Fluorine-containing tetradentate-coordinate platinum(II) complexes, electronic devices, apparatus and their use

Abstract

To provide a fluorine-containing tetradentate platinum (II) complex with excellent chemical stability that enhances transport of holes and electrons, facilitating more efficient energy transfer between the host and guest materials, specifically, enabling improved current efficiency and an extended lifespan when applied in an organic electroluminescent device.SOLUTION: The present invention provides a complex with a structure shown in formula (I) or formula (II) [where Fn indicates that there are one or more F substitutions on a benzene ring where it is located, n is a positive integer from 1 to 5, and R1-R4 are independently selected from the group consisting of H, N, a C1-C30 alkyl, a C1-C30 cycloalkyl, and a C6-C60 aryl).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention belongs to the field of organic electroluminescence and, more specifically, relates to fluorine-containing tetradentate-coordinate platinum(II) complexes, electronic devices, apparatus, and their use. [Background technology]

[0002] Organic light-emitting diodes (OLEDs) are a next-generation full-color display and lighting technology. Compared to liquid crystal displays (LCDs), which have drawbacks such as slow response speed, narrow viewing angles, the need for backlights, and high energy consumption, OLEDs are self-emissive devices, do not require backlights, are energy-efficient, have low drive voltages, fast response speeds, high resolution and contrast, wide viewing angles, and excellent low-temperature characteristics. OLED devices can be made even thinner, can be formed into flexible structures, and also have advantages such as low production costs, simple production processes, and the ability to produce large areas. Therefore, OLEDs are expected to have great potential for application in high-end electronic products and aerospace. With increased investment, further research and development, and upgrades and modifications of production equipment, a wide range of applications and future development potential for OLEDs are anticipated.

[0003] The core of OLED development lies in the design and development of light-emitting materials. In currently used OLED devices, the light-emitting layer almost always uses a host-guest light-emitting system mechanism, that is, a guest light-emitting material is doped into the host material. The energy system of the host material is generally larger than that of the guest light-emitting material, and energy is transferred from the host material to the guest material, exciting the guest material and causing it to emit light. Commonly used organic phosphorescent guest materials are heavy metal atoms such as iridium(III), platinum(II), and Pd(II). Commonly used phosphorescent organic materials mCBP (3,3'-bis(9-carbazolyl)-biphenyl) and 2,6-mCPy (2,6-bis(9-carbazolyl)-pyridine) possess high efficiency and high triplet energy levels, and when used as organic materials, they can efficiently transfer triplet energy from the light-emitting organic material to the guest phosphorescent light-emitting material. However, mCBP has the characteristic of easily transporting holes but poorly transporting electrons, and 2,6-mCPy has insufficient hole transport, which disrupts the charge balance in the light-emitting layer and reduces the current efficiency of the device. In addition, the heavy metal phosphorescent organic complex molecules currently in use are ring metal iridium(III) complex molecules, and their number is limited. The content of metallic platinum element in the Earth's crust and the annual global production are about 10 times that of metallic iridium, and the price of IrCl3·H2O, which is used to manufacture iridium(III) complex phosphorescent materials, is also much higher than the price of platinum(II) complex phosphorescent material PtCl2. Furthermore, the production of iridium(III) complex phosphorescent materials involves four reaction steps: iridium(III)-containing dimer synthesis, iridium(III) intermediate ligand exchange, synthesis of mer-iridium(III) complexes, and conversion from mer- to fac-iridium(III) complex isomers. This significantly reduces the overall yield, drastically decreases the utilization rate of the starting material IrCl3·H2O, and increases the production cost of iridium(III) complex phosphorescent materials.In contrast, the production of platinum(II) complex phosphorescent materials involves a platinum salt reaction in the final stage of ligand metallization, resulting in a high utilization rate of the platinum element and further reducing the production cost of platinum(II) complex phosphorescent materials. As described above, the production cost of platinum(II) complex phosphorescent materials is far lower than that of iridium(III) complex phosphorescent materials. However, there are still technical difficulties in the development of platinum complex materials and devices, and how to improve the efficiency and lifespan of devices remains a crucial research topic. Therefore, the development of new phosphorescent metallic platinum(II) complexes is urgently needed. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The present invention aims to provide a fluorine-containing tetradentate-coordinate platinum(II) complex, electronic devices, apparatus, and their use. The fluorine-containing tetradentate-coordinate platinum(II) complex of the present invention can impart excellent properties to devices as a guest phosphorescent material in the light-emitting layer. Furthermore, when combined with specific host materials, it can improve the current efficiency of electronic devices, particularly organic electroluminescent devices, extend the device lifespan, and reduce the operating voltage of the device. [Means for solving the problem]

[0005] The present invention provides a fluorine-containing tetradentate-coordinating platinum(II) complex having a structure represented by formula (I) or formula (II). [ka] (In equation (I) or equation (II), F n This indicates that there is one or more F substitutions on the benzene ring on which it exists, where n is a positive integer from 1 to 5. R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, nitrogen, C1-C30 alkyl groups, C1-C30 cycloalkyl groups, and C6-C60 aryl groups.

[0006] Preferably, at least one hydrogen of R1, R2, R3, and R4 may be replaced with deuterium.

[0007] Furthermore, each of R1 to R4 is independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C1-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C18 arylamino, and substituted or unsubstituted C6-C18 heterocycloamino.

[0008] Preferably, the fluorine-containing four-coordinate platinum(II) complex is any one selected from the following chemical structures, and "D" represents deuterium.

Chemical formula

[0009] Furthermore, the present invention also provides the use of fluorine-containing tetradentate-coordinate platinum(II) complexes having the structure represented by formula (I) or formula (II) in electronic devices.

[0010] 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 photodetectors, organic photoreceptors, organic electric field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), and organic laser diodes (O-lasers).

[0011] In another aspect, the present invention also provides an organic electroluminescent device comprising a cathode, an anode, and an organic functional layer interposed therebetween, wherein the organic functional layer contains a fluorine-containing tetradentate-coordinate platinum(II) complex represented by formula (I) or formula (II).

[0012] Furthermore, the organic functional layer includes a light-emitting layer containing a fluorine-containing tetradentate-coordinate platinum(II) complex having the structure shown in formula (I) or formula (II).

[0013] Furthermore, the light-emitting layer further contains a fluorescent doping material, the fluorescent doping material being selected from compounds having a structure represented by formula (BN1) or formula (BN2). [ka] (Here, X is O, S, Se or NR) 300 And X1 is either Se or N, R a ~R d These independently represent a single substitution, a double substitution, a triple substitution, a quadruple substitution, or no substitution, and R a ~R d Each of these is independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl. R5 and R6 are each independently selected from substituted or unsubstituted diphenylamino and substituted or unsubstituted carbazolyl, and if substituents are present, the substituents are selected from deuterium, C1-C30 alkyl, and C6-C30 aryl.

[0014] Furthermore, the fluorescent doped material is one of the following chemical structures selected from those shown below, where Ph represents phenyl. [ka] JPEG0007849802000070.jpg211157 JPEG0007849802000071.jpg211155 JPEG0007849802000072.jpg220155 JPEG0007849802000073.jpg220155 JPEG0007849802000074.jpg208155 JPEG0007849802000075.jpg200155 JPEG0007849802000076.jpg209155 JPEG0007849802000077.jpg210155 JPEG0007849802000078.jpg216155 JPEG0007849802000079.jpg220155 JPEG0007849802000080.jpg219155 JPEG0007849802000081.jpg55155

[0015] In another embodiment, the present invention also provides an organic optoelectronic device comprising a substrate layer, a first electrode on the substrate, an organic light-emitting functional layer on the first electrode, and a second electrode on the organic light-emitting functional layer, wherein the organic light-emitting functional layer comprises a fluorine-containing tetradentate-coordinate platinum(II) complex having a structure represented by formula (I) or formula (II). For example, the platinum(II) complex may be included in the organic light-emitting functional layer as a light-emitting material.

[0016] Furthermore, the organic light-emitting functional layer further includes a fluorescent doped material having the structure shown by formula (BN1) or formula (BN2) above.

[0017] The present invention also provides a composition comprising a fluorine-containing tetradentate-coordinate platinum(II) complex having the structure represented by formula (I) or formula (II) above. Preferably, the composition further comprises a fluorescent doped material having the structure represented by formula (BN1) or formula (BN2) above.

[0018] The present invention also provides a formulation comprising a fluorine-containing tetradentate-coordinate platinum(II) complex having the structure represented by formula (I) or formula (II) above, or the composition thereof, and at least one solvent. The solvent is not particularly limited and may be known to those skilled in the art, for example, unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene; halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, and bromocyclohexane; halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; ether solvents such as tetrahydrofuran and tetrahydropyran; and ester solvents such as alkyl benzoate.

[0019] Preferably, the composition further comprises a fluorescent doped material having the structure represented by formula (BN1) or formula (BN2) above.

[0020] The present invention also provides a display or illumination device comprising one or more of the aforementioned organic optoelectronic devices. [Effects of the Invention]

[0021] Compared to conventional technology, the beneficial effects of the present invention are as follows:

[0022] This invention provides a fluorine-containing tetradentate-coordinate platinum(II) complex phosphorescent material. By introducing fluorine atoms at appropriate positions in the ligand, the charge distribution of its excited state is improved, and the excited state of the material is more of a charge transfer state from metal to pyridocarbene. 3 By incorporating MLCTs, it is advantageous to increase the emissivity and further extend the lifespan of the device. The materials according to the present invention all have good chemical and thermal stability, facilitating the manufacture of vapor-deposited OLED devices. By combining them with fluorescent doping materials, the transport of holes and electrons can be balanced, and energy transfer between the host and guest can be made more efficient. Organic electroluminescent devices using the compounds of the present invention as the light-emitting layer show significant improvements in both current efficiency and lifespan, and the ignition voltage can be greatly reduced. In particular, by using them in combination with phosphorescent boron-containing compounds, the optical color purity of the device can be improved. [Brief explanation of the drawing]

[0023] [Figure 1] These are the room-temperature emission spectra of platinum complexes Pt-169, Pt-170, and Pt-172 in dichloromethane solution. [Modes for carrying out the invention]

[0024] The present invention will now be described in detail. The following descriptions of constituent elements may be based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples.

[0025] As used in this invention, the term “substituted” is assumed to include all permissible substituents of an organic compound. Broadly speaking, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of an organic compound. Exemplary substituents include, for example, those listed below. For a preferred organic compound, there may be one or more permissible substituents, and they may be the same or different. For the purposes of this invention, a heteroatom (e.g., nitrogen) may have a hydrogen substituent and / or any permissible substituent of the organic compound described in this invention that fills the bonds of the heteroatom. This invention is not intended to imply any limitation using permissible substituents of an organic compound. Similarly, the terms “substituted” or “substituted” imply the implicit condition that the substitution matches the permissible bonds of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously convert (e.g., by rearrangement, cyclization, elimination, etc.)). Furthermore, in some embodiments, independent substituents may be further optionally substituted (i.e., may be further substituted or not) unless explicitly stated otherwise.

[0026] When defining various terms, "R1" to "R6" are used in this invention as general symbols to represent various specific substituents. These symbols are not limited to those disclosed herein and may represent any substituent, and may be limited in some cases to specific substituents, or in other cases to other substituents.

[0027] The terms "R1", "R2", "R3" ... "R" used in this invention n) (where n is an integer) may independently have one or more of the groups listed above. For example, if R1 is a linear alkyl group, one hydrogen atom of the alkyl group may be optionally substituted with hydroxyl, alkoxy, alkyl, halogen, etc. Depending on the selected group, the first group may be bonded to the second group, or the first group may be pendanted to the second group, i.e., linked to the second group. For example, in the phrase "alkyl group containing amino," the amino may be bonded to the main chain of the alkyl group, or the amino may be linked to the main chain of the alkyl group. The properties of the selected group determine whether the first group is embedded in or linked to the second group.

[0028] As used in this invention, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group having 1 to 60 carbon atoms, 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, eicosanyl, and tetradecyl. This alkyl may be cyclic or acyclic. This alkyl may be branched or unbranched. This alkyl may be substituted or unsubstituted. For example, this alkyl may be substituted with one or more groups, including but not limited to, the optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxy, nitro, silyl, sulfo-oxo, or mercapto groups described in this invention.

[0029] As used in this invention, the term "aryl" means any carbon-based aromatic group having 5 to 60 carbon atoms, including but not limited to phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenantrenyl, etc. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom introduced into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "nonheteroaryl" (also included in the term "aryl") defines a group containing an aromatic group that does not contain a heteroatom. Aryls may be substituted or unsubstituted. Aryls include, but are not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azide, nitro, silyl, sulfooxo (sulfo-oxo), or mercapto as described in this invention, and may be substituted with one or more groups.

[0030] The compounds of the present invention may include "optionally substituted" moieties. Generally, the term "substituted" means that one or more hydrogens of the moiety in question are substituted with appropriate substituents (whether or not the term "optional" is present at the same time). Unless otherwise stated, an "optionally substituted" group may have appropriate substituents at each of its substituted positions, and if, in a given structure, one or more substituents selected from a particular group are substituted at one or more positions, the substituents at each position may be the same or different. It is preferable that the substituent combinations envisioned by the present invention form stable compounds or chemically feasible compounds. In some embodiments, unless explicitly indicated otherwise, it is also covered that individual substituents may be further optionally substituted (i.e., may be further substituted or not substituted).

[0031] The structure of the compound may also be represented by the following formula.

Chem.

[0032] This is understood to correspond to the following formula.

Chem.

[0033] The compounds disclosed herein can exhibit desired properties and have an emission and / or absorption spectrum that can be adjusted by selecting an appropriate ligand. In another aspect, the present invention can exclude any one or more of the compounds, structures, or portions thereof specifically described herein.

[0034] 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.

[0035] Note that the above general description and the following detailed description are both illustrative and explanatory and not restrictive.

[0036] This application can be more easily understood by referring to the following specific embodiments and the examples included therein.

[0037] 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 synthesis methods (as shown separately) or specific reagents (as shown separately), as they may vary. Furthermore, it should be understood that the terms used in the present invention are used solely for the purpose of describing specific embodiments and are not intended to be limiting. Similar or equivalent methods and materials to those described in the present invention may be used for such implementation or testing, but exemplary methods and materials are described below. All raw materials and solvents in the synthesis examples are commercially available unless otherwise noted, and all solvents are used directly without further processing.

[0038] The substrate of the present invention can be any substrate used in typical organic photoelectric devices. It may be a glass or transparent plastic substrate, an opaque material substrate such as silicon or stainless steel, or a flexible PI film. Mechanical strength, thermal stability, transparency, surface smoothness, and waterproofness differ depending on the substrate, and the direction of use differs depending on the properties of the substrate. As the material for the hole injection layer, hole transport layer, and electron injection layer, any material can be selected from known related materials used in OLED devices, and the present invention is not particularly limited thereto.

[0039] Synthesis Examples The following examples relating to the synthesis, components, devices, or methods of compounds are provided to offer general methods to the relevant industry and are not intended to limit the scope of protection of the patent. While every effort is made to ensure the accuracy of the data described in the patent (quantities, temperatures, etc.), some errors may exist. Unless otherwise specified, measurements are taken separately, temperatures are in °C or room temperature, and pressures are approximately atmospheric pressure.

[0040] The following examples provide methods for producing novel compounds, but the production of such compounds is not limited to these methods. In the art, the compounds protected in this invention are readily available for modification and production, and may be produced by the methods listed below or by other methods. The following examples are merely illustrative and are not intended to limit the scope of protection of this patent. Temperature, catalyst, concentration, reactants, and reaction process can be modified to produce the compounds by selecting different conditions for different reactants.

[0041] 1 1H NMR (500 MHz), 1 1H NMR (400 MHz), 13 The 13C NMR (126 MHz) spectra were measured using an ANANCE III (500M) NMR spectrometer. Unless otherwise specified, nuclear magnetic fields were measured using DMSO-d6 or CDCl3 containing 0.1% TMS as the solvent. 1 For 1H NMR spectroscopy, when CDCl3 is used as the solvent, TMS (δ=0.00 ppm) is used as the internal standard. When DMSO-d6 is used as the solvent, TMS (δ=0.00 ppm), the residual DMSO peak (δ=2.50 ppm), or the residual water peak (δ=3.33 ppm) is used as the internal standard. 13 For 13C NMR spectra, CDCl3 (δ=77.00 ppm) or DMSO-d6 (δ=39.52 ppm) was used as the internal standard. HPLC-MS was measured using an Agilent 6210 TOF LC / MS mass spectrometer. HRMS spectra were measured using an Agilent 6210 TOF LC / MS liquid chromatography-time-of-flight mass spectrometer. 1 In 1H NMR spectral data, s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, m=multiplet, and br=broad.

[0042] Example 1: Synthesis of intermediate dF-NH2 The synthesis scheme for the intermediate dF-NH2 is as follows: [ka] Synthesis of the intermediate (dBr-NH2): Add A (15.0 g, 100 mmol, 1.0 equivalent) to a necked flask equipped with a magnetic stirrer, dissolve with methylene chloride (200 mL), and slowly add N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equivalents) at low temperature. Finally, react at room temperature for 48 hours. After removing the solvent by vacuum distillation, the crude product was separated by silica gel chromatography column (eluent: petroleum ether / ethyl acetate = 80:1) to obtain 28.69 g of red liquid, with a yield of 87%. This was used directly in the next step without structural characterization. Synthesis of the intermediate (dBr-NO2): dBr-NH2 (13.3 g, 43.3 mmol, 1.0 equivalent) was added to a three-necked flask equipped with a magnetic stirrer and dissolved with N-methylpyrrolidone (100 mL). Sodium hydride (5.20 g, 130 mmol, 3.0 equivalents) was slowly added at low temperature, and finally, o-fluoronitrobenzene (7.95 g, 56.3 mmol, 1.3 equivalents) was slowly added. The mixture was reacted at room temperature for 48 hours. After removing the solvent by vacuum distillation, the crude product was separated by silica gel chromatography column (eluent: petroleum ether / ethyl acetate = 50:1) to obtain 13.61 g of a yellow solid with a yield of 75%. This solid was used directly in the next step without structural characterization. Synthesis of the intermediate (dBr-2NH2): 29.6 g of dBr-NO2 (69.2 mmol, 1.0 equivalent) was added to a three-necked flask equipped with a magnetic stirrer. Next, 29.6 g of stannous chloride (277 mmol, 4.0 equivalents) was added. After three nitrogen purgings, 250 mL of ethyl acetate and 250 mL of ethanol were added under nitrogen protection. The mixture was reacted in an oil bath at 78°C for 24 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The crude product was separated by silica gel chromatography column (eluent: petroleum ether / ethyl acetate = 30:1 to 20:1) to obtain 22.4 g of a white solid, with a yield of 81%. This solid was used directly in the next step without structural characterization. Synthesis of the intermediate (dF-NH2): dBr-2NH2 (15.0 g, 37.7 mmol, 1.0 equivalent) was added to a three-necked flask equipped with a magnetic stirrer, followed by the addition of p-fluorophenylboronic acid (15.8 g, 113 mmol, 3.0 equivalents), tetrakis(triphenylphosphine)palladium (871 mg, 0.75 mmol, 0.02 equivalents), and sodium carbonate (12 g, 113 mmol, 3.0 equivalents). After three nitrogen purgings, toluene (150 mL), ethanol (60 mL), and water (15 mL) were added under nitrogen protection. After reacting in a 90°C oil bath for 24 hours, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was then separated by silica gel chromatography column (eluent: petroleum ether / ethyl acetate = 30:1 to 20:1) to obtain 13.41 g of a white solid, with a yield of 83%. 1 H NMR (400 MHz, DMSO) δ 7.43 (dd, J = 8.4, 5.6 Hz, 4H), 7.28 (s, 2H), 7.07 (t, J = 8.8 Hz, 4H), 6.35 - 6.27 (m, 2H), 6.14 (t, J = 7.6 Hz, 1H), 6.02 (d, J = 7.6 Hz, 1H), 5.65 (s, 1H), 4.48 (s, 2H), 1.34 (s, 9H). The above provides only one feasible manufacturing scheme for an intermediate of the present invention, and the intermediates required for each example can be manufactured by referring to the synthesis process of intermediate dF-NH2. The manufacture of such intermediate compounds is not limited to this method. They can be manufactured by the methods listed above or by other methods known in the art. This does not limit the scope of protection of the present invention.

[0043] Example 2: Synthesis of Pt-169 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-169 is as follows. [ka] JPEG0007849802000086.jpg98164 Synthesis of intermediate (M1): 2-methoxycarbazole (20 g, 101 mmol, 1.0 equivalent), 4-(t-butyl)-2-chloropyridine (20.6 g, 121.2 mmol, 1.2 equivalents), tris(dibenzylideneacetone)dipalladium(0) (925 mg, 1.01 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (904 mg, 3.03 mmol, 6 mol%), and sodium tert-butoxide (19.41 g, 202 mmol, 2.0 equivalents) were added to a reaction flask, and toluene (200 mL) was added. The reaction was stopped at 110°C for 48 hours, cooled to room temperature, and the organic phase was separated and concentrated. Silica gel column chromatography was performed to obtain 32.7 g of a white solid, with a yield of 98%. The solid was used directly in the next step without structural characterization. Synthesis of intermediate (M2): M1 (32.7 g, 2.5 mmol, 1.0 equivalent) and hydrogen bromide (80.1 g, 990 mmol, 10.0 equivalents) were added to a reaction flask. The reaction was carried out at 120°C for 24 hours, after which the reaction was stopped, the mixture was cooled to room temperature, the organic phase was separated and concentrated, and subjected to silica gel column chromatography to obtain 862 g of a white solid with a yield of 97%. The solid was used directly in the next step without structural characterization. Synthesis of intermediate (1b): In a reaction flask, M2 (8.0 g, 25.3 mmol, 1.0 equivalent), m-chlorobromobenzene (5.34 g, 27.8 mmol, 1.1 equivalent), 2-picolinic acid (623 mg, 5.06 mmol, 20 mmol%), cuprous iodide (481 mg, 2.53 mmol, 10 mmol%), and potassium phosphate (10.74 g, 50.6 mmol, 2.0 equivalent) were added, and dimethyl sulfoxide (80 mL) was added. The reaction was carried out at 100 °C for 48 hours, after which the reaction was stopped, cooled to room temperature, the organic phase was separated and concentrated, and subjected to silica gel column chromatography to obtain 10.0 g of a white solid with a yield of 93%. The solid was used directly in the next step without structural characterization. Synthesis of intermediate (La-169): dF-NH2 (1.96 mg, 4.60 mmol, 1.0 equivalent) was added to a Schlenk tube equipped with a magnetic stirrer, followed by 1b (2.32 mg, 5.52 mmol, 1.2 equivalents), tris(dibenzylideneacetone)dipalladium(0) (126 mg, 0.14 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (82 mg, 0.28 mmol, 6 mol%), and sodium tert-butoxide (884 mg, 9.20 mmol, 2.0 equivalents). After three nitrogen purgings, toluene (5 mL) was added under nitrogen protection. After reacting in an oil bath at 110°C for 12 hours, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was then separated by silica gel chromatography column (eluent: petroleum ether / ethyl acetate = 60:1 to 20:1) to obtain 2.60 g of a white solid, with a yield of 69%. Ligand (L b -169) Synthesis: L in a Schlenk tube with a magnetic stirrer a -169 (1.10 g, 1.30 mmol, 1.0 equivalent) was added, followed by ammonium hexafluoride phosphate (423 mg, 2.6 mmol, 2.0 equivalent). Then, nitrogen purging was performed three times, and triethyl orthoformate (5 mL) was added under nitrogen protection. The mixture was reacted in an 80°C oil bath for 8 hours, then cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel chromatography column (eluent: petroleum ether / methylene chloride 1:1 - methylene chloride) to obtain 806 g of a white solid, with a yield of 63%. 1H NMR (500 MHz, DMSO-d6) δ 1.28 (s, 9H) 1.44 (s, 9H), 7.02 (t, J = 8.5 Hz, 4H), 7.18 (td, J = 7.5, 8.0, 5.5 Hz, 2H), 7.23- 7.25 (m, 5H), 7.34 - 7.39 (m, 2H), 7.45 - 7.50 (m, 4H), 7.53 - 7.59 (m, 2H), 7.67 - 7.78 (m, 6H), 8.26 (d, J = 7.5 Hz, 1H), 8.34 (d, J = 8.5 Hz, 1H), 8.58 (d, J = 5.0 Hz, 1H), 10.31 (s, 1H), . Synthesis of Pt-169: In a sealed tube with a magnetic stirrer, L a -169 (700g, 0.74 mmol, 1.0 equivalent) was added, followed by dichloro(1,5-cyclooctadiene)platinum(II) (271mg, 0.78 mmol, 1.05 equivalents) and sodium acetate (182mg, 2.22 mmol, 3.0 equivalents). Afterward, nitrogen purging was performed three times, and under nitrogen protection, diethylene glycol dimethyl ether (10mL) was added, and oxygen was removed by nitrogen bubbling for 30 minutes. The mixture was reacted in an oil bath at 120°C for 72 hours, then cooled to room temperature. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel chromatography column (eluent: petroleum ether / methylene chloride 4:1) to obtain 250mg of a blue-yellow solid, with a yield of 33%. 1H NMR (500 MHz, CDCl3) δ 1.21 (s, 9H) , 1.41 (s, 9H), 6.28 (dd, J = 6.0, 4.0 Hz, 1H), 6.86 (d, J = 8.0 Hz, 1H), 7.06 - 7.09 (m, 5H), 7.25 - 7.29 (m, 5H), 7.34 (d, J = 8.0 Hz, 1H), 7.41 - 7.50 (m, 7H), 7.81 (d, J = 8.0 Hz, 1H), 7.85 (d, J = 7.5 Hz, 1H), 7.92 (d, J = 2.0 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 8.11 - 8.13 (m, 1H), 9.00 (d, J = 6.0 Hz, 1H).

[0044] Example 3: Synthesis of Pt-170 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-170 is as follows. [ka] Intermediate (L a Synthesis of -170): 2a (dF-NH2, 850 mg, 1.98 mmol, 1.0 equivalent) was added to a Schlenk tube equipped with a magnetic stirrer, followed by 2b (1.15 mg, 2.38 mmol, 1.2 equivalents), tris(dibenzylideneacetone)dipalladium(0) (55 mg, 0.06 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (36 mg, 0.12 mmol, 6 mol%), and sodium tert-butoxide (380 mg, 3.96 mmol, 2.0 equivalents). After three nitrogen purgings, toluene (5 mL) was added under nitrogen protection. After reacting in an oil bath at 110°C for 12 hours, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was then separated by silica gel chromatography column (eluent: petroleum ether / ethyl acetate = 60:1 to 20:1) to obtain 1.40 g of a white solid, with a yield of 81%. Ligand (L b-170) Synthesis: L in a Schlenk tube with a magnetic stirrer a -170 (1.40 g, 1.80 mmol, 1.0 equivalent) was added, followed by ammonium hexafluoride phosphate (586 mg, 3.6 mmol, 2.0 equivalents). Then, nitrogen purging was performed three times, and triethyl orthoformate (5 mL) was added under nitrogen protection. The mixture was reacted in an 80°C oil bath for 8 hours, then cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel chromatography column (eluent: petroleum ether / methylene chloride 1:1 - methylene chloride) to obtain 1.04 g of a white solid, with a yield of 56%. 1 H NMR (500 MHz, DMSO-d6) δ 1.27 (s, 9H) 1.28 (s, 9H), 1.44 (s, 9H), 6.88 (t, J = 3.5 Hz, 1H), 7.01 (t, J = 9.0 Hz, 4H), 7.11 (t, J = 2.0 Hz, 1H), 7.16 - 7.18 (m, 1H), 7.21 - 7.24 (m, 4H), 7.33 - 7.36 (m, 1H), 7.45 - 7.58 (m, 7H), 7.66 (d, J = 1.5 Hz,1H), 7.72 - 7.76 (m, 4H), 1H), 8.25 (d, J = 8.0 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 8.57 (d, J = 5.5 Hz, 1H), 10.27 (s, 1H), . Pt-170 synthesis: L in a sealed tube with a magnetic stirrer a-170 (400g, 0.39 mmol, 1.0 equivalent) was added, followed by dichloro(1,5-cyclooctadiene)platinum(II) (142mg, 0.41 mmol, 1.05 equivalent) and sodium acetate (96mg, 1.17 mmol, 3.0 equivalent). After three nitrogen purgings, diethylene glycol dimethyl ether (10mL) was added under nitrogen protection, and oxygen was removed by 30 minutes of nitrogen bubbling. The mixture was reacted in an oil bath at 120°C for 72 hours, then cooled to room temperature. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel chromatography column (eluent: petroleum ether / methylene chloride 4:1) to obtain 372 mg of a blue-yellow solid, with a yield of 86%. 1 H NMR (500 MHz, DMSO-d6) δ 1.21 (s, 9H), 1.39 (s, 9H), 1.42 (s, 9H), 5.97 - 6.24 (m, 2H), 6.58 (dd, J = 6.5, 4.5 Hz, 1H), ), 6.90 - 7.19 (m, 8H), 7.35 - 7.62 (m, 8H), 7.84 (d, J = 8.5 Hz, 1H), 7.90 (d, J = 1.5 Hz, 1H), 8.04 (d, J = 8.5 Hz, 1H), 8.16 (d, J = 8.5 Hz, 1H), 8.21 (d, J = 8.0 Hz, 1H), 8.86 (d, J = 6.0 Hz, 1H), .

[0045] Example 4: Synthesis of Pt-172 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-172 is as follows. [ka] Intermediate (L aSynthesis of -172): 3a (dF-NH2, 500 mg, 1.17 mmol, 1.0 equivalent) was added to a Schlenk tube equipped with a magnetic stirrer, followed by 3b (687 mg, 1.17 mmol, 1.2 equivalents), tris(dibenzylideneacetone)dipalladium(0) (32 mg, 0.04 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (20 mg, 0.07 mmol, 6 mol%), and sodium tert-butoxide (224 mg, 2.34 mmol, 2.0 equivalents). After three nitrogen purgings, toluene (5 mL) was added under nitrogen protection. After reacting in an oil bath at 110°C for 12 hours, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was then separated by silica gel chromatography column (eluent: petroleum ether / ethyl acetate = 60:1 to 20:1) to obtain 358 g of a white solid, with a yield of 40%. Ligand (L b -172) Synthesis: L in a Schlenk tube with a magnetic stirrer a -172 (250 mg, 0.26 mmol, 1.0 equivalent) was added, followed by ammonium hexafluoride phosphate (83 mg, 0.52 mmol, 2.0 equivalents). Then, nitrogen purging was performed three times, and triethyl orthoformate (5 mL) was added under nitrogen protection. The mixture was reacted in an 80°C oil bath for 8 hours, then cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel chromatography column (eluent: petroleum ether / methylene chloride 1:1 - methylene chloride) to obtain 110 mg of a white solid, with a yield of 37%. 1H NMR (500 MHz, DMSO-d6) δ 1.04-1.12 (m, 12H). 1.28 (s, 9H), 1.45 (s, 9H), 6.86 (s, 1H), 7.00 (t, J = 8.5 Hz, 5H), 7.19 - 7.23 (m, 3H), 7.24 - 7.27 (m, 4H), 7.32 - 7.35 (m, 2H), 7.44 - 7.49 (m, 3H), 7.53 - 7.59 (m, 2H), 7.62 - 7.66 (m, 2H), 7.69 - 7.70 (m, 1H), 7.73 - 7.76 (m, 3H), 7.81 (d, J = 8.5 Hz, 1H), 8.24 (d, J = 7.5 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 8.55 (d, J = 5.0 Hz, 1H), 10.34 (s, 1H). Synthesis of Pt-172: In a sealed tube with a magnetic stirrer a -172 (60g, 0.05 mmol, 1.0 equivalent) was added, followed by dichloro(1,5-cyclooctadiene)platinum(II) (19mg, 0.06 mmol, 1.05 equivalent) and sodium acetate (13mg, 1.17 mmol, 3.0 equivalent). Afterward, nitrogen purging was performed three times, and under nitrogen protection, diethylene glycol dimethyl ether (10mL) was added, and oxygen was removed by nitrogen bubbling for 30 minutes. The mixture was reacted in an oil bath at 120°C for 72 hours, then cooled to room temperature. The solvent was removed by vacuum distillation, and the crude product was separated by silica gel chromatography column (eluent: petroleum ether / methylene chloride 4:1) to obtain 29 mg of a blue-yellow solid, with a yield of 47%. 1H NMR (500 MHz, Chloroform-d) δ 1.15 - 1.17(m, 12H) 1.22 (s, 9H), 1.42 (s, 9H), 6.29 (dd, J = 6.5, 4.5 Hz, 1H), 6.86 - 6.90 (m, 2H), 7.05 (t, J = 7.5 Hz, 1H), 7.17 - 7.20 (m, 2H), 7.24 - 7.26(m, 9H), 7.34 - 7.51 (m, 7H), 7.81 - 7.88 (m, 3H), 7.94 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 7.0 Hz, 1H), 9.03 (d, J = 6.0 Hz, 1H). Figure 1 shows the room-temperature emission spectra of the prepared complexes Pt-169, Pt-170, and Pt-172 in a methylene chloride solution. As can be seen from Figure 1, the complexes Pt-169, Pt-170, and Pt-172 all emit deep blue light and have high color purity. Pt-169 has a maximum emission peak of 457.4 nm and a full width at half maximum of 20 nm. The present invention improves the charge distribution of its excited state by introducing fluorine atoms at appropriate positions in its ligand, thereby increasing the excited state of the material to a charge transfer state from metal to pyridinocarbene. 3 Having MLCTs (Multiple Cellular Coherence Tolerances) is advantageous for increasing emissivity and extending device lifespan. This provides a useful means for designing platinum(II) complexes for high-quality blue phosphorescent materials.

[0046] Example 5: Synthesis of Pt-4 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-4 is as follows. [ka] Pt-4 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product La-4 was synthesized in 74% yield from 1.09 g of a pale green foamy solid. The target product Lb-4 was synthesized in 65% yield from 801 mg of a pale green foamy solid. Molecular weight [M]+: 896.3. The target product Pt-4 was synthesized in 33% yield from 325 mg of a yellow solid. Molecular weight [M+H]+: 1089.4.

[0047] Example 6: Synthesis of Pt-52 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-52 is as follows. [ka] Pt-52 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product La-52 was synthesized as 1.19 g of a pale green foamy solid in 67% yield. The target product Lb-52 was synthesized as 721 mg of a pale green foamy solid in 63% yield. Molecular weight [M]+: 972.4. The target product Pt-52 was synthesized as 335 mg of a yellow solid in 36% yield. Molecular weight [M+H]+: 1165.3.

[0048] Example 7: Synthesis of Pt-86 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-86 is as follows. [ka] Pt-86 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product La-86 was synthesized as 1.15 g of a pale green foamy solid in 72% yield. The target product Lb-86 was synthesized as 835 mg of a pale green foamy solid in 63% yield. Molecular weight [M]+: 952.4. The target product Pt-86 was synthesized as 319 mg of a yellow solid in 30% yield. Molecular weight [M+H]+: 1144.3.

[0049] Example 8: Synthesis of Pt-144 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material 1Pt-144 is as follows. [ka] Pt-144 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product La-144 was synthesized in 76% yield from 1.23 g of a pale green foamy solid. The target product Lb-144 was synthesized in 65% yield from 823 mg of a pale green foamy solid. Molecular weight [M]+: 990.4. The target product Pt-144 was synthesized in 37% yield from 349 mg of a yellow solid. Molecular weight [M+H]+: 1127.5.

[0050] Example 9: Synthesis of Pt-171 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-171 is as follows. [ka] Pt-171 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product La-171 was synthesized as 1.49 g of a pale green foamy solid in 79% yield. The target product Lb-171 was synthesized as 793 mg of a pale green foamy solid in 63% yield. Molecular weight [M]+: 906.3. The target product Pt171 was synthesized as 325 mg of a yellow solid in 33% yield. Molecular weight [M+H]+: 1099.3.

[0051] Example 10: Synthesis of Pt-312 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-312 is as follows. [ka] Pt-312 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product La-312 was synthesized as 1.22 g of a pale green foamy solid in 77% yield. The target product Lb-312 was synthesized as 811 mg of a pale green foamy solid in 66% yield. Molecular weight [M]+: 1046.5. The target product Pt312 was synthesized as 315 mg of a yellow solid in 32% yield. Molecular weight [M+H]+: 1267.6.

[0052] Example 11: Synthesis of Pt-338 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-338 is as follows. [ka] Pt-338 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product La-338 was synthesized as 1.19 g of a pale green foamy solid in 72% yield. The target product Lb-338 was synthesized as 813 mg of a pale green foamy solid in 64% yield. Molecular weight [M]+: 998.2. The target product Pt-338 was synthesized as 319 mg of a yellow solid in 30% yield. Molecular weight [M+H]+: 1191.5.

[0053] Example 13: Synthesis of Pt-394 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-394 is as follows. [ka] Pt-394 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product La-394 was synthesized as 1.24 g of a pale green foamy solid in 77% yield. The target product Lb-394 was synthesized as 811 mg of a pale green foamy solid in 65% yield. Molecular weight [M]+: 922.3. The target product Pt-394 was synthesized as 309 mg of a yellow solid in 30% yield. Molecular weight [M+H]+: 1115.3.

[0054] Example 14: Synthesis of Pt-422 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-422 is as follows. [ka] Pt-422 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product, La-422, was synthesized as 1.16 g of a pale green foamy solid in 77% yield. The target product, Lb-422, was synthesized as 803 mg of a pale green foamy solid in 63% yield. Molecular weight [M] + : 960.3. The target product Pt-422 was synthesized as 315 mg of yellow solid in a yield of 30%. Molecular weight [M+H] + :1181.4.

[0055] Example 15: Synthesis of Pt-478 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-478 is as follows. [ka] Pt-478 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product, La-478, was synthesized as 1.17 g of a pale green foamy solid in 77% yield. The target product, Lb-478, was synthesized as 814 mg of a pale green foamy solid in 66% yield. Molecular weight [M] + :958.2. The target product Pt-478 was synthesized as 326 mg of yellow solid in a yield of 34%. Molecular weight [M+H] + :1151.3.

[0056] Example 16: Synthesis of Pt-646 The synthesis scheme for the tetradentate-coordinate platinum(II) complex phosphorescent material Pt-646 is as follows. [ka] Pt-646 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-169. The target product, La-646, was synthesized as 1.19 g of a pale green foamy solid in 77% yield. The target product, Lb-646, was synthesized as 823 mg of a pale green foamy solid in 66% yield. Molecular weight [M] + :1030.2. The target product, Pt-646, was synthesized from 314 mg of yellow solid with a yield of 30%. Molecular weight [M+H] + :1246.6.

[0057] Explanation of theoretical calculations The geometric structure of the ground state (S0) molecule was optimized using density functional theory (DFT). DFT calculations were performed using the B3LYP functional, where the 6-31G(d) basis set was used for C, H, O, and N atoms, and the LANL2DZ basis set was used for Pt atoms.

[0058] [Table 1] JPEG0007849802000101.jpg214162 JPEG0007849802000102.jpg213162 JPEG0007849802000103.jpg209162 JPEG0007849802000104.jpg155162

[0059] As can be seen from the above calculation data, the compound materials according to the present invention all have a large energy gap (>2.86 eV) and can meet the demand for blue light materials. Furthermore, the frontier orbital energy levels (HOMO and LUMO) of the platinum(II) complex can be adjusted by controlling the ligand structure. The majority of the LUMO of the pyridocarbene platinum(II) complex is located in the pyridocarbene portion, and in this invention, by introducing a fluorine atom at an appropriate position in the ligand, the charge distribution of its excited state can be improved, and the excited state of the material can be a state of charge transfer from more metal to pyridocarbene. 3The MLCT component is incorporated. Furthermore, since both a coordinate bond and a feedback π bond exist between the carbene and platinum(II), its stability is higher than that of the coordinate bond between pyridine and platinum(II). These results are advantageous for increasing emissivity and extending the device lifespan.

[0060] Manufacturing of OLED devices As a reference manufacturing method for the device embodiment, the present invention involves depositing a p-doped material onto the surface or anode of an ITO glass with an emissive area of ​​2 mm × 2 mm, or co-depositing this p-doped material with a hole injection material at a concentration of 1% to 50%, thereby forming a 5-100 nm hole injection layer (HIL) and a 5-200 nm hole transport layer (HTL). Subsequently, an emissive layer (EML) of 10-100 nm (which may contain the compound of the present invention) is formed on the hole transport layer, followed by the formation of a 20-200 nm electron transport layer (ETL) and a 50-200 nm cathode. An electron blocking layer (EBL) is optionally placed between the HTL and EML layers, and an electron injection layer (EIL) is placed between the ETL and the cathode to fabricate an OLED device. The above OLED was then tested using a standard method. Unless otherwise specified, all device materials according to the present invention can be obtained by known synthesis methods. In a preferred specific embodiment, the structure of Device Example 1 according to the present invention is as follows: ITO / P-4 (10 nm) / NPD (60 nm) / HTH-85 (5 nm) / Platinum(II) complex: HTH-85:ETH-45 (25 nm) (Pt-169:HTH-85:ETH-45 mass ratio 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0061] Device Examples 2 to 15 and Comparative Example 1 were manufactured using a structure similar to Device Example 1, except that Pt-170, Pt-172, Pt-4, Pt-52, Pt-86, Pt-144, Pt-171, Pt-394, Pt-312, Pt-338, Pt-394, Pt-422, Pt-478, Pt-646, and R1 were used instead of Pt-169 in Device Example 1. Table 2 shows the data obtained by testing the luminescence characteristics of the above-manufactured comparative examples and each device example using a standard method. The structural formula of the device is as follows. Here, P-4 is HATCN and ET-14 is BPyTP. [ka] TIFF0007849802000106.tif33134

[0062] [Table 2]

[0063] As can be seen from Table 2, compared to Comparative Example 1, Device Examples 1 to 15 manufactured in this application show superior device performance in terms of drive voltage, current efficiency, and device life. The improvement in the performance of each device example is based on the fact that the specific compound material of the present invention has better electron transport capability. It has been found that by manufacturing electronic devices using this as the light-emitting layer material, it is possible to reduce the drive voltage, improve current efficiency, and extend the device life. It is clear that the compounds according to the present invention have a certain commercial value.

[0064] In a preferred specific embodiment, the structure of device example 16 according to the present invention is as follows: ITO / P-4 (10 nm) / NPD (60 nm) / HTH-85 (5 nm) / platinum(II) complex:boron-containing compound:HTH-85:ETH-45 (25 nm) (Pt169:BN1-8:HTH-85:ETH-45 mass ratio 10:1:59:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0065] Device Examples 17 to 30 were fabricated using the same structure as Device Example 16, except that the compounds listed in Table 3 were used instead of the fluorine-containing tetradentate-coordinate platinum(II) complex and boron-containing compound in Device Example 16. The structure and luminescence properties of the devices are shown in Table 3.

[0066] [Table 3]

[0067] As can be seen from Table 3, by applying the compounds of the present invention as sensitizers, together with boron-containing compounds, as luminescent materials in devices, the performance of each device is significantly improved. Furthermore, it becomes clear that the compounds of the present invention have a certain commercial value.

[0068] Furthermore, all devices manufactured according to this invention are deep blue light devices with a CIEy value of less than 0.20. By adding a boron-containing compound to sensitize the device structure, the CIEy value can be further reduced, and the emission color purity of the device can be improved.

[0069] The foregoing is merely a better specific embodiment of the present invention, and the scope of protection of the present invention is not limited thereto. Those skilled in the art can make equivalent substitutions or modifications based on the technical solutions and inventive concepts of the present invention within the technical scope disclosed herein, and all such substitutions or modifications are included within the scope of protection of the present invention.

Claims

1. A fluorine-containing tetradentate-coordinate platinum(II) complex characterized by having the structure represented by formula (I) or formula (II). 【Chemistry 1】 (In formula (I) or formula (II), F n This indicates that there is one or more F substitutions on the benzene ring in which it exists, where n is a positive integer from 1 to 5, and R 1 , R 2 , R 3 , R 4 Each of these is independently selected from the group consisting of hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C1-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C18 arylamino, and substituted or unsubstituted C6-C18 heterocycloamino, provided that R1, R2, R3, and R4 are not simultaneously hydrogen.

2. The fluorine-containing tetradentate-coordinating platinum(II) complex according to Claim 1, characterized in that when R2 is selected from the group consisting of substituted C1-C30 alkyl, substituted C1-C30 cycloalkyl, substituted C1-C30 heterocycloalkyl, substituted C6-C60 aryl, substituted C6-C18 arylamino, and substituted C6-C18 heterocycloamino, at least one hydrogen of R2 is substituted with deuterium.

3. The fluorine-containing tetradentate-coordinate platinum(II) complex is one selected from the chemical structures shown below, and "D" represents deuterium, as described in claim 1. 【Chemistry 2】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】

4. Use of a fluorine-containing tetradentate-coordinate platinum(II) complex according to any one of claims 1 to 3 in an electronic device.

5. The use according to claim 4, characterized in that the electronic device includes an organic electroluminescent 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 photodetector, an organic photoreceptor, an organic electric field quenching device, a light-emitting electrochemical cell, and an organic laser diode.

6. An organic electroluminescent device comprising a cathode, an anode, and an organic functional layer interposed therebetween, wherein the organic functional layer contains a fluorine-containing tetradentate-coordinate platinum(II) complex as described in any one of claims 1 to 3.

7. The organic electroluminescent device according to claim 6, characterized in that the organic functional layer includes a light-emitting layer containing a fluorine-containing tetradentate-coordinate platinum(II) complex as described in any one of claims 1 to 3.

8. The organic electroluminescent device according to claim 7, characterized in that the light-emitting layer further comprises a fluorescent doping material, the fluorescent doping material being selected from compounds represented by formula (BN1) or formula (BN2). 【Transformation 3】 (Here, X is O, S or Se, X 1 is either Se or N, R a ~R d each independently represents mono-substitution, di-substitution, tri-substitution, tetra-substitution or no substitution, and R a ~R d each independently is selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl, R 5 and R 6 are each independently selected from a substituted or unsubstituted diphenylamino and a substituted or unsubstituted carbazolyl. When containing a substituent, the substituent is selected from deuterium, C1-C30 alkyl, and C6-C30 aryl.)

9. The organic electroluminescent device according to claim 8, characterized in that the fluorescent doped material is one selected from the chemical structures shown below, and Ph represents a phenyl group. 【Chemistry 4】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】

10. Organic optoelectronic devices, An organic optoelectronic device comprising a substrate layer, a first electrode on the substrate, an organic light-emitting functional layer on the first electrode, and a second electrode on the organic light-emitting functional layer, wherein the organic light-emitting functional layer contains a fluorine-containing tetradentate-coordinate platinum(II) complex as described in any one of claims 1 to 3.

11. The organic optoelectronic device according to claim 10, characterized in that the organic light-emitting functional layer further comprises a fluorescent doping material, the fluorescent doping material being selected from compounds represented by formula (BN1) or formula (BN2). 【Transformation 5】 (Here, X is O, S or Se, X 1 is either Se or N, R a ~R d Each of these independently indicates a single substitution, a double substitution, a triple substitution, a quadruple substitution, or no substitution, R a ~R d Each of these is independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl. R 5 and R 6 are each independently selected from a substituted or unsubstituted diphenylamino and a substituted or unsubstituted carbazolyl, and when including a substituent, the substituent is selected from deuterium, C1-C30 alkyl, and C6-C30 aryl.)

12. A composition characterized by containing a fluorine-containing tetradentate-coordinate platinum(II) complex as described in any one of claims 1 to 3.

13. A device characterized by containing a fluorine-containing tetradentate-coordinate platinum(II) complex according to any one of claims 1 to 3.

14. A display or lighting device characterized by comprising one or more of the organic electroluminescent devices described in claim 6.

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