CN108586764A - A kind of zinc-base fluorescent material and preparation method thereof synthesized by solvent-induced strategy - Google Patents
A kind of zinc-base fluorescent material and preparation method thereof synthesized by solvent-induced strategy Download PDFInfo
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Abstract
The zinc-base fluorescent material and preparation method thereof that the invention discloses a kind of to be synthesized by solvent-induced strategy, belongs to organic inorganic hybridization technical field of compound preparation.The present invention has synthesized three kinds of products by solvent-induced：The first compound [Zn5(bdcpp)3(DMF)(H2O)4]n, molecular formula C66H42N4O29Zn5, belong to C2/m space groups；Second of compound [Zn2(bdcpp)(Hbdcpp)]n, molecular formula C42H19N2O16Zn2, belong to P ī space groups；The third compound [Zn2(bdcpp)(DMF)(H2O)2]n, molecular formula C24H20N2O11Zn2, belong to C2/c space groups.The present invention uses cheap inorganic zinc salt and organic carboxyl acid for reactant, has synthesized three homologous MOFs materials with distinct structure feature by hydro-thermal method, has been the new product of laboratory synthesis；The present invention be it is a kind of the chemical reagent of any costliness is not added by the solvent-induced zinc-base fluorescent material synthesized, product luminous intensity is significantly stronger than starting material；Three MOFs material synthesis methods of the present invention are identical, and synthesis section is not overlapped, and is easy to industrialize, be can be widely applied to the fields such as chemical probe, biomarker, power-saving technology, imaging technique.
Description
Technical field
The invention belongs to organic and inorganic chemistry hybrid molecule technical field of material, and specially one kind is by solvent-induced
The zinc-base fluorescent material and preparation method thereof of strategy synthesis.
Background technology
In recent years, by metal or metal cluster and organic ligand assembling metal-organic framework materials (abbreviation：MOFs research)
Cause the extensive concern of vast chemistry and materialogy worker.Function MOFs materials are in gas storage, separation, sensing
The fields such as device, catalysis, bionical, photoelectric material and magnetic material present tempting foreground.The fast development of MOFs materials is based on
The diversity and designability of metal node and connection primitive, carry to construct novel topology and charming function MOFs materials
More selections are supplied.Meanwhile some external factor in MOFs building-up processes also influence formation, structure and the work(of MOFs materials
Can, e.g., solvent (ratio, polarity), crystallization temperature, pH value, rate of temperature fall, template, additional kind of crystalline substance etc..Crystal engineering it is final
Target is to realize the controlledly synthesis of molecular self-assembling in solid material, however consider based on above-mentioned factor, regulates and controls MOFs materials
The synthesis of material is still a huge challenge.Wherein, solvent is as the important factor in order in MOFs materials synthesis, to material
Micro-structure formation play an important roll.Solvent can be used as ligand to participate in coordination in MOFs materials synthesis；It can also be used as
Guest molecule fills duct；Ligand and object dual role can also be played the part of simultaneously；In addition, solvent is also used as structure directing
Agent, the induction composite structure even various metal organic framework of property.Currently, in the document of report, system research synthesis
The solvent effects of MOFs materials it is relatively fewer [GAO Lijuan, Wang Li, Wang Shengyan, the refined wave of well, Chemical Journal of Chinese Universities, 2016,37
(9):1589]。
In MOFs material assembling process, aromatic carboxy acid compound has rotatable flexible carboxylic group,
Carboxyl has different deprotonation degree, can not only be used as hydrogen-bond donating body but also can be used as Hydrogen Bond Acceptors, be good
Function construction unit, can be with the various MOFs materials of construction structure.Wherein, bis- (2', the 4'- phthalic acid) pyridines of 2,6-
(H4Bdcpp) there are one undersaturated pyridine groups on molecular skeleton, and porous structure is advantageously formed as rigid ligand, and
The aromatic carboxylic acid ligand can be selected to construct MOFs materials in conjunction with stable wheel paddle structure is formed positioned at 2- two carboxyls
With topological structure it is various and have excellent performance characteristic [J.Zhao, Y.-N.Wang, W.-W.Dong, Y.-P.Wu, D.-S.Li,
Q.-C.Zhang,Inorg.Chem.,2016,55(7):3265]。
Using traditional solution reaction, organic ligand and inorganic metal salt directly mixing would generally be generated into unknown precipitation
The molecular structure of object, product is very single.In order to obtain the crystal prototype that suitable single crystal diffraction test needs, the hot method of hydrothermal/solvent
It is a kind of ideal synthetic method, efficient, inexpensive, easy to operate, the experimental method of this " one kettle way " tends to
To some unexpected experimental results.Therefore, very convenient using the hot method of hydrothermal/solvent in synthesis.To target starting material
Carried out a large amount of hydrothermal/solvent thermal synthesis it was found that, solvent plays key effect to the synthesis of MOFs materials.Pass through tune
The volume ratio of whole two kinds of solvent DMFs and deionized water has obtained the totally different MOFs materials of three kinds of structures.DMF and water are as conventional
Polar solvent, derive from a wealth of sources, it is of low cost.Meanwhile starting material is identical, and the raw material purchased is needed significantly to subtract in synthesis
It is few, and the equipment used in synthesizing is less, and its equipment can be used mutually in the building-up process of three kinds of materials, be conducive to significantly drop
Low cost.
Up to the present, at home and abroad have tentatively by the method that solvent ratios adjust control synthesis fluorescence MOFs materials
Development, the fluorescent material synthesized using this method can be widely applied to chemical probe, imaging, biomarker, illumination, energy saving skill
The various fields such as art, imaging technique.
Invention content
1. technical problems to be solved by the inivention
It is an object of the invention to reduce the cost of raw material of conventional synthesis luminescent material, Widening Technique scope and selection to use
Material range simplifies production technology, provides a kind of zinc-base fluorescent material and preparation method thereof synthesized by solvent-induced strategy.This
Three zinc-base fluorescence MOFs materials that invention provides are constructed by homologous starting material, structure novel, the fluorescence radiation of batch material
Intensity is big, and preparation method is identical, is the new product of laboratory synthesis, is not seen in any report；Its synthesis technology is simple, former material
Expect that source is sufficient and cheap, low energy consumption, synthetic product is easy to get and can be adjusted to product species using solvent ratios as variable
Control, control methods are simple and practicable.
2. technical solution
The technical solution adopted by the present invention is：
A kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the present invention includes three kinds of homologous MOFs, structural formula
For：The first compound [Zn5(bdcpp)3(DMF)(H2O)4]n(referred to as：1), molecular formula C66H42N4O29Zn5；Second
Compound [Zn2(bdcpp)(Hbdcpp)]n(referred to as：2), molecular formula C42H19N2O16Zn2；The third compound [Zn2
(bdcpp)(DMF)(H2O)2]n(referred to as：3), molecular formula C24H20N2O11Zn2；Wherein bdcpp is bis- (2', the 4'- benzene of 2,6-
Dioctyl phthalate) pyridine, DMF N, N '-dimethyl formamide.
Compound 1 recited above belongs to monoclinic system, C2/m space groups, and cell parameter is： α=γ=90 °, β=102.728 (3) °；Compound 2
Belong to anorthic system, P ī space groups, cell parameter is：α=
95.789 (7) °, β=106.877 (7) °, γ=90.060 (7) °；Compound 3 belongs to monoclinic system, C2/c space groups, structure cell ginseng
Number is： α=γ=90 °, β=118.713 (6) °.
The zinc-base fluorescence MOFs materials recited above synthesized by solvent-induced strategy, synthetic method are：Hydro-thermal method.
The preparation method of zinc-base fluorescent material recited above, include the following steps for：
1) by inorganic zinc salt and 2, bis- (2', 4'- phthalic acid) the pyridine powders of 6- are added in reaction vessel, inorganic zinc salt
Molar ratio with bis- (2', the 4'- phthalic acid) pyridines of 2,6- is 1~2：1；
2) DMF and deionized water mixed solution are added in reaction vessel obtained by step 1), the DMF and deionized water of addition
Volume ratio be from 2：1 arrives DMF pure phases, stirs 5min；
3) few drops of concentrated nitric acids are added to rubber head dropper in step 2) gained mixed solution, the quantity of concentrated nitric acid is 1-3
Drop；
4) mixed solution obtained by step 3) is transferred in the closed steel bomb with polytetrafluoroethyllining lining, 90~
1~3d is reacted under 110 DEG C of self-generated pressures, then cooled to room temperature is washed, and is filtered, and is spontaneously dried, obtained it is described by
Three kinds of compounds of solvent-induced strategy synthesis.
Further, the mass fraction of the concentrated nitric acid described in step 1) is 63%.
Further, the inorganic zinc salt described in step 2) is zinc sulfate or zinc nitrate or zinc acetate.
3. advantageous effect
Using technical solution provided by the invention, compared with existing known technology, there is following remarkable result：
(1) a kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the invention, raw material are cheap and easy to get, the source of goods fills
Foot, using cheap inorganic zinc salt and 2, bis- (2', the 4'- phthalic acid) pyridines of 6- are reactant, using DMF and water as polarity
Solvent has obtained three homologous fluorescence MOFs materials with distinct structure feature by preparation method of hydro-thermal method.
(2) a kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the invention is the new product of laboratory synthesis,
Its synthesis technology and synthesis device are simple, and the reaction time is quick, and reaction process is easily controllable, and final product type is more, product kind
Class governing factor is clear, no coupling product, and experiment favorable reproducibility, ultimate yield are high.
(3) a kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the invention does not add in building-up process any
Expensive chemical reagent, the luminous intensity of material are significantly stronger than bis- (2', the 4'- phthalic acid) pyridines of 2,6-, three MOFs materials
Crystal starting material is homologous and synthetic method is identical, synthesis section be not overlapped, be easy to industrialize, can be widely applied to chemical probe,
The various fields such as imaging, biomarker, illumination, power-saving technology, imaging technique.
Description of the drawings：
Fig. 1 be the present invention a kind of zinc-base fluorescent material synthesized by solvent-induced strategy in 1 zinc atom coordination mould
Formula figure (atom being not marked in figure is carbon atom)；
Fig. 2 be the present invention a kind of zinc-base fluorescent material synthesized by solvent-induced strategy in 1 two-dimensional double-layer frame diagram；
Fig. 3 be the present invention a kind of zinc-base fluorescent material synthesized by solvent-induced strategy in 2 zinc atom coordination mould
Formula figure (atom being not marked in figure is carbon atom)；
Fig. 4 be the present invention a kind of zinc-base fluorescent material synthesized by solvent-induced strategy in 2 two-dimension single layer frame diagram；
Fig. 5 be the present invention a kind of zinc-base fluorescent material synthesized by solvent-induced strategy in 3 zinc atom coordination mould
Formula figure (atom being not marked in figure is carbon atom)；
Fig. 6 be the present invention a kind of zinc-base fluorescent material synthesized by solvent-induced strategy in 3 wheel paddle Zn2(COO)4With
The one-dimensional loop chains figure that organic ligand is constituted；
Fig. 7 be the present invention a kind of zinc-base fluorescent material synthesized by solvent-induced strategy in three MOFs thermogravimetric analysis
Figure；
Fig. 8 is bis- for three MOFs and 2,6- in a kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the present invention
The solid fluorescence collection of illustrative plates of (2', 4'- phthalic acid) pyridine.
Specific implementation mode：
To further appreciate that present disclosure, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1
In order to reduce the cost of raw material, Widening Technique scope and selection timber range, simplify production technology, inventor passes through
Deep theory analysis and a large amount of exploratory compound experiment verifications, provide one kind and synthesizing zinc-base phosphor by solvent-induced strategy
The perfect scheme of material：Cheap ZnSO is used in experiment4·7H2Bis- (2', the 4'- phthalic acid) pyridines of O and 2,6- are reactant,
Using DMF and water as solvent, above-mentioned zinc-base fluorescence MOFs materials can be prepared using hydro-thermal method.
The specific preparation method of the present embodiment is：
As Figure 1-Figure 8, by 0.2mmol ZnSO4·7H2Bis- (2', the 4'- phthalic acid) pyrroles of O and 0.2mmol 2,6-
Pyridine powder is added in reaction vessel, under agitation, DMF and deionized water mixed solution 15mL is added to above-mentioned system
In, it is stirred to react 5min；The concentrated nitric acid that 1 drop mass fraction is 63% is add to the above mixed solution, 5min is stirred, by institute
It obtains mixed solution to be transferred in the closed steel bombs of the 25mL with polytetrafluoroethyllining lining, be reacted under 105 DEG C of self-generated pressures
3d；Then natural cooling filters, and washs, and spontaneously dries, has obtained the zinc-base fluorescent material.As DMF and deionization water body
Accumulating ratio is：DMF/H2When O=7/3, the bulk crystals 1 of rule, yield 0.069g, with bis- (2', the 4'- benzene two of 2,6- have been obtained
Formic acid) pyridine be reference, yield is about 61%, infrared data (KBr, cm–1)：3404,3068,2790,2486,2359,
1654,14387,1369,1253,1174,1102,1023,923,818,781,731,697,569,483.When in dicyandiamide solution
Including when entering minute quantity deionized water, some colourless bulk crystals 2, yield 0.047g, with bis- (2', the 4'- benzene of 2,6- have been obtained
Dioctyl phthalate) pyridine be reference, yield is about 50%, infrared data (KBr, cm–1)：3404,3068,2790,2486,2359,
1654,14387,1369,1253,1174,1102,1023,923,818,781,731,697,569,483.When in dicyandiamide solution
It is not aqueous, when all DMF, obtain colourless bulk crystals 3, yield 0.074g, with 2,6- bis- (2', 4'- phthalic acids)
Pyridine is reference, and yield is about 57%, infrared data (KBr, cm–1)：3430,2934,2358,1666,1497,1437,
1379,1253,1171,1103,1062,819,788,734,667,568,485.
Pass through Bruker SMART APEX II CCD X-rays single crystal diffractometer, Bruker D8ADVANCE type powder
X-ray diffractometer, Nicolet Avatar 360FTIR ESP types Fourier infrared spectrographs (KBr tablettings), METTLER-
TOLEDO TGA/STDA 851eType synchronous solving and Hitachi F-7000 type Fluorescence Spectrometer conjunctive uses are to this
The novel zinc-base fluorescent material of embodiment synthesized by solvent-induced strategy carries out the analysis of microstructure and physicochemical property.
The crystal structure determination synthesized by solvent-induced strategy：
Under stereomicroscope choose suitable dimension novel zinc-base fluorescence MOFs materials 1-3 monocrystal at room temperature into
Row crystal structure is tested, and radiation source is the Mo-K alpha rays purified through graphite monochromatorCrystal structure makes
It is determined with SHELXS-97 program direct methods, then passes through SHELXL-97 complete matrix least square method F2Refine amendment is to structure
Convergence is present in the highly disordered object in compound 1 and 2 skeletons using the SQUEEZE programs processing in PLATON softwares
Molecule and anion, to all non-aqueous H atoms using theoretical plus H method, to the H atom difference Fourier method of hydrone
It is determined.
Crystal data is as follows：
Molecular structural data is as follows, wherein bond distanceBond angle (°)：
Symmetrical code：1:#1x,y,z+1；#2x,-y+1,z；#3-x,-y+1,-z+2；#4-x,y,-z+2；#5x,-y,
z.2:#1-x+1,-y+1,-z+2；#2-x,-y,-z+2；#3x,y+1,z.3:#1-x+1,y,-z+1/2；#2x,y-1,z.
As depicted in figs. 1 and 2, in compound 1, the centers Zn1 are four-coordination patterns, and coordination geometry is tetrahedron structure
Type is connected with three carboxyl oxygen atoms of three bdcpp ligands and a ligand hydrone respectively, and the center Zn2, Zn3 and Zn4 is
Pentacoordinate pattern, coordination geometry is tetragonal pyramid configuration.Wherein, four 2- carboxyls that two Zn2 pass through two bdcpp ligands
The wheel paddle unit of a standard is connected and composed, axial direction is the DMF molecules of two coordinations；Adjacent Zn3 and Zn4 and Zn2 structures
At wheel paddle structure it is the same, also by carboxyl form wheel paddle unit.Four Zn1 and four wheel paddle cell formations are similar at one
The quadrangle star secondary structure unit SBUs of macrocycle molecule porphyrin, these quadrangle star structural units are connected by the centers Zn1, in c-axis
Direction leans to each other constitutes 1D chain structures, and further, between the star 1D chains of quadrangle taking turns paddle by Zn2-Zn2 extends to 2D bilayers
Structure.In compound 2 (as shown in Figure 3 and Figure 4), two kinds of Zn (II) centers are all pentacoordinate patterns, take the four of distortion
Side's cone geometric configuration, adjacent two Zn1 constitute wheel paddle list by four carboxyls of the bdcpp ligands of two complete deprotonations
Member, axial position are the Hbdcpp ligands of two part deprotonations；Two adjacent Zn2 also constitute wheel paddle unit.It is four long
Spend similar Zn2(COO)4Wheel paddle is connected with each other with four organic ligands, irregular square grid is formed, if by these
Cubic grid is interconnected to constitute 2D single layer veils as basic unit, then neighbouring grid.(such as Fig. 5 and figure in compound 3
Shown in 6), Zn1 and Zn2 are pentacoordinate pattern { ZnO5, form rectangular pyramid coordination polyhedrom, Zn1 and two bdcpp anion
Four carboxyl coordinations formed Zn2(COO)4Paddle structure is taken turns, and DMF molecules occupy axial position；Zn2 and two bdcpp ligand
Two carboxyls and the effect of two water of coordination molecule, by Zn2(COO)4Two organic ligands of paddle structure and connection are taken turns as 4-
The Zn2 interconnections of c nodes and 2-c nodes form a regular one-dimensional loop chain structure.
Thermogravimetric analysis is carried out to the three zinc-base MOFs materials synthesized by solvent-induced strategy of the present embodiment：Amount of samples
About 10mg, 25-1000 DEG C of temperature range, 10 DEG C/min of heating rate, with high purity N2As protection gas.As shown in fig. 6, chemical combination
Object 1-3 does not have mass loss in the range of less than 50 DEG C, 55 DEG C and 90 DEG C respectively.Temperature increase after, thermogravimetric curve continuously into
It has gone weightless several times, may include losing unknown unordered solvent molecule, ligand solvent molecule etc., and continue to that base metal has
Machine frame structure, which starts to disintegrate, caves in, until obtaining final product ZnO.Compound 1 is finished in 530 DEG C of weightlessness, and main framing is whole
Degradation, obtains 22.03% final product ZnO.Compound 2 is finished in 540 DEG C of weightlessness, obtains 17.15% final product
ZnO.Start at 90 DEG C to lose coordination guest molecule in compound 3, then main body frame starts to collapse at 220 DEG C of inflection points, directly
It all degrades to 535 DEG C of skeletons, obtained final product is ZnO.Thermogravimetric analysis shows the zinc-base MOFs material powders of the present embodiment
End shows good thermal stability, can meet the thermal stability requirement in practical application.
Solid fluorescence performance test is carried out to the three zinc-base MOFs materials synthesized by solvent-induced strategy of the present embodiment：
Free ligand H4Bdcpp generates emission peak by 340nm excitations at 390nm.To MOFs materials 1-3 at 290nm
Excitation, three kinds of materials produce stronger fluorescence emission peak at 357nm, 363nm, 353nm respectively.The transmitting spectral peak of product and
Free ligand H4Compared to there is apparent blue shift, emission band should be attributed to the fact that with internal π → π * transition bdcpp.Study carefully it
Root, spectral peak blue shift may be because of the coordination between Zn/bdcpp, the high forces between wheel paddle structure and crystal heap
HOMO-LUMO spacing is increased when product to result in internal electric charge transfer ILCT.With bis- (2', the 4'- phthalic acid) pyrroles of 2,6-
Pyridine H4The emission spectrum of bdcpp compares, and the emission peak of three compounds is very sharp, and it is special to show as excellent fluorescence spectrum
Property.
A kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the present embodiment, raw material are cheap and easy to get, the source of goods fills
Foot has obtained three homologous fluorescence MOFs materials with distinct structure feature, building-up process by preparation method of hydro-thermal method
In do not add the chemical reagent of any costliness, the luminous intensity of material is significantly stronger than bis- (2', the 4'- phthalic acid) pyridines of 2,6-,
Three MOFs material crystals starting materials are homologous and synthetic method is identical, and synthesis section is not overlapped, and is easy to industrialize, and environmental protection is without dirt
Dye, low energy consumption.The zinc-base fluorescent material synthesized by solvent-induced strategy of the present embodiment has good application value.
A kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the present embodiment, can be widely applied to chemical probe,
The various fields such as imaging, biomarker, illumination, power-saving technology, imaging technique.
Embodiment 2
As Figure 1-Figure 8, the preparation side of a kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the present embodiment
Method, substantially with embodiment 1, the difference is that：The process that the present embodiment prepares novel zinc-base fluorescent material is：
By 0.3mmol ZnSO4·7H2Bis- (2', 4'- phthalic acid) the pyridine powders of O and 0.2mmol 2,6- are added to instead
It answers in container, under agitation, DMF and deionized water mixed solution 15mL is added in above-mentioned system, are stirred to react
5min；The concentrated nitric acid that 2 drop mass fractions are 63% is add to the above mixed solution, 5min is stirred, by gained mixed solution
It is transferred in the closed steel bombs of the 25mL with polytetrafluoroethyllining lining, reacts 2d under 95 DEG C of self-generated pressures；Then natural
It is cooling, it filters, washs, spontaneously dry, obtained the zinc-base fluorescent material, the wherein yield of crystal 1 is 0.072g, crystal
2 yield is 0.051g, and the yield of crystal 3 is 0.078g.
Embodiment 3
As Figure 1-Figure 8, the preparation side of a kind of zinc-base fluorescent material synthesized by solvent-induced strategy of the present embodiment
Method, substantially with embodiment 1, the difference is that：The process that the present embodiment prepares novel zinc-base fluorescent material is：
By 0.4mmol ZnSO4·7H2Bis- (2', 4'- phthalic acid) the pyridine powders of O and 0.2mmol 2,6- are added to instead
It answers in container, under agitation, DMF and deionized water mixed solution 15mL is added in above-mentioned system, are stirred to react
5min；The concentrated nitric acid that 3 drop mass fractions are 63% is add to the above mixed solution, 5min is stirred, by gained mixed solution
It is transferred in the closed steel bombs of the 25mL with polytetrafluoroethyllining lining, reacts 1d under 85 DEG C of self-generated pressures；Then natural
It is cooling, it filters, washs, spontaneously dry, obtained the zinc-base fluorescent material.Wherein the yield of crystal 1 is 0.075g, crystal
2 yield is 0.056g, and the yield of crystal 3 is 0.080g.
A kind of preparation method of zinc-base fluorescent material synthesized by solvent-induced strategy described in Examples 1 to 3 is experiment
The new product of room synthesis, raw material are cheap and easy to get, ample supply and prompt delivery, and synthesis technology and synthesis device are simple, and the reaction time is quick,
Reaction process is easily controllable, and final product type is more, and product category governing factor is clear, no coupling product, experiment favorable reproducibility, most
Whole yield is high, and synthesis section is not overlapped, and is easy to industrialize, environment friendly and pollution-free, low energy consumption, has good application value,
It can be widely applied to the various fields such as chemical probe, imaging, biomarker, illumination, power-saving technology, imaging technique.
Claims (5)
1. a kind of zinc-base fluorescent material synthesized by solvent-induced strategy, it is characterised in that：By solvent-induced, there are three types of final
The structural formula of product, wherein the first compound is：[Zn5(bdcpp)3(DMF)(H2O)4]n(referred to as：1), molecular formula is
C66H42N4O29Zn5, belong to monoclinic system, C2/m space groups, cell parameter is： α=γ=90 °, β=102.728 (3) °；The structural formula of second of compound is：[Zn2(bdcpp)
(Hbdcpp)]n(referred to as：2), molecular formula C42H19N2O16Zn2, belong to anorthic system, P ī space groups, cell parameter is： α=95.789 (7) °, β=106.877 (7) °, γ=
90.060(7)°；The structural formula of the third compound is：[Zn2(bdcpp)(DMF)(H2O)2]n(referred to as：3), molecular formula is
C24H20N2O11Zn2, belong to monoclinic system, C2/c space groups, cell parameter is：α=γ=90 °, β=118.713 (6) °.
2. a kind of zinc-base fluorescent material and preparation method thereof synthesized by solvent-induced strategy as claimed in claim 1, feature
It is：The compound is to use inorganic zinc salt and 2, and bis- (2', the 4'- phthalic acid) pyridines of 6- lead to as homologous starting material
Cross what solvent-thermal method was prepared.
3. a kind of zinc-base fluorescent material and preparation method thereof synthesized by solvent-induced strategy as claimed in claim 1, feature
To include the following steps：
1) by inorganic zinc salt and 2, bis- (2', 4'- phthalic acid) the pyridine powders of 6- are added in reaction vessel, inorganic zinc salt and 2,
The molar ratio of bis- (2', the 4'- phthalic acid) pyridines of 6- is 1~2：1；
2) DMF and deionized water mixed solution are added in reaction vessel obtained by step 1), the DMF of addition and the body of deionized water
Product is than being from 2：1 arrives DMF pure phases, stirs 5min；
3) few drops of concentrated nitric acids are added to rubber head dropper in step 2) gained mixed solution, the quantity of concentrated nitric acid is 1-3 drops；
4) mixed solution obtained by step 3) is transferred in the closed steel bomb with polytetrafluoroethyllining lining, 90~110
1~3d is reacted under DEG C self-generated pressure, then cooled to room temperature, washed, filtered, spontaneously dry, obtained described by molten
Three kinds of compounds of agent induction strategies synthesis.
4. such as a kind of zinc-base fluorescent material and preparation method thereof synthesized by solvent-induced strategy in claim 3, feature
It is：The inorganic zinc salt is zinc sulfate or zinc nitrate or zinc acetate.
5. such as a kind of zinc-base fluorescent material and preparation method thereof synthesized by solvent-induced strategy in claim 3, feature
It is：A concentration of the 68% of the concentrated nitric acid solution.
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| CN103041778A (en) * | 2012-12-28 | 2013-04-17 | 浙江大学 | Metal-organic frame material for absorbing and storing acetylene and preparation method thereof |
| JP2015117203A (en) * | 2013-12-18 | 2015-06-25 | 新日鐵住金株式会社 | Coordination polymer complex containing fluorine, gas adsorbent, gas separation apparatus and gas storage apparatus using the same |
| CN107602596A (en) * | 2017-09-14 | 2018-01-19 | 河南城建学院 | A kind of Zn MOF fluorescent sensing materials and preparation method thereof |
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| CN103041778A (en) * | 2012-12-28 | 2013-04-17 | 浙江大学 | Metal-organic frame material for absorbing and storing acetylene and preparation method thereof |
| JP2015117203A (en) * | 2013-12-18 | 2015-06-25 | 新日鐵住金株式会社 | Coordination polymer complex containing fluorine, gas adsorbent, gas separation apparatus and gas storage apparatus using the same |
| CN107602596A (en) * | 2017-09-14 | 2018-01-19 | 河南城建学院 | A kind of Zn MOF fluorescent sensing materials and preparation method thereof |
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