CN103755731A - Double-nitroxide-free-radical rare earth metal complex as well as synthetic method and application thereof - Google Patents
Double-nitroxide-free-radical rare earth metal complex as well as synthetic method and application thereof Download PDFInfo
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Abstract
The invention discloses a double-nitroxide-free-radical rare earth metal complex as well as a synthetic method and an application thereof. Double nitroxide free radicals have a structure formula as shown in a figure and have a potential application value, and the two free radicals are easily coordinated with rare earth metal ions in a chelated manner to form a complex with a zero-position structure; double nitroxide free radical ligands are combined with hexafluoroacetylacetonates of metal ions Dy(III) to obtain a mononuclear three-spin complex [Dy(hfac)3NITPy(i)mbis], so that an important way is provided for synthesizing a single-molecular magnet from the free radical ligands; moreover, the double nitroxide free radical ligands have the characteristics of few synthetic steps, simplicity for operation, high yield and the like.
Description
The present invention obtains the subsidy of state natural sciences fund (21371133) and Tianjin Natural Science Fund In The Light (12JCZDJC27600).
Technical field
The present invention relates to the preparation of diradical compound and title complex thereof, particularly a kind of rare earth metal-dinitrogen oxyradical title complex novel dinitrogen oxyradical rare earth metal complex and synthetic method and application.
Background technology
In recent years, the molecule nano magnet that has a slow specific magnetising moment relaxation phenomena becomes the challenge subjects of molecule magnetic fields.At present, the molecule nano magnet of scientist's research mainly comprises single molecular magnets (single-molecular magnets, SMMs) and single-chain magnets (single-chain magnets, SCMs).These Novel magnetic bodies may be finally for highdensity information reservation equipment, and molecule nano magnet contributes to people to understand nano-scale magnetic ion physics character, thereby explain that from macro-scale macroscopical Magnetic behavior provides fundamental basis.
Nitroxyl free radical refers to the organic free radical that contains N-O group, and it is a part with paramagnetic center, and the title complex obtaining after itself and paramagnetic metallic ion coordination may demonstrate magnetic and light, and magnetic and electricity wait the uncommon character being associated.Italian Gatteschi in 1989 etc. have obtained the title complex of nitroxyl free radical-metal first, experimental results show that this title complex is molecule ferro-magnetic [A. Caneschi etc., Inorg. Chem., 1989,28,2940].2007, D. Gatteschi reported first case nitroxyl free radical-rare earth single molecular magnets [Dy (hfac)
3nIT
mpy]
2, crystalline structure shows that this title complex is that double-core four selfs are revolved.Magnetic Measurement shows Dy in system
3+and between free radical, be ferromagnetic interaction, this title complex has shown specific magnetising moment relaxation phenomena slowly [G. Poneti etc., Chem. Commun., 2007,1807] at low temperatures.Compare with single nitroxyl free radical part, dinitrogen oxyradical part has following two advantages: the first, there is more spin center, and increase the quantity of spin plasmid in list of coordination units with metallic ion coordination, thereby can further strengthen magnetic interaction; The second, there are more ligating atom and coordination mode, during with metal-complexing, under different condition, can obtain different structures, final by controlling position and the experiment condition of ligating atom in part, realize the regulation and control to title complex magnetic.
Summary of the invention
The object of the invention is to be directed to above-mentioned analysis, the synthetic method of a kind of dinitrogen oxyradical and title complex thereof is provided, this title complex is by hexafluoroacetylacetone, to be closed the title complex of monokaryon three spins that dysprosium and dinitrogen oxyradical be assembled into.It is a kind of single molecular magnets title complex with potential using value.
For this reason, the invention discloses following technical scheme:
Object of the present invention is to disclose a kind of rare earth metal-dinitrogen oxyradical title complex, it is characterized in that: be monokaryon three spin structures, its chemical formula is: [Dy (hfac)
3(NITPy
mbis)]
2, wherein Dy is rare earth metal dysprosium;
Hfac is hexafluoroacetylacetone; NITPy
mbisit is 2,6-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-oxidation-1-oxygen base free radical) pyridine.
Another object of the present invention has been to disclose the crystal of rare earth metal-dinitrogen oxyradical title complex, this complex crystal belongs to triclinic(crystalline)system, spacer is P-1, unit cell parameters is: a=12.223 (2), b=12.935 (3), c=31.349 (6), a=89.49 (3) °, b=80.03 (3) °, g=75.48 (3) °: in minimum repeating unit, contain two dysprosium ions, respectively with six Sauerstoffatoms from three hfac with from a NITPy
mbistwo Atomic coordinates, formed the title complex of monokaryon three spins, axonometry data are as follows:.
Further object of the present invention has been to disclose the preparation method of rare earth metal-dinitrogen oxyradical complex crystal, it is characterized in that comprising the following steps:
(1) 2, the synthesis step of 6-pyridine dicarbaldehyde: add 2,6-pyridine dimethanol and activated manganese dioxide in anhydrous chloroform, 65 ℃ of reactions 6 hours, reaction solution is down to after room temperature, filter, with chloroform, wash 3-5 time, collect filtrate, decompression is lower concentrated, by column chromatography to thick purifying products (sherwood oil: ethyl acetate=6:1), obtain 2,6-pyridine dicarbaldehyde;
(2) 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) synthetic method of pyridine: with anhydrous methanol solvent, by 2,3-dimethyl-2, after 3-dihydroxyl butane and 2,6-pyridine dicarbaldehyde are mixed, room temperature reaction 2 days, suction filtration, with a small amount of anhydrous methanol washing, obtain 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine;
(3) NITPy
mbis's is synthetic: get above-mentioned 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine product is dissolved in chloroform, under cryosel bath condition, slowly adding the sodium periodate aqueous solution (1 gram of sodium periodate is dissolved in 20 ml waters, and concentration is 0.2 mol/L), stir after 20 minutes, separatory, collects organic phase, washing once, dry, filters, decompression backspin steams, and obtains mazarine solid;
(4) [Dy (hfac)
3nITPy
mbis]
2synthesizing of title complex: by Dy (hfac)
32H
2o is dissolved in normal heptane, and backflow 1-2 hour drops to 50 ℃ by the temperature of solution, then simultaneously to dinitrogen oxyradical (NITPy in solution
mbis) dichloromethane solution, reaction is carried out after 0.5-1 hour reactant cool to room temperature, filters, and finally filtrate is sealed in the refrigerator of 0-4 ℃, after two weeks, separates out bluish voilet crystal; Dy is rare earth metal dysprosium;
The mol ratio of the pyridine dimethanol described in step (1) and activated manganese dioxide is 1:15-30, and during preferred 1:20, productive rate is the highest, and in step (1), the volumetric molar concentration of pyridine dimethanol in anhydrous chloroform is 0.072 mol/L.
The mol ratio of the DMNB described in step (2) and pyridine dicarbaldehyde is 4:1-3, preferably 4:1.
The invention provides the synthetic method of the novel dinitrogen oxyradical part that a kind of reaction conditions is gentle, the reaction times is short, yield is good.It is a kind of dinitrogen oxyradical with potential using value, has formed with the hexafluoroacetylacetone salt binding of rare earth metal Dy (II) [the Dy (hfac) that monokaryon three spins
3nITPymbis]
2title complex, for the synthetic single molecular magnets of free radical provides important channel.And it is few, simple to operate that this diradical part also has synthesis step, productive rate high.
, can there is strong ferromagnetic magnetic interaction in the synthetic and magnetic characteristic that the present invention further discloses dinitrogen oxyradical rare earth metal complex crystal, likely become the single molecular magnets of excellent performance between rare earth metal dysprosium and free radical.Single molecular magnets, for the preparation of computer memory device, can not only improve the arithmetic speed of computer, and can greatly improve the store content of computer, aspect computer miniaturization, has potential using value.
Accompanying drawing explanation
Fig. 1 is compound [Dy (hfac)
3nITPy
mbis]
2structural representation;
Fig. 2 is compound [Dy (hfac)
3nITPy
mbis]
2powder diagram;
Fig. 3 is compound [Dy (hfac)
3nITPy
mbis]
2molar susceptibility and the product variation with temperature curve of temperature.
Embodiment
Below in conjunction with embodiment, the present invention is further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.Various raw material of the present invention all has commercially available.
Embodiment 1
The structure of rare earth metal-dinitrogen oxyradical title complex, is monokaryon three spin structures, and its chemical formula is: [Dy (hfac)
3(NITPy
mbis)]
2, wherein hfac is hexafluoroacetylacetone, NITPy
mbisbe 2,6-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-oxidation-1-oxygen base free radical); In minimum repeating unit, contain two dysprosium ions, respectively with six Sauerstoffatoms from three hfac with from a NITPy
mbistwo Atomic coordinates, formed the title complex of monokaryon three spins, Fig. 1 is [Dy (hfac)
3(NITPy
mbis)]
2structural representation, its preparation process is as follows:
(1) active MnO
2synthetic
In the large beaker of 1L, add 48g KMnO
4with 300 mL water, under 90 ℃ of conditions of oil bath, drip the aqueous sodium hydroxide solution of manganese sulfate solution (42.25 g manganous sulfates are dissolved in 75 mL water), 58.5 mL 40% simultaneously, after dripping off, reaction 1 h.After reaction finishes, suction filtration, with washing with water, until filtrate clarification.The brown solid obtaining is dried 60 h at 110 ℃.Then with benzene and water trap 2 h that reflux, a small amount of water is removed, filtered, obtain the active MnO of brownish black
218.2g, productive rate is 88%
Synthesizing of (2) 2,6-pyridine dicarbaldehyde
Under nitrogen protection, in 100 mL anhydrous chloroforms, add 1 g 2,6-pyridine dimethanol and 12.5 g activated manganese dioxides, 10 h reflux.After reaction finishes, filter, with chloroform, wash repeatedly, collect filtrate, the desolventizing of decompression backspin.By column chromatography to thick purifying products (PE:EA=6:1).In reaction process, the mol ratio of pyridine dimethanol and Manganse Dioxide is 1:20.Obtain pyridine dicarbaldehyde 0.69g, productive rate is 72%.
Reaction formula
(3) NITPy
mbis's is synthetic
By 2 of 5.92 g (40 mmol), 3-dimethyl-2,3-dihydroxyl butane adds in 150 ml anhydrous methanols to all dissolving, under stirring, add 1.35 g (10 mmol) 2,6-pyridine dicarbaldehyde, room temperature reaction 3 days, adularescent powdery product forms, suction filtration, with a small amount of anhydrous methanol washing, obtains white powder; White powder is dissolved in 100 ml chloroforms, under cryosel is bathed, slowly drips the solution that 1 g sodium periodate is dissolved in 20 ml water, react 10 minutes at 0 ℃, separatory, collects organic phase, dry, filters, and the lower rotary evaporated to dryness of decompression, obtains mazarine solid; With sherwood oil: ethyl acetate=1:1 (volume), do leacheate and cross post, collect dark blue colour band, obtain mazarine solid and be NITPy
mbis, productive rate 23%.
Reaction formula:
(4) [Dy[(hfac)
3nITPy
mbis]
2synthetic method: by 82 mg (0.1 mmol) Dy (hfac)
32H
2o is dissolved in 20 mol normal heptanes, after refluxing about one hour, the temperature of solution is dropped to 60 ℃, then to the NITPy that adds 38.9 mg (0.1 mmol) in above-mentioned solution
mbis is dissolved in the solution of 10 mL methylene dichloride, and 0.5 h is carried out in reaction, by reactant cool to room temperature, filters, and finally filtrate is sealed in the refrigerator of 0-4 ℃.After two weeks, separate out bluish voilet crystal, productive rate is 60%.
[Dy (hfac)
3nITPy
mbis]
2structural characterization:
1) crystal structure determination:
Crystalline structure adopts Bruker Smart Apex II CCD type X-ray single crystal diffractometer, uses the Mo-K through graphite monochromatization
aray (l=0.71073) is incident radiation, with ω-φ scan mode, collects point diffraction, through least-squares refinement, obtains unit cell parameters, from difference Fourier electron density map, utilizes SHELXL-97 direct method to solve crystalline structure.All H atoms are synthesized by difference Fourier and determine through desirable position calculation.Axonometry data are in Table 1.
Table 1 is the crystallographic data of dysprosium title complex:
Fig. 1 is [Dy (hfac)
3nITPy
mbis]
2structural representation.
2) mensuration of powdery diffractometry:
Powder diffraction data is collected on Rigaku D/Max-2500 diffractometer and completes, and instrumentation voltage is 40 KV, and electric current is 100 mA, uses the copper target X ray of graphite monochromatization.Density data collect to be used 2q/q scan pattern, and within the scope of 3 ° to 60 °, continuous sweep completes, sweep velocity be 8 °/per second, span be 0.02 °/each.Data fitting is used Cerius 2 programs, and the simulation of single crystal structure powdery diffractometry transforms uses Mercury1.42.
Fig. 2 is title complex [Dy (hfac)
3nITPy
mbis]
2powder diagram.
3) magnetic measurement:
Magnetic test is used Quantum Design MPMS XL-7SQUID device to complete.
Fig. 3 is the product variation with temperature graphic representation of molar susceptibility and the temperature of this magneticsubstance.In figure, show: metal dysprosium-free radical title complex has strong ferromagnetic interaction at low temperatures, likely becomes the single molecular magnets of excellent performance.Single molecular magnets, for the preparation of computer memory device, can not only improve the arithmetic speed of computer, and can greatly improve the store content of computer, aspect computer miniaturization, has potential using value.
The preparation method of dinitrogen oxyradical rare earth metal complex crystal:
The synthesis step of (1) 2,6-pyridine dicarbaldehyde: add 2,6-pyridine dimethanol and activated manganese dioxide in anhydrous chloroform, 65 ℃ of reactions 6 hours, reaction solution is down to after room temperature, filters, and with chloroform, washes 3 times, collect filtrate, decompression is lower concentrated, adopts column chromatography to thick purifying products, solvent for use volume ratio sherwood oil: ethyl acetate=6:1 drip washing, obtain 2,6-pyridine dicarbaldehyde; Wherein said 2, the mol ratio of 6-pyridine dimethanol and activated manganese dioxide is 1:15; Described 2, the concentration of 6-pyridine dimethanol is 0.072 mol/L;
(2) 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) synthetic method of pyridine: with anhydrous methanol solvent, by 2,3-dimethyl-2, after 3-dihydroxyl butane and 2,6-pyridine dicarbaldehyde are mixed, room temperature reaction 2 days, suction filtration, with a small amount of anhydrous methanol washing, obtain 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine; The mol ratio of described DMNB and pyridine dicarbaldehyde is 4:1;
(3) 2,6-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-oxidation-1-oxygen base free radical) pyridine (NITPy
mbis) synthetic: get above-mentioned 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine product is dissolved in chloroform, under cryosel bath condition, slowly adding the sodium periodate aqueous solution, stir after 20 minutes, separatory, collects organic phase, and washing once, dry, filter, decompression backspin steams, and obtains mazarine solid; The described sodium periodate aqueous solution refers to: 1 gram of sodium periodate is dissolved in 20 ml waters, and concentration is 0.2 mol/L;
(4) [Dy (hfac)
3nITPy
mbis]
2synthesizing of title complex: by Dy (hfac)
32H
2o is dissolved in normal heptane, and backflow 1-2 hour drops to 50 ℃ by the temperature of solution, then simultaneously to dinitrogen oxyradical (NITPy in solution
mbis) dichloromethane solution, reaction is carried out after 0.5-1 hour reactant cool to room temperature, filters, and finally filtrate is sealed in the refrigerator of 0-4 ℃, after two weeks, separates out bluish voilet crystal; Described dinitrogen oxyradical (NITPy
mthe concentration of dichloromethane solution bis) is 0.072 mol/L.
Embodiment 3
The preparation method of dinitrogen oxyradical rare earth metal complex crystal:
The synthesis step of (1) 2,6-pyridine dicarbaldehyde: add 2,6-pyridine dimethanol and activated manganese dioxide in anhydrous chloroform, 65 ℃ of reactions 6 hours, reaction solution is down to after room temperature, filters, and with chloroform, washes 5 times, collect filtrate, decompression is lower concentrated, adopts column chromatography to thick purifying products, solvent for use volume ratio sherwood oil: ethyl acetate=6:1 drip washing, obtain 2,6-pyridine dicarbaldehyde; Wherein said 2, the mol ratio of 6-pyridine dimethanol and activated manganese dioxide is 1:30, described 2, and the concentration of 6-pyridine dimethanol is 0.072 mol/L;
(2) 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) synthetic method of pyridine: with anhydrous methanol solvent, by 2,3-dimethyl-2, after 3-dihydroxyl butane and 2,6-pyridine dicarbaldehyde are mixed, room temperature reaction 2 days, suction filtration, with a small amount of anhydrous methanol washing, obtain 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine; The mol ratio of described DMNB and pyridine dicarbaldehyde is 2:1;
(3) 2,6-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-oxidation-1-oxygen base free radical) pyridine (NITPy
mbis) synthetic: get above-mentioned 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine product is dissolved in chloroform, under cryosel bath condition, slowly adding the sodium periodate aqueous solution, stir after 20 minutes, separatory, collects organic phase, and washing once, dry, filter, decompression backspin steams, and obtains mazarine solid; The described sodium periodate aqueous solution refers to: 1 gram of sodium periodate is dissolved in 20 ml waters, and concentration is 0.2 mol/L;
(4) [Dy (hfac)
3nITPy
mbis]
2synthesizing of title complex: by Dy (hfac)
32H
2o is dissolved in normal heptane, and backflow 1-2 hour drops to 50 ℃ by the temperature of solution, then simultaneously to dinitrogen oxyradical (NITPy in solution
mbis) dichloromethane solution, reaction is carried out after 0.5-1 hour reactant cool to room temperature, filters, and finally filtrate is sealed in the refrigerator of 0-4 ℃, after two weeks, separates out bluish voilet crystal; Described dinitrogen oxyradical (NITPy
mthe concentration of dichloromethane solution bis) is 0.072 mol/L.
Claims (4)
1. a dinitrogen oxyradical rare earth metal complex, is characterized in that this title complex is monokaryon three spin structures, and its chemical formula is: [Dy (hfac)
3(NITPy
mbis)]
2,
Wherein Dy is rare earth metal dysprosium;
Hfac is hexafluoroacetylacetone;
NITPy
mbisit is 2,6-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-oxidation-1-oxygen base free radical) pyridine.
2. the crystal of dinitrogen oxyradical rare earth metal complex described in claim 1, this complex crystal belongs to triclinic(crystalline)system, spacer is P-1, unit cell parameters is: a=12.223 (2), b=12.935 (3), c=31.349 (6), a=89.49 (3) °, b=80.03 (3) °, g=75.48 (3) °: in minimum repeating unit, contain two dysprosiums, respectively with six Sauerstoffatoms from three hfac with from a NITPy
mbistwo Atomic coordinates, formed the title complex of monokaryon three spins, crystal data is as follows:
。
3. the preparation method of dinitrogen oxyradical rare earth metal complex crystal described in claim 2, is characterized in that being undertaken by following step:
The synthesis step of (1) 2,6-pyridine dicarbaldehyde: add 2,6-pyridine dimethanol and activated manganese dioxide in anhydrous chloroform, 65 ℃ of reactions 6 hours, reaction solution is down to after room temperature, filters, and with chloroform, washes 3-5 time, collect filtrate, decompression is lower concentrated, adopts column chromatography to thick purifying products, solvent for use volume ratio sherwood oil: ethyl acetate=6:1 drip washing, obtain 2,6-pyridine dicarbaldehyde;
(2) 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) synthetic method of pyridine: with anhydrous methanol solvent, by 2,3-dimethyl-2, after 3-dihydroxyl butane and 2,6-pyridine dicarbaldehyde are mixed, room temperature reaction 2 days, suction filtration, with a small amount of anhydrous methanol washing, obtain 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine;
(3) 2,6-bis--(4,4,5,5-tetramethyl-tetrahydroglyoxaline-3-oxidation-1-oxygen base free radical) pyridine (NITPy
mbis) synthetic: get above-mentioned 2,6-bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine product is dissolved in chloroform, under cryosel bath condition, slowly adding the sodium periodate aqueous solution, stir after 20 minutes, separatory, collects organic phase, and washing once, dry, filter, decompression backspin steams, and obtains mazarine solid; The described sodium periodate aqueous solution refers to: 1 gram of sodium periodate is dissolved in 20 ml waters, and concentration is 0.2 mol/L;
(4) [Dy (hfac)
3nITPy
mbis]
2synthesizing of title complex: by Dy (hfac)
32H
2o is dissolved in normal heptane, and backflow 1-2 hour drops to 50 ℃ by the temperature of solution, then simultaneously to dinitrogen oxyradical (NITPy in solution
mbis) dichloromethane solution, reaction is carried out after 0.5-1 hour reactant cool to room temperature, filters, and finally filtrate is sealed in the refrigerator of 0-4 ℃, after two weeks, separates out bluish voilet crystal;
2 described in step (1) wherein, the mol ratio of 6-pyridine dimethanol and activated manganese dioxide is 1:15-30, described 2, the concentration of 6-pyridine dimethanol is 0.072 mol/L;
The mol ratio of the DMNB described in step (2) and pyridine dicarbaldehyde is 4:1-3;
Dinitrogen oxyradical (NITPy described in step (4)
mthe concentration of dichloromethane solution bis) is 0.072 mol/L.
4. described in claim 2, this magneticsubstance of product variation with temperature curve shows of mole alternating temperature susceptibility of the crystal of rare earth metal-dinitrogen oxyradical title complex and temperature has strong ferromagnetic interaction at low temperatures, has certain application prospect preparing aspect computer memory device.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103951656A (en) * | 2014-05-08 | 2014-07-30 | 天津师范大学 | Double nitroxide free radicals and preparation method and application thereof |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101786989A (en) * | 2010-03-17 | 2010-07-28 | 南开大学 | 4,4-di(4,4,5,5-tetramethyl imidazoline-3-oxidation-1-oxy radical) phenyl ether and preparation method thereof |
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 |
-
2014
- 2014-02-10 CN CN201410046180.7A patent/CN103755731B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101786989A (en) * | 2010-03-17 | 2010-07-28 | 南开大学 | 4,4-di(4,4,5,5-tetramethyl imidazoline-3-oxidation-1-oxy radical) phenyl ether and preparation method thereof |
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 |
Non-Patent Citations (3)
Title |
---|
KEVIN BERNOT ET AL.: "Single molecule magnet behaviour in robust dysprosium-biradical complexes", 《SINGLE MOLECULE MAGNET BEHAVIOUR IN ROBUST DYSPROSIUM-BIRADICAL COMPLEXES》, vol. 46, 17 August 2010 (2010-08-17), pages 6458 - 6460 * |
KYOUNG CHUL KO ET AL.: "Scaling Approach for Intramolecular Magnetic Coupling Constants of Organic Diradicals", 《THE JOURNAL OF PHYSICAL CHEMISTRY》, vol. 117, 2 April 2013 (2013-04-02), pages 3561 - 3568 * |
RAYMOND ZIESSEL ET AL.: "Oligopyridine bis(nitronyl nitroxides):synthesis, structures, electrochemical, magnetic and electronic properties", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 9, 31 December 1999 (1999-12-31), pages 1435 - 1448 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103951656A (en) * | 2014-05-08 | 2014-07-30 | 天津师范大学 | Double nitroxide free radicals and preparation method and application thereof |
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CN109111472B (en) * | 2018-09-20 | 2020-08-04 | 杭州电子科技大学 | Single-double-core eutectic rare earth magnetic complex and preparation method thereof |
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 |
CN114560881A (en) * | 2022-03-04 | 2022-05-31 | 江苏科技大学 | High-energy barrier dysprosium single-ion magnet and preparation method and application thereof |
CN114560881B (en) * | 2022-03-04 | 2023-11-28 | 江苏科技大学 | High-energy-barrier dysprosium single-ion magnet and preparation method and application thereof |
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