CN106750350A - A kind of ternary RE organic frame crystalline material, its synthetic method and application - Google Patents
A kind of ternary RE organic frame crystalline material, its synthetic method and application Download PDFInfo
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Abstract
The application is related to a kind of ternary RE organic frame crystalline material, and its chemical formula is [Me2NH2][EuxTbyGd1‑x‑yL(H2O)4]；Wherein, 0 ＜ x≤0.05,0 ＜ y≤0.1；Me represents methyl；L represents the organic ligand formed by the M-phthalic acid of pyridine 2,6；The crystal belongs to rhombic system, and space group is Pnma, and the crystal belongs to rhombic system, and space group is Pnma, and cell parameter is
Description
Technical field
A kind of ternary RE organic frame crystalline material, its synthetic method and the application in temperature sensing, belong to crystal
Material Field.
Background technology
Metal-organic framework materials (metal-organic frameworks, MOFs) are one kind by metal ion or gold
Category cluster assembles the novel porous crystalline material to be formed with organic bridge ligand by coordination.Metal-organic framework materials have
There is the duct of special topological structure, the systematicness of internal arrangement and specific dimensions and shape, but frame material shows more
The physicochemical properties of big structurally variable, tunable characteristic and more horn of plenty.In luminescent metal-organic framework materials, no
Only inorganic metal ion and organic ligand can provide in luminescent properties, and frame material duct assemble guest molecule or from
Son can also produce it is luminous, additionally, the luminescent properties of frame material and chemical environment, coordination configuration, crystal structure and its and hole
The interaction of guest molecule is also all closely related in road.So, relative to other luminescent materials, luminescent metal-organic frame
The advantage of material is its various light emitting species, and its adjustable luminescent properties.Rare earth-organic framework materials
(lanthanide metal-organic frameworks) combines the excellent luminescent properties of rare earth ion and metal-have
Machine frame material emission is various informative and advantage of luminous adjustable, fluorescence detection, it is luminous with display and biomedicine into
The fields such as picture all have great application value.The similar coordination property of rare earth ion can make different rare earth ion codopes
To in same rare earth-organic framework materials, the rare earth-organic frame of doping is formed.This kind of material can possess different rare earths
Ion it is luminous, and its glow color can be adjusted by adjusting the ratio of component.Meanwhile, because concentration quenching effect subtracts
Weak or disappearance, the luminous intensity of rare earth doped-organic framework materials and life-span can also potentially get greatly enhancing.Therefore, it is this kind of
Material causes the extensive concern of people in terms of illumination field especially fluorescence thermometer and white light emitting material.
Temperature is a basic thermodynamic parameter, and it is carried out accurately in modern scientific research and technology development
Determine it is critical that.In various methods of temperature of the measurement, based on luminous detection method because its is noninvasive, accurate, quick
The characteristics of response, high-space resolution, or even adapt to receive extensive pass in the object in forceful electric power, magnetic field and quick motion
Note.Existing fluorescence thermometer, for example：Organic dyestuff, polymer, semiconductor nano, rare earth doped inorganic/organic hybrid
The sensors such as material are typically to realize TEMP with the property that temperature increase makes luminous intensity reduction using them.However,
Most fluorescence thermometer often relies on an emission peak, thus in detectable concentration, excite or detection efficiency changes, or spirit
In the case of quick property difference, measurement result is easily caused inaccurate.Codope rare earth-organic framework materials possess two kinds of rare earth ions
Characteristic luminescence, using two luminous strength ratios of characteristic luminescence, can be with self calibration, it is not necessary to additional baseline calibrate, overcome
Sensitivity is steady by detection centre concentration, excitation source stability and detector when being detected using single luminous peak intensity in the past
The defect of qualitative effect.
Carrying out temperature sensing using double rare earth-organic framework materials before this has had some to report, finds a kind of stabilization
And can detect that the material especially comprising normal temperature area and high-temperature region is still a huge challenge in wide temperature range.Mesh
Before have no the report that ternary RE-organic framework materials are studied as ratio thermometer.
The content of the invention
According to the one side of the application, there is provided a kind of ternary RE organic frame crystalline material, the material is that ternary is dilute
Earth metal organic frame compound, with heat endurance and air stability very high；Under the exciting of ultraviolet light, can send out simultaneously
Project the characteristic emission of europium ion and terbium ion, its ratio has good linear response to temperature in 77-450K, thus can be with
As in broad range of temperature sensing.
Gadolinium ion has price relatively low, the features such as not lighted in f-f transition, in traditional europium terbium binary rare-earth-have machine frame
It is ratio fluorescent thermometer gadolinium ion to be introduced on the basis of frame material and forms europium terbium gadolinium ternary doping rare earth-organic framework materials
Research provides new approaches.Meanwhile, the part of transmitting blue light is introduced, europium terbium gadolinium ternary doping rare earth-organic framework materials then may
Launch blue simultaneously, green, red three kinds light, adjusted by adjusting the ratio and excitation wavelength of doping three kinds it is luminous relatively strong
Degree, then be capable of the glow color of modulating compound and obtain white light emitting material.
The ternary RE organic frame crystalline material, its chemical formula is shown in formula I：
[Me2NH2][EuxTbyGd1-x-yL(H2O)4] Formulas I；
Wherein, 0 ＜ x≤0.05,0 ＜ y≤0.1；
Me represents methyl；
L represents the organic ligand formed by the M-phthalic acid of pyridine -2,6；
The crystal belongs to rhombic system, and space group is Pnma, and cell parameter is α=90, β=90, γ=90, Z=4.
Preferably, 0 ＜ x≤0.013 in Formulas I.It is further preferred that 0.0062≤x≤0.013；
Preferably, 0 ＜ y≤0.060 in Formulas I.It is further preferred that 0.0087≤y≤0.060.
The structural formula of the M-phthalic acid of pyridine -2,6 is as shown in Formula II：
The structure of the crystalline material is as shown in figure 1, in Pnma space groups, asymmetric cell includes that half crystallography is only
Vertical rare earth ion Eu or Tb or Gd, the part and a water of coordination molecule of half complete deprotonation.Eu or Tb or Gd take eight
The form of coordination, matches somebody with somebody with the four overseas Chinese federation carboxylate oxygen atoms and two monodentate carboxylate oxygen atoms from different ligands and two respectively
Position water oxygen Atomic coordinate., part [L]4-It is four connection modes, two of which carboxylic acid takes the bidentate coordination mode of two connections, separately
Outer two carboxylic acids then take monodentate ligand pattern.Adjacent rare earth atom Eu or Tb or Gd is connected by the carboxylate oxygen atoms of overseas Chinese federation
And it is expanded into an one-dimensional rare earth atom-carboxylic acid chain [Ln2(μ2-COO)2]n.Adjacent one-dimensional chain is by same part
Two monodentate carboxylic acid oxygen are connected and form a two-dimensional layered structure.These two-dimensional layers further connect into three-dimensional by part
Skeleton.The three-dimensional framework is negatively charged, by the dimethylamine cation balancing charges for producing in situ of DMF in reaction.
, in the case where wavelength is for the laser excitation of 335nm, fluorescence spectrum is in 545nm for the ternary RE organic frame crystalline material
With there is emission peak at 613nm；Wherein, the intensity of emission peak is reduced as temperature is raised at 545nm, emission peak at 613nm
Intensity increases as temperature is raised.
The ternary RE organic frame crystalline material launches blue, green, red primaries, by changing x and y in Formulas I
Value realizes the regulation to the ternary RE organic frame crystalline material glow color.Because the ternary RE organic frame is brilliant
Body material can send primaries, by the ratio and excitation wave that change europium element, terbium element and gadolinium element in crystalline material
It is long, thus it is possible to vary the ratio of primaries, and then realize any regulation to material emission color.
It is described according to the another aspect of the application, there is provided the method for preparing the ternary RE organic frame crystalline material
Preparation method is simple, and the yield and purity of products therefrom are high, is adapted to large-scale industrial production.
The method for preparing the ternary RE organic frame crystalline material, at least comprises the following steps：
A) by the solution I containing europium element, terbium element and gadolinium element with contain the M-phthalic acid of pyridine -2,6, N, N- diformazans
The solution II mixing of base formamide and/or DMA, obtains mixed liquor I II；
B) mixed liquor I II is placed in closed container, constant temperature is cooled to room temperature after 1~7 day at 60~150 DEG C, filters
To the crystalline material.
Preferably, the solution I containing europium element, terbium element and gadolinium element described in step a) is by europium source, terbium source and gadolinium source
It is soluble in water to obtain；
The mol ratio of gadolinium element is in terbium element and gadolinium source in europium element, terbium source in europium source：
Eu：Tb：Gd=1~10：1~10：80~98.
Preferably, the europium source is selected from least one in europium salt.It is further preferred that the europium source be selected from europium nitrate,
At least one in Europium chloride, acetic acid europium.
Preferably, the terbium source is selected from least one in terbium salt.It is further preferred that the terbium source be selected from terbium nitrate,
At least one in terbium chloride, acetic acid terbium.
Preferably, the gadolinium source is selected from least one in gadolinium salt.It is further preferred that the gadolinium source be selected from gadolinium nitrate,
At least one in gadolinium chloride, gadolinium.
Preferably, in the solution I containing europium element, terbium element and gadolinium element described in step a), europium element, terbium element and gadolinium
The molar concentration sum of element is 0.01~0.2mol/L.
Preferably, contain pyridine -2 described in step b), the solution II of 6 M-phthalic acids and DMF by
The M-phthalic acid of pyridine -2,6 is dissolved in the organic solvent containing N,N-dimethylformamide and/or DMAC N,N' dimethyl acetamide
Obtain；
In solution II, pyridine -2, the molar concentration of 6 M-phthalic acids is 0.01~0.2mol/L.
As a kind of implementation method, N, N- diethyl acetamides, dimethyl sulfoxide (DMSO), second are also contained in the organic solvent
At least one in nitrile, methyl alcohol, dioxane, tetrahydrofuran.
Preferably, by pyridine -2,6 M-phthalic acids are dissolved in DMF to solution II described in step b)
And/or obtained in N,N-dimethylformamide.
Preferably, the molal quantity sum of europium element, terbium element and gadolinium element is equal to pyridine -2 in solution II in solution I, between 6
The molal quantity of phthalic acid.
According to the another aspect of the application, there is provided a kind of method of detection temperature, it is characterised in that use above-mentioned any three
First rare earth organic frame crystalline material and/or the ternary RE organic frame crystalline material prepared according to above-mentioned any means
As temperature sensing material, temperature sensing is carried out in the range of 77K to 450K.
Used as a kind of implementation method, the method for the detection temperature includes：
A) the ternary RE organic frame crystalline material is under the laser excitation that wavelength is 335nm under detecting different temperatures
The terbium of generation5D4→7F5Emission peak peak intensity ITbWith europium5D0→7F2Emission peak peak intensity IEu, obtain a the and b values in formula III：
ITb/IEu=a-bT formula IIIs
In formula III, T is absolute temperature；
B) the ternary RE organic frame crystalline material is under the laser excitation that wavelength is 335nm under detecting temperature to be measured
The terbium of generation5D4→7F5Emission peak peak intensity ITbWith europium5D0→7F2Emission peak peak intensity IEu, it is calculated according to formula III and treats testing temperature.
The beneficial effect of the application is included but is not limited to：
1) ternary RE organic frame crystalline material provided herein, with heat endurance and air-stable very high
Property；Under the exciting of ultraviolet light, can simultaneously launch the characteristic emission of europium ion and terbium ion.And two peak intensity ratio with temperature
Degree has preferable linear relationship, is capable of achieving self calibration detection, with sensitivity is high, fast response time, strong antijamming capability etc.
Advantage.
2) ternary RE organic frame crystalline material provided herein is used for temperature sensing, can be used for temperature sensing
Scope is 77-450K.The temperature range not only also covers physiological temp area and high-temperature region comprising low-temperature space, be to realize at present
Detection temperature scope most wide.
3) ternary RE organic frame crystalline material provided herein is used for temperature test, and maximum relative sensitivity can
It is the maximum of the wide scope ratio thermometer reported at present up to 6.11%/K.
4) preparation method of crystalline material provided herein, the preparation method is simple, the yield of products therefrom and
Purity is high, is adapted to large-scale industrial production.
5) ternary RE organic frame crystalline material provided herein, can be simultaneously emitted by blue, green, red three primary colors
Light, by changing x and y values and excitation wavelength in Formulas I, can obtain the light of random color, such as white light.
Brief description of the drawings
Fig. 1 is crystal structure schematic diagram of the herein described ternary RE organic frame crystalline material along [100] direction.
Fig. 2 is to excite lower sample 1-1 in the light of 335nm wavelength#Fluorescence emission spectrum.
Fig. 3 is to excite lower sample 1-2 in the light of 335nm wavelength#Fluorescence emission spectrum.
Fig. 4 is to excite lower sample 2-1 in the light of 335nm wavelength#The fluorescence light varied with temperature in the range of 77K-450K
Spectrogram.
Fig. 5 is to excite lower sample 2-1 in 335nm#In, terbium5D4→7F5The D of emission peak and europium0→7F2Transmitting peak intensity with
The different changes of temperature.
Fig. 6 is to excite lower sample 2-1 in 335nm#In, two peak intensity ratio (I614/I544) linear relationship and temperature between.
Fig. 7 is to excite lower sample 2-1 in 335nm#Launching light cie color coordinate at different temperatures.
Fig. 8 is to excite lower sample 2-2 in 335nm#The fluorescence spectra varied with temperature in the range of 77K-450K.
Fig. 9 is to excite lower sample 2-2 in 335nm#In, terbium5D4→7F5The D of emission peak and europium0→7F2Transmitting peak intensity with
The different changes of temperature.
Figure 10 is to excite lower sample 2-2 in 335nm#In, two peak intensity ratio (I614/I544) linearly closed and temperature between
System.
Figure 11 is to excite lower sample 2-2 in 335nm#Launching light cie color coordinate at different temperatures.
Figure 12 is to excite lower sample 3-1 in the light of 335nm wavelength#The fluorescence light varied with temperature in the range of 77K-450K
Spectrogram.
Figure 13 is to excite lower sample 3-1 in the light of 335nm wavelength#In, terbium5D4→7F5The D of emission peak and europium0→7F2Hair
Penetrate difference change of the peak intensity with temperature.
Figure 14 is to excite lower sample 3-1 in the light of 335nm wavelength#In, two peak intensity ratio (I614/I544) and temperature between
Linear relationship.
Figure 15 is to excite lower sample 3-1 in the light of 335nm wavelength#Launching light cie color coordinate at different temperatures.
Figure 16 is sample 3-2#The cie color coordinate of the launching light under different excitation wavelengths.
Figure 17 is sample 3-2#Fluorescence emission spectrum under the light in 380nm, 385nm, 390nm wavelength is excited respectively.
Figure 18 is sample 1-1#~1-3#X-ray powder diffraction spectrogram and the XRD spectra pair that is obtained according to fitting data
Than.
Figure 19 is sample 2-1#~2-5#, sample 3-1#~3-3#X-ray powder diffraction spectrogram with according to fitting data
The XRD spectra contrast for obtaining.
Figure 20 is sample 2-1#High temperature XRD spectrogram.
Figure 21 is sample 2-1#Air stability test result.
Specific embodiment
With reference to embodiment in detail the application is described in detail, but the application is not limited to these embodiments.
In embodiment, fluorescence analysis uses the Fluorolog-3 type instruments of Horiba companies.
X-ray powder diffraction uses the powder diffractometers of Rigaku companies MiniFlex 600, uses CuK α radiation sources
Thermogravimetric analysis uses the thermal analyzer of the STA 449C of Netzsch companies.
Elementary analysis uses Ultima2 inductively coupled plasmas (ICP) emission spectrometer.
The M-phthalic acid of pyridine -2,6 raw material of use is purchased from Reagent Company.
The preparation of the sample of embodiment 1
At least one being added in the water of 10mL in europium source, terbium source and gadolinium source is made solution I；By the isophthalic of pyridine -2,6
(europium element molal quantity+terbium element molal quantity+gadolinium element rubs dioctyl phthalate in the molal quantity=solution I of the M-phthalic acid of pyridine -2,6
That number) it is added in the organic solvent of 10mL, obtain solution II；Solution I and solution II are well mixed, closed hydro-thermal is put into
In kettle, after keeping certain hour at a certain temperature, gained solid is centrifuged, be vacuum dried after, obtain final product the crystal material
Material.Gained sample has good stability with organic solvent in atmosphere.Elementary analysis is carried out to gained sample, obtains each
Sample corresponding x values and y values in Formulas I.
The numbering of gained crystalline material and europium source, the addition in terbium source and gadolinium source, the species for using organic solvent, holding
The relation of temperature and time, color sample/size and yield, and the relation of the result of each sample elementary analysis is as shown in table 1.
Table 1
The fluorometric investigation of embodiment 2
To the gained sample 1-1 of embodiment 1#~1-3#、2-1#~2-5#、3-1#~3-4#And pure part H4L is carried out
Fluorometric investigation.
Sample 1-1#~1-3#And pure part H4L results are as follows：
Pure part H4L under 341nm excitation wavelengths, from the broad peak of 370-475nm launch, and peak center is located at by display
412nm.Sample 1-1#Test result as shown in Fig. 2 under the exciting light of 335nm, Me2NH2·EuL(H2O)4Show
The Eu characteristic luminescences of 587nm, 610nm, 652nm, 696nm, correspond to Eu ions5D0→7FJ(J=1-4) energy level transition；Match somebody with somebody
The emission peak of body L is very weak.Sample 1-2#Test result as shown in figure 3, under the exciting light of 335nm, Me2NH2·TbL(H2O)4
The terbium ion characteristic luminescence of 489nm, 542nm, 584nm, 620nm is shown, terbium ion is corresponded to5D4→7FJ(J=6-3) energy
Order transition；The emission peak of ligand L is very weak.Sample 1-3#Under 341nm excitation wavelengths, it is shown that the blue light of ligand L.To crystal
Luminescent lifetime and quantum yield are tested, and are as a result shown：Me2NH2·EuL(H2O)4Luminescent lifetime be 0.35 millisecond, quantum
Yield is 9.75%, Me2NH2·TbL(H2O)4Luminescent lifetime be 0.47 millisecond, quantum yield is 26.30%.
Sample 2-1#~2-5#Result it is as follows：
Sample 2-1#Main glow peak is respectively 545 and 613nm under 335nm excitation peaks, its fluorescence with temperature and occur
Change (as shown in Figure 4), the characteristic luminescence peak-to-peak intensity of 613nm europium ions is raised with temperature and risen, and the spy of 545nm terbium ions
Photopeak peak intensity of levying is raised with temperature and reduces (as shown in Figure 5).The ratio of the two luminous peak intensities and temperature present compared with
Good linear relationship (as shown in Figure 6), I545/I613=13.516-0.0319T, wherein T are temperature, and I is luminous intensity；That is formula
A=13.516 in III, b=0.0319.Its glow color gradually becomes red with the change of temperature from green, its chromaticity coordinates
As shown in Figure 7.
Sample 2-2#Under 335nm excitation peaks main glow peak be 545 and 613nm, its fluorescence with temperature and change
(as shown in Figure 8)；The characteristic luminescence peak-to-peak intensity of 613nm europium ions is raised with temperature and risen, and the feature of 545nm terbium ions is sent out
Photopeak peak intensity is raised with temperature and reduces (as shown in Figure 9).The ratio of the two luminous peak intensities is presented preferable with temperature
Linear relationship (as shown in Figure 10), I545/I613=9.107-0.0207T；That is, a=9.107, b=0.0207 in formula III.Its hair
Light color gradually becomes red with the change of temperature from green, and its chromaticity coordinates is as shown in Figure 11.
Sample 2-3#~2-5#Fluorometric investigation result and above-mentioned sample 2-1#With sample 2-2#Result is approximate：Swash in 335nm
Main glow peak is 545 and 613nm under hair peak；The characteristic luminescence peak-to-peak intensity of 613nm europium ions is raised with temperature and risen, and
The characteristic luminescence peak-to-peak intensity of 545nm terbium ions is raised and reduced with temperature.The ratio of the two luminous peak intensities is in temperature
Existing preferable linear relationship.
Sample 3-1#~3-4#Result it is as follows：
Sample 3-1#Main glow peak is respectively 545 and 613nm under 335nm excitation peaks, its fluorescence with temperature and occur
Change (as shown in figure 12), the characteristic luminescence peak-to-peak intensity of 613nm europium ions is raised with temperature and risen, and 545nm terbium ions
Characteristic luminescence peak-to-peak intensity is raised with temperature and reduces (as shown in figure 13).The ratio of the two luminous peak intensities is in 77K-250K
Preferable linear relationship (as shown in figure 14), I is presented with temperature in interval545/I613=2.932-0.0587T (R2=0.989),
Wherein T is temperature, and I is luminous intensity；That is a=2.932 in formula III, b=0.0587.Its glow color is with the change of temperature
Gradually become red from yellow green, its chromaticity coordinates is as shown in figure 15.
Sample 3-2#Under 335nm excitation peaks main glow peak be 545 and 613nm, its fluorescence with temperature and change；
The characteristic luminescence peak-to-peak intensity of 613nm europium ions with temperature raise rise, and the characteristic luminescence peak-to-peak intensity of 545nm terbium ions with
Temperature is raised and reduced, and ratio and the temperature of the two luminous peak intensities are presented preferable linear relationship.Sample 3-2#In 350nm
Under the excitation wavelength of~390nm, the blue light of the fluorescence presentation part of material, the green characteristic of terbium ion are luminous and europium ion
Red characteristic luminescence three is re-emissioned.With the difference of excitation wavelength, three luminous intensities re-emissioned are varied from, so that material
It is luminous also to change therewith.When excitation wavelength changes to 390nm from 335nm, the glow color of material is changed into yellowish-white by yellow
Color eventually becomes white luminous (as shown in figure 16).Under the excitation wavelength of 380nm, 385nm, 390nm, sample 2#It is luminous fall
In white light area (as shown in figure 17), its cie color coordinate is respectively (0.36,0.34), (0.32,0.33) and (0.29,0.32),
The closely cie color coordinate (0.33,0.33) of pure white light.
Sample 3-3#~3-4#Fluorometric investigation result and above-mentioned sample 3-1#With sample 3-2#Result is approximate：Swash in 335nm
Main glow peak is 545 and 613nm under hair peak；The characteristic luminescence peak-to-peak intensity of 613nm europium ions is raised with temperature and risen, and
The characteristic luminescence peak-to-peak intensity of 545nm terbium ions is raised and reduced with temperature.The ratio of the two luminous peak intensities is in temperature
Existing preferable linear relationship.
In the emission spectrum containing europium and/or terbium, the emission peak of part is very weak, indicate the part can be very good it is quick
Change europium ion and terbium ion.
The sample structure of embodiment 3 is analyzed and heat endurance experiment
To sample 1-1#~1-3#、2-1#~2-5#、3-1#~3-4#X-ray powder diffraction test has been carried out respectively, and has been adopted
The method being fitted with powder, obtains crystallographic data.
Sample 1-1#~1-3#X-ray powder diffraction figure and the XRD that is obtained according to fitting data to such as Figure 18 institutes
Show.Sample 1-1#~1-3#Fitting result it is as shown in table 2.Sample 1-1#In bond distance's bond angle data it is as shown in table 3；Sample 1-
2#In bond distance's bond angle data it is as shown in table 4；Sample 1-3#In bond distance's bond angle data it is as shown in table 5.
By Figure 18 and Biao 2 as can be seen that the fitting XRD spectra obtained according to fitting data is consistent with actually detected result,
R1And wR2(reflection) data are small, illustrate that fitting result is accurate.
Table 2
Table 3
Symmetrical code:(i)1-x,-1/2+y,1-z；(ii)1-x,1-y,1-z；(iii)x,1/2-y,z；(iv)1/2+x,
y,3/2-z；(v)1/2+x,1/2-y,3/2-z.
Table 4
Symmetrical code:(i)1-x,-1/2+y,1-z；(ii)1-x,1-y,1-z；(iii)x,1/2-y,z；(iv)1/2+x,
y,3/2-z；(v)1/2+x,1/2-y,3/2-z.
Table 5
Symmetrical code:(i)1-x,-1/2+y,1-z；(ii)1-x,1-y,1-z；(iii)x,1/2-y,z；(iv)1/2+x,
y,3/2-z；(v)1/2+x,1/2-y,3/2-z.
Sample 2-1#~2-5#, sample 3-1#~3-4#Fitting result show, sample 2-1#~2-5#With sample 3-1#~
3-4#With sample 1-1#~1-3#Crystal structure be similar to, belong to rhombic system, space group is Pnma, and the crystal belongs to orthogonal
Crystallographic system, space group is Pnma, and cell parameter is α
=90, β=90, γ=90, Z=4.Crystal structure is as shown in Figure 1：In Pnma space groups, asymmetric cell includes half crystalline substance
Body independent rare earth ion Eu or Tb or Gd, the part and a water of coordination molecule of half complete deprotonation.Eu or Tb or Gd
Take the form of eight-coordinate, respectively with the four overseas Chinese federation carboxylate oxygen atoms and two monodentate carboxylate oxygen atoms from different ligands and
Two water of coordination oxygen atom ligands., part [L]4-It is four connection modes, two of which carboxylic acid takes the double coordination mould of two connections
Formula, two other carboxylic acid then takes monodentate ligand pattern.Adjacent rare earth atom Eu or Tb or Gd is former by the carboxylic acid oxygen of overseas Chinese federation
Son is connected and is expanded into an one-dimensional rare earth atom-carboxylic acid chain [Ln2(μ2-COO)2]n.Adjacent one-dimensional chain is matched somebody with somebody by same
Two monodentate carboxylic acid oxygen on body are connected and form a two-dimensional layered structure.These two-dimensional layers are further connected by part
Into three-dimensional framework.The three-dimensional framework is negatively charged, by the dimethylamine cation balancing charges for producing in situ of DMF in reaction.
Sample 2-1#~2-5#, sample 3-1#~3-3#X-ray powder diffraction spectrogram with obtained according to fitting data
XRD spectra contrast is as shown in figure 19.As seen from the figure, the fitting XRD spectra and actually detected knot for being obtained according to fitting data
Fruit is consistent, illustrates that fitting result is accurate.
To sample 1-1#~1-3#、2-1#~2-5#、3-1#~3-4#Thermogravimetric analysis has been carried out respectively, has as a result shown institute
Stating crystalline material can keep its skeleton structure until 480 DEG C of decomposition；To sample 1-1#~1-3#、2-1#~2-5#、3-1#~3-
4#XRD spectra is determined (with sample 2-1 under having carried out high temperature respectively#It is Typical Representative, its high temperature XRD spectrogram is as shown in figure 20), knot
Fruit shows that its crystalline framework can be stablized to 450 DEG C；Illustrate that herein described rare earth organic frame crystalline material possesses good heat
Stability.
The sample air stability test of embodiment 4
To sample 1-1#~1-3#、2-1#~2-5#、3-1#~3-4#Air stability test, specific steps have been carried out respectively
For：
By sample respectively exposed to (medial humidity is about 64%) one day, two days, three days, five days, seven in malaria
After it, its powder diffractogram is recorded respectively, and determine its structural stability with initial powder diffractogram contrast.
Result shows, sample 1-1#~1-3#、2-1#~2-5#、3-1#~3-4#XRD spectra after depositing 7 days is without too big
Change is (with sample 2-1#It is Typical Representative, its XRD spectra is changed over time as shown in figure 21), the rare earth organic frame crystal
Material can steadily in the long term exist with air in.
The above, is only several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, but and be not used to limit the application, any those skilled in the art are not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Effect case study on implementation, belongs in the range of technical scheme.
Claims (10)
1. a kind of ternary RE organic frame crystalline material, its chemical formula is shown in formula I：
[Me2NH2][EuxTbyGd1-x-yL(H2O)4] Formulas I；
Wherein, 0 ＜ x≤0.05,0 ＜ y≤0.1；
Me represents methyl；
L represents the organic ligand formed by the M-phthalic acid of pyridine -2,6；
The crystal belongs to rhombic system, and space group is Pnma, and cell parameter is α=90, β=90, γ=90, Z=4；
Preferably, 0 ＜ x≤0.013 in Formulas I；It is further preferred that 0.0062≤x≤0.013；
Preferably, 0 ＜ y≤0.060 in Formulas I；It is further preferred that 0.0087≤y≤0.060.
2. ternary RE organic frame crystalline material according to claim 1, it is characterised in that the ternary RE is organic
In the case where wavelength is for the laser excitation of 335nm, there is emission peak in fluorescence spectrum to framework crystalline material at 545nm and 613nm；
Wherein, the intensity of emission peak is reduced as temperature is raised at 545nm, and the intensity of emission peak is with temperature rising at 613nm
Increase.
3. ternary RE organic frame crystalline material according to claim 1, it is characterised in that the ternary RE is organic
Framework crystalline material launches blue, green, red primaries, organic to the ternary RE by changing the realization of the x and y values in Formulas I
The regulation of framework crystalline material glow color.
4. the method for preparing ternary RE organic frame crystalline material described in any one of claims 1 to 3, it is characterised in that extremely
Comprise the following steps less：
A) by the solution I containing europium element, terbium element and gadolinium element with contain the M-phthalic acid of pyridine -2,6, N, N- dimethyl methyls
The solution II mixing of acid amides and/or DMA, obtains mixed liquor I II；
B) mixed liquor I II is placed in closed container, constant temperature is cooled to room temperature after 1~7 day at 60 DEG C~150 DEG C, is filtrated to get
The crystalline material.
5. method according to claim 4, it is characterised in that contain europium element, terbium element and gadolinium unit described in step a)
The solution I of element is by europium source, terbium source and gadolinium source is soluble in water obtains；
The mol ratio of gadolinium element is in terbium element and gadolinium source in europium element, terbium source in europium source：
Eu：Tb：Gd=1~10：1~10：80~98.
6. method according to claim 4, it is characterised in that step a) is described to contain europium element, terbium element and gadolinium element
Solution I in, the molar concentration sum of europium element, terbium element and gadolinium element is 0.01~0.2mol/L.
7. method according to claim 4, it is characterised in that contain pyridine -2 described in step b), 6 M-phthalic acids and
The solution II of N,N-dimethylformamide is dissolved in containing N,N-dimethylformamide and/or N by the M-phthalic acid of pyridine -2,6,
Obtained in the organic solvent of N- dimethylacetylamides；
In solution II, pyridine -2, the molar concentration of 6 M-phthalic acids is 0.01~0.2mol/L.
8. method according to claim 4, it is characterised in that the molal quantity of europium element, terbium element and gadolinium element in solution I
Sum is equal to the molal quantity of the M-phthalic acid of pyridine -2,6 in solution II.
9. a kind of method for detecting temperature, it is characterised in that organic using the ternary RE described in any one of claims 1 to 3
The ternary RE organic frame that framework crystalline material and/or the method according to any one of claim 4 to 8 are prepared is brilliant
Body material carries out temperature sensing as temperature sensing material in the range of 77K to 450K.
10. method according to claim 9, it is characterised in that the method for the detection temperature includes：
A) the ternary RE organic frame crystalline material is produced in the case where wavelength is for the laser excitation of 335nm under detection different temperatures
Terbium5D4→7F5Emission peak peak intensity ITbWith europium5D0→7F2Emission peak peak intensity IEu, obtain a the and b values in formula III：
ITb/IEu=a-bT formula IIIs
In formula III, T is absolute temperature；
B) the ternary RE organic frame crystalline material is produced in the case where wavelength is for the laser excitation of 335nm under detecting temperature to be measured
Terbium5D4→7F5Emission peak peak intensity ITbWith europium5D0→7F2Emission peak peak intensity IEu, it is calculated according to formula III and treats testing temperature.
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