CN104194774B - One class antimonio fluorescent material and preparation method thereof - Google Patents
One class antimonio fluorescent material and preparation method thereof Download PDFInfo
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- CN104194774B CN104194774B CN201410424241.9A CN201410424241A CN104194774B CN 104194774 B CN104194774 B CN 104194774B CN 201410424241 A CN201410424241 A CN 201410424241A CN 104194774 B CN104194774 B CN 104194774B
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Abstract
The application relate to a kind of ultraviolet light can change into high intensity visible ray compound, and its production and use.With glyoxaline ion liquid, chlorine source, antimony source and water for raw material, after being dissolved in organic solvent, obtain through removing solvent.Preparation technology is simple, raw material environmental friendliness and cheap and easy to get, and quantum yield is up to more than 70%, and products obtained therefrom purity is high, and fluorescence property is excellent, good stability, is very easily processed processing, and is the desirable fluorescent material for LED and relevant display, illuminating device.
Description
Technical field
The application relates to the class antimonio fluorescent material and preparation method thereof for light emitting diode, fluorescent lamp and other associated light fields.Described material is electric light illuminating material, belongs to fluorescent material field
Background technology
Semiconductor lighting, refers to the semiconductor light-emitting-diode (light-emittingdiode, the be called for short LED) solid state lighting as light source, is a kind of emerging technology.Because it has the plurality of advantages not available for traditional electric source lighting, such as: energy-saving and environmental protection, long service life, volume are little, fast response time, shock-resistant etc., thus inviting domestic and international many leading companys to put into huge fund be engaged in research and the product development of association area, wherein Ya Co., Ltd. of Japan develops high-brightness blue LED first based on GaN, making LED manufacturer can produce three primary colors (red, green and blue) LED, being possibly realized so that realizing 16,700,000 colors；PHILIPS Co. of Holland is made that a lot of effort in the domestic applications of LED；Other also Germany Osram-photo semiconductor company, Hewlett-Packard company of the U.S. etc..
In all kinds of LED product, white light LEDs, owing to efficiency is high and brightness is big, 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 generally all on chip coating fluorescent powder to realize white light emission, i.e. fluorescent conversion type white light LEDs.Typical example such as 1997 Nian Ya companies utilize InGaN blue chip to excite the YAG:Ce fluorescent material of gold-tinted to produce first commercial white light-emitting diodes.Thus, all kinds of high-efficiency fluorescence powder are prepared by one of key technology realizing white light LEDs.No matter ultraviolet conversion type fluorescent material (excitation wavelength 200～350nm) or near ultraviolet conversion phosphor (excitation wavelength 350～450nm), its major part patent is all grasped by developed country.The fluorescent material with independent intellectual property right of development of new has important practical significance.
Existing fluorescent material is broadly divided into inorganic fluorescent material and the big class of organic fluorescence materials two, and inorganic fluorescent material has the advantage that stability is higher, but more or less has again some shortcomings simultaneously, for instance: synthesis temperature is higher, and energy resource consumption is more；Wherein applying the composition lacking HONGGUANG in more aluminate fluorescent powder spectrum, color rendering index is not high；Silicate fluorescent powder emission peak is narrow, and humidity is more sensitive；Nitride phosphor manufacturing cost is higher；Sulphide fluorescent material is more sensitive etc. to humidity.Organic fluorescence materials synthesis temperature generally relatively low (less than 200 DEG C), but heat stability aspect is not as inorganic material.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 is not only likely to effectively merge inorganic fluorescent material good stability and the high advantage of organic fluorescence materials quantum efficiency, the high consumption to the energy of the conventional inorganic fluorescent material high-temperature nuclei can also be avoided, and the interaction of organic moiety and inorganic part, it is possible to realize high quantum yield.
Ionic liquid, as a kind of room temperature molten salt, has the feature such as insignificant vapour pressure and high heat stability, and wherein the ionic liquid containing alkyl imidazolium cation is most commonly seen.If it can be used as organic moiety to be incorporated in hybrid fluorescent material, it is possible to the character of material is produced important impact, for instance can be incorporated in product by character relatively low for fusing point, material is made to be prone to processing and device.On the other hand, ionic liquid both as reactant, can dissolve other reactants as solvent again, thus realizing at a lower temperature being fully contacted and augmenting response speed with other reactants, this will greatly save the energy, have important effect in Green Chemistry.Combining with ionic liquid cation and metal complex anion, forming the class ionic liquid structure containing metal is the effective means realizing high-efficiency fluorescence powder.More external seminars possess some special knowledge in this respect, for instance the ionic liquid [C containing rare earth metal that the ionic liquid that Mudring etc. (Angew.Chem.Int.Ed., the 2008,47, the 7635th 7638 page) report is formed with rare earth metal6MIm]5-x[Dy(SCN)8-x(H2O)x] (x=0～2) except there is fluorescence property, also there is magnetic；Chinese patent CN103073500A also illustrates a class and has the rare earth ion liquid Cat of fluorescence and magnetic+(Ln[NO3]6)3-；[BMIm] that Nockemann etc. (J.Am.Chem.Soc., 2006,128,13658-13659 page) reportx-3[Ln(NCS)x(H2O)y] (x=6-8；Y=0-2；x+y<10；Ln=Y, La-Yb), all can prepare below 100 DEG C, rare earth element therein maintains good photoluminescence performance, the part of ionic liquid then make it inherit fusing point is not high, be prone to processing feature.In transition metal, the existing fluorescence ion liquid [C containing Au, AgnMIm][M(CN)2] (M=Au, Ag, n=12,14,18) (DaltonTrans., the 2010,39, the 10574th 10576 page) and the fluorescence ion liquid [C containing MnnMIm]2[MnX4] and [CnMIm][Mn(Tf2N)3] (n=2,3,4,6, X=Cl-、Br-) (Chem.Eur.J., the 2010,16, the 3355th 3365 page) be in the news.By contrast, this compounds containing main group metal is then rarely reported, and only has been reported that an example Bi3+There is the Near-Infrared Photoluminescence phenomenon (Opt.Lett., 2011,36,100-102 page) of liquid as the ionic liquid of activator doping
But, from existing compound, the compound containing rare earth, Au, Ag drastically increases its cost due to metal fancy price, and anion is [Tf2N]-The building-up process of ionic liquid also complex, cause that price is costly, and the quantum yield of this kind of fluorescence ion liquid containing metal reported general not high (being up to 65.3%: Chinese patent CN103073500A).Additionally, there are a lot of species not occur in end product in the raw material that adds in preparation process of this compounds reported, atom utilization is low, does not meet Atom economy, simultaneously because the generation of by-product and cause the difficulty of separation.Therefore, utilize metal cheap and easy to get and ionic liquid, the method that easy to use and atom utilization is high, prepare the fluorescent material with high quantum production rate and remain a challenge.
Summary of the invention
For solving above-mentioned technical problem, the application provides a kind of compound, it is characterised in that have structural formula as shown in formula (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 ring1、R2、R3Separately optional from hydrogen, C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Alkynyl.
The application provides a kind of compound, it is characterised in that have structural formula as shown in formula (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 ring1For methyl；R2Optional from C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Alkynyl；R3For hydrogen or methyl.
In the application, C1-C8Alkyl refers to the alkyl that carbon number is 1～8, containing straight chained alkyl with the alkyl of side chain；Described C2-C8Thiazolinyl refers to the thiazolinyl that carbon number is 2～8, containing straight-chain alkenyl with the thiazolinyl of side chain；C2-C8Alkynyl refers to the alkynyl that carbon number is 2～8, containing straight-chain alkynyl with the alkynyl of side chain.
As one preferred embodiment, described C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Any hydrogen atom in alkynyl can independently by optional from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical substituent group replace.Such as the methyl (C that carbon number is 11Alkyl) go up the nitrile methyl-CH that any hydrogen is formed by itrile group replacement2-CN, carbon number is the straight chain octyl (C of 88Alkyl) arbitrarily hydrogen is substituted by phenyl the phenyl-octane base-(CH of formation in upper terminal methyl group2)8-Ph etc..
As one preferred embodiment, the substituent R on imidazole ring in formula (1)1、R2、R3Separately optional from C3-C6Alkyl, C3-C6Thiazolinyl, C3-C6Alkynyl, wherein C3-C6Alkyl, C3-C6Thiazolinyl, C3-C6Any hydrogen atom in alkynyl can independently by optional from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical substituent group replace.
As one preferred embodiment, it is characterised in that in formula (1)Optionally (it is abbreviated as [BMIm] from 1-butyl-3-Methylimidazole. ion+), 1-benzyl-3-Methylimidazole. ion (be abbreviated as [BzMIm]+), 1-butyl-2,3-Methylimidazole. ion (be abbreviated as [BMMIm]+), 1-propyl group-3-Methylimidazole. ion (be abbreviated as [PrMIm]+), 1-carboxymethyl-3-Methylimidazole. ion (be abbreviated as [HOOCMMIm]+) at least one therein or at least one therein (be abbreviated as [-OOCMMIm with 1-carboxylate radical methyl-3-Methylimidazole.+]) combination.In described formula (1)Optionally (it is abbreviated as [BMIm] from 1-butyl-3-Methylimidazole. ion+), 1-benzyl-3-Methylimidazole. ion (be abbreviated as [BzMIm]+), 1-butyl-2,3-Methylimidazole. ion (be abbreviated as [BMMIm]+), 1-propyl group-3-Methylimidazole. ion (be abbreviated as [PrMIm]+), 1-carboxymethyl-3-Methylimidazole. ion (be abbreviated as [HOOCMMIm]+) at least one therein and 1-carboxylate radical methyl-3-Methylimidazole. (be abbreviated as [-OOCMMIm+]) combination, refer in formula (1)Optional combination at least one in 1-carboxylate radical methyl-3-Methylimidazole. with 1-butyl-3-Methylimidazole. ion, 1-benzyl-3-Methylimidazole. ion, 1-butyl-2,3-Methylimidazole. ion, 1-propyl group-3-Methylimidazole. ion, 1-carboxymethyl-3-Methylimidazole. ion.
In the application, described compound is the crystalline compound formed by ionic liquid cation and antimony chloride anion,For ionic liquid cation, inorganic anion can use formula [SbCly]3-yRepresenting, this compound can be expressed from the next:Formula (1), for ease of statement, hereinafter abbreviated as: [R1R2R3Im]x[SbCly][H2O]z.Wherein: Im is imidazolesR1、R2、R3For the substituent group on imidazole ring in formula (1), x is the integer in 2～6 scopes, and y is 5 or 6, z is 0 or 1.
Typically, there is the compound of structural formula as shown in formula (1) have:
[BMIm]2[SbCl5], BMIm=1-butyl-3-Methylimidazole. ion, this compound crystal belongs to Cc space group, and its cell parameter is: β=102.004 (2) °,Z=12.This compound has two emission peaks of 480nm and 583nm under the exciting of ultraviolet light, and the intensity at its peak changes along with the change of excitation wavelength.Being 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 ultraviolet light, its solid state quantum productivity is 86.3%, and fluorescence lifetime is 4.275 μ s.
[HOOCMMIm]3[SbCl6], HOOCMMIm=1-carboxymethyl-3-Methylimidazole. ion, this compound crystal belongs to P21/ c space group, cell parameter is: β=114.991 (6) °,Z=4.This compound can send the yellowish green light of 533nm under the exciting of 350nm ultraviolet light, and to record its solid state quantum productivity be 73.19%, and fluorescence lifetime is 3.185 μ s.
[HOOCMMIm]3[OOCMMIm]3[SbCl6][H2O], HOOCMMIm=1-carboxymethyl-3-Methylimidazole. ion, OOCMMIm=1-carboxylate radical methyl-3-Methylimidazole., this compound crystal belongs to R-3 space group, and cell parameter is: Z=3.This compound, under the exciting of 365nm ultraviolet light, can send the green glow of 510nm, and to record its solid state quantum productivity be 84.74%, and fluorescence lifetime is 2.033 μ s.
Three of the above is only the Typical Representative of herein described compound, and herein described have the compound of structural formula as shown in formula (1) and be not limited to this.
The another purpose of the application is in that the preparation method providing described compound, solves the problems such as fluorescent material field existing materials synthesis temperature is higher, cost is high, complex process.Described preparation method cost is low, simple process, energy-conserving and environment-protective (all can prepare below 100 DEG C), atom utilization are high, and reactant used almost can realize 100% conversion, eliminates the separation difficulty that by-product brings.
As a kind of embodiment, the preparation method of described compound, it is characterised in that including at least following steps:
A) glyoxaline ion liquid, chlorine source, antimony source and water are mixed, obtain having imidazoles construction unit in glyoxaline ion liquidAntimony element, chlorine element, water molar ratio beSb:Cl:H2The mixture of O=2～6:1:5～6:0～1；
B) step a) gained mixture is dissolved in organic solvent, removes organic solvent, obtain described compound.
Preferably, imidazoles construction unit in glyoxaline ion liquid in the described mixture of step a)Antimony element, chlorine element, water molar ratio are the stoichiometric proportion in formula (1),Sb:Cl:H2O=x:1:y:z；Wherein, x is optionally from 2,3,4,5,6；Y optionally from 5,6, z optionally from 0,1.
In described mixture, H2When the molar ratio of O is 0, without water of crystallization in gained compound crystal.
Those skilled in the art can according to the stoichiometric proportion of target compound or mol ratio, select the proportioning raw materials needed, should be appreciated that, part material can freely change addition in rational scope, the generation of target compound can not be affected under certain condition, only with the open certain embodiments of relatively inexpensive scheme in the application.
In the application, described glyoxaline ion liquid is contain in cationThe ionic liquid of construction unit, with anion, for instance the compound that halide ion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc. are formed.Wherein substituent R1、R2、R3Separately optional from hydrogen, C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Alkynyl；Described C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Any hydrogen atom in alkynyl can independently by optional from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical substituent group replace.
As one preferred embodiment, the substituent R on glyoxaline ion liquid imidazole ring1、R2、R3Separately optional from C3-C6Alkyl, C3-C6Thiazolinyl, C3-C6Alkynyl；Described C3-C6Alkyl, C3-C6Thiazolinyl, C3-C6Any hydrogen atom in alkynyl can independently by optional from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical substituent group replace.
As one preferred embodiment, described glyoxaline ion liquid is contain in cationThe ionic liquid of construction unit, with anion, for instance the compound that halide ion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc. are formed.Wherein R1For methyl；R2Optional from hydrogen, C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Alkynyl；R3For hydrogen or methyl.Described C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Any hydrogen atom in alkynyl can independently by optional from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical substituent group replace.
In the application, chlorine source is optionally from the material containing chlorine element.Preferably, chlorine source is optionally from containing chloride ion Cl-Compound in one or more.Chlorine source can come from independent interpolation, it is also possible to from glyoxaline ion liquid and/or antimony source.When not chloride in glyoxaline ion liquid and antimony source, or chloride less when being not enough to reach chlorinity in target mixture, it is necessary to separately add other chlorine source；When chloride in glyoxaline ion liquid and/or antimony source, and when chlorine sufficiently achieves chlorinity in target mixture, then need not separately add other chlorine source.Such as, described preparation method chlorination 1-propyl group-3-Methylimidazole. ionic liquid and Butter of antimony. are raw material, and the chlorine in chlorination 1-propyl group-3-Methylimidazole. ionic liquid and Butter of antimony. is chlorine source, it is not necessary to additionally add other chlorine sources.
Preferably, chlorine source is from the glyoxaline ion liquid containing chloride ion and/or the antimony source containing chloride ion.
In the application, described antimony source, it is possible to for any material containing antimony element；Preferably, optional from containing one or more in trivalent antimony ionic compound；It is further preferred that 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, according to specific embodiment, the organic solvent being suitable for, it is possible to dissolve all reactants and volatile organic solvent all can reach to prepare the purpose of target material.The amount that organic solvent adds, under the premise that can dissolve reactant, those skilled in the art arbitrarily can select in rational scope.
Preferably, described organic solvent, optionally one or more in methanol, ethanol, acetonitrile；It is further preferred that described organic solvent is ethanol.
According to general knowledge known in this field, those skilled in the art can according to concrete reactant, organic solvent and the requirement to product, ensure that under the premise that reactant fully dissolves in ionic liquid, selective response thing dissolves temperature and the dissolution time of employing in organic solvent in suitable scope.
Preferably, in described step b), mixture is dissolved in the process of organic solvent, and temperature is 20～200 DEG C, and mixture keeps a period of time to be completely dissolved to mixture after dissolving in this temperature range, then removes organic solvent；Further preferably, in described step b), mixture is dissolved in the process of organic solvent, the temperature range upper limit is optionally from 100 DEG C, 150 DEG C, 200 DEG C, temperature range lower limit is optionally from 20 DEG C, 50 DEG C, 90 DEG C, mixture is kept for no more 48 hours after dissolving in this temperature range, then removes organic solvent；It is further preferred that mixture is dissolved in the process of organic solvent in described step b), temperature is 50～150 DEG C, and mixture keeps 1～3 hour after dissolving in this temperature range, then removes organic solvent；It is further preferred that mixture is dissolved in the process of organic solvent in described step b), temperature is 80 DEG C, and mixture keeps 2 hours after dissolving in this temperature range, then removes organic solvent.
The another purpose of the application is in that to provide a kind of fluorescent material, it is characterised in that containing described arbitrary compound with formula (1) structural formula and/or the compound prepared according to any of the above-described method.
Described fluorescent material can make ultraviolet light be converted into visible ray.
The another purpose of the application is in that to provide a kind of fluorescent lamp, it is characterised in that containing described arbitrary compound with formula (1) structural formula and/or the compound prepared according to any of the above-described method.
The another purpose of the application is in that to provide a kind of light emitting diode, it is characterised in that containing described arbitrary compound with formula (1) structural formula and/or the compound prepared according to any of the above-described method.
Quantum yield in the application, refers to fluorescence quantum yield, refers to that the molecule being returned to ground state in excited state molecule by emitting fluorescence accounts for the mark of whole excited state molecule.
Fluorescence in the application, refer to a kind of photo-induced cold luminescence phenomenon, when certain room temperature material irradiates through the incident illumination (usually ultraviolet or X ray) of certain wavelength, absorb luminous energy laggard enter excited state, subsequently de excitation send out and send emergent light (usual wavelength ratio incident illumination wavelength long, at visible light wave range).
In the application, Im is imidazoles ,-CN to be itrile group ,-OH be hydroxyl ,-Ph are phenyl ,-Bz to be benzyl ,-COOH be carboxyl ,-COO are carboxylate radical, M to be methyl, Pr be propyl group, B are butyl, HOOCM is carboxymethyl.
Should be understood that within the scope of herein disclosed technical scheme, above-mentioned each technical characteristic of the application and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus constituting new or preferred technical scheme.As space is limited, tired no longer one by one state at this.
Compared with prior art, the application has the advantages that
(1) having synthesized a class antimony Sb based compound of novel burst of ultraviolel, gained compound has good fluorescence property, and relatively stable, cheap and easy to get and be prone to storage.
(2) the purely inorganic fluorescent material that synthetic method is more traditional is compared comparatively gentle, and namely major part can be prepared below 100 DEG C, and preparation process is relatively simple, and atom utilization is high, and quantum yield is more than 70%, and energy resource consumption is little.The compound using metallic antimony also efficiently avoid expensive rare earth compound as raw material, is the fluorescent material of a kind of Cheap highly effective.
(3) when in described compound without H2When O, although be solid at normal temperatures, but still there is the feature of ionic liquid.Also as fusing point is high and have the feature of easily processing except environmental protection.Such as just can by [BMIm] at 76 DEG C2[SbCl5] melt, then covering the surface of purple LED bulb equably, this compound has high quantum yield, it is possible to the ultraviolet close to 90% is converted into bright yellow visible light, significantly reduces possible ultraviolet light and pollutes the injury that human body is caused.
Accompanying drawing explanation
Fig. 1 is sample 1# [BMIm]2[SbCl5] crystal structure schematic diagram.
Fig. 2 is sample 2# [HOOCMMIm]3[SbCl6] crystal structure schematic diagram.
Fig. 3 is sample 3# [HOOCMMIm]3[OOCMMIm]3[SbCl6][H2O] crystal structure schematic diagram.
Fig. 4 is sample 1# [BMIm]2[SbCl5] X-ray powder diffraction.
Fig. 5 is sample 2# [HOOCMMIm]3[SbCl6] X-ray powder diffraction.
Fig. 6 is sample 3# [HOOCMMIm]3[OOCMMIm]3[SbCl6][H2O] X-ray powder diffraction.
Fig. 7 is sample 1# [BMIm]2[SbCl5] excitation spectrum.
Fig. 8 is sample 1# [BMIm]2[SbCl5] emission spectrum.
Fig. 9 is sample 2# [HOOCMMIm]3[SbCl6] excitation and emission spectra.
Figure 10 is sample 3# [HOOCMMIm]3[OOCMMIm]3[SbCl6][H2O] excitation and emission spectra.
Detailed description of the invention
The features described above that the application mentions, or the feature that embodiment is mentioned can be in any combination.The disclosed all features of present specification can with any composition forms use, each feature disclosed in description, it is possible to identical by any offer, impartial or similar purpose alternative characteristics replaces.Therefore except having special instruction, disclosed feature to be only impartial or similar features general example.
Below in conjunction with embodiment, the application is expanded on further.Should be understood that these embodiments are merely to illustrate the application rather than restriction scope of the present application.The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition or according to manufacturer it is proposed that condition.When not doing specified otherwise, raw material used in this application, buy each through commercial sources, directly use without special handling.
If no special instructions, in embodiment, the test condition of sample is as follows:
X ray powder diffraction material phase analysis (XRD) carries out on the MiniFlex2 type X-ray diffractometer of Rigaku company, Cu target, K α radiation source (λ=0.154184nm).
Excitation and emission spectra carries out on the LS55 type Fluorescence spectrophotometer of PerkinElmer company.
X ray single crystal diffraction carries out on the XcaliburE type single crystal diffractometer of Agilent company, Mo target, K α radiation source (λ=0.07107nm), tests temperature 295K.And by Shelxtl97 to carrying out structure elucidation.
The preparation of embodiment 1 sample 1#～sample 5#
By the proportioning mixing shown in table 1 of glyoxaline ion liquid, chlorine source, antimony source and water, add organic solvent, it is heated to uniform temperature being stirred continuously and is completely dissolved to system transparent, after keeping a period of time to form supersaturated solution, cool down and be stirred continuously to there being clear crystal to precipitate out, after crystal precipitates out completely, using absolute ethanol washing two to three times under room temperature, the dry organic solvent that removes can obtain respective sample.Temperature in sample number into spectrum and reactant ratio, organic solvent kind, course of dissolution and the time, the product that keep at such a temperature are as shown in table 1.
Table 1 sample number into spectrum, proportioning raw materials, relation between preparation condition and product
The structural characterization of embodiment 2 sample
Adopt x-ray single crystal diffraction that sample 1#～sample 5# is characterized, and by Shelxtl97, sample structure resolved.Result shows, sample 1#～sample 5# is respectively provided with formula shown in formula (1), describes in detail with sample 1#～sample 3# for Typical Representative below.
Wherein, the crystal structure of sample 1# is obtained by x-ray single crystal diffraction, as shown in Figure 1.Sample 1# crystal belongs to Cc space group, and its cell parameter is: β=102.004 (2) °,Z=12.The ball of ater big in Pyramid in Fig. 1 represents Sb atom, and the ball of the grey black being attached thereto represents Cl atom, and the black ball on five-membered ring represents that atom N, linen ball represent C atom, and the ball of white represents H atom.The powder XRD pattern of sample 1# is composed as shown in Figure 4, simulates the theoretical XRD diffracting spectrum obtained according to its crystal structure, as simulated shown in peak spectrogram below Fig. 4, sample peak above Fig. 4 is actually measured diffraction pattern, two figure compare, and peak position is consistent, it was shown that gained sample is pure phase.
The crystal structure of sample 2# is obtained by x-ray single crystal diffraction, as shown in Figure 2.Sample 2# crystal belongs to P21/ c space group, cell parameter is: β=114.991 (6) °,Z=4.The ball of ater bigger in Fig. 2 represents Sb atom, and the ball of the grey black being attached thereto represents that Cl atom, the dotted line between Sb and one of them Cl atom represent secondary key.Black ball on five-membered ring represents atom N, and linen ball represents C atom, and the ball of Lycoperdon polymorphum Vitt represents O atom, and the ball of white represents H atom, and visible in order to become apparent from, the H atom being connected with C atom in figure is omitted.The powder XRD pattern spectrum of sample 2# as it is shown in figure 5, simulate the theoretical XRD diffracting spectrum obtained according to crystal structure, as simulated shown in peak spectrogram below Fig. 5, sample peak above Fig. 5 is actually measured diffraction pattern, two figure compare, and peak position is consistent, it was shown that gained sample is pure phase..
The crystal structure of sample 3# is obtained by x-ray single crystal diffraction, as shown in Figure 3.Sample 3# crystal belongs to R-3 space group, and cell parameter is: Z=3.The ball of ater bigger in Fig. 3 represents Sb atom, and the ball of the grey black being attached thereto represents that Cl atom, the dotted line between Sb and one of them Cl atom represent secondary key.Black ball on five-membered ring represents atom N, and linen ball represents C atom, and the ball of Lycoperdon polymorphum Vitt represents O atom, and the ball of white represents H atom, and visible in order to become apparent from, the H atom being connected with C atom in figure is omitted.The powder XRD pattern of sample 2# is composed as shown in Figure 6, simulates the theoretical XRD diffracting spectrum obtained according to its crystal structure, as simulated shown in peak spectrogram below Fig. 6, sample peak above Fig. 6 is actually measured diffraction pattern, two figure compare, and peak position is consistent, it was shown that gained sample is pure phase.
Embodiment 3
The excitation spectrum of sample 1# as it is shown in fig. 7, emission spectrum as shown in Figure 8.It can be seen that sample 1# has two emission peaks of 480nm and 583nm under the exciting of ultraviolet light, and the intensity at its peak changes along with the change of excitation wavelength.Being 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 ultraviolet light, its solid state quantum productivity is 86.3%, and fluorescence lifetime is 4.275 μ s.
The excitation and emission spectra of sample 2# is as shown in Figure 9, it can be seen that sample 2# can send the yellowish green light of 533nm under the exciting of 350nm ultraviolet light, and to record its solid state quantum productivity be 73.19%, and fluorescence lifetime is 3.185 μ s.
The excitation and emission spectra of sample 3# is as shown in Figure 10, it can be seen that sample 3#, under the exciting of 365nm ultraviolet light, can send the green glow of 510nm, and to record its solid state quantum productivity be 84.74%, and fluorescence lifetime is 2.033 μ s..
Embodiment 4
Sample 1# is placed at 76 DEG C and is melted into liquid sample 1#, dip operative liquid sample 1# with the ultraviolet LED bulb that can launch 365～370nm, and make liquid sample 1# namely have the light of yellow to send after LED bulb surface solidification, energising under room temperature.
Embodiment 5
0.2g sample 1# is positioned on the circular glass sheet of 1 diameter 50mm, after melting at 76 DEG C, uses other sheet glass slightly to press it to be dispersed in bottom sheet glass to liquid.Then turn off heating to sample 1# again crystallization, obtain the sample 1# thin film being substrate with sheet glass, this thin film is placed under the irradiation of uviol lamp, it is possible to demonstrate characteristic fluorescence.
The above, it is only several embodiments of the application, not the application is done any type of restriction, although the application discloses as above with preferred embodiment, but and be not used to restriction the application, any those skilled in the art, without departing from the scope of technical scheme, the technology contents utilizing the disclosure above makes a little variation or modification is all equal to equivalence case study on implementation, belongs within the scope of technical scheme.
Claims (16)
1. a compound is as the application of fluorescent material, it is characterised in that described compound has the structural formula as shown in 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 ring1、R2、R3Separately optional from hydrogen, C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Alkynyl.
2. compound according to claim 1 is as the application of fluorescent material, it is characterised in that have structural formula as shown in 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 ring1For methyl；R2Optional from C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Alkynyl；R3For hydrogen or methyl.
3. compound according to claim 1 is as the application of fluorescent material, it is characterised in that described C1-C8Alkyl, C2-C8Thiazolinyl, C2-C8Any hydrogen atom in alkynyl can independently by optional from itrile group, hydroxyl, phenyl, carboxylic acid group, carboxylate radical substituent group replace.
4. compound according to claim 1 is as the application of fluorescent material, it is characterised in that in formula (1)The optional at least one or therein at least one combination with 1-carboxylate radical methyl-3-Methylimidazole. in 1-butyl-3-Methylimidazole. ion, 1-benzyl-3-Methylimidazole. ion, 1-butyl-2,3-Methylimidazole. ion, 1-propyl group-3-Methylimidazole. ion, 1-carboxymethyl-3-Methylimidazole. ion.
5. compound according to claim 1 is as the application of fluorescent material, it is characterised in that the preparation method of described compound includes at least following steps:
A) glyoxaline ion liquid, chlorine source, antimony source and water are mixed, obtain having in imidazole-like ionic liquidAntimony element, chlorine element, water molar ratio beSb:Cl:H2The mixture of O=2～6:1:5～6:0～1；
B) step a) gained mixture is dissolved in organic solvent, removes organic solvent, obtain described compound.
6. compound according to claim 5 is as the application of fluorescent material, it is characterised in that in the described mixture of step a) in imidazole-like ionic liquidThe stoichiometric proportion that antimony element, chlorine element, water molar ratio are in formula (1) isSb:Cl:H2O=x:1:y:z；
Wherein, x is optionally from 2,3,4,5,6；Y optionally from 5,6, z optionally from 0,1.
7. compound according to claim 5 is as the application of fluorescent material, it is characterised in that step a) chlorine source is from the glyoxaline ion liquid containing chloride ion and/or the antimony source containing chloride ion.
8. compound according to claim 5 is as the application of fluorescent material, it is characterised in that described antimony source is one or more in the compound containing trivalent antimony ion optionally.
9. compound according to claim 5 is as the application of fluorescent material, it is characterised in that described antimony source is Butter of antimony..
10. compound according to claim 5 is as the application of fluorescent material, it is characterised in that described organic solvent is one or more in methanol, ethanol, acetonitrile optionally.
11. compound according to claim 5 is as the application of fluorescent material, it is characterised in that described organic solvent is ethanol.
12. compound according to claim 5 is as the application of fluorescent material, it is characterized in that, in described step b), mixture is dissolved in the process of organic solvent, temperature is 20～200 DEG C, mixture keeps a period of time to be completely dissolved to mixture after dissolving in this temperature range, then removes organic solvent.
13. compound according to claim 5 is as the application of fluorescent material, it is characterized in that, in described step b), mixture is dissolved in the process of organic solvent, and temperature is 50～150 DEG C, mixture keeps 1～3 hour after dissolving in this temperature range, then removes organic solvent.
14. compound according to claim 1 is as the application of fluorescent material, it is characterised in that ultraviolet light can be made to be converted into visible ray.
15. a fluorescent lamp, it is characterised in that containing the fluorescent material described in good grounds any one of claim 1-14.
16. a light emitting diode, it is characterised in that containing the fluorescent material described in good grounds any one of claim 1-14.
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| 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 |
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| 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 |
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| 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 |
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| Novel organic–inorganic hybrid ferroelectric: bis(imidazolium)pentachloroantimonate(III), (C3N2H5)2SbCl5;Anna Piecha等;《J. Mater. Chem.》;20111123;第22卷;333-336 * |
| Structure of chloroantimonates(III) with an imidazolium cation: (C3H5N2)[SbCl4] and (C3H5N2)2[SbCl5];Maciej Bujak等;《Journal of Molecular Structure》;20030228;121-128 * |
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