CN104194774A - Antimony-based fluorescent material and preparation method thereof - Google Patents
Antimony-based fluorescent material and preparation method thereof Download PDFInfo
- Publication number
- CN104194774A CN104194774A CN201410424241.9A CN201410424241A CN104194774A CN 104194774 A CN104194774 A CN 104194774A CN 201410424241 A CN201410424241 A CN 201410424241A CN 104194774 A CN104194774 A CN 104194774A
- Authority
- CN
- China
- Prior art keywords
- compound
- optionally
- antimony
- organic solvent
- 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
Landscapes
- Luminescent Compositions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The application relates to a compound capable of transforming ultraviolet light into a high-strength visible light, as well as a preparation method and application of the compound. The compound is prepared by the following steps: dissolving the raw materials (imidazolium ionic liquid, a chlorine source, an antimony source and water) into an organic solvent and finally removing the solvent. The preparation process is simple; the raw materials are friendly to the environment, cheap and easily available; the quantum yield is over 70%; the obtained product has the advantages of high purity, excellent fluorescence property and good stability, is easily processed and treated, and is an ideal fluorescent material for LEDs and LED-related display and lighting devices.
Description
Technical field
The application relates to a class for photodiode, luminescent lamp and other antimony base fluorescent materials in luminous fields and preparation method thereof of being correlated with.Described material is electric light an illuminating material, belongs to fluorescent material field
Background technology
Semiconductor lighting, refers to that as the solid state lighting of light source, be a kind of emerging technology with semiconductor light-emitting-diode (light-emitting diode is called for short LED).Because it has the not available plurality of advantages of traditional electrical light illumination,, fast response time little such as: energy-saving and environmental protection, long service life, volume, shock-resistant etc., thereby invite domestic and international many leading companys to drop into research and the product development that huge fund is engaged in association area, wherein Japanese Ya Co., Ltd. has developed high-brightness blue LED first based on GaN, make LED manufacturer can produce three primary colors (red, green and blue) LED, thereby make to realize 1,670 ten thousand looks, become possibility; Holland PHILIPS Co. is making a lot of effort aspect the domestic applications of LED; Other also have German Osram-photo semiconductor company, U.S. Hewlett-Packard company etc.
In all kinds of LED products, white light LEDs, because efficiency is high and brightness is large, is even hopeful simulating nature light and is considered light source of new generation.At present, the white light LEDs of industrialization is all some complex light, be all conventionally on chip coating fluorescent powder to realize white light emission, i.e. fluorescent conversion type white light LEDs.Typical example excites the YAG:Ce fluorescent material of gold-tinted to produce first commercial white light-emitting diodes as 1997 Nian Ya companies utilize InGaN blue chip.Thereby all kinds of high-efficiency fluorescence powder preparations are one of gordian techniquies that realize white light LEDs.No matter ultraviolet conversion hysteria fluorescent material (excitation wavelength 200～350nm) or near ultraviolet conversion phosphor (excitation wavelength 350～450nm), its most of patent Dou Wei developed country grasps.The fluorescent material with independent intellectual property right of development of new has important practical significance.
Existing fluorescent material is mainly divided into inorganic fluorescent material and the large class of organic fluorescence materials two, and inorganic fluorescent material has advantages of that stability is higher, but more or less has again some shortcomings simultaneously, for example: synthesis temperature is higher, more to energy consumption; Wherein apply the composition that lacks ruddiness in more aluminate fluorescent powder spectrum, colour rendering index is not high; Silicate fluorescent powder emission peak is narrow, more responsive to humidity; Nitride phosphor manufacturing cost is higher; Sulphide fluorescent material is more responsive etc. to humidity.Organic fluorescence materials synthesis temperature is lower (200 ℃ following) conventionally, but thermostability aspect is not as inorganic materials.In the exploitation of novel fluorescent material, people day by day notice the huge applications potentiality that hybrid inorganic-organic materials has.This hybrid material not only may merge inorganic fluorescent material good stability and the high advantage of organic fluorescence materials quantum yield effectively, can also avoid the synthetic high flow rate to the energy of traditional inorganic fluorescent material high temperature, and the interaction of organic moiety and inorganic part, may realize high quantum yield.
Ionic liquid, as a kind of room temperature melting salt, has insignificant vapour pressure and the high features such as thermostability, wherein common containing the ionic liquid of alkyl imidazolium cation.If be incorporated in hybrid fluorescent material it as organic moiety, may produce important impact to the character of material, for example the lower character of fusing point can be incorporated in product, make material be easy to processing and device.On the other hand, ionic liquid can, both as reactant, again as other reactants of dissolution with solvents, thereby be realized and fully contacting and augmenting response speed with other reactants at the temperature compared with low, this is save energy greatly, has important effect aspect Green Chemistry.With ionic liquid positively charged ion and metal complex anion combination, forming metallic class ionic liquid structure is to realize the effective means of high-efficiency fluorescence powder.More external seminars possess some special knowledge in this respect, such as the ionic liquid of (Angew.Chem.Int.Ed., the 2008,47,7635th 7638 pages of the –) reports such as Mudring and the ionic liquid [C containing rare earth metal that rare earth metal forms
6mIm]
5-x[Dy (SCN)
8-x(H
2o)
x] (x=0～2) except thering is fluorescence property, also there is magnetic; Chinese patent CN 103073500 A have also described the rare earth ion liquid Cat that a class has fluorescence and magnetic
+(Ln[NO
3]
6)
3-; [BMIm] of Nockemann etc. (J.Am.Chem.Soc., 2006,128,13658-13659 page) report
x-3[Ln (NCS)
x(H
2o)
y] (x=6-8; Y=0-2; X+y<10; Ln=Y, La-Yb), all at 100 ℃, can prepare below, rare earth element has wherein kept good photoluminescence performance, and the part of ionic liquid makes it inherit the feature that fusing point is not high, be easy to processing.Aspect transition metal, the existing fluorescence ion liquid [C containing Au, Ag
nmIm] [M (CN)
2] (M=Au, Ag, n=12,14,18) (Dalton Trans., the 2010,39,10574th 10576 pages of –) and containing the fluorescence ion liquid [C of Mn
nmIm]
2[MnX
4] and [C
nmIm] [Mn (Tf
2n)
3] (n=2,3,4,6, X=Cl
-, Br
-) (Chem.Eur.J., the 2010,16,3355th 3365 pages of –) be in the news.By contrast, containing this compounds of main group metal rarely seen report, only there is report one routine Bi
3+ionic liquid as activator doping has liquid Near-Infrared Photoluminescence phenomenon (Opt.Lett., 2011,36,100-102 page)
Yet, from existing compound, contain the compound of rare earth, Au, Ag because metal fancy price has greatly improved its cost, and negatively charged ion is [Tf
2n]
-the building-up process of ionic liquid also comparatively complicated, cause price comparatively expensive, and the quantum yield of the metallic fluorescence ion liquid of this class of having reported is generally not high (is up to 65.3%: Chinese patent CN 103073500 A).In addition, in the raw material that this compounds of having reported adds in preparation process, have a lot of species in final product, not occur, atom utilization is low, does not meet Atom economy, and the generation due to by product simultaneously causes separated difficulty.Therefore, utilize metal cheap and easy to get and ionic liquid, easy to use and method that atom utilization is high, makes the fluorescent material with high quantum production rate and remains a challenge.
Summary of the invention
For solving the problems of the technologies described above, the application provides a kind of compound, it is characterized in that, has suc as formula structural formula shown in (1):
formula (1)
In formula (1), the valence state of antimony Sb is trivalent; X is optionally from 2,3,4,5,6; Y is optionally from 5,6; Z is optionally from 0,1; Substituent R on imidazole ring
1, R
2, R
3respectively independently optionally from hydrogen, C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl.
The application provides a kind of compound, it is characterized in that, has suc as formula structural formula shown in (2):
formula (2)
In formula (2), the valence state of antimony Sb is trivalent; X is optionally from 2,3,4,5,6; Y is optionally from 5,6; Z is optionally from 0,1; Substituent R on imidazole ring
1for methyl; R
2optionally from C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl; R
3for hydrogen or methyl.
In the application, C
1-C
8alkyl refers to that carbonatoms is 1～8 alkyl, containing straight chained alkyl with the alkyl of side chain; Described C
2-C
8thiazolinyl refers to that carbonatoms is 2～8 thiazolinyl, containing straight-chain alkenyl with the thiazolinyl of side chain; C
2-C
8alkynyl refers to that carbonatoms is 2～8 alkynyl, containing straight-chain alkynyl with the alkynyl of side chain.
As one preferred embodiment, described C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8any hydrogen atom in alkynyl can be replaced by the optional substituting group from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical independently.As the carbonatoms methyl (C that is 1
1alkyl) upper any hydrogen is replaced the nitrile methyl-CH forming by itrile group
2-CN, the straight chain octyl (C that carbonatoms is 8
8alkyl) in upper terminal methyl group, hydrogen is substituted by phenyl the phenyl octyl-(CH of formation arbitrarily
2)
8-Ph etc.
As one preferred embodiment, the substituent R in formula (1) on imidazole ring
1, R
2, R
3respectively independently optionally from C
3-C
6alkyl, C
3-C
6thiazolinyl, C
3-C
6alkynyl, wherein C
3-C
6alkyl, C
3-C
6thiazolinyl, C
3-C
6any hydrogen atom in alkynyl can be replaced by the optional substituting group from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical independently.
Preferred embodiment it is characterized in that as one, in formula (1)
optionally from 1-butyl-3-Methylimidazole ion, (be abbreviated as [BMIm]
+), 1-benzyl-3-Methylimidazole ion (is abbreviated as [BzMIm]
+), 1-butyl-2,3-Methylimidazole ion (is abbreviated as [BMMIm]
+), 1-propyl group-3-Methylimidazole ion (is abbreviated as [PrMIm]
+), 1-carboxymethyl-3-Methylimidazole ion (is abbreviated as [HOOCMMIm]
+) wherein at least one or wherein at least one and 1-carboxylate radical methyl-3-Methylimidazole (be abbreviated as [OOCMMIm
+]) combination.In described formula (1)
optionally from 1-butyl-3-Methylimidazole ion, (be abbreviated as [BMIm]
+), 1-benzyl-3-Methylimidazole ion (is abbreviated as [BzMIm]
+), 1-butyl-2,3-Methylimidazole ion (is abbreviated as [BMMIm]
+), 1-propyl group-3-Methylimidazole ion (is abbreviated as [PrMIm]
+), 1-carboxymethyl-3-Methylimidazole ion (is abbreviated as [HOOCMMIm]
+) at least one and 1-carboxylate radical methyl-3-Methylimidazole wherein (be abbreviated as [OOCMMIm
+]) combination, refer in formula (1)
optionally from 1-carboxylate radical methyl-3-Methylimidazole and 1-butyl-3-Methylimidazole ion, 1-benzyl-3-Methylimidazole ion, 1-butyl-2, the combination of at least one in 3-Methylimidazole ion, 1-propyl group-3-Methylimidazole ion, 1-carboxymethyl-3-Methylimidazole ion.
In the application, described compound is the crystalline compound being formed by ionic liquid positively charged ion and antimony chloride anion,
for ionic liquid positively charged ion, inorganic anion can be used general formula [SbCl
y]
3-yrepresent, this compound can be expressed from the next:
formula (1), for ease of statement, is below abbreviated as: [R
1r
2r
3im]
x[SbCl
y] [H
2o]
z.Wherein: Im is imidazoles
r
1, R
2, R
3for the substituting group on imidazole ring in formula (1), x is the integer in 2～6 scopes, y be 5 or 6, z be 0 or 1.
Typically, the compound having suc as formula structural formula shown in (1) has:
[BMIm]
2[SbCl
5], BMIm=1-butyl-3-Methylimidazole ion, this compound crystal belongs to Cc spacer, and its unit cell parameters is:
β=102.004 (2) °,
z=12.This compound has 480nm and two emission peaks of 583nm under the exciting of UV-light, and the intensity at its peak is along with the variation of excitation wavelength changes.Be embodied in along with excitation wavelength is from 270～303～376nm, the visible ray of its transmitting changes between yellow～white～yellow.Under the exciting of 376nm UV-light, its solid-state quantum yield is 86.3%, and fluorescence lifetime is 4.275 μ s.
[HOOCMMIm]
3[SbCl
6], HOOCMMIm=1-carboxymethyl-3-Methylimidazole ion, this compound crystal belongs to P2
1/ c spacer, unit cell parameters is:
β=114.991 (6) °,
z=4.This compound can send the yellowish green light of 533nm under the exciting of 350nm UV-light, and to record its solid-state quantum yield be 73.19%, and fluorescence lifetime is 3.185 μ s.
[HOOCMMIm]
3[OOCMMIm]
3[SbCl
6] [H
2o], HOOCMMIm=1-carboxymethyl-3-Methylimidazole ion, OOCMMIm=1-carboxylate radical methyl-3-Methylimidazole, this compound crystal belongs to R-3 spacer, and unit cell parameters is:
z=3.This compound, under the exciting of 365nm UV-light, can send the green glow of 510nm, and to record its solid-state quantum yield be 84.74%, and fluorescence lifetime is 2.033 μ s.
Above three kinds is only the Typical Representative of compound described in the application, and the compound having suc as formula structural formula shown in (1) described in the application is not limited to this.
The application's another object is to provide the preparation method of described compound, has solved the problems such as the existing material synthesis temperature in fluorescent material field is higher, cost is high, complex process.Described preparation method's cost is low, simple process, energy-conserving and environment-protective (all can prepare below at 100 ℃), atom utilization are high, and reactant used almost can be realized 100% conversion, has got rid of the separation difficulty that by product brings.
As a kind of embodiment, the preparation method of described compound, is characterized in that, at least comprises following steps:
A) glyoxaline ion liquid, chlorine source, antimony source and water are mixed, obtain having imidazoles structural unit in glyoxaline ion liquid
the molar ratio of antimony element, chlorine element, water is
sb:Cl:H
2the mixture of O=2～6:1:5～6:0～1;
B) by step a) gained mixture be dissolved in organic solvent, remove organic solvent, obtain described compound.
Preferably, a) imidazoles structural unit in glyoxaline ion liquid in described mixture of step
antimony element, chlorine element, water molar ratio are the stoichiometric ratio in formula (1),
sb:Cl:H
2o=x:1:y:z; Wherein, x is optionally from 2,3,4,5,6; Y is optionally from 5,6, and z is optionally from 0,1.
In described mixture, H
2the molar ratio of O is 0 o'clock, does not contain crystal water in gained compound crystal.
Those skilled in the art can be according to the stoichiometric ratio of target compound or mol ratio, select the proportioning raw materials needing, should be appreciated that, part material reasonably can freely change addition in scope, can not affect the generation of target compound under certain condition, in the application, only with comparatively economic scheme, disclose part embodiment.
In the application, described glyoxaline ion liquid is to contain in positively charged ion
the ionic liquid of structural unit, with negatively charged ion, the compound forming such as halide-ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc.Substituent R wherein
1, R
2, R
3respectively independently optionally from hydrogen, C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl; Described C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8any hydrogen atom in alkynyl can be replaced by the optional substituting group from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical independently.
As one preferred embodiment, the substituent R on glyoxaline ion liquid imidazole ring
1, R
2, R
3respectively independently optionally from C
3-C
6alkyl, C
3-C
6thiazolinyl, C
3-C
6alkynyl; Described C
3-C
6alkyl, C
3-C
6thiazolinyl, C
3-C
6any hydrogen atom in alkynyl can be replaced by the optional substituting group from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical independently.
As one preferred embodiment, described glyoxaline ion liquid is to contain in positively charged ion
the ionic liquid of structural unit, with negatively charged ion, the compound forming such as halide-ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc.R wherein
1for methyl; R
2optionally from hydrogen, C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl; R
3for hydrogen or methyl.Described C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8any hydrogen atom in alkynyl can be replaced by the optional substituting group from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical independently.
In the application, the optional material from containing chlorine element in described chlorine source.Preferably, described chlorine source is optional from containing chlorion Cl
-compound in one or more.Described chlorine source can be from independent interpolation, also can be from glyoxaline ion liquid and/or antimony source.Not chloride in glyoxaline ion liquid and antimony source, or in the chloride less situation that is not enough to reach cl content in target mixture, need to separately add other chlorine source; Chloride in glyoxaline ion liquid and/or antimony source, and chlorine is enough to reach in the situation of cl content in target mixture, do not need separately to add other chlorine source.For example, described preparation method is raw material with chlorination 1-propyl group-3-Methylimidazole ionic liquid and butter of antimony, and the chlorine in chlorination 1-propyl group-3-Methylimidazole ionic liquid and butter of antimony is chlorine source, does not need to add in addition other chlorine sources.
Preferably, described chlorine source is from the glyoxaline ion liquid that contains chlorion and/or the antimony source of containing chlorion.
In the application, described antimony source, can be for containing any material of antimony element; Preferably, optional from containing one or more in trivalent antimony ionic compound; Further preferably, described antimony source is butter of antimony.
According to general knowledge known in this field, described organic solvent, those skilled in the art can adopt applicable organic solvent according to specific embodiment, can dissolve all reactants and volatile organic solvent all can reach the object of preparing target material.The amount that organic solvent adds, under can the prerequisite of solubilizing reaction thing, those skilled in the art can reasonably select arbitrarily in scope.
Preferably, described organic solvent, optional one or more in methyl alcohol, ethanol, acetonitrile; Further preferably, described organic solvent is ethanol.
According to general knowledge known in this field, those skilled in the art can be according to concrete reactant, organic solvent and the requirement to product, guarantee that, under the prerequisite of reactant abundant dissolving in ionic liquid, selective reaction thing dissolves temperature and the dissolution time adopting in organic solvent in suitable scope.
Preferably, described step b) in, mixture is dissolved in the process of organic solvent, and temperature is 20～200 ℃, and mixture keeps for some time to mixture to dissolve completely after dissolving in this temperature range, then removes organic solvent; Further preferably, described step b) in, mixture is dissolved in the process of organic solvent, the temperature range upper limit is optionally from 100 ℃, 150 ℃, 200 ℃, temperature range lower limit is optionally from 20 ℃, 50 ℃, 90 ℃, after mixture dissolves, in this temperature range, keep being no more than 48 hours, then remove organic solvent; Further preferably, described step b) in, mixture is dissolved in the process of organic solvent, and temperature is 50～150 ℃, and mixture keeps 1～3 hour after dissolving in this temperature range, then removes organic solvent; Further preferably, described step b) in, mixture is dissolved in the process of organic solvent, and temperature is 80 ℃, and mixture keeps 2 hours after dissolving in this temperature range, then removes organic solvent.
The application's another object is to provide a kind of fluorescent material, it is characterized in that, contains described arbitrary the have compound of formula (1) structural formula and/or the compound of preparing according to above-mentioned either method.
Described fluorescent material can make UV-light be converted into visible ray.
The application's another object is to provide a kind of luminescent lamp, it is characterized in that, contains described arbitrary the have compound of formula (1) structural formula and/or the compound of preparing according to above-mentioned either method.
The application's another object is to provide a kind of photodiode, it is characterized in that, contains described arbitrary the have compound of formula (1) structural formula and/or the compound of preparing according to above-mentioned either method.
Quantum yield in the application, refers to fluorescence quantum yield, refers in excited state molecule that the molecule of getting back to ground state by emitting fluorescence accounts for the mark of whole excited state molecules.
Fluorescence in the application, refer to a kind of photo-induced cold luminescence phenomenon, when the incident light (normally ultraviolet ray or X ray) of certain normal temperature material through certain wavelength irradiates, absorb that luminous energy is laggard enters excited state, subsequently de excitation send out and send emergent light (conventionally wavelength ratio incident light wavelength long, at visible light wave range).
In the application, Im is that imidazoles ,-CN are that itrile group ,-OH are that hydroxyl ,-Ph are that phenyl ,-Bz are that benzyl ,-COOH are that carboxyl ,-COO are that carboxylate radical, M are that methyl, Pr are that propyl group, B are that butyl, HOOCM are carboxymethyl.
Should be understood that within the scope of the technical scheme disclosing in the application, above-mentioned each technical characterictic of the application and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, at this, tire out and state no longer one by one.
Compared with prior art, the application has following beneficial effect:
(1) synthesized a class antimony Sb based compound of novel burst of ultraviolel, gained compound has good fluorescence property, and comparatively stable, cheap and easy to get and be easy to storage.
(2) the pure inorganic fluorescent material that synthetic method is more traditional is compared comparatively gentle, and major part can be prepared below at 100 ℃, and preparation process is comparatively simple, and atom utilization is high, and quantum yield surpasses 70%, little to energy consumption.Using the compound of metallic antimony also effectively to avoid expensive rare earth compound as raw material, is a kind of fluorescent material of Cheap highly effective.
(3) in described compound, do not contain H
2in the situation of O, although be solid at normal temperatures, but still there is the feature of ionic liquid.Except environmental protection, also because fusing point is not high, there is the feature of easy processing.For example just can be by [BMIm] at 76 ℃
2[SbCl
5] melt, then covering equably the surface of purple LED bulb, this compound has high quantum yield, the ultraviolet ray that approaches 90% can be converted into bright yellow visible light, has greatly reduced possible UV-light and has polluted the injury that human body is caused.
Accompanying drawing explanation
Fig. 1 is sample 1#[BMIm]
2[SbCl
5] crystalline structure schematic diagram.
Fig. 2 is sample 2#[HOOCMMIm]
3[SbCl
6] crystalline structure schematic diagram.
Fig. 3 is sample 3#[HOOCMMIm]
3[OOCMMIm]
3[SbCl
6] [H
2o] crystalline structure schematic diagram.
Fig. 4 is sample 1#[BMIm]
2[SbCl
5] X-ray powder diffraction.
Fig. 5 is sample 2#[HOOCMMIm]
3[SbCl
6] X-ray powder diffraction.
Fig. 6 is sample 3#[HOOCMMIm]
3[OOCMMIm]
3[SbCl
6] [H
2o] X-ray powder diffraction.
Fig. 7 is sample 1#[BMIm]
2[SbCl
5] excitation spectrum.
Fig. 8 is sample 1#[BMIm]
2[SbCl
5] emmission spectrum.
Fig. 9 is sample 2#[HOOCMMIm]
3[SbCl
6] excitation and emission spectra.
Figure 10 is sample 3#[HOOCMMIm]
3[OOCMMIm]
3[SbCl
6] [H
2o] excitation and emission spectra.
Embodiment
The above-mentioned feature that the application mentions, or the feature that embodiment mentions can arbitrary combination.All features that present specification discloses can with any composition forms use, each feature disclosing in specification sheets, can be replaced by any alternative characteristics of identical, impartial or similar object that provide.Therefore apart from special instruction, the feature disclosing is only the general example of equalization or similar features.
Below in conjunction with embodiment, further set forth the application.Should be understood that these embodiment are only not used in restriction the application's scope for the application is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition or the condition of advising according to manufacturer.Do not do in the situation of specified otherwise, raw material that the application uses, all buys by commercial sources, without special processing, directly uses.
If no special instructions, in embodiment, the test condition to sample is as follows:
X – ray powder diffraction material phase analysis (XRD) carries out on the MiniFlex2 of Rigaku company type X-ray diffractometer, Cu target, K α source of radiation (λ=0.154184nm).
Excitation and emission spectra carries out on the LS55 type Fluorescence spectrophotometer of Perkin Elmer company.
X – ray single crystal diffraction carries out on the Xcalibur of Agilent company E type single crystal diffractometer, Mo target, K α source of radiation (λ=0.07107nm), probe temperature 295K.And by Shelxtl97 to carrying out structure elucidation.
The preparation of embodiment 1 sample 1#～sample 5#
Glyoxaline ion liquid, chlorine source, antimony source and water are mixed according to proportioning shown in table 1, add organic solvent, being heated to certain temperature and being constantly stirred to system dissolves transparent completely, keep for some time to form after supersaturated solution, cooling and be constantly stirred to clear crystal and separate out, after crystal is separated out completely, under room temperature, use absolute ethanol washing two to three times, dry remove organic solvent and can obtain respective sample.Temperature in sample number into spectrum and reactant ratio, organic solvent kind, dissolution process and the time keeping at this temperature, product are as shown in table 1.
Relation between table 1 sample number into spectrum, proportioning raw materials, preparation condition and product
The structural characterization of embodiment 2 samples
Adopt x-ray single crystal diffraction to characterize sample 1#～sample 5#, and by Shelxtl97, sample structure is resolved.Result demonstration, sample 1#～sample 5# all has general formula shown in formula (1), take sample 1#～sample 3# below as Typical Representative detailed description.
Wherein, the crystalline structure of sample 1# is obtained by x-ray single crystal diffraction, as shown in Figure 1.Sample 1# crystal belongs to Cc spacer, and its unit cell parameters is:
β=102.004 (2) °,
z=12.In Fig. 1, in Pyramid, the ball of large ater represents Sb atom, and the ball of the grey black being attached thereto represents Cl atom, and the black bead on five-ring represents N atom, and linen ball represents C atom, and the ball of white represents H atom.As shown in Figure 4, the theoretical XRD diffracting spectrum obtaining according to its crystalline structure simulation, as shown in simulation peak, Fig. 4 below spectrogram for the powder X-ray RD diffracting spectrum of sample 1#, the sample peak of Fig. 4 top is the actual diffractogram recording, two figure compare, and peak position is consistent, show that gained sample is pure phase.
The crystalline structure of sample 2# is obtained by x-ray single crystal diffraction, as shown in Figure 2.Sample 2# crystal belongs to P2
1/ c spacer, unit cell parameters is:
β=114.991 (6) °,
z=4.In Fig. 2, the ball of larger ater represents Sb atom, and the ball of the grey black being attached thereto represents Cl atom, and the dotted line between Sb and one of them Cl atom represents secondary key.Black bead on five-ring represents N atom, and linen ball represents C atom, and the ball of grey represents O atom, and the ball of white represents H atom, and for more high-visible, the H atom being connected with C atom in figure is omitted.As shown in Figure 5, the theoretical XRD diffracting spectrum that simulation obtains according to crystalline structure, as shown in simulation peak, Fig. 5 below spectrogram for the powder X-ray RD diffracting spectrum of sample 2#, the sample peak of Fig. 5 top is the actual diffractogram recording, two figure compare, and peak position is consistent, show that gained sample is pure phase.。
The crystalline structure of sample 3# is obtained by x-ray single crystal diffraction, as shown in Figure 3.Sample 3# crystal belongs to R-3 spacer, and unit cell parameters is:
z=3.In Fig. 3, the ball of larger ater represents Sb atom, and the ball of the grey black being attached thereto represents Cl atom, and the dotted line between Sb and one of them Cl atom represents secondary key.Black bead on five-ring represents N atom, and linen ball represents C atom, and the ball of grey represents O atom, and the ball of white represents H atom, and for more high-visible, the H atom being connected with C atom in figure is omitted.As shown in Figure 6, the theoretical XRD diffracting spectrum obtaining according to its crystalline structure simulation, as shown in simulation peak, Fig. 6 below spectrogram for the powder X-ray RD diffracting spectrum of sample 2#, the sample peak of Fig. 6 top is the actual diffractogram recording, two figure compare, and peak position is consistent, show that gained sample is pure phase.
Embodiment 3
As shown in Figure 7, emmission spectrum as shown in Figure 8 for the excitation spectrum of sample 1#.Can find out, sample 1# has 480nm and two emission peaks of 583nm under the exciting of UV-light, and the intensity at its peak is along with the variation of excitation wavelength changes.Be embodied in along with excitation wavelength is from 270～303～376nm, the visible ray of its transmitting changes between yellow～white～yellow.Under the exciting of 376nm UV-light, its solid-state quantum yield is 86.3%, and fluorescence lifetime is 4.275 μ s.
The excitation and emission spectra of sample 2# as shown in Figure 9, can find out, sample 2# can send the yellowish green light of 533nm under the exciting of 350nm UV-light, and to record its solid-state quantum yield be 73.19%, and fluorescence lifetime is 3.185 μ s.
The excitation and emission spectra of sample 3# as shown in figure 10, can find out, sample 3#, under the exciting of 365nm UV-light, can send the green glow of 510nm, and to record its solid-state quantum yield be 84.74%, and fluorescence lifetime is 2.033 μ s.。
Embodiment 4
Sample 1# is placed at 76 ℃ and is melted into liquid sample 1#, dip operative liquid sample 1#, and under normal temperature, make liquid sample 1# in LED bulb surface solidification with the ultraviolet LED bulb that can launch 365～370nm, energising has yellow light to send later.
Embodiment 5
0.2g sample 1# is positioned on the circular glass sheet of 1 diameter 50mm, after melting at 76 ℃, uses other sheet glass slightly to press it to be dispersed in bottom sheet glass to uniform liquid.Then stop being heated to sample 1# crystallization again, the sample 1# film that to obtain take sheet glass be substrate, is placed in this film under the irradiation of ultraviolet lamp, can demonstrate characteristic fluorescence.
The above, only several embodiment of the application, not the application is done to any type of restriction, although the application discloses as above with preferred embodiment, yet not in order to limit the application, any those skilled in the art, within not departing from the scope of present techniques scheme, utilize the technology contents of above-mentioned announcement to make a little change or modify and be all equal to equivalent case study on implementation, all belong within the scope of technical scheme.
Claims (10)
1. a compound, is characterized in that, has suc as formula structural formula shown in (1):
formula (1)
In formula (1), the valence state of antimony Sb is trivalent; X is optionally from 2,3,4,5,6; Y is optionally from 5,6; Z is optionally from 0,1; Substituent R on imidazole ring
1, R
2, R
3respectively independently optionally from hydrogen, C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl;
Described C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8any hydrogen atom in alkynyl can be replaced by the optional substituting group from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical independently.
2. compound according to claim 1, is characterized in that, has suc as formula structural formula shown in (2):
formula (2)
In formula (2), the valence state of antimony Sb is trivalent; X is optionally from 2,3,4,5,6; Y is optionally from 5,6; Z is optionally from 0,1; Substituent R on imidazole ring
1for methyl; R
2optionally from C
1-C
8alkyl, C
2-C
8thiazolinyl, C
2-C
8alkynyl; R
3for hydrogen or methyl.
3. compound according to claim 1, is characterized in that, in formula (1)
optionally from 1-butyl-3-Methylimidazole ion, 1-benzyl-3-Methylimidazole ion, 1-butyl-2, at least one in 3-Methylimidazole ion, 1-propyl group-3-Methylimidazole ion, 1-carboxymethyl-3-Methylimidazole ion or wherein at least one and the combination of 1-carboxylate radical methyl-3-Methylimidazole.
4. the method for preparing compound described in claim 1, is characterized in that, at least comprises following steps:
A) glyoxaline ion liquid, chlorine source, antimony source and water are mixed, obtain having in imidazole-like ionic liquid
the molar ratio of antimony element, chlorine element, water is
sb:Cl:H
2the mixture of O=2～6:1:5～6:0～1;
B) by step a) gained mixture be dissolved in organic solvent, remove organic solvent, obtain described compound.
5. method according to claim 4, is characterized in that, step is a) in described mixture in imidazole-like ionic liquid
antimony element, chlorine element, water molar ratio are that the stoichiometric ratio in formula (1) is
sb:Cl:H
2o=x:1:y:z;
Wherein, x is optionally from 2,3,4,5,6; Y is optionally from 5,6, and z is optionally from 0,1;
Step a) described chlorine source from the glyoxaline ion liquid that contains chlorion and/or the antimony source of containing chlorion; Optional one or more in the compound that contains trivalent antimony ion in described antimony source; Preferably, described antimony source is butter of antimony; Described organic solvent is one or more in methyl alcohol, ethanol, acetonitrile optionally; Preferably, described organic solvent is ethanol.
6. method according to claim 4, it is characterized in that described step b) in mixture be dissolved in the process of organic solvent, temperature is 20～200 ℃, mixture keeps for some time to mixture to dissolve completely after dissolving in this temperature range, then removes organic solvent; Preferably, described step b) in, mixture is dissolved in the process of organic solvent, and temperature is 50～150 ℃, and mixture keeps 1～3 hour after dissolving in this temperature range, then removes organic solvent.
7. a fluorescent material, is characterized in that, containing the arbitrary compound described in good grounds claim 1-3 and/or the compound of preparing according to either method described in claim 4-6.
8. fluorescent material according to claim 7, is characterized in that, can make UV-light be converted into visible ray.
9. a luminescent lamp, is characterized in that, containing the arbitrary compound described in good grounds claim 1-3 and/or the compound of preparing according to either method described in claim 4-6.
10. a photodiode, is characterized in that, containing the arbitrary compound described in good grounds claim 1-3 and/or the compound of preparing according to either method described in claim 4-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410424241.9A CN104194774B (en) | 2014-08-26 | 2014-08-26 | One class antimonio fluorescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410424241.9A CN104194774B (en) | 2014-08-26 | 2014-08-26 | One class antimonio fluorescent material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104194774A true CN104194774A (en) | 2014-12-10 |
| CN104194774B CN104194774B (en) | 2016-07-06 |
Family
ID=52080147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410424241.9A Active CN104194774B (en) | 2014-08-26 | 2014-08-26 | One class antimonio fluorescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104194774B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606954A (en) * | 2020-06-30 | 2020-09-01 | 深圳职业技术学院 | Sb3+Green fluorescent powder and preparation method thereof |
| CN114524849A (en) * | 2020-11-23 | 2022-05-24 | 吉林大学 | Guanidyl metal halogen complex luminescent material and preparation method and application thereof |
| CN114736127A (en) * | 2022-04-02 | 2022-07-12 | 中山大学 | Antimony pentachloride fluorescent compound, crystal, preparation method and application thereof |
| CN116217489A (en) * | 2023-02-16 | 2023-06-06 | 山东大学 | Antimony-based luminescent ionic liquid based on organic-inorganic hybrid metal halide structure, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006043110A1 (en) * | 2004-10-22 | 2006-04-27 | The Queen's University Of Belfast | Light emitting complex salts |
| CN103073500A (en) * | 2013-01-06 | 2013-05-01 | 四川大学 | Rare earth metal ionic liquid, preparation method and application thereof |
-
2014
- 2014-08-26 CN CN201410424241.9A patent/CN104194774B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006043110A1 (en) * | 2004-10-22 | 2006-04-27 | The Queen's University Of Belfast | Light emitting complex salts |
| CN103073500A (en) * | 2013-01-06 | 2013-05-01 | 四川大学 | Rare earth metal ionic liquid, preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| A. PIECHA-BISIOREK等: "Dynamics of Ferroelectric Bis(imidazolium) Pentachloroantimonate(III) by Means of Nuclear Magnetic Resonance 1H Relaxometry and Dielectric Spectroscopy", 《J. PHYS. CHEM. A》 * |
| ANNA PIECHA等: "Novel organic–inorganic hybrid ferroelectric: bis(imidazolium)pentachloroantimonate(III), (C3N2H5)2SbCl5", 《J. MATER. CHEM.》 * |
| MACIEJ BUJAK等: "Structure of chloroantimonates(III) with an imidazolium cation: (C3H5N2)[SbCl4] and (C3H5N2)2[SbCl5]", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
| MACIEJ BUJAK等: "Structure of chloroantimonates(III) with an imidazolium cation: (C3H5N2)[SbCl4] and (C3H5N2)2[SbCl5]", 《JOURNAL OF MOLECULAR STRUCTURE》, 28 February 2003 (2003-02-28), pages 121 - 128, XP027108856 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606954A (en) * | 2020-06-30 | 2020-09-01 | 深圳职业技术学院 | Sb3+Green fluorescent powder and preparation method thereof |
| CN114524849A (en) * | 2020-11-23 | 2022-05-24 | 吉林大学 | Guanidyl metal halogen complex luminescent material and preparation method and application thereof |
| CN114736127A (en) * | 2022-04-02 | 2022-07-12 | 中山大学 | Antimony pentachloride fluorescent compound, crystal, preparation method and application thereof |
| CN116217489A (en) * | 2023-02-16 | 2023-06-06 | 山东大学 | Antimony-based luminescent ionic liquid based on organic-inorganic hybrid metal halide structure, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104194774B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Full-colour fluorescent materials based on mixed-lanthanide (iii) metal–organic complexes with high-efficiency white light emission | |
| Haque et al. | Luminescent properties of Eu3+-activated molybdate-based novel red-emitting phosphors for LEDs | |
| Haque et al. | Luminescent properties of Eu3+ activated MLa2 (MoO4) 4 based (M= Ba, Sr and Ca) novel red-emitting phosphors | |
| CN102851026B (en) | Red light material for bi-primary-color white light LEDs (light-emitting diodes) and preparation method thereof | |
| Guo et al. | Luminescent properties of UV excitable blue emitting phosphors MSr4 (BO3) 3: Ce3+ (M= Li and Na) | |
| Jiao et al. | A potential red-emitting phosphor CaSrAl2SiO7: Eu3+ for near-ultraviolet light-emitting diodes | |
| Li et al. | Cyan-emitting Ba3Y2B6O15: Ce3+, Tb3+ phosphor: a potential color converter for near-UV-excited white LEDs | |
| Ma et al. | Luminescence properties of full-color single-phased phosphors for white LEDs | |
| Liu et al. | Garnet-based red emitting phosphors Li6MLa2Nb2O12: Eu3+ (M= Ca, Sr, Ba): photoluminescence improvement by changing crystal lattice | |
| Yang et al. | Synthesis and luminescent properties of Eu3+, Eu3+/Bi3+ and Gd3+ codoped YAG: Ce3+ phosphors and their potential applications in warm white light-emitting diodes | |
| CN102876320B (en) | Cuprous complex luminescent material and preparation method thereof | |
| CN102899029B (en) | Luminescent material of cuprous iodide complex and preparation method thereof | |
| Qian et al. | Combustion synthesis and luminescence properties of NaY1− xEux (WO4) 2 phosphors | |
| Yu et al. | Tunable color emitting of CaAl2Si2O8: Eu, Tb phosphors for light emitting diodes based on energy transfer | |
| Liu et al. | Blue light excited Li6CaLa2M2O12: Eu3+ (M= Ta, Sb) red-emitting phosphors: structure and photoluminescence properties | |
| CN104194774B (en) | One class antimonio fluorescent material and preparation method thereof | |
| Lu et al. | Single-phased silicate-hosted phosphor with 660 nm-featured band emission for biological light-emitting diodes | |
| Hou et al. | Synthesis, structure and photoluminescence properties of tetragonal tungsten bronze-type Eu3+-doped K2LaNb5O15 niobate phosphor | |
| Park et al. | Synthesis and photoluminescence properties of CaGd2 (MoO4) 4: Eu3+ red phosphors | |
| Liu et al. | Structure, properties and luminescence mechanism of Sr1. 93B2O5: 0.07 Eu3+ red phosphors | |
| Sun et al. | KBaBP2O8: Eu2+: A novel near-ultraviolet converting blue phosphor for white light-emitting diodes | |
| Yu et al. | Preparation and luminescence of blue-emitting phosphor Ca2PO4Cl: Eu2+ for n-UV white LEDs | |
| Jia et al. | Electronic structure and photoluminescence properties of Eu2+-activated Ca4Si2O7F2 | |
| Li et al. | Synthesis red-emitting Ca2LaNbO6: xSm3+ phosphors for good color-rendering-index white-LED devices | |
| Li et al. | Novel energy transfer mechanism in single-phased color-tunable Sr2CeO4: Eu3+ phosphors for WLEDs |
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 |