CN103159790A - Luminescent microporous polymer as material and method for preparing same - Google Patents
Luminescent microporous polymer as material and method for preparing same Download PDFInfo
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- CN103159790A CN103159790A CN2013101009827A CN201310100982A CN103159790A CN 103159790 A CN103159790 A CN 103159790A CN 2013101009827 A CN2013101009827 A CN 2013101009827A CN 201310100982 A CN201310100982 A CN 201310100982A CN 103159790 A CN103159790 A CN 103159790A
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Abstract
The invention relates to a luminescent microporous polymer material and a method for preparing the luminescent material. The crystal of the luminescent material belongs to a triclinic system, htpa is a p-carboxyl phenylacetate anionic carboxylate ligand, and trz is a 1, 2, 4-triazole nitrogenous ligand. The method for synthesizing the polymer is simple and is convenient to operate, the synthesized crystalline polymer has good thermal stability, high purity and good reproducibility, and the data of the fluorescence spectrum of a crystal sample show that the composition has strong fluorescence emission performance and can be used as a novel luminescent material.
Description
Technical field
The present invention relates to the luminescent material preparation field, be specifically related to a kind of preparation method of microporous polymer luminescent material.
Background technology
Ligand polymer is with a wide range of applications.Especially aspect Materials science, that ligand polymer has is unique, structure diversification, be rich in the characteristics such as transition metal ion, uncommon photovoltaic effect, and it is all had broad application prospects in all many-sides such as luminescent material, nonlinear optical material, magneticsubstance, superconducting material and catalytic materials.In numerous ligand polymer, the compound of constructing with the benzene carboxylic acid salt part is in occupation of critical role, this is because the benzene carboxylic acid salt part not only has the skeleton of rigidity but also can take flexible and changeable configuration and coordination mode, has enriched thus structure type and the functional performance of ligand polymer.
Summary of the invention
The present invention is in order to overcome above-mentioned the deficiencies in the prior art, a kind of microporous polymer fluorescent material and preparation method thereof is provided, synthetic crystalline state polymer Heat stability is good, purity is high, and favorable reproducibility, the fluorescence data of crystal prototype shows that this title complex has stronger fluorescent emission performance, can be used as novel fluorescent material.
The present invention is the deficiency that solves the problems of the technologies described above, and the technical scheme that adopts is: a kind of microporous polymer luminescent material, and the structural formula of this luminescent material is:
, the crystal of this luminescent material belongs to triclinic(crystalline)system, and spacer is
P-1, unit cell parameters is
a=10.337 (7)
,
b=11.522 (8)
,
c=12.723 (9)
,
α=79.949 (7) °,
β=86.813 (8) °,
γ=84.831 (8) °,
V=1484.8 (18)
Wherein, htpa is to carboxylphenylaceticacid acid anionic carboxylic acid part, and trz is 1,2,4-triazole containing n-donor ligand, and the skeleton symbol of two kinds of parts is as follows:
H2htpa Htrz
The asymmetric unit of this luminescent material title complex comprises the Zn atom of three different coordination modes, two htpa
2-Negatively charged ion, two trz
–Negatively charged ion, two coordinated water molecules and three crystal water molecules, the expansion of structure is to pass through htpa
2-Carboxylic acid oxo bridge on negatively charged ion connection zinc atom consists of one dimension carboxylic acid chain, and phase o-carboxylic acid chain is that the containing n-donor ligand by triazole further is expanded into the pertusate two-dimensional layer of tool, by weak effects such as hydrogen bonds, structure is expanded into three-dimensional structure between two-dimensional layer.
The preparation method of above-mentioned microporous polymer luminescent material comprises the following steps: carboxylphenylaceticacid acid, triazole and zinc acetate and appropriate alkaline liquor are dissolved in solvent, enclose in reactor, speed with 10 ℃/h is heated to 100 ~ 180 ℃, and keep 4d, then naturally be cooled to room temperature, can obtain crystal, with this crystal separation out, through washing, drying treatment, obtain luminescent material successively;
Every 1L solvent adds the carboxylphenylaceticacid acid of 0.005 ~ 0.020 mol, the triazole of 0.005 ~ 0.020 mol, the zinc acetate of 0.005 ~ 0.020 mol and the alkali of 0 ~ 0.020 mol.
Described solvent be water, dehydrated alcohol or water and ethanol arbitrarily than mixed solvent.
Described alkali lye is that concentration is potassium hydroxide or sodium hydroxide solution.
Beneficial effect
(1) microporous polymer luminescent material synthesis step of the present invention is simple, easy to operate, synthetic crystalline state polymer Heat stability is good, purity is high, and favorable reproducibility, the fluorescence data of crystal prototype show that this title complex has stronger fluorescent emission performance, can be used as novel fluorescent material.
(2) the benzene carboxylic acid salt part that uses of the present invention for to carboxylphenylaceticacid acid, utilizes part to participate in metal-complexing at two carboxyls that the phenyl ring contraposition exists as good bridge linkage group on the one hand; Utilize on the other hand the different carbon chain lengths of two carboxyls, construct the framework with pore space structure; Have again, consider the structure of the introducing energy Effective Regulation ligand polymer of assistant ligand, therefore introduced containing n-donor ligand in system, obtained one by to carboxylphenylaceticacid acid and containing n-donor ligand bridging Metal Zn (II) and the ligand polymer that forms, this compound not only has pore space structure but also has shown stronger fluorescence emitting characteristics, is expected to become a kind of advanced luminescent material.
Description of drawings
Fig. 1 is the thermogravimetric curve figure of microporous polymer luminescent material of the present invention;
Fig. 2 is powdery diffractometry (PXRD) figure of microporous polymer luminescent material of the present invention;
Fig. 3 is the solid state fluorescence spectrogram of microporous polymer luminescent material of the present invention;
Fig. 4 is the coordination environment figure of zinc in microporous polymer luminescent material of the present invention;
Fig. 5 is the one-dimensional chain that in microporous polymer luminescent material of the present invention, carboxylate salt part and Zn coordination form;
Fig. 6 is the two-dimentional pore space structure that exists in microporous polymer luminescent material of the present invention;
Fig. 7 is the main crystallographic data chart of microporous polymer luminescent material of the present invention;
Fig. 8 is important bond distance and the bond angle data drawing list of microporous polymer luminescent material of the present invention.
Embodiment
A kind of microporous polymer luminescent material, the structural formula of this luminescent material is:
, the crystal of this luminescent material belongs to triclinic(crystalline)system, and spacer is
P-1, unit cell parameters is
a=10.337 (7)
,
b=11.522 (8)
,
c=12.723 (9)
,
α=79.949 (7) °,
β=86.813 (8) °,
γ=84.831 (8) °,
V=1484.8 (18)
Wherein, htpa is to carboxylphenylaceticacid acid anionic carboxylic acid part, and trz is 1,2,4-triazole containing n-donor ligand, and the skeleton symbol of two kinds of parts is as follows:
H
2htpa Htrz
The asymmetric unit of this luminescent material title complex comprises the Zn atom of three different coordination modes, two htpa
2-Negatively charged ion, two trz
–Negatively charged ion, two coordinated water molecules and three crystal water molecules, the expansion of structure is to pass through htpa
2-Carboxylic acid oxo bridge on negatively charged ion connection zinc atom consists of one dimension carboxylic acid chain, and phase o-carboxylic acid chain is that the containing n-donor ligand by triazole further is expanded into the pertusate two-dimensional layer of tool, by weak effects such as hydrogen bonds, structure is expanded into three-dimensional structure between two-dimensional layer.
A kind of preparation method of microporous polymer luminescent material, carboxylphenylaceticacid acid, triazole and zinc acetate and appropriate alkaline liquor are dissolved in solvent, enclose in reactor, speed with 10 ℃/h is heated to 100 ~ 180 ℃, and keeps 4d, then naturally is cooled to room temperature, can obtain crystal, with this crystal separation out, through washing, drying treatment, obtain luminescent material successively;
Every 1L solvent adds the carboxylphenylaceticacid acid of 0.005 ~ 0.020 mol, the triazole of 0.005 ~ 0.020 mol, the zinc acetate of 0.005 ~ 0.020 mol and the alkali of 0 ~ 0.020 mol.
Described solvent be water, dehydrated alcohol or water and ethanol arbitrarily than mixed solvent.
Described alkali lye is potassium hydroxide or sodium hydroxide solution.
The microporous polymer fluorescent material that the present invention proposes is with to carboxylphenylaceticacid acid and containing n-donor ligand and metal-complexing formation, and its structrual description is: this title complex asymmetric unit comprises the Zn atom of three different coordination modes, two htpa
2 –Negatively charged ion, two trz
–Negatively charged ion, two coordinated water molecules and three crystal water molecules (as Fig. 4).It is to pass through htpa that structure is expanded
2 –Carboxylic acid oxo bridge connection Zn atomic building one dimension carboxylate salt chain (as Fig. 5) on negatively charged ion, phase o-carboxylic acid chain is that the further expansion by the nitrogen-atoms of triazole forms and has the thick-layer structure (as Fig. 6) of pore space structure, and the PLATON program is calculated and shown that the hole occupation rate of this compound is 16%.
By following specific embodiment as further instruction technology contents of the present invention
Will be to carboxylphenylaceticacid acid (0.05 mmol, 9.0 mg), triazole (0.05 mmol, 3.5 mg) and zinc acetate (0.10mmol, 24.0mg) be dissolved in aqueous solvent (10 mL), enclose in the reactor of 25mL, be heated to 120 ℃ with the speed of 10 ℃ per hour, kept this temperature 4 days, then naturally cool to room temperature, can obtain colourless bulk crystals, with this crystal separation out, successively through washing, drying treatment, obtain target product, productive rate approximately 58%.Main infrared absorption peak is: 3234 w, 1609 s, 1519 m, 1415 m, 1373 s, 1291 m, 1262 m, 1205w, 1161 m, 1081s, 1035w, 1010m, 941w, 863w, 825m, 781s, 724 s.
Get the gained microporous polymer and further characterize, its process is as follows:
(1) crystal structure determination of title complex
Crystal is to collect diffraction data at Bruker Apex II X-ray single crystal diffractometer, at the 293K temperature, adopts the Mo of graphite monochromator monochromatization
Ka Ray (
λ=0.071073nm), scan mode is
φ – ωScanning.The crystalline diffraction data are used the TEXSAN programe reduction, and crystal structure analysis work is to resolve with SHELX-97 programming systems on PC.Diffracted intensity data warp
LpThe factor and experience absorption correction adopt direct method to resolve and obtain just structure.Fourie is synthetic through number wheel difference, finds whole non-hydrogen atoms.The coordinate of all non-hydrogen atoms and anisotropic temperature factor carry out refine with the complete matrix method of least squares.Hydrogen atom on water molecules obtains and is fixed in refine on parent atom by the difference Fourier synthesis method, and the hydrogen on carbon atom adopts how much hydrogenation methods to obtain.Detailed axonometry data are seen Fig. 7; Important bond distance and bond angle data are seen Fig. 8.Crystalline structure is seen Fig. 4, Fig. 5 and Fig. 6.
(2) thermostability of title complex characterizes
Thermogravimetric analysis (seeing Fig. 1) shows that title complex is warming up to 105 ℃ corresponding to lose (actual weightlessness is 11.0%, and theoretical weightlessness is 11.6%) of 5 water moleculess from room temperature.Subsequently, temperature until 350 ℃ obvious weight loss does not all occur, illustrate that the framework of releasing water molecule can keep higher thermostability below 350 ℃, this is that it is as the important guarantee of practical application fluorescent material.(instrument model: SII EXStar6000 TG/DTA6300).
(3) the PXRD crystalline phase purity of title complex characterizes
The PXRD of title complex characterizes and shows that it has higher crystalline phase purity, for its application as fluorescent material provides the purity assurance, sees Fig. 2.(instrument model: Bruker/D8 Advance).
(4) the solid fluorescence performance study of title complex
Complex crystal sample after enrichment is processed carries out the test of solid fluorescence: learn that by fluorescence pattern analysis (as Fig. 3) this title complex is subjected to 310nm place's optical excitation, there is strong fluorescent absorption peak at the place at the 418nm light wave.Answer this, this title complex can be used as fluorescent material and is further used.(instrument model: HITACHI/F-4500).
Other reaction conditions becomes dehydrated alcohol with embodiment 1 with solvent replacement, obtains colourless bulk crystals, and crystal is through washing, filtration, drying, and the final product productive rate is about 48%.This crystal is through the infrared spectrum test, and the characteristic peak that presents and embodiment 1 are identical, can verify that this crystal is target product.
Other reaction conditions becomes solvent replacement the mixed solvent (volume ratio of dehydrated alcohol and water is 1:1) of dehydrated alcohol and water with embodiment 1, can obtain colourless bulk crystals.Crystal is through washing, filtration, drying, and the final product productive rate is about 67%.This crystal is through the infrared spectrum test, and the characteristic peak that presents and embodiment 1 are identical, can verify that this crystal is target product.
Other reaction conditions is with embodiment 1, change consumption and the ratio of carboxylic acid and containing n-donor ligand, concrete operations are as follows: will be to carboxylphenylaceticacid acid (0.05 mmol, 9.0 mg), triazole (0.10 mmol, 6.9 mg) with zinc acetate (0.10mmol, 24.0 mg) be dissolved in aqueous solvent (10mL), the later stage operation is identical with embodiment 1, can obtain colourless bulk crystals.Crystal is through washing, filtration, drying, and the final product productive rate is about 52%.This crystal is through the infrared spectrum test, and the characteristic peak that presents and embodiment 1 are identical, can verify that this crystal is target product.
Other reaction conditions is with embodiment 1, change consumption and the ratio of carboxylic acid and containing n-donor ligand, concrete operations are as follows: will be to carboxylphenylaceticacid acid (0.10 mmol, 18.0 mg), triazole (0.05 mmol, 3.5 mg) with zinc acetate (0.10mmol, 24.0 mg) be dissolved in aqueous solvent (10mL), the later stage operation is identical with embodiment 1, can obtain colourless bulk crystals.Crystal is through washing, filtration, drying, and the final product productive rate is about 50%.This crystal is through the infrared spectrum test, and the characteristic peak that presents and embodiment 1 are identical, can verify that this crystal is target product.
With embodiment 1,4 and 5, in the situation that other condition is all identical, the add-on of each reactant is all doubled, the productive rate of last gained crystal is respectively 49%, 46% and 43%.These crystal are through the infrared spectrum test, and the characteristic peak that presents and embodiment 1 are identical, can verify that this crystal is target product.
As described in Example 1, under other condition same case, add the pH value of 0.10mmol potassium hydroxide regulator solution in system, the later stage operation is identical with embodiment 1, can obtain colourless bulk crystals.Crystal is through washing, filtration, drying, and the final product productive rate is about 45%.This crystal is through the infrared spectrum test, and the characteristic peak that presents and embodiment 1 are identical, can verify that this crystal is target product.
As described in Example 1, under other condition same case, add the pH value of 0.20mmol sodium hydrate regulator solution in system, the later stage operation is identical with embodiment 1, can obtain colourless bulk crystals.Crystal is through washing, filtration, drying, and the final product productive rate is about 43%.This crystal is through the infrared spectrum test, and the characteristic peak that presents and embodiment 1 are identical, can verify that this crystal is target product.
As described in Example 1, under other condition same case, the temperature that the change system is kept, early stage operation is identical with embodiment 1, at last system is heated to 100 ℃ with the speed of 10 ℃ per hour, keeps this temperature 4 days, then naturally cool to room temperature, can obtain colourless bulk crystals.Crystal is through washing, filtration, drying, and the final product productive rate is about 47%.This crystal is through the infrared spectrum test, and institute's expression characteristics peak and embodiment 1 are identical, can verify that this crystal is target product.
As described in Example 1, under other condition same case, the temperature that the change system is kept, early stage operation is identical with embodiment 1, at last system is heated to 180 ℃ with the speed of 10 ℃ per hour, keeps this temperature 4 days, then naturally cool to room temperature, can obtain colourless bulk crystals.Crystal is through washing, filtration, drying, and the final product productive rate is about 40%.This crystal is through the infrared spectrum test, and institute's expression characteristics peak and embodiment 1 are identical, can verify that this crystal is target product.
Claims (4)
1. microporous polymer luminescent material, it is characterized in that: the structural formula of this luminescent material is:
Wherein, htpa is to carboxylphenylaceticacid acid anionic carboxylic acid part, and trz is 1,2,4-triazole containing n-donor ligand, and the skeleton symbol of two kinds of parts is as follows:
H
2htpa Htrz
The asymmetric unit of this luminescent material title complex comprises the Zn atom of three different coordination modes, two htpa
2-Negatively charged ion, two trz
–Negatively charged ion, two coordinated water molecules and three crystal water molecules, the expansion of structure is to pass through htpa
2-Carboxylic acid oxo bridge on negatively charged ion connection zinc atom consists of one dimension carboxylic acid chain, and phase o-carboxylic acid chain is that the containing n-donor ligand by triazole further is expanded into the pertusate two-dimensional layer of tool, by weak effects such as hydrogen bonds, structure is expanded into three-dimensional structure between two-dimensional layer.
2. the preparation method of a kind of microporous polymer luminescent material as claimed in claim 1, it is characterized in that: carboxylphenylaceticacid acid, triazole and zinc acetate and appropriate alkaline liquor are dissolved in solvent, enclose in reactor, speed with 10 ℃/h is heated to 100 ~ 180 ℃, and keeps 4d, then naturally is cooled to room temperature, can obtain crystal, with this crystal separation out, through washing, drying treatment, obtain luminescent material successively;
Every 1L solvent adds the carboxylphenylaceticacid acid of 0.005 ~ 0.020 mol, the triazole of 0.005 ~ 0.020 mol, the zinc acetate of 0.005 ~ 0.020 mol and the alkali of 0 ~ 0.020 mol.
3. the preparation method of a kind of microporous polymer luminescent material as claimed in claim 2 is characterized in that: described solvent be water, dehydrated alcohol or water and ethanol arbitrarily than mixed solvent.
4. the preparation method of a kind of microporous polymer luminescent material as claimed in claim 2, it is characterized in that: described alkali lye is potassium hydroxide or sodium hydroxide solution.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665006A (en) * | 2013-12-13 | 2014-03-26 | 南开大学 | Porous metal-organic framework hybrid material as well as preparation method and application thereof |
| CN103965265A (en) * | 2014-04-28 | 2014-08-06 | 洛阳师范学院 | High thermal stability energetic complex and preparation method thereof |
| CN104370949A (en) * | 2014-11-13 | 2015-02-25 | 东北师范大学 | Chiral naphthyl diacetic acid-bis(triazolyl)zinc coordination compound and preparation method thereof |
| CN110105406A (en) * | 2019-06-27 | 2019-08-09 | 商丘师范学院 | A kind of [CdNa based on o-carboxyl phenylacetic acid ligand2] different metal fluorescent material and preparation method thereof |
| CN110194782A (en) * | 2019-06-27 | 2019-09-03 | 商丘师范学院 | A kind of [Cd based on o-carboxyl phenylacetic acid ligand2Na2] different metal fluorescent material and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665006A (en) * | 2013-12-13 | 2014-03-26 | 南开大学 | Porous metal-organic framework hybrid material as well as preparation method and application thereof |
| CN103665006B (en) * | 2013-12-13 | 2016-01-06 | 南开大学 | A kind of porous metal metal-organic framework hybrid material and its preparation method and application |
| CN103965265A (en) * | 2014-04-28 | 2014-08-06 | 洛阳师范学院 | High thermal stability energetic complex and preparation method thereof |
| CN103965265B (en) * | 2014-04-28 | 2016-03-30 | 洛阳师范学院 | A kind of high heat-resistant quality energetic compound and preparation method thereof |
| CN104370949A (en) * | 2014-11-13 | 2015-02-25 | 东北师范大学 | Chiral naphthyl diacetic acid-bis(triazolyl)zinc coordination compound and preparation method thereof |
| CN110105406A (en) * | 2019-06-27 | 2019-08-09 | 商丘师范学院 | A kind of [CdNa based on o-carboxyl phenylacetic acid ligand2] different metal fluorescent material and preparation method thereof |
| CN110194782A (en) * | 2019-06-27 | 2019-09-03 | 商丘师范学院 | A kind of [Cd based on o-carboxyl phenylacetic acid ligand2Na2] different metal fluorescent material and preparation method thereof |
| CN110105406B (en) * | 2019-06-27 | 2021-06-11 | 商丘师范学院 | CdNa based on o-carboxyl phenylacetic acid ligand2]Dissimilar metal fluorescent material and preparation method thereof |
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