in the fields of OLED display and illumination.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of organic electroluminescent materials, and particularly relates to a tetradentate cyclometalated platinum(II) complex guest phosphorescent material with a substituted phenyl structure, an electronic device, an apparatus and their applications. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technologies. Compared with liquid crystal displays, which have disadvantages such as slow response speed, small viewing angle, the need for a backlight, and high energy consumption, OLEDs, as a self-luminous device, do not require a backlight and are energy-saving; moreover, they have a low driving voltage, fast response speed, high resolution and contrast ratio, wide viewing angle, and excellent low-temperature performance; OLED devices can be made thinner and can be made into a flexible structure. In addition, they also have the advantages of low production cost, simple production process, and the ability to perform large-area production. Therefore, OLEDs have broad and huge application prospects in high-end electronic products and aerospace; with the gradual increase in investment, further in-depth research and development, and the upgrading and transformation of production equipment, OLEDs will have a very wide range of application scenarios and development prospects in the future.

[0003] The core of the development of OLEDs is the design and development of luminescent materials. In early OLED devices, the luminescent materials were mainly organic small molecule fluorescent materials. However, spin statistical quantum mechanics shows that in the case of electroluminescence, the generated singlet excitons and triplet excitons are 25% and 75% respectively. Since traditional fluorescent materials can only utilize the singlet excitons, their maximum theoretical internal quantum efficiency is only 25%, and the remaining 75% of the triplet excitons are lost through non-radiative transitions. Due to the strong spin-orbit coupling effect of heavy metal atoms, excitons can more easily undergo intersystem crossing (ISC) from the singlet state to the triplet state, so that OLED devices can make full use of all singlet and triplet excitons generated by electrical excitation, and the theoretical internal quantum efficiency of the luminescent materials can reach 100%.

[0004] In currently applied OLED devices, the light-emitting layer almost entirely uses the host-guest light-emitting system mechanism, that is, a guest light-emitting material is doped in the host material. The energy level of the host material is generally greater than that of the guest light-emitting material, and the energy is transferred from the host material to the guest material, causing the guest material to be excited and emit light. Commonly used organophosphorescent guest materials are generally heavy metal atoms such as iridium(III), platinum(II), Pd(II), etc. The currently applied heavy metal phosphorescent organic complex molecule is a cyclometalated iridium(III) complex molecule, and the quantity is limited. In addition, when preparing the iridium(III) complex phosphorescent material, it involves four-step reactions including iridium(III) dimer containing, ligand exchange of iridium(III) intermediate, synthesis of mer-iridium(III) complex, and isomer conversion from mer- to fac-iridium(III) complex, which greatly reduces the total yield and significantly increases the preparation cost of the raw material IrCl3 . The utilization rate of H2O and increases the preparation cost of the iridium(III) complex phosphorescent material. In contrast, the preparation of the platinum(II) complex phosphorescent material only has the last step of the metallization design of the ligand to react with the platinum salt. The utilization rate of platinum element is high, and the preparation cost of the platinum(II) complex phosphorescent material can be further reduced. To sum up, the platinum(II) complex phosphorescent material has the advantage of low cost. However, there are still some technical difficulties in the development of current platinum complex materials and devices, such as how to improve the chemical stability and thermal stability of the materials, avoid red shift or luminescence quenching caused by molecular aggregation, and thus improve the device operation life, etc. Therefore, it is urgent to develop new phosphorescent metal platinum(II) complexes. Summary of the Invention

[0005] The object of the present invention is to provide a tetradentate cyclometalated platinum(II) complex guest phosphorescent material with a substituted phenyl structure, an electronic device, a device and their applications. By introducing a bulky alkyl group at the ortho position of the N-heterocyclic carbene-substituted phenyl to increase steric hindrance, the red shift or luminescence quenching caused by molecular aggregation can be avoided; by adjusting the peripheral substituted functional groups of the ligand, the photophysical properties of the material can be regulated to achieve fine regulation of the emission color; deuteration of the periphery of the cyclometalated ligand can improve the chemical stability and thermal stability and is easy to prepare an evaporated OLED device. The organic electroluminescent device made of the complex of the present invention as the light-emitting layer material has obvious improvements in both current efficiency and life, and has great application prospects in the fields of OLED display and lighting.

[0006] The object of the present invention is achieved by the following technical solutions;

[0007] In many embodiments, the present invention provides a platinum(II) complex guest phosphorescent material having the structure shown in formula (I):

[0008]

[0009] In formula (I), Ra , R b , R c , R d , R e , R f Each independently represents mono-substituted or multi-substituted; R a -R f Each independently represents hydrogen, deuterium, CN, halogen, substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, C3–C30 heterocycloalkyl, substituted or unsubstituted C6–C30 aryl, C4–C30 heteroaryl; when containing substitution, the substitution is selected from one or more of deuterium, halogen, and C1-C10 alkyl; R 1 , R 2 Each is the same as or different from each other and is selected from hydrogen, deuterium, CN, CF3, C4–C30 alkyl, C4–C30 deuterated alkyl, C4–C30 halogenated alkyl, C3–C30 cycloalkyl, C3–C30 heterocycloalkyl; independently, two or more adjacent substituents can form a saturated or unsaturated C3–C18 ring with the carbon atom to which they are commonly attached, and the ring can be substituted or unsubstituted.

[0010] Preferably, in formula (I), R a -R f Each independently represents hydrogen, deuterium, CN, F, C3–C12 alkyl, C3–C12 deuterated alkyl, C3–C12 F-substituted alkyl, C3–C12 cycloalkyl, C3–C12 N-heterocycloalkyl, C6–C12 aryl substituted or unsubstituted with C1-C5 alkyl, C4–C18 N-heteroaryl; R 1 , R 2 Each is the same as or different from each other and is selected from hydrogen, deuterium, CN, CF3, C4–C12 alkyl, C4–C12 deuterated alkyl, C4–C12 F-substituted alkyl, C3–C12 cycloalkyl, C3–C12 N-heterocycloalkyl.

[0011] In a certain embodiment, R a , R b , R c , R d , R e , R fEach independently the same or different and selected from one or more of hydrogen, deuterium, -CN, F, CF3, 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, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantyl, methyl-substituted cyclohexyl, pyridyl, and phenyl substituted or unsubstituted with a C1-C10 alkyl group.

[0012] In one embodiment, R 1 , R 2 Each independently the same or different and selected from one or more of CN, F, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, azetidinyl, piperidinyl, azepanyl, cyclopentane, cyclohexane, cycloheptane, cyclooctane, and adamantyl.

[0013] Preferably, R 1 , R 2 Are not simultaneously selected from hydrogen or deuterium. More preferably, R 1 , R 2 Is not selected from hydrogen.

[0014] Preferably, in the platinum(II) complex of the structure shown in formula (I), the hydrogen atoms can be partially or completely replaced by deuterium or F.

[0015] In one embodiment, the platinum(II) complex host phosphorescent material is selected from any one of the following chemical structures: where "D" represents deuterium:

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] In many embodiments, the present invention also provides an application of the platinum(II) complex guest phosphorescent material having the structure shown in formula (I) above in the preparation of electronic devices.

[0025] Further, the electronic device includes one or more of an organic electroluminescent device, an organic optoelectronic 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 quenching device, a light emitting electrochemical cell, or an organic laser diode.

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

[0027] More preferably, the light emitting layer further includes a fluorescent doping material; the fluorescent doping material is preferably a boron-containing organic molecular luminescent material, and more preferably a boron-containing compound.

[0028] In many embodiments, the present invention also provides an organic optoelectronic device, which includes: 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 includes the platinum(II) complex guest phosphorescent material having the structure shown in formula (I) above. For example, the platinum(II) complex can be included as a luminescent material in the organic light emitting functional layer.

[0029] Further, the organic light emitting functional layer further includes any one or more fluorescent doping materials, and the fluorescent doping material is preferably a boron-containing organic molecular luminescent material, and more preferably a boron-containing compound that can be phosphorescently sensitized.

[0030] In the present invention, as a reference preparation method, an organic optoelectronic device can form an anode by sputtering coating, electron beam evaporation, vacuum evaporation or other methods to deposit a metal, a conductive oxide or their alloy on a substrate; a hole injection layer, a hole transport layer, a light-emitting layer, an air barrier layer and an electron transport layer are sequentially deposited on the surface of the prepared anode, and then a cathode is deposited. In addition to the above methods, an organic electroluminescent device is fabricated by depositing a cathode, an organic functional layer and an anode on the substrate in sequence. The organic functional layer may include a multi-layer structure such as a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer and an electron transport layer. In the present invention, the organic functional layer can be prepared by using a polymer material according to solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing or thermal-imaging, etc.) instead of the evaporation method, which can reduce the number of device layers.

[0031] The present invention also provides a composition, which comprises a platinum (II) complex guest phosphorescent material having the structure shown in formula (I) as described above. Preferably, the composition further comprises a fluorescent doping material, and the fluorescent doping material is preferably a boron-containing organic molecular luminescent material, and more preferably a boron-containing compound that can be phosphorescently sensitized.

[0032] The present invention also provides a preparation, which comprises a platinum (II) complex guest phosphorescent material having the structure shown in formula (I) as described above and at least one solvent. The solvent is not particularly limited and can be those well-known to those skilled in the art.

[0033] The present invention also provides a display device, which comprises one or more of the above-mentioned organic electroluminescent devices or organic optoelectronic devices.

[0034] The present invention also provides a lighting device, which comprises one or more of the above-mentioned organic electroluminescent devices or organic optoelectronic devices.

[0035] Preferably, the organic electroluminescent device of the present invention is any one of an organic photovoltaic device, an organic light-emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-paper), an organic photoreceptor (OPC), an organic thin film transistor (OTFT), an organic memory device (Organic Memory Element), a lighting device and a display device.

[0036] The materials used in the organic electroluminescent device according to the present invention can be divided into top emission, bottom emission or double-sided emission.

[0037] The compounds of the organic electroluminescent device according to the embodiments of the present invention can be applied to electro-optic devices such as organic solar cells, OLEDs for lighting, flexible OLEDs, organic photoreceptors, and organic thin-film transistors based on the similar principle of organic light-emitting devices.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] (1) By introducing large steric hindrance groups (CN, substituted or unsubstituted C4–C30 alkyl groups, C3–C30 cycloalkyl groups, C3–C30 heterocycloalkyl groups, etc.) at the 3-position and 5-position of the phenyl group connected to the carbene group, the steric hindrance can be increased, the distance between molecules can be enlarged, the molecular resonance can be reduced, and the red shift or luminescence quenching caused by molecular aggregation can be avoided;

[0040] (2) Deuteration on the periphery of the cyclometalated ligand can improve the stability of C-H bonds, and further enable the phosphorescent materials shown in the present invention to have good chemical stability and thermal stability, and are easy to prepare vapor-deposited OLED devices;

[0041] (3) After making the phosphorescent material provided by the present invention into an organic electroluminescent device as the light-emitting layer material, it has more excellent performance improvement; the energy transfer between the host and the guest is more efficient, and there are obvious improvements in current efficiency and lifetime. Among them, for Pt1 at an initial brightness of 1000 cd / m 2 The estimated LT90 lifetime of the device based on the platinum(II) complex Pt1 emitter reaches 88,000 hours (n = 1.7). Its lifetime is leading in the industry among green-light tetradentate platinum complexes and meets the commercial requirements of high-end display products (usually ≥ 10,000 hours), providing a better phosphorescent material solution for the commercial application of green-light-emitting guest materials for OLED full-color displays. Description of the Drawings

[0042] Figure 1 is the room-temperature emission spectrum of the platinum(II) complex Pt1 in dichloromethane and toluene solutions;

[0043] Figure 2 is the room-temperature emission spectrum of the platinum(II) complex Pt1 in solutions with different polarities;

[0044] Figure 3 is the CIE chromaticity coordinates of Device Example 1;

[0045] Figure 4 is the density functional theory calculation diagram and natural orbital analysis diagram of the frontier orbitals of the platinum(II) complex Pt1;

[0046] Figure 5 is the electroluminescence spectrum of Device Example 1;

[0047] Figure 6 It is the operation life diagram of Device Example 1. Detailed implementation mode

[0048] As used in the present invention, the term "optional" or "optionally" means that the subsequent described event or situation may or may not occur, and this description includes the situation where the said event or situation occurs and the situation where it does not occur.

[0049] The term "substituted" used in the present invention is intended to include all permissible substituents of organic compounds. In a broad aspect, the 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 suitable organic compounds, the permissible substituents can be one or more, the same or different. For the purposes of the present invention, a heteroatom (such as nitrogen) can have a hydrogen substituent and / or any permissible substituent of the organic compounds described in the present invention, which satisfies the valence bond of the heteroatom. The present disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" imply the implicit condition that such substitution conforms to the permissible valence bonds of the substituted atom and the substituent, and the substitution results in a stable compound (for example, a compound that does not spontaneously undergo transformation (such as by rearrangement, cyclization, elimination, etc.)). It is also contemplated that in some aspects, unless explicitly stated to the contrary, a single substituent can further optionally be substituted (i.e., further substituted or unsubstituted).

[0050] When defining various terms, R a -R f is used as a general symbol in the present invention to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed in the present invention, and when they are defined as certain substituents in one case, they can be defined as some other substituents in other cases.

[0051] As used herein, the term "alkyl" refers to a saturated, branched or unbranched hydrocarbyl group having from 1 to 30 carbon atoms. Preferred alkyl groups are those having from 1 to 24 carbon atoms, more preferably from 1 to 9 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be substituted with one or more groups including, but not limited to, an optionally substituted alkyl group, cycloalkyl group, alkoxy group, amino group, halogen, hydroxyl group, nitro group, silyl group, sulfo-oxo group, or mercapto group as described herein.

[0052] Throughout this specification, the term "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 term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "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.

[0053] When terms such as "cycloalkyl" refer to both unsubstituted and substituted cycloalkyl moieties, the substituted moieties can be specifically identified in this invention; for example, a specifically substituted cycloalkyl can be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy can be specifically referred to as, for example, "halogenated alkoxy", and a specifically substituted alkenyl can be, for example, "enol", etc. Likewise, the practice of using a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" is not intended to imply that the general term does not simultaneously encompass the specific term.

[0054] As used herein, the term "cycloalkyl" refers to a non-aromatic carbon-based ring composed of at least three carbon atoms. Preferred cycloalkyl groups are those having from 3 to 30 carbon atoms, more preferably from 3 to 12 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, adamantyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is included within the meaning of the term "cycloalkyl", wherein at least one ring carbon atom is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups can be substituted with one or more groups including, but not limited to, an alkyl group, cycloalkyl group, alkoxy group, amino group, halogen, hydroxyl group, nitro group, silyl group, sulfo-oxo group, or mercapto group as described herein.

[0055] The term "aryl" as used in the present invention refers to any carbon-based aromatic group containing 6 to 30 carbon atoms. Preferred aryl groups are aromatic groups containing 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. The carbon-based aromatic groups include, but are not limited to, phenyl, naphthyl, phenyl group, biphenyl, phenoxyphenyl, anthracenyl, phenanthryl, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group having at least one heteroatom within the ring introducing the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group can be substituted or unsubstituted. The aryl group can 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 the present invention.

[0056] In the compounds mentioned in the present invention, unless explicitly defined, for example, adjacent substituents can optionally be linked to form a ring, adjacent substituents in the compounds cannot be linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can optionally be linked to form a ring, which includes both the case where adjacent substituents can be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be linked to form a ring, the formed ring can be a monocyclic or polycyclic ring (including spiro ring, bridged ring, fused ring, etc.), and an alicyclic, heteroalicyclic, aromatic or heteroaromatic ring. The carbon atoms are preferably C3-C30, more preferably C3-C18. Even more preferably C3-C6 in this expression. Adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to more distant carbon atoms. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0057] The expression that adjacent substituents can optionally be linked to form a ring is also intended to be considered to mean that two substituents bonded to the same carbon atom are connected to each other by a chemical bond to form a ring. The expression that adjacent substituents can optionally be linked to form a ring is also intended to be considered to mean that two substituents bonded to carbon atoms directly bonded to each other are connected to each other by a chemical bond to form a ring. The expression that adjacent substituents can optionally be linked to form a ring is also intended to be considered to mean that two substituents bonded to more distant carbon atoms are connected to each other by a chemical bond to form a ring. In addition, the expression that adjacent substituents can optionally be linked to form a ring is also intended to be considered to mean that, in the case where one of the two adjacent substituents represents hydrogen, the second substituent is bonded to the position where the hydrogen atom is bonded, thereby forming a ring.

[0058] This disclosure relates to compounds or complex complexes containing platinum. The terms compound or complex may be used interchangeably in the present invention. Additionally, the compounds disclosed herein have a neutral charge.

[0059] The compounds disclosed herein are suitable for a variety of optical and electro-optical devices, including but not limited to light absorption devices such as solar and photosensitive devices, organic light-emitting diodes, light-emitting devices or devices capable of compatible light absorption and emission, and as markers for biological applications.

[0060] As described above, the disclosed compounds are platinum complexes. Also, the compounds disclosed herein can be used as host materials for OLED applications, such as full-color displays.

[0061] The compounds disclosed herein can be used in various applications. As a luminescent material, the compound can be used in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

[0062] In addition, compared with traditional materials, the compounds in the present invention used in light-emitting devices (such as OLEDs) can improve the luminescence efficiency and the operating time of the devices.

[0063] 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.

[0064] The compounds disclosed in the embodiments of the present invention are suitable for a variety of optical and electro-optical devices, including but not limited to light absorption devices such as solar and photosensitive devices, organic light-emitting diodes (OLEDs), light-emitting devices or devices having both light absorption and light emission capabilities, and as markers for biological applications.

[0065] The compounds provided by the embodiments of the present invention can be used in a light-emitting device such as an OLED. The device includes at least one cathode, at least one anode, and at least one light-emitting layer, and at least one of the light-emitting layers includes a platinum(II) complex guest phosphorescent material having the structure shown in formula (I). Specifically, the light-emitting device may include an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode deposited in sequence. The hole transport layer, the light-emitting layer, and the electron transport layer are all organic layers, and the anode and the cathode are electrically connected.

[0066] It should be noted that the above general description and the following detailed description are only exemplary and explanatory and are not restrictive.

[0067] The present disclosure can be more easily understood by reference to the following detailed description and the examples contained therein.

[0068] 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 can of course vary. It should also be understood that the terms used in the present invention are for the purpose of describing specific aspects only and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used in this practice or test, exemplary methods and materials are described below.

[0069] Synthesis Examples

[0070] The following examples of compound synthesis, compositions, devices, or methods are only provided to give a general method to the industry field and are not used to limit the scope of protection of this patent. For the data (quantities, temperatures, etc.) mentioned in the patent, every effort is made to ensure accuracy, but there may be some errors. Unless otherwise specified, weighings are done separately, the temperature is 25 °C, or room temperature, and the pressure is near atmospheric pressure.

[0071] The following examples provide methods for preparing new compounds, but the preparation of such compounds is not limited to these methods. In this technical field, since the compounds protected in this patent are easy to modify and prepare, their preparation can be carried out using the methods listed below or other methods. The following examples are only for illustration and are not used to limit the scope of protection of this patent. The temperature, catalyst, concentration, reactants, and reaction process can all be changed to select different conditions for preparing the compounds for different reactants.

[0072] Determined on an Agilent 6210TOF LC / MS type mass spectrometer; the HRMS spectrum was determined on an Agilent 6210TOF LC / MS type liquid chromatography - time - of - flight mass spectrometer; 1 The 1H NMR spectrum was determined on a BRUKER - 500 or BRUKER - 400 nuclear magnetic resonance spectrometer.

[0073] Synthesis Route

[0074] Example 1: Tetradentate cyclometalated platinum(II) complex Pt1

[0075] The synthesis route is as follows:

[0076]

[0077] Synthesis of Intermediate 1-Br: Add Cz-Br (1.2 equivalents), N-Br (1.0 equivalent), copper(I) iodide (0.1 equivalent), N-methylimidazole (0.2 equivalent), and lithium tert-butoxide (2.0 equivalents) into the reaction flask in sequence. Evacuate and refill with nitrogen three times, then add toluene (250 mL). Stir and react at 130 °C for 35 hours, filter, and remove the solvent by distillation under reduced pressure. Purify by silica gel column chromatography with the eluent: petroleum ether / ethyl acetate = 30:1 to obtain 21 g of white solid 1-Br with a yield of 90%, MS: m / z 387.07 (M+H) + 。

[0078] Synthesis of Intermediate DCz-Cl: Add 1-Br (1.1 equivalents), Cz-Cl (1.0 equivalent), copper(I) iodide (0.2 equivalent), trans-cyclohexanediamine (0.4 equivalent), and potassium phosphate (2.0 equivalents) into the reaction flask in sequence. Evacuate and refill with nitrogen three times, then add xylene (130 mL). Stir and react at 100 °C for 35 hours, extract with water / ethyl acetate three times, and remove the solvent by distillation under reduced pressure. Purify by silica gel column chromatography with the eluent: petroleum ether / ethyl acetate = 20:1 to obtain 17.40 g of white solid with a yield of 86%, 1 HNMR (400 MHz, CDCl3) δ 1.40 (s, 9H), 7.26 (dd, J = 8.4, 2.0 Hz, 1H), 7.28–7.34 (m, 2H), 7.37–7.45 (m, 2H), 7.48 (m, 3H), 7.51–7.59 (td, J = 7.2, 1.2 Hz, 1H), 7.69 (d, J = 1.6 Hz, 1H), 7.84 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 2.0 Hz, 1H), 8.06 (d, J = 8.4 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.23 (d, J = 7.6 Hz, 1H), 8.34 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 5.6 Hz, 1H).

[0079]

[0080] Synthesis of Intermediate (1-1): Add NH2-NO2 (20.00 g, 144.80 mmol, 1.0 equiv), DtBu-Br (39.00 g, 144.80 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium(0) (2.00 g, 2.17 mmol, 1.5 mol%), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) (3 mol%) (2.33 g, 4.34 mmol, 3 mol%) and cesium carbonate (12.12 g, 87.70 mmol, 2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and refill with nitrogen three times, and add toluene (300 mL) under nitrogen protection. After reacting in an oil bath at 105 °C for 24 h, cool to room temperature, extract with ethyl acetate, and after removing the solvent by rotary evaporation under reduced pressure, separate and filter the crude product through a silica gel column chromatography. Eluent: petroleum ether / ethyl acetate = 40:1, to obtain 44.24 g of a red oil, yield 93%, MS: m / z 326.20 (M+H) + .

[0081] Synthesis of Intermediate (1-2): Add 1-1 (44.24 g, 135.52 mmol, 1.0 equiv) and palladium on carbon (10%) (4.33 g, 40.66 mmol, 3 mol%) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and refill with nitrogen three times, add ethanol (150 mL) and ethyl acetate (150 mL) under nitrogen protection, and then evacuate and refill with hydrogen three times. After reacting in an oil bath at 45 °C under a hydrogen atmosphere for 65 h, cool to room temperature, filter, and remove the solvent by rotary evaporation under reduced pressure to obtain 35.88 g of a gray solid, yield 85%, MS: m / z 296.22 (M+H) + .

[0082] Synthesis of Intermediate (1-3): Add 1-2 (8.77 g, 29.60 mmol, 1.0 equiv), DCz-Cl (14.80 g, 29.60 mmol, 1.0 equiv), 1-2 (8.77 g, 29.60 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium(0) (813 mg, 0.89 mmol, 3 mol%), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) (0.85 g, 1.75 mmol, 6 mol%) and sodium tert-butoxide (5.69 g, 59.20 mmol, 2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and refill with nitrogen three times, and add toluene (145 mL) under nitrogen protection. After reacting in an oil bath at 90 °C for 35 h, cool to room temperature, extract with water / ethyl acetate, and after removing the solvent by rotary evaporation under reduced pressure, separate and filter the crude product through a silica gel column chromatography. Petroleum ether / ethyl acetate = 30:1, to obtain 19.00 g of a dark red solid, yield 84%, MS: m / z 759.43 (M+H)+ 。

[0083] Synthesis of ligand L1: Add 1-3 (19.00 g, 25.00 mmol, 1.0 equiv) and ammonium hexafluorophosphate (8.15 g, 50.00 mmol, 2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Flush with nitrogen three times and add triethyl orthoformate (55 mL) under nitrogen protection. After reacting in an oil bath at 75 °C for 1 h, cool to room temperature, distill off the solvent under reduced pressure, and separate by silica gel column chromatography. Eluent: dichloromethane / methanol = 200:1 - 100:1, obtaining 22.38 g of a brown solid with a yield of 99%. 1 1H NMR (500 MHz, CDCl3) δ 1.37 (s, 9H), 1.38 (s, 18H), 7.29 (dd, J = 5.5, 2.0 Hz, 1H), 7.32–7.39 (m, 2H), 7.46–7.51 (m, 2H), 7.53 (m, 3H), 7.59 (dd, J = 8.0, 2.0 Hz, 1H), 7.60–7.67 (m, 4H), 7.69 (t, J = 1.5 Hz, 1H), 7.70–7.74 (m, 3H), 7.75 (d, J = 2.0 Hz, 1H), 8.08 (d, J = 2.0 Hz, 1H), 8.18 (t, J = 8.0 Hz, 2H), 8.34 (d, J = 8.0 Hz, 1H), 8.37 (d, J = 8.0 Hz, 1H), 8.52 (d, J = 5.5 Hz, 1H), 9.29 (s, 1H).

[0084] Synthesis of Pt1: Add L1 (12.00 g, 13.30 mmol, 1.0 equiv) and (1,5-cyclooctadiene)platinum(II) dichloride (4.98 g, 13.30 mmol, 1.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Flush with nitrogen three times and add N,N-dimethylformamide (350 mL) under nitrogen protection. Bubble nitrogen through the solution for 30 min to remove oxygen. React in an oil bath at 120 °C for 72 h. After cooling to room temperature, distill off the solvent under reduced pressure. Separate the obtained crude product by silica gel column chromatography. Eluent: petroleum ether / dichloromethane = 3:1, obtaining 3.59 g of a yellow solid with a yield of 28%. 11H NMR (500 MHz, CDCl3) δ 1.12 (s, 9H), 1.21 (s, 9H), 1.51 (s, 9H), 6.19 (dd, J = 6.5, 2.0 Hz, 1H), 7.25 (d, J = 7.0 Hz, 1H), 7.29–7.44 (m, 6H), 7.48 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), δ 7.57 (s, 1H), δ 7.63 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.91 (d, J = 2.5 Hz, 1H), 7.92 (d, J = 8.5 Hz, 1H), 7.95 (d, J = 8.0 Hz, 1H), 8.11 (td, J = 8.0, 1.5 Hz, 2H), 8.18–8.38 (m, 3H), 8.63 (d, J = 6.5 Hz, 1H).

[0085] Example 2: Tetradentate cyclometalated platinum(II) complex Pt20

[0086] The synthesis route is as follows:

[0087]

[0088]

[0089] Synthesis of intermediate (2-1): Add NH2-NO2 (1.0 equiv.), Ad-Br (1.0 equiv.), tris(dibenzylideneacetone)dipalladium(0) (1.5 mol%), 2-bis(cyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (XPhos) (3 mol%) and cesium carbonate (2.0 equiv.) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and refill with nitrogen three times, and add toluene (300 mL) under nitrogen protection. After reacting in an oil bath at 105 °C for 12 h, cool to room temperature, extract with ethyl acetate, and remove the solvent by rotary evaporation under reduced pressure. The crude product is separated and filtered through a silica gel column chromatography. Eluent: petroleum ether / ethyl acetate = 40:1, to obtain 15.5 g of a red oil, yield 85%, MS: m / z 482.29 (M+H) + .

[0090] Synthesis of intermediate (2-2): Add 2-1 (1.0 equiv.) and palladium on carbon (10%) (4.5 mol%) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and refill with nitrogen three times, add ethanol (150 mL) and ethyl acetate (150 mL) under nitrogen protection, and then evacuate and refill with hydrogen three times. React in an oil bath at 45 °C for 48 h under a hydrogen atmosphere, cool to room temperature, filter, and remove the solvent by rotary evaporation under reduced pressure to obtain 13.0 g of a gray solid, yield 82%, MS: m / z 452.32 (M+H) + .

[0091] Synthesis of Intermediate (2-3): Add 2-2 (1.0 equiv), DCz-Cl (1.0 equiv), tris(dibenzylideneacetone)dipalladium(0) (3 mol%), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) (6 mol%), and sodium tert-butoxide (2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and refill with nitrogen three times, and add toluene (145 mL) under nitrogen protection. After reacting in an oil bath at 100 °C for 20 h, cool to room temperature, extract with water / ethyl acetate, and remove the solvent by rotary evaporation under reduced pressure. The crude product is separated and filtered through a silica gel column chromatography. Petroleum ether / ethyl acetate = 30:1, obtaining 18.00 g of a dark red solid with a yield of 80%, MS: m / z 915.52 (M+H) + 。

[0092] Synthesis of Ligand L20: Add 2-3 (1.0 equiv) and ammonium hexafluorophosphate (2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times, and add triethyl orthoformate (50 mL) under nitrogen protection. After reacting in an oil bath at 75 °C for 1 h, cool to room temperature, remove the solvent by rotary evaporation under reduced pressure, and separate by silica gel column chromatography. Eluent: dichloromethane / methanol = 200:1 - 100:1, obtaining 18.1 g of a brown solid with a yield of 83%, MS: m / z 926.52 (M+H) + 。

[0093] Synthesis of Pt20: Add L20 (1.0 equiv) and dichlorobis(1,5-cyclooctadiene)platinum(II) (1.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times, and add N,N-dimethylformamide (450 mL) under nitrogen protection. Bubble nitrogen through the solution for 30 min to remove oxygen. React in an oil bath at 120 °C for 72 h, cool to room temperature after the reaction, remove the solvent by rotary evaporation under reduced pressure, and separate the crude product by silica gel column chromatography. Eluent: petroleum ether / dichloromethane = 3:1, obtaining 4.2 g of a yellow solid with a yield of 30%, MS: m / z 1119.47 (M+H) + 。

[0094] Example 3: Tetradentate Cyclometalated Platinum(II) Complex Pt4

[0095] Prepare the complex Pt4 by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 118 mg of a yellow solid is obtained with a yield of 20%. MS: m / z 975.45 (M+H) + 。

[0096] Example 4: Tetradentate Cyclometalated Platinum(II) Complex Pt5

[0097] Prepare the synthetic complex Pt5 according to the synthetic method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 100 mg of a yellow solid was obtained with a yield of 22%. MS: m / z 985.51 (M+H) + 。

[0098] Example 5: Tetradentate cyclometalated platinum(II) complex Pt8

[0099] Prepare the synthetic complex Pt8 according to the synthetic method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 114 mg of a yellow solid was obtained with a yield of 32%. MS: m / z 992.55 (M+H) + 。

[0100] Example 6: Tetradentate cyclometalated platinum(II) complex Pt9

[0101] Prepare the synthetic complex Pt9 according to the synthetic method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 198 mg of a yellow solid was obtained with a yield of 26%. MS: m / z 935.34 (M+H) + 。

[0102] Example 7: Tetradentate cyclometalated platinum(II) complex Pt11

[0103] Prepare the synthetic complex Pt11 according to the synthetic method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 128 mg of a yellow solid was obtained with a yield of 25%. MS: m / z 1187.62 (M+H) + 。

[0104] Example 8: Tetradentate cyclometalated platinum(II) complex Pt14

[0105] Prepare the synthetic complex Pt14 according to the synthetic method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 124 mg of a yellow solid was obtained with a yield of 35%. MS: m / z 989.39 (M+H) + 。

[0106] Example 9: Tetradentate cyclometalated platinum(II) complex Pt15

[0107] Prepare the synthetic complex Pt15 according to the synthetic method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 105 mg of a yellow solid was obtained with a yield of 32%. MS: m / z 977.39 (M+H) + 。

[0108] Example 10: Tetradentate cyclometalated platinum(II) complex Pt16

[0109] The complex Pt16 was synthesized by referring to the synthesis method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 145 mg of a yellow solid was obtained, with a yield of 29%. MS: m / z 981.48 (M+H) + 。

[0110] Example 11: Tetradentate cyclometalated platinum(II) complex Pt17

[0111] The complex Pt17 was synthesized by referring to the synthesis method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 137 mg of a yellow solid was obtained, with a yield of 33%. MS: m / z 1047.47 (M+H) + 。

[0112] Example 12: Tetradentate cyclometalated platinum(II) complex Pt22

[0113] The complex Pt22 was synthesized by referring to the synthesis method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 125 mg of a yellow solid was obtained, with a yield of 27%. MS: m / z 987.37 (M+H) + 。

[0114] Example 13: Tetradentate cyclometalated platinum(II) complex Pt25

[0115] The complex Pt25 was synthesized by referring to the synthesis method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 125 mg of a yellow solid was obtained, with a yield of 26%. MS: m / z 933.32 (M+H) + 。

[0116] Example 14: Tetradentate cyclometalated platinum(II) complex Pt26

[0117] The complex Pt26 was synthesized by referring to the synthesis method of complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 136 mg of a yellow solid was obtained, with a yield of 22%. MS: m / z 1041.42 (M+H) + 。

[0118] Example 15: Tetradentate cyclometalated platinum(II) complex Pt32

[0119] The synthesis of complex Pt32 was carried out in the same way as that of complex Pt1 in Reference Example 1, except that the ligand raw material of the corresponding fragment in Example 1 was replaced. Finally, 132 mg of yellow solid was obtained with a yield of 36%. MS: m / z 1071.46 (M+H) + 。

[0120] Example 16: Tetradentate cyclometalated platinum(II) complex Pt35

[0121] The synthesis of complex Pt35 was carried out in the same way as that of complex Pt1 in Reference Example 1, except that the ligand raw material of the corresponding fragment in Example 1 was replaced. Finally, 137 mg of yellow solid was obtained with a yield of 28%. MS: m / z 979.28 (M+H) + 。

[0122] Example 17: Tetradentate cyclometalated platinum(II) complex Pt36

[0123] The synthesis of complex Pt36 was carried out in the same way as that of complex Pt1 in Reference Example 1, except that the ligand raw material of the corresponding fragment in Example 1 was replaced. Finally, 145 mg of yellow solid was obtained with a yield of 22%. MS: m / z 987.26 (M+H) + 。

[0124] Example 18: Tetradentate cyclometalated platinum(II) complex Pt37

[0125] The synthesis of complex Pt37 was carried out in the same way as that of complex Pt1 in Reference Example 1, except that the ligand raw material of the corresponding fragment in Example 1 was replaced. Finally, 153 mg of yellow solid was obtained with a yield of 27%. MS: m / z 975.30 (M+H) + 。

[0126] Example 19: Tetradentate cyclometalated platinum(II) complex Pt38

[0127] The synthesis of complex Pt38 was carried out by referring to the synthesis method of complex Pt1 in Reference Example 1, except that the ligand raw material of the corresponding fragment in Example 1 was replaced. Finally, 140 mg of yellow solid was obtained with a yield of 29%. MS: m / z1287.20 (M+H) + 。

[0128] Example 20: Tetradentate cyclometalated platinum(II) complex Pt39

[0129] The synthesis of complex Pt39 was carried out in the same way as that of complex Pt1 in Reference Example 1, except that the ligand raw material of the corresponding fragment in Example 1 was replaced. Finally, 142 mg of yellow solid was obtained with a yield of 21%. MS: m / z 901.24 (M+H) + 。

[0130] Example 21: Tetradentate cyclometalated platinum(II) complex Pt40

[0131] The complex Pt40 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 113 mg of a yellow solid was obtained, with a yield of 22%. MS: m / z 923.30 (M+H) + 。

[0132] Example 22: Tetradentate cyclometalated platinum(II) complex Pt41

[0133] The complex Pt41 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 156 mg of a yellow solid was obtained, with a yield of 26%. MS: m / z 1071.31 (M+H) + 。

[0134] Example 23: Tetradentate cyclometalated platinum(II) complex Pt45

[0135] The complex Pt45 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 126 mg of a yellow solid was obtained, with a yield of 29%. MS: m / z 993.42 (M+H) + 。

[0136] Example 24: Tetradentate cyclometalated platinum(II) complex Pt46

[0137] The complex Pt46 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 122 mg of a yellow solid was obtained, with a yield of 31%. MS: m / z 1031.36 (M+H) + 。

[0138] Example 25: Tetradentate cyclometalated platinum(II) complex Pt51

[0139] The complex Pt51 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 118 mg of a yellow solid was obtained, with a yield of 50%. MS: m / z 1035.38 (M+H) + 。

[0140] Example 26: Tetradentate cyclometalated platinum(II) complex Pt53

[0141] The complex Pt53 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 102 mg of yellow solid was obtained, with a yield of 29%. MS: m / z 1049.97 (M+H) + 。

[0142] Example 27: Tetradentate cyclometalated platinum(II) complex Pt56

[0143] The complex Pt56 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 138 mg of yellow solid was obtained, with a yield of 27%. MS: m / z 1255.61 (M+H) + 。

[0144] Example 28: Tetradentate cyclometalated platinum(II) complex Pt61

[0145] The complex Pt61 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 139 mg of yellow solid was obtained, with a yield of 31%. MS: m / z 1062.40 (M+H) + 。

[0146] Example 29: Tetradentate cyclometalated platinum(II) complex Pt66

[0147] The complex Pt66 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 115 mg of yellow solid was obtained, with a yield of 33%. MS: m / z 1187.45 (M+H) + 。

[0148] Example 30: Tetradentate cyclometalated platinum(II) complex Pt69

[0149] The complex Pt69 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 122 mg of yellow solid was obtained, with a yield of 37%. MS: m / z 1083.39 (M+H) + 。

[0150] Example 31: Tetradentate cyclometalated platinum(II) complex Pt73

[0151] The complex Pt73 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 133 mg of yellow solid was obtained, with a yield of 45%. MS: m / z 1355.19 (M+H)+ .

[0152] Example 32: Tetradentate cyclometalated platinum(II) complex Pt76

[0153] The complex Pt76 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 122 mg of yellow solid was obtained, with a yield of 24%. MS: m / z 989.36 (M+H) + .

[0154] Example 33: Tetradentate cyclometalated platinum(II) complex Pt77

[0155] The complex Pt77 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 127 mg of yellow solid was obtained, with a yield of 31%. MS: m / z 1017.39 (M+H) + .

[0156] Example 34: Tetradentate cyclometalated platinum(II) complex Pt78

[0157] The complex Pt78 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 133 mg of yellow solid was obtained, with a yield of 27%. MS: m / z 1045.42 (M+H) + .

[0158] Example 35: Tetradentate cyclometalated platinum(II) complex Pt82

[0159] The complex Pt82 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 134 mg of yellow solid was obtained, with a yield of 30%. MS: m / z 1073.48 (M+H) + .

[0160] Example 36: Tetradentate cyclometalated platinum(II) complex Pt92

[0161] The complex Pt92 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 163 mg of yellow solid was obtained, with a yield of 28%. MS: m / z 1185.61 (M+H) + .

[0162] Example 37: Tetradentate cyclometalated platinum(II) complex Pt96

[0163] The complex Pt96 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 121 mg of a yellow solid was obtained, with a yield of 21%. MS: m / z 1151.53 (M+H) + 。

[0164] Example 38: Tetradentate cyclometalated platinum(II) complex Pt101

[0165] The complex Pt101 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 161 mg of a yellow solid was obtained, with a yield of 21%. MS: m / z 1097.33 (M+H) + 。

[0166] Example 39: Tetradentate cyclometalated platinum(II) complex Pt104

[0167] The complex Pt104 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 157 mg of a yellow solid was obtained, with a yield of 31%. MS: m / z 1011.35 (M+H) + 。

[0168] Example 40: Tetradentate cyclometalated platinum(II) complex Pt108

[0169] The complex Pt108 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 132 mg of a yellow solid was obtained, with a yield of 31%. MS: m / z 1260.61 (M+H) + 。

[0170] Example 41: Tetradentate cyclometalated platinum(II) complex Pt116

[0171] The complex Pt116 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 161 mg of a yellow solid was obtained, with a yield of 37%. MS: m / z 988.37 (M+H) + 。

[0172] Example 42: Tetradentate cyclometalated platinum(II) complex Pt131

[0173] The complex Pt131 was synthesized by referring to the synthesis method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 101 mg of a yellow solid was obtained, with a yield of 21%. MS: m / z 1144.46 (M+H)+ .

[0174] Example 43: Tetradentate Cyclometalated Platinum(II) Complex Pt134

[0175] The complex Pt134 was synthesized by referring to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 111 mg of a yellow solid was obtained, with a yield of 33%. MS: m / z 1040.40 (M+H) + .

[0176] Example 44: Tetradentate Cyclometalated Platinum(II) Complex Pt140

[0177] The complex Pt140 was synthesized by referring to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 135 mg of a yellow solid was obtained, with a yield of 32%. MS: m / z 1028.40 (M+H) + .

[0178] Example 45: Tetradentate Cyclometalated Platinum(II) Complex Pt146

[0179] The complex Pt146 was synthesized by referring to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 131 mg of a yellow solid was obtained, with a yield of 35%. MS: m / z 1031.36 (M+H) + .

[0180] Example 46: Tetradentate Cyclometalated Platinum(II) Complex Pt152

[0181] The complex Pt152 was synthesized by referring to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 121 mg of a yellow solid was obtained, with a yield of 32%. MS: m / z 1099.35 (M+H) + .

[0182] Example 47: Tetradentate Cyclometalated Platinum(II) Complex Pt154

[0183] The complex Pt154 was synthesized by referring to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 129 mg of a yellow solid was obtained, with a yield of 30%. MS: m / z 1056.35 (M+H) + .

[0184] Example 48: Tetradentate Cyclometalated Platinum(II) Complex Pt155

[0185] Prepare the synthetic complex Pt155 according to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 114 mg of a yellow solid was obtained with a yield of 37%. MS: m / z 988.37 (M+H) + 。

[0186] Example 49: Tetradentate cyclometalated platinum(II) complex Pt158

[0187] Prepare the synthetic complex Pt158 according to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 108 mg of a yellow solid was obtained with a yield of 31%. MS: m / z 984.34 (M+H) + 。

[0188] Example 50: Tetradentate cyclometalated platinum(II) complex Pt159

[0189] Prepare the synthetic complex Pt159 according to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 132 mg of a yellow solid was obtained with a yield of 33%. MS: m / z 1151.53 (M+H) + 。

[0190] Example 51: Tetradentate cyclometalated platinum(II) complex Pt160

[0191] Prepare the synthetic complex Pt160 according to the synthetic method of the complex Pt1 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 128 mg of a yellow solid was obtained with a yield of 31%. MS: m / z 1019.43 (M+H) + 。

[0192] Photophysical properties:

[0193] Figure 1 is the room-temperature emission spectrum of the platinum(II) complex Pt1 in dichloromethane and toluene solutions. Figure 2 is the room-temperature emission spectrum of the platinum(II) complex Pt1 in solutions with different polarities. Table 1 shows the photophysical property test results of some metal platinum(II) complexes of the present invention in dichloromethane and toluene solutions at room temperature.

[0194] Table 1. Photophysical property test results of some metal platinum(II) complexes of the present invention in toluene solution at room temperature

[0195]

[0196]

[0197] From Figure 1 、 Figure 2 and the data in Table 1, it can be seen that for the phosphorescent material of platinum metal complex in polar solvents (such as ethanol) and non-polar solvents (such as hexane), the spectral shift of Pt1 is small, which is in line with the characteristics of the local excited state. Its emission wavelength is in the green light emission region around 525 nm; the full width at half maximum is small, all below 35 nm, with high color purity. The quantum efficiency of platinum(II) complex Pt1 in polymethyl methacrylate (PMMA) is relatively high, and the quantum efficiency of Pt1 is 79%. Deuteration of the ligand periphery can ensure the improvement of material stability while hardly affecting the emission wavelength and full width at half maximum; in addition, by regulating the substituents of R a 、R b 、R c 、R d 、R e 、R f 、R 1 、R 2 , fine adjustment of the emission wavelength can be achieved.

[0198] Preparation of OLED device:

[0199] On the surface or anode of ITO glass with a light-emitting area of 2.5 mm × 2.5 mm, a p-doped material is evaporated or the p-doped material is co-evaporated with a hole injection material at a concentration of 1% - 50% to form a hole injection layer (HIL) of 5 - 100 nm and a hole transport layer (HTL) of 5 - 200 nm. Subsequently, a light-emitting layer (EML) of 10 - 100 nm (which may contain the compound described in the present invention) is formed on the hole transport layer, and an electron transport layer (ETL) of 20 - 200 nm and a cathode of 50 - 200 nm are formed; 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 to fabricate an OLED device. And the OLED described is tested by standard methods. The device materials involved in the present invention can be obtained by known synthesis methods if not specifically stated.

[0200] In a preferred specific embodiment, the structure of the top-emitting device Example 1 provided by the present invention is: ITO / Ag / ITO(12 nm / 100 nm / 10 nm) / BFSFA:FCN(97:3, 10 nm) / BFSFA(145 nm) / BFSFA(50 nm) / premixed-host1:premixed-host2:Pt1(45:45:10, 30 nm) / NAPPBI:Liq(50:50, 35 nm) / Yb(1 nm) / Ag:Mg(90:10, 14 nm) / BBPNABA(70 nm).

[0201] Device Examples 2 - 26 and Comparative Example 1 were prepared respectively using a structure similar to that of Device Example 1, with the only difference being that the Pt1 in Device Example 1 was replaced with the platinum(II) complexes in Table 2 respectively. The luminescence characteristic data of the above-prepared Comparative Example and each Device Example were tested by standard methods and are shown in Table 2. The device structural formulas involved are as follows.

[0202]

[0203] Table 2. Luminescence characteristic data of devices prepared from some compounds

[0204]

[0205]

[0206] As can be seen from Table 2, compared with Comparative Example 1, Device Examples 1 - 26 prepared in this application all demonstrated good device performance in terms of driving voltage, current efficiency, and device lifetime; the performance improvement of each Device Example was based on the specific compound material of the present invention having high chemical stability and better electron transport ability.

[0207] Figure 3 are the International Commission on Illumination (CIE) chromaticity coordinates of Device Example 1; from Figure 3 it can be seen that the CIE coordinates of the Pt1 emitter are (0.23, 0.74), which is close to the ideal green light CIE (0.17, 0.79) in the BT.2020 standard, indicating that the prepared devices are all green light devices, and the CIEy values are all around 0.75, which are suitable for high color saturation display technologies. Figure 4 is the density functional theory calculation diagram and natural orbital analysis diagram of the frontier orbitals of the platinum(II) complex Pt1; from Figure 4 it can be seen that Pt1 presents a local excited state, which is consistent with its emission spectrum showing a narrow-band emission.

[0208] Figure 5 is the electroluminescence spectrum diagram of Device Example 1; from Figure 5 it can be seen that the maximum emission wavelength of the platinum(II) complex Pt1 emitter is 533 nm, and the full width at half maximum (FWHM) is 16.5 nm.

[0209] Figure 6 is the operating lifetime diagram of Device Example 1. From Figure 6 it can be seen that at a current density of 50 mA / cm², when the initial brightness (L0) is 41827 cd / m² -2 , the time (LT 90 ) required for the brightness to decay from the initial value to 90% of it is 155 h. According to the power-law decay model estimation formula for the OLED brightness lifetime:

[0210]

[0211] When n = 1.7, the estimated initial luminance (L0) is 1000 cd / m² -2 at this time, its LT 90 is 88,000 h.

[0212] It can be seen that when it is used as a light-emitting layer material to prepare an electronic device, it has higher current efficiency, device life, and color purity while reducing the driving voltage. This indicates that the compound provided by the present invention has certain commercial application value.

[0213] As described above, only the preferred specific embodiments of the present invention are given, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

Claims

1. A platinum(II) complex guest phosphorescent material, characterized in that, It has the structure shown in formula (I): In formula (I), R a , R b , R c , R d , R e , R f each independently represents mono-substituted or multi-substituted; R a -R f each independently represents hydrogen, deuterium, CN, halogen, substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, C3–C30 heterocycloalkyl, substituted or unsubstituted C6–C30 aryl, C4–C30 heteroaryl; when containing a substitution, the substitution is selected from one or more of deuterium, halogen, C1-C10 alkyl; R 1 , R 2 are each the same or different and are selected from hydrogen, deuterium, CN, CF3, C4–C30 alkyl, C4–C30 deuterated alkyl, C4–C30 haloalkyl, C3–C30 cycloalkyl, C3–C30 heterocycloalkyl; independently, two or more adjacent substituents may form a saturated or unsaturated C3–C18 ring with the carbon atom to which they are commonly attached, and the ring may be substituted or unsubstituted.

2. The platinum (II) complex guest phosphorescent material according to claim 1, characterized in that, R a -R f Each independently represents hydrogen, deuterium, CN, F, an alkyl group having 3 to 12 carbon atoms, a deuterated alkyl group having 3 to 12 carbon atoms, a fluorinated alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an N-heterocyclic alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which is substituted or unsubstituted with a C1-C5 alkyl group, an N-heteroaryl group having 4 to 18 carbon atoms; R 1 、R 2 are each independently selected from hydrogen, deuterium, CN, CF3, an alkyl group having 4 to 12 carbon atoms, a deuterated alkyl group having 4 to 12 carbon atoms, a fluorinated alkyl group having 4 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an N-heterocyclic alkyl group having 3 to 12 carbon atoms.

3. The platinum (II) complex guest phosphorescent material according to claim 1, characterized in that, R 1 and R 2 are each independently selected from CN, F, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, azetidinyl, piperidinyl, azepanyl, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantyl.

4. The platinum (II) complex guest phosphorescent material according to claim 1, characterized in that, In the platinum (II) complex guest phosphorescent material, the hydrogen atoms can be partially or completely replaced by deuterium or F.

5. The platinum (II) complex guest phosphorescent material according to claim 1, wherein The phosphorescent material is selected from any one of the chemical structures shown below, where "D" represents deuterium:

6. Use of the platinum (II) complex guest phosphorescent material according to any one of claims 1-5 in the preparation of electronic devices.

7. The application according to claim 6, wherein The electronic devices include one or more of organic light-emitting 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 photoreceptors, organic field quenching devices, light-emitting electrochemical cells or organic laser diodes.

8. An organic electroluminescent device, characterized in that, The organic light-emitting device includes a cathode, an anode, and an organic functional layer therebetween; the organic functional layer includes a light-emitting layer, and the light-emitting layer includes the platinum (II) complex guest phosphorescent material according to any one of claims 1-5.

9. The organic electroluminescent device according to claim 8, wherein The organic functional layer further includes a fluorescent doping material, and the fluorescent doping material is a boron-containing compound.

10. 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; a second electrode on the organic light-emitting functional layer; wherein, the organic light-emitting functional layer includes the platinum (II) complex guest phosphorescent material according to any one of claims 1-5.

11. A composition, characterized in that, The composition includes the platinum (II) complex guest phosphorescent material according to any one of claims 1-5.

12. A preparation, characterized in that, The preparation includes the platinum (II) complex guest phosphorescent material according to any one of claims 1-5.

13. A display or lighting device, characterized in that, The device includes one or more of the organic light-emitting device according to claim 8 or the organic optoelectronic device according to claim 10.

Images