CN102827195B - Rare-earth organic coordination polymer constructed by using m-phthalic acid and 2-pyridylformic acid as mixed ligand, and preparation method and application thereof - Google Patents
Rare-earth organic coordination polymer constructed by using m-phthalic acid and 2-pyridylformic acid as mixed ligand, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a rare-earth organic coordination polymer constructed by using m-phthalic acid and 2-pyridylformic acid as a mixed ligand, and a preparation method and application thereof. The preparation method is characterized by comprising the following steps: dissolving a rare-earth compound, m-phthalic acid, 2-pyridylformic acid and a nitrogen-containing compound in a solvent, wherein the mol ratio of rare-earth compound to m-phthalic acid is 1:(0.05-15), the mol ratio of rare-earth compound to 2-pyridylformic acid is 1:(0.05-15), the mol ratio of rare-earth compound to nitrogen-containing compound is 1:(0.05-15), and the mol ratio of rare-earth compound to solvent is 1:(500-10000); evenly mixing, regulating the pH value of the reaction system to 5-10 with acid or alkali, and adding the reaction system into a reaction kettle; and heating to 80-300 DEG C to react for 1-240 hours, gradually cooling to room temperature, filtering, washing with water, and drying to obtain the rare-earth organic coordination polymer constructed by using m-phthalic acid and 2-pyridylformic acid as a mixed ligand.
Description
Technical field
The present invention relates to rare earth organic coordination polymer constructed with m-phthalic acid and 2-pyridine carboxylic acid mixed ligand and preparation method thereof and application, belong to rare earth organic coordination polymer Material Field.
Background technology
The class that ligand polymer (Coordination Polymer) refers to metal ion center and organic ligand self-assembly and formed has the metallic organic framework polymkeric substance of one dimension, two dimension or three-dimensional unlimited periodic network structure.This compounds is also referred to as simultaneously: Inorganic-Organic Hybrid Material (Inorganic-Organic Hybrid Materials) or metallic organic framework (Metal-Organic Frameworks, MOFs).Ligand polymer combines the feature of organic polymer and coordination compound, has both been different from general organic polymer, is also different from the inorganic polymer of Si-O class.Existing covalent linkage, coordinate bond in ligand polymer, comprise again weak force between hydrogen bond and pi-pi accumulation effect equimolecular.
In recent years, the design of ligand polymer, synthesis, structural analysis and performance study are one of very active research fields.This is not only because this kind of material has multiple hole, bigger serface, special host-guest relationship and various molecular architecture and topological framework and causes the great interest of people, and because this kind of material has the performances such as luminescence, gas storage and separation, catalysis, magnetic and conduction as functional materials.
M-phthalic acid has strong coordination ability, multiple coordination mode as organic ligand, easily forms the feature such as hydrogen bond and pi-pi accumulation effect.Pyridine acids part is the multi-functional part that typical case contains N and carboxyl.This kind of part, owing to having donor atom N and O of difference in functionality simultaneously, thus has more rich coordination mode and stronger coordination ability.At present, the title complex constructed by pyridine carboxylic acid class part has potential application prospect in fields such as supramolecule device, fluorescence and magnetic, is the very active field of a research.
About using two kinds of acid also considerably less as the report of the ligand polymer of mixed ligand in current document.Nitration mixture is used in synthetic materials, to have very large development space as part synthesizing rare-earth ligand polymer.
Rare earth element has the substantially identical outer electronic structure internal layer 4f electronics close with energy level, and this special electronic configuration makes them in optical, electrical, magnetic etc., have the character of many uniquenesses, is described as the treasure-house of novel material.China is the abundantest country of content of rare earth, and synthesis and the application thereof of research rare earth compound have important theoretical and practical significance.It is large that rare earth element has atomic radius, and the features such as valency is variable, and ligancy is more, the synthesis difficulty of rare earth coordination polymer is larger.At present, the synthesis of rare earth coordination polymer aspect is few.
Summary of the invention
The object of the invention is to provide the rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid for the deficiencies in the prior art.Be characterized in utilizing m-phthalic acid and 2-pyridine carboxylic acid to have stronger coordination ability, multiple coordination mode, easily form the feature such as hydrogen bond and the effect of aromatic ring pi-pi accumulation, first with m-phthalic acid and 2-pyridine carboxylic acid for mixed ligand, prepared the rare earth organic coordination polymer of a class formation novelty.It is special that this kind of title complex has multiple hole, bigger serface and configuration, and in luminous, catalysis, the fields such as absorption, magnetic, ion-exchange, macromolecular material auxiliary agent have good application prospect.
Object of the present invention is realized by following technical measures, and wherein said raw material number, except specified otherwise, is molfraction.
With the rare earth organic coordination polymer chemical formula that m-phthalic acid and 2-pyridine carboxylic acid are constructed for mixed ligand be: [Re
2(ip)
2(pic)
2]
n, wherein ip is m-phthalic acid dianion, and pic is 2-pyridine carboxylic acid negatively charged ion, at least one in Re=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y etc., and n is the polymerization degree.
The rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid raw material composed of the following components:
The mol ratio of rare earth compound and m-phthalic acid is 1: 0.05 ~ 15
The mol ratio of rare earth compound and 2-pyridine carboxylic acid is 1: 0.05 ~ 15
The mol ratio of rare earth compound and nitrogenous compound is 1: 0.05 ~ 15
The mol ratio of rare earth compound and solvent is 1: 500 ~ 10000
Wherein, 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-polymer complex; Described rare earth be in La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y at least one.
The crystal of the described rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid belongs to triclinic(crystalline)system.
The preparation method of the described rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid comprises the steps:
(1) be 1: 0.05 ~ 15 by the mol ratio of rare earth compound and m-phthalic acid, be preferably 1: 0.1 ~ 10, the mol ratio of rare earth compound and 2-pyridine carboxylic acid is 1: 0.05 ~ 15, be preferably 1: 0.1 ~ 10, the mol ratio of rare earth compound and nitrogenous compound is 1: 0.05 ~ 15, be preferably 1: 0.1 ~ 10, the mol ratio of rare earth compound and solvent is 1: 500 ~ 1: 10000, be preferably 1: 800 ~ 8000, be dissolved in solvent, stir, regulate the pH value of reaction system to be 5 ~ 10 with acid or alkali, then join in reactor;
(2) be heated to 80 DEG C ~ 300 DEG C, be preferably 120 DEG C ~ 260 DEG C, reaction 1 ~ 240h, be preferably 12 ~ 200h, progressively cooling degree is to room temperature, filters, wash with water, dry, the obtained rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid.
Wherein, 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-polymer complex; Described rare earth be in La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y at least one.
Described nitrogenous compound is pyridine, imidazoles, 2,2'-dipyridyls or 4, any one in 4 '-dipyridyl.
Described solvent is at least one in water, N, N'-dimethyl formamide (DMF), methyl alcohol and ethanol.
Described alkali is any one in triethylamine, pyridine, sodium hydroxide or potassium hydroxide.
Described acid is any one in nitric acid, hydrochloric acid, sulfuric acid or acetic acid.
The described rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid, in luminous, catalysis, is applied in absorption, magnetic, ion-exchange or macromolecular material auxiliary agent.
Tool of the present invention has the following advantages:
(1) the present invention has obtained the rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid, novel structure, uniqueness.
(2) the present invention adopts the m-phthalic acid of low cost and 2-pyridine carboxylic acid as raw material, and with water (solvent) thermal synthesis method, environmentally friendly, simple, cost is low, and productive rate is high, is easy to large-scale industrial production.
(3) title complex of gained of the present invention has multiple hole, bigger serface and configuration uniqueness, and in luminous, catalysis, the fields such as absorption, magnetic, ion-exchange, macromolecular material auxiliary agent have good application prospect.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 is from the structure iron (mallet formula) viewed from a direction of principal axis
Fig. 2 is that embodiment 1 is from the structure iron (mallet formula) viewed from b direction of principal axis
Fig. 3 is that embodiment 2 is from the structure iron (wire frame formula) viewed from a direction of principal axis
Fig. 4 is that embodiment 2 is from the structure iron (wire frame formula) viewed from b direction of principal axis
Fig. 5 is that embodiment 3 is from the structure iron (rod formula) viewed from a direction of principal axis
Fig. 6 is that embodiment 3 is from the structure iron (rod formula) viewed from b direction of principal axis
Fig. 7 is that embodiment 4 is from the structure iron (polyhedron formula) viewed from a direction of principal axis
Fig. 8 is that embodiment 4 is from the structure iron (polyhedron formula) viewed from b direction of principal axis
Fig. 9 is that embodiment 5 is from the structure iron (mallet formula) viewed from a direction of principal axis
Figure 10 is that embodiment 5 is from the structure iron (mallet formula) viewed from b 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 utilizing emitted light spectrogram of embodiment 6
Figure 18 is the abosrption spectrogram of embodiment 7
Figure 19 is the utilizing emitted light spectrogram of embodiment 7
Embodiment
By the following examples the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; the restriction to invention protection domain can not be interpreted as, some nonessential improvement and adjustment that the person skilled in the art in this field can make according to the content of the invention described above.
Embodiment 1: the preparation of rare earth organic coordination polymer
By Pr (NO
3)
36H
2o 218mg (0.5mmol), m-phthalic acid 83mg (0.5mmol), 2-pyridine carboxylic acid 123mg (1mmol), 2,2 '-dipyridyl 78mg (0.5mmol) is dissolved in 15ml distilled water, stirs, and regulates pH value=9 ~ 10 of reaction system with sodium hydroxide solution, then join in reactor, heat temperature raising, at temperature 130 DEG C reaction 48h, progressively cooling degree is to room temperature, filter, wash with water, dry, obtain green bulk crystals.Gained crystal, on the Rigaku RAXIS-RAPID Advances in crystal X-ray diffraction instrument of Rigaku company, with graphite monochromatised molybdenum target MoK alpha-ray (λ=0.71073), collects diffraction data with ω scan mode under 293 (2) K.Crystal original texture uses SHELX-97 program direct method to solve, and then obtain whole non-hydrogen atom coordinate by difference Fourier synthesis method and method of least squares, whole non-hydrogen atom adopts F
2complete matrix method of least squares carries out anisotropy refine, obtains whole hydrogen atom coordinate by theoretical hydrogenation and difference Fourier synthesis method, and the structural formula obtaining this ligand polymer is [Pr
2(ip)
2(pic)
2]
n.
Table 1 is the predominant crystal data of this ligand polymer.
Result shows, the asymmetric cell composition C of this ligand polymer
28h
16n
2o
12pr
2with structural formula [Pr
2(ip)
2(pic)
2]
nunanimously.The crystal of this ligand polymer belongs to triclinic(crystalline)system.
Fig. 1 and Fig. 2 is the structure iron of being made by crystal graphics software according to measurement result.
As can be seen from structure iron, the structural formula of this ligand polymer is [Pr
2(ip)
2(pic)
2]
n.This ligand polymer is reticulated structure, m-phthalic acid and 2-pyridine carboxylic acid all with metal-complexing.
Figure 11 is this ligand polymer KBr compressing tablet, at 400 ~ 4000 cm
-1the infrared spectrogram that BRUKER TENSOR infrared spectrometer records is used in scope.
As can be seen from infrared spectrogram, carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of a dioctyl phthalate and 2-pyridine carboxylic acid appear at 1691.88cm respectively
-1and 1397.78cm
-1.
The predominant crystal data of this ligand polymer of table 1
The preparation of embodiment 2 rare earth organic coordination polymer
By Nd
2o
384mg (0.25mmol), m-phthalic acid 623mg (3.75mmol), 2-pyridine carboxylic acid 461mg (3.75mmol), 4,4 '-dipyridyl 390mg (2.5mmol) is dissolved in 40ml distilled water and 10ml methyl alcohol, stir, pH value=6 ~ 7 of reaction system are regulated with hydrochloric acid, then join in reactor, heat temperature raising, at temperature 150 DEG C reaction 24h, progressively be cooled to room temperature, filter, wash with water, dry, obtain purple bulk crystals.Gained crystal, on the Rigaku RAXIS-RAPID Advances in crystal X-ray diffraction instrument of Rigaku public affairs, with graphite monochromatised molybdenum target MoK alpha-ray (λ=0.71073), collects diffraction data with ω scan mode under 293 (2) K.Crystal original texture uses SHELX-97 program direct method to solve, and then obtain whole non-hydrogen atom coordinate by difference Fourier synthesis method and method of least squares, whole non-hydrogen atom adopts F
2complete matrix method of least squares carries out anisotropy refine, obtains whole hydrogen atom coordinate by theoretical hydrogenation and difference Fourier synthesis method, and the structural formula obtaining this ligand polymer is [Nd
2(ip)
2(pic)
2]
n.
Table 2 is the predominant crystal data of this ligand polymer.
Result shows, the asymmetric cell composition C of this ligand polymer
28h
16n
2nd
2o
12with structural formula [Nd
2(ip)
2(pic)
2]
nunanimously.The crystal of this ligand polymer belongs to triclinic(crystalline)system.
Fig. 3 and Fig. 4 is the structure iron of being made by crystal graphics software according to measurement result.
As can be seen from structure iron, the structural formula of this ligand polymer is [Nd
2(ip)
2(pic)
2]
n.This ligand polymer is reticulated structure, m-phthalic acid and 2-pyridine carboxylic acid all with metal-complexing.
Figure 12 is this ligand polymer KBr compressing tablet, at 400 ~ 4000 cm
-1the infrared spectrogram that BRUKER TENSOR 27 infrared spectrometer records is used in scope.
As can be seen from infrared spectrogram, carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of a dioctyl phthalate and 2-pyridine carboxylic acid appear at 1692.19cm respectively
-1and 1417.74cm
-1.
The predominant crystal data of this ligand polymer of table 2
The preparation of embodiment 3 rare earth organic coordination polymer
By EuCl
36H
2o 183mg (0.5mmol), m-phthalic acid 166mg (1.0mmol), 2-pyridine carboxylic acid 246mg (2mmol), imidazoles 68mg (1.0mmol) are dissolved in 10ml distilled water and 10ml ethanol, stir, pH value=8 ~ 9 of reaction system are regulated with potassium hydroxide solution, then join in reactor, heat temperature raising, at temperature 80 DEG C reaction 240h, progressively be cooled to room temperature, filter, wash with water, drying, obtains faint yellow bulk crystals.Gained crystal, on the Rigaku RAXIS-RAPID Advances in crystal X-ray diffraction instrument of Rigaku company, with graphite monochromatised molybdenum target MoK alpha-ray (λ=0.71073), collects diffraction data with ω scan mode under 293 (2) K.Crystal original texture uses SHELX-97 program direct method to solve, and then obtain whole non-hydrogen atom coordinate by difference Fourier synthesis method and method of least squares, whole non-hydrogen atom adopts F
2complete matrix method of least squares carries out anisotropy refine, obtains whole hydrogen atom coordinate by theoretical hydrogenation and difference Fourier synthesis method, and the structural formula obtaining this ligand polymer is [Eu
2(ip)
2(pic)
2]
n.
Table 3 is the predominant crystal data of this ligand polymer.
Result shows, the asymmetric cell composition C of this ligand polymer
28h
16eu
2n
2o
12with structural formula [Eu
2(ip)
2(pic)
2]
nunanimously.The crystal of this ligand polymer belongs to triclinic(crystalline)system.
Fig. 5 and Fig. 6 is the structure iron of being made by crystal graphics software according to measurement result.
As can be seen from structure iron, the structural formula of this ligand polymer is [Eu
2(ip)
2(pic)
2]
n.This ligand polymer is reticulated structure, m-phthalic acid and 2-pyridine carboxylic acid all with metal-complexing.
Figure 13 is this ligand polymer KBr compressing tablet, at 400 ~ 4000 cm
-1the infrared spectrogram that BRUKER TENSOR27 infrared spectrometer records is used in scope.
As can be seen from infrared spectrogram, carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of a dioctyl phthalate and 2-pyridine carboxylic acid appear at 1606.02cm respectively
-1and 1398.80cm
-1.
The predominant crystal data of this ligand polymer of table 3
The preparation of embodiment 4 rare earth organic coordination polymer
By (CH
3cOO)
3tbH
2o 88mg (0.25mmol), m-phthalic acid 125mg (0.75mmol), 2-pyridine carboxylic acid 123mg (1mmol), pyridine 158mg (2.0mmol) are dissolved in 10ml distilled water, stir, regulate pH value=7 ~ 8 of reaction system with triethylamine, then join in reactor, heat temperature raising, at temperature 300 DEG C reaction 1h, progressively be cooled to room temperature, filter, wash with water, drying, obtains light green bulk crystals.Gained crystal, on the Rigaku RAXIS-RAPID Advances in crystal X-ray diffraction instrument of Rigaku company, with graphite monochromatised molybdenum target MoK alpha-ray (λ=0.71073), collects diffraction data with ω scan mode under 293 (2) K.Crystal original texture uses SHELX-97 program direct method to solve, and then obtain whole non-hydrogen atom coordinate by difference Fourier synthesis method and method of least squares, whole non-hydrogen atom adopts F
2complete matrix method of least squares carries out anisotropy refine, obtains whole hydrogen atom coordinate by theoretical hydrogenation and difference Fourier synthesis method, and the structural formula obtaining this ligand polymer is [Tb
2(ip)
2(pic)
2]
n.
Table 4 is the predominant crystal data of this ligand polymer.
Result shows, the asymmetric cell composition C of this ligand polymer
28h
16n
2o
12tb
2with structural formula [Tb
2(ip)
2(pic)
2]
nunanimously.The crystal of this ligand polymer belongs to triclinic(crystalline)system.
Fig. 7 and Fig. 8 is the structure iron of being made by crystal graphics software according to measurement result.
As can be seen from structure iron, the structural formula of this ligand polymer is [Tb
2(ip)
2(pic)
2]
n.This ligand polymer is reticulated structure, m-phthalic acid and 2-pyridine carboxylic acid all with metal-complexing.
Figure 14 is this ligand polymer KBr compressing tablet, at 400 ~ 4000 cm
-1the infrared spectrogram that BRUKER TENSOR 27 infrared spectrometer records is used in scope.
As can be seen from infrared spectrogram, carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of a dioctyl phthalate and 2-pyridine carboxylic acid appear at 1606.59cm respectively
-1and 1399.77cm
-1.
The predominant crystal data of this ligand polymer of table 4
The preparation of embodiment 5 rare earth organic coordination polymer
By Ho (OH)
3108mg (0.50mmol), m-phthalic acid 4.15mg (0.025mmol), 2-pyridine carboxylic acid 3mg (0.025mmol), imidazoles 1.7mg (0.025mmol) are dissolved in 4.5ml distilled water and 0.5mlDMF, stir, pH value=5 ~ 6 of reaction system are regulated with salpeter solution, then join in reactor, heat temperature raising, at temperature 160 DEG C reaction 120h, progressively be cooled to room temperature, filter, wash with water, drying, obtains orange bulk crystals.Gained crystal, on the Rigaku RAXIS-RAPID Advances in crystal X-ray diffraction instrument of Rigaku company, with graphite monochromatised molybdenum target MoK alpha-ray (λ=0.71073), collects diffraction data with ω scan mode under 293 (2) K.Crystal original texture uses SHELX-97 program direct method to solve, and then obtain whole non-hydrogen atom coordinate by difference Fourier synthesis method and method of least squares, whole non-hydrogen atom adopts F
2complete matrix method of least squares carries out anisotropy refine, obtains whole hydrogen atom coordinate by theoretical hydrogenation and difference Fourier synthesis method, and the structural formula obtaining this ligand polymer is [Ho
2(ip)
2(pic)
2]
n.
Table 5 is the predominant crystal data of this ligand polymer.
Result shows, the asymmetric cell composition C of this ligand polymer
28h
16ho
2n
2o
12with structural formula [Ho
2(ip)
2(pic)
2]
nunanimously.The crystal of this ligand polymer belongs to triclinic(crystalline)system.
Fig. 9 and Figure 10 is the structure iron of being made by crystal graphics software according to measurement result.
As can be seen from structure iron, the structural formula of this ligand polymer is [Ho
2(ip)
2(pic)
2]
n.This ligand polymer is reticulated structure, m-phthalic acid and 2-pyridine carboxylic acid all with metal-complexing.
Figure 15 is this ligand polymer KBr compressing tablet, at 400 ~ 4000 cm
-1the infrared spectrogram that BRUKER TENSOR 27 infrared spectrometer records is used in scope.
As can be seen from infrared spectrogram, carboxylate radical antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak of a dioctyl phthalate and 2-pyridine carboxylic acid appear at 1605.39cm respectively
-1and 1412.19cm
-1.
The predominant crystal data of this ligand polymer of table 5
The mensuration of this rare earth organic coordination polymer of embodiment 6 (embodiment 3 obtains) luminescent properties
The absorption spectrum of this ligand polymer is measured with Hitachi's U-3010 ultraviolet-visible spectrophotometer.
Figure 16 is the abosrption spectrogram of this ligand polymer.Can find out that this ligand polymer has a wider absorption band within the scope of wavelength 200 ~ 300nm from abosrption spectrogram.
With the emmission spectrum of this ligand polymer of Hitachi F-4500 fluorescent spectrophotometer assay.
Figure 17 is the utilizing emitted light spectrogram of this ligand polymer after the incident light of 230 ~ 250nm excites.
Can find out that this ligand polymer can send the very high ruddiness of strong purity from utilizing emitted light spectrogram.Illustrate that this ligand polymer can be used as luminescent material for generation of the very high ruddiness of purity.
The mensuration of this rare earth organic coordination polymer of embodiment 7 (embodiment 4 obtains) luminescent properties
The absorption spectrum of this ligand polymer is measured with Hitachi's U-3010 ultraviolet-visible spectrophotometer.
Figure 18 is the abosrption spectrogram of this ligand polymer.
Can find out that this ligand polymer has a wider absorption band within the scope of wavelength 200 ~ 300nm from abosrption spectrogram.With the emmission spectrum of this ligand polymer of Hitachi F-4500 fluorescent spectrophotometer assay.
Figure 19 is the utilizing emitted light spectrogram of this ligand polymer after the incident light of 265 ~ 280nm excites.
Can find out that this ligand polymer can send the very high green glow of strong purity from utilizing emitted light spectrogram.Illustrate that this ligand polymer can be used as luminescent material for generation of the very high green glow of purity.
Claims (6)
1., with the rare earth organic coordination polymer that m-phthalic acid and 2-pyridine carboxylic acid are constructed for mixed ligand, it is characterized in that its chemical formula is: [Re
2(ip)
2(pic)
2]
n, wherein ip is m-phthalic acid dianion, and pic is 2-pyridine carboxylic acid negatively charged ion, the one in Re=Pr, Nd, Eu, Tb, Ho, and n is the polymerization degree, and the crystal of this ligand polymer is triclinic(crystalline)system, and spacer is P
;
As Re=Pr, the chemical formula of the asymmetric cell of this ligand polymer is C
28h
16n
2o
12pr
2, unit cell parameters is as follows:
α=69.29 (3) °, β=70.59 (3) °, γ=81.17 (3) °;
As Re=Nd, the chemical formula of the asymmetric cell of this ligand polymer is C
28h
16n
2nd
2o
12, unit cell parameters is as follows:
α=69.14 (3) °, β=70.90 (3) °, γ=81.42 (3) °;
As Re=Eu, the chemical formula of the asymmetric cell of this ligand polymer is C
28h
16eu
2n
2o
12, unit cell parameters is as follows:
α=68.66 (3) °, β=71.49 (3) °, γ=81.93 (3) °;
As Re=Tb, the chemical formula of the asymmetric cell of this ligand polymer is C
28h
16n
2o
12tb
2, unit cell parameters is as follows:
α=68.44 (3) °, β=71.41 (3) °, γ=81.74 (3) °;
As Re=Ho, the chemical formula of the asymmetric cell of this ligand polymer is C
28h
16ho
2n
2o
12, unit cell parameters is as follows:
α=68.24 (3) °, β=71.52 (3) °, γ=81.79 (3) °.
2. the preparation method of the rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid according to claim 1, is characterized in that the method comprises the steps:
(1) be 1: 0.05 ~ 15 by the mol ratio of rare earth compound and m-phthalic acid, the mol ratio of rare earth compound and 2-pyridine carboxylic acid is 1: 0.05 ~ 15; The mol ratio of rare earth compound and nitrogenous compound is 1: 0.05 ~ 15; The mol ratio of rare earth compound and solvent is 1: 500 ~ 10000 be dissolved in solvent, stirs, regulates the pH value of reaction system to be 5 ~ 10, then join in reactor with acid or alkali;
(2) be heated to 80 DEG C ~ 300 DEG C, reaction 1 ~ 240h, progressively cooling degree is to room temperature, filters, washes with water, dry, the obtained rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid;
Wherein, 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-polymer complex; Described rare earth is any one in Pr, Nd, Eu, Tb, Ho; Described nitrogenous compound is pyridine, imidazoles, 2,2'-dipyridyls or 4, any one in 4 '-dipyridyl.
3. the preparation method of the rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid according to claim 2, is characterized in that described solvent is at least one in water, N, N'-dimethyl formamide, methyl alcohol and ethanol.
4. the preparation method of the rare earth organic coordination polymer constructed for mixed ligand with m-phthalic acid and 2-pyridine carboxylic acid according to claim 2, is characterized in that alkali is any one in triethylamine, pyridine, sodium hydroxide or potassium hydroxide.
5., according to claim 2 with the rare earth organic coordination polymer preparation method that m-phthalic acid and 2-pyridine carboxylic acid are constructed for mixed ligand, it is characterized in that acid is for any one in nitric acid, hydrochloric acid, sulfuric acid or acetic acid.
6. described in claim 1 with the application of rare earth organic coordination polymer in illumination field that m-phthalic acid and 2-pyridine carboxylic acid are constructed for mixed ligand.
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| CN106867519B (en) * | 2017-01-23 | 2019-06-11 | 西北大学 | A kind of rear-earth-doped complex white light LED fluorescent powder and preparation method thereof |
| CN115850716A (en) * | 2022-12-02 | 2023-03-28 | 桂林理工大学 | Dysprosium-lanthanum-heterorare earth coordination polymer and stepwise synthesis method and application thereof |
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| CN102153578A (en) * | 2011-02-28 | 2011-08-17 | 华南理工大学 | Rare-earth organic coordination polymer taking 4,4'-bipyridyl as template, and preparation method and application thereof |
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