CN109336932A - Amphipathic platinum (II) complex and its preparation and the application for constructing white luminous system - Google Patents
Amphipathic platinum (II) complex and its preparation and the application for constructing white luminous system Download PDFInfo
- Publication number
- CN109336932A CN109336932A CN201811406835.1A CN201811406835A CN109336932A CN 109336932 A CN109336932 A CN 109336932A CN 201811406835 A CN201811406835 A CN 201811406835A CN 109336932 A CN109336932 A CN 109336932A
- Authority
- CN
- China
- Prior art keywords
- platinum
- amphipathic
- complex
- compound
- formula
- 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.)
- Granted
Links
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- -1 sterol chloro-formate Chemical class 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- IKXNIQJDNKPPCH-UHFFFAOYSA-N hydron;prop-2-yn-1-amine;chloride Chemical group [Cl-].[NH3+]CC#C IKXNIQJDNKPPCH-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229930182558 Sterol Natural products 0.000 claims 1
- 210000000232 gallbladder Anatomy 0.000 claims 1
- 235000003702 sterols Nutrition 0.000 claims 1
- 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 9
- 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
- 235000012000 cholesterol Nutrition 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000007445 Chromatographic isolation Methods 0.000 description 2
- 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011097 chromatography purification Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 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
- 230000003595 spectral effect Effects 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 101100246029 Mus musculus Ptpn2 gene Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 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
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
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 a kind of amphipathic platinum (II) complex and its preparation and the application for constructing white luminous system, the structural formulas of the complex are as follows:The integer that m is 3~5 in formula, n=1 or 2, which is using ether oxygen chain as hydrophilic segment, and using cholesterol as hydrophobic part, with self assembly characteristic, and preparation method is simple, and reaction condition is mild.Amphipathic platinum (II) complex of the present invention emits white light under dimethyl sulfoxide/water mixed solvent of different moisture content, different temperatures, different excitation wavelengths, and the quantum yield of white luminous system reaches as high as 5.8%, is a kind of platinum complex one pack system white luminescent material that luminescent properties are excellent.
Description
Technical field
The invention belongs to the preparation technical fields of luminescent material, and in particular to a kind of amphipathic platinum with self-assembling function
(II) complex and preparation method thereof, and white luminous system is constructed in dimethyl sulfoxide/aqueous solution using the complex.
Background technique
In recent years, white light emitting material is got more and more extensive concerning of people, since it is in display equipment, lighting apparatus
With many potential applications in sensor.Usual this kind of white luminescent material is to utilize two kinds (as blue and orange) or three kinds
(such as red, green and blue) fluorogen is doped, and the ratio by adjusting different component realizes the transmitting of full spectral region
Construct white luminous system.However construct the method for white luminous system using multi-component doped there are still some disadvantages, such as: system
Standby process is complicated, doping ratio is difficult to, synthesis cost height etc..Compared to multicomponent white luminescence system, one pack system white
Luminescence system has many advantages, such as good stability, favorable reproducibility and prepares simple, thus the favor by vast researcher.
Platinum (II) complex with plane coordination structure becomes luminescent material in recent years because of its luminosity abundant
The research hotspot in field, by changing microenvironment locating for platinum (II) complex (such as: solvent composition, counter ion type, pH value)
Pi-pi accumulation effect and PtPt interaction, realize a variety of excitations of platinum complex between adjustable platinum (II) complex molecule
State coexists, and obtains the multiple groups fluorescent emission of visible region, final to obtain one pack system white luminescent material.Although this seminar is
Being successfully prepared the white luminous system of one pack system, (publication No. is the patent of CN 107118761A: based on amphipathic platinum complex
White luminescent material), but the white luminous system quantum yield of one pack system prepared in previous work is lower (1.1%).
Summary of the invention
It is an object of the invention to overcome various ingredients doping to prepare disadvantage present in white luminescent material, one kind is provided
One pack system white luminescent material --- the amphipathic platinum that preparation method is simple, reaction condition is mild, favorable reproducibility, quantum yield are high
(II) preparation method of complex and the complex and the complex construct the application of white luminescent material.
For above-mentioned purpose, the structural formula of amphipathic platinum (II) complex of the present invention is as follows:
The integer that m is 3~5 in formula, n=1 or 2.
The preparation method of above-mentioned amphipathic platinum (II) complex comprises the steps of:
1, syntheticcompoundofformulaⅰ
Under nitrogen protection, it by ynamine hydrochloride salt in triethylamine and dichloromethane solution, is dripped under condition of ice bath
The dichloromethane solution for entering cholesteryl chloroformate continues to be stirred at room temperature 10~15 hours after being added dropwise, isolates and purifies, obtain
Type I compound.
Above-mentioned ynamine hydrochloride is propargylamine hydrochloride, any one in alkynes butylamine hydrochloride.
2, synthesizing amphipathic platinum (II) complex
Under nitrogen protection, II compound of formula is dissolved in triethylamine and dichloromethane solution, I chemical combination of formula is then added
The cuprous iodide of object, catalytic amount, room temperature are protected from light stirring 20~30 hours, isolate and purify, and obtain amphipathic platinum (II) complex.
In above-mentioned steps 1, preferably the molar ratio of cholesteryl chloroformate and ynamine hydrochloride is 1:(2~2.5).
In above-mentioned steps 2, the molar ratio of II compound of preferred formula and type I compound is 1:(2.5~3), cuprous iodide
Additional amount is the 15%~25% of II compound mole of formula, wherein II compound of the formula refers to J.Mater.Chem.C,
The preparation of method disclosed in 2013,1,1130-1136, only need to be by the iodo triethylene glycol monomethyl ether iodo tetraethylene glycol in the document
Monomethyl ether or the replacement of five glycol monomethyl ether of iodo, that is, can be prepared into II compound of formula.
Amphipathic platinum (II) complex of the present invention is in the application for constructing white luminous system, specific construction method are as follows: with two
The mixed liquor of first sulfoxide and water is solvent, compound concentration be 45~55 μm of amphipathic platinum of ol/L (II) complex solutions and 50~
It is heated 1~1.5 hour at 60 DEG C, stands 20~30 hours after cooled to room temperature；When the volumetric concentration of water in solvent is
It is at room temperature the amphipathic platinum of light source activation (II) complex solution of 340nm with wavelength, system emits when 30%~60%
White light；It is at room temperature the light source of 350nm with wavelength when the volumetric concentration of water in solvent is respectively 20% and 70%~90%
Amphipathic platinum (II) complex solution is excited, system emits white light；When the volumetric concentration of water in solvent is 20%, with wavelength
For the amphipathic platinum of light source activation (II) complex solution of 350nm, temperature is controlled within the scope of 40~60 DEG C, system also emits white
Light.
Beneficial effects of the present invention are as follows:
1, amphipathic platinum (II) complex of the invention be using ether oxygen chain as hydrophilic segment, using cholesterol as hydrophobic part,
It is with self assembly characteristic, and preparation method is simple, and reaction condition is mild.
2, amphipathic platinum (II) complex of the present invention is in dimethyl sulfoxide/water mixed solvent of different moisture content, not equality of temperature
Emit white light under degree, under different excitation wavelengths, and the quantum yield of white luminous system reaches as high as 5.8%, luminous efficiency
6 times are improved than previous work, is a kind of platinum complex one pack system white luminescent material that luminescent properties are more excellent, and is expanded
The scope of application of material.
Detailed description of the invention
Fig. 1 is the 50 μm of amphipathic platinum of ol/L (II) complexs room in dimethyl sulfoxide/water mixed solvent of different moisture content
Using 340nm as the fluorescence emission spectrum of excitation wavelength under the conditions of temperature.
Fig. 2 is the 50 μm of amphipathic platinum of ol/L (II) complexs room in dimethyl sulfoxide/water mixed solvent of different moisture content
Using 340nm as the luminescent chromaticity coordinate diagram of excitation wavelength under the conditions of temperature.
Fig. 3 is the 50 μm of amphipathic platinum of ol/L (II) complexs room in dimethyl sulfoxide/water mixed solvent of different moisture content
Using 350nm as the fluorescence emission spectrum of excitation wavelength under the conditions of temperature.
Fig. 4 is the 50 μm of amphipathic platinum of ol/L (II) complexs room in dimethyl sulfoxide/water mixed solvent of different moisture content
Using 350nm as the luminescent chromaticity coordinate diagram of excitation wavelength under the conditions of temperature.
Fig. 5 is the 50 μm of amphipathic platinum of ol/L (II) complexs room in dimethyl sulfoxide/water mixed solvent of different moisture content
Using 340nm as excitation wavelength under the conditions of temperature, the point and line chart of fluorescent emission intensity ratio at 550nm and 390nm.
Fig. 6 is the 50 μm of amphipathic platinum of ol/L (II) complexs room in dimethyl sulfoxide/water mixed solvent of different moisture content
Using 350nm as excitation wavelength under the conditions of temperature, the point and line chart of fluorescent emission intensity ratio at 550nm and 390nm.
Fig. 7 is the 50 μm of amphipathic platinum of ol/L (II) complexs in dimethyl sulfoxide/water mixed solvent that water content is 50%
Using 350nm as excitation wavelength, temperature is the fluorescence emission spectrum of 20~80 DEG C of temperature-rise periods.
Fig. 8 is the 50 μm of amphipathic platinum of ol/L (II) complexs in dimethyl sulfoxide/water mixed solvent that water content is 50%
Using 350nm as excitation wavelength, temperature is the luminescent chromaticity coordinate diagram of 20~80 DEG C of temperature-rise periods.
Fig. 9 is the 50 μm of amphipathic platinum of ol/L (II) complexs in dimethyl sulfoxide/water mixed solvent that water content is 50%
Using 350nm as excitation wavelength, temperature is the fluorescence emission spectrum of 70~20 DEG C of temperature-fall periods.
Figure 10 is the 50 μm of amphipathic platinum of ol/L (II) complexs in dimethyl sulfoxide/water mixed solvent that water content is 50%
Using 350nm as excitation wavelength, temperature is the luminescent chromaticity coordinate diagram of 70~20 DEG C of temperature-fall periods.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited to this
A little embodiments.
Embodiment 1
1, I -1 compound of formula is synthesized
Under nitrogen protection, 369mg (4mmol) propargylamine hydrochloride, 1.3mL tri- are sequentially added into 250mL there-necked flask
Ethamine and 40mL methylene chloride；897mg (2mmol) is sequentially added in constant pressure funnel) cholesteryl chloroformate and 100mL dichloro
Methane is added dropwise in there-necked flask and is stirred under condition of ice bath, is stirred at room temperature after being added dropwise 12 hours.After reaction,
Reaction solution is washed with distilled water three times, merges organic phase, is dried over anhydrous sodium sulfate rear evaporating solvent under reduced pressure, is slightly produced
Object, by gained crude product using the volume ratio of methylene chloride and petroleum ether for 5:1 mixed liquor as mobile phase, silica gel be stationary phase into
Row column chromatographic isolation and purification obtains I -1 compound of formula (white solid 762mg, yield 82%), and reaction equation is as follows:
The structural characterization data of I -1 compound of formula are as follows: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, synthesizing amphipathic platinum (II) complex
Under nitrogen protection, II -1 compound of 277mg (0.29mmol) formula is dissolved in 1.5mL triethylamine and 45mL dichloromethane
In alkane, I -1 compound of 371mg (0.79mmol) formula and 12mg (0.06mmol) cuprous iodide are then sequentially added, condition is protected from light
Under be stirred at room temperature for 24 hours.After reaction, reaction solution successively washed once with 1mol/L HCL aqueous solution, deionized water is washed
Three times, merge organic phase, be dried over anhydrous sodium sulfate rear evaporating solvent under reduced pressure, obtain crude product, by gained crude product with dichloro
The mixed liquor that methane and methanol volume ratio are 15:1 is mobile phase, silica gel is that stationary phase carries out column chromatographic isolation and purification, obtains formula
Amphipathic platinum (II) complex (yellow solid 160mg, yield 40%) shown in III -1, reaction equation is as follows:
The structural characterization data of the amphipathic platinum of gained (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).
Embodiment 2
Amphipathic platinum (II) complex prepared by embodiment 1 is in the application for constructing white luminous system
Using the mixed liquor of the dimethyl sulfoxide of different moisture content and water as solvent, compound concentration is 50 μm of amphipathic platinum of ol/L
(II) complex solution, and heated 1 hour at 50~60 DEG C, 24 hours are stood after cooled to room temperature.
It is at room temperature 340nm's with wavelength when the volumetric concentration of water in solvent is 30%, 40%, 50% and 60%
The amphipathic platinum of light source activation (II) complex solution, system can emit white light, and (fluorescence emission spectrum is shown in Fig. 1, chromaticity coordinate figure
See Fig. 2), when wherein the volumetric concentration of water is 50%, quantum yield highest is 5.8%.
When the volumetric concentration of water in solvent is respectively 20%, 70%, 80% and 90%, it is with wavelength at room temperature
The amphipathic platinum of the light source activation of 350nm (II) complex solution, system can emit white light (fluorescence emission spectrum is shown in Fig. 3)；Its
When the volumetric concentration of middle water is 20%, chromaticity coordinate is (0.30,0.25), and when the volumetric concentration of water is 70%, coloration is sat
It is designated as (0.35,0.34), when the volumetric concentration of water is 80%, chromaticity coordinate is (0.34,0.32)；The volumetric concentration of water is
When 90%, chromaticity coordinate is (0.34,0.34) (chromaticity coordinate figure is shown in Fig. 4).
By the 50 μm of amphipathic platinum of ol/L (II) complex solutions using 340nm as excitation light source under at the 550nm that measures it is glimmering
Light emitting intensity is compared with fluorescent emission intensity at 390nm, and draws I550/I390It is worth the point and line chart with change of moisture content,
As a result see Fig. 5；By the 50 μm of amphipathic platinum of ol/L (II) complex solutions using 350nm as excitation light source under at the 550nm that measures
Fluorescent emission intensity is compared with fluorescent emission intensity at 390nm, and draws I550/I390It is worth the dotted line with change of moisture content
Figure, is as a result shown in Fig. 6.By Fig. 5 and Fig. 6 as it can be seen that with water content increase, I550/I390Value presentation first increases the trend weakened afterwards,
It is consistent with the evolving trend that shines in chromaticity coordinate Fig. 2 and Fig. 4.When water content is 50%, I550/I390Ratio reach maximum.
The 50 μm of amphipathic platinum of ol/L (II) complex solutions are further regulated and controled luminescent material by temperature effect by inventor
Luminescent properties, specific test situation is as follows:
Under the conditions of different temperatures (20,30,40,50,60,70,80 DEG C), using 350nm as excitation light source, use
The mixed liquor of dimethyl sulfoxide and water that the measurement of FLS980 type single photon counting time resolution fluorescence spectral instrument is 50% with water content
For solvent, the luminescent properties of the 50 μm of amphipathic platinum of ol/L (II) complex solutions of preparation, fluorescence emission spectrum is shown in Fig. 7.By Fig. 7
As it can be seen that corresponding fluorescent emission peak intensity increases with temperature and is enhanced at 390nm, corresponding fluorescent emission at 550nm and 595nm
Peak intensity increases with temperature and is weakened, and amphipathic platinum (II) complex fluorescent evolves as white light (chromaticity coordinate figure by yellow light
See Fig. 8).When temperature range is 40~60 DEG C, using 350nm as excitation light source, system can emit white light.By the solution with
Temperature interval is 10 DEG C and cools down that, using 350nm as excitation light source, fluorescence emission spectrum is shown in Fig. 9.As seen from Figure 9,390nm
Locating corresponding fluorescent emission peak intensity reduces with temperature and is weakened, and corresponding fluorescent emission peak intensity is with temperature at 550nm and 595nm
Degree reduces and enhances, and amphipathic platinum (II) complex fluorescent is gradually converted into yellow light (chromaticity coordinate figure is shown in Figure 10) by white light, when
When temperature range is 40~60 DEG C, using 350nm as excitation light source, system can emit white light.
Claims (7)
1. a kind of amphipathic platinum (II) complex, it is characterised in that the structural formula of the complex is as follows:
The integer that m is 3~5 in formula, n=1 or 2.
2. a kind of preparation method of amphipathic platinum (II) complex described in claim 1, it is characterised in that it is by following steps
Composition:
(1) syntheticcompoundofformulaⅰ
Under nitrogen protection, by ynamine hydrochloride salt in triethylamine and dichloromethane solution, gallbladder is instilled under condition of ice bath
The dichloromethane solution of sterol chloro-formate continues to be stirred at room temperature 10~15 hours after being added dropwise, isolates and purifies, obtain formula I
Compound；
Above-mentioned ynamine hydrochloride is propargylamine hydrochloride or alkynes butylamine hydrochloride；
(2) synthesizing amphipathic platinum (II) complex
Under nitrogen protection, II compound of formula is dissolved in triethylamine and dichloromethane solution, type I compound is then added, urges
The cuprous iodide of change amount, room temperature are protected from light stirring 20~30 hours, isolate and purify, and obtain amphipathic platinum (II) complex；
The value of n is 1 or 2 in above-mentioned type I compound, and the value of m is 3~5 integers in II compound of formula.
3. the preparation method of amphipathic platinum (II) complex according to claim 2, it is characterised in that: in step (1),
The molar ratio of the cholesteryl chloroformate and ynamine hydrochloride is 1:(2~2.5).
4. the preparation method of amphipathic platinum (II) complex according to claim 2, it is characterised in that: in step (2),
The molar ratio of II compound of formula and type I compound is 1:(2.5~3).
5. the preparation method of amphipathic platinum (II) complex according to claim 2, it is characterised in that: in step (2),
The additional amount of the cuprous iodide is the 15%~25% of II compound mole of formula.
6. amphipathic platinum (II) complex described in claim 1 is in the application for constructing white luminous system.
7. amphipathic platinum (II) complex according to claim 6 is in the application for constructing white luminous system, feature exists
In: using the mixed liquor of dimethyl sulfoxide and water as solvent, compound concentration is 45~55 μm of amphipathic platinum of ol/L (II) complex solutions
And heated 1~1.5 hour at 50~60 DEG C, 20~30 hours are stood after cooled to room temperature；When the volume of water in solvent
It is at room temperature the amphipathic platinum of light source activation (II) complex solution of 340nm, system with wavelength when concentration is 30%~60%
Emit white light；It is at room temperature 350nm with wavelength when the volumetric concentration of water in solvent is respectively 20% and 70%~90%
The amphipathic platinum of light source activation (II) complex solution, system emits white light；When the volumetric concentration of water in solvent is 20%,
It is the amphipathic platinum of light source activation (II) complex solution of 350nm with wavelength, controls temperature within the scope of 40~60 DEG C, system
Emit 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 true CN109336932A (en) | 2019-02-15 |
| CN109336932B 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981917A (en) * | 2019-12-13 | 2020-04-10 | 中国科学院化学研究所 | Amphiphilic double platinum complex and application thereof in preparation of luminescent nano assembly |
| CN112778375A (en) * | 2021-01-08 | 2021-05-11 | 陕西师范大学 | Amphiphilic chiral platinum complex, self-assembled temperature-sensitive single-component luminescent material thereof and application |
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 |
|---|
| CHARLOTTE PO等: "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", 《CHEM. SCI.》 * |
| VICTOR CHUN-HEI WONG等: "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", 《J. AM. CHEM. SOC.》 * |
| 梁建军: "铂（Ⅱ）配合物超分子组装及其诱导聚集磷光增强", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
| 雷海瑞: "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", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981917A (en) * | 2019-12-13 | 2020-04-10 | 中国科学院化学研究所 | Amphiphilic double platinum complex and application thereof in preparation of luminescent nano assembly |
| 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 |
| CN112778375A (en) * | 2021-01-08 | 2021-05-11 | 陕西师范大学 | Amphiphilic chiral platinum complex, self-assembled temperature-sensitive single-component luminescent material thereof and application |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109336932B (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107383094B (en) | A kind of novel chiral gathering induced luminescence material and its preparation method and application | |
| Huo et al. | Novel phosphorescent tetradentate bis-cyclometalated C^ C∗ N^ N-coordinated platinum complexes: Structure, photophysics, and a synthetic adventure | |
| CN103242298B (en) | 1,2,4-triazole class derivative and its preparation method and application and organic electroluminescence device | |
| CN109336932A (en) | Amphipathic platinum (II) complex and its preparation and the application for constructing white luminous system | |
| JP6643804B2 (en) | Rare earth metal complex and light emitting device using the same | |
| CN105542751B (en) | A kind of metal-organic framework material for launching white light and its synthetic method and application | |
| CN101838291A (en) | Preparation and application of platinum complex material with aggregated-state induced phosphorescence emission characteristic | |
| Cañada et al. | Blue-phosphorescent bis-cyclometalated iridium complexes with aryl isocyanide ancillary ligands | |
| CN101085915A (en) | Divinyl double-dipole red organic electroluminescence material and preparation method thereof | |
| CN111729610A (en) | Tetraphenyl vinyl alkyl ammonium bromide salt surfactant and preparation and application thereof | |
| CN107033175B (en) | The connected fluorine boron fluorescent dye oligomer and its preparation method and application of diacetylene | |
| JP6048643B2 (en) | Luminescent material | |
| CN110437133A (en) | A kind of long-life room temperature phosphorimetry material and its preparation method and application | |
| 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 | |
| US20050194885A1 (en) | Red emission organic phosphor with broad excitation band | |
| CN113501817A (en) | Quinolinone derivative containing arylamine group and preparation and application thereof | |
| JP2020164476A (en) | Blue solid light emitting material, method for producing blue solid light emitting material, and organic light emitting element | |
| CN113201022A (en) | Small conjugated phosphorescent metal iridium (III) complex with isomer and preparation method and application thereof | |
| JP7335377B2 (en) | Rare earth metal complex and light emitting device using the same | |
| Cheon et al. | Chemiluminescent properties of blue fluorophores containing naphthalene unit | |
| JP7456076B2 (en) | Compound, method for producing compound, and organic light emitting device | |
| JP2019031446A (en) | Rare earth metal complex and light-emitting device using the same | |
| KR101754977B1 (en) | new platinum complexes with phenanthroline derivative, a preparation method thereof and organic light emitting diode containing the same | |
| CN105176517B (en) | A kind of optical oxygen sensing composite material without heavy metal element and preparation method thereof |
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 |