CN102993222A - 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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- CN102993222A CN102993222A CN201210559155XA CN201210559155A CN102993222A CN 102993222 A CN102993222 A CN 102993222A CN 201210559155X A CN201210559155X A CN 201210559155XA CN 201210559155 A CN201210559155 A CN 201210559155A CN 102993222 A CN102993222 A CN 102993222A
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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 have the polymer materials of single molecular magnets behavior, particularly a kind of have solvent molecule magnetic response dysprosium coordination polymer material and a preparation method.
[background technology]
Magnetics is an important branch in the physics, and the application of magneticsubstance has brought tremendous influence to the development and progress of human society.For a long time, the more researchs of people be the character of conventional magnet, mainly be alloy and metal oxide, metal complexes based on the long-range effect of three-dimensional extended lattice, and the macroscopic magnetization energy that under domain structure is arranged, produces.In the last few years, as emerging physics and chemistry cross discipline, the magnetic that is embodied with exploration open shell molecule and open shell molecule aggregates was characterized as the concern that the molecules of interest magnetics more and more is subject to people.In this field, single molecular magnets has numerous special performances, so become especially study hotspot because this body structure is nano magnetic unit independently.Gondola Sessoli in 1993 etc. have reported unit molecule [Mn
12O
12(O2CR)
16(H
2O)
4] have at low temperatures after the article of superparamagnetic, referring to Sessoli R etc., J.Am.Chem.Soc.1993,115,1804, the correlative study of this quasi-molecule has caused 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, referring to Girolami G S etc., Science 1995,268,397, single molecular magnets becomes one of international emerging research frontier of 21st century gradually.Yet the ligand polymer that has at present the single molecular magnets behavior mostly is zero dimension, have three-dimensional open-framework and change regulation and control character that can be by guest molecule monomolecular magnetic material research seldom.
[summary of the invention]
The objective of the invention is for the above-mentioned state of the art, a kind of have solvent molecule magnetic response dysprosium coordination polymer material and preparation method be provided.
Technical scheme of the present invention:
A kind of dysprosium coordination polymer material with solvent molecule magnetic response is dysprosium (III) ligand polymer with single molecular magnets behavior, and its chemical formula is { [Dy (INO)
2(NO
3)], in the formula: part HINO is the γ-picolinic acid oxynitride; Dysprosium ion and the HINO part that has three kinds of connection modes that a kind of coordination environment is arranged 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) °; The dysprosium ion that a kind of coordination environment is arranged in the 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 that come from respectively six γ-picolinic acid oxynitride with come from two oxygen atom ligands on the nitrate radical; Form a double-core dysprosium unit by two μ 2 Sauerstoffatoms and two carboxyl oxygen atom bridgings between two dysprosium ions, further be connected to form three-dimensional cavernous structure by two parts between the double-core dysprosium unit.
A kind of described preparation method with solvent molecule magnetic response dysprosium coordination polymer material, step is as follows:
1) with Dy (NO
3)
36H
2O and the polytetrafluoroethylliner liner of putting into hydrothermal reaction kettle mixing of HINO add dissolution with solvents;
2) above-mentioned hydrothermal reaction kettle is put into baking oven, 80 ° of C heating 72 hours, be cooled to 30 ° of C with 1 ° of C/h speed again, filter, with behind the solvent wash, get the ligand polymer Primary product;
3) above-mentioned ligand polymer Primary product and acetonitrile solvent are mixed in container, put into 40 degree baking ovens and heat, changed an acetonitrile solvent, and obtained ligand polymer exchange of solvent product after 72 hours in per 24 hours;
4) above-mentioned ligand polymer exchange of solvent product is heated one hour to remove acetonitrile solvent at 200 ° of C, can obtain target compound dysprosium coordination polymer material.
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.
A kind of described application with dysprosium coordination polymer material of solvent molecule magnetic response is as information storage material.
Advantage of the present invention and positively effect:
Dysprosium coordination polymer material novel structure with single molecular magnets behavior of the present invention, for based on γ-picolinic acid oxynitride part and contain the three-dimensional coordination polymer of nano aperture, showing slow magnetic relaxation behavior under the 0Oe foreign field with under the temperature that is lower than 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.
[description of drawings]
Fig. 1 is the structural representation of the asymmetric cell of this dysprosium ligand polymer.
Fig. 2 is the three-dimensional structure synoptic diagram of this dysprosium ligand polymer.
Fig. 3 is the DC magnetic rate test pattern of this dysprosium ligand polymer.
Fig. 4 is the ac magnetic susceptibility test pattern of this dysprosium ligand polymer.
Fig. 5 is that DMF is as the ac magnetic susceptibility test pattern of the ligand polymer Primary product of solvent preparation.
Fig. 6 is that ethanol is as the ac magnetic susceptibility test pattern of the ligand polymer Primary product of solvent preparation.
Fig. 7 is the ac magnetic susceptibility test pattern of ligand polymer exchange of solvent product.
[embodiment]
Embodiment 1:
A kind of described preparation method with solvent molecule magnetic response dysprosium coordination polymer material, step is as follows:
1) with 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) the etoh solvent dissolving, with the inner bag reactor of packing into;
2) above-mentioned hydrothermal reaction kettle is put into baking oven, 80 ° of C heating 72 hours, be cooled to 30 ° of C with 1 ° of C/h speed again, filter, with the alcohol solvent washing, obtain Primary product, outward appearance is faint yellow bulk crystals.The Primary product productive rate that calculates based on the metal dysprosium ion is 41%;
3) with 0.512g(1mmol) above-mentioned ligand polymer Primary product and 0.820g(20mmol) acetonitrile solvent mixes in container, putting into 40 degree baking ovens heats, changed an acetonitrile solvent, and obtained ligand polymer exchange of solvent product after 72 hours in per 24 hours;
4) above-mentioned ligand polymer exchange of solvent product is heated one hour to remove acetonitrile solvent at 200 ° of C, can obtain target compound dysprosium coordination polymer material.
Embodiment 2:
Basic identical with method among the embodiment 1, difference is: solvent for use changes to 1.240g(17.00mmol in the step 1)) DMF(N, dinethylformamide); Step 2) in, used cleaning solvent changes to DMF.The Primary product productive rate that calculates based on the metal dysprosium ion is 41%.
The dysprosium coordination polymer material with solvent molecule magnetic response that more than makes can be used as information storage material.
Sign with 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
Supernova type X-ray single crystal diffractometer is adopted in crystal structure determination, uses the Mo-K alpha-ray through the graphite monochromatization
Be incident radiation, with
Scan mode is collected point diffraction, obtains unit cell parameters through least-squares refinement, utilizes the SHELXL-97 direct method to solve crystalline structure from the difference Fourier electron density map, and through Lorentz and polarizing effect correction.All H atoms are synthetic and definite through desirable position calculation by difference Fourier.Detailed axonometry data see Table 1; Structure as depicted in figs. 1 and 2.
2) has the magnetic properties of the dysprosium coordination polymer material of solvent molecule magnetic response
Have the solvent molecule magnetic response the dysprosium coordination polymer material the dc magnetization rate curve as shown in Figure 3.As can be seen from the figure, DMF only has as the ligand polymer Primary product of solvent preparation and just shows at low temperatures obvious ferromegnetism character, and removal and change by solvent molecule, target ligand polymer, ethanol have shown omnidistance ferromegnetism behavior as ligand polymer Primary product and the ligand polymer exchange of solvent product of solvent preparation.
Fig. 4 is the ac magnetic susceptibility test pattern of this dysprosium ligand polymer, Fig. 5 is that DMF is as the ac magnetic susceptibility test pattern of the ligand polymer Primary product of solvent preparation, Fig. 6 is ethanol as the ac magnetic susceptibility test pattern of the ligand polymer Primary product of solvent preparation, and Fig. 7 is the ac magnetic susceptibility test pattern of ligand polymer exchange of solvent product.As can be seen from the figure, DMF the imaginary part peak value do not occur as the ligand polymer Primary product of solvent preparation, and removal and change by solvent molecule, target ligand polymer, ethanol have shown obvious peak value as the ligand polymer Primary product of solvent preparation and the ac magnetic susceptibility imaginary part of ligand polymer exchange of solvent product, show that they have the single molecular magnets behavior.And it can be confirmed that target ligand polymer, ethanol have solvent molecule magnetic response behavior as ligand polymer Primary product and the ligand polymer exchange of solvent product of solvent preparation.
Table 1 has the crystallographic data of the dysprosium ligand polymer of single molecular magnets behavior
Claims (5)
1. dysprosium coordination polymer material with solvent molecule magnetic response, it is characterized in that: be dysprosium (III) ligand polymer with single molecular magnets behavior, its chemical formula is { [Dy (INO)
2(NO
3)], in the formula: part HINO is the γ-picolinic acid oxynitride; Dysprosium ion and the HINO part that has three kinds of connection modes that a kind of coordination environment is arranged 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) °; The dysprosium ion that a kind of coordination environment is arranged in the described dysprosium ligand polymer, dysprosium ion are positioned at one and are similar to C
4vSymmetric symmetry centre is with seven carboxyl oxygen atoms that come from respectively six γ-picolinic acid oxynitride with come from two oxygen atom ligands on the nitrate radical; Form a double-core dysprosium unit by two μ 2 Sauerstoffatoms and two carboxyl oxygen atom bridgings between two dysprosium ions, further be connected to form three-dimensional cavernous structure by two parts between the double-core dysprosium unit.
2. preparation method who has as claimed in claim 1 solvent molecule magnetic response dysprosium coordination polymer material is characterized in that step is as follows:
1) with Dy (NO
3)
36H
2O and the polytetrafluoroethylliner liner of putting into hydrothermal reaction kettle mixing of HINO add dissolution with solvents;
2) above-mentioned hydrothermal reaction kettle is put into baking oven, 80 ° of C heating 72 hours, be cooled to 30 ° of C with 1 ° of C/h speed again, filter, with behind the solvent wash, get the ligand polymer Primary product;
3) above-mentioned ligand polymer Primary product and acetonitrile solvent are mixed in container, put into 40 degree baking ovens and heat, changed an acetonitrile solvent, and obtained ligand polymer exchange of solvent product after 72 hours in per 24 hours;
4) above-mentioned ligand polymer exchange of solvent product is heated one hour to remove acetonitrile solvent at 200 ° of C, can obtain target compound dysprosium coordination polymer material.
3. described preparation method with solvent molecule magnetic response dysprosium coordination polymer material according to claim 2, it is characterized in that: 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.
4. described preparation method with solvent molecule magnetic response dysprosium coordination polymer material according to claim 2, it is characterized in that: the mol ratio of described ligand polymer Primary product and acetonitrile solvent is 1:20.
5. application that has as claimed in claim 1 the dysprosium coordination polymer material of solvent molecule magnetic response is characterized in that: as information storage material.
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Cited By (7)
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| CN103219148A (en) * | 2013-04-27 | 2013-07-24 | 黑龙江大学 | Preparation method of single-molecule magnetic body |
| CN104497027A (en) * | 2015-01-08 | 2015-04-08 | 黑龙江大学 | Dy monomolecular magnetic material and preparation method thereof |
| CN107556341A (en) * | 2017-09-15 | 2018-01-09 | 南开大学 | Hexa-coordinate chirality dysprosium single ion magnet and its synthetic method with electromagnetic coupling effect |
| CN109485869A (en) * | 2018-11-27 | 2019-03-19 | 广东工业大学 | Two core dysprosium coordination polymers of a kind of one-dimensional chain mixing and preparation method thereof |
| CN112316911A (en) * | 2020-10-28 | 2021-02-05 | 青岛理工大学 | Dual-functional metal organic framework membrane material and preparation method and application thereof |
| CN114524831A (en) * | 2022-02-21 | 2022-05-24 | 温州大学 | Dysprosium complex and preparation method and application thereof |
| CN114656491A (en) * | 2022-04-24 | 2022-06-24 | 郑州轻工业大学 | Multi-core rare earth-based organic-inorganic hybrid magnetic material and preparation method and application thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103219148A (en) * | 2013-04-27 | 2013-07-24 | 黑龙江大学 | Preparation method of single-molecule magnetic body |
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| CN104497027A (en) * | 2015-01-08 | 2015-04-08 | 黑龙江大学 | Dy monomolecular magnetic material and preparation method thereof |
| 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 |
| CN107556341A (en) * | 2017-09-15 | 2018-01-09 | 南开大学 | Hexa-coordinate chirality dysprosium single ion magnet and its synthetic method with electromagnetic coupling effect |
| CN109485869A (en) * | 2018-11-27 | 2019-03-19 | 广东工业大学 | Two core dysprosium coordination polymers of a kind of one-dimensional chain mixing and preparation method thereof |
| 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 |
| CN112316911A (en) * | 2020-10-28 | 2021-02-05 | 青岛理工大学 | Dual-functional metal organic framework membrane material and preparation method and application thereof |
| CN114524831A (en) * | 2022-02-21 | 2022-05-24 | 温州大学 | Dysprosium complex 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 |
| CN114656491A (en) * | 2022-04-24 | 2022-06-24 | 郑州轻工业大学 | Multi-core rare earth-based organic-inorganic hybrid magnetic material 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 |
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