CN103714933A - Mn zero-dimension single-molecular magnet material, preparation method and application of Mn zero dimension single-molecular magnet material - Google Patents
Mn zero-dimension single-molecular magnet material, preparation method and application of Mn zero dimension single-molecular magnet material Download PDFInfo
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- CN103714933A CN103714933A CN201310745384.5A CN201310745384A CN103714933A CN 103714933 A CN103714933 A CN 103714933A CN 201310745384 A CN201310745384 A CN 201310745384A CN 103714933 A CN103714933 A CN 103714933A
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Abstract
The invention discloses an Mn zero-dimension single-molecular magnet material, a preparation method and application of the Mn zero dimension single-molecular magnet material and belongs to the technical field of molecular base materials. The chemical structural formula is [Mn2(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 manganous 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 manganous nitrate is (0.5-3):1, every 0.1 millimole of the organic ligand L corresponds to 2-5mL of ethyl alcohol or methyl alcohol. Large ferromagnetic coupling action exists among manganese ions of a single-molecular magnet, and the Mn zero dimension single-molecular magnet material can be used as a molecular base magnetic material.
Description
Technical field
The invention belongs to the technical field of molecular based material, design metal-organic coordination polymer material, particularly a kind of zero dimension single molecular magnets, preparation method 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 zero dimension single molecular magnets magnetic material, preparation method and application thereof.
A kind of zero dimension single molecular magnets magnetic material of the present invention, is characterized in that, chemical structural formula is [Mn
2(L)
3(NO
3)]
2(NO
3)
2, L is organic ligand 2-ethyl-4,5-hydroxymethyl-imidazole.
Zero dimension single molecular magnets magnetic material secondary building unit is: crystal belongs to monoclinic system, and space group is P2 (1)/n, and cell parameter is:
β=96.0160 °, α=γ=90 °; From connecting the angle of constructing, this single molecular magnets has the manganese of two kinds of configurations, the first configuration comprises that two manganese are designated as respectively Mn1, Mn1A, the second configuration comprises that two manganese are designated as respectively Mn2, Mn2A, Mn1 is the atom that configuration and connected mode are identical with Mn1A, and Mn2 is the atom that configuration and connected mode are identical with Mn2A, wherein, Mn1 is connected with 4 parts, and Mn2 is connected with 1 nitrate anion with 3 parts; Wherein, the connected mode of manganese ion and part be with part on N and with the μ on pendant hydroxyl group
2-O and μ
3-O connects, and all manganese is hexa-coordinate, forms 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 sealing condition, organic ligand L(2-ethyl-4,5-hydroxymethyl-imidazole) with manganese nitrate in ethanol or methyl alcohol, via thermal response, obtain the crystal of zero dimension single molecular magnets material; Wherein said organic ligand L (2-ethyl-4,5-hydroxymethyl-imidazole) is (0.5～3) with the mol ratio of manganese nitrate: 1, and ethanol or the methyl alcohol of the corresponding 2-5mL 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 ferromagnetic coupling effect, can be used as molecule based magnetic materials.
Single molecular magnets material [Mn of the present invention
2(L)
3(NO
3)]
2(NO
3)
2, aspect material, there is ferromagnetic property, can be used as molecule based magnetic materials, at material science, have a good application prospect.
Accompanying drawing explanation
Accompanying drawing 1[Mn
2(L)
3(NO
3)]
2(NO
3)
2in [Mn
2(L)
3(NO
3)]
2crystal structure figure;
Wherein, O1 is identical with configuration and the connected mode of O1A, O2 is identical with configuration and the connected mode of O2A, O3 is identical with configuration and the connected mode of O3A, O4 is identical with configuration and the connected mode of O4A, and O5 is identical with configuration and the connected mode of O5A, and N1 is identical with configuration and the connected mode of N1A, N2 is identical with configuration and the connected mode of N2A, and N3 is identical with configuration and the connected mode of N3A.
Accompanying drawing 2[Mn
2(L)
3(NO
3)]
2(NO
3)
2molar susceptibility curve chart.
Accompanying drawing 3[Mn
2(L)
3(NO
3)]
2(NO
3)
2variable field susceptibility curve figure.
Embodiment
Below in conjunction with embodiment, 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 manganese 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.
By organic ligand 2-ethyl-4,5-hydroxymethyl-imidazole (0.1 mM) stirs in 4mL ethanol with manganese 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 manganese 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 test result of the product of above-described embodiment gained is identical, specifically sees following:
(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 manganese ion of two kinds of configurations, be designated as respectively Mn1, Mn1A and Mn2, Mn2A, Mn1 is the atom that configuration and connected mode are identical with Mn1A, and Mn2 is the atom that configuration and connected mode are identical with Mn2A.Wherein, Mn1 is connected with 4 parts, and Mn2 is connected with 1 nitrate anion with 3 parts.Wherein, manganese ion is with the N on part and is connected with μ 2-O and μ 3-O on same pendant hydroxyl group with the connected mode of part.All manganese ions 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 increases, and illustrates that claim 1 magnetic material all exists strong ferromagnetic coupling effect.
Claims (7)
1. a zero dimension unimolecule material, is characterized in that, chemical structural formula is [Mn
2(L)
3(NO
3)]
2(NO
3)
2, 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)/n, and cell parameter is:
β=96.0160 °, 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 manganese of two kinds of configurations, and the first configuration comprises that two manganese are designated as respectively Mn1, Mn1A, the second configuration comprises that two manganese are designated as respectively Mn2, Mn2A, Mn1 is the atom that configuration and connected mode are identical with Mn1A, and Mn2 is the atom that configuration and connected mode are identical with Mn2A, wherein, Mn1 is connected with 4 parts, and Mn2 is connected with 1 nitrate anion with 3 parts; Wherein, the connected mode of manganese ion and part be with part on N and with the μ on pendant hydroxyl group
2-O and μ
3-O connects, and all manganese is hexa-coordinate, forms the octoploids structure of distortion.
4. the method for preparation material claimed in claim 1, is characterized in that, comprises the following steps:
Under sealing condition, organic ligand L(2-ethyl-4,5-hydroxymethyl-imidazole) with manganese nitrate in ethanol or methyl alcohol, via thermal response, obtain the crystal of zero dimension single molecular magnets material; Wherein said organic ligand L (2-ethyl-4,5-hydroxymethyl-imidazole) is (0.5～3) with the mol ratio of manganese nitrate: 1, and ethanol or the methyl alcohol of the corresponding 2-5mL of organic ligand L of every 0.1 mM.
5. preparation method claimed in claim 1, is characterized in that, the reaction condition of described thermal response is 40 ℃-80 ℃, and the reaction time is 2-4 days.
6. preparation method claimed in claim 5, is characterized in that, the reaction time is 3 days.
7. a kind of zero dimension unimolecule material claimed in claim 1 is as molecule based magnetic materials.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104505210A (en) * | 2014-12-29 | 2015-04-08 | 广西师范大学 | Mixed-valence manganese cluster molecule-based magnetic material and preparation 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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| US20030109377A1 (en) * | 2001-11-15 | 2003-06-12 | Industrial Technology Research Institute | Catalyst composition and process for preparing olefin polymers |
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| WO2013066269A1 (en) * | 2011-11-02 | 2013-05-10 | Nanyang Technological University | Method of forming od, id, or 3d graphene and use thereof |
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2013
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| US20030109377A1 (en) * | 2001-11-15 | 2003-06-12 | Industrial Technology Research Institute | Catalyst composition and process for preparing olefin polymers |
| CN102417201A (en) * | 2011-08-31 | 2012-04-18 | 北京大学 | Method for preparing one-dimensional self-assembly material with ZnO nanorod array as template |
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Cited By (2)
| 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 |
| CN104505210A (en) * | 2014-12-29 | 2015-04-08 | 广西师范大学 | Mixed-valence manganese cluster molecule-based magnetic material and preparation method thereof |
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Effective date of registration: 20200916 Address after: Huai Zhen Bei Yang Cun, Xian County, Cangzhou City, Hebei Province 061000 Patentee after: Cangzhou Hengbo Machinery Equipment Co.,Ltd. Address before: Room 1424, Floor 4, Peony Pioneer Building, No. 2 Garden Road, Haidian District, Beijing, 100191 Patentee before: Beijing Zhonglian Technology Service Co.,Ltd. Effective date of registration: 20200916 Address after: Room 1424, Floor 4, Peony Pioneer Building, No. 2 Garden Road, Haidian District, Beijing, 100191 Patentee after: Beijing Zhonglian Technology Service Co.,Ltd. Address before: 100124 Chaoyang District, Beijing Ping Park, No. 100 Patentee before: Beijing University of Technology |