CN102618255A - Method for preparing photoluminescent phosphomolybdate isonicotinic acid crystal - Google Patents
Method for preparing photoluminescent phosphomolybdate isonicotinic acid crystal Download PDFInfo
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- CN102618255A CN102618255A CN2012100717636A CN201210071763A CN102618255A CN 102618255 A CN102618255 A CN 102618255A CN 2012100717636 A CN2012100717636 A CN 2012100717636A CN 201210071763 A CN201210071763 A CN 201210071763A CN 102618255 A CN102618255 A CN 102618255A
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Abstract
The invention relates to a method for preparing a photoluminescent phosphomolybdate isonicotinic acid crystal. The method comprises the following steps of: 1, preparing a solution A; 2, preparing a solution B; 3, dripping the solution B in the solution A, and dripping pyridine; 4, reacting a mixed solution with magnetic force stirring; 5, preparing a solution C; 6, dripping the solution C in the mixed solution in the step 4, regulating the pH value and continuously reacting; and 7, filtering the mixed solution, and putting a filtrate into a container for standing; and 8, after 2 to 4 weeks, and taking a crystal generated in the standing container out and drying to obtain a target product, namely the photoluminescent phosphomolybdate isonicotinic acid crystal, wherein the chemical formula of the photoluminescent phosphomolybdate isonicotinic acid crystal is (C6H6NO2).(C5H6N)2.[PMo12O40].(C6H5NO2).2H2O. The prepared photoluminescent phosphomolybdate isonicotinic acid crystal has the photochromic performance, and has potential application prospect in aspects of catalysis, electrical conduction, host-guest chemistry, magnetic devices, gas storage, optical materials and the like.
Description
Technical field
The present invention relates to a kind of pl-phospho-molybdic acid Yi Yansuan crystalline preparation method, it can synthesize a kind of novel phospho-molybdic acid Yi Yansuan super molecular compound with ability of reverse photochromism performance.
Background technology
One type of being made up of through the oxygen atom ligand bridging by certain structure heteroatoms (like P, Si, Fe, Co etc.) and polyatom (like Mo, W, V, Nb, Ta etc.) of heteropolyacid contains the oxygen polyacid; Has very high catalytic activity; It not only has acidity; And have oxidation-reduction quality, be a kind of multifunctional novel catalyzer.Photochemical reaction takes place with organic polymer, thereby gives the polymer hybrid material distinct colors as a kind of photosensitizers in heteropolyacid easily under illumination condition.In recent years, the polyacid ligand polymer is owing to having the extensive attention that the potential using value receives the researchist at aspects such as catalysis, conductivity, host-guest chemistry, magnetic device, gas storage and optical materials.
Multi-acid salt has the stronger ability of accepting electronics, can with outstanding electron donor(ED), combine to form super molecular compound like organic molecule, organo-metallic etc. through electrostatic force and intermolecular forces.Polyacid can be carried out the reversible redox reaction; Usually demonstrate the polyoxometallic acid salt anionic of O → M (lotus of part → metal moves) absorption band in the ultraviolet region; In case be reduced or absorb the light of certain wavelength; Charge migration and cause intense absorption between the internal cause atom of visible region then still getting back to initial state after the oxidation or after sending the light of certain wavelength, therefore has important application prospects at aspects such as energy transformation, smart sensor, light modulation device and high-density storages.
Study in the polyacid compound the most extensively, what have better application prospect is with polyanionic [XW
12O
40]
N-(Si is B) as the Keggin type polyoxometallate of constructing piece basically for X=P, Ge.Because the doping of organic group; Synergy appears between the organic and inorganic component; Thereby can prepare matrix material with compatibility or synergistic effect, as: the charge-transfer complex that tetrathiafulvalene, oxine and various organic amine or amino acid and polyacid form.These compounds have structure variation and big, unique light, electricity, the magnetic property of specific surface area, have the potential application prospect in fields such as catalysis, conduction and nonlinear optical materials.
Yi Yansuan is claimed the 4-VPP again, is a kind of medicine intermediate, is mainly used in preparation anti-tuberculosis drugs vazadrine.Because Yi Yansuan plays an important role, therefore caused that people are to its interest of studying in the metabolic processes of all viable cell.Yi Yansuan has N-and two kinds of functional groups of O-, and coordination mode is than horn of plenty, can multiple coordination mode and metallic ion coordination, thus form structure and the diversified function title complex of performance.
Summary of the invention
The object of the present invention is to provide a kind of compound method with polyacid crystal of pl-, it can synthesize a kind of novel phospho-molybdic acid Yi Yansuan super molecular compound (C
6H
6NO
2) (C
5H
6N)
2[PMo
12O
40] (C
6H
5NO
2) 2H
2O, this compound is Heat stability is good not only, and has the ability of reverse photochromism performance.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
A kind of pl-phospho-molybdic acid Yi Yansuan crystalline preparation method is characterized in that, may further comprise the steps:
(1) preparation solution A: take by weighing the Sodium orthomolybdate of 1.0～1.4mmol volumetric molar concentration, it is dissolved in the 10mL zero(ppm) water, bath temperature is 45～55 ℃, obtains solution A;
(2) preparation solution B: 0.9～1.1mmol trisodium phosphate is dissolved in the 2mL aqueous solution, obtains solution B;
(3) solution B with step (2) preparation is added drop-wise in the solution A of step (1) preparation, and at a mixed solution and dripping number pyridine;
(4) mixing solutions with step (3) reacted on the water-bath magnetic stirring apparatus 2～4 hours;
(5) preparation solution C: 0.5～1.2mmol Yi Yansuan is dissolved in 5mL, 50～80 ℃ the hydrothermal solution, obtains solution C;
(6) solution C that step (5) is prepared is added drop-wise in the mixing solutions behind step (4) stirring reaction, and regulating the pH value is 3, continues reaction 1～3 hour;
(7) mixing solutions after step (6) is handled filters, and filtrating is put into clean container and left standstill;
(8) 2-4 generates yellow bulk crystals after week in the said container that leaves standstill, and it is at room temperature dry to take out crystal, obtains title product pl-phospho-molybdic acid Yi Yansuan crystal.
Positively effect of the present invention is: the prepared pl-phospho-molybdic acid Yi Yansuan crystal of the present invention has photochromic properties, can issue the look that changes at UV-irradiation, by the faint yellow yellow-green colour that becomes originally; After one week, crystal can revert to original light yellow again.Has the potential application prospect at aspects such as catalysis, conductivity, host-guest chemistry, magnetic device, gas storage and optical materials.
Description of drawings
Accompanying drawing 1 is a kind of pl-phospho-molybdic acid of the present invention Yi Yansuan crystalline preparing method's FB(flow block);
Accompanying drawing 2 is the structure iron of phospho-molybdic acid Yi Yansuan monocrystalline;
Accompanying drawing 3 is pl-phospho-molybdic acid Yi Yansuan crystalline ultraviolet absorption curve figure.
Embodiment
Below in conjunction with a kind of pl-phospho-molybdic acid of accompanying drawing continuation explanation the present invention Yi Yansuan crystalline preparing method's practical implementation situation, still, enforcement of the present invention is not limited to following embodiment.
Embodiment 1
Referring to accompanying drawing 1.A kind of pl-phospho-molybdic acid Yi Yansuan crystalline preparation method may further comprise the steps:
(1) preparation solution A: the Sodium orthomolybdate of 1.0mmol (volumetric molar concentration) is dissolved in the 10mL zero(ppm) water, and bath temperature is 45 ℃, obtains solution A;
(2) preparation solution B: the trisodium phosphate of 0.9mmol (volumetric molar concentration) is dissolved in the 2mL aqueous solution, obtains solution B;
(3) solution B with step (2) preparation is added drop-wise in the solution A of step (1) preparation, and at a mixed solution and dripping number pyridine;
(4) mixing solutions with step (3) reacted 2 hours on the water-bath magnetic stirring apparatus;
(5) preparation solution C: the Yi Yansuan of 0.5mmol (volumetric molar concentration) is dissolved in 5mL, the 50 ℃ of hot water, obtains solution C;
(6) solution C that step (5) is prepared is added drop-wise in the mixing solutions behind step (4) stirring reaction, and regulating the pH value is 3, continues reaction 1 hour;
(7) mixing solutions after step (6) processing is filtered, filtrating is put into clean beaker leave standstill;
After (8) 2～4 weeks, generate yellow bulk crystals in the beaker that leaves standstill, it is at room temperature dry to take out crystal, obtains title product pl-phospho-molybdic acid Yi Yansuan crystal.
Embodiment 2
A kind of pl-phospho-molybdic acid Yi Yansuan crystalline preparation method may further comprise the steps:
(1) preparation solution A: the Sodium orthomolybdate of 1.4mmol (volumetric molar concentration) is dissolved in the 10mL zero(ppm) water, and bath temperature is 55 ℃, obtains solution A;
(2) preparation solution B: the trisodium phosphate of 1.1mmol (volumetric molar concentration) is dissolved in the 2mL aqueous solution, obtains solution B;
(3) solution B with step (2) preparation is added drop-wise in the solution A of step (1) preparation, and at a mixed solution and dripping number pyridine;
(4) mixing solutions with step (3) reacted 4 hours on the water-bath magnetic stirring apparatus;
(5) preparation solution C: the Yi Yansuan of 1.2mmol (volumetric molar concentration) is dissolved in 5mL, the 80 ℃ of hot water, obtains solution C;
(6) solution C that step (5) is prepared is added drop-wise in the mixing solutions behind step (4) stirring reaction, and regulating the pH value is 3, continues reaction 3 hours;
(7) mixing solutions after step (6) processing is filtered, filtrating is put into clean beaker leave standstill;
After (8) 2～4 weeks, generate yellow bulk crystals in the beaker that leaves standstill, it is at room temperature dry to take out crystal, obtains title product pl-phospho-molybdic acid Yi Yansuan crystal.
Adopt method of the present invention preparation to have pl-phospho-molybdic acid Yi Yansuan crystal be triclinic(crystalline)system, its chemical formula is: (C
6H
6NO
2) (C
5H
6N)
2[PMo
12O
40] (C
6H
5NO
2) 2H
2O, this crystalline spacer does
P-1.
Can choose and sizeablely have pl-phospho-molybdic acid Yi Yansuan monocrystalline and carry out single crystal diffraction test.
On Bruker Apex-II CCD single crystal diffractometer, adopt MoK
αRay (
λ=0.71073), diffraction data under 296 (2) K to the crystalline diffraction data gathering, with
φ-
ωScan mode in the certain angle sweep limit, is collected the point diffraction number altogether, and chooses the may observe point diffraction and be used for structure elucidation.Crystalline structure solves with direct method and the optimization of process complete matrix method of least squares, all data warp
LpThe factor and experience absorption correction, all non-hydrogen atoms are through the anisotropic refine, and organic Wasserstoffatoms adopts how much hydrogenation to obtain, and the H atom does not have the location on the water molecules.Crystal is resolved whole evaluation works and is adopted the SHELXTL-97 program to accomplish on computers.
Mathematic(al) representations such as the least square function that uses in the structural analysis process, discrepancy factor, weight discrepancy factor, weighting factor are following:
Least square function:
;
Temperature factor:
;
Deviation factor:
?;
Weight discrepancy factor:
;
Weighting factor:
,
.
Single-crystal X-ray diffraction analysis shows that each asymmetric cell is by 1 12 phosphorus molybdenum polyoxoanion [PMo
12O
40]
3-, 2 molecule pyridines, 2 molecule Yi Yansuan and 2 crystal water molecules constitute (referring to Fig. 2).Compound (C
6H
6NO
2) (C
5H
6N)
2[PMo
12O
40] (C
6H
5NO
2) 2H
2O is by polyanionic [PMo
12O
40]
3-Pass through the super molecular compound that hydrogen bond action power forms with pyridine molecule, Yi Yansuan molecule; Wherein protonated Yi Yansuan molecule is assembled into one-dimensional chain through hydrogen bond; With polyanionic inclusion center, free pyridine molecule is filled out between the space by hydrogen bond, firm crystalline structure.
This phospho-molybdic acid Yi Yansuan crystalline solid ultraviolet absorption curve is as shown in Figure 3, and the strong absorption in 200～400nm scope can ascribe O to
t→ Mo and O
B, cTransfer transport between the → Mo.Irradiation is after 2 hours under uv lamp, and the crystalline color is by the faint yellow yellow-green colour that becomes.Show on the spectrogram that one low intensively appears at the visible region at 750nm place than broad absorption band, this is one of characteristic of Keggin structure heteropoly blue compound, can ascribe charge transfer between the interior Mo atom of polyanionic to, Mo
5+→ Mo
6+ ,Explain between organic molecule and polyanionic charge transfer has taken place.After one week, crystal can revert to original light yellow again.
Test result shows: the pl-phospho-molybdic acid Yi Yansuan crystal of the present invention's preparation is reversible embedded photoluminescent material.
The above is merely preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the inventive method; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (2)
1. a pl-phospho-molybdic acid Yi Yansuan crystalline preparation method is characterized in that, may further comprise the steps:
(1) preparation solution A: take by weighing the Sodium orthomolybdate of 1.0～1.4mmol volumetric molar concentration, it is dissolved in the 10mL zero(ppm) water, bath temperature is 45～55 ℃, obtains solution A;
(2) preparation solution B: 0.9～1.1mmol trisodium phosphate is dissolved in the 2mL aqueous solution, obtains solution B;
(3) solution B with step (2) preparation is added drop-wise in the solution A of step (1) preparation, and at a mixed solution and dripping number pyridine;
(4) mixing solutions with step (3) reacted on the water-bath magnetic stirring apparatus 2～4 hours;
(5) preparation solution C: 0.5～1.2mmol Yi Yansuan is dissolved in 5mL, 50～80 ℃ the hydrothermal solution, obtains solution C;
(6) solution C that step (5) is prepared is added drop-wise in the mixing solutions behind step (4) stirring reaction, and regulating the pH value is 3, continues reaction 1～3 hour;
(7) mixing solutions after step (6) is handled filters, and filtrating is put into clean container and left standstill;
(8) 2-4 generates yellow bulk crystals after week in the said container that leaves standstill, and it is at room temperature dry to take out crystal, obtains title product pl-phospho-molybdic acid Yi Yansuan crystal.
2. a kind of pl-phospho-molybdic acid Yi Yansuan crystalline preparation method according to claim 1 is characterized in that said title product pl-phospho-molybdic acid Yi Yansuan crystal is a triclinic(crystalline)system, and its chemical formula is: (C
6H
6NO
2) (C
5H
6N)
2[PMo
12O
40] (C
6H
5NO
2) 2H
2O, said crystalline spacer does
P-1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110470389A (en) * | 2019-09-06 | 2019-11-19 | 京东方科技集团股份有限公司 | A kind of UV sensor, smart machine and preparation method |
| CN113797968A (en) * | 2021-08-19 | 2021-12-17 | 万华化学集团股份有限公司 | Preparation of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst and preparation method of polyglycerol fatty acid ester |
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| US5792721A (en) * | 1990-03-05 | 1998-08-11 | Catalytica, Inc. | Preparation of phosphomolybdovanadate polyoxoanions |
| CN102218348A (en) * | 2011-04-27 | 2011-10-19 | 哈尔滨师范大学 | Preparation method for substituted molybdophosphate crystal catalyst |
-
2012
- 2012-03-19 CN CN2012100717636A patent/CN102618255A/en active Pending
Patent Citations (2)
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|---|---|---|---|---|
| US5792721A (en) * | 1990-03-05 | 1998-08-11 | Catalytica, Inc. | Preparation of phosphomolybdovanadate polyoxoanions |
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Non-Patent Citations (6)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技I辑》 20120215 林燕燕 多酸类有机-无机杂化材料的合成、表征及性能研究 正文43-44页 1 , 第2期 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110470389A (en) * | 2019-09-06 | 2019-11-19 | 京东方科技集团股份有限公司 | A kind of UV sensor, smart machine and preparation method |
| CN113797968A (en) * | 2021-08-19 | 2021-12-17 | 万华化学集团股份有限公司 | Preparation of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst and preparation method of polyglycerol fatty acid ester |
| CN113797968B (en) * | 2021-08-19 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation of 2-chloroisonicotinic acid-phosphomolybdic acid catalyst and preparation method of polyglycerol fatty acid ester |
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Application publication date: 20120801 |