CN103714932A - Co zero-dimension single-molecular magnet material, preparation method and application of Co zero dimension single-molecular magnet material - Google Patents
Co zero-dimension single-molecular magnet material, preparation method and application of Co zero dimension single-molecular magnet material Download PDFInfo
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- CN103714932A CN103714932A CN201310744435.2A CN201310744435A CN103714932A CN 103714932 A CN103714932 A CN 103714932A CN 201310744435 A CN201310744435 A CN 201310744435A CN 103714932 A CN103714932 A CN 103714932A
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Abstract
The invention discloses a Co zero-dimension single-molecular magnet material, a preparation method and application of the Co zero dimension single-molecular magnet material and belongs to the technical field of molecular base materials. The chemical formula is [Co2(L)3(NO3)]2 (NO3)2, wherein L is an organic ligand 2-ethyl-4, 5- dihydroxy methylimidazole. In a sealed state, the organic ligand L and cobalt nitrate receive a thermal reaction in ethyl alcohol or methyl alcohol to obtain a crystal of the zero-dimension single-molecular magnet material. The molar ratio of the organic ligand L and the cobalt nitrate is (0.5-3):1, every 0.1 millimole of the organic ligand L corresponds to 2-4mL of the ethyl alcohol or methyl alcohol. Large antiferromagnetic coupling action exists among manganese ions of a single-molecular magnet, and the Co zero dimension single-molecular magnet material can be used as a molecular base magnetic material.
Description
Technical field
The invention belongs to molecular based material technology field, design metal-organic coordination polymer material, particularly a kind of preparation method of zero dimension single molecular magnets and application thereof.
Background technology
Single molecular magnets research (Single-Molecule Magnets, SMMs) is the novel research field of rising in recent years.Single molecular magnets is the new material between molecular based magnet and nano magnetic material.Single molecular magnets, because this body structure is nano magnetic unit independently, has numerous special performances, so become study hotspot.1993, Sessoli research group found the first single molecular magnets [Mn
12o
12(O
2cMe)
16(H
2o)
4] 2 (CH
3cOOH) 4H
2o is referring to Sessoli R etc., J.Am.Chem.Soc.1993,115,1804.After this people such as Sessoli and Girolami has carried out system research and analysis to the feature of single molecular magnets and character, referring to Girolami G S etc., Science1995,268,397, single molecular magnets becomes one of international emerging research frontier of 21st century gradually.Single molecular magnets has been subject to current single molecular magnets mainly by the transition metal single molecular magnetses such as Mn, Co, Cu, the rare earth metal single molecular magnetses such as Dy, Tb and 3d-4f(transition-rare earth) metal single molecular magnets composition.Single molecular magnets has the peculiar properties such as quantum tunneling magnetization effect and quantum Interference, and they are likely widely used in many-sides such as quantum computers.Single molecular magnets material, the special dimensional effect or the quantum effect that cause due to its huge surface/volume, with and the improvement of small yardstick response time, energy loss and the efficiency of transmission brought and be expected to become superelevation information density storage medium.Therefore, the correlative study of this quasi-molecule has caused the extensive attention of countries in the world.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application thereof of zero dimension single molecular magnets magnetic material.
Zero dimension single molecular magnets magnetic material of the present invention, is characterized in that, chemical formula is [Co
2(L)
3(NO
3)]
2(NO
3)
2, wherein L is organic ligand 2-ethyl-4,5-hydroxymethyl-imidazole.
Above-mentioned zero dimension single molecular magnets magnetic material, its secondary building unit is: crystal belongs to monoclinic system, and space group is P2 (1)/C, and cell parameter is:
β=118.78
°, α=γ=90
°; From connecting the angle of constructing, this single molecular magnets has the cobalt of two kinds of configurations, be designated as respectively Co1, Co1A, Co2, Co2A, Co1 and Co1A are identical configuration and connected modes, Co2 and Co2A are identical configuration and connected modes, wherein, Co1 is connected with 1 nitrate anion with 3 parts, and Co2 is connected with 4 parts; Wherein, the connected mode of cobalt and part be with part on N and with the μ on pendant hydroxyl group
2-O and μ
3-O connects; All cobalts are hexa-coordinate, form the octoploids structure of distortion.
Organic ligand 2-ethyl-4 wherein, the chemical structural formula of 5-hydroxymethyl-imidazole is:
The synthetic method of zero dimension single molecular magnets of the present invention, comprises the following steps:
Under closed state, organic ligand L(2-ethyl-4,5-hydroxymethyl-imidazole), in ethanol or methyl alcohol, via thermal response, obtain the crystal of zero dimension single molecular magnets material with cobalt nitrate; Wherein said organic ligand L (2-ethyl-4,5-hydroxymethyl-imidazole) is (0.5～3) with the mol ratio of cobalt nitrate: 1, and ethanol or the methyl alcohol of the corresponding 2-4mL of organic ligand L of every 0.1 mM.
The reaction condition of described thermal response is 40 ℃-80 ℃, and the reaction time is 2-4 days, preferably 3 days.Via thermal response, within 3 days, obtain acicular crystal.
Between this single molecular magnets manganese ion, there is larger antiferromagnetic coupling effect, can be used as molecule based magnetic materials.
This single molecular magnets material has antiferromagnetic character aspect material, can be used as molecule based magnetic materials, at material science, has a good application prospect.
Accompanying drawing explanation
Accompanying drawing 1 is [Co
2(L)
3(NO
3)]
2(NO
3)
2in [Co
2(L)
3(NO
3)]
2crystal structure figure.
Accompanying drawing 2Co
2(L)
3(NO
3)]
2(NO
3)
2molar susceptibility curve chart.
Accompanying drawing 3Co
2(L)
3(NO
3)]
2(NO
3)
2variable field susceptibility curve figure.
Embodiment
Below in conjunction with specifically having implemented, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
By organic ligand 2-ethyl-4,5-hydroxymethyl-imidazole (0.1 mM) stirs in 3mL ethanol with cobalt nitrate (0.05 mM), encloses in bottle.At 60 ℃, via thermal response, within 3 days, obtain the crystal of zero dimension single molecular magnets material.
Embodiment 2
By organic ligand 2-ethyl-4,5-hydroxymethyl-imidazole (0.1 mM) stirs in 4mL ethanol with cobalt nitrate (0.1 mM), encloses in bottle.At 60 ℃, via thermal response, within 3 days, obtain the crystal of zero dimension single molecular magnets material.
Embodiment 3
By organic ligand 2-ethyl-4,5-hydroxymethyl-imidazole (0.1 mM) stirs in 4mL methyl alcohol with cobalt nitrate (0.1 mM), encloses in bottle.At 60 ℃, via thermal response, within 3 days, obtain the crystal of zero dimension single molecular magnets material.
The data that above-described embodiment products obtained therefrom is waken up with a start test are identical, the sign to embodiment complex:
(1) crystal structure determination:
Choose under the microscope the monocrystalline of suitable size, under room temperature, at Bruker SMART1000CCD face, visit on diffractometer, use the alpha ray through the Mo-K of graphite monochromator monochromatization, in ω-φ mode, collect diffraction data.All diffraction datas are used SADABS program to carry out absorption correction.Cell parameter is used least square method to determine.Data reduction and structure elucidation are used respectively SAINT and SHELXTL program to complete.First by difference functions method and least square method, determine whole non-hydrogen atom coordinates, and obtain hydrogen atom position with theoretical hydrogenation method, then with SHELXTL, crystal structure is carried out to refine.Fig. 1 is shown in by structure chart.Crystallographic data is in Table 1.
The crystallographic data of table 1 complex
The structure chart of Fig. 1 shows: in the single molecular magnets making, have the cobalt ions of two kinds of configurations, be respectively Co1, Co1A and Co2, Co2A, Co1 is the atom that configuration and connected mode are identical with Co1A, and Co2 is the atom that configuration and connected mode are identical with Co2A.Wherein, Co1 is connected with 1 nitrate anion with 3 parts, and Co2 is connected with 4 parts.Wherein, the connected mode of cobalt ions and part be with part on N and with the μ on pendant hydroxyl group
2-O and μ
3-O connects.All cobalt ionss are hexa-coordinate, form the octoploids structure of distortion.(2) magnetic performance characterizes:
Fig. 2-Fig. 3 is the magnetic characterization of claim 1.In Fig. 2, along with the reduction of temperature, X
mt value decreases, and illustrates that claim 1 magnetic material all exists antiferromagnetic coupling effect.
Claims (7)
1. a zero dimension unimolecule material, is characterized in that, chemical formula is [Co
2(L)
3(NO
3)]
2(NO
3)
2, wherein L is organic ligand 2-ethyl-4,5-hydroxymethyl-imidazole.
2. a kind of zero dimension unimolecule material of claim 1, is characterized in that, secondary building unit is: crystal belongs to monoclinic system, and space group is P2 (1)/C, and cell parameter is:
β=118.78 °, α=γ=90 °.
3. a kind of zero dimension unimolecule material of claim 1, it is characterized in that, from connecting the angle of constructing, this single molecular magnets has the cobalt of two kinds of configurations, is designated as respectively Co1, Co1A, Co2, Co2A, and Co1 and Co1A are identical configuration and connected modes, Co2 and Co2A are identical configuration and connected modes, wherein, Co1 is connected with 1 nitrate anion with 3 parts, and Co2 is connected with 4 parts; Wherein, the connected mode of cobalt and part be with part on N and with the μ on pendant hydroxyl group
2-O and μ
3-O connects; All cobalts are hexa-coordinate, form the octoploids structure of distortion.
4. prepare a kind of zero dimension unimolecule material claimed in claim 1, it is characterized in that, comprise the following steps: under closed state, organic ligand L(2-ethyl-4,5-hydroxymethyl-imidazole), in ethanol or methyl alcohol, via thermal response, obtain the crystal of zero dimension single molecular magnets material with cobalt nitrate; Wherein said organic ligand L (2-ethyl-4,5-hydroxymethyl-imidazole) is (0.5～3) with the mol ratio of cobalt nitrate: 1, and ethanol or the methyl alcohol of the corresponding 2-4mL of organic ligand L of every 0.1 mM.
5. according to the method for claim 4, it is characterized in that, the reaction condition of described thermal response is 40 ℃-80 ℃, and the reaction time is 2-4 days.
6. according to the method for claim 5, it is characterized in that, the reaction time is 3 days.
7. the zero dimension unimolecule material of claim 1 is as molecule based magnetic materials.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070497A (en) * | 2015-08-25 | 2015-11-18 | 广西大学 | Cobalt-based single-molecular magnet synthesizing method |
| CN105225779A (en) * | 2015-10-19 | 2016-01-06 | 广西大学 | A kind of cobalt-based single-chain magnets and synthetic method thereof |
| CN103994792B (en) * | 2014-05-30 | 2017-01-25 | 北京理工大学 | Polyacid dysprosium single-molecular magnets and preparation method thereof |
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| JP4379575B2 (en) * | 2003-06-23 | 2009-12-09 | 日産化学工業株式会社 | Single molecule magnet and method for producing the same |
| JP4651111B2 (en) * | 2006-03-09 | 2011-03-16 | 国立大学法人九州大学 | Single molecule magnet |
| CN102087900A (en) * | 2010-12-14 | 2011-06-08 | 黑龙江大学 | Salen-like and diketone-base dysprosium tetranuclear cluster compound type monomolecular magnetic material and preparation method thereof |
| CN103310938A (en) * | 2013-06-27 | 2013-09-18 | 黑龙江大学 | Co-Dy type single molecule magnetic material and preparation method thereof |
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| JP4379575B2 (en) * | 2003-06-23 | 2009-12-09 | 日産化学工業株式会社 | Single molecule magnet and method for producing the same |
| JP4651111B2 (en) * | 2006-03-09 | 2011-03-16 | 国立大学法人九州大学 | Single molecule magnet |
| CN101092477A (en) * | 2006-06-21 | 2007-12-26 | 拜尔材料科学有限公司 | Polyether monols and polyols containing pendant acrylate and/or methacrylate esters |
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| CN103310938A (en) * | 2013-06-27 | 2013-09-18 | 黑龙江大学 | Co-Dy type single molecule magnetic material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103994792B (en) * | 2014-05-30 | 2017-01-25 | 北京理工大学 | Polyacid dysprosium single-molecular magnets and preparation method thereof |
| CN105070497A (en) * | 2015-08-25 | 2015-11-18 | 广西大学 | Cobalt-based single-molecular magnet synthesizing method |
| CN105070497B (en) * | 2015-08-25 | 2017-08-25 | 广西大学 | Cobalt-based single molecular magnetses synthetic method |
| CN105225779A (en) * | 2015-10-19 | 2016-01-06 | 广西大学 | A kind of cobalt-based single-chain magnets and synthetic method thereof |
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