Phenol oxygen coordinated fluorine-containing N / C / N / O tetradentate metal platinum (II) complex and application thereof

Abstract

The invention belongs to the field of organic electroluminescence, and particularly relates to a phenol oxygen coordinated fluorine-containing N / C / N / O tetradentate metal platinum (II) complex and application thereof. Fluorine atoms are introduced into the tetradentate metal platinum (II) complex to regulate and control charge distribution in molecules, energy transmission between a subject and an object is facilitated, the current efficiency of a device is improved, and the service life of the device is prolonged. The phosphorescent material provided by the invention has good chemical stability and can balance hole and electron transport, energy transmission between a subject and an object is more efficient, which is specifically shown as improvement of the current efficiency of the light-emitting device when the complex is used as a light-emitting layer of the organic light-emitting device, so that the luminous efficiency of the organic light-emitting device is improved. The organic light emitting diode has a great application prospect in the field of OLED display and illumination.

Description

Technical Field

[0001] The invention belongs to the field of organic electroluminescence, and specifically relates to a phenolic oxygen coordinated fluorine-containing N / C / N / O tetradentate metal platinum (II) complex and application thereof. Background Art

[0002] Organic Light Emitting Diode (OLED) is abbreviated as OLED display. Compared with liquid crystal display, it has higher brightness, thinner volume, faster response, low energy consumption, high contrast, wide viewing angle, full color, and wide operating temperature range.

[0003] Organic light-emitting materials are a very critical component of OLED devices and have undergone several generations of updates and development. There are many different types of heavy metal complex phosphorescent materials. According to the number of teeth, they can be divided into bidentate, tridentate and tetradentate platinum complex phosphorescent materials. As the number of teeth increases, non-radiative transitions weaken and intersystem crossings increase. In addition, compared with bidentate and tridentate, tetradentate platinum complexes have good material stability, long life, flexible ligand structure, strong molecular rigidity, and high efficiency of the manufactured devices. Therefore, tetradentate heavy metal complexes are a hot topic in the current OLED research field. In recent years, people have conducted in-depth research on heavy metal platinum complex phosphorescent materials. Designing phosphorescent materials with novel structures and superior performance is a goal that people have always pursued.

[0004] The light-emitting layer in the currently used OLED devices almost all uses the host-guest light-emitting system mechanism, that is, the guest light-emitting material is doped in the main material, the energy system of the main material is generally greater than that of the guest light-emitting material, and the energy is transferred from the main material to the guest material, so that the guest material is excited and emits light. Commonly used organic phosphorescent guest materials are generally heavy metal atoms such as iridium (III), platinum (II), Pd (II), etc. Compared with metallic iridium, the metal platinum element is available in large quantities in the world and is cheap; in addition, the preparation of iridium (III) complex phosphorescent materials involves four steps of reactions, including iridium (III) dimer, iridium (III) intermediate ligand exchange, synthesis of mer-iridium (III) complex, and conversion of mer- to fac-iridium (III) complex isomers, which greatly reduces the overall yield, greatly reduces the utilization rate of the raw material IrCl3.H2O, and improves the preparation cost of iridium (III) complex phosphorescent materials. In contrast, the preparation of platinum (II) complex phosphorescent materials only involves the last step of metallization of the ligand to design the reaction of the platinum salt. The utilization rate of the platinum element is high, which can further reduce the preparation cost of platinum (II) complex phosphorescent materials. In summary, the preparation cost of platinum (II) complex phosphorescent materials is much lower than that of iridium (III) complex phosphorescent materials. However, there are still some technical difficulties in the development of platinum and palladium complex materials and devices. How to improve the efficiency and life of the device is a relatively important research issue. Therefore, it is urgent to develop new phosphorescent metal platinum (II) complexes. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide a fluorinated N / C / N / O tetradentate metal platinum (II) complex coordinated by phenol oxygen and its application. Fluorine atoms are introduced into the tetradentate metal platinum (II) complex of the present invention to regulate the charge distribution in the molecule, which is beneficial to the energy transfer between the host and the guest, and improves the current efficiency and life of the device.

[0006] To achieve the above technical objectives, the technical solution of the present invention is as follows:

[0007] The present invention provides a fluorine-containing N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen, the structure of which is shown in formula (I):

[0008]

[0009] In formula (I), R 1 -R 8 Each independently represents a single substitution to the maximum amount of substitution, or no substitution; R 1 -R 8 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, CN, C1-C30 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, and combinations thereof; wherein adjacent substituents may form a cyclic structure.

[0010] Furthermore, R 1 -R 8 Each is independently selected from the group consisting of 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, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, and combinations thereof.

[0011] Optionally, the R 1 Selected from hydrogen, deuterium, CN, isopropyl, tert-butyl, benzene, and combinations thereof.

[0012] Optional, R 3 , R 5 , R 6 , R 7 Each is independently selected from the group consisting of hydrogen, deuterium, F, methyl, ethyl, propyl, tert-butyl, and combinations thereof.

[0013] Optionally, the R 4 Selected from hydrogen, deuterium, tert-butyl, benzene, and combinations thereof.

[0014] Optionally, the R 8 Selected from hydrogen, deuterium, F, 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, isoheptyl, sec-heptyl, tert-heptyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzene, and combinations thereof.

[0015] Optionally, the fluorinated N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen is selected from any one of the chemical structures shown below: wherein "-D" represents deuterium, -Ph represents phenyl, and -Ph-d5 represents that five hydrogen atoms on the phenyl group are deuterated:

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030] Furthermore, the present invention also provides the use of the fluorinated N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen having the structure shown in formula (I) in electronic devices.

[0031] Furthermore, the electronic devices include organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs), and organic laser diodes (O-lasers).

[0032] In another aspect, the present invention also provides an organic electroluminescent device, which comprises the fluorine-containing N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen and having a structure shown in formula (I) as described above.

[0033] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the fluorinated N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen and having the structure shown in formula (I) as described above.

[0034] Preferably, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the fluorinated N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen and having the structure shown in formula (I) as described above.

[0035] Furthermore, the light-emitting layer further comprises a fluorescent doping material; the fluorescent doping material is preferably a boron-containing organic molecular light-emitting material.

[0036] In another aspect, the present invention also provides an organic photoelectric device, which comprises: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; a second electrode, which is on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises a phenolic oxygen-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex having a structure shown in formula (I) as above. For example, the platinum (II) complex can be included in the organic light-emitting functional layer as a light-emitting material.

[0037] Furthermore, the organic light-emitting functional layer further comprises any one or more fluorescent doping materials, and the fluorescent doping material is preferably a boron-containing organic molecular light-emitting material, preferably a phosphorescence-sensitized boron-containing compound.

[0038] In the present invention, the organic photoelectric device can be prepared by evaporating metal or conductive oxides and their alloys on a substrate to form an anode by using a method such as sputtering coating, electron beam evaporation, vacuum evaporation, etc.; a hole injection layer, a hole transport layer, a light-emitting layer, an air blocking layer and an electron transport layer are sequentially evaporated on the surface of the prepared anode, and then a cathode is evaporated. In addition to the above method, an organic electroluminescent device is prepared by evaporating a cathode, an organic layer and an anode on a substrate in sequence. The organic layer can also include a multilayer 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 layer is 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.

[0039] The present invention also provides a composition, which comprises a fluorine-containing N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen having a structure as shown in formula (I) above. Preferably, the composition further comprises a fluorescent doping material, and the fluorescent doping material is preferably a boron-containing organic molecular luminescent material, preferably a phosphorescently sensitized boron-containing compound.

[0040] The present invention also provides a preparation, which comprises the fluorine-containing N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen having the structure shown in formula (I) as above or the composition as described above and at least one solvent.

[0041] The solvent is not particularly limited and may be used, for example, unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, butyl chloride, butyl bromide, pentyl chloride, pentyl bromide, hexyl chloride, hexyl bromide, cyclohexyl chloride, cyclohexyl bromide, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran, tetrahydropyran, and ester solvents such as alkyl benzoate.

[0042] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] The introduction of fluorine atoms into the tetradentate platinum (II) complex of the present invention can regulate the charge distribution in the molecule, facilitate the energy transfer between the host and the guest, and improve the current efficiency and life of the device. The phosphorescent material provided by the present invention has good chemical stability, can balance the transport of holes and electrons, and the energy transfer between the host and the guest is more efficient, which is specifically manifested in the use of the complex of the present invention as the light-emitting layer of the organic electroluminescent device, and the current efficiency of the light-emitting device is improved, which has great application prospects in the field of OLED display and lighting. DETAILED DESCRIPTION

[0045] The contents of the present invention will be described in detail below. The description of the constituent elements described below may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0046] The term "substituted" used in the present invention is intended to include all allowed substituents of organic compounds. In a wide aspect, allowed 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, allowed substituents can be one or more, the same or different. For the purpose of the present invention, the present invention is not intended to be any restriction in any way with the allowed substituents of organic compounds. Similarly, the term "substituted" or "substituted with" contains implicit conditions that this substitution conforms to the allowed valence of the substituted atom and the substituent, and the substitution leads to a stable compound (for example, a compound that will not spontaneously undergo transformation (for example, by rearrangement, cyclization, elimination, etc.)). It is also expected that, in some aspects, unless explicitly indicated to the contrary, a single substituent can be further optionally substituted (that is, further substituted or unsubstituted).

[0047] In defining various terms, “R 1 ”-“R 8 " are used as general symbols 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 limited to certain substituents in one case, they can be limited to some other substituents in other cases. The "R" used in the present invention can be any substituent, not limited to those disclosed in the present invention, and when they are limited to certain substituents in one case, they can be limited to some other substituents in other cases. 1 ”, “R 2 ”…“R n " ”(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R 1 If it is a straight chain alkyl, then one of the hydrogen atoms of the alkyl may be optionally substituted with a hydroxyl, alkoxy, alkyl, halogen, etc. Depending on the groups selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendant, ie attached to the second group.

[0048] The term "alkyl" used in the present invention is a saturated hydrocarbon group of 1 to 30 carbon atoms that is branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, silyl, sulphur-oxo or sulfhydryl groups described in the present invention.

[0049] The term "aryl" used in the present invention is a group containing any carbon-based aromatic group of 5 to 30 carbon atoms, and the carbon-based aromatic group includes but is not limited to phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group, and the aromatic group has 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. Similarly, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group containing an aromatic group, and the aromatic group does not contain heteroatoms. Aryl can be substituted or unsubstituted. The aryl group 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, azido, nitro, silyl, sulfo-oxo or thiol groups described herein.

[0050] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be tuned by selecting appropriate ligands. In another aspect, the invention can exclude any one or more compounds, structures or portions thereof specifically recited herein.

[0051] The compounds of the present invention may be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0052] It should be noted that the above general description and the following detailed description are only exemplary and explanatory, and are not limiting. The present application can be more easily understood by referring to the following specific implementation manner and the examples contained therein.

[0053] 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 otherwise indicated), or specific reagents (otherwise otherwise indicated), as this can of course vary. It should also be understood that the terms used in the present invention are only used for the purpose of describing specific aspects 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 the practice or test, exemplary methods and materials are described below. Synthesis Examples All raw materials and solvents are commercially available unless otherwise specified, and solvents are used directly without further treatment.

[0054] The substrate of the present invention can be any substrate used in typical organic optoelectronic devices. It can be a glass or transparent plastic substrate, or a substrate of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, the use direction is different. As the material for the hole injection layer, the hole transport layer, and the electron injection layer, any material can be selected from the known related materials for OLED devices, and the present invention does not make specific restrictions thereon.

[0055] Synthesis Example

[0056] The following examples of compound synthesis, composition, device or method are only to provide a general method for the industry, and are not intended to limit the scope of protection of the patent. The data (quantity, temperature, etc.) mentioned in the patent are as accurate as possible, but there may be some errors. Unless otherwise specified, weighing is separate weighing, temperature is ℃, or room temperature, and pressure is close to normal pressure.

[0057] The following examples provide methods for preparing new compounds, but the preparation of such compounds is not limited to this method. In this professional and technical field, since the protected compounds in the present invention are easy to modify and prepare, their preparation can adopt the following methods or other methods. The following examples are only examples and are not intended to limit the scope of protection of this patent. Temperature, catalyst, concentration, reactants and reaction process can all be changed to select different conditions for preparing the compounds for different reactants.

[0058] 1 H NMR (500MHz), 1 H NMR (400MHz), 13 C NMR (126 MHz) spectra were measured on an ANANCE III (500M) NMR spectrometer. Unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR. 1 When CDCl3 is used as the solvent, TMS (δ=0.00 ppm) is used as the internal standard for H NMR spectra. When DMSO-d6 is used as the solvent, TMS (δ=0.00 ppm) or the residual DMSO peak (δ=2.50 ppm) or the residual water peak (δ=3.33 ppm) is used as the internal standard. 13 In the C NMR spectrum, CDCl3 (δ=77.00 ppm) or DMSO-d6 (δ=39.52 ppm) was used as the internal standard. HPLC-MS was measured on an Agilent 6210TOF LC / MS mass spectrometer; HRMS spectrum was measured on an Agilent 6210TOF LC / MS liquid chromatography-time of flight mass spectrometer. 1 In H NMR spectrum data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0059] Intermediate Synthesis Route

[0060] In order to better understand the present invention, the present invention provides a synthetic route and a synthetic process of an exemplary intermediate for reference. It should be noted that the following example only provides a feasible preparation scheme of one or more intermediates of the present invention, and the intermediates required for each embodiment can be prepared with reference to the following synthetic process. However, the preparation of such intermediate compounds is not limited to this method. The preparation can be carried out by the methods listed below or by other methods known in the art. It is not intended to limit the scope of protection of the present invention.

[0061] The synthetic route of the intermediate t-Bu-F is as follows

[0062]

[0063] Synthesis of intermediate t-Bu-Br: Add 3-tert-butyl-2-hydroxybenzaldehyde (8.0 g, 44.9 mmol, 1.0 equivalent) to the reaction bottle, add dichloromethane (50 mL) to dissolve it and cool the reaction system to 0 ° C, then dissolve liquid bromine (7.2 g, 44.9 mmol, 1.0 equivalent) in dichloromethane and drip it into the reaction bottle with a dropping funnel, keep the temperature low for 1 hour, react at room temperature for 23 hours, and then stop the reaction. Add Na2S2O3 to quench, extract with H2O / DCM, concentrate, separate by silica gel column chromatography, eluent: petroleum ether, and obtain 10.6 g of solid, with a yield of 92%. Use it directly in subsequent reactions.

[0064] Synthesis of intermediate t-Bu-F: Add t-Bu-Br (10.3g, 40.1mmoL, 1.0 equivalent), p-fluorophenylboric acid (6.2g, 44.1mmoL, 1.1 equivalent), tetrakis(triphenylphosphine)palladium (926mg, 0.8mmoL, 0.02 equivalent), potassium carbonate (11.1g, 80.1mmoL, 2.0 equivalent) to the reaction bottle, replace nitrogen, then add dioxane (120mL) and water (30mL), gradually warm to 100°C for 14 hours, and then stop the reaction. Cool to room temperature, concentrate, separate by silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 50:1, and obtain 8.86g of solid, yield 81%. Used directly in subsequent reactions. 1 H NMR (500MHz, CDCl3): δ1.47 (s, 9H), 7.14-7.16 (m, 2H), 7.49-7.52 (m, 2H), 7.54 (d, J = 2.5Hz, 1H), 7.70 (d, J = 2.5Hz, 1H), 9.95 (s, 1H), 11.78 (s, 1H).

[0065] The synthetic route of the intermediate t-Ph-Br-F is as follows

[0066]

[0067] Synthesis of intermediate t-Bu-Br-NH2: Add p-tert-butylaniline (10 g, 67 mmol, 1.0 equivalent) to the reaction flask, add dichloromethane (50 mL) to dissolve it and cool the reaction system to 0 ° C, then slowly add N-bromosuccinimide (NBS) (13.1 g, 73.7 mmol, 1.1 equivalent) to the reaction flask, react at room temperature for 10 hours, and then stop the reaction. Add Na2S2O3 to quench, extract with H2O / DCM, concentrate, separate by silica gel column chromatography, eluent: petroleum ether: dichloromethane = 80:1, and obtain 10.1 g of solid, with a yield of 66%. Use it directly in subsequent reactions.

[0068] Synthesis of intermediate t-Ph-NH2: Add t-Bu-Br-NH2 (10 g, 43.8 mmoL, 1.0 equivalent), phenylboronic acid (5.8 g, 48.2 mmoL, 1.1 equivalent), tetrakis(triphenylphosphine)palladium (1.01 g, 0.88 mmoL, 0.02 equivalent), potassium carbonate (12.1 g, 88 mmoL, 2.0 equivalent), dioxane (120 mL) and water (30 mL) to the reaction bottle. After 36 hours at 100 ° C, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography. The eluent was petroleum ether~petroleum ether: dichloromethane = 30:1, and 8.2 g of solid was obtained, with a yield of 83%. It was directly used for subsequent reactions.

[0069] Synthesis of intermediate t-Ph-Br-NO2: Add t-Ph-NH2 (2.4 g, 10.7 mmoL, 1.0 equivalent) to the reaction bottle, replace nitrogen, add tetrahydrofuran, cool to -78 ° C, slowly add n-butyl lithium (7.0 mL, 11.2 mmoL, 1.05 equivalent), keep low temperature for 1 hour, continue to add 2-bromo-6-fluoronitrobenzene (2.34 g, 10.7 mmoL, 1.0 equivalent) at low temperature, react at room temperature for 5 hours, stop the reaction, add NH4Cl to quench, extract with H2O and EA, concentrate, separate by silica gel column chromatography, eluent: petroleum ether: dichloromethane = 20:1 to obtain 2.4 g of solid, yield 53%. Used directly in subsequent reactions.

[0070] Synthesis of intermediate t-Ph-Br-NH2: Add t-Ph-Br-NO2 (2.4 g, 5.7 mmoL, 1.0 equivalent) and stannous chloride dihydrate (6.4 g, 28.3 mmoL, 5.0 equivalent) to the reaction bottle, add ethanol (50 mL), react at 75 ° C for 11 hours to stop the reaction. Neutralize with NaHCO3 solution, extract with EA, concentrate, separate by silica gel column chromatography, eluent: petroleum ether ~ petroleum ether: dichloromethane = 100:1, and obtain 1.65 g of brown solid with a yield of 74%. Use it directly in subsequent reactions.

[0071] Synthesis of intermediate t-Ph-Br-F: Add t-Ph-Br-NH2 (1.65g, 4.2mmoL, 1.0 equivalent), t-Bu-F (1.2g, 4.4mmoL, 1.05 equivalent), sodium pyrosulfite (952mg, 5mmoL, 1.2 equivalent) to the reaction bottle, then add N,N-dimethylformamide, react at 90℃ for 20 hours to stop the reaction. Concentrate, separate by silica gel column chromatography, eluent: petroleum ether: dichloromethane = 100:1-10:1, and obtain 1.7g of solid, yield 63%. Use it directly in subsequent reactions. 1H NMR (500MHz, CDCl3): δ1.44(s,9H),1.47(s,9H),6.55-6.57(m,2H),6.93-6.99(m,6H),7.00(d,J=2.5Hz,1H),7.05-7.08(m,1H),7.11-7.1 9(m,2H),7.4(d,J=2.0Hz,1H),7.50-7.52(m,1H),7.55(d,J=8.0Hz,1H),7.58(d,J=2.5Hz,1H),7.69(dd,J=8.5,2.5Hz,1H),12.74(s,1H).

[0072] The synthetic route of the intermediate t-dPh-Cl is as follows

[0073]

[0074] Synthesis of intermediate t-Bu: Add p-tert-butylaniline (5 g, 33.5 mmoL, 1.0 equivalent) to the reaction bottle, replace nitrogen, add tetrahydrofuran, cool to -78 ° C, slowly add n-butyllithium (14 mL, 35.2 mmoL, 1.05 equivalent), keep the temperature at low temperature for 1 hour, continue to add 2-chloro-6-fluoronitrobenzene (5.88 g, 33.5 mmoL, 1.0 equivalent) at low temperature, react at room temperature for 15 hours, stop the reaction, add NH4Cl to quench, extract with H2O and EA, concentrate, separate by silica gel column chromatography, eluent: petroleum ether: dichloromethane = 50:1 to obtain 7.3 g of solid, yield 71%. Used directly in subsequent reactions.

[0075] Synthesis of intermediate t-Bu-Br: t-Bu (7.3 g, 24 mmoL, 1.0 equivalent) was added to the reaction flask, dichloromethane (100 mL) was added to dissolve it and the reaction system was cooled to 0 ° C, then liquid bromine (7.65 g, 47.9 mmoL, 2.0 equivalent) was dissolved in dichloromethane and dripped into the reaction flask with a dropping funnel, kept at low temperature for 1 hour, reacted at room temperature for 10 hours, and then the reaction was stopped. Na2S2O3 was added to quench, extracted with H2O / DCM, concentrated, separated by silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 20:1, and 9.97 g of solid was obtained, with a yield of 90%. It was directly used for subsequent reactions. 1 H NMR (500MHz, DMSO): δ1.30 (s, 9H), 6.14 (d, J = 9.2Hz, 1H), 7.63 (d, J = 9.2Hz, 1H), 7.75 (s, 2H), 8.44 (s, 1H).

[0076] Synthesis of intermediate t-Bu-Br-NH2: Add t-Bu-Br (5 g, 10.8 mmoL, 1.0 equivalent) and stannous chloride dihydrate (9.76 g, 43.2 mmoL, 4.0 equivalent) to a reaction flask, add ethanol (50 mL), react at 75 ° C for 3 hours to stop the reaction. Neutralize with NaHCO3 solution, extract with EA, concentrate, separate by silica gel column chromatography, eluent: petroleum ether: dichloromethane = 100:1-50:1, and obtain 3.8 g of yellow solid with a yield of 81%. Use it directly in subsequent reactions. 1 H NMR (500MHz, DMSO): δ1.30 (s, 9H), 5.50 (s, 2H), 5.78 (d, J = 9.0Hz, 1H), 6.73 (d, J = 8.5Hz, 1H), 6.84 (s, 1H), 7.70 (s, 2H).

[0077] Synthesis of intermediate t-Bu-dPh-NH2: t-Bu-Br-NH2 (816 mg, 1.89 mmoL, 1.0 equivalent), phenylboronic acid (483 mg, 3.96 mmoL, 2.1 equivalent), tetrakis(triphenylphosphine)palladium (44 mg, 0.038 mmoL, 0.02 equivalent), potassium carbonate (1.3 g, 9.43 mmoL, 5.0 equivalent), dioxane (12 mL) and water (3 mL) were added to the reaction bottle. The reaction was stopped after 12 hours at 90°C, cooled to room temperature, concentrated, and separated by silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 100: 1, to obtain 715 mg of solid, yield 88%. It was directly used for subsequent reactions.

[0078] Synthesis of intermediate t-Bu-dPh-Cl: Add t-Ph-Br-NH2 (1.4 g, 3.3 mmoL, 1.05 equivalents), t-Bu-F (856 mg, 3.1 mmoL, 1.0 equivalents), sodium pyrosulfite (888 mg, 4.68 mmoL, 1.5 equivalents) to the reaction flask, then add N,N-dimethylformamide, react at 155°C for 12 hours to stop the reaction. Concentrate, separate by silica gel column chromatography, eluent: petroleum ether: ethyl acetate = 20:1, and obtain 1.15 g of solid, yield 54%. Use it directly in subsequent reactions.

[0079] The synthetic route of intermediate A-1 is as follows

[0080]

[0081] Synthesis of intermediate A-1-I: Add A-1-Cl (1.53 g, 8.07 mmoL, 1.0 equivalent) to the reaction bottle, then add 1,1-bis(diphenylphosphine)diferronichloridopalladium (590 mg, 0.8 mmoL, 0.1 equivalent), N,N'-dimethylethylenediamine (142 mg, 1.61 mmoL, 0.2 equivalent), sodium iodide (2.41 g, 16.1 mmoL, 2.0 equivalent), and toluene (20 mL). After reacting at 110°C for 18 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 1.52 g of solid with a yield of 67%. It was directly used for subsequent reactions.

[0082] Synthesis of intermediate t-Bu-A-1-Br: Add A-1-I (1.52 g, 5.4 mmoL, 1.0 equivalent) to a reaction flask, then add B-1 (2.75 g, 8.1 mmoL, 1.5 equivalent), tetrakis(triphenylphosphine)palladium (125 mg, 0.11 mmoL, 0.02 equivalent), potassium carbonate (1.49 g, 1.1 mmoL, 2.0 equivalent), ethylene glycol dimethyl ether (16 mL), ethanol (4 mL) and water (4 mL). After reacting at 70 ° C for 12 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 1.58 g of solid with a yield of 80%. It was directly used for subsequent reactions.

[0083] Synthesis of intermediate A-1: ​​Add t-Bu-A-1-Br (1.58 g, 4.3 mmoL, 1.0 equivalent) to the reaction bottle, then add 1,1-bis(diphenylphosphine)diferronichloridopalladium (63 mg, 0.086 mmoL, 0.02 equivalent), potassium acetate (1.05 g, 10.7 mmoL, 2.5 equivalent), biboric acid pinacol ester (1.64 g, 6.5 mmoL, 1.5 equivalent), dioxane (20 mL). After reacting at 90 ° C for 22 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 1.47 g of solid with a yield of 83%. It was directly used for subsequent reactions.

[0084] Example 1: Phenoloxy-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex Pt1

[0085] The synthetic route is as follows:

[0086]

[0087] Synthesis of ligand L1: Add A-1 (1.14 g, 2.8 mmoL, 1.05 equivalents) to a reaction flask, then add t-Ph-Br-F (1.7 g, 2.6 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (61 mg, 0.05 mmoL, 0.02 equivalents), potassium carbonate (726 mg, 5.2 mmoL, 2.0 equivalents), dioxane (12 mL) and water (3 mL). After reacting at 100°C for 14 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 1.7 g of solid with a yield of 75%. It was directly used for subsequent reactions.

[0088] Synthesis of metal complex Pt1: Add L1 (1.7 g, 2 mmol, 1.0 equivalent) to the reaction flask, add potassium tetrachloroplatinate (991 mg, 2.4 mmol, 1.2 equivalent), reflux in a mixed solvent of acetic acid and water for 24 hours, stop the reaction, cool to room temperature, concentrate, separate by silica gel column chromatography, and obtain 896 mg of solid, with a yield of 43%. MS: m / z 1047.40 (M+H) + .

[0089] Example 2: Phenoloxy-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex Pt2

[0090] The synthetic route is as follows

[0091]

[0092] Synthesis of ligand L2: Add A-1 (728 mg, 1.77 mmoL, 1.05 equivalents) to a reaction flask, then add t-Bu-dPh-Cl (1.14 g, 1.68 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (39 mg, 0.034 mmoL, 0.02 equivalents), potassium carbonate (464 mg, 3.4 mmoL, 2.0 equivalents), dioxane (12 mL) and water (3 mL). After reacting at 100 ° C for 10 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 1.37 g of solid with a yield of 88%. It was directly used for subsequent reactions.

[0093] Synthesis of metal complex Pt2: Add L2 (1.37 g, 1.47 mmol, 1.0 equivalent) and potassium tetrachloroplatinate (734 mg, 1.77 mmol, 1.2 equivalent) to a reaction flask, reflux in a mixed solvent of acetic acid and water for 24 hours, stop the reaction, cool to room temperature, concentrate, and separate by silica gel column chromatography to obtain 496 mg of solid, with a yield of 30%. MS: m / z 1123.42 (M+H) + .

[0094] Example 3: Phenoloxy-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex Pt3

[0095] The synthetic route is as follows

[0096]

[0097] Synthesis of intermediate A-3: Referring to the synthesis of intermediate A-1, replace A-1-Cl with 2-chloro-4-(p-tolyl)pyridine and continue the subsequent reaction to obtain A-3.

[0098] Synthesis of ligand L3: Add A-3 (1 g, 2.4 mmoL, 1.05 equivalents) to a reaction flask, then add t-Ph-Br-F (1.5 g, 2.3 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (54 mg, 0.046 mmoL, 0.02 equivalents), potassium carbonate (640 mg, 4.6 mmoL, 2.0 equivalents), dioxane (12 mL) and water (3 mL). After reacting at 100 ° C for 10 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 1.64 g of solid with a yield of 82%. It was directly used for subsequent reactions.

[0099] Synthesis of metal complex Pt3: Add L3 (1.64 g, 1.88 mmol, 1.0 equivalent) and potassium tetrachloroplatinate (940 mg, 2.3 mmol, 1.2 equivalent) to a reaction flask, reflux in a mixed solvent of acetic acid and water for 15 hours, stop the reaction, cool to room temperature, concentrate, and separate by silica gel column chromatography to obtain 902 mg of solid, with a yield of 45%. MS: m / z 1061.41 (M+H) + .

[0100]

[0101] Example 4: Phenoloxy-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex Pt4

[0102] The synthetic route is as follows

[0103] Synthesis of intermediate A-4: Referring to the synthesis of intermediate A-1, replace A-1-Cl with 2-chloro-4-(4-isopropylphenyl)pyridine and continue the subsequent reaction to obtain A-4.

[0104] Synthesis of ligand L4: Add A-4 (1.1 g, 2.4 mmoL, 1.05 equivalents) to a reaction flask, then add t-Ph-Br-F (1.5 g, 2.3 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (54 mg, 0.046 mmoL, 0.02 equivalents), potassium carbonate (640 mg, 4.6 mmoL, 2.0 equivalents), dioxane (12 mL) and water (3 mL). After reacting at 100 ° C for 10 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 1.85 g of solid with a yield of 89%. It was directly used for subsequent reactions.

[0105] Synthesis of metal complex Pt4: Add L4 (1.85 g, 2.1 mmol, 1.0 equivalent) and potassium tetrachloroplatinate (1.03 g, 2.5 mmol, 1.2 equivalent) to a reaction flask, reflux in a mixed solvent of acetic acid and water for 15 hours, stop the reaction, cool to room temperature, concentrate, and separate by silica gel column chromatography to obtain 832 mg of solid, with a yield of 37%. MS: m / z 1089.44 (M+H) + .

[0106] Example 5: Phenoloxy-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex Pt5

[0107] The synthetic route is as follows

[0108]

[0109] Synthesis of intermediate A-5: Referring to the synthesis of intermediate A-1, replace A-1-Cl with 4-(4-(tert-butyl)phenyl)-2-chloropyridine and continue the subsequent reaction to obtain A-5.

[0110] Synthesis of ligand L5: Add A-5 (1.14 g, 2.4 mmoL, 1.05 equivalents) to a reaction flask, then add t-Ph-Br-F (1.5 g, 2.3 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (54 mg, 0.046 mmoL, 0.02 equivalents), potassium carbonate (640 mg, 4.6 mmoL, 2.0 equivalents), dioxane (12 mL) and water (3 mL). After reacting at 100 ° C for 10 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 1.96 g of solid with a yield of 93%. It was directly used for subsequent reactions.

[0111] Synthesis of metal complex Pt5: Add L5 (1.96 g, 2.15 mmol, 1.0 equivalent) and potassium tetrachloroplatinate (1.07 g, 2.6 mmol, 1.2 equivalent) to a reaction flask, reflux in a mixed solvent of acetic acid and water for 15 hours, stop the reaction, cool to room temperature, concentrate, and separate by silica gel column chromatography to obtain 950 mg of solid, with a yield of 40%. MS: m / z 1103.46 (M+H) + .

[0112] Example 6: Phenoloxy-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex Pt365

[0113] The synthetic route is as follows

[0114]

[0115] Synthesis of intermediate A-365: Referring to the synthesis of intermediate A-1, replace A-1-Cl with 2-chloro-4-(3,5-di-tert-butylphenyl)pyridine-6-d and continue the subsequent reaction to obtain A-365.

[0116] Synthesis of ligand L365: Add A-365 (1.46 g, 2.4 mmoL, 1.05 equivalents) to a reaction flask, then add t-Ph-Br-F (1.5 g, 2.3 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (54 mg, 0.046 mmoL, 0.02 equivalents), potassium carbonate (640 mg, 4.6 mmoL, 2.0 equivalents), dioxane (12 mL) and water (3 mL). After reacting at 100 ° C for 14 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 2.13 g of solid, with a yield of 89%. It was directly used for subsequent reactions.

[0117] Synthesis of metal complex Pt365: Add L365 (2.13 g, 2.04 mmol, 1.0 equivalent) and potassium tetrachloroplatinate (1.01 g, 2.45 mmol, 1.2 equivalent) to a reaction flask, reflux in a mixed solvent of acetic acid and water for 15 hours, stop the reaction, cool to room temperature, concentrate, and separate by silica gel column chromatography to obtain 959 mg of solid, with a yield of 38%. MS: m / z 1236.56 (M+H) + .

[0118] Example 7: Phenoloxy-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex Pt377

[0119] The synthetic route is as follows

[0120]

[0121] Synthesis of intermediate A-377: Referring to the synthesis of intermediate A-1, replace A-1-Cl with 4-(4-(tert-butyl)phenyl)-2-chloropyridine-6-d, replace B-1 with 2-(5-bromo-2',6'-diisopropyl-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane and continue the subsequent reaction to obtain A-377.

[0122] Synthesis of ligand L377: Add A-377 (1.39 g, 2.4 mmoL, 1.05 equivalents) to a reaction flask, then add t-Ph-Br-F (1.5 g, 2.3 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (54 mg, 0.046 mmoL, 0.02 equivalents), potassium carbonate (640 mg, 4.6 mmoL, 2.0 equivalents), dioxane (12 mL) and water (3 mL). After reacting at 100 ° C for 11 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 2.10 g of solid, with a yield of 90%. It was directly used for subsequent reactions.

[0123] Synthesis of metal complex Pt377: Add L377 (2.10 g, 2.07 mmol, 1.0 equivalent) and potassium tetrachloroplatinate (1.03 g, 2.48 mmol, 1.2 equivalent) to a reaction flask, reflux in a mixed solvent of acetic acid and water for 15 hours, stop the reaction, cool to room temperature, concentrate, and separate by silica gel column chromatography to obtain 824 mg of solid, with a yield of 33%. MS: m / z 1208.53 (M+H) + .

[0124] Example 8: Phenoloxy-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex Pt385

[0125] The synthetic route is as follows

[0126]

[0127] Synthesis of intermediate A-385: Referring to the synthesis of intermediate A-1, replace A-1-Cl with 2-chloro-4-(3,5-di-tert-butylphenyl)pyridine-6-d, replace B-1 with 2-(5-bromo-2',4',6'-triisopropyl-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane and continue the subsequent reaction to obtain A-385.

[0128] Synthesis of ligand L385: Add A-385 (1.62 g, 2.4 mmoL, 1.05 equivalents) to a reaction flask, then add t-DPh-Br-F (1.5 g, 2.3 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (54 mg, 0.046 mmoL, 0.02 equivalents), potassium carbonate (640 mg, 4.6 mmoL, 2.0 equivalents), dioxane (12 mL) and water (3 mL). After reacting at 100 ° C for 8 hours, the reaction was stopped, cooled to room temperature, concentrated, and separated by silica gel column chromatography to obtain 2.13 g of solid, with a yield of 83%. It was directly used for subsequent reactions.

[0129] Synthesis of metal complex Pt385: Add L385 (2.13 g, 1.90 mmol, 1.0 equivalent) and potassium tetrachloroplatinate (948 mg, 2.3 mmol, 1.2 equivalent) to a reaction flask, reflux in a mixed solvent of acetic acid and water for 15 hours, stop the reaction, cool to room temperature, concentrate, and separate by silica gel column chromatography to obtain 999 mg of solid, with a yield of 40%. MS: m / z 1311.66 (M+H) + .

[0130] Example 9: Synthesis of Pt6

[0131] Pt6 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (832 mg) with a yield of 29%. MS: m / z 1065.38 (M+H) + .

[0132] Example 10: Synthesis of Pt9

[0133] Pt9 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (552 mg) with a yield of 40%. MS: m / z 1115.46 (M+H) + .

[0134] Example 11: Synthesis of Pt10

[0135] Pt10 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (583 mg) with a yield of 44%. MS: m / z 1129.48 (M+H) + .

[0136] Example 12: Synthesis of Pt25

[0137] Pt10 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (632 mg) with a yield of 49%. MS: m / z 1103.44 (M+H) + .

[0138] Example 13: Synthesis of Pt28

[0139] Pt10 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (819 mg) with a yield of 53%. MS: m / z 1131.48 (M+H) + .

[0140] Example 14: Synthesis of Pt30

[0141] Pt30 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (721 mg) with a yield of 35%. MS: m / z 1086.41 (M+H) + .

[0142] Example 15: Synthesis of Pt52

[0143] Pt52 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (725 mg) with a yield of 41%. MS: m / z 1103.46 (M+H) + .

[0144] Example 16: Synthesis of Pt92

[0145] Pt92 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (883 mg) with a yield of 43%. MS: m / z 1283.55 (M+H) + .

[0146] Example 17: Synthesis of Pt112

[0147] Pt112 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (832 mg) with a yield of 39%. MS: m / z 1187.55 (M+H) + .

[0148] Example 18: Synthesis of Pt135

[0149] Pt135 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (552 mg) with a yield of 38%. MS: m / z 1103.46 (M+H) + .

[0150] Example 19: Synthesis of Pt148

[0151] Pt148 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (583 mg) with a yield of 36%. MS: m / z 1283.55 (M+H) + .

[0152] Example 20: Synthesis of Pt194

[0153] Pt194 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (832 mg) with a yield of 39%. MS: m / z 1145.51 (M+H) + .

[0154] Example 21: Synthesis of Pt213

[0155] Pt213 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (769 mg) with a yield of 42%. MS: m / z 1269.54 (M+H) + .

[0156] Example 22: Synthesis of Pt249

[0157] Pt249 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (825 mg) with a yield of 43%. MS: m / z 1173.54 (M+H) + .

[0158] Example 23: Synthesis of Pt295

[0159] Pt295 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (881 mg) with a yield of 37%. MS: m / z 1191.53 (M+H) + .

[0160] Example 24: Synthesis of Pt311

[0161] Pt311 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (953 mg) with a yield of 49%. MS: m / z 1209.44 (M+H) + .

[0162] Example 25: Synthesis of Pt316

[0163] Pt316 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (964 mg) with a yield of 34%. MS: m / z 1205.51 (M+H)+ .

[0164] Example 26: Synthesis of Pt321

[0165] Pt321 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (899 mg) with a yield of 32%. MS: m / z 1183.43 (M+H) + .

[0166] Example 27: Synthesis of Pt336

[0167] Pt336 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (952 mg) with a yield of 38%. MS: m / z 1280.52 (M+H) + .

[0168] Example 28: Synthesis of Pt363

[0169] Pt363 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (938 mg) with a yield of 45%. MS: m / z 1357.66 (M+H) + .

[0170] Example 29: Synthesis of Pt387

[0171] Pt387 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (490 mg) with a yield of 41%. MS: m / z 1336.66 (M+H) + .

[0172] Example 30: Synthesis of Pt389

[0173] Pt389 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1 in Example 1. The target product was obtained as a yellow solid (557 mg) with a yield of 36%. MS: m / z 1337.69 (M+H) + .

[0174] Theoretical calculation description: Density functional theory (DFT) was used to optimize the geometric structure of the ground state (S0) molecule. DFT calculations were performed using the B3LYP functional, with the 6-31G(d) basis set for C, H, O, and N atoms and the LANL2DZ basis set for Pt atoms. RPt was used as a comparative example.

[0175] Table 1. Frontier orbital distribution of some metal complexes of the present invention

[0176]

[0177]

[0178] From the calculated data in Table 1, it can be seen that the introduction of substituents at different positions in the molecule can change the frontier orbital of the molecule.

[0179] Table 2. Frontier orbital energy levels of some metal complexes

[0180]

[0181]

[0182] It can be seen from Tables 1 and 2 that the HOMO of the parent core is mainly distributed on the benzene ring where the central metal atom and the phenolic oxygen are located and the benzene ring containing fluorine atoms connected to it, while the LUMO is mainly distributed on the p-phenylpyridine unit. Compared with RPt, the HOMO orbital distribution of fluorinated molecules is more delocalized, which is conducive to hole transport and thus helps to increase the carrier rate.

[0183] Pt3, Pt4, and Pt5 introduce electron-donating groups on the benzene ring of phenylpyridine based on Pt1, which has little effect on the distribution of HOMO orbitals and only a small effect on the distribution of LUMO orbitals, but can increase its steric hindrance and improve the thermal stability of the molecule. However, the energy level difference of Pt3, Pt4, and Pt5 is larger than that of Pt1, so it is expected that their emission spectra will have a blue shift.

[0184] Pt6 introduces fluorine atoms on the benzene ring of p-phenylpyridine on the basis of Pt1, which has a great influence on the distribution of frontier molecular orbitals. As can be seen from Table 2, the HOMO and LUMO orbital energies are reduced, and the energy level difference is slightly reduced compared with Pt1. It is expected that its emission spectrum will produce red shift. For Pt22, Pt24, Pt25, Pt26, and Pt28, substituents are introduced next to the fluorine atoms. Except for the introduction of the tert-butyl group with larger steric hindrance, the energy level difference of Pt25 is slightly increased, and the energy level differences of the other several are reduced, among which Pt26 has the lowest energy level difference, and it is expected that its luminescence may be redder. It can be seen that the complex provided by the present invention introduces substituents at different positions of the molecule, and the frontier orbital energy level of the platinum (II) complex can be adjusted by regulating the ligand structure.

[0185] Fabrication of OLED devices:

[0186] In an organic light-emitting element, carriers are injected into the light-emitting material from the positive and negative electrodes to generate an excited state of the light-emitting material and make it emit light. The fluorine-containing N / C / N / O tetradentate metal platinum (II) complex shown in formula (I) of the present invention can be used as a phosphorescent light-emitting material in excellent organic light-emitting elements such as organic photoluminescent elements or organic electroluminescent elements. The organic photoluminescent element has a structure in which at least a light-emitting layer is formed on a substrate. In addition, the organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer at least includes a light-emitting layer, which can be composed only of a light-emitting layer, or it can have more than one organic layer in addition to the light-emitting layer. As such other organic layers, hole transport layers, hole injection layers, electron blocking layers, hole blocking layers, electron injection layers, electron transport layers, exciton blocking layers, etc. can be listed. The hole transport layer can also be a hole injection transport layer with a hole injection function, and the electron transport layer can also be an electron injection transport layer with an electron injection function. The hole transport layer can include one or more p-type dopants, and each layer can be preferably selected from known or unknown materials without special restrictions. Each layer of the organic light-emitting device of the present invention can be formed by vacuum evaporation, sputtering, ion plating and the like, or wet film forming methods such as spin coating, printing, and the like, and the solvent used is not particularly limited.

[0187] As a reference preparation method for a device embodiment, the present invention deposits a p-doped material on the surface of an ITO glass or an anode with a light-emitting area of ​​2 mm×2 mm, or co-evaporates the p-doped material with a hole injection material at a concentration of 1% to 50% to form a 5-100 nm hole injection layer (HIL), a 5-200 nm hole transport layer (HTL), and then forms a 10-100 nm light-emitting layer (EML) on the hole transport layer (which may contain the complex described in the present invention), an electron transport layer (ETL) of 20-200 nm and a cathode of 50-200 nm; 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 manufacture an OLED device. The OLED is tested by a standard method. The device materials involved in the present invention, unless otherwise specified, can be obtained by known synthesis methods.

[0188] In a preferred specific embodiment, the structure of device example 1 provided by the present invention is: ITO / HT-1:P-3 (95:5v / v%) (10nm) / HT-1 (90nm) / HT-10 (10nm) / H-1: platinum (II) complex (95:5v / v%) (10nm) / ET-13: LiQ (50:50v / v%) (35nm) / ET-14 (40nm) / Al (70nm).

[0189] Device Examples 2 to 30 and Comparative Example 1 were prepared using structures similar to those of Device Example 1, except that Pt2, Pt3, Pt4, Pt5, Pt365, Pt377, Pt385, Pt6, Pt9, Pt10, Pt25, Pt28, Pt30, Pt52, Pt92, Pt112, Pt135, Pt148, Pt194, Pt213, Pt249, Pt295, Pt311, Pt316, Pt321, Pt336, Pt363, Pt387, Pt389 and R1 were used to replace Pt1 in Device Example 1. The luminescence characteristics of the comparative examples and device examples prepared above were tested by standard methods, and the data are shown in Table 2. The device structures involved are as follows:

[0190]

[0191] Table 3. Device luminescence characteristics data table

[0192]

[0193]

[0194] It can be seen from Table 3 that compared with Comparative Example 1, Device Examples 1 to 30 prepared in the present application all show good device performance improvement in driving voltage, current efficiency and device life, indicating that the OLED devices doped with the fluorinated N / C / N / O tetradentate metal platinum (II) complex provided by the present invention can all exhibit strong circularly polarized luminescence signals, and have great application prospects in circularly polarized luminescence and have certain commercial application value.

[0195] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A fluorinated N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen, characterized in that: It has the general structure shown in formula (I): In formula (I), R 1 -R 8 Each independently represents a single substitution to the maximum amount of substitution, or no substitution; R 1 -R 8 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, CN, C1-C30 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, and combinations thereof; wherein adjacent substituents may form a cyclic structure.

2. The fluorinated N / C / N / O tetradentate metal platinum (II) complex according to claim 1, characterized in that: R 1 -R 8 Each is independently selected from the group consisting of 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, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, and combinations thereof.

3. The fluorinated N / C / N / O tetradentate metal platinum (II) complex according to claim 1, characterized in that: The R 1 Selected from hydrogen, deuterium, CN, isopropyl, tert-butyl, benzene, and combinations thereof.

4. The fluorinated N / C / N / O tetradentate metal platinum (II) complex according to claim 1, characterized in that: R 3 , R 5 , R 6 , R 7 Each is independently selected from the group consisting of hydrogen, deuterium, F, methyl, ethyl, propyl, tert-butyl, and combinations thereof.

5. The fluorinated N / C / N / O tetradentate metal platinum (II) complex according to claim 1, characterized in that: The R 4 Selected from hydrogen, deuterium, tert-butyl, benzene, and combinations thereof.

6. The fluorinated N / C / N / O tetradentate metal platinum (II) complex according to claim 1, characterized in that: The R 8 Selected from hydrogen, deuterium, F, 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, isoheptyl, sec-heptyl, tert-heptyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, benzene, and combinations thereof.

7. The fluorinated N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen according to claim 1, characterized in that: Select any one of the chemical structures shown below, wherein "-D" represents deuterium, -Ph represents phenyl, and -Ph-d5 represents that five hydrogen atoms on the phenyl group are deuterated:

8. Use of the fluorinated N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen according to any one of claims 1 to 7 in electronic devices, wherein the electronic devices include one or more of organic electroluminescent 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.

9. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the phenolic oxygen coordinated fluorine-containing N / C / N / O tetradentate metal platinum (II) complex according to any one of claims 1 to 7.

10. An organic electroluminescent device, characterized in that: The organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the fluorine-containing N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen as claimed in any one of claims 1 to 7.

11. The organic electroluminescent device according to claim 9, characterized in that: The light-emitting layer also contains a fluorescent doping material, and the fluorescent doping material is a boron-containing compound.

12. An organic optoelectronic device, characterized in that: The organic photoelectric device comprises: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; and a second electrode, which is on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises the phenolic oxygen-coordinated fluorinated N / C / N / O tetradentate metal platinum (II) complex according to any one of claims 1 to 7.

13. The organic optoelectronic device according to claim 12, characterized in that: The organic light-emitting functional layer further comprises a fluorescent doping material, and the fluorescent doping material is a boron-containing compound.

14. A composition, characterized in that The composition comprises the fluorine-containing N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen as described in any one of claims 1 to 7.

15. A preparation, characterized in that The preparation comprises the fluorine-containing N / C / N / O tetradentate metal platinum (II) complex coordinated by phenolic oxygen as described in any one of claims 1 to 7.

16. A display or lighting device, characterized in that: The device comprises one or more of the organic electroluminescent devices according to any one of claims 9 to 11.

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