CN102153578A - Rare-earth organic coordination polymer taking 4,4'-bipyridyl as template, and preparation method and application thereof - Google Patents
Rare-earth organic coordination polymer taking 4,4'-bipyridyl as template, and preparation method and application thereof Download PDFInfo
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- CN102153578A CN102153578A CN2011100481898A CN201110048189A CN102153578A CN 102153578 A CN102153578 A CN 102153578A CN 2011100481898 A CN2011100481898 A CN 2011100481898A CN 201110048189 A CN201110048189 A CN 201110048189A CN 102153578 A CN102153578 A CN 102153578A
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Abstract
The invention relates to a rare-earth organic coordination polymer, and a preparation method and application thereof. The rare-earth organic coordination polymer has the following chemical formula: {(bpy)[Re(ip)1.5(H2O)4]}n, wherein bpy is 4,4'-bipyridyl, ip is isophthalic acid divalent negative ions, Re is one or more of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y and the like, and n is degree of polymerization. A hydro (solvent)-thermal synthesis method is used for preparing the rare-earth organic coordination polymer, is environment-friendly and easy to operate, low in cost and high in yield, and is suitable for large-scale industrial production. The prepared rare-earth organic coordination polymer has the good application prospects in fields of luminescence, catalysis, adsorption, magnetism, ion exchange, high polymer material aids and the like.
Description
Technical field
The present invention relates to RE compound material, particularly relate to 4,4 '-dipyridyl is the rare earth organic coordination polymer of template, be specifically related to 4,4 '-dipyridyl is template, is rare earth organic coordination polymer of part and preparation method thereof with the m-phthalic acid dianion.Prepared rare earth organic coordination polymer is in luminous, catalysis, and fields such as absorption, magnetic, ion-exchange, macromolecular material auxiliary agent have good application prospects.
Background technology
Ligand polymer is meant that metal or metal cluster and organic ligand by the polymkeric substance with periodic no limit structure that self-assembly forms, are called metal organic frame material, inorganic-organic hybridization material etc. again.Wherein do not have limit structure and comprise one-dimensional chain, two-dimensional layer and tridimensional network.Be different from molecule by interatomic covalent bonds mode, existing covalent linkage, coordinate bond in the ligand polymer comprise intermolecular weak force again.
In recent years, ligand polymer is because its porousness, bigger serface, configuration variation and caused the great interest of people by the formed special Subjective and Objective relation of self-assembly.This class material reported have gas storage and separation, catalysis, magnetic, conduction and performance such as luminous.As, Li, H., Eddaoudi, M., O ' Keeffe, M., Yaghi, O.M.Nature 1999,402,276-279; Zhao, X., Xiao, B., Fletcher, J.A., Thomas, K.M., Bradshaw, D.and Rosseins ky, M.J.Science 2004,306,1012-1015; Seo, J.S., Whang, D., Lee, H., Jun, S.I., Oh, J., Jeon, Y.J.and Kim, K.Nature 2000,404,982-986; Zou, R.-Q., Sakurai, H.and Xu, Q.Angew.Chem., Int.Ed.2006,45,2542-2546; Halder, G.J., Kepert, C.J., Moubaraki, B., Murray, K.S., Cashion, J.D.Science 2002,298,1762-1765; Fuma, Y., Ebihara, M., Kutsumizu, S.and Kawamura, T.J.Am.Chem.Soc.2004,126,12238-12239; Sadakiyo, M., Yamada, T.and Kitagawa, H.J.Am.Chem.Soc.2009,131,9906-9907; Rieter, W.J., Taylor, K.M.L., and Lin, W.J.Am.Chem.Soc.2007,129,9852-9853; White, K.A., Chengelis, D.A., Gogick, K.A., Stehman, J., Rosi, N.L.and Petoud, S.J.Am.Chem.Soc.2009,131,18069-18071.
M-phthalic acid and have strong coordination ability, multiple coordination mode, easily form characteristics such as hydrogen bond and the effect of aromatic ring pi-pi accumulation as organic ligand.4,4 '-dipyridyl can make the variation of complex structure and performance as organic ligand, and improve the stability of title complex.But with 4,4 '-dipyridyl is the also few at present report of ligand polymer of template.
Rare earth element has the essentially identical outer electronic structure internal layer 4f electronics close with energy level, and this special electronic configuration makes them that the character of many uniquenesses be arranged at aspects such as light, electricity, magnetic, is described as the treasure-house of novel material.China is the abundantest country of content of rare earth, and the synthetic and application of research rare earth compound has important theory and practical significance.
Rare earth element has characteristics such as atomic radius is big, and valency is variable, and ligancy is more, and the synthetic difficulty of rare earth coordination polymer is bigger.At present, the rare earth coordination polymer aspect is synthetic few.
Summary of the invention
First technical problem to be solved by this invention is, provide a kind of have multiple hole, bigger serface with 4,4 '-dipyridyl is the rare earth organic coordination polymer of template.
Second technical problem to be solved of the present invention provide above-mentioned with 4,4 '-dipyridyl is the preparation method of the rare earth organic coordination polymer of template, this method is environmentally friendly, and is simple, cost is low, the productive rate height is easy to large-scale industrial production.
The 3rd purpose of the present invention be to provide above-mentioned with 4,4 '-dipyridyl be the rare earth organic coordination polymer of template in luminous, catalysis, the application in fields such as absorption, magnetic, ion-exchange, macromolecular material auxiliary agent.
The present invention utilizes m-phthalic acid to have stronger coordination ability, multiple coordination mode, easily form characteristics such as hydrogen bond and aromatic ring accumulation, first with 4,4 '-dipyridyl is a template, the rare earth organic coordination polymer (4,4 '-dipyridyl is the rare earth m-phthalic acid ligand polymer of template) that has prepared a class formation novelty.This class title complex has multiple hole, bigger serface and has formed the special Subjective and Objective relation of configuration, and in luminous, catalysis, fields such as absorption, magnetic, ion-exchange, macromolecular material auxiliary agent have good application prospects.
In order to achieve the above object, the present invention adopts following technical scheme:
Rare earth organic coordination polymer of the present invention possesses following chemical formula is arranged is { (bpy) [Re (ip)
1.5(H
2O)
4]
n, wherein bpy be 4,4 '-dipyridyl, ip is the m-phthalic acid dianion, one or more among Re=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, the Y etc., n is the polymerization degree.
The crystal of rare earth organic coordination polymer of the present invention belongs to oblique system, and spacer is C2/c.
The preparation method of rare earth organic coordination polymer of the present invention comprises the steps:
(1) with rare earth compound, m-phthalic acid, 4,4 '-dipyridyl is dissolved in the solvent, stirs, the pH value with acid or alkali conditioned reaction system joins in the reactor then.
(2) after heat temperature raising, reactant react one section at a certain temperature, progressively reduce temperature, be cooled to room temperature, filter, wash with water, drying, make with 4,4 '-dipyridyl is the rare earth organic coordination polymer of template.
The used rare earth compound of the present invention is rare-earth salts, rare-earth hydroxide and rare earth oxide; Used rare-earth salts is rare earth nitrate, rare earth chloride, rare earth sulfate, lanthanon acetate and rare earth perchlorate; Used rare earth is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y;
The used solvent of the present invention is one or more in water, DMF, methyl alcohol and the ethanol;
The rare earth compound that the present invention is used and the mol ratio of m-phthalic acid are 1: 0.05～1: 15, rare earth compound and 4,4 '-mol ratio of dipyridyl is 1: 0.05～1: 15; The mol ratio of rare earth compound and solvent is 1: 500～1: 10000;
The pH value of reaction system of the present invention is 5～10, and used alkali is organic bases or mineral alkali; Used organic bases is triethylamine or pyridine; Used mineral alkali is sodium hydroxide or potassium hydroxide;
The used acid of the present invention is nitric acid, hydrochloric acid, sulfuric acid or acetic acid;
Temperature of reaction of the present invention is 80 ℃～300 ℃;
Reaction times of the present invention is 1～240 hour.
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) institute of the present invention synthetic rare earth organic coordination polymer novel structure, uniqueness.
(2) the present invention adopt cheaply m-phthalic acid and 4,4 '-dipyridyl is as raw material, adopts water (solvent) thermal synthesis method, environmentally friendly, simple, cost is low, the productive rate height is easy to large-scale industrial production.
(3) the present invention is with 4,4 '-dipyridyl is a template, the title complex of gained has multiple hole, bigger serface and has formed the special Subjective and Objective relation of configuration, and in luminous, catalysis, fields such as absorption, magnetic, ion-exchange, macromolecular material auxiliary agent have good application prospects.
Description of drawings
Fig. 1 is the structure iron (polyhedron formula) that embodiment 1 sees from the b direction of principal axis.
Fig. 2 is the structure iron (polyhedron formula) that embodiment 1 sees from the c direction of principal axis.
Fig. 3 is the structure iron (wire frame formula) that embodiment 2 sees from the b direction of principal axis.
Fig. 4 is the structure iron (wire frame formula) that embodiment 2 sees from the c direction of principal axis.
Fig. 5 is the structure iron (polyhedron formula) that embodiment 3 sees from the b direction of principal axis.
Fig. 6 is the structure iron (polyhedron formula) that embodiment 3 sees from the c direction of principal axis.
Fig. 7 is the structure iron (mallet formula) that embodiment 4 sees from the b direction of principal axis.
Fig. 8 is the structure iron (mallet formula) that embodiment 4 sees from the c direction of principal axis.
Fig. 9 is the structure iron (rod formula) that embodiment 5 sees from the b direction of principal axis.
Figure 10 is the structure iron (rod formula) that embodiment 5 sees from the c direction of principal axis.
Figure 11 is the infrared spectrogram of embodiment 1.
Figure 12 is the infrared spectrogram of embodiment 2.
Figure 13 is the infrared spectrogram of embodiment 3.
Figure 14 is the infrared spectrogram of embodiment 4.
Figure 15 is the infrared spectrogram of embodiment 5.
Figure 16 is the abosrption spectrogram of embodiment 6.
Figure 17 is the emmission spectrum figure of embodiment 6.
Figure 18 is the abosrption spectrogram of embodiment 7.
Figure 19 is the emmission spectrum figure of embodiment 7.
Embodiment
The invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1:
{ (bpy) [Pr (ip)
1.5(H
2O)
4]
nSynthetic
With Pr (NO
3)
36H
2O (0.5mmol, 218mg), m-phthalic acid (0.5mmol, 83mg), 4,4 '-(0.5mmol 78mg) is dissolved in the 15ml distilled water dipyridyl, stirs, with pH value=7～8 of triethylamine conditioned reaction system, join in the reactor heat temperature raising then, after 72 hours, progressively reduce temperature 120 ℃ of reactions, be cooled to room temperature, filter, wash with water, drying obtains block green crystal.The gained crystal is on the Rigaku of Japan company of science RAXIS-RAPID monocrystalline x-ray diffractometer, with the molybdenum target MoK alpha-ray of graphite monochromatization
Under 293 (2) K, collect diffraction data with the ω scan mode.The crystal original texture uses the SHELX-97 program to solve with direct method, obtains whole non-hydrogen atom coordinates with difference Fourier synthesis method and method of least squares then, and all non-hydrogen atom adopts F
2The complete matrix method of least squares is carried out the anisotropy refine, obtains whole hydrogen atom coordinates by theoretical hydrogenation and difference Fourier synthesis method, and the structure that obtains this ligand polymer is { (bpy) [Pr (ip)
15(H
2O)
4]
nTable 1 is the main crystallographic data of this ligand polymer.Fig. 1 and Fig. 2 are the structure iron of this ligand polymer.From structure iron as can be seen, 4,4 '-dipyridyl is positioned at the duct of ligand polymer as template, not with metal-complexing.Figure 11 is for this ligand polymer KBr compressing tablet, at 400～4000cm
-1The infrared spectrogram of using BRUKER TENSOR 27 infrared spectrometers to record in the scope.The carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of m-phthalic acid appear at 1607.12cm respectively as can be seen from infrared spectrogram
-1And 1400.93cm
-1
Table 1{ (bpy) [Pr (ip)
1.5(H
2O)
4]
nMain crystallographic data
Embodiment 2
{ (bpy) [Nd (ip)
1.5(H
2O)
4]
nSynthetic
With Nd (OH)
3(0.25mmol, 49mg), m-phthalic acid (3.75mmol, 623mg), 4,4 '-(3.75mmol 585mg) is dissolved in 25ml distilled water and the 25ml methyl alcohol dipyridyl, stirs, with pH value=6～7 of hydrochloric acid conditioned reaction system, join in the reactor heat temperature raising then, after 240 hours, progressively reduce temperature 80 ℃ of reactions, be cooled to room temperature, filter, wash with water, drying obtains block purple crystals.The gained crystal is on the Rigaku of Japan company of science RAXIS-RAPID monocrystalline x-ray diffractometer, with the molybdenum target MoK alpha-ray of graphite monochromatization
Under 293 (2) K, collect diffraction data with the ω scan mode.The crystal original texture uses the SHELX-97 program to solve with direct method, obtains whole non-hydrogen atom coordinates with difference Fourier synthesis method and method of least squares then, and all non-hydrogen atom adopts F
2The complete matrix method of least squares is carried out the anisotropy refine, obtains whole hydrogen atom coordinates by theoretical hydrogenation and difference Fourier synthesis method, and the structure that obtains this ligand polymer is { (bpy) [Nd (ip)
15(H
2O)
4]
nTable 2 is the main crystallographic data of this ligand polymer.Fig. 3 and Fig. 4 are the structure iron of this ligand polymer.From structure iron as can be seen, 4,4 '-dipyridyl is positioned at the duct of ligand polymer as template, not with metal-complexing.Figure 12 is for this ligand polymer KBr compressing tablet, at 400～4000cm
-1The infrared spectrogram of using BRUKERTENSOR 27 infrared spectrometers to record in the scope.The carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of m-phthalic acid appear at 1608.60cm respectively as can be seen from infrared spectrogram
-1And 1408.50cm
-1
Table 2{ (bpy) [Nd (ip)
1.5(H
2O)
4]
nMain crystallographic data
Embodiment 3
{ (bpy) [Sm (ip)
1.5(H
2O)
4]
nSynthetic
With SmCl
36H
2O (0.5mmol, 182mg), m-phthalic acid (2.0mmol, 332mg), 4,4 '-(1.0mmol 156mg) is dissolved in 10ml distilled water and the 5ml ethanol dipyridyl, stirs, with pH value=8～9 of sodium hydroxide solution conditioned reaction system, join in the reactor heat temperature raising then, after 24 hours, progressively reduce temperature 140 ℃ of reactions, be cooled to room temperature, filter, wash with water, drying obtains block yellow crystals.The gained crystal is on the RigakuRAXIS-RAPID of Japan company of science monocrystalline x-ray diffractometer, with the molybdenum target MoK alpha-ray of graphite monochromatization
(collect diffraction data under the 2K with the ω scan mode 293.The crystal original texture uses the SHELX-97 program to solve with direct method, obtains whole non-hydrogen atom coordinates with difference Fourier synthesis method and method of least squares then, and all non-hydrogen atom adopts F
2The complete matrix method of least squares is carried out the anisotropy refine, obtains whole hydrogen atom coordinates by theoretical hydrogenation and difference Fourier synthesis method, and the structure that obtains this ligand polymer is { (bpy) [Sm (ip)
15(H
2O)
4]
nTable 3 is the main crystallographic data of this ligand polymer.Fig. 5 and Fig. 6 are the structure iron of this ligand polymer.From structure iron as can be seen, 4,4 '-dipyridyl is positioned at the duct of ligand polymer as template, not with metal-complexing.Figure 13 is for this ligand polymer KBr compressing tablet, at 400～4000cm
-1The infrared spectrogram of using BRUKER TENSOR 27 infrared spectrometers to record in the scope.The carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of m-phthalic acid appear at 1607.21cm respectively as can be seen from infrared spectrogram
-1And 1405.58cm
-1
Table 3{ (bpy) [Sm (ip)
1.5(H
2O)
4]
nMain crystallographic data
Embodiment 4
{ (bpy) [Eu (ip)
1.5(H
2O)
4]
nSynthetic
With Eu
2O
3(0.25mmol, 88mg), m-phthalic acid (0.75mmol, 125mg), 4,4 '-(2.0mmol 312mg) is dissolved in the 10ml distilled water dipyridyl, stirs, with pH value=5～7 of sulphuric acid soln conditioned reaction system, join in the reactor heat temperature raising then, after 1 hour, progressively reduce temperature 300 ℃ of reactions, be cooled to room temperature, filter, wash with water, drying obtains block light yellow crystal.The gained crystal is on the Rigaku of Japan company of science RAXIS-RAPID monocrystalline x-ray diffractometer, with the molybdenum target MoK alpha-ray of graphite monochromatization
Under 293 (2) K, collect diffraction data with the ω scan mode.The crystal original texture uses the SHELX-97 program to solve with direct method, obtains whole non-hydrogen atom coordinates with difference Fourier synthesis method and method of least squares then, and all non-hydrogen atom adopts F
2The complete matrix method of least squares is carried out the anisotropy refine, obtains whole hydrogen atom coordinates by theoretical hydrogenation and difference Fourier synthesis method, and the structure that obtains this ligand polymer is { (bpy) [Eu (ip)
15(H
2O)
4]
nTable 4 is the main crystallographic data of this ligand polymer.Fig. 7 and Fig. 8 are the structure iron of this ligand polymer.From structure iron as can be seen, 4,4 '-dipyridyl is positioned at the duct of ligand polymer as template, not with metal-complexing.Figure 14 is for this ligand polymer KBr compressing tablet, at 400～4000cm
-1The infrared spectrogram of using BRUKER TENSOR 27 infrared spectrometers to record in the scope.The carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of m-phthalic acid appear at 1610.70cm respectively as can be seen from infrared spectrogram
-1And 1398.79cm
-1
Table 4{ (bpy) [Eu (ip)
1.5(H
2O)
4]
nMain crystallographic data
Embodiment 5
{ (bpy) [Gd (ip)
1.5(H
2O)
4]
nSynthetic
With (CH
3COO)
3Gd4H
2O (0.5mmol, 206mg), m-phthalic acid (0.025mmol, 4.15mg), 4,4 '-(0.025mmol 3.9mg) is dissolved among 4.5ml distilled water and the 0.5mlDMF dipyridyl, stirs, with pH value=6～7 of potassium hydroxide solution conditioned reaction system, join in the reactor heat temperature raising then, after 12 hours, progressively reduce temperature 160 ℃ of reactions, be cooled to room temperature, filter, wash with water, drying obtains block light green crystal.The gained crystal is on the Rigaku of Japan company of science RAXIS-RAPID monocrystalline x-ray diffractometer, with the molybdenum target MoK alpha-ray of graphite monochromatization
Under 293 (2) K, collect diffraction data with the ω scan mode.The crystal original texture uses the SHELX-97 program to solve with direct method, obtains whole non-hydrogen atom coordinates with difference Fourier synthesis method and method of least squares then, and all non-hydrogen atom adopts F
2The complete matrix method of least squares is carried out the anisotropy refine, obtains whole hydrogen atom coordinates by theoretical hydrogenation and difference Fourier synthesis method, and the structure that obtains this ligand polymer is { (bpy) [Gd (ip)
15(H
2O)
4]
nTable 5 is the main crystallographic data of this ligand polymer.Fig. 9 and Figure 10 are the structure iron of this ligand polymer.From structure iron as can be seen, 4,4 '-dipyridyl is positioned at the duct of ligand polymer as template, not with metal-complexing.Figure 15 is for this ligand polymer KBr compressing tablet, at 400～4000cm
-1The infrared spectrogram of using BRUKER TENSOR 27 infrared spectrometers to record in the scope.The carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of m-phthalic acid appear at 1606.10cm respectively as can be seen from infrared spectrogram
-1And 1401.72cm
-1
Table 5{ (bpy) [Gd (ip)
1.5(H
2O)
4]
nMain crystallographic data
Embodiment 6
{ (bpy) [Eu (ip)
1.5(H
2O)
4]
nThe mensuration of (embodiment 4 gained) luminescent properties
Measure the absorption spectrum of this ligand polymer with Hitachi's U-3010 ultraviolet-visible spectrophotometer.Figure 16 is the abosrption spectrogram of this ligand polymer.From abosrption spectrogram as can be seen this ligand polymer the absorption band of one broad is arranged in wavelength 200～350nm scope greatly.Emmission spectrum with this ligand polymer of the F-4500 of Hitachi fluorescent spectrophotometer assay.Figure 17 is the emmission spectrum figure of this ligand polymer after the incident light of 220～265nm excites.From emmission spectrum figure as can be seen this ligand polymer can send the very high orange-colored light of intensive purity.Illustrate that this ligand polymer can be used as luminescent material and is used to produce the very high orange-colored light of purity.
Embodiment 7
{ (bpy) [Gd (ip)
1.5(H
2O)
4]
nThe mensuration of (embodiment 5 gained) luminescent properties
Measure the absorption spectrum of this ligand polymer with Hitachi's U-3010 ultraviolet-visible spectrophotometer.Figure 18 is the abosrption spectrogram of this ligand polymer.From abosrption spectrogram as can be seen this ligand polymer the absorption band of one broad is arranged in wavelength 200～300nm scope greatly.Emmission spectrum with this ligand polymer of the F-4500 of Hitachi fluorescent spectrophotometer assay.Figure 19 is the emmission spectrum figure of this ligand polymer after the incident light of 220～295nm excites.From emmission spectrum figure as can be seen this ligand polymer can send intensive UV-light, purple light, blue light, green glow.Illustrate that this ligand polymer can be used as luminescent material and is used to produce UV-light, purple light, blue light, green glow.
Claims (6)
- One kind with 4,4 '-dipyridyl is the rare earth organic coordination polymer of template, it is characterized in that its chemical formula is: { (bpy) [Re (ip) 1.5(H 2O) 4] n, wherein, bpy is 4,4 '-dipyridyl, ip is the m-phthalic acid dianion, and Re is one or more among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and the Y, and n is the polymerization degree.
- 2. according to claim 1 with 4,4 '-dipyridyl is the rare earth organic coordination polymer of template, it is characterized in that: the crystal of described rare earth organic coordination polymer belongs to oblique system, spacer is C2/c.
- Claim 1 described with 4,4 '-dipyridyl is the preparation method of the rare earth organic coordination polymer of template, it is characterized in that comprising the steps:(1) with rare earth compound, m-phthalic acid, 4,4 '-dipyridyl is dissolved in the solvent, stir, be 5～10 with the pH value of acid or alkali conditioned reaction system, join in the reactor then; Described alkali is organic bases or mineral alkali;Described rare earth compound is rare-earth salts, rare-earth hydroxide and rare earth oxide; Described rare-earth salts is rare earth nitrate, rare earth chloride, rare earth sulfate, lanthanon acetate and rare earth perchlorate; Described rare earth is one or more among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and the Y;Described solvent is one or more in water, DMF, methyl alcohol and the ethanol;The mol ratio of described rare earth compound and m-phthalic acid is 1: 0.05～1: 15, rare earth compound and 4,4 '-mol ratio of dipyridyl is 1: 0.05～1: 15; The mol ratio of rare earth compound and solvent is 1: 500～1: 10000;(2) heat temperature raising to 80 ℃～300 ℃ reacted after 1～240 hour, progressively reduced temperature, was cooled to room temperature, filtered, wash with water, and drying, make with 4,4 '-dipyridyl is the rare earth organic coordination polymer of template.
- According to claim 3 described with 4,4 '-dipyridyl is the preparation method of the rare earth organic coordination polymer of template, it is characterized in that: described organic bases is triethylamine or pyridine; Described mineral alkali is sodium hydroxide or potassium hydroxide.
- According to claim 3 described with 4,4 '-dipyridyl is the preparation method of the rare earth organic coordination polymer of template, it is characterized in that: described acid is nitric acid, hydrochloric acid, sulfuric acid or acetic acid.
- Claim 1 described with 4,4 '-dipyridyl be the rare earth organic coordination polymer of template in luminous, catalysis, the application in absorption, magnetic, ion-exchange or the macromolecular material auxiliary agent.
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