CN102993222B - Dysprosium coordination polymer material with solvent molecule magnetic response and preparation method thereof - Google Patents
Dysprosium coordination polymer material with solvent molecule magnetic response and preparation method thereof Download PDFInfo
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- CN102993222B CN102993222B CN201210559155.XA CN201210559155A CN102993222B CN 102993222 B CN102993222 B CN 102993222B CN 201210559155 A CN201210559155 A CN 201210559155A CN 102993222 B CN102993222 B CN 102993222B
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Abstract
The invention relates to a dysprosium coordination polymer material with solvent molecule magnetic response, which is a dysprosium (III) coordination polymer with unimolecular magnet behaviors. The chemical formula of the dysprosium coordination polymer material is {[Dy(INO)2(NO3)]}, each asymmetric unit contains dysprosium ions which exist in one coordination environment and stores three HINO ligands in connection modes, and dicaryon dysprosium units are further connected through two ligands to form a three-dimensional porous structure. The preparation method of the dysprosium coordination polymer material comprises the following steps of: mixing Dy (NO3)3.6H2O with HINO, and dissolving in a solvent; carrying out heating reaction, and then mixing solids obtained through filtering and washing with acetonitrile; and removing the acetonitrile after the heating reaction. The dysprosium coordination polymer material disclosed by the invention is novel in structure and based on an isonicotinic nitrogen oxide ligand, contains the nanometer-pore three-dimensional coordination polymer, shows the slow magnetic relaxation behavior and can be used as an information storage material; and the preparation method of the dysprosium coordination polymer material has the advantages of simple process, easiness for implementation and high productivity, and is conductive to large-scale popularization and application.
Description
[technical field]
The present invention relates to the polymer materials with single molecular magnets behavior, particularly one and there is solvent molecule magnetic response dysprosium coordination polymer material and preparation method.
[background technology]
Magnetics is an important branch in physics, and the application of magneticsubstance brings tremendous influence to the development and progress of human society.For a long time, the more research of people be the character of conventional magnet, mainly alloy and metal oxide, metal complexes are based on the long-range effect of three-dimensional extended lattice, and the macroscopic magnetization energy produced under domain structure arrangement.In the last few years, as emerging physics and chemistry cross discipline, the magnetic embodied to explore open shell molecule and open shell molecule aggregates is characterized as the concern that molecules of interest magnetics is more and more subject to people.In this field, single molecular magnets is independently nano magnetic unit due to this body structure, has numerous special performance, so become study hotspot especially.Gondola Sessoli in 1993 etc. report unit molecule [Mn
12o
12(O2CR)
16(H
2o)
4] there is the article of superparamagnetic at low temperatures after, see Sessoli R etc., J.Am.Chem.Soc.1993,115,1804, the correlative study of this quasi-molecule causes the extensive attention of countries in the world.After the people such as Sessoli and Girolami have carried out systematic study to the feature of single molecular magnets and character and have analyzed, see Girolami G S etc., Science 1995,268,397, single molecular magnets becomes one of 21st century international emerging research frontier gradually.But the ligand polymer at present with single molecular magnets behavior mostly is zero dimension, there is three-dimensional open-framework and the research of monomolecular magnetic material by the change regulation and control character of guest molecule is little.
[summary of the invention]
The object of the invention is for the above-mentioned state of the art, provide one to have solvent molecule magnetic response dysprosium coordination polymer material and preparation method.
Technical scheme of the present invention:
Have a dysprosium coordination polymer material for solvent molecule magnetic response, for having dysprosium (III) ligand polymer of single molecular magnets behavior, its chemical formula is { [Dy (INO)
2(NO
3)], in formula: part HINO is γ-picolinic acid oxynitride; A kind of dysprosium ion of coordination environment and the HINO part having three kinds of connection modes is had in this dysprosium ligand polymer; This dysprosium ligand polymer belongs to crystal and belongs to oblique system, and spacer is P2
1/ c, unit cell parameters is:
α=γ=90 °, β=108.959 (3) °; A kind of dysprosium ion of coordination environment is had in described dysprosium ligand polymer, dysprosium ion is positioned at one and is similar to the symmetric symmetry centre of C4v, with seven carboxyl oxygen atoms coming from six γ-picolinic acid oxynitride respectively and two oxygen atom ligands come from a nitrate radical; Form a double-core dysprosium unit by two μ 2 Sauerstoffatoms and two carboxyl oxygen atom bridgings between two dysprosium ions, between double-core dysprosium unit, be connected to form three-dimensional cavernous structure further by two parts.
Described in there is the preparation method of solvent molecule magnetic response dysprosium coordination polymer material, step is as follows:
1) by Dy (NO
3)
36H
2the polytetrafluoroethylliner liner of hydrothermal reaction kettle is put in the mixing of O and HINO, adds dissolution with solvents;
2) above-mentioned hydrothermal reaction kettle is put into baking oven, heat 72 hours at 80 ° of C, then be cooled to 30 ° of C with 1 ° of C/h speed, filter, with after solvent wash, obtain ligand polymer Primary product;
3) above-mentioned ligand polymer Primary product and acetonitrile solvent are mixed in a reservoir, put into 40 degree of baking ovens and heat, within every 24 hours, change an acetonitrile solvent, after 72 hours, obtain ligand polymer exchange of solvent product;
4) above-mentioned ligand polymer exchange of solvent product is heated one hour to remove acetonitrile solvent at 200 ° of C, target compound dysprosium coordination polymer material can be obtained.
Described solvent is DMF (DMF) or ethanol (C
2h
5oH), Dy (NO
3)
36H
2the mol ratio of O, HINO and solvent is 4:3:68.
The mol ratio of described ligand polymer Primary product and acetonitrile solvent is 1:20.
Described in there is the application of the dysprosium coordination polymer material of solvent molecule magnetic response, as information storage material.
Advantage of the present invention and positively effect:
The dysprosium coordination polymer material novel structure with single molecular magnets behavior of the present invention, for the three-dimensional coordination polymer based on γ-picolinic acid oxynitride part and containing nano aperture, under 0Oe foreign field and lower than showing slow magnetic relaxation behavior at the temperature of 10K, can be used as information storage material; Preparation method's technique of the present invention is simple, easy to implement, and productive rate is high, is conducive to large-scale promotion application.
[accompanying drawing explanation]
Fig. 1 is the structural representation of the asymmetric cell of this dysprosium ligand polymer.
Fig. 2 is the three-dimensional structure schematic diagram of this dysprosium ligand polymer.
Fig. 3 is the DC magnetic susceptibility test pattern of this dysprosium ligand polymer.
Fig. 4 is the ac magnetic susceptibility test pattern of this dysprosium ligand polymer.
Fig. 5 is the ac magnetic susceptibility test pattern of the ligand polymer Primary product that DMF is prepared as solvent.
Fig. 6 is the ac magnetic susceptibility test pattern of the ligand polymer Primary product that ethanol is prepared as solvent.
Fig. 7 is the ac magnetic susceptibility test pattern of ligand polymer exchange of solvent product.
[embodiment]
Embodiment 1:
Described in there is the preparation method of solvent molecule magnetic response dysprosium coordination polymer material, step is as follows:
1) by 0.104g(0.75mmol) γ-picolinic acid oxynitride (HINO), 0.456g(1.00mmol) Dy (NO
3)
36H
2o is mixed to join in the polytetrafluoroethylliner liner of hydrothermal reaction kettle, adds 0.780g(17.00 mmol) etoh solvent dissolving, inner bag is loaded reactor;
2) above-mentioned hydrothermal reaction kettle is put into baking oven, heat 72 hours at 80 ° of C, then be cooled to 30 ° of C with 1 ° of C/h speed, filter, with alcohol solvent washing, obtain Primary product, outward appearance is faint yellow bulk crystals.The Primary product productive rate calculated based on metal dysprosium ion is 41%;
3) by 0.512g(1mmol) above-mentioned ligand polymer Primary product and 0.820g(20mmol) acetonitrile solvent mixes in a reservoir, put into 40 degree of baking ovens to heat, within every 24 hours, change an acetonitrile solvent, after 72 hours, obtain ligand polymer exchange of solvent product;
4) above-mentioned ligand polymer exchange of solvent product is heated one hour to remove acetonitrile solvent at 200 ° of C, target compound dysprosium coordination polymer material can be obtained.
Embodiment 2:
Substantially identical with method in embodiment 1, difference is: in step 1), solvent for use changes to 1.240g(17.00mmol) DMF(N, dinethylformamide); Step 2) in, cleaning solvent used changes to DMF.The Primary product productive rate calculated based on metal dysprosium ion is 41%.
The more than obtained dysprosium coordination polymer material with solvent molecule magnetic response, can be used as information storage material.
There is the sign of the dysprosium coordination polymer material of solvent molecule magnetic response behavior:
1) structure determination of the dysprosium coordination polymer material of solvent molecule magnetic response behavior
Crystal structure determination adopts Supernova type X-ray single crystal diffraction instrument, uses through graphite monochromatised Mo-K alpha-ray
for incident radiation, with
scan mode collects point diffraction, obtains unit cell parameters, utilize SHELXL-97 direct method to solve crystalline structure from difference Fourier electron density map through least-squares refinement, and through Lorentz and polarizing effect correction.All H atom are synthesized by difference Fourier and are determined through desirable position calculation.Detailed axonometry data are in table 1; Structure as depicted in figs. 1 and 2.
2) there is the magnetic properties of the dysprosium coordination polymer material of solvent molecule magnetic response
There is the DC magnetization rate curve of the dysprosium coordination polymer material of solvent molecule magnetic response as shown in Figure 3.As can be seen from the figure, DMF only has as ligand polymer Primary product prepared by solvent and just shows obvious ferromagnetic properties at low temperatures, and by the removal of solvent molecule and change, the ligand polymer Primary product that target ligand polymer, ethanol are prepared as solvent and ligand polymer exchange of solvent product illustrate omnidistance ferromegnetism behavior.
Fig. 4 is the ac magnetic susceptibility test pattern of this dysprosium ligand polymer, Fig. 5 is the ac magnetic susceptibility test pattern of the ligand polymer Primary product that DMF is prepared as solvent, Fig. 6 is the ac magnetic susceptibility test pattern of the ligand polymer Primary product that ethanol is prepared as solvent, and Fig. 7 is the ac magnetic susceptibility test pattern of ligand polymer exchange of solvent product.As can be seen from the figure, there is not imaginary part peak value in the ligand polymer Primary product that DMF is prepared as solvent, and pass through removal and the change of solvent molecule, the ac magnetic susceptibility imaginary part of the ligand polymer Primary product that target ligand polymer, ethanol are prepared as solvent and ligand polymer exchange of solvent product has shown obvious peak value, shows that they have single molecular magnets behavior.And it can be confirmed, the ligand polymer Primary product that target ligand polymer, ethanol are prepared as solvent and ligand polymer exchange of solvent product have solvent molecule magnetic response behavior.
Table 1 has the crystallographic data of the dysprosium ligand polymer of single molecular magnets behavior
。
Claims (3)
1. there is a dysprosium coordination polymer material for solvent molecule magnetic response, it is characterized in that: for having dysprosium (III) ligand polymer of single molecular magnets behavior, its chemical formula is { [Dy (INO)
2(NO
3)], in formula: part HINO is γ-picolinic acid oxynitride; A kind of dysprosium ion of coordination environment and the HINO part having three kinds of connection modes is had in this dysprosium ligand polymer; This dysprosium ligand polymer belongs to crystal and belongs to oblique system, and spacer is
p2
1/
c, unit cell parameters is:
a=10.1317 (3),
b=17.2620 (4),
c=11.2762 (3),
α=
γ=90 °,
β=108.959 (3) °; Have a kind of dysprosium ion of coordination environment in described dysprosium ligand polymer, dysprosium ion is positioned at one and is similar to
c 4vsymmetric symmetry centre, with seven carboxyl oxygen atoms coming from six γ-picolinic acid oxynitride respectively and two oxygen atom ligands come from a nitrate radical; By two between two dysprosium ions
μ2 Sauerstoffatoms and two carboxyl oxygen atom bridgings form a double-core dysprosium unit, are connected to form three-dimensional cavernous structure further between double-core dysprosium unit by two parts.
2. there is a preparation method for solvent molecule magnetic response dysprosium coordination polymer material as claimed in claim 1, it is characterized in that step is as follows:
1) by Dy (NO
3)
36H
2the polytetrafluoroethylliner liner of hydrothermal reaction kettle is put in the mixing of O and HINO, adds dissolution with solvents;
2) above-mentioned hydrothermal reaction kettle is put into baking oven, 80 DEG C of heating 72 hours, then be cooled to 30 DEG C with 1 DEG C/h speed, filter, with after solvent wash, obtain ligand polymer Primary product;
3) above-mentioned ligand polymer Primary product and acetonitrile solvent are mixed in a reservoir, put into 40 degree of baking ovens and heat, within every 24 hours, change an acetonitrile solvent, after 72 hours, obtain ligand polymer exchange of solvent product;
4) above-mentioned ligand polymer exchange of solvent product is heated one hour to remove acetonitrile solvent at 200 DEG C, target compound dysprosium coordination polymer material can be obtained;
Described solvent is DMF (DMF) or ethanol (C
2h
5oH), Dy (NO
3)
36H
2the mol ratio of O, HINO and solvent is 4:3:68;
The mol ratio of described ligand polymer Primary product and acetonitrile solvent is 1:20.
3. there is an application for the dysprosium coordination polymer material of solvent molecule magnetic response as claimed in claim 1, it is characterized in that: as information storage material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103219148B (en) * | 2013-04-27 | 2015-08-19 | 黑龙江大学 | A kind of preparation method of single molecular magnets |
| CN104497027B (en) * | 2015-01-08 | 2016-03-09 | 黑龙江大学 | A kind of Dy monomolecular magnetic material and preparation method thereof |
| CN107556341B (en) * | 2017-09-15 | 2019-03-26 | 南开大学 | Hexa-coordinate chirality dysprosium single ion magnet and its synthetic method with electromagnetic coupling effect |
| CN109485869B (en) * | 2018-11-27 | 2021-07-13 | 广东工业大学 | One-dimensional chain-like mixed dinuclear dysprosium coordination polymer and preparation method thereof |
| CN112316911B (en) * | 2020-10-28 | 2021-11-16 | 青岛理工大学 | Dual-functional metal organic framework membrane material and preparation method and application thereof |
| CN114524831B (en) * | 2022-02-21 | 2023-06-13 | 温州大学 | Dysprosium complex and preparation method and application thereof |
| CN114656491B (en) * | 2022-04-24 | 2024-01-30 | 郑州轻工业大学 | Polynuclear rare earth-based organic-inorganic hybrid magnetic material, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006043075A1 (en) * | 2004-10-22 | 2006-04-27 | U.S. Borax, Inc. | Selective oxidation of organic compounds |
| WO2010055040A1 (en) * | 2008-11-12 | 2010-05-20 | Solvay Sa | Phosphorescent light-emitting material |
| CN102136339A (en) * | 2011-01-24 | 2011-07-27 | 南开大学 | Dysprosium monomer magnet with dual functions of ferromagnetic and ferroelectric and preparation method thereof |
| CN102360674A (en) * | 2011-09-09 | 2012-02-22 | 南开大学 | Metal-radical one-dimensional coordination polymer magnetic material as well as preparation method and application thereof |
| CN102516316A (en) * | 2011-11-04 | 2012-06-27 | 南开大学 | Preparation method of oxamide macrocyclic octanuclear complex [Cu6Ln2] (Ln=Gd, tb, dy, ho) |
-
2012
- 2012-12-20 CN CN201210559155.XA patent/CN102993222B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006043075A1 (en) * | 2004-10-22 | 2006-04-27 | U.S. Borax, Inc. | Selective oxidation of organic compounds |
| WO2010055040A1 (en) * | 2008-11-12 | 2010-05-20 | Solvay Sa | Phosphorescent light-emitting material |
| CN102136339A (en) * | 2011-01-24 | 2011-07-27 | 南开大学 | Dysprosium monomer magnet with dual functions of ferromagnetic and ferroelectric and preparation method thereof |
| CN102360674A (en) * | 2011-09-09 | 2012-02-22 | 南开大学 | Metal-radical one-dimensional coordination polymer magnetic material as well as preparation method and application thereof |
| CN102516316A (en) * | 2011-11-04 | 2012-06-27 | 南开大学 | Preparation method of oxamide macrocyclic octanuclear complex [Cu6Ln2] (Ln=Gd, tb, dy, ho) |
Non-Patent Citations (2)
| Title |
|---|
| A novel dimeric complex of dysprosium with pyridine-3-carboxylic acid: structure and photophysical properties;Bing Yan et al.;《Journal of Coordination of Chemistry》;20100512;第56卷(第15期);1285-1290 * |
| 镝与对氟苯甲酸、2, 2"-联吡啶三元配合物的合成、晶体结构与表征;李夏等;《应用化学》;20061231;第23卷(第12期);1407-1409 * |
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