CN115700254B - A divalent platinum complex and its preparation method and use - Google Patents
A divalent platinum complex and its preparation method and use Download PDFInfo
- Publication number
- CN115700254B CN115700254B CN202110857684.7A CN202110857684A CN115700254B CN 115700254 B CN115700254 B CN 115700254B CN 202110857684 A CN202110857684 A CN 202110857684A CN 115700254 B CN115700254 B CN 115700254B
- Authority
- CN
- China
- Prior art keywords
- platinum complex
- divalent platinum
- organic
- light
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
本发明涉及电子材料技术领域，具体涉及一种二价铂络合物及其制备方法和用途。本发明提供的二价铂络合物，具有如式Ⅰ所示的结构，本发明提供的二价铂络合物，该二价铂络合物作为磷光发光材料可以发黄磷光，并且具有色纯度好、稳定性好且效率高，适合作为OLED相关产品中的有机黄磷光发光体。
The present invention relates to the technical field of electronic materials, and in particular to a divalent platinum complex and a preparation method and use thereof. The divalent platinum complex provided by the present invention has a structure as shown in Formula I. The divalent platinum complex provided by the present invention can emit yellow phosphorescence as a phosphorescent material, and has good color purity, good stability and high efficiency, and is suitable as an organic yellow phosphorescent light emitter in OLED related products.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a bivalent platinum complex, a preparation method and application thereof.
Background
Organic electroluminescence refers to a luminescence process in which an organic material converts electric energy into light energy upon excitation by an electric current and an electric field, and this electroluminescence phenomenon was discovered at the earliest in 1963 by the teachings of Pope at university of New York in usa. Organic luminescent materials may be more closely related to the demand for light adaptation than inorganic luminescent materials. Displays and light emitters manufactured based on Organic Light Emitting Diode (OLED) technology have flexible profiles and add many artistic elements to electronic devices. The earliest organic electroluminescent devices were developed by Eastman Kodak with small aromatic amine organic molecules as the hole transport layer and 8-hydroxyquinoline aluminum as the light emitting layer. Such devices with organic molecules as core luminescent materials are known as Organic Light Emitting Diodes (OLEDs), which can be applied in the field of new displays and illumination, with numerous advantages and potential. The light-emitting device prepared from the organic material has the advantages of high quantum efficiency, high brightness, high luminous efficiency and the like, and the light-emitting device prepared from the organic light-emitting material has the advantages of light, thinness, softness and the like on the appearance, and particularly the light-emitting device prepared from the organic light-emitting material can be prepared into flexible equipment which is incomparable with other light-emitting materials. Conventional OLEDs can be classified into fluorescent-type OLEDs and phosphorescent-type OLEDs according to the core electroluminescent materials. Phosphorescent OLEDs (100% of theoretical luminous efficiency) are the main direction of OLED technology research and development due to their higher luminous efficiency compared to fluorescent OLEDs (25% of theoretical luminous efficiency).
Currently, yellow phosphorescent materials are mainly applied to illumination and yellow lamps, such as television backboard technology, automobile steering lamps and the like. In terms of luminescence, yellow is a "combined" color, which is not one of the three primary colors of "RGB", and is a component color of equal amounts of red light and green light, so in colorimetry, yellow phosphorus light is formed by filtering blue light by white phosphorescence, and is also often a complementary auxiliary color of blue light. Yellow phosphorescent heavy metal complexes are not only indispensable components satisfying the requirements of full-color displays, but they also greatly contribute to realization of high-performance two-color (blue and yellow) white diodes which exhibit advantages in terms of device efficiency and manufacturing costs as compared with trichromatic (blue, green and red) analogues as solid-state light sources. Meanwhile, in the four-color (blue, green, yellow and red) spectrum, the yellow phosphorus light heavy metal complex is beneficial to improving the device efficiency and the color rendering index/color temperature index. The development of yellow phosphorus light materials also faces many challenges, and the single-molecule light emission spectrum of many materials is not wide enough to cover all green light and red light parts, and the requirements of standard yellow light cannot be met, which greatly limits the practical application. Therefore, developing yellow phosphorus light materials with high efficiency, broad spectrum, stability and long service life has practical application value in display and illumination.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a yellow phosphorus light material with high efficiency, wide spectrum, stability and long service life, and further provides a bivalent platinum complex and a preparation method and application thereof.
The scheme adopted by the invention is as follows:
a divalent platinum complex having the structure shown below:
Wherein R 1-R15 are the same or different and are each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C3-C30 heteroaryl, and substituted or unsubstituted C3-C30 silyl.
Preferably, R 1-R15 is the same or different and is independently selected from deuterium, -CDH 2、-CD2H、-CD3、-CDRbRc、-CD2Rd, wherein R b-Rd is the same or different and is independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C3-C30 heteroaryl, and substituted or unsubstituted C3-C30 silyl.
Preferably, the substituted C1-C30 alkyl, substituted C6-C30 aryl, substituted C3-C30 cycloalkyl, substituted C3-C30 cycloalkenyl, substituted C3-C30 heteroaryl, substituted C3-C30 silyl groups are optionally substituted with one or more substituents R a, each R a is independently selected from hydrogen, halogen, C1-C30 alkyl, C6-C30 aryl.
Preferably, the hydrogen is deuterium, the halogen is selected from fluorine, chlorine and bromine, the alkyl of C1-C30 is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, the aryl of C6-C30 is selected from phenyl, naphthyl and biphenyl, and the cycloalkyl of C3-C30 is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
Preferably, R 1-R15 are identical or different, are each independently selected from the group consisting of methyl, deuteromethyl, benzyl, diphenylmethyl, triphenylmethyl, ethyl, 2-phenylethyl, 2-trifluoroethyl, propyl, isopropyl, 3-trifluoropropyl, 1, 3-hexafluoro-2-propyl, butyl, isobutyl, hexafluoroisobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2, 3-dimethylphenyl, 2, 3-diethylphenyl, 2, 3-diisopropylphenyl, 2, 3-diisobutylphenyl, 2, 3-dicyclohexylphenyl cyclopentyl, cyclohexyl, cycloheptyl, phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl 4-tert-butylphenyl group, 2, 3-dimethylphenyl group, 2, 3-diethylphenyl group, 2, 3-diisopropylphenyl group, 2, 3-diisobutylphenyl group, 2, 3-dicyclohexylphenyl group, 3, 5-dicyclohexylphenyl, 3, 5-dicyclopentylphenyl, 2,3,5, 6-tetramethylphenyl, 2,4, 6-trimethylphenyl, 2,4, 6-triethylphenyl, 2,4, 6-triisopropylphenyl, 2,4, 6-triisobutylphenyl, 2,4, 6-tricyclohexylphenyl, 2,4, 6-tricyclopropylphenyl, 2,4, 6-tricyclobutylphenyl, 2,4, 6-tricyclopentylphenyl.
Preferably, the divalent platinum complex has the structure shown below:
The divalent platinum complex provided by the invention can generate red shift aggregate emission by introducing a dibenzofuran structure into a ligand of the divalent platinum complex, wherein the aggregate has platinum-platinum interaction or pi-pi accumulation, the M-M interaction or pi-pi accumulation degree is closely related with intermolecular distance, single molecules are green light emission, and red light emission is realized when the single molecules are in an aggregation state, the single molecules and the aggregation state can emit light simultaneously, the divalent platinum complex is a spectrum-adjustable phosphorescence luminescent material, a double-emission mechanism emits light with high efficiency, and the light emission peak ratio of about 540nm and 600nm can be regulated and controlled by a broad spectrum. The molecular dual emission mechanism is as follows:
the invention also provides a preparation method of the bivalent platinum complex, which comprises the following steps:
the compound shown in the A and the compound shown in the B are subjected to coupling reaction to obtain a compound shown in an intermediate 1, and the compound shown in the intermediate 1 and platinum salt are subjected to cyclometalation reaction to obtain a compound shown in the formula I;
The preparation route of the compound shown in the formula I is as follows:
Wherein X 1 is halogen, preferably X 1 is bromine or chlorine, X 2 is a coupling group, preferably X 2 is a tin group or a boron group.
The invention also provides an application of the divalent platinum complex or the divalent platinum complex prepared by the preparation method in an organic photoelectric device.
Preferably, the divalent platinum complex is used as a phosphorescent light emitting material in the organic photoelectric device, and preferably, the divalent platinum complex is used as a yellow phosphorescent light emitting material in the organic photoelectric device.
The invention also provides an organic photoelectric device, which comprises a positive electrode, a negative electrode and an organic layer arranged between the positive electrode and the negative electrode, wherein the organic layer comprises any one or a combination of at least two of the divalent platinum complexes.
Preferably, the organic layer comprises a light emitting layer comprising any one or a combination of at least two of the divalent platinum complexes described above;
Preferably, the light-emitting layer contains a host material and a dopant material, and the host material or the dopant material includes any one or a combination of at least two of the divalent platinum complexes described above.
Preferably, the organic photoelectric device is a yellow organic photoelectric device.
The invention also provides application of the divalent platinum complex or the divalent platinum complex prepared by the preparation method in a display device or a lighting device.
Alternatively, the divalent platinum complex is used as a light, display, special yellow organic optoelectronic device.
The organic layer of the organic electroluminescent device of the present application may be composed of a single layer structure, but may also be composed of a multi-layer structure in which two or more organic layers are stacked. For example, as a representative example of the organic electroluminescent device of the present application, the organic electroluminescent device may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic electronic device is not limited thereto, and may include a smaller number of organic layers.
In one exemplary embodiment of the present application, each of the first and second stacks is an organic material layer including a light emitting layer, and the organic material layer may include one or more organic material layers, such as a hole injection layer, a hole buffer layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, in addition to the light emitting layer.
Optionally, the organic layer comprises a light emitting layer comprising any one or a combination of at least two of the organometallic complexes described above.
The organic electroluminescent device of the present invention may be manufactured by materials and methods known in the art, except that one or more layers of the organic material layer comprise the compound of the present invention, i.e. the compound.
When the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.
The organic electroluminescent device of the present invention may be manufactured by materials and methods known in the art, except that one or more layers of the organic layer comprise the compound of the present invention, i.e., the compound represented by formula I. For example, the organic electroluminescent device of the present invention may be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. In this case, the organic electroluminescent device may be manufactured by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate by using a Physical Vapor Deposition (PVD) method such as sputtering or electron beam evaporation to form a positive electrode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a negative electrode thereon. In addition to the methods described above, the organic electronic device may be fabricated by sequentially depositing a negative electrode material, an organic layer, and a positive electrode material on a substrate.
In addition, in the manufacture of an organic electroluminescent device, the compound of formula I may be formed into an organic layer not only by a vacuum deposition method but also by a solution application method. Here, the solution application method means spin coating, dip coating, blade coating, ink jet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
Alternatively, the preparation method comprises sequentially placing a crucible containing organic material of OLED and a crucible containing aluminum particles of metal on the organic evaporation source and the inorganic evaporation source. Closing the cavity, and performing primary vacuumizing and high-vacuum vacuumizing steps to ensure that the vacuum degree of evaporation in the OLED evaporation equipment reaches 10 < -7 > Torr. The OLED evaporation film forming method comprises the steps of turning on an OLED organic evaporation source, preheating an OLED organic material at 100 ℃ for 15 minutes, and guaranteeing that water vapor in the OLED organic material is further removed. Then, carrying out quick heating treatment on the organic material to be evaporated, opening a baffle above an evaporation source until the organic material of the evaporation source of the material runs out, slowly heating until the evaporation rate is detected by a crystal oscillator detector, opening the baffle right below a mask plate until the evaporation rate is stabilized at 1A/s, carrying out OLED film forming, and closing the mask plate baffle and the baffle right above the evaporation source and closing an evaporation source heater of the organic material when the computer end observes that the organic film on the ITO substrate reaches a preset film thickness. The evaporation process of other organic materials and cathode metal materials is as described above. The encapsulation adopts UV epoxy resin for photo-curing encapsulation.
In one exemplary embodiment of the application, the first electrode is a positive electrode and the second electrode is a negative electrode, and in another exemplary embodiment, the first electrode is a negative electrode and the second electrode is a positive electrode.
As the positive electrode material, a material having a large work function is generally preferable to smoothly inject holes into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof, metal oxides such as zinc oxide, indium Tin Oxide (ITO) and Indium Zinc Oxide (IZO), combinations of metals and oxides such as ZnO: al or SnO2: sb, conductive polymers such as poly (3-methylthiophene), polypyrrole, polyaniline, and the like, but are not limited thereto.
As the negative electrode material, a material having a small work function is generally preferable to smoothly inject electrons into the organic layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof, and multilayered structural materials such as LiF/Al or LiO2/Al, etc., but are not limited thereto.
The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound that has an ability to transport holes and thus has an effect of injecting holes at the positive electrode and an excellent effect of injecting holes for the light emitting layer or the light emitting material, prevents excitons generated by the light emitting layer from migrating to the electron injection layer or the electron injection material, and is also excellent in the ability to form a thin film. Preferably, the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-based and polythiophene-based conductive polymer, and the like, but are not limited thereto.
The hole transporting layer is a layer that receives holes from the hole injecting layer and transports the holes to the light emitting layer, and the hole transporting material is suitably a material that can receive holes transported from the positive electrode or the hole injecting layer to transfer holes to the light emitting layer and has high mobility to holes. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugated moiety and a non-conjugated moiety are simultaneously present, and the like, but are not limited thereto.
The light-emitting layer material is preferably a material that can receive holes and electrons transported by the hole transporting layer and the electron transporting layer, respectively, and combine the holes and electrons to emit light in the visible light region and has good quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include 8-hydroxy-quinoline aluminum complex (Alq 3), carbazole-based compound, dimeric styryl compound, BAlq, 10-hydroxybenzoquinoline-metal compound, benzoxazole, benzothiazole and benzimidazole-based compound, poly (p-phenylene vinylene) (PPV) -based polymer, spiro compound, polyfluorene, rubrene and the like, but are not limited thereto.
The light emitting layer may include a host material and a dopant material. Examples of the host material include fused aromatic ring derivatives or heterocyclic compounds and the like. Specific examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and specific examples of the heterocyclic compound include compounds, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto.
The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and the electron transport material is suitably a material that can well receive electrons from the negative electrode and transfer electrons to the light emitting layer and has high mobility to electrons. Specific examples thereof include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic radical compounds, hydroxyflavone-metal complexes, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material used according to the prior art. In particular, suitable examples of cathode materials are typical materials with a low work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
The electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound that has an ability to transport electrons, has an effect of injecting electrons from the negative electrode and an excellent effect of injecting electrons into the light emitting layer or the light emitting material, prevents excitons generated by the light emitting layer from migrating to the hole injection layer, and is also excellent in the ability to form a thin film. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, diazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and the like and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives and the like, but are not limited thereto.
The hole blocking layer is a layer that blocks holes from reaching the negative electrode, and may be generally formed under the same conditions as those of the hole injection layer. Specific examples thereof include, but are not limited to, diazole derivatives or triazole derivatives, phenanthroline derivatives, aluminum complexes, and the like.
The organic light emitting device according to the present specification may be of a top emission type, a bottom emission type, or a double side emission type, depending on the materials used.
The invention has the beneficial effects that:
The divalent platinum complex provided by the invention can generate red shift aggregate emission by introducing a dibenzofuran structure into a ligand of the divalent platinum complex, wherein the aggregate is prone to form an aggregate with platinum-platinum interaction or pi-pi accumulation, the M-M interaction or pi-pi accumulation degree is closely related to intermolecular distance, single molecules are green light emission, red light emission is realized when the single molecules are in an aggregation state, single molecules and aggregation state luminescence can be realized simultaneously, the divalent platinum complex is a spectrum adjustable phosphorescence luminescent material, a double-emission mechanism emits light with high efficiency, the spectral luminescence is wide, the half-peak width can reach 140nm at most, the light-emission peak proportion regulation of the range of about 540nm and 600nm can be realized, and the series of platinum complexes can be used for developing yellow monochromatic light devices and also can be used for white light devices and products of illumination, display and special yellow lamps.
The bivalent platinum complex is a yellow phosphorus light-emitting material, can emit yellow phosphorescence as a phosphorescence light-emitting material, has good color purity, good stability and high efficiency, and is completely suitable for being used as an organic yellow phosphorus light-emitting body in OLED related products. In addition, the compound provided by the invention is easy to prepare and sublimate and purify, is soluble in common organic solvents, and can be simultaneously suitable for device manufacturing processes of vapor deposition and solution processing. The stable complex luminescent material provided by the invention has the CIE coordinates and luminous efficiency which are more in line with the requirements of flat panel display, and has great development potential in the display and illumination fields.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing luminescence spectrum of complex 1 in solution;
FIG. 2 is a graph showing the luminescence spectrum of complex 2 in a thin film;
FIG. 3 is a graph showing the luminescence spectrum of complex 3 in a thin film;
FIG. 4 is a graph of the ultraviolet visible absorption spectrum of complex 2;
FIG. 5 is a graph of the luminescence spectrum of complex 2 in dependence of concentration in a thin film;
FIG. 6 is a 1 H NMR nuclear magnetic spectrum of complex 2;
FIG. 7 is a 1 H NMR nuclear magnetic spectrum of complex 3;
FIG. 8 is a mass spectrum of complex 1;
FIG. 9 is a mass spectrum of complex 2;
FIG. 10 is a mass spectrum of complex 3;
FIG. 11 is a cross-sectional view of an OLED device of the present invention;
FIG. 12 is an electroluminescent spectrum of an organic light-induced power generation device of complex 2;
FIG. 13 is a device lifetime graph for the preparation of complex 2;
FIG. 14 is a graph of voltage versus current density for a device prepared from complex 2;
FIG. 15 is a graph of voltage versus luminance for a device prepared from complex 2;
reference numerals illustrate:
1-anode layer, 2-hole injection layer, 3-hole transport layer, 4-light emitting layer, 5-electron transport layer, 6-cathode layer.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In the following specific examples of the present invention, the synthesis method, properties and performances of the divalent platinum complex provided by the present invention when used as a light emitting material will be specifically described by taking complexes 1,2 and 3 as examples.
Various methods of preparing the compounds provided herein are exemplary. These methods are illustrative of various methods of preparation, but are not intended to be limited to any particular method, and the temperature, catalyst, concentration, reactant composition, and other process conditions may vary.
Furthermore, in the examples, 1 HNMR (hydrogen nuclear magnetic resonance) and 13 C NMR (carbon nuclear magnetic resonance) spectra were recorded by Varian liquid nuclear magnetic resonance in CDCl 3 or DMSO-d 6 solutions at 300, 400 or 500MHz, with chemical shifts based on residual protonated solvent. If CDCl 3 is used as solvent, 1 H NMR (hydrogen nuclear magnetic resonance) spectrum is recorded with tetramethylsilane (δ=0.00 ppm) as internal reference, and 13 C NMR (carbon nuclear magnetic resonance) spectrum is recorded with CDCl 3 (δ=77.00 ppm) as internal reference. If DMSO-d 6 is used as solvent, the 1 H NMR (hydrogen nuclear magnetic resonance) spectrum is recorded with residual H 2 O (δ=3.33 ppm) as internal reference, and the 13 C NMR (carbon nuclear magnetic resonance) spectrum is recorded with DMSO-d 6 (δ=39.52 ppm) as internal reference. The following abbreviations are used to illustrate the diversity of 1 H NMR (hydrogen nuclear magnetic resonance) s=singlet, d=double-line, t=triplet, q=four-line, p=five-line, m=multiple-line, br=broad.
Example 1
The present embodiment provides a complex 1, the preparation method of which specifically includes the following steps:
1) Synthesis of 2- (2- (3- (1- (1H-pyrazol-1-yl) phenoxy) dibenzo [ b, d ] furan-4-yl) pyridine:
To a 15mL tube sealer with a magnetic rotor was added 1- (3- ((4-chlorodibenzo [ b, d ] furan-2-yl) oxy) phenyl) -1H-pyrazole (540 mg,1.5 mmol), 2- (tributylstannyl) pyridine (552 mg,1.5 mmol), palladium acetate (21.9 mg,0.025 mmol), tri-tert-butylphosphine (18 mg,0.09 mmol), cesium fluoride (500 mg,3.3 mmol) and 1,4 dioxane (3 mL), the resulting mixture was heated to 120℃after bubbling with nitrogen for 48 hours, cooled to room temperature, quenched with water, saturated aqueous potassium fluoride was added and stirred overnight at room temperature, then extracted with ethyl acetate, the organic phase was combined, washed with an appropriate amount of saturated aqueous sodium chloride solution and dried with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography on petroleum ether: ethyl acetate=10:1 (volume ratio), to give yellow solid 2- (1-H-benzo [ b, d ] furan-2-yl) phenoxy) pyridine, 30%.
2) Complex 1 synthesis:
To a 75mL tube sealer with a magnetic rotor was added 2- (2- (3- (1- (1H-pyrazol-1-yl) phenoxy) dibenzo [ b, d ] furan-4-yl) pyridine (53 mg,0.13 mmol), potassium chloroplatinite (58 mg,0.14 mmol) and acetic acid (13 mL), and the resulting mixture was bubbled with nitrogen for 10 minutes, stirred at 30℃for 24 hours, then heated to 120℃for stirring for 24 hours, cooled to room temperature, quenched with water, extracted with dichloromethane, the organic phases were combined, washed with a suitable amount of saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, distilled under reduced pressure to remove the solvent, and the resulting crude product was purified by column chromatography on silica gel with an eluent of dichloromethane: petroleum ether=1:1 (volume ratio) to give yellow solid complex 1 in 50% yield.
Example 2
The embodiment provides a complex 2, and the preparation method specifically comprises the following steps:
1) Synthesis of 2- (2- (3, 5-dimethyl-1H-pyrazol-1-yl) phenoxy) dibenzo [ b, d ] furan-4-yl) pyridine:
to a 48mL tube sealer with a magnetic rotor was added 1- (3- ((4-chlorodibenzo [ b, d ] furan-2-yl) oxy) phenyl) -3, 5-dimethyl-1H-pyrazole (800 mg,2.1 mmol), 2- (tributylstannyl) pyridine (1.5 g,4.2 mmol), palladium acetate (27.45 mg,0.03 mmol), tri-tert-butylphosphine (26.3 mg,0.13 mmol), cesium fluoride (630 mg,4.16 mmol) and 1,4 dioxane (10 mL), the resulting mixture was heated to 120℃after bubbling with nitrogen for 10min, stirred for 48 hours, cooled to room temperature, quenched with water, stirred overnight at room temperature with saturated aqueous potassium fluoride, then extracted with ethyl acetate, the organic phase was combined, washed with an appropriate amount of saturated aqueous sodium chloride, dried with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography on silica gel with petroleum ether: ethyl acetate=10:1 (volume ratio), yellow solid (3- (3, 5-d-dimethyl-furan-2-yl) phenoxy) was obtained, 1-diphenyl-1-d-furan [ 2-yl ] pyridine, 35-1-d ] at a yellow yield.
2) Complex 2 synthesis:
To a 350mL tube sealer with a magnetic rotor was added 2- (2- (3, 5-dimethyl-1H-pyrazol-1-yl) phenoxy) dibenzo [ b, d ] furan-4-yl) pyridine (780 mg,1.8 mmol), potassium chloroplatinite (81mg, 1.9 mmol)) and acetic acid (150 mL), and the resulting mixture was bubbled with nitrogen for 10 minutes, stirred at 30℃for 24 hours and then heated to 120℃for 24 hours, cooled to room temperature, quenched with water for reaction, extracted with dichloromethane, the organic phases were combined, washed with a suitable amount of saturated aqueous sodium chloride solution and then dried with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography on silica gel with eluent of dichloromethane: petroleum ether=1:1 (volume ratio) to give yellow solid complex 2 in 70% yield.
Example 3
The present embodiment provides a complex 3, the preparation method of which specifically includes the following steps:
1) Synthesis of 3, 5-dimethyl-1- (3- (((4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) dibenzo [ b, d ] furan-2-yl) oxy) phenyl) -1H-pyrazole:
To a 15mL tube sealer with a magnetic rotor was added 1- (3- ((4-chlorodibenzo [ b, d ] furan-2-yl) oxy) phenyl) -3, 5-dimethyl-1H-pyrazole (24.75 mg,0.11 mmol), pinacol biboronate (55 mg,0.22 mmol), bis (dibenz-ylacetone) palladium (7 mg,0.0075 mmol), tricyclohexylphosphine (5 mg,0.018 mmol), potassium acetate (37 mg,0.4 mmol) and 1,4 dioxane (1.5 mL), the resulting mixture was heated to 120℃after bubbling with nitrogen for 10 min, stirred for 24 hours, cooled to room temperature, quenched with water, extracted with ethyl acetate, the organic phase was combined, dried with an appropriate amount of saturated aqueous sodium chloride solution, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography with ethyl acetate=10:1 to give a yellow solid 3, 5-dimethyl-1- (4, 5-dioxa-2-furane [ 2, 5-dioxa-2-yl ] pyrazole, 1, 5- ([ 2, 5-dioxa-2-yl) at 120 ℃.
2) Synthesis of 4- (tert-butyl) -2- (2- (3- (3-, 3, 5-dimethyl-1H-pyrazol-1-yl) phenoxy) dibenzo [ b, d ] furan-4-yl) pyridine:
to a 15mL tube sealer with a magnetic rotor was added 3, 5-dimethyl-1- (3- (((4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) dibenzo [ b, d ] furan-2-yl) oxy) phenyl) -1H-pyrazole (148 mg,0.3 mmol), 2-bromo-5- (tert-butyl) pyridine (92 mg,0.75 mmol), tetrakis triphenylphosphine palladium (11 mg,0.009 mmol), potassium carbonate (62 mg,0.45 mmol) and toluene (1 mL), the resulting mixture was heated to 100℃after 10 minutes with nitrogen bubbling for 24H, cooled to room temperature, quenched with water, extracted with ethyl acetate, the combined organic phases were washed with an appropriate amount of saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography on silica gel with ethyl acetate=8:1 (volume ratio) to give yellow solid 4- (tert-butyl) -2- (3, 5-dimethyl-furan-1, 3-yl) phenoxy-1, 75% of benzene.
3) Synthesis of Complex 3
To a 75mL tube sealer with a magnetic rotor was added 4- (tert-butyl) -2- (2- (3- (3-, 3, 5-dimethyl-1H-pyrazol-1-yl) phenoxy) dibenzo [ b, d ] furan-4-yl) pyridine (70 mg,0.13 mmol), potassium chloroplatinite (62 mg,0.15 mmol) and acetic acid (10 mL), and the resulting mixture was bubbled with nitrogen for 10 minutes, stirred at 30℃for 24 hours and then heated to 120℃for 24 hours, cooled to room temperature, quenched with water, extracted with dichloromethane, the organic phases were combined, washed with a suitable amount of saturated aqueous sodium chloride solution and then dried with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by column chromatography on silica gel with an eluent of dichloromethane: petroleum ether=1:1 (volume ratio) to give yellow solid complex 3, yielding 50%.
Device example 1
The present embodiment provides an organic electroluminescent device, as shown in fig. 11, in the cross-sectional views of OLED devices in embodiments 1-3, platinum complexes 1,2 and 3 are doped as light-emitting materials into a host material to prepare an OLED device, the doping amount is 5-10%, the OLED device is prepared, ITO is an Anode (Anode) of the OLED device, al is a Cathode (Cathode) of the OLED device, the device structure is ITO/HIL/HTL/EML/ETL/Al, wherein the HIL hole injection layer may be but is not limited to HATCN, re2O3, HTL is a hole transport layer may be but is not limited to TAPC, NPD, TCTA, PT%, BCP, mCP, m-MTDATA, TPTA, BTB, TPD, the EML layer is a light-emitting layer complex, host material=5%: 95% host material may be but is not limited to CBP, mCBP, 2,6mcpy, 26DCzPPY, TCP, BPyPPM, DPEPO, and the ETL layer is an electron transport layer may be but is not limited to TmPyPb, TPBi, DPPS, bphen, bmPyPb, DBFTrz, tpPyPb. The method comprises the following steps:
HATCN (chinese name: 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene material, english name: 2,3,6,7,10, 11-Hexaazatriphenylenehexacabonitrile);
re2O3 (Chinese name: molybdenum trioxide, english name: molybdenum (VI) oxide);
TAPC (Chinese name: 4,4 '-cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ], english name: 4,4' -cyclohexylidenebis [ N, N-bis (p-tolyl) aniline ];
NPD (Chinese name: N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, english name: N, N '-Bis- (1-NAPHTHALENYL) -N, N' -Bis-phenyl- (1, 1 '-biphenyl) -4,4' -diamine);
TCTA (Chinese name: 4,4',4"-Tris (carbazol-9-yl) triphenylamine, english name: 4,4',4" -Tris (carbazol-9-yl) triphenylamine);
PT301 (Chinese name: 4,4'-Bis [ N, N-di (biphenyl-4-yl) amino ] -1,1' -biphenyl, english name: 4,4'-Bis [ N, N-di (biphenyl-4-yl) amino ] -1,1' -biphenyl);
BCP (Chinese name: 2,9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, english name: 2,9-dimethyl-4,7-diphenyl-1, 10-Phenanthroline);
mCP (Chinese name: 1,3-bis (N-carbazolyl) benzene, english name: 1,3-bis (N-carbazolyl) benzene);
m-MTDATA (Chinese name: 4,4',4"-Tris [ phenyl (m-tolyl) amino ] triphenylamine, english name: 4,4',4" -Tris [ phenyl (m-tolyl) amino ] triphenylamine);
TPTA (Chinese name: 4,4',4"-trimethyltriphenylamine, english name: 4,4',4" -TRIMETHYLTRIPHENYLAMINE);
BTB (Chinese name: 4,4'-bis (4, 6-diphenyl-1,3, 5-triazine-2-) biphenyl, english name: 4,4' -bis (4, 6-diphenyl-1,3, 5-Triazine-2-yl) biphenyl);
TPD (Chinese name: N, N '-diphenyl-N, N' -Bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, english name: N, N '-Bis (3-METHYLPHENYL) -N, N' -Bis (phenyl) benzodine);
CBP (Chinese name: 4,4' -Bis (9-carbazolyl) biphenyl, english name: 4,4' -Bis (9-carbazolyl) -1,1' -biphenyl);
mCBP (chinese name: 3,3 '-bis (9H-carbazol-9-yl) -1,1' -biphenyl, english name: 3,3'-Di (9H-carbazol-9-yl) -1,1' -biphenyl (purified by sublimation);
2,6mCPy (Chinese name: 2, 6-bis (9-carbazolyl) pyridine, english name: 2,6-Di (9H-carbazol-9-yl) pyridine);
26DCzPPY (Chinese name: 2,6-bis ((9H-carbazol-9-yl) -3, 1-phenylene) pyridine, english name: 2,6-bis (3- (9H-carbazol-9-yl) phenyl) pyridine);
TCP (Chinese name: 1,3, 5-tris (9-carbazolyl) benzene, english name: 1,3,5-Tri (9-carbazolyl) benzene);
BPyPPM (Chinese name: 2-phenyl-bis-4,6- (3, 5-bipyridylphenyl) pyrimidine, english name: 2-phenyl-bis-4,6- (3, 5-DIPYRIDYLPHENYL) pyrimidine);
DPEPO (Chinese name: bis [2- (diphenylphosphoryl) phenyl ] ether Bis [2- (oxo-diphenylphosphino) phenyl ] ether, english name: bis [2- (diphenylphosphoryl) phenyl ] etherBis [2- (oxodiphenylphosphino) phenyl ] ether)
TmPyPb (Chinese name: 3,3'- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 '-terphenyl ] -3, 3' -diyl ] bipyridine, english name: 1,3,5-tri [ (3-pyridyl) -phen-3-yl ] benzene);
TPBi (Chinese name: 1,3,5-Tris (1-phenyl-1H-benzimidazol-2-yl) benzene, english name: 1,3,5-Tris (1-phenyl-1H-benzimidazol-2-yl) benzene);
DPPS (Chinese name: diphenyldi [4- (pyridin-3-yl) phenyl ] silane, english name: diphenylbis (4- (pyridin-3-yl) phenyl) silane);
Bphen (Chinese name: 4,7-diphenyl-1,10-phenanthroline, english name: 4,7-diphenyl-1, 10-phenanthrine);
BmPyPb (Chinese name: 1,3-bis (3, 5-bipyridin-3-ylphenyl) benzene, english name: 1,3-bis [3,5-di (pyridin-3-yl) phenyl ] benzene);
DBFTrz (Chinese name: 2,8-bis (4, 6-diphenyl-1,3, 5-triazin-2-yl) dibenzo [ b, d ] furan, 2,8-bis (4, 6-diphenyl-1,3, 5-triazin-2-yl) dibenzo [ b, d ] furan)
TpPyPb (Chinese name: 1,3, 5-tris (4-pyridin-3-ylphenyl) benzene, english name: 1,3,5-Tri (4-pyrid-3-ylphenyl) benzene).
Device example 2
The embodiment provides an organic electroluminescent device, as shown in fig. 11, comprising an anode layer 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5 and a cathode layer 6 which are sequentially arranged on a glass substrate from bottom to top, wherein the device structure is ITO/HIL (10 nm)/HTL (50 nm)/EML (30 nm)/ETL (40 nm)/Al (150 nm).
The anode layer 1 is made of ITO material, namely indium tin oxide material;
the hole injection layer 2 is made of HATCN material;
The hole transport layer 3 is made of TAPC material;
The light-emitting layer 4 is formed by co-doping a host material and a guest material, wherein the host material is a mCBP material, the guest material is a complex 1, and the mass of the complex 1 accounts for 5% of the total mass of the host material and the guest material;
the electron transport layer 5 is made of Bphen;
The cathode layer 6 is made of metal Al.
Device example 3
This example provides an organic electroluminescent device differing from the organic electroluminescent device provided in device example 2 in that complex 2 is selected as the guest material in the light-emitting layer.
Device example 4
This example provides an organic electroluminescent device differing from the organic electroluminescent device provided in device example 2 in that complex 3 is selected as the guest material in the light-emitting layer.
Alternatively, the guest material of the light emitting layer may be any one of the complexes shown in complexes 1 to 30.
Alternatively, the guest material of the light emitting layer may be any other complex having a chemical structure shown in formula I.
Test example 1
For the complex of the present invention, the solution was formed by dissolving 5% by weight in Dichloromethane (DCM) and the film was obtained by doping in methyl methacrylate (PMMA), and the obtained solution or film was subjected to the following test:
Photoelectric energy level test of electroluminescent materials band gap value (Eg), lowest Unoccupied Molecular Orbital (LUMO) and Highest Occupied Molecular Orbital (HOMO) values of the materials were measured using Cyclic Voltammetry (CV). The whole test process is carried out on a CHI600D electrochemical workstation (Shanghai Chen Hua instruments Co.) in a glove box (Lab 2000, etelux), a three-electrode system is formed by taking a Pt column as a working electrode, ag/AgCl as a reference electrode and Pt wire as an auxiliary electrode, a medium adopted in the test process is a 0.1M solution of tetrabutylammonium hexafluorophosphate (Bu 4NPF 6) in Dimethylformamide (DMF), and the measured potentials all take the added ferrocene (Fc) as an internal standard. Where λ is the peak wavelength of the divalent platinum complex dissolved in dichloromethane, FWHM is its half-width, and the triplet photon energy (ET 1) of the material is calculated from the formula 1240/λ0→1 (λ0→1 is the first oscillation peak at 77K) in electron volts (eV). The test results are shown in tables 1 and 2.
Table 1 luminescent Properties of the Complex
Wherein, a dichloromethane solution and b PMMA film
TABLE 2 energy level data for complexes
As shown in the data of Table 1, the peak wavelength of the complex prepared by the invention is 530-542 nm, the half-width of the complex is about 52-68nm, the fluorescence efficiency of photoluminescence is 63-99%, and the bivalent platinum complex with the structure of the general formula I is a yellow phosphorus light-emitting material with high efficiency and wide spectrum. From the data in Table 2, the triplet energy of the divalent platinum complex of complex 2 was 2.34eV, which is mainly related to the parent core structure.
FIG. 1 shows the luminescence spectrum of complex 1 in solution, with the luminescence wavelength in methylene dichloride solution at 530nm under 380nm ultraviolet excitation, the complex wavelength in yellow phosphorus region, and the complex has no aggregation state luminescence due to larger intermolecular space in solution, and single molecule emission. The complex is shown to be an excellent yellow light emitting material.
FIG. 2 shows the luminescence spectrum of the platinum complex 2 in the film, under 380nm ultraviolet excitation, the luminescence wavelength in PMMA is 540nm, the half-width is 71nm, and a distinct emission spectrum appears at 650nm, where the emission spectrum is due to better molecular plane type, and the emission spectrum is broadened by the generation of concentrated luminescence in the film, so that the green-red light region is better covered, and the complex wavelength is in the yellow-phosphorus light region.
FIG. 3 shows the luminescence spectrum of complex 3 in the film, with a luminescence wavelength in PMMA of 534nm and a half-width of 62nm under 380nm ultraviolet excitation, the spectrum of complex 3 in the film being blue shifted compared to complex 2, as is the apparent emission spectrum at 650nm, which is also due to the better molecular planarity, resulting in the generation of concentrated luminescence in the film, as is complex 2.
Fig. 4 shows the ultraviolet-visible absorption spectrum of complex 2 in DCM solution, from which it can be seen that the absorption spectrum is very strong in the 200-400 nm range. The complex 2 has a strong absorption band at about 225-300 nm, the absorption region is classified into 1LC (pi-pi) transition allowed by the spin of the ligand, the absorption band in the range of 350-400 nm is classified into charge transfer transition (1 MLCT) from the metal allowed by the spin to the ligand and charge transfer transition (1 LLCT) from the ligand to the ligand, and the weak absorption band at the position higher than 400nm belongs to 3MLCT and 3LC transition of spin forbidden. The energy absorption of such molecules is very efficient and can be used as a preferred molecular structure for the dopant molecules.
FIG. 5 is a graph of luminescence spectrum of concentration dependence of complex 2 in a thin film, according to the graph of concentration dependence, it can be seen that as doping concentration of complex 2 in the thin film increases, molecular aggregation state luminescence is more obvious, the molecules show double-emission characteristics of single molecules and aggregation state, single-molecule luminescence shows green light emission, aggregation state luminescence shows red light emission, spectrum is widened, maximum half peak width is 165nm, green light and red light spectrum regions are fully covered, and the material is a good yellow light material.
Test example 2
The organic electroluminescent devices provided in device examples 2 to 4 were tested and the results are shown in table 3:
TABLE 3 device Performance test results
Table 3 shows the optical properties of phosphorescent devices prepared by complexes 1,2 and 3, the device peak wavelengths for device examples 2 to 4 are 535nm, 547nm and 540nm, respectively, the half-widths reach 128nm, 118nm and 116nm, and the CIE coordinate values are (0.55,0.45), (0.50,0.48) and (0.52,0.49), respectively, which very well cover the yellow light window. The device has the highest current efficiency energy efficiency (PE) of 40.2 lm.W-1, the highest Current Efficiency (CE) of 35.2 cd.A-1 and the highest External Quantum Efficiency (EQE) of 16.1 percent, and belongs to a high-efficiency light-emitting device.
FIG. 12 shows the electroluminescent spectrum of the organic light-emitting device of complex 2, the wavelength on the abscissa, the normalized intensity on the ordinate, the emission spectrum in a dual emission state, the maximum emission wavelength being 547nm and 590nm, respectively, the half-width being 118nm, the spectrum covering the green and red regions, being a good yellow spectrum, the chromaticity coordinate value being CIE (0.50,0.48) calculated, indicating that the device is suitable for use as a yellow light-emitting device.
FIG. 13 is a graph of device lifetime measurements at 20mA/cm2 for OLED devices prepared using Complex 2 as the yellow light doping material at ambient temperature using a photovoltaic test system. The test results show that the light-emitting device adopting the platinum complex provided by the invention is very stable and has very long service life. As can be seen from fig. 13, the light-emitting device was prepared with a decay lifetime LT97 of up to 162 hours from 9000cd/m2 luminance.
Fig. 14 is a graph showing the current density-voltage test result of an OLED device prepared by using the complex 2 as a yellow light doping material using a photoelectric test system, and the test result shows that the light emitting device using the complex of the present invention can perform charge transport well.
Fig. 15 is a graph showing the effect of brightness-voltage test of an OLED device prepared by using complex 2 as a yellow light doping material using a photoelectric test system at normal temperature, and the test result shows that the light emitting device using the complex of the present invention has low turn-on voltage, thereby reducing power consumption and improving device efficiency. As shown in the figure, the turn-on voltage of the yellow OLED device prepared by the method is 2.4V.
The invention has the structural general formula I as a yellow phosphorescence doping material by way of illustration, and can be used for preparing single-doped yellow phosphorus light devices and white phosphorus light devices, wherein each material is not limited to the example structure, and the device structure can be a bottom light emitting device or a top light emitting device based on application. Wherein the ETL layer and HTL may further comprise one or more transport layer materials, there may be another charge injection layer in the vicinity of the electrode and in the divalent platinum complex. The material of the injection layer may include EIL (electron injection layer), HIL (hole injection layer) and CPL (cathode capping layer), which may be in the form of a single layer or dispersed in an electron or hole transport material. The host material may be any suitable host material known in the art. The emission color of an OLED is determined by the emission energy (optical energy gap) of the EML (light emitting layer) material, which can be tuned by tuning the electron structure of the emissive divalent platinum complex and/or host material as described above. The hole transporting material in the HTL layer and the electron transporting material in the ETL layer may comprise any suitable hole transporter known in the art. The divalent platinum complex provided by embodiments of the present invention may exhibit phosphorescence. Phosphorescent OLEDs (i.e., OLEDs having phosphorescent emitters) generally have higher device efficiencies than other OLEDs such as fluorescent OLEDs. An electrophosphorescent emitter-based light emitting device is described in more detail in WO2000/070655 on pages 151-154 of Nature 395, which is incorporated herein by reference as if fully contained in relation to OLEDs, especially fluorescent OLEDs.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110857684.7A CN115700254B (en) | 2021-07-28 | 2021-07-28 | A divalent platinum complex and its preparation method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110857684.7A CN115700254B (en) | 2021-07-28 | 2021-07-28 | A divalent platinum complex and its preparation method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115700254A CN115700254A (en) | 2023-02-07 |
| CN115700254B true CN115700254B (en) | 2025-05-13 |
Family
ID=85120687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110857684.7A Active CN115700254B (en) | 2021-07-28 | 2021-07-28 | A divalent platinum complex and its preparation method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115700254B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009267244A (en) * | 2008-04-28 | 2009-11-12 | Fujifilm Corp | Organic electroluminescent element |
| CN104693243A (en) * | 2013-10-14 | 2015-06-10 | 代表亚利桑那大学的亚利桑那校董事会 | Platinum complexes and devices |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200755A (en) * | 2017-06-20 | 2017-09-26 | 南京工业大学 | platinum complex coordinated by four-coordinate deuterated ligand |
-
2021
- 2021-07-28 CN CN202110857684.7A patent/CN115700254B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009267244A (en) * | 2008-04-28 | 2009-11-12 | Fujifilm Corp | Organic electroluminescent element |
| CN104693243A (en) * | 2013-10-14 | 2015-06-10 | 代表亚利桑那大学的亚利桑那校董事会 | Platinum complexes and devices |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115700254A (en) | 2023-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101773936B1 (en) | New organic electroluminescent compounds and organic electroluminescent device comprising the same | |
| KR101996649B1 (en) | Pyrene derivative compounds and organic light-emitting diode including the same | |
| CN102598344B (en) | Organic electroluminescent element | |
| JP4628435B2 (en) | Organic electroluminescence device | |
| KR20110123701A (en) | Anthracene-based compound and organic electroluminescent device comprising the same | |
| CN102362551A (en) | organic electroluminescent element | |
| CN107068880B (en) | A kind of organic electroluminescent device containing diaryl ketone compound and its application | |
| Wen et al. | Engineering of aggregation-induced emission luminogens by isomeric strategy to achieve high-performance optoelectronic device | |
| Liu et al. | Efficient Non‐doped Blue Fluorescent Organic Light‐Emitting Diodes Based on Anthracene–Triphenylethylene Derivatives | |
| KR101601679B1 (en) | Compound Containing 5-Membered Heterocycle And Organic Electronic Element Using The Same, Terminal Thereof | |
| KR20190129509A (en) | Multicyclic compound and organic light emitting device comprising the same | |
| JP2009126793A (en) | Novel di (pyridylphenyl) derivative, electron transport material comprising the same, and organic electroluminescence device including the same | |
| CN106898709B (en) | A red phosphorescent organic electroluminescent device | |
| US8941099B2 (en) | Organic light emitting device and materials for use in same | |
| CN113056471A (en) | Compound and organic light emitting diode comprising same | |
| KR102518765B1 (en) | Novel compound and organic light-emitting diode using them | |
| CN112939990B (en) | A kind of light-emitting compound with organic condensed ring and its preparation method and organic electroluminescent device | |
| CN111961089A (en) | Organic metal complex and preparation method and application thereof | |
| KR102247292B1 (en) | Multicyclic compound and organic light emitting device comprising the same | |
| CN113056468A (en) | Compound and organic light emitting device including the same | |
| CN115700254B (en) | A divalent platinum complex and its preparation method and use | |
| KR20200011911A (en) | Multicyclic compound and organic light emitting device comprising the same | |
| CN117642045A (en) | Organic electroluminescent device | |
| CN105131940A (en) | Organic luminescent material containing spirobifluorene and dibenzothiophene and luminescent device | |
| KR102128299B1 (en) | Novel organic electroluminescent compound, organic electroluminescent device including the same and electric apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |