CN104610382A - Green fluorescent complex containing terbium and preparation method and application thereof - Google Patents
Green fluorescent complex containing terbium and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a green fluorescent complex containing terbium and a preparation method and application thereof. The chemical formula of the green fluorescent complex is [Tb2Cu3(PDC)6(H2O)12].(H2O)14(CH3CH2OH)6.5, wherein PDC is 3,4-dipicolinic acid. The preparation method comprises the following steps: mixing copper salt, terbium salt, 3,4-dipicolinic acid, triethylamine and ethyl alcohol, flowing back for 2 hours, filtering, and standing filtrate, so as to obtain microcrystal; filtering, and drying. The complex can be used as a photoluminescent material or a magnetic material. The complex is prepared with a solution method, can realize atomic-scale mixing of materials, and is good in purity of powder and high in crystal yield. The complex can be used as a fluorescence material, can present a spontaneous magnetization behavior at low temperature, and can also be used as a novel molecule-based magnetic material. The preparation method is simple, the cost is low, and the preparation process is conveniently operated and controlled.
Description
Technical field
The present invention relates to a kind of containing terbium green fluorescence title complex and its preparation method and application, belong to fluorescence complex technical field.
Background technology
Transition metal complex chemistry is cross discipline closely-related with crystallography, Organometallic Chemistry, bio-inorganic chemistry, catalytic chemistry and theoretical chemistry, and its research plays an important role for the development of these relevant cross disciplines.China has rare earth resources the abundantest in the world, carries out synthesis and the dependency Quality Research of rare earth compounding in a deep going way, and for making full use of resources advantage, development rare earth high technology industry is significant.
Organic carboxyl acid compounds, what particularly aromatic carboxylic acid was larger because its aromatic nucleus has grips rigid plane altogether, the rare earth organic carboxyl acid title complex formed by the oxygen in carboxyl and rare-earth ion coordination has good stability and luminescent properties, simultaneously, rare earth organic carboxyl acid title complex relates to much interesting luminescence phenomenon, is expected to develop into the luminescent material that light is stored, light conversion is significant with photochemical syntheses for simulation life system.
Rare earth compounding can produce the visible ray corresponding to central rare earth f-f transition after near ultraviolet region is stimulated.Its reason is: the part that excites that (l) comes from the perturbation of acceptor center ion is launched; (2) come from the excitation center emission of ions by part perturbation, namely by exciting part by radiationless intramolecular energy transfer, transmission ofenergy will be excited to central ion, and send the characteristic fluorescence of ion.
The part that is stimulated of rare earth organic complex will be excited transmission ofenergy to central rare earth by radiationless intramolecular energy transfer, make rare earth organic complex send the characteristic fluorescence of rare earth element, the part of rare earth compounding by ultraviolet or radiation of visible light occur π ?π
*or n ?π
*after absorption, lowest excited singlet state S1 is transitted to by ground state S0, again through intersystem crossing to excited triplet state T1 or T2, then by lowest excited triplet state T1, carry out energy trasfer to rare earth ion vibrational level, the ground state electron of rare earth ion is stimulated and transits to excited state, when electronics gets back to ground state by excited level, send the characteristic light of rare earth ion, complete the luminescence process of rare earth compounding.From the luminescence process of rare earth compounding, part mainly bears the effect absorbing energy and transferring energy, and the luminous intensity of rare earth compounding is relevant with the efficiency that the light absorbing efficiency of part and part shift energy to central rare earth.Therefore, when selecting part, the most important thing is to investigate the light absorbing efficiency of part, only there is the part of π key often likely to the efficient transferring energy of rare earth ion, the luminescence of sensitization rare earth ion.
In prior art, if part does not have conjugated structure and often do not have fluorescence property in title complex, even have the title complex of fluorescence property, often luminous efficiency is not high yet, have impact on its application as embedded photoluminescent material.Meanwhile, part has the three-dimensional title complex of fluorescence property, and the solvability in water or organic solvent is poor, also limit the range of application of title complex.Therefore, synthesis one can be dissolved in water or organic solvent, has the fluorescence complex of high-luminous-efficiency, seems particularly necessary.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide a kind of containing terbium green fluorescence title complex and its preparation method and application, gained has high luminous efficiency containing terbium green fluorescence title complex, its preparation method is simple to operation, and gained title complex can be used as embedded photoluminescent material or magneticsubstance.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
A kind of containing terbium green fluorescence title complex, chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, wherein, PDC is 3,4-pyridine dicarboxylic acid.
Aforementioned complex is three-D space structure, P21/n spacer, and unit cell parameters is: a=13.931 ~ 13.937nm, b=30.716 ~ 30.728nm, c=20.490 ~ 20.498nm, β=98.68 ° ~ 98.74 °,
z=4.
Further, crystal color is blue-greenish colour.
Containing a preparation method for terbium green fluorescence title complex, comprise the following steps:
(1) mantoquita and terbium salt are dissolved in deionized water, obtain solution A;
(2) 3,4-pyridine dicarboxylic acid is dissolved in ethanol, add triethylamine, obtain solution B;
(3) solution A is mixed with solution B, stir, filter and obtain solution C;
(4) solution C is left standstill, obtain crystallite, filter, be drying to obtain.
Further, preparation method comprises the following steps:
(1) by mol ratio be 2.5 ~ 3.5: 1.5 ~ 2.5 mantoquita and terbium salt dissolve in deionized water, obtain solution A;
(2) dissolved in ethanol by 3,4-pyridine dicarboxylic acid, add triethylamine, the mol ratio of 3,4-pyridine dicarboxylic acid and triethylamine is 5 ~ 7: 11 ~ 13, obtains solution B;
(3) solution A is mixed with solution B, after stirring 0.5h ~ 12h, obtain blue solution, filter and remove impurity, obtain solution C;
(4) solution C is left standstill, obtain sky blue sexangle crystallite, filter, drying at room temperature and get final product.
Containing a preparation method for terbium green fluorescence title complex, comprise the following steps:
(1) get mantoquita, terbium salt, 3,4-pyridine dicarboxylic acids and triethylamine, dissolve in ethanol, backflow, filter and obtain solution;
(2) solution left standstill after filtering, obtains crystallite, filters, is drying to obtain.
Further, preparation method comprises the following steps:
(1) get mol ratio be 2.5 ~ 3.5: 1.5 ~ 2.5: 5 ~ 7: 11 ~ 13 mantoquita, terbium salt, 3,4-pyridine dicarboxylic acids and triethylamine, be dissolved in ethanol, reflux 2 hours, filter and obtain light blue solution;
(2) solution left standstill after filtering, obtains sky blue sexangle crystallite, filters, is drying to obtain.
In aforementioned preparation process, mantoquita is the soluble salt of copper, and terbium salt is the soluble salt of terbium.
Further, in aforementioned preparation process, mantoquita is one or more in cupric chloride, cupric nitrate or copper sulfate; Terbium salt is one or more in terbium chloride, acetic acid terbium or Terbium trinitrate.
Containing the application of terbium green fluorescence title complex in embedded photoluminescent material or magneticsubstance.
In the present invention, dinicotinic acid has multiple coordination mode as shown in Figure 1.Select the green-blue crystals of a 0.2mm × 0.18mm × 0.16mm, with Xcalibur single crystal X-ray diffraction instrument, use through graphite monochromatised MoK alpha-ray (λ=0.71073nm), collect diffraction data with φ-ω scan mode.Diffracted intensity has carried out Lp correction.And having carried out empirical absorption correction, single crystal structure is solved by direct method, finds out whole non-hydrogen atom through difference Fourier synthesis method, and has carried out least-squares refinement to whole non-hydrogen atom coordinate.The molecular structure of this title complex as shown in Figure 2.As seen from Figure 2, containing exist in the unsymmetrical structure of terbium green fluorescence title complex two independently Tb1 and Tb2 ion coordination unit, three Cu ions, six there are 3 of 4 kinds of different coordination modes, 4-pyridine dicarboxylic acid molecule and 12 coordinated water molecules, 12 crystal water, 6.5 non-coordinated ethanol molecules.3,4-pyridine dicarboxylic acid is as bridge ligand.Tb1 and Tb2 ion is all nine coordinations, forms a kind of two cap pyrometric cone configurations of distortion.The Sauerstoffatom of four carboxyl oxygen atoms of two pyridine polyacid molecules, five coordinated water molecules and Tb1 coordination; The Sauerstoffatom of five carboxylate oxygen atoms and four coordinated water molecules and Tb2 ion coordination.Three Cu ions adopt two kinds of different coordination modes, Cu1 and Cu3 is pentacoordinate, form quadrangular pyramid coordination configuration.Quadrangular pyramid footing is occupied by two Sauerstoffatoms of 3,4-pyridine dicarboxylic acid and two nitrogen-atoms, and quadrangular pyramid summit is occupied by coordinated water molecule.Cu2 ion takes the octoploids structure of distortion, and six summits are occupied by three Sauerstoffatoms of 3,4-pyridine dicarboxylic acid and the Sauerstoffatom of two nitrogen-atoms and a coordinated water molecule respectively.Nitrogen-atoms always with cupric ion coordination, the carboxyl oxygen atom that 3,4-pyridine dicarboxylic acid is 4 always carries out monodentate or double coordination with cupric ion, and the carboxyl oxygen atom of 3 tends to and rare-earth ion coordination.
Rely on pyridine dicarboxylic acid as bridge ligand, form a kind of 3d-4f (transition metal-rare earth metal) expanding pore space structure with transition metal Cu and coordinate skeletonisation compound, cupric ion and pyridine dicarboxylic acid can play antenna effect, by the transmission ofenergy of UV-light to rare earth ion, title complex whole lighting efficiency is improved.
Containing terbium green fluorescence title complex structure as shown in Figure 3, have three-dimensional pore space structure as can be seen from Figure in title complex, empty radius is about 0.4nm.Table 1 is part bond distance, bond angle table.Can see that each cupric ion connects 43 by Fig. 3,4-pyridine dicarboxylic acid molecule, each 3,4-pyridine dicarboxylic acid molecule bridging two cupric ions, form an irregular two dimensional surface of expansion, cupric ion list of coordination units, between these two dimensional surfaces, is coupled together formation three-dimensional frame structure by terbium ion.Wherein Tb1 connects 4 cupric ion unit, and Tb2 connects 6 cupric ion unit.
Table 1 part bond distance bond angle table
Symmetry transformations used to generate equivalent atoms (atom of equal value produced by symmetry operation):
#1 x+1/2，-y+1/2，z+1/2；#2 x+1，y，z；#3 -x+1/2，y+1/2，-z+3/2；
#4 x-1，y，z；#5 -x-1/2，y-1/2，-z+3/2。
The test of polycrystal powder diffraction is carried out to title complex, as shown in Figure 4, according to the analogue value of single crystal structure with experiment test value is extraordinary coincide, has proved that the powder purity of preparation is higher.In order to test the stability of title complex further, carry out thermogravimetric test room temperature-750 DEG C, as shown in Figure 5.As shown in Figure 5, title complex starts to lose crystal water 65 DEG C ~ 180 DEG C scopes, and rate of weight loss is about 25%, comparatively identical with theoretical value.Title complex starts quick weight loss at 300 DEG C, and surface crystal skeleton caves in, and part occurs melting and starts to decompose.Final title complex oxygenolysis is Tb
2o
3and CuO.
Title complex can be used as embedded photoluminescent material.Ultraviolet test is carried out to title complex, has had stronger absorption peak at 270nm place, be attributed to the transition of electron of part 3,4-pyridine dicarboxylic acid.Test the fluorescence property of title complex and free ligand 3,4-pyridine dicarboxylic acid, when using 270nm as excitation wavelength, free ligand 3,4-pyridine dicarboxylic acid has emission peak at 338nm place, is attributed to the π → π of part
*or n → π
*emission peak.And in title complex, part 3, there is red shift in the emission spectrum of 4-pyridine dicarboxylic acid, appears near 360 ~ 370nm, as shown in Figure 6.Form π system more widely after showing the coordination of part 3,4-pyridine dicarboxylic acid, reduce π → π
*or n → π
*between energy difference.Fluorescence intensity improves a lot simultaneously, and after showing coordination, the system rigidity that part 3,4-pyridine dicarboxylic acid and metal ion are formed is comparatively large, reduces nonradiative loss.
When using 271nm UV-light to excite, having there are 4 stronger emission peaks in title complex, is attributed at the strongest emission peak at 545nm place in visible region
5d
4→
7f
5f-f transition of electron, luminous intensity is higher, can reach 1000a.u..Be attributed at the emission peak at 485nm, 545nm, 621nm place
5d
4→
7f
6,
55d
4→
7f
4,
5d
4→
7f
3transition of electron peak, as shown in Figure 7.
Common can poorly soluble in water or organic solvent of luminous three-dimensional title complex, gained solution luminous is weak.And in title complex water soluble of the present invention or organic solvent, solvability is good, thus make the solution formed can be luminous, and form stable luminous, expand the range of application of title complex greatly.
Title complex can be used as magneticsubstance.Title complex is tested in room temperature to the variable temperature magnetic susceptibility of 1.8K temperature range, as shown in Figure 8 under the magnetic field condition of 1000e.When 300K, the χ of title complex
mt value is 25.3cm
3kmol
-1, this and three Cu ion (C=0.375cm
3kmol
-1) and two Tb ions (S=3, L=3,
7f
6, g=3/2, C=11.815cm
3kmol
-1) theoretical value 24.8cm
3kmol
-1consistent.Along with the reduction of temperature, χ
mt value starts slowly to increase, and reaches maximum value 28.4cm when 15K
3kmol
-1.This may be because there is ferromagnetic coupling effect between metal ion.According to Curie-Weiss formula fitting respective magnetic data, obtain parameter C=24.9923cm
3kmol
-1, θ=2.06K.Less θ value illustrates that between metal ion, magnetic interaction is more weak.
Usefulness of the present invention is: of the present invention containing the preparation of terbium green fluorescence title complex employing solution method, the order spontaneous by crystal carries out self-assembly, avoids the mismatch of composition, and powder purity is good, crystal earning rate is high, can obtain the Green phosphor of pure color; This title complex relies on pyridine dicarboxylic acid to be bridge ligand, utilize transition metal Cu to form a kind of 3d-4f expanding pore space structure and coordinate skeletonisation compound, the 3d-4f title complex of preparation relies on part, greatly improve phototranstormation efficiency, cupric ion and pyridine dicarboxylic acid can play antenna effect, by the transmission ofenergy of UV-light to rare earth ion, title complex whole lighting efficiency is improved.In title complex water soluble of the present invention or organic solvent, solvability is good, makes the solution formed have stable luminous.Title complex of the present invention not only has novel geometry topological framework, also can be used as fluorescence luminescent material; And it presents spontaneous magnetization behavior at cold condition, can be used as novel molecular base magnetic material, have larger application space at material science.Preparation technology of the present invention is simple, step is few, cost is low, reaction conditions is gentle, preparation process convenient operation and control.
Accompanying drawing explanation
Fig. 1 is the multiple coordination mode figure of dinicotinic acid of the present invention;
Fig. 2 is for being intended to containing terbium green fluorescence title complex Middle molecule structural diagrams;
Fig. 3 is for containing terbium green fluorescence title complex three-dimensional structure schematic diagram;
Fig. 4 is the polycrystal powder diffractogram containing terbium green fluorescence title complex;
Fig. 5 is for containing terbium green fluorescence title complex thermogravimetric curve figure;
Fig. 6 is the fluorescence emission spectrum of pyridine dicarboxylic acid when 270nm excites in title complex;
Fig. 7 is for containing terbium green fluorescence title complex visible region fluorescence emission spectrum when 271nm excites;
Fig. 8 is the variable temperature magnetic susceptibility figure containing terbium green fluorescence title complex.
Embodiment
Below in conjunction with specific embodiment, the present invention is further introduced.
All raw materials are commercially available prod, analytical pure.
Embodiment 1
A kind of containing terbium green fluorescence title complex, chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, wherein, PDC is 3,4-pyridine dicarboxylic acid, is obtained by following steps:
(1) get mol ratio be 2.5: 1.5: 5: 11 cupric chloride, terbium chloride, 3,4-pyridine dicarboxylic acids and triethylamine, dissolve in ethanol, reflux 2 hours, filtration obtains light blue solution;
(2) solution left standstill after filtering, obtains sky blue sexangle crystallite, filters, is drying to obtain.Yield 45%.
Embodiment 2
A kind of containing terbium green fluorescence title complex, chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, wherein, PDC is 3,4-pyridine dicarboxylic acid, is obtained by following steps:
(1) get mol ratio be 3.5: 2.5: 7: 13 cupric nitrate, acetic acid terbium, 3,4-pyridine dicarboxylic acids and triethylamine, dissolve in ethanol, reflux 2 hours, filtration obtains light blue solution;
(2) solution left standstill after filtering, obtains sky blue sexangle crystallite, filters, is drying to obtain.Yield 45%.
Embodiment 3
A kind of containing terbium green fluorescence title complex, chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, wherein, PDC is 3,4-pyridine dicarboxylic acid, is obtained by following steps:
(1) by mol ratio be 3: 2 copper sulfate and Terbium trinitrate dissolve in deionized water, obtain solution A;
(2) dissolved in ethanol by 3,4-pyridine dicarboxylic acid, add triethylamine, the mol ratio of 3,4-pyridine dicarboxylic acid and triethylamine is 6: 12, obtains solution B;
(3) solution A is mixed with solution B, after stirring 30min, obtain blue solution, filter and remove impurity, obtain solution C;
(4) solution C is left standstill, obtain sky blue sexangle crystallite, filter, drying at room temperature and get final product.Yield 46%.
Embodiment 4
A kind of containing terbium green fluorescence title complex, chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, wherein, PDC is 3,4-pyridine dicarboxylic acid, is obtained by following steps:
(1) by mol ratio be 2.8: 1.9 mantoquita and terbium salt dissolve in deionized water, mantoquita is the mixture of cupric chloride and cupric nitrate, and terbium salt is the mixture of terbium chloride, acetic acid terbium and Terbium trinitrate, obtains solution A;
(2) dissolved in ethanol by 3,4-pyridine dicarboxylic acid, add triethylamine, the mol ratio of 3,4-pyridine dicarboxylic acid and triethylamine is 5.5: 12.5, obtains solution B;
(3) solution A is mixed with solution B, stir and obtain blue solution after 12 hours, filter and remove impurity, obtain solution C;
(4) solution C is left standstill, obtain sky blue sexangle crystallite, filter, drying at room temperature and get final product.Yield 46%.
Embodiment 5
A kind of containing terbium green fluorescence title complex, chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, wherein, PDC is 3,4-pyridine dicarboxylic acid, is obtained by following steps:
(1) by mol ratio be 3.3: 1.7 mantoquita and terbium salt dissolve in deionized water, mantoquita is the mixture of copper sulfate and cupric nitrate, and terbium salt is the mixture of terbium chloride and acetic acid terbium, obtains solution A;
(2) dissolved in ethanol by 3,4-pyridine dicarboxylic acid, add triethylamine, the mol ratio of 3,4-pyridine dicarboxylic acid and triethylamine is 6.5: 11.5, obtains solution B;
(3) solution A is mixed with solution B, stir and obtain blue solution after 8 hours, filter and remove impurity, obtain solution C;
(4) solution C left standstill, obtain sky blue sexangle crystallite, filter, air drying obtains containing terbium green fluorescence title complex powder.Yield 45%.
Embodiment 6
A kind of containing terbium green fluorescence title complex, chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, wherein, PDC is 3,4-pyridine dicarboxylic acid, is obtained by following steps:
(1) by mol ratio be 2.6: 2.2 mantoquita and terbium salt dissolve in deionized water, mantoquita is the mixture of cupric chloride, nitric acid copper and copper sulfate, and terbium salt is the mixture of terbium chloride and Terbium trinitrate, obtains solution A;
(2) dissolved in ethanol by 3,4-pyridine dicarboxylic acid, add triethylamine, the mol ratio of 3,4-pyridine dicarboxylic acid and triethylamine is 5.2: 12.8, obtains solution B;
(3) solution A is mixed with solution B, stir and obtain blue solution after 10 hours, filter and remove impurity, obtain solution C;
(4) solution C is left standstill, obtain sky blue sexangle crystallite, filter, drying at room temperature and get final product.Yield 45%.
Embodiment 7
A kind of containing terbium green fluorescence title complex, chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, PDC is 3,4-pyridine dicarboxylic acid, is obtained by following steps:
(1) get mol ratio be 3: 2: 6: 12 mantoquita, terbium salt, 3,4-pyridine dicarboxylic acids and triethylamine, dissolve in ethanol, reflux 2 hours, filtration obtains light blue solution, and mantoquita is the mixture of chlorination copper and copper sulfate, and terbium salt is the mixture of acetic acid terbium and Terbium trinitrate;
(2) solution left standstill after filtering, obtains sky blue sexangle crystallite, filters, is drying to obtain.Yield 46%.
Prepare in above embodiment containing terbium green fluorescence title complex, have fluorescence property, in title complex water soluble or organic solvent, the solution of formation has stable luminous, and therefore title complex can be used as embedded photoluminescent material.Title complex presents spontaneous magnetization behavior at cold condition, can be used as novel molecular base magnetic material.
Claims (10)
1., containing a terbium green fluorescence title complex, it is characterized in that: chemical formula is [Tb
2cu
3(PDC)
6(H
2o)
12] (H
2o)
14(CH
3cH
2oH)
6.5, wherein PDC is 3,4-pyridine dicarboxylic acid.
2. according to claim 1 containing terbium green fluorescence title complex, it is characterized in that: described title complex is three-D space structure, P21/n spacer, unit cell parameters is: a=13.931 ~ 13.937nm, b=30.716 ~ 30.728nm, c=20.490 ~ 20.498nm, β=98.68 ° ~ 98.74 °
z=4.
3. according to claim 2 containing terbium green fluorescence title complex, it is characterized in that: crystal color is blue-greenish colour.
4. the preparation method containing terbium green fluorescence title complex as described in any one of claims 1 to 3, is characterized in that: comprise the following steps:
(1) mantoquita and terbium salt are dissolved in deionized water, obtain solution A;
(2) 3,4-pyridine dicarboxylic acid is dissolved in ethanol, add triethylamine, obtain solution B;
(3) solution A is mixed with solution B, stir, filter and obtain solution C;
(4) solution C is left standstill, obtain crystallite, filter, be drying to obtain.
5. the preparation method containing terbium green fluorescence title complex according to claim 4, is characterized in that: comprise the following steps:
(1) by mol ratio be 2.5 ~ 3.5: 1.5 ~ 2.5 mantoquita and terbium salt dissolve in deionized water, obtain solution A;
(2) dissolved in ethanol by 3,4-pyridine dicarboxylic acid, add triethylamine, the mol ratio of 3,4-pyridine dicarboxylic acid and triethylamine is 5 ~ 7: 11 ~ 13, obtains solution B;
(3) solution A is mixed with solution B, after stirring 0.5h ~ 12h, obtain blue solution, filter and remove impurity, obtain solution C;
(4) solution C is left standstill, obtain sky blue sexangle crystallite, filter, drying at room temperature and get final product.
6. the preparation method containing terbium green fluorescence title complex as described in any one of claims 1 to 3, is characterized in that: comprise the following steps:
(1) get mantoquita, terbium salt, 3,4-pyridine dicarboxylic acids and triethylamine, be dissolved in ethanol, backflow, filter and obtain solution;
(2) solution left standstill after filtering, obtains crystallite, filters, is drying to obtain.
7. the preparation method containing terbium green fluorescence title complex according to claim 6, is characterized in that: comprise the following steps:
(1) get mol ratio be 2.5 ~ 3.5: 1.5 ~ 2.5: 5 ~ 7: 11 ~ 13 mantoquita, terbium salt, 3,4-pyridine dicarboxylic acids and triethylamine, be dissolved in ethanol, reflux 2 hours, filter and obtain light blue solution;
(2) solution left standstill after filtering, obtains sky blue sexangle crystallite, filters, is drying to obtain.
8. the preparation method containing terbium green fluorescence title complex according to any one of claim 4 ~ 7, it is characterized in that: described mantoquita is the soluble salt of copper, described terbium salt is the soluble salt of terbium.
9. the preparation method containing terbium green fluorescence title complex according to claim 8, is characterized in that: described mantoquita is one or more in cupric chloride, cupric nitrate or copper sulfate; Described terbium salt is one or more in terbium chloride, acetic acid terbium or Terbium trinitrate.
10. as described in any one of claims 1 to 3 containing the application of terbium green fluorescence title complex in embedded photoluminescent material or magneticsubstance.
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| CN105859757A (en) * | 2016-04-26 | 2016-08-17 | 广东工业大学 | 8-hydroxyquinoline terbium complex tetramer crystal as well as preparation method and application thereof |
| CN105921177A (en) * | 2016-04-26 | 2016-09-07 | 东南大学 | Rare earth luminescence catalyst, and preparation method and applications thereof |
| CN107056826A (en) * | 2017-05-22 | 2017-08-18 | 东北大学 | A kind of rare earth Pr complexs and its preparation method and application |
| CN107141311A (en) * | 2017-05-18 | 2017-09-08 | 东北大学秦皇岛分校 | A kind of metal organic complex containing Dy and its preparation method and application |
| CN110078933A (en) * | 2019-04-30 | 2019-08-02 | 华南农业大学 | Novel coordination polymer crystalline material and preparation method thereof and fluorescent applications |
| CN114716688A (en) * | 2022-05-17 | 2022-07-08 | 山西大学 | Terbium complex and preparation method and application thereof |
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| CN105859757B (en) * | 2016-04-26 | 2017-12-05 | 广东工业大学 | A kind of polycrystal of 8 hydroxyquinoline class rare-earth terbium complex four, its preparation method and its application |
| CN105921177B (en) * | 2016-04-26 | 2018-12-14 | 东南大学 | A kind of rare earth luminous catalyst and its preparation method and application |
| CN107141311A (en) * | 2017-05-18 | 2017-09-08 | 东北大学秦皇岛分校 | A kind of metal organic complex containing Dy and its preparation method and application |
| CN107141311B (en) * | 2017-05-18 | 2019-09-27 | 东北大学秦皇岛分校 | One kind metal organic complex containing Dy and its preparation method and application |
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| CN110078933A (en) * | 2019-04-30 | 2019-08-02 | 华南农业大学 | Novel coordination polymer crystalline material and preparation method thereof and fluorescent applications |
| CN114716688A (en) * | 2022-05-17 | 2022-07-08 | 山西大学 | Terbium complex and preparation method and application thereof |
| CN114716688B (en) * | 2022-05-17 | 2022-12-30 | 山西大学 | Terbium complex and preparation method and application thereof |
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