CN111909219A - Platinum compound with photoluminescence performance and preparation method thereof - Google Patents
Platinum compound with photoluminescence performance and preparation method thereof Download PDFInfo
- Publication number
- CN111909219A CN111909219A CN202010910364.9A CN202010910364A CN111909219A CN 111909219 A CN111909219 A CN 111909219A CN 202010910364 A CN202010910364 A CN 202010910364A CN 111909219 A CN111909219 A CN 111909219A
- Authority
- CN
- China
- Prior art keywords
- platinum compound
- reaction
- photoluminescence
- intermediate product
- finished
- 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.)
- Pending
Links
- 238000005424 photoluminescence Methods 0.000 title claims abstract description 53
- 150000003058 platinum compounds Chemical class 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 86
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000013067 intermediate product Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- 239000012074 organic phase Substances 0.000 claims description 34
- 239000003446 ligand Substances 0.000 claims description 31
- 238000002390 rotary evaporation Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 239000012043 crude product Substances 0.000 claims description 21
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 19
- 238000004440 column chromatography Methods 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- DMIYKWPEFRFTPY-UHFFFAOYSA-N 2,6-dichlorobenzaldehyde Chemical compound ClC1=CC=CC(Cl)=C1C=O DMIYKWPEFRFTPY-UHFFFAOYSA-N 0.000 claims description 7
- UUOLETYDNTVQDY-UHFFFAOYSA-N 2-chloro-3-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CN=C1Cl UUOLETYDNTVQDY-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 12
- 230000005284 excitation Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000003480 eluent Substances 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002910 rare earth metals Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Abstract
The invention belongs to the technical field of synthesis of organic complexes, and particularly relates to a platinum compound with photoluminescence performance and a preparation method thereof. A platinum compound with photoluminescence property and a molecular formula of C29H30ClN3O2The structural formula of Pt is shown in a formula I. The maximum excitation wavelength of the platinum compound with the photoluminescence performance is 329nm, and the maximum emission wavelengths are 517nm and 540 nm; the photoluminescence quantum efficiency of the solid powder at 293K reaches 22.08%, the service life reaches 9.53 mu s, and the solid powder is a potential high-efficiency OLED photoluminescence material.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic complexes, and particularly relates to a platinum compound with photoluminescence performance and a preparation method thereof.
Background
With the continuous development of society and scientific technology, luminescent materials become one of the most active topics in the field of material research. Luminescent materials are of various types, and can be classified into photoluminescence, electroluminescence, bioluminescence, chemiluminescence, and the like, by the classification of the luminescent energy source. Electroluminescent devices are continually being investigated in various different light emission types. Organic Light Emitting Diodes (OLEDs) are becoming the mainstream trend of energy-saving lighting and novel display technologies due to their excellent characteristics of ultra-light weight, low power consumption, high contrast, natural color, flexible display, etc., and have been used in life, for example, the latest mobile display terminals nowadays are the P40 series. The core of the organic electroluminescent device is a stable, efficient and cheap luminescent material.
The influential and pioneering search of s.r.forrest et al in 1998 found that organometallic complexes, due to their strong spin-orbit coupling (SOC), can achieve rapid intersystem crossing (ISC) and long-lived phosphorescence decay. Research finds that phosphorescent complexes using rare earth metal atoms are receiving more and more attention because they can simultaneously capture singlet and triplet excitons, improve the luminescence efficiency of the complexes and theoretically achieve 100% internal quantum efficiency in OLEDs, and particularly, research on Ir (i) complexes is abundant, however, rare earth metal Ir is expensive and has great pollution, which hinders their application in mass production. Therefore, it is highly desirable to develop inexpensive metal complexes.
In photoluminescent applications, platinum metal is considered to be an alternative to phosphorescent iridium complexes due to its low price. Therefore, the platinum metal has unique advantages in the aspect of developing new cheap high-performance luminescent materials, and further development of divalent platinum complexes as OLED luminescent materials has extremely important scientific research value and economic value.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention is primarily directed to a platinum compound with photoluminescence properties, which has a better photoluminescence function.
The invention also aims to provide a preparation method of the platinum compound with the photoluminescence performance, which has mild reaction conditions and low cost.
Another object of the present invention is to provide the use of the above platinum compound having photoluminescence properties.
The purpose of the invention is realized by the following technical scheme:
a platinum compound with photoluminescence property has a molecular formula of C29H30ClN3O2Pt, the structural formula of which is shown in formula I:
the platinum compound with the photoluminescence property comprises one complex molecule in each asymmetric unit, and a central metal Pt atom in each complex molecule is respectively coordinated with C, N atoms on a ligand L and two O atoms from an auxiliary ligand 2,2,6, 6-tetramethyl-3, 5-heptanedione (dpm), so that a typical planar quadrilateral structure is finally formed;
the bond lengths of two Pt-O bonds in the complex molecule are respectively
And
the bond lengths of the Pt-N bond and the Pt-C bond are respectively
And
the bond angle C-Pt-N is 80.0(5) °;
the structural unit of the platinum compound with photoluminescence property belongs to a monoclinic system, and the space group is P21The unit cell parameters are:
α＝90.00(3)°，γ＝90.00(3)°，β＝94.519(2)°；
the preparation method of the platinum compound with the photoluminescence property comprises the following steps:
(1) dissolving 2-chloro-3-nitropyridine and aniline in ethylene glycol, and reacting and refluxing for 48-56 hours at the temperature of 60-65 ℃; purifying the product after the reaction is finished to obtain an intermediate product A;
(2) adding the intermediate product A prepared in the step (1) and sodium hydrosulfite into a mixed solvent consisting of ethanol and water, and carrying out reflux reaction at 100-105 ℃ for 4-5 h; purifying the product after the reaction is finished to obtain an intermediate product B;
(3) adding the intermediate product B prepared in the step (2) and 2, 6-dichlorobenzaldehyde into absolute ethyl alcohol, and carrying out reflux reaction at 80 ℃ for 48-60 h under the protection of argon; purifying the product after the reaction is finished to obtain an intermediate product C;
(4) adding the intermediate product C prepared in the step (3) and 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) into dichloromethane, and stirring for 36-48 h at 20-35 ℃ under the protection of argon; purifying the product after the reaction is finished to obtain a ligand L;
(5) adding the ligand L prepared in the step (4) and potassium tetrachloroplatinate into a mixed solvent consisting of ethylene glycol and water, and reacting for 48-60 h at 80 ℃ under the protection of argon; after the reaction is finished, cooling the reaction system, adding water into the reaction liquid until solid is separated out, and filtering to obtain solid, namely an intermediate compound D, wherein the filtrate can be further subjected to rotary evaporation to recover the mixed solvent for recycling;
(6) adding the intermediate product D prepared in the step (5) and 2,2,6, 6-tetramethylheptanedione into ethylene glycol, adding sodium carbonate, refluxing for 6-7 h at 130 ℃ under the protection of argon, cooling a reaction system after the reaction is finished, performing rotary evaporation to recover a solvent, extracting residual solids by using water and dichloromethane in sequence, and collecting an organic phase; concentrating the organic phase to obtain a crude product, and further performing column chromatography separation to obtain a platinum compound with photoluminescence performance;
the structural formulas of the intermediate product A, the intermediate product B, the intermediate product C and the intermediate compound D are shown in formulas III-VI:
the molar ratio of the 2-chloro-3-nitropyridine to the aniline in the step (1) is preferably 1: 1;
the purification described in step (1) is preferably:
after the reaction is finished, cooling the reaction system to room temperature, then sequentially adding dichloromethane and water for extraction, and collecting an organic phase; the organic phase is evaporated in a rotary manner to recover the organic solvent, and the residual solid is an intermediate product A;
the mol ratio of the intermediate product A to the sodium hydrosulfite in the step (2) is preferably 1: 4;
the volume ratio of the ethanol to the water in the step (2) is preferably 5: 1;
the purification in step (2) is preferably:
after the reaction is finished, cooling the reaction system to room temperature, recovering the solvent by rotary evaporation, then sequentially adding dichloromethane and water for extraction, and collecting an organic phase; concentrating the organic phase to obtain a crude product, further performing column chromatography, and performing vacuum drying to obtain an intermediate product B; the eluent of the column chromatography is petroleum ether: ethyl acetate 5:1 (V: V);
the molar ratio of the intermediate product B to the 2, 6-dichlorobenzaldehyde in the step (3) is preferably 1: 1.2;
the purification in step (3) is preferably:
after the reaction is finished, cooling the reaction system to room temperature, and performing rotary evaporation to recover the solvent to obtain a crude product; washing the crude product with methanol, performing suction filtration, and performing vacuum drying to obtain an intermediate product C;
the molar ratio of the intermediate product C to the 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) in the step (4) is preferably 1: 2;
the purification in step (4) is preferably:
after the reaction is finished, recovering the solvent by rotary evaporation, then sequentially adding ethyl acetate and saturated sodium bicarbonate aqueous solution for extraction, and collecting an organic phase; concentrating the organic phase to obtain a crude product, further performing column chromatography, and performing vacuum drying to obtain a ligand L; the eluent of the column chromatography is petroleum ether: ethyl acetate 5:1 (V: V);
the molar ratio of the ligand L to the potassium tetrachloroplatinate in the step (5) is preferably 2: 1;
the volume ratio of the ethylene glycol to the water in the mixed solvent in the step (5) is preferably (3:1) to (1: 1);
the molar ratio of the intermediate compound D, 2,6, 6-tetramethylheptanedione and sodium carbonate in the step (6) is preferably 1:3: 10;
the eluent for column chromatography in the step (6) is petroleum ether: ethyl acetate 10:1 (V: V);
the platinum compound with photoluminescence performance is applied to the field of OLED luminescent materials;
compared with the prior art, the invention has the following advantages and effects:
(1) the platinum compound with the photoluminescence performance provided by the invention is simple in preparation process and mild in reaction condition.
(2) The organic solvents such as ethylene glycol, dichloromethane and ethanol used in the preparation process of the platinum compound with the photoluminescence performance provided by the invention can be recycled, and the pollution is small.
(3) The maximum excitation wavelength of the platinum compound with the photoluminescence performance is 329nm, and the maximum emission wavelengths are 517nm and 540 nm;
(4) the solid powder of the platinum compound with the photoluminescence performance provided by the invention has the photoluminescence quantum efficiency of 22.08% at 293K, and the service life of 9.53 mu s.
Drawings
Fig. 1 is a crystal structure diagram of a platinum compound having photoluminescence properties.
FIG. 2 is a diagram showing an ultraviolet-visible absorption spectrum of a ligand L and a platinum compound having a photoluminescent property.
Fig. 3 is a graph of excitation and emission spectra of a platinum compound having photoluminescence properties, where ex represents the excitation spectrum and em represents the emission spectrum.
FIG. 4 is a diagram of a synthesis method of ligand L.
Fig. 5 is a diagram of a synthesis method of a platinum compound having a photoluminescence property.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Dissolving 2-chloro-3-nitropyridine (1.585g, 0.01mol) and aniline (0.938g, 0.01mol) in 50mL of ethylene glycol, and reacting at 60 ℃ for 48h under reflux; after the reaction is finished, cooling the reaction system to room temperature, then sequentially adding 10ml of dichloromethane and 10ml of water for extraction, and collecting an organic phase; the organic phase is subjected to rotary evaporation to recover organic solvents ethylene glycol and dichloromethane, and the residual red solid is the intermediate product A;
(2) adding the intermediate product A (2.15g, 0.010mol) prepared in the step (1) and sodium hydrosulfite (7g, 0.04mol) into a mixed solvent (volume ratio of ethanol to water is 5:1) composed of 24ml of ethanol and water, and carrying out reaction reflux for 5h at 100 ℃; after the reaction is finished, cooling the reaction system to room temperature, carrying out rotary evaporation to recover ethanol and water in the system, then sequentially adding 10ml of dichloromethane and 10ml of water for extraction, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain crude product, further performing column chromatography with petroleum ether/ethyl acetate (volume ratio 5:1) as eluent, and vacuum drying to obtain white solid powder intermediate product B;
(3) adding the intermediate product B (1.85g, 0.010mol) prepared in the step (2) and 2, 6-dichlorobenzaldehyde (2.1g, 0.012mol) into 50mL of absolute ethanol solution, and carrying out reflux reaction at 80 ℃ for 48h under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, and performing rotary evaporation to recover absolute ethyl alcohol to obtain a crude product; washing the crude product with 5ml of methanol for several times, then carrying out suction filtration by using a cloth type funnel and carrying out vacuum drying to obtain an intermediate product C;
(4) adding the intermediate product C (3.41g and 10mmol) prepared in the step (3) and 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) (4.54g and 20mmol) into 30mL of anhydrous dichloromethane solution, and stirring at room temperature for 36h under the protection of argon; after the reaction is finished, performing rotary evaporation to recover dichloromethane in the system, then sequentially adding 25ml of ethyl acetate and 25ml of saturated sodium bicarbonate aqueous solution for extraction, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain crude product, further performing chromatography with petroleum ether/ethyl acetate (volume ratio 5:1) as eluent column to obtain white solid powder, and vacuum drying to obtain ligand L; FIG. 4 is a diagram showing a method for synthesizing the ligand L.
(5) Adding the ligand L (1.36g and 4mmol) prepared in the step (4) and potassium tetrachloroplatinate (0.83g and 2mmol) into 20ml of mixed solvent consisting of ethylene glycol and water (the volume ratio of the ethylene glycol to the water is 3:1), and reacting for 48h at 80 ℃ under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, adding 20mL of water into the reaction solution to separate out solids, filtering to obtain solids, namely an intermediate compound D, and performing rotary evaporation on the filtrate to recover a mixed solvent of ethylene glycol and water for recycling;
(6) adding the intermediate compound D (1.071g, 1mmol) prepared in the step (5) and 2,2,6, 6-tetramethylheptanedione (0.553g, 3mmol) into 50mL of ethylene glycol solvent, adding sodium carbonate (1.060g, 10mmol), and refluxing at 130 ℃ for 6h under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, recovering the solvent ethylene glycol by rotary evaporation, sequentially extracting the residual solid by using 100mL of water and 50mL of dichloromethane, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain a crude product, and further performing column chromatography separation with petroleum ether/ethyl acetate (volume ratio 10:1) as an eluent to obtain a yellow-green solid final product, namely a platinum compound with photoluminescence performance, with a yield of 46%, wherein fig. 5 is a synthetic method diagram of the platinum compound with photoluminescence performance.
Example 2
(1) 2-chloro-3-nitropyridine (15.85g, 0.1mol) and aniline (9.38g, 0.1mol) are dissolved in 100mL of glycol, and the mixture is reacted and refluxed for 56h at 60 ℃; after the reaction is finished, cooling the reaction system to room temperature, then sequentially adding 70ml of dichloromethane and 80ml of water for extraction, and collecting an organic phase; the organic phase is subjected to rotary evaporation to recover organic solvents ethylene glycol and dichloromethane, and the residual red solid is the intermediate product A;
(2) adding the intermediate product A (21.5g, 0.1mol) prepared in the step (1) and sodium hydrosulfite (70g, 0.4mol) into a mixed solvent (the volume ratio of ethanol to water is 5:1) consisting of 200ml of ethanol and water, and carrying out reaction reflux for 5h at 100 ℃; after the reaction is finished, cooling the reaction system to room temperature, carrying out rotary evaporation to recover ethanol and water in the system, then sequentially adding 70ml of dichloromethane and 80ml of water for extraction, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain crude product, further performing column chromatography with petroleum ether/ethyl acetate (volume ratio 5:1) as eluent, and vacuum drying to obtain white solid powder intermediate product B;
(3) adding the intermediate product B (18.5g, 0.1mol) prepared in the step (2) and 2, 6-dichlorobenzaldehyde (21g, 0.12mol) into 120mL of anhydrous ethanol solution, and carrying out reflux reaction for 60h at 80 ℃ under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, and performing rotary evaporation to recover absolute ethyl alcohol to obtain a crude product; washing the crude product with 40ml of methanol for several times, then carrying out suction filtration by using a cloth type funnel and carrying out vacuum drying to obtain an intermediate product C;
(4) adding the intermediate product C (34.1g and 0.1mol) prepared in the step (3) and 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) (45.4g and 0.2mol) into 180mL of anhydrous dichloromethane solution, and stirring at room temperature for 48 hours under the protection of argon; after the reaction is finished, performing rotary evaporation to recover dichloromethane in the system, then sequentially adding 150ml of ethyl acetate and 200ml of saturated sodium bicarbonate aqueous solution for extraction, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain crude product, further performing column chromatography with petroleum ether/ethyl acetate (volume ratio 5:1) as eluent to obtain white solid powder, and vacuum drying to obtain ligand L;
(5) adding the ligand L (13.6g, 0.04mol) prepared in the step (4) and potassium tetrachloroplatinate (8.3g, 0.02mol) into 120ml of mixed solvent consisting of ethylene glycol and water (the volume ratio of the ethylene glycol to the water is 1:1), and reacting for 60h at 80 ℃ under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, adding 200mL of water into the reaction solution to separate out a solid, filtering to obtain a solid, namely an intermediate compound D, and performing rotary evaporation on the filtrate to recover a mixed solvent of ethylene glycol and water for recycling;
(6) adding the intermediate compound D (10.71g, 0.01mol) prepared in the step (5) and 2,2,6, 6-tetramethylheptanedione (5.53g, 0.03mol) into 150mL of ethylene glycol solvent, adding sodium carbonate (10.6g, 0.1mol), and refluxing at 130 ℃ for 6h under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, recovering the solvent ethylene glycol by rotary evaporation, sequentially extracting the residual solid by using 250mL of water and 200mL of dichloromethane, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain crude product, and further separating by column chromatography with petroleum ether/ethyl acetate (volume ratio 10:1) as eluent to obtain yellow-green solid final product with photoluminescence property of platinum compound with yield of 50%.
Example 3
(1) 2-chloro-3-nitropyridine (15.85g, 0.1mol) and aniline (9.38g, 0.1mol) are dissolved in 100mL of ethylene glycol, and the mixture is reacted at 65 ℃ for reflux for 55 h; after the reaction is finished, cooling the reaction system to room temperature, then sequentially adding 70ml of dichloromethane and 80ml of water for extraction, and collecting an organic phase; the organic phase is subjected to rotary evaporation to recover organic solvents ethylene glycol and dichloromethane, and the residual red solid is the intermediate product A;
(2) adding the intermediate product A (21.5g, 0.1mol) prepared in the step (1) and sodium hydrosulfite (70g, 0.4mol) into a mixed solvent (the volume ratio of ethanol to water is 5:1) consisting of 200ml of ethanol and water, and carrying out reaction reflux for 4h at 105 ℃; after the reaction is finished, cooling the reaction system to room temperature, carrying out rotary evaporation to recover ethanol and water in the system, then sequentially adding 70ml of dichloromethane and 80ml of water for extraction, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain crude product, further performing column chromatography with petroleum ether/ethyl acetate (volume ratio 5:1) as eluent, and vacuum drying to obtain white solid powder intermediate product B;
(3) adding the intermediate product B (18.5g, 0.1mol) prepared in the step (2) and 2, 6-dichlorobenzaldehyde (21g, 0.12mol) into 120mL of anhydrous ethanol solution, and carrying out reflux reaction at 80 ℃ for 55h under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, and performing rotary evaporation to recover absolute ethyl alcohol to obtain a crude product; washing the crude product with 40ml of methanol for several times, then carrying out suction filtration by using a cloth type funnel and carrying out vacuum drying to obtain an intermediate product C;
(4) adding the intermediate product C (34.1g and 0.1mol) prepared in the step (3) and 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) (45.4g and 0.2mol) into 180mL of anhydrous dichloromethane solution, and stirring at room temperature for 40 hours under the protection of argon; after the reaction is finished, performing rotary evaporation to recover dichloromethane in the system, then sequentially adding 150ml of ethyl acetate and 200ml of saturated sodium bicarbonate aqueous solution for extraction, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain crude product, further performing column chromatography with petroleum ether/ethyl acetate (volume ratio 5:1) as eluent to obtain white solid powder, and vacuum drying to obtain ligand L;
(5) adding the ligand L (13.6g, 0.04mol) prepared in the step (4) and potassium tetrachloroplatinate (8.3g, 0.02mol) into 120ml of mixed solvent consisting of ethylene glycol and water (the volume ratio of the ethylene glycol to the water is 1:1), and reacting for 55h at 80 ℃ under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, adding 200mL of water into the reaction solution to separate out a solid, filtering to obtain a solid, namely an intermediate compound D, and performing rotary evaporation on the filtrate to recover a mixed solvent of ethylene glycol and water for recycling;
(6) adding the intermediate compound D (10.71g, 0.01mol) prepared in the step (5) and 2,2,6, 6-tetramethylheptanedione (5.53g, 0.03mol) into 150mL of ethylene glycol solvent, adding sodium carbonate (10.6g, 0.1mol), and refluxing at 130 ℃ for 7h under the protection of argon; after the reaction is finished, cooling the reaction system to room temperature, recovering the solvent ethylene glycol by rotary evaporation, sequentially extracting the residual solid by using 250mL of water and 200mL of dichloromethane, and collecting an organic phase; concentrating the organic phase under reduced pressure to obtain crude product, and further performing column chromatography with petroleum ether/ethyl acetate (volume ratio 10:1) as eluent to obtain yellow-green solid final product platinum compound with photoluminescence property with yield of 48%.
Effects of the embodiment
Characterization and detection of the platinum compound with photoluminescence property prepared in examples 1 to 3:
(1) crystal structure
Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a saturated solution in dichloromethane and methanol at room temperature. Selecting single crystal with proper size under microscope, placing on Bruker SMART CCD AREA DETECTOR single crystal X-diffractometer, and monochromating Mo-Ka ray with graphite
The complex was measured at 293K on a Bruker P4 four-circle diffractometer using Mo-Ka radiation monochromatized with a graphite monochromator at 293K at 2.49 °<θ<30967 diffraction points were collected in the 26.371 ° range, with 5400 independent diffraction points; all diffraction data were absorption corrected using the SADABS program; the unit cell parameters are determined by a least square method; data reduction and structural deconstruction were done using SAINT and SHELXTL programs, respectively. Firstly, determining all non-hydrogen atom coordinates by a difference function method and a least square method, obtaining hydrogen atom positions by a theoretical hydrogenation method, and then refining the crystal structure by the least square method. The crystal structure of the platinum compound having photoluminescence properties is schematically shown in fig. 1. Some of the parameters for crystallographic diffraction point data collection and structure refinement are shown in table 1.
TABLE 1 crystallographic diffraction Point data for platinum Compounds having photoluminescent Properties obtained in examples 1 to 3
(2) Ultraviolet-visible absorption spectroscopy
Ultraviolet-visible absorption Spectroscopy Using an ultraviolet-visible spectrophotometer of UV-1800PC, ligand L and a platinum compound were dissolved in a dichloromethane solution (concentration 1.0X 10) at room temperature-5mol/L) are measured. The ultraviolet-visible absorption spectrum of the compound is shown in figure 2: the absorption of the compound in the short-wave region is mainly derived from the absorption of the ligand, and the ultraviolet absorption peak near 325nm can be assigned as pi → pi electron transition absorption (ILCT) between the insides of the pyridoimidazole C ^ N ligands, and possibly mixed with a small amount of d → pi transition, i.e. electron transition absorption (MLCT) of platinum atoms onto the pyridoimidazole C ^ N ligands and electron transition absorption (L' LCT) on the ancillary ligands dpm and the pyridoimidazole C ^ N ligands. Careful observation revealed that the complex had a broad intermediate absorption band between 350nm and 410nm, which was mainly due to electron transition absorption (L' LCT) on the ancillary ligands dpm and the pyridoimidazole C ^ N ligand, charge transfer transitions within the ligand (ILCT) and metal to ligand (MLCT).
(3) Analysis of photoluminescence Properties
Emission spectrum analysis was performed using an F-4600 type fluorescence spectrometer, as shown in FIG. 3, in which ex represents an excitation spectrum, em represents an emission spectrum, and the maximum excitation wavelength of the platinum compound having a photoluminescent property was 329nm, and the maximum emission wavelengths were 517nm and 540 nm; the luminescence life is measured by an FLS980 type steady-state transient fluorescence spectrometer, and the luminescence life of the platinum compound solid powder with photoluminescence performance reaches 9.53 mu s under the condition of 293K; the absolute quantum yield is measured by an FLS980 type steady-state transient fluorescence spectrometer with an integrating sphere, and the photoluminescence quantum efficiency of the platinum compound solid powder with photoluminescence performance reaches 22.08% under the condition of 293K.
(4) Nuclear magnetic characterization
The nuclear magnetic characterization of the platinum compound with photoluminescence property is carried out by adopting a Br ker DPX-400MGHz superconducting nuclear magnetic resonance instrument (taking TMS as an internal standard).
Ligand L:1H NMR(600MHz,CDCl3)8.50(d,J＝4.5Hz,1H),8.26(d,J＝7.9Hz,1H),7.42(m,7.0Hz,6H),7.34(q,J＝5.5Hz,3H),7.26(s,1H).
platinum compound:1H NMR(600MHz,CDCl3)8.98(dd,J＝8.1,1.2Hz,1H),8.43(d,J＝1.2Hz,1H),7.78(d,J＝7.5Hz,1H),7.57-7.44(m,5H),7.38(m,2H),7.11(t,J＝7.7Hz,1H),6.92(d,J＝7.7Hz,1H),5.91(s,1H),1.47-1.20(m,18H).
the solid powder of the platinum compound with the photoluminescence performance provided by the invention has the photoluminescence quantum efficiency of 22.08% at 293K, the service life of 9.53 mu s, and is a potential high-efficiency OLED photoluminescence material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A platinum compound with photoluminescence property is characterized in that the molecular formula is C29H30ClN3O2Pt, the structural formula of which is shown in formula I:
2. the platinum compound having photoluminescence properties as recited in claim 1, wherein:
the platinum compound with the photoluminescence property comprises one complex molecule in each asymmetric unit, and a central metal Pt atom in each complex molecule is respectively coordinated with C, N atoms on a ligand L and two O atoms from an auxiliary ligand 2,2,6, 6-tetramethyl-3, 5-heptanedione, so that a typical planar quadrilateral structure is finally formed.
3. The platinum compound having photoluminescence properties as recited in claim 1, wherein:
the structural unit of the platinum compound with photoluminescence property belongs to a monoclinic system, and the space group is P21The unit cell parameters are:
α＝90.00(3)°，γ＝90.00(3)°，β＝94.519(2)°。
4. the method for preparing a platinum compound having a photoluminescent property according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) dissolving 2-chloro-3-nitropyridine and aniline in ethylene glycol, and reacting and refluxing for 48-56 hours at the temperature of 60-65 ℃; purifying the product after the reaction is finished to obtain an intermediate product A;
(2) adding the intermediate product A prepared in the step (1) and sodium hydrosulfite into a mixed solvent consisting of ethanol and water, and carrying out reflux reaction at 100-105 ℃ for 4-5 h; purifying the product after the reaction is finished to obtain an intermediate product B;
(3) adding the intermediate product B prepared in the step (2) and 2, 6-dichlorobenzaldehyde into absolute ethyl alcohol, and carrying out reflux reaction at 80 ℃ for 48-60 h under the protection of argon; purifying the product after the reaction is finished to obtain an intermediate product C;
(4) adding the intermediate product C prepared in the step (3) and 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone into dichloromethane, and stirring for 36-48 h at 20-35 ℃ under the protection of argon; purifying the product after the reaction is finished to obtain a ligand L;
(5) adding the ligand L prepared in the step (4) and potassium tetrachloroplatinate into a mixed solvent consisting of ethylene glycol and water, and reacting for 48-60 h at 80 ℃ under the protection of argon; after the reaction is finished, cooling the reaction system, adding water into the reaction liquid until solid is separated out, and filtering to obtain solid, namely an intermediate compound D;
(6) adding the intermediate product D prepared in the step (5) and 2,2,6, 6-tetramethylheptanedione into ethylene glycol, adding sodium carbonate, refluxing for 6-7 h at 130 ℃ under the protection of argon, cooling a reaction system after the reaction is finished, performing rotary evaporation to recover a solvent, extracting residual solids by using water and dichloromethane in sequence, and collecting an organic phase; and concentrating the organic phase to obtain a crude product, and further performing column chromatography separation to obtain the platinum compound with photoluminescence performance.
5. The method for preparing a platinum compound having photoluminescence properties according to claim 4, wherein:
the structural formulas of the intermediate product A, the intermediate product B, the intermediate product C and the intermediate compound D are shown in formulas III-VI:
6. the method for preparing a platinum compound having photoluminescence properties according to claim 4, wherein:
the molar ratio of the 2-chloro-3-nitropyridine to the aniline in the step (1) is 1: 1;
the molar ratio of the intermediate product A to the sodium hydrosulfite in the step (2) is 1: 4.
7. The method for preparing a platinum compound having photoluminescence properties according to claim 4, wherein:
the molar ratio of the intermediate product B to the 2, 6-dichlorobenzaldehyde in the step (3) is 1: 1.2.
8. The method for preparing a platinum compound having photoluminescence properties according to claim 4, wherein:
the molar ratio of the intermediate product C to the 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) in the step (4) is 1: 2;
the molar ratio of the ligand L to the potassium tetrachloroplatinate in the step (5) is 2: 1.
9. The method for preparing a platinum compound having photoluminescence properties according to claim 4, wherein:
the molar ratio of the intermediate compound D, the 2,2,6, 6-tetramethylheptanedione and the sodium carbonate in the step (6) is 1:3: 10.
10. Use of the platinum compound with photoluminescence performance according to any one of claims 1 to 3 in the field of OLED luminescent materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010910364.9A CN111909219A (en) | 2020-09-02 | 2020-09-02 | Platinum compound with photoluminescence performance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010910364.9A CN111909219A (en) | 2020-09-02 | 2020-09-02 | Platinum compound with photoluminescence performance and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111909219A true CN111909219A (en) | 2020-11-10 |
Family
ID=73267441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010910364.9A Pending CN111909219A (en) | 2020-09-02 | 2020-09-02 | Platinum compound with photoluminescence performance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111909219A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726606A (en) * | 2002-11-08 | 2006-01-25 | 通用显示公司 | Organic light emitting materials and devices |
| CN109796499A (en) * | 2017-11-17 | 2019-05-24 | 北京夏禾科技有限公司 | The metal complex of nitrogen-containing hetero benzothiazole |
-
2020
- 2020-09-02 CN CN202010910364.9A patent/CN111909219A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726606A (en) * | 2002-11-08 | 2006-01-25 | 通用显示公司 | Organic light emitting materials and devices |
| CN109796499A (en) * | 2017-11-17 | 2019-05-24 | 北京夏禾科技有限公司 | The metal complex of nitrogen-containing hetero benzothiazole |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110407710B (en) | Triphenylamine derivative pure organic room temperature phosphorescent material and preparation method thereof | |
| CN111875634A (en) | Benzimidazole bidentate ligand-based luminescent copper compound and preparation method thereof | |
| CN111925392B (en) | Copper compound with photoluminescence performance and preparation method thereof | |
| CN111848676B (en) | Luminescent copper compound based on benzimidazole diphosphine ligand and preparation method thereof | |
| CN106008501B (en) | Bipolarity compound containing pyrido-pyrazine unit and its preparation method and application | |
| CN112028943A (en) | Platinum luminescent compound based on pyridine imidazole derivative and preparation method thereof | |
| Sun et al. | Mixed-solvothermal synthesis, structures, surface photovoltage, luminescence and molecular recognition properties of three new transition metal phosphonates with 3D framework and supramolecular structures | |
| CN113292607B (en) | Ionic luminescent platinum complex based on benzimidazole phosphine ligand and preparation method thereof | |
| CN114591365B (en) | Luminous copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof | |
| CN102030702B (en) | Hole-transporting material and synthesis method thereof | |
| CN111909219A (en) | Platinum compound with photoluminescence performance and preparation method thereof | |
| CN112028942B (en) | Pt (II) photoluminescent compound based on pyridoimidazole derivative and preparation method thereof | |
| CN111808097B (en) | Solvent yellow 184 derivative and preparation method and application thereof | |
| JP5967663B2 (en) | Platinum complex | |
| CN113201022A (en) | Small conjugated phosphorescent metal iridium (III) complex with isomer and preparation method and application thereof | |
| CN110229192B (en) | Deuterated iridium complex and preparation method and application thereof | |
| CN112010904B (en) | Benzimidazole diphosphine Cu (I) complex and preparation method thereof | |
| CN113461698A (en) | Trimeric indenyl dicumarol-corrole triplet photosensitizer and preparation method and application thereof | |
| CN111892628B (en) | Luminescent copper (I) complex based on pyridoimidazole diphosphine derivative and preparation method thereof | |
| CN109369726A (en) | The preparation and application of a kind of double-nuclear ring metal platinum (III) complex near-infrared light-emitting material | |
| CN108690091A (en) | A kind of complex of iridium and its preparation method and application | |
| CN113444117B (en) | Star-shaped compound of BODIPY bridged tetraperylene diimide derivative and preparation method thereof | |
| CN113563380B (en) | Efficient light-emitting cuprous complex based on triazole phosphine derivatives and preparation method thereof | |
| CN117567518A (en) | Efficient yellow light emitting ionic platinum complex based on benzimidazole phosphine ligand and preparation method thereof | |
| CN113402422B (en) | Synthetic method and application of alpha-cyanoethylene aggregation induced luminophor |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201110 |