CN109336932B - Amphiphilic platinum (II) complex, preparation thereof and application thereof in constructing white luminescent system - Google Patents
Amphiphilic platinum (II) complex, preparation thereof and application thereof in constructing white luminescent system Download PDFInfo
- Publication number
- CN109336932B CN109336932B CN201811406835.1A CN201811406835A CN109336932B CN 109336932 B CN109336932 B CN 109336932B CN 201811406835 A CN201811406835 A CN 201811406835A CN 109336932 B CN109336932 B CN 109336932B
- Authority
- CN
- China
- Prior art keywords
- platinum
- amphiphilic
- complex
- formula
- white light
- 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.)
- Expired - Fee Related
Links
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- QNEPTKZEXBPDLF-JDTILAPWSA-N [(3s,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] carbonochloridate Chemical compound C1C=C2C[C@@H](OC(Cl)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 QNEPTKZEXBPDLF-JDTILAPWSA-N 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- IKXNIQJDNKPPCH-UHFFFAOYSA-N hydron;prop-2-yn-1-amine;chloride Chemical group [Cl-].[NH3+]CC#C IKXNIQJDNKPPCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 13
- 239000012046 mixed solvent Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006862 quantum yield reaction Methods 0.000 abstract description 5
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 235000012000 cholesterol Nutrition 0.000 abstract description 2
- ILYCWAKSDCYMBB-OPCMSESCSA-N dihydrotachysterol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)/C=C/[C@H](C)C(C)C)=C\C=C1/C[C@@H](O)CC[C@@H]1C ILYCWAKSDCYMBB-OPCMSESCSA-N 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- COSRMLFFGBGUMT-UHFFFAOYSA-N 2-[2-(2-iodo-2-methoxyethoxy)ethoxy]ethanol Chemical compound COC(COCCOCCO)I COSRMLFFGBGUMT-UHFFFAOYSA-N 0.000 description 1
- VYYYKBMLQCSSSB-UHFFFAOYSA-N 2-[2-[2-(2-iodo-2-methoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound COC(I)COCCOCCOCCO VYYYKBMLQCSSSB-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- -1 iodopentaethylene glycol monomethyl ether Chemical compound 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002277 temperature effect Effects 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 Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table 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
-
- 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
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an amphiphilic platinum (II) complex, a preparation method thereof and application thereof in constructing a white luminescent system, wherein the complex has the structural formula:wherein m is an integer of 3-5, n is 1 or 2, the amphiphilic platinum (II) complex takes an ether oxygen chain as a hydrophilic part and cholesterol as a hydrophobic part, and has the characteristics of self-assembly, simple preparation method and mild reaction conditions. The amphiphilic platinum (II) complex emits white light under different water contents of dimethyl sulfoxide/water mixed solvents, different temperatures and different excitation wavelengths, and the quantum yield of a white light-emitting system can reach 5.8% at most, so that the amphiphilic platinum (II) complex is a platinum complex single-component white light-emitting material with excellent light-emitting performance.
Description
Technical Field
The invention belongs to the technical field of preparation of luminescent materials, and particularly relates to an amphiphilic platinum (II) complex with a self-assembly function, a preparation method thereof, and a white luminescent system constructed in dimethyl sulfoxide/water solution by using the complex.
Background
In recent years, white light emitting materials have received much attention due to their many potential applications in display devices, lighting devices and sensors. In general, such white light emitting materials are doped with two (e.g., blue and orange) or three (e.g., red, green and blue) fluorophores, and the white light emitting system is constructed by adjusting the ratio of different components to realize emission in the full spectrum range. However, the method of constructing a white light emitting system by using multi-component doping still has some disadvantages, such as: the preparation process is complex, the doping proportion is difficult to regulate and control, the synthesis cost is high, and the like. Compared with a multi-component white light-emitting system, the single-component white light-emitting system has the advantages of good stability, good reproducibility, simple preparation and the like, thereby being popular with the researchers.
The platinum (II) complex with a plane coordination structure becomes a research hotspot in the field of luminescent materials in recent years due to rich luminescent properties, pi-pi accumulation and Pt-Pt interaction among platinum (II) complexes can be adjusted by changing the microenvironment (such as solvent composition, counter ion type, pH value and the like) of the platinum (II) complex, so that coexistence of multiple excitation states of the platinum (II) complex is realized, multi-group fluorescence emission of a visible light region is obtained, and finally a single-component white luminescent material is obtained. Although this subject group has succeeded in preparing a one-component white light-emitting system (patent publication No. CN 107118761A: white light-emitting material based on amphiphilic platinum complex), the one-component white light-emitting system prepared in the previous work had a low quantum yield (1.1%).
Disclosure of Invention
The invention aims to overcome the defects of the preparation of a white luminescent material by doping various components, and provides a single-component white luminescent material, namely an amphiphilic platinum (II) complex, which has the advantages of simple preparation method, mild reaction conditions, good reproducibility and high quantum yield, a preparation method of the complex and application of the complex in constructing the white luminescent material.
In view of the above object, the amphiphilic platinum (II) complex used in the present invention has the following structural formula:
wherein m is an integer of 3 to 5, and n is 1 or 2.
The preparation method of the amphiphilic platinum (II) complex comprises the following steps:
1. synthesis of Compounds of formula I
Under the protection of nitrogen, dissolving alkynylamine hydrochloride in a triethylamine and dichloromethane solution, dripping a dichloromethane solution of cholesteryl chloroformate under an ice bath condition, continuing stirring at room temperature for 10-15 hours after finishing dripping, and separating and purifying to obtain the compound shown in the formula I.
The alkynylamine hydrochloride is any one of propargylamine hydrochloride and propargylamine hydrochloride.
2. Synthesis of amphiphilic platinum (II) complexes
Under the protection of nitrogen, dissolving a compound shown in the formula II in a triethylamine and dichloromethane solution, adding a compound shown in the formula I and a catalytic amount of cuprous iodide, stirring at room temperature in a dark place for 20-30 hours, and separating and purifying to obtain the amphiphilic platinum (II) complex.
In the step 1, the molar ratio of the cholesteryl chloroformate to the alkynylamine hydrochloride is preferably 1 (2-2.5).
In the step 2, the molar ratio of the compound shown in the formula II to the compound shown in the formula I is preferably 1 (2.5-3), the addition amount of cuprous iodide is 15-25% of the molar amount of the compound shown in the formula II, wherein the compound shown in the formula II is prepared by the method disclosed in J.Mater.chem.C,2013,1, 1130-1136, and the compound shown in the formula II can be prepared by only replacing iodotriethylene glycol monomethyl ether in the document with iodotetraethylene glycol monomethyl ether or iodopentaethylene glycol monomethyl ether.
The invention relates to application of an amphiphilic platinum (II) complex in construction of a white light-emitting system, which comprises the following specific construction methods: taking a mixed solution of dimethyl sulfoxide and water as a solvent, preparing an amphiphilic platinum (II) complex solution with the concentration of 45-55 mu mol/L, heating at 50-60 ℃ for 1-1.5 hours, naturally cooling to room temperature, and standing for 20-30 hours; when the volume concentration of water in the solvent is 30-60%, exciting an amphiphilic platinum (II) complex solution by a light source with the wavelength of 340nm at room temperature, and emitting white light by the system; when the volume concentration of water in the solvent is 20 percent and 70-90 percent respectively, exciting an amphiphilic platinum (II) complex solution by a light source with the wavelength of 350nm at room temperature, and emitting white light by the system; when the volume concentration of water in the solvent is 20%, a light source with the wavelength of 350nm is used for exciting the amphiphilic platinum (II) complex solution, the temperature is controlled within the range of 40-60 ℃, and the system also emits white light.
The invention has the following beneficial effects:
1. the amphiphilic platinum (II) complex takes an ether oxygen chain as a hydrophilic part and cholesterol as a hydrophobic part, has the self-assembly characteristic, and has the advantages of simple preparation method and mild reaction conditions.
2. The amphiphilic platinum (II) complex emits white light in dimethyl sulfoxide/water mixed solvents with different water contents, at different temperatures and under different excitation wavelengths, the quantum yield of a white light-emitting system can reach 5.8 percent at most, the light-emitting efficiency is improved by 6 times compared with that of the previous work, and the amphiphilic platinum (II) complex is a platinum complex single-component white light-emitting material with more excellent light-emitting performance, and the application range of the material is expanded.
Drawings
FIG. 1 is a fluorescence emission spectrum of 50. mu. mol/L amphiphilic platinum (II) complex at an excitation wavelength of 340nm in a dimethyl sulfoxide/water mixed solvent with different water contents at room temperature.
FIG. 2 is a graph of luminescence chromaticity at an excitation wavelength of 340nm in a mixed solvent of dimethyl sulfoxide and water having different water contents at room temperature of 50. mu. mol/L of amphiphilic platinum (II) complex.
FIG. 3 is a fluorescence emission spectrum of 50. mu. mol/L amphiphilic platinum (II) complex at an excitation wavelength of 350nm in a dimethyl sulfoxide/water mixed solvent with different water contents at room temperature.
FIG. 4 is a graph of luminescence chromaticity at 350nm as excitation wavelength of 50. mu. mol/L amphiphilic platinum (II) complex in a dimethyl sulfoxide/water mixed solvent with different water contents at room temperature.
FIG. 5 is a point diagram of fluorescence emission intensity ratio at 550nm and 390nm with 340nm as excitation wavelength of 50 μmol/L amphiphilic platinum (II) complex in dimethyl sulfoxide/water mixed solvent with different water contents at room temperature.
FIG. 6 is a point diagram of fluorescence emission intensity ratio at 550nm and 390nm with 350nm as excitation wavelength of 50 μmol/L amphiphilic platinum (II) complex in dimethyl sulfoxide/water mixed solvent with different water content at room temperature.
FIG. 7 is a fluorescence emission spectrum of 50. mu. mol/L amphiphilic platinum (II) complex in a dimethyl sulfoxide/water mixed solvent with a water content of 50% and at a temperature of 20-80 ℃ and an excitation wavelength of 350 nm.
FIG. 8 is a chromaticity diagram of luminescence of 50 μmol/L amphiphilic platinum (II) complex in a dimethylsulfoxide/water mixed solvent with a water content of 50% at an excitation wavelength of 350nm and a temperature of 20-80 deg.C during a temperature rise process.
FIG. 9 shows fluorescence emission spectra of 50 μmol/L amphiphilic platinum (II) complex in a dimethyl sulfoxide/water mixed solvent with a water content of 50% and at a temperature of 70-20 deg.C and an excitation wavelength of 350 nm.
FIG. 10 is a chromaticity diagram of luminescence of 50 μmol/L amphiphilic platinum (II) complex in a dimethylsulfoxide/water mixed solvent with a water content of 50% at an excitation wavelength of 350nm and a temperature of 70-20 ℃ during a cooling process.
Detailed Description
The invention will be further explained in more detail below with reference to the drawings and examples, without limiting the scope of the invention to these examples.
Example 1
1. Synthesis of Compounds of formula I-1
Under nitrogen protection, 369mg (4mmol) of propargylamine hydrochloride, 1.3mL of triethylamine and 40mL of dichloromethane are added in sequence to a 250mL three-necked flask; 897mg (2mmol)) of cholesteryl chloroformate and 100mL of methylene chloride are sequentially added to a constant pressure funnel, and the mixture is added dropwise to a three-necked flask under ice bath conditions and stirred, and then stirred at room temperature for 12 hours after the dropwise addition. After the reaction is finished, washing the reaction liquid with distilled water for three times, combining organic phases, drying the organic phases through anhydrous sodium sulfate, and then distilling the solvent under reduced pressure to obtain a crude product, and performing column chromatography separation and purification on the crude product by taking a mixed liquid as a mobile phase and silica gel as a stationary phase, wherein the volume ratio of dichloromethane to petroleum ether is 5:1, so as to obtain the compound of the formula I-1 (762 mg of white solid, the yield is 82%), wherein the reaction equation is as follows:
the structural characterization data for the compounds of formula I-1 are:1H NMRδH(600MHz,CDCl3,Me4Si):5.37(1H,C=CH),4.80(1H,NH),4.52(1H,OCH),3.97(2H,HC≡CCH 2),2.24(1H,C≡CH),0.67-2.28(m,43H)。
2. synthesis of amphiphilic platinum (II) complexes
277mg (0.29mmol) of the compound of the formula II-1 is dissolved in 1.5mL of triethylamine and 45mL of dichloromethane under nitrogen protection, and 371mg (0.79mmol) of the compound of the formula I-1 and 12mg (0.06mmol) of cuprous iodide are added in succession and stirred at room temperature for 24h in the absence of light. After the reaction is finished, washing the reaction liquid with 1mol/L HCl aqueous solution once and washing the reaction liquid with deionized water three times in sequence, combining organic phases, drying the organic phases through anhydrous sodium sulfate, then performing reduced pressure evaporation to remove the solvent to obtain a crude product, and performing column chromatography separation and purification on the crude product by taking a mixed solution of dichloromethane and methanol in a volume ratio of 15:1 as a mobile phase and silica gel as a stationary phase to obtain the amphiphilic platinum (II) complex (160 mg of yellow solid, the yield is 40%) shown in formula III-1, wherein the reaction equation is as follows:
the structural characterization data of the obtained amphiphilic platinum (II) complex are as follows:1H NMRδH(600MHz,CDCl3,Me4Si):8.86(2H,NCCH),8.67(1H,NCCHCH),8.18(2H,C6H4),7.51(2H,C6H4),7.34(2H,C6H4),7.12(2H,C6H4),6.99(1H,NH),5.41(1H,C=CH),4.87(4H,NCH 2CH2),4.66(OCH,1H),4.54(2H,C≡CCH2),3.98(4H,NCH2CH 2O),3.52-3.34(24H,OCH2),3.11(6H,OCH3),2.46-0.71(m,43H)。
example 2
Application of amphiphilic platinum (II) complex prepared in example 1 in construction of white light-emitting system
The method comprises the steps of taking a mixed solution of dimethyl sulfoxide and water with different water contents as a solvent, preparing an amphiphilic platinum (II) complex solution with the concentration of 50 mu mol/L, heating at 50-60 ℃ for 1 hour, naturally cooling to room temperature, and standing for 24 hours.
When the volume concentration of water in the solvent is 30%, 40%, 50% and 60%, the amphiphilic platinum (II) complex solution can emit white light when excited by a light source with the wavelength of 340nm at room temperature (the fluorescence emission spectrum is shown in figure 1, and the chromaticity coordinate is shown in figure 2), wherein the quantum yield is the highest and is 5.8% when the volume concentration of water is 50%.
When the volume concentration of water in the solvent is respectively 20%, 70%, 80% and 90%, the amphiphilic platinum (II) complex solution is excited by a light source with the wavelength of 350nm at room temperature, and the system can emit white light (the fluorescence emission spectrum is shown in figure 3); wherein the chromaticity coordinates are (0.30, 0.25) when the volume concentration of water is 20%, the chromaticity coordinates are (0.35, 0.34) when the volume concentration of water is 70%, and the chromaticity coordinates are (0.34, 0.32) when the volume concentration of water is 80%; at a water concentration of 90% by volume, the chromaticity coordinates were (0.34 ) (see fig. 4 for the chromaticity diagram).
Comparing the fluorescence emission intensity at 550nm and the fluorescence emission intensity at 390nm measured by 50 mu mol/L amphiphilic platinum (II) complex solution under the excitation light source of 340nm, and drawing I550/I390Point plots of values as a function of moisture content, see FIG. 5; measuring the fluorescence emission intensity at 550nm and the fluorescence at 390nm of 50 mu mol/L amphiphilic platinum (II) complex solution under the condition of taking 350nm as an excitation light sourceThe light emission intensities were compared and I was plotted550/I390The results are shown in FIG. 6, which is a point graph of the change in value with water content. As can be seen from FIGS. 5 and 6, as the water content increases, I550/I390The values show a trend of increasing first and then decreasing, which is consistent with the trend of the light emission evolution in the chromaticity coordinates of fig. 2 and 4. When the water content is 50%, I550/I390The ratio of (a) to (b) is maximized.
The inventor further regulates and controls the luminous performance of the luminescent material by 50 mu mol/L amphiphilic platinum (II) complex solution through temperature effect, and the specific test conditions are as follows:
under the conditions of different temperatures (20, 30, 40, 50, 60, 70 and 80 ℃), 350nm is used as an excitation light source, an FLS980 type single photon counting time-resolved fluorescence spectrometer is adopted to measure the luminescence property of the amphiphilic platinum (II) complex solution which is prepared by using a mixed solution of dimethyl sulfoxide and water with the water content of 50% as a solvent, and the fluorescence emission spectrum is shown in figure 7. As can be seen from FIG. 7, the fluorescence emission peak intensity at 390nm increases with increasing temperature, the fluorescence emission peak intensities at 550nm and 595nm decrease with increasing temperature, and the fluorescence of the amphiphilic platinum (II) complex gradually evolves from yellow light to white light (the chromaticity diagram is shown in FIG. 8). When the temperature is in the range of 40-60 ℃, the system can emit white light by taking 350nm as an excitation light source. The solution was cooled at 10 ℃ intervals, and the fluorescence emission spectrum was shown in FIG. 9 using 350nm as the excitation light source. As can be seen from FIG. 9, the fluorescence emission peak intensity at 390nm is reduced with the temperature reduction, the fluorescence emission peak intensity at 550nm and 595nm is enhanced with the temperature reduction, the fluorescence of the amphiphilic platinum (II) complex is gradually changed from white light to yellow light (the chromaticity coordinate diagram is shown in FIG. 10), and when the temperature range is 40-60 ℃, 350nm is used as an excitation light source, and the system can emit white light.
Claims (7)
2. A process for the preparation of amphiphilic platinum (ii) complexes according to claim 1, characterized in that it consists of the following steps:
(1) synthesis of Compounds of formula I
Under the protection of nitrogen, dissolving alkynylamine hydrochloride in a triethylamine and dichloromethane solution, dripping a dichloromethane solution of cholesteryl chloroformate under an ice bath condition, continuing stirring at room temperature for 10-15 hours after finishing dripping, and separating and purifying to obtain a compound shown in a formula I;
Ⅰ
the alkynylamine hydrochloride is propargylamine hydrochloride or propargylamine hydrochloride;
(2) synthesis of amphiphilic platinum (II) complexes
Under the protection of nitrogen, dissolving a compound shown in a formula II in a triethylamine and dichloromethane solution, adding a compound shown in a formula I and a catalytic amount of cuprous iodide, stirring at room temperature in a dark place for 20-30 hours, and separating and purifying to obtain an amphiphilic platinum (II) complex;
Ⅱ
the value of n in the compound shown in the formula I is 1 or 2, and the value of m in the compound shown in the formula II is an integer from 3 to 5.
3. The process for the preparation of amphiphilic platinum (ii) complexes as claimed in claim 2, characterized in that: in the step (1), the molar ratio of the cholesteryl chloroformate to the alkynylamine hydrochloride is 1 (2-2.5).
4. The process for the preparation of amphiphilic platinum (ii) complexes as claimed in claim 2, characterized in that: in the step (2), the molar ratio of the compound of the formula II to the compound of the formula I is 1 (2.5-3).
5. The process for the preparation of amphiphilic platinum (ii) complexes as claimed in claim 2, characterized in that: in the step (2), the addition amount of the cuprous iodide is 15-25% of the molar amount of the compound shown in the formula II.
6. Use of the amphiphilic platinum (II) complex as claimed in claim 1 for the construction of white light emitting systems.
7. The use of an amphiphilic platinum (II) complex according to claim 6 for the construction of white light emitting systems, characterized in that: taking a mixed solution of dimethyl sulfoxide and water as a solvent, preparing an amphiphilic platinum (II) complex solution with the concentration of 45-55 mu mol/L, heating at 50-60 ℃ for 1-1.5 hours, naturally cooling to room temperature, and standing for 20-30 hours; when the volume concentration of water in the solvent is 30-60%, exciting an amphiphilic platinum (II) complex solution by a light source with the wavelength of 340nm at room temperature, and emitting white light by the system; when the volume concentration of water in the solvent is 20 percent and 70 to 90 percent respectively, the amphiphilic platinum (II) complex solution is excited by a light source with the wavelength of 350nm at room temperature, and the system emits white light.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811406835.1A CN109336932B (en) | 2018-11-23 | 2018-11-23 | Amphiphilic platinum (II) complex, preparation thereof and application thereof in constructing white luminescent system |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811406835.1A CN109336932B (en) | 2018-11-23 | 2018-11-23 | Amphiphilic platinum (II) complex, preparation thereof and application thereof in constructing white luminescent system |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109336932A CN109336932A (en) | 2019-02-15 |
CN109336932B true CN109336932B (en) | 2021-02-02 |
Family
ID=65317593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811406835.1A Expired - Fee Related CN109336932B (en) | 2018-11-23 | 2018-11-23 | Amphiphilic platinum (II) complex, preparation thereof and application thereof in constructing white luminescent system |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109336932B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110981917B (en) * | 2019-12-13 | 2020-10-27 | 中国科学院化学研究所 | Amphiphilic double platinum complex and application thereof in preparation of luminescent nano assembly |
CN112778375B (en) * | 2021-01-08 | 2024-03-01 | 陕西师范大学 | Amphiphilic chiral platinum complex, self-assembled temperature-sensitive single-component luminescent material and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107118761A (en) * | 2017-06-15 | 2017-09-01 | 陕西师范大学 | White luminescent material based on amphipathic platinum complex |
-
2018
- 2018-11-23 CN CN201811406835.1A patent/CN109336932B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107118761A (en) * | 2017-06-15 | 2017-09-01 | 陕西师范大学 | White luminescent material based on amphipathic platinum complex |
Non-Patent Citations (4)
Title |
---|
A metallo-amphiphile with unusual memory behaviour: effect of temperature and structure on the self-assembly of triethylene glycol (TEG)–pendant platinum(II) bzimpy complexe;Charlotte Po等;《Chem. Sci.》;20141231;第5卷;第4868–4872页 * |
Formation of 1D Infinite Chains Directed by Metal-Metal and/or π-π Stacking Interactions of Water-Soluble Platinum(II) 2,6-Bis(benzimidazol-2′-yl)pyridine Double Complex Salts;Victor Chun-Hei Wong等;《J. Am. Chem. Soc.》;20180105;第140卷;第657-666页 * |
基于两亲分子自组装的荧光敏感界面的构筑及其传感应用;雷海瑞;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20180515;B014-77 * |
铂(Ⅱ)配合物超分子组装及其诱导聚集磷光增强;梁建军;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20150315;B014-99 * |
Also Published As
Publication number | Publication date |
---|---|
CN109336932A (en) | 2019-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Gusev et al. | Luminescent properties of Zn complexes based on tetradentate N2O2-donor pyrazolone schiff bases | |
CN109400899B (en) | Lead coordination polymer and preparation method and application thereof | |
CN108780852B (en) | Luminescent compounds | |
CN108690201B (en) | MOF/dye composite high-quantum-yield white light fluorescent powder material and preparation method thereof | |
Shao et al. | Diphenylethyne based β-diketonate europium (III) complexes as red phosphors applied in LED | |
CN108912337B (en) | Rare earth metal organic framework material with high quantum yield and preparation method thereof | |
CN103242298B (en) | 1,2,4-triazole class derivative and its preparation method and application and organic electroluminescence device | |
CN109336932B (en) | Amphiphilic platinum (II) complex, preparation thereof and application thereof in constructing white luminescent system | |
CN101838291A (en) | Preparation and application of platinum complex material with aggregated-state induced phosphorescence emission characteristic | |
CN109824722A (en) | Dinitrogen list phosphine compound and its preparation method and application and cuprous halide complex and its preparation method and application | |
Zhang | Spectroscopic studies on the luminescence properties of ternary europium complexes with different ligands | |
CN103242358B (en) | Siliceous dianthranide derivative and its preparation method and application and organic electroluminescence device | |
CN110862420B (en) | Energy transfer luminescent material based on triplet donor material and acceptor material and application thereof | |
CN110016057A (en) | The four tooth platinum complex phosphor material of quinazoline ditosylate salt and preparation method thereof of sulphur bridge connection | |
JP6048643B2 (en) | Luminescent material | |
CN114437139A (en) | Luminescent material of tetradentate 6/5/6 cyclometalated platinum (II) complex based on azacarbazole-spirofluorene structure and application thereof | |
CN113583056A (en) | 6/5/6 tetradentate cyclometalated platinum or palladium complex luminescent material based on spirofluorene-spirofluorene structure and application thereof | |
CN112174988A (en) | Novel terbium trimerization complex and preparation method thereof | |
JP2020164476A (en) | Blue solid light emitting material, method for producing blue solid light emitting material, and organic light emitting element | |
KR101754977B1 (en) | new platinum complexes with phenanthroline derivative, a preparation method thereof and organic light emitting diode containing the same | |
CN112209968B (en) | Cuprous halide cluster compound of furan diphosphine ligand, synthetic method, application, device, ligand and synthetic method thereof | |
JP7335377B2 (en) | Rare earth metal complex and light emitting device using the same | |
CN113292454B (en) | AIE molecule with cinnamonitrile as framework structure and preparation method and application thereof | |
CN111675709B (en) | Fluorescent material and synthetic method thereof | |
JP7456076B2 (en) | Compound, method for producing compound, and organic light emitting device |
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 | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210202 Termination date: 20211123 |