CN102952079A - Novel imidazolium salt ionic liquid and related luminescent material thereof - Google Patents
Novel imidazolium salt ionic liquid and related luminescent material thereof Download PDFInfo
- Publication number
- CN102952079A CN102952079A CN2012104914991A CN201210491499A CN102952079A CN 102952079 A CN102952079 A CN 102952079A CN 2012104914991 A CN2012104914991 A CN 2012104914991A CN 201210491499 A CN201210491499 A CN 201210491499A CN 102952079 A CN102952079 A CN 102952079A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- rare earth
- imidazole salts
- imidazole
- rare
- 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
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title abstract description 26
- 150000004693 imidazolium salts Chemical class 0.000 title abstract 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 138
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 116
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002460 imidazoles Chemical class 0.000 claims description 129
- 229910052693 Europium Inorganic materials 0.000 claims description 64
- -1 imidazole salt ion Chemical class 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000002360 preparation method Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 238000013329 compounding Methods 0.000 claims description 19
- 238000010025 steaming Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 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 10
- 229910052771 Terbium Inorganic materials 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 8
- 229910052691 Erbium Inorganic materials 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 229910052689 Holmium Inorganic materials 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 229910052775 Thulium Inorganic materials 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 8
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 6
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 6
- KIBNCPNBBQWFQK-UHFFFAOYSA-N dodecane;1h-imidazole Chemical class C1=CNC=N1.CCCCCCCCCCCC KIBNCPNBBQWFQK-UHFFFAOYSA-N 0.000 claims description 4
- LHZVWIMFLHJNEO-UHFFFAOYSA-N hexadecane 1H-imidazole Chemical class N1C=NC=C1.CCCCCCCCCCCCCCCC LHZVWIMFLHJNEO-UHFFFAOYSA-N 0.000 claims description 4
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 claims description 3
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- 229910020808 NaBF Inorganic materials 0.000 claims description 3
- SROPKFOGVUYJCW-UHFFFAOYSA-N [Li].[SH2]=N.C(F)(F)F Chemical compound [Li].[SH2]=N.C(F)(F)F SROPKFOGVUYJCW-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 56
- 238000005660 chlorination reaction Methods 0.000 description 50
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 39
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 28
- 238000000695 excitation spectrum Methods 0.000 description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 10
- 238000012544 monitoring process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 8
- 239000012312 sodium hydride Substances 0.000 description 8
- 229910000104 sodium hydride Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 4
- 238000003809 water extraction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- 0 C*1c[n](Cc(cc2)ccc2C(O)=O)cc1 Chemical compound C*1c[n](Cc(cc2)ccc2C(O)=O)cc1 0.000 description 1
- 244000124209 Crocus sativus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012742 biochemical analysis Methods 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001857 fluorescence decay curve Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- ACCBVLDMNMOXDN-UHFFFAOYSA-N heptane;hydrobromide Chemical compound Br.CCCCCCC ACCBVLDMNMOXDN-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Landscapes
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses novel imidazolium salt ionic liquid and a related luminescent material thereof. The ionic liquid has a structural formula which is shown in the specification, wherein X is Br, [BF4], [PF6] or [Tf2N]; and n is equal to 0-15. The imidazolium salt ionic liquid and rare earth ion can extremely easily produce coordination and have excellent luminescent performance. An obtained rare earth/imidazolium salt complex has the advantages of rich luminescence, high color purity, long fluorescence lifetime and good water solubility, and meanwhile, a rare earth/imidazolium salt ionic gel material has high plasticity and thermal reversibility, can also realize transition dimming from red light to green light, is an optical material with great value and can be applied to the fields such as display and development, new light sources and X-ray intensifying screens.
Description
Technical field
The invention belongs to the Rare Earth Functional Materials field, be specially the preparation method of a kind of novel imidazole salt ion liquid and relevant luminescent material thereof.
Background technology
Rare earth ion is because unique 4f layer electronic configuration, thereby have an excellent luminescent properties (high such as purity of color, fluorescence lifetime is long, the spectral line of emission is abundant etc.), in demonstration, optical waveguides amplification, solid statelaser, medical science, biomarker, the field such as false proof potential using value is arranged.Non-volatile, the characteristics such as the liquid journey is wide, high conductivity, thermostability is high and can regulate that ionic liquid has, thereby be regarded as the most rising solvent in Green Chemistry and the cleaning procedure.Thereby advantage and the rare earth ion special characteristics of luminescence of ionic liquid in luminous field combined, have wide Research Prospects.
This imidazole salt ionic liquid is that non-ionic liquid at room temperature is solid near room temperature namely, and the ionic liquid of functionalization is easy to carry out coordination with unoccupied orbital because it has lone-pair electron.
Summary of the invention
The objective of the invention is: a kind of novel imidazole salt ion liquid is provided, and by control reaction conditions such as pH, solvent etc., synthesizes imidazole salts ionic liquid/rare earth compounding and imidazole salts ionic liquid/rare earth gel.
The technical scheme that technical solution problem of the present invention adopts:
A kind of novel imidazole salt ion liquid, the structural formula of this ionic liquid is:
Wherein X is Br, [BF
4], [PF
6] or [Tf
2N]; N=0～15.
The preparation method of above-mentioned imidazole salts is one of following any two kinds of methods:
Method one may further comprise the steps:
The bromine para Toluic Acid is joined in the ethanol, dissolve complete gradually under 80 ℃ of stirrings, then add equimolar substance A, under 80 ℃ of stirrings, react 17h, revolve the steaming desolventizing, then add and the isopyknic ether of ethanol, constantly stir, until white precipitate occurs, then wash with ether, revolve the steaming desolventizing, put into baking oven; Make the imidazole salts that X is Br;
Wherein substance A is Methylimidazole, butyl imidazole or long-chain imidazoles.
Perhaps, method two may further comprise the steps:
1) preparation X is the imidazole salts of Br, and step is with top method one;
2) X that the upper step was obtained is that (water among the present invention in the mixed solution and ethanol are any proportioning in the fully water-soluble and alcohol mixeding liquid of the imidazole salts of Br, as long as and the mixed solution aequum can dissolve imidazole salts in the dissolving), add substance B, stirring at room back flow reaction 24 hours, centrifugal, get [PF three times with the distilled water washing precipitation
6]
-, [BF
4]
-Or [Tf
2N]
-Imidazole salts for negatively charged ion; Its mole proportioning is substance B: imidazole salts when substituent X is Br=1 ~ 2:1;
Wherein substance B is NaBF
4(sodium tetrafluoroborate), KPF
6(Potassium Hexafluorophosphate) or C
2F
6LiNO
4S
2(two fluoroform sulfimide lithium).
Described long-chain imidazoles is specially seven alkane imidazoles, eight alkane imidazoles, dodecane imidazoles or n-Hexadecane imidazoles.
A kind of imidazole salts ionic liquid/rare earth compounding, its structural formula is
Wherein X is Br, [BF
4], [PF
6] or [Tf
2N]; N=0～15, m=1 ~ 3;
Rare earth ion Ln wherein is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er or Tm;
The preparation method of described imidazole salts ionic liquid/rare earth compounding may further comprise the steps:
The proportioning of ionic liquid: rare earth chloride=3:1 in molar ratio, ionic liquid is dissolved in ethanol after, add again rare earth chloride, then the NaOH with 1mol/L regulates pH to 7-8, stirs, and is centrifugal, precipitation washing with alcohol 3 times make imidazole salts ionic liquid/rare earth compounding.
A kind of imidazole salts ionic liquid/rare earth gel, its structural formula is
Wherein X is Br, [BF
4], [PF
6] or [Tf
2N]; N=0～15;
Rare earth ion Ln wherein is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er or Tm;
The preparation method of described imidazole salts ionic liquid/rare earth gel may further comprise the steps:
The proportioning of ionic liquid: rare earth chloride=3:1 in molar ratio, ionic liquid is dissolved in ethanol after, add again rare earth chloride, then churning time is 5 hours, revolves the steaming desolventizing after the reaction, puts into baking oven, gets imidazole salts ionic liquid/rare earth gel.
Wherein said rare earth chloride is NdCl
3, SmCl
3, EuCl
3, GdCl
3, TbCl
3, DyCl
3, HoCl
3, ErCl
3Or TmCl
3
The invention has the beneficial effects as follows:
1) this imidazole salts ionic liquid and rare earth ion very easily produce coordination, and good luminescent properties is arranged.Can well see the characteristic peak of rare earth ion in the spectrogram in emission, illustrate that rare earth ion and imidazole salts carried out coordination, make rare earth ion find new part to make it luminous.
2) above gained imidazole salts ionic liquid/rare earth compounding is luminous abundant, purity of color is high, fluorescence lifetime is long, good water solubility, imidazole salts ionic liquid/rare earth gel plasticity-is high simultaneously, and heat is reversible, also can realize the excessive light modulation from ruddiness to the green glow, be a kind of of great value optical material, can be applied in fields such as showing video picture, new light sources, X ray intensifying screen.
Description of drawings
Fig. 1 is the exciting light spectrogram of the luminescent material among the embodiment 1;
Fig. 2 is the utilizing emitted light spectrogram of the luminescent material among the embodiment 1;
Fig. 3 is the life-span spectrogram of the luminescent material among the embodiment 1;
Fig. 4 is the exciting light spectrogram of the luminescent material among the embodiment 2;
Fig. 5 is the utilizing emitted light spectrogram of the luminescent material among the embodiment 2;
Fig. 6 is the life-span spectrogram of the luminescent material among the embodiment 2;
Fig. 7 is the exciting light spectrogram of the luminescent material among the embodiment 3;
Fig. 8 is the utilizing emitted light spectrogram of the luminescent material among the embodiment 3;
Fig. 9 is the life-span spectrogram of the luminescent material among the embodiment 3;
Embodiment
For clearer explanation the present invention, enumerate following examples, but its to scope of invention without any restriction.
Embodiment 1
(1) 2.171g 4-bromine para Toluic Acid (commercially available) is dissolved in the 30mL ethanol, dissolve complete gradually under 80 ℃ of stirrings, then add 0.829g Methylimidazole (commercially available), under 80 ℃ of stirrings, react 17h, revolve the steaming desolventizing, then add the 30mL ether, constantly stir, until white precipitate appears, then with ether washing 5 times, revolve the steaming desolventizing, it is for subsequent use to put into 80 ℃ of baking ovens.The imidazole salts ionic liquid that reaction makes is designated as C
1IL-BA (wherein, X=Br, n=0 molecular weight=297.14).
(2) ionic liquid in molar ratio: rare-earth chlorination europium=3:1 proportioning, after the 1.2mmol ionic liquid is dissolved in alcohol solvent, again 0.4mmol rare-earth chlorination europium is added in the reactor, stir lower reaction 8 hours, revolve steaming, desolventizing obtains such as the described light yellow imidazole salts ionic liquid of front structure formula/rare earth gel.(wherein, X=Br, Ln are Eu, n=0)
By nmr analysis and mass spectrum imidazole salts is measured, utilize absorption spectrometer and fluorescence spectrophotometer to the luminescent properties of this material (such as absorption spectrum, emmission spectrum, excitation spectrum, fluorescence decay curve etc.) measure, utilize thermal weight loss, differential heat scan calorimetry is measured thermostability.
Test to such an extent that the nuclear-magnetism of imidazole salts ionic liquid is as follows:
1H?NMR(400MHz,DMSO)δ
H=11.0(s,1H),8.92(s,1H),8.09(d,2H),7.75(d,1H),7.64(d,1H),7.44(d,2H),5.96(s,2H),3.72(s,3H)
Test to such an extent that the physical and chemical parameter of gained imidazole salts ionic liquid/rare earth gel is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 261nm): 612nm, 579nm, 592nm, 650nm, 700nm
Fig. 1,2,3 are respectively exciting among the embodiment 1, emission, life-span spectrogram; The data that shown this imidazole salts ionic liquid/rare earth gel.In emission figure, can well see the characteristic peak of europium, illustrate that europium and imidazole salts carried out coordination, make europium ion luminous.612nm main peak area accounts for 65.10% of total peak area simultaneously, and purity of color is high.This gel has thermal reversibility simultaneously, does not flow when 25 ℃ of room temperatures, can flow when being heated to 50 ℃, is cooled to room temperature and returns to again stagnant condition.
With after obtaining the 1.2mmol ionic liquid in embodiment 1 step (2) and being dissolved in alcohol solvent, after adding 0.4mmol rare-earth chlorination europium in the reactor again, NaOH with 1mol/L regulates pH to 7-8 again, stir lower reaction 8 hours, centrifugation, then use washing with alcohol 3 times, make at last imidazole salts ionic liquid/rare earth compounding.(wherein, X=Br, Ln are Eu, n=0, m=3)
Test to such an extent that the physical and chemical parameter of this material is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 285nm): 612nm, 579nm, 592nm, 650nm, 700nm
Fig. 4,5,6 are respectively exciting among the embodiment 2, emission, life-span spectrogram; The data that shown this imidazole salts ionic liquid/rare earth compounding.In emission figure, can well see the characteristic peak of europium, illustrate that europium and imidazole salts carried out coordination, make europium ion luminous.612nm main peak area accounts for 75.33% of total peak area simultaneously, and purity of color is high.Fluorescence lifetime is 0.58ms.
Embodiment 3
Just the alcohol solvent in embodiment 1 step (2) changes methanol solvate into, and all the other conditions make imidazole salts ionic liquid/rare earth gel at last with embodiment 1.(wherein, X=Br, Ln are Eu, n=0)
Test to such an extent that the physical and chemical parameter of this material is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 285nm): 612nm, 579nm, 592nm, 650nm, 700nm
Fig. 7,8,9 are respectively exciting among the embodiment 3, emission, life-span spectrogram; The data that shown this imidazole salts ionic liquid/rare earth gel.In emission figure, can well see the characteristic peak of europium, illustrate that europium and imidazole salts carried out coordination, make europium ion luminous.612nm main peak area accounts for 67.09% of total peak area simultaneously, and purity of color is high.This gel has thermal reversibility simultaneously, does not flow when 25 ℃ of room temperatures, can flow when being heated to 50 ℃, is cooled to room temperature and returns to again stagnant condition.
Change the alcohol solvent in embodiment 1 step (2) into the DMF solvent, all the other conditions make imidazole salts ionic liquid/rare earth gel at last with embodiment 1.(wherein, X=Br, Ln are Eu, n=0)
Test to such an extent that the physical and chemical parameter of this material is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 285nm): 612nm, 579nm, 592nm, 650nm, 700nm
Embodiment 5
Change the Methylimidazole in embodiment 1 step (1) into butyl imidazole (commercially available), the imidazole salts ionic liquid is designated as C
4IL-BA (X=B r, n=3, molecular weight=339.14).All the other conditions make imidazole salts ionic liquid/rare earth gel at last with embodiment 1.(wherein, X=Br, Ln are Eu, n=3)
Test to such an extent that the nuclear-magnetism of this imidazole salts is as follows:
1H?NMR(400MHz,DMSO)δ
H=11.0(s,1H),8.92(s,1H),8.09(d,2H),7.75(d,1H),7.64(d,1H),7.44(d,2H),5.96(s,2H),4.04(t,2H),1.74(m,2H),1.31(m,2H),0.90(t,3H).
Test to such an extent that the physical and chemical parameter of this material is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 261nm): 612nm, 579nm, 592nm, 650nm, 700nm
The 10mmol imidazoles is dissolved in the 8mL tetrahydrofuran (THF), the 15mmol sodium hydride is dissolved in the 4mL tetrahydrofuran (THF), imidazoles solution is added dropwise in the tetrahydrofuran solution of sodium hydride, produces a large amount of bubbles, dripped stirring at room 1 hour, tetrabutylammonium iodide 0.3mmol is added system, and vacuum nitrogen filling gas was dissolved in the 6mL tetrahydrofuran (THF) adding system stirring at room to heptane bromide 10mmol 18 hours, filter, filtrate is revolved steaming, with ether and water extraction, make seven alkane imidazoles.
Change the Methylimidazole in embodiment 1 step (1) into seven alkane imidazoles, the imidazole salts ionic liquid is designated as C
7IL-BA (X=Br, n=6, molecular weight=381.14).All the other conditions make imidazole salts ionic liquid/rare earth gel at last with embodiment 1.(wherein, X=Br, Ln are Eu, n=6)
Test to such an extent that the nuclear-magnetism of this imidazole salts is as follows:
1H?NMR(400MHz,DMSO)δ
H=11.0(s,1H),8.92(s,1H),8.09(d,2H),7.75(d,1H),7.64(d,1H),7.44(d,2H),5.96(s,2H),4.04(t,2H),1.74(m,2H),1.31(m,2H),1.29(m,6H),0.88(t,3H).
Test to such an extent that the physical and chemical parameter of this material is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 261nm): 612nm, 579nm, 592nm, 650nm, 700nm
Embodiment 7
The 10mmol imidazoles is dissolved in the 8mL tetrahydrofuran (THF), the 15mmol sodium hydride is dissolved in the 4mL tetrahydrofuran (THF), imidazoles solution is added dropwise in the tetrahydrofuran solution of sodium hydride, produces a large amount of bubbles, dripped stirring at room 1 hour, tetrabutylammonium iodide 0.3mmol is added system, and vacuum nitrogen filling gas was dissolved in the 6mL tetrahydrofuran (THF) adding system stirring at room to bromooctane 10mmol 18 hours, filter, filtrate is revolved steaming, with ether and water extraction, make eight alkane imidazoles.
Change the Methylimidazole in embodiment 1 step (1) into eight alkane imidazoles, the imidazole salts ionic liquid is designated as C
8IL-BA (X=Br, n=7, molecular weight=395.14).All the other conditions make imidazole salts ionic liquid/rare earth gel at last with embodiment 1.(wherein, X=Br, Ln are Eu, n=7)
Test to such an extent that the nuclear-magnetism of this imidazole salts is as follows:
1H?NMR(400MHz,DMSO)δ
H=11.0(s,1H),8.92(s,1H),8.09(d,2H),7.75(d,1H),7.64(d,1H),7.44(d,2H),5.96(s,2H),4.04(t,2H),1.74(m,2H),1.31(m,2H),1.29(m,8H),0.88(t,3H)
Test to such an extent that the physical and chemical parameter of this material is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 261nm): 612nm, 579nm, 592nm, 650nm, 700nm
The 10mmol imidazoles is dissolved in the 8mL tetrahydrofuran (THF), the 15mmol sodium hydride is dissolved in the 4mL tetrahydrofuran (THF), imidazoles solution is added dropwise in the tetrahydrofuran solution of sodium hydride, produces a large amount of bubbles, dripped stirring at room 1 hour, tetrabutylammonium iodide 0.3mmol is added system, and vacuum nitrogen filling gas was dissolved in the 6mL tetrahydrofuran (THF) adding system stirring at room to bromododecane 10mmol 18 hours, filter, filtrate is revolved steaming, with ether and water extraction, make the dodecane imidazoles.
Change the Methylimidazole in embodiment 1 step (1) into the dodecane imidazoles, the imidazole salts ionic liquid is designated as C
12IL-BA (X=Br, n=11, molecular weight=465.14).All the other conditions make imidazole salts ionic liquid/rare earth gel at last with embodiment 1.(wherein, X=Br, Ln are Eu, n=11)
Test to such an extent that the nuclear-magnetism of this imidazole salts is as follows:
1H?NMR(400MHz,DMSO)δ
H=11.0(s,1H),8.92(s,1H),8.09(d,2H),7.75(d,1H),7.64(d,1H),7.44(d,2H),5.96(s,2H),4.04(t,2H),1.74(m,2H),1.31(m,2H),1.29(m,10H),1.26(m,6H),0.88(t,3H)
Test to such an extent that the physical and chemical parameter of this material is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 261nm): 612nm, 579nm, 592nm, 650nm, 700nm
Embodiment 9
The 10mmol imidazoles is dissolved in the 8mL tetrahydrofuran (THF), the 15mmol sodium hydride is dissolved in the 4mL tetrahydrofuran (THF), imidazoles solution is added dropwise in the tetrahydrofuran solution of sodium hydride, produces a large amount of bubbles, dripped stirring at room 1 hour, tetrabutylammonium iodide 0.3mmol is added system, and vacuum nitrogen filling gas was dissolved in the 6mL tetrahydrofuran (THF) adding system stirring at room to bromohexadecane 10mmol 18 hours, filter, filtrate is revolved steaming, with ether and water extraction, make the n-Hexadecane imidazoles.
Change the Methylimidazole in embodiment 1 step (1) into the n-Hexadecane imidazoles, the imidazole salts ionic liquid is designated as C
12IL-BA (X=Br, n=15, molecular weight=465.14).All the other conditions make imidazole salts ionic liquid/rare earth gel at last with embodiment 1.(wherein, X=Br, Ln are Eu, n=15)
Test to such an extent that the nuclear-magnetism of this imidazole salts is as follows:
1H?NMR(400MHz,DMSO)δ
H=11.0(s,1H),8.92(s,1H),8.09(d,2H),7.75(d,1H),7.64(d,1H),7.44(d,2H),5.96(s,2H),4.04(t,2H),1.74(m,2H),1.31(m,2H),1.29(m,10H),1.26(m,14H),0.88(t,3H)
Test to such an extent that the physical and chemical parameter of this material is as follows:
Excitation spectrum (monitoring wavelength: 612nm): 200 ~ 480nm
Emmission spectrum (excitation spectrum: 261nm): 612nm, 579nm, 592nm, 650nm, 700nm
Change the rare-earth chlorination europium in embodiment 1 step (2) into the rare-earth chlorination neodymium, preparation imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Nd, n=0)
Embodiment 11
Change the rare-earth chlorination europium in embodiment 1 step (2) into the rare-earth chlorination samarium, preparation imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Sm, n=0)
Embodiment 12
Change the rare-earth chlorination europium in embodiment 1 step (2) into the rare-earth chlorination gadolinium, preparation imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Gd, n=0)
Embodiment 13
Change the rare-earth chlorination europium in embodiment 1 step (2) into the rare-earth chlorination holmium, preparation imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Ho, n=0)
Embodiment 14
Change the rare-earth chlorination europium in embodiment 1 step (2) into the rare-earth chlorination erbium, preparation imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Er, n=0)
Embodiment 15
Change the rare-earth chlorination europium in embodiment 1 step (2) into the rare-earth chlorination dysprosium, preparation imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Dy, n=0)
Embodiment 16
Change the rare-earth chlorination europium in embodiment 1 step (2) into the rare-earth chlorination thulium, preparation imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Tm, n=0)
Embodiment 17
Change the rare-earth chlorination europium in embodiment 1 step (2) into the rare-earth chlorination terbium, preparation imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Tb, n=0)
Embodiment 18
Change the rare-earth chlorination europium in embodiment 2 steps (2) into the rare-earth chlorination neodymium, preparation imidazole salts ionic liquid/rare earth compounding.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Nd, n=0, m=3)
Embodiment 19
Change the rare-earth chlorination europium in embodiment 2 steps (2) into the rare-earth chlorination samarium, preparation imidazole salts ionic liquid/rare earth compounding.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Sm, n=0, m=3)
Embodiment 20
Change the rare-earth chlorination europium in embodiment 2 steps (2) into the rare-earth chlorination gadolinium, preparation imidazole salts ionic liquid/rare earth compounding.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Gd, n=0, m=3)
Embodiment 21
Change the rare-earth chlorination europium in embodiment 2 steps (2) into the rare-earth chlorination holmium, preparation imidazole salts ionic liquid/rare earth compounding.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Ho, n=0, m=3)
Embodiment 22
Change the rare-earth chlorination europium in embodiment 2 steps (2) into the rare-earth chlorination erbium, preparation imidazole salts ionic liquid/rare earth compounding.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Er, n=0, m=3)
Embodiment 23
Change the rare-earth chlorination europium in embodiment 2 steps (2) into the rare-earth chlorination dysprosium, preparation imidazole salts ionic liquid/rare earth compounding.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Dy, n=0, m=3)
Embodiment 24
Change the rare-earth chlorination europium in embodiment 2 steps (2) into the rare-earth chlorination thulium, preparation imidazole salts ionic liquid/rare earth compounding.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Tm, n=0, m=3)
Embodiment 25
Change the rare-earth chlorination europium in embodiment 2 steps (2) into the rare-earth chlorination terbium, preparation imidazole salts ionic liquid/rare earth compounding.All the other conditions are with embodiment 1.Wherein, X=Br, Ln are Tb, n=0, m=3)
Embodiment 26
Step (1) prepares C with embodiment 1 step (1)
1IL-BA.
(2) according to mol ratio imidazole salts: KPF
6(Potassium Hexafluorophosphate)=1:1, with above-mentioned imidazole salts in the fully water-soluble and alcohol mixeding liquid (water among the present invention in the mixed solution and ethanol are any proportioning, as long as and the mixed solution aequum can be with the imidazole salts dissolving in the dissolving), adding KPF
6, centrifugal stirring at room back flow reaction 24 hours, with distilled water washing precipitation three times [PF
6]
-Imidazole salts for negatively charged ion.
(3) imidazole salts in molar ratio: rare-earth chlorination europium=3:1 proportioning, the 0.1mmol imidazole salts is dissolved in the ethanol, then 0.033mmol rare-earth chlorination europium is added in the reactor, stirred 8 hours, revolve the steaming desolventizing, make imidazole salts ionic liquid/rare earth gel.Wherein, X=PF
6, Ln is Eu, n=0)
Embodiment 27
Step (1) prepares C with embodiment 5 steps (1)
4IL-BA.
(2) according to mol ratio imidazole salts: KPF
6(Potassium Hexafluorophosphate)=1:1 in the fully water-soluble and alcohol mixeding liquid, adds KPF with above-mentioned imidazole salts
6, centrifugal stirring at room back flow reaction 24 hours, with distilled water washing precipitation three times [PF
6]
-Imidazole salts for negatively charged ion.
(3) imidazole salts in molar ratio: rare-earth chlorination europium=3:1 proportioning, 0.1mmol imidazole salts and rare-earth chlorination europium are added in the reactor, stirred 8 hours, revolve the steaming desolventizing, make imidazole salts ionic liquid/rare earth gel.Wherein, X=PF
6, Ln is Eu, n=3)
Embodiment 28
Step (1) prepares C with embodiment 6 steps
7IL-BA.
(2) according to mol ratio imidazole salts: KPF
6(Potassium Hexafluorophosphate)=1:1 in the fully water-soluble and alcohol mixeding liquid, adds KPF with above-mentioned imidazole salts
6, centrifugal stirring at room back flow reaction 24 hours, with distilled water washing precipitation three times [PF
6]
-Imidazole salts for negatively charged ion.
(3) imidazole salts in molar ratio: rare-earth chlorination europium=3:1 proportioning, 0.1mmol imidazole salts and rare-earth chlorination europium are added in the reactor, stirred 8 hours, revolve the steaming desolventizing, make imidazole salts ionic liquid/rare earth gel.Wherein, X=PF
6, Ln is Eu, n=6)
Embodiment 29
Step (1) prepares C with embodiment 7 steps
8IL-BA.
(2) according to mol ratio imidazole salts: KPF
6(Potassium Hexafluorophosphate)=1:1 in the fully water-soluble and alcohol mixeding liquid, adds KPF with above-mentioned imidazole salts
6, centrifugal stirring at room back flow reaction 24 hours, with distilled water washing precipitation three times [PF
6]
-Imidazole salts for negatively charged ion.
(3) imidazole salts in molar ratio: rare-earth chlorination europium=3:1 proportioning, 0.1mmol imidazole salts and rare-earth chlorination europium are added in the reactor, stirred 8 hours, revolve the steaming desolventizing, make imidazole salts ionic liquid/rare earth gel.Wherein, X=PF
6, Ln is Eu, n=7)
Embodiment 30
Step (1) prepares C with embodiment 8 steps
12IL-BA.
(2) according to mol ratio imidazole salts: KPF
6(Potassium Hexafluorophosphate)=1:1 in the fully water-soluble and alcohol mixeding liquid, adds KPF with above-mentioned imidazole salts
6, centrifugal stirring at room back flow reaction 24 hours, with distilled water washing precipitation three times [PF
6]
-Imidazole salts for negatively charged ion.
(3) imidazole salts in molar ratio: rare-earth chlorination europium=3:1 proportioning, 0.1mmol imidazole salts and rare-earth chlorination europium are added in the reactor, stirred 8 hours, revolve the steaming desolventizing, make imidazole salts ionic liquid/rare earth gel.Wherein, X=PF
6, Ln is Eu, n=11)
Embodiment 31
Step (1) prepares C with embodiment 9 steps
16IL-BA.
(2) according to mol ratio imidazole salts: KPF
6(Potassium Hexafluorophosphate)=1:1 in the fully water-soluble and alcohol mixeding liquid, adds KPF with above-mentioned imidazole salts
6, centrifugal stirring at room back flow reaction 24 hours, with distilled water washing precipitation three times [PF
6]
-Imidazole salts for negatively charged ion.
(3) imidazole salts in molar ratio: rare-earth chlorination europium=3:1 proportioning, 0.1mmol imidazole salts and rare-earth chlorination europium are added in the reactor, stirred 8 hours, revolve the steaming desolventizing, make imidazole salts ionic liquid/rare earth gel.Wherein, X=PF
6, Ln is Eu, n=15)
Embodiment 32
With the KPF in the step among the embodiment 18 (2)
6(Potassium Hexafluorophosphate) changes NaBF into
4(sodium tetrafluoroborate) makes imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 18.Wherein, X=BF
4, Ln is Eu, n=0)
Embodiment 33
With the KPF in the step among the embodiment 18 (2)
6(Potassium Hexafluorophosphate) changes C into
2F
6LiNO
4S
2(two fluoroform sulfimide lithium) makes imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 18.Wherein, X=Tf
2N, Ln are Eu, n=0)
Embodiment 34
Change the rare-earth chlorination europium in embodiment 1 step (2) into rare-earth chlorination europium and rare-earth chlorination terbium, Eu:Tb=8:0 in molar ratio, 7:1,5:3,1:1,3:5,0:8 prepares respectively imidazole salts ionic liquid/rare earth gel.All the other conditions are with embodiment 1.(wherein, X=Br, Ln are Eu and Tb, n=0)
Be shiny red under the imidazole salts of Eu:Tb=8:0 ionic liquid/rare earth gel ultraviolet lamp wherein, be light red under the imidazole salts ionic liquid of Eu:Tb=7:1/rare earth gel ultraviolet lamp, be safran under the imidazole salts ionic liquid of Eu:Tb=5:3/rare earth gel ultraviolet lamp, be glassy yellow under the imidazole salts ionic liquid of Eu:Tb=1:1/rare earth gel ultraviolet lamp, be simple yellow under the imidazole salts ionic liquid of Eu:Tb=3:5/rare earth gel ultraviolet lamp, be green under the imidazole salts ionic liquid of Eu:Tb=0:8/rare earth gel ultraviolet lamp, realized by ruddiness excessive to the light modulation of green glow.
As from the foregoing, imidazole salts of the present invention is high for the preparation of the doping content of novel rare-earth/imidazole salts ionic liquid luminescent material, luminescent properties is strong and have long characteristics of life-span, can be widely used in fluorescence imaging, bio-sensing, the fields such as highly sensitive time resolved fluorescence biochemical analysis.
Claims (9)
1. novel imidazole salt ion liquid, the structural formula that it is characterized by this ionic liquid is:
Wherein X is Br, [BF
4], [PF
6] or [Tf
2N]; N=0～15.
2. the preparation method of novel imidazole salt ion liquid as claimed in claim 1 is characterized by one of following any two kinds of methods:
Method one may further comprise the steps:
The bromine para Toluic Acid is joined in the ethanol, dissolve complete gradually under 80 ℃ of stirrings, then add equimolar substance A, under 80 ℃ of stirrings, react 17h, revolve the steaming desolventizing, then add and the isopyknic ether of ethanol, constantly stir, until white precipitate occurs, then wash with ether, revolve the steaming desolventizing, put into baking oven; Make the imidazole salts that X is Br;
Wherein substance A is Methylimidazole, butyl imidazole or long-chain imidazoles;
Perhaps, method two may further comprise the steps:
1) preparation X is the imidazole salts of Br, and step is with top method one;
2) X that the upper step was obtained is in the fully water-soluble and alcohol mixeding liquid of the imidazole salts of Br, adds substance B, and is centrifugal stirring at room back flow reaction 24 hours, with distilled water washing precipitation three times [PF
6]
-, [BF
4]
-Or [Tf
2N]
-Imidazole salts for negatively charged ion; Its mole proportioning is substance B: imidazole salts when substituent X is Br=1 ~ 2:1;
Wherein substance B is NaBF
4(sodium tetrafluoroborate), KPF
6(Potassium Hexafluorophosphate) or C
2F
6LiNO
4S
2(two fluoroform sulfimide lithium).
3. the preparation method of novel imidazole salt ion liquid as claimed in claim 2 is characterized by described long-chain imidazoles and is specially seven alkane imidazoles, eight alkane imidazoles, dodecane imidazoles or n-Hexadecane imidazoles.
4. imidazole salts ionic liquid/rare earth compounding is characterized by structural formula and is
Wherein X is Br, [BF
4], [PF
6] or [Tf
2N]; N=0～15, m=1 ~ 3;
Rare earth ion Ln is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er or Tm.
5. the preparation method of imidazole salts ionic liquid/rare earth compounding as claimed in claim 4 is characterized by and may further comprise the steps:
The proportioning of ionic liquid: rare earth chloride=3:1 in molar ratio, ionic liquid is dissolved in ethanol after, add again rare earth chloride, NaOH with 1mol/L regulates pH to 7-8, stirs, and is centrifugal, precipitation is used washing with alcohol, makes imidazole salts ionic liquid/rare earth compounding.
6. the preparation method of imidazole salts ionic liquid/rare earth compounding as claimed in claim 5, it is characterized by described rare earth chloride is NdCl
3, SmCl
3, EuCl
3, GdCl
3, TbCl
3, DyCl
3, HoCl
3, ErCl
3Or TmCl
3
7. imidazole salts ionic liquid/rare earth gel, it is as follows to it is characterized by structural formula:
Wherein X is Br, [BF
4], [PF
6] or [Tf
2N]; N=0～15;
Rare earth ion Ln wherein is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er or Tm.
8. the preparation method of imidazole salts ionic liquid/rare earth gel as claimed in claim 7 is characterized by and may further comprise the steps:
The proportioning of ionic liquid: rare earth chloride=3:1 in molar ratio, ionic liquid is dissolved in ethanol after, add again rare earth chloride, churning time 5 hours is revolved the steaming desolventizing after the reaction, put into baking oven, gets imidazole salts ionic liquid/rare earth gel.
9. the preparation method of imidazole salts ionic liquid/rare earth gel as claimed in claim 8, it is characterized by described rare earth chloride is NdCl
3, SmCl
3, EuCl
3, GdCl
3, TbCl
3, DyCl
3, HoCl
3, ErCl
3Or TmCl
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210491499.1A CN102952079B (en) | 2012-11-27 | 2012-11-27 | Novel imidazolium salt ionic liquid and related luminescent material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210491499.1A CN102952079B (en) | 2012-11-27 | 2012-11-27 | Novel imidazolium salt ionic liquid and related luminescent material thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102952079A true CN102952079A (en) | 2013-03-06 |
| CN102952079B CN102952079B (en) | 2014-10-15 |
Family
ID=47761523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210491499.1A Expired - Fee Related CN102952079B (en) | 2012-11-27 | 2012-11-27 | Novel imidazolium salt ionic liquid and related luminescent material thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102952079B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418511A (en) * | 2016-01-04 | 2016-03-23 | 温州医科大学 | 1-butyl-3-methylimidazole naphthoic formate ionic liquid and preparation method and application thereof |
| CN106084188A (en) * | 2016-06-23 | 2016-11-09 | 福建师范大学 | A kind of preparation method of imidazole radicals porous organic ionic polymer elasticity |
| CN108676173A (en) * | 2018-05-18 | 2018-10-19 | 东华大学 | Using ionic bond as poly ion liquid of skeleton and preparation method thereof |
| CN108676555A (en) * | 2018-05-28 | 2018-10-19 | 青岛农业大学 | One kind red light material of liquid containing europium ion and preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009123569A1 (en) * | 2008-03-31 | 2009-10-08 | Agency For Science, Technology And Research | Method for treating neurological disorders with imidazolium and imidazolinium compounds |
| CN101983057A (en) * | 2008-01-30 | 2011-03-02 | 新加坡科技研究局 | Methods of treating fibrosis and cancer with imidazole and imidazoline compounds |
-
2012
- 2012-11-27 CN CN201210491499.1A patent/CN102952079B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101983057A (en) * | 2008-01-30 | 2011-03-02 | 新加坡科技研究局 | Methods of treating fibrosis and cancer with imidazole and imidazoline compounds |
| WO2009123569A1 (en) * | 2008-03-31 | 2009-10-08 | Agency For Science, Technology And Research | Method for treating neurological disorders with imidazolium and imidazolinium compounds |
Non-Patent Citations (4)
| Title |
|---|
| DHRUBA SARKAR等: "A Novel Recyclable Organocatalytic System for the Highly Asymmetric Michael Addition of Aldehydes to Nitroolefins in Water", 《SYNTHESIS》, vol. 12, 13 May 2011 (2011-05-13), pages 1993 * |
| HUANRONG LI等: "Green synthesis of luminescent soft materials derived from task-specific ionic liquid for solubilizing lanthanide oxides and organic ligand", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 19, 18 June 2009 (2009-06-18), pages 5534 * |
| JESSICA LEMKE等: "The Synthesis of Ruthenium and Rhodium Complexes with Functionalized N-Heterocyclic Carbenes and Their Use in Solid Phase Peptide Synthesis", 《EUR. J. INORG. CHEM》, vol. 2008, no. 21, 18 June 2008 (2008-06-18), pages 3361 - 9 * |
| 李焕荣等: "新型稀土/功能化离子液体发光软材料", 《第七届全国稀土发光材料学术研讨会会议论文摘要集》, 12 May 2011 (2011-05-12), pages 29 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418511A (en) * | 2016-01-04 | 2016-03-23 | 温州医科大学 | 1-butyl-3-methylimidazole naphthoic formate ionic liquid and preparation method and application thereof |
| CN106084188A (en) * | 2016-06-23 | 2016-11-09 | 福建师范大学 | A kind of preparation method of imidazole radicals porous organic ionic polymer elasticity |
| CN106084188B (en) * | 2016-06-23 | 2018-03-16 | 福建师范大学 | A kind of preparation method of the porous organic ionic polymer elasticity of imidazole radicals |
| CN108676173A (en) * | 2018-05-18 | 2018-10-19 | 东华大学 | Using ionic bond as poly ion liquid of skeleton and preparation method thereof |
| CN108676173B (en) * | 2018-05-18 | 2020-12-18 | 东华大学 | Polyion liquid with ionic bond as framework and preparation method thereof |
| CN108676555A (en) * | 2018-05-28 | 2018-10-19 | 青岛农业大学 | One kind red light material of liquid containing europium ion and preparation method and application |
| CN108676555B (en) * | 2018-05-28 | 2020-11-20 | 青岛农业大学 | Europium-containing ionic liquid red light material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102952079B (en) | 2014-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107011469B (en) | A kind of side chain type liquid crystal macromolecule and preparation method thereof with aggregation-induced emission performance | |
| CN102190673B (en) | Rare earth/ionic liquid luminescent material | |
| EP2868661B1 (en) | Bipyridyl triazole rare earth complex and preparation process therefor | |
| CN102952079B (en) | Novel imidazolium salt ionic liquid and related luminescent material thereof | |
| CN102180873B (en) | Functional ionic liquid and preparation method thereof | |
| CN102965099B (en) | Novel rare earth/terpyridyl functionalized ionic liquid luminescent material | |
| CN101608115A (en) | A kind of rare earth and preparation method thereof | |
| CN103896972B (en) | A kind of preparation method of chiral binuclear europium beta-diketone complex luminescent material | |
| CN109608644A (en) | Imide derivative and preparation method and purposes as fluorine ion fluorescence probe | |
| Xu et al. | Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline | |
| CN110283217A (en) | A kind of phosphorescent lifetime response type complex of iridium and the preparation method and application thereof containing purpurine unit | |
| CN102731479B (en) | Organic ligand, rare earth organic fluorescent probe material thereof and preparation method thereof | |
| CN105543958B (en) | A kind of luminescence generated by light crystalline material boric acid europium potassium and its preparation method and application | |
| CN103044405B (en) | Functionalized polyion liquid and metal luminescent material thereof | |
| CN102887915B (en) | Heteronuclear bimetallic complex light-emitting material and preparation method and application thereof | |
| CN105238386B (en) | A kind of method of the fluorescent material for preparing rare earth doped complex | |
| CN103193812B (en) | A kind of two-dimensional terbium ligand polymer green fluorescent material containing oxalic acid and preparation method thereof | |
| CN103012464B (en) | Novel cage type low polysilsesquioxane and rare earth light-emitting material thereof | |
| CN104449672A (en) | Long-arm benzoic acid rare earth luminescent material and preparation method thereof | |
| CN105837568A (en) | Fluorenyl-[beta]-carboline compound, application thereof as organic light-emitting material and aggregation-induced emission enhancement material, and preparation method of the compound | |
| CN102127101B (en) | Multi-rare-earth organic complex and preparation method thereof | |
| Sun et al. | Performance of near-IR luminescent xerogel materials covalently bonded with ternary lanthanide (ErIII, NdIII, YbIII) complexes | |
| CN109988141A (en) | One kind based on hot activation delayed fluorescence has fluorescein derivative compound, preparation method and the application of up-conversion luminescence performance | |
| CN101899038B (en) | Near-infrared light emitting ionic complex and preparation method thereof | |
| CN102816176A (en) | Preparation method and application of trivalent europium ternary complex liquid material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| 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: 20141015 |