CN103755731B - Dinitrogen oxyradical rare earth metal complex and synthetic method thereof and application - Google Patents
Dinitrogen oxyradical rare earth metal complex and synthetic method thereof and application Download PDFInfo
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Abstract
The invention discloses metal-bis-nitroxyl free radical complex and preparation method thereof and application.The structural formula of dinitrogen oxyradical schemes to represent as follows, and it is a kind of dinitrogen oxyradical with potential using value, and two free radicals easily form the title complex of zero-bit structure with the form of chelating and rare earth ion coordination.The hexafluoroacetylacetone salt binding of this dinitrogen oxyradical part and metal ion Dy (III) is obtained the title complex that a monokaryon three spins: [Dy (hfac)
3nITPy<i>mbis</iG reatT.GreaT.GT], for free radical part synthesis single molecular magnets provides important channel, and it is few that this dinitrogen oxyradical part has synthesis step, simple to operate, productive rate high.
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-bis-nitroxyl free radical complex novel dinitrogen oxyradical rare earth metal complex and synthetic method thereof and application.
Background technology
In recent years, the molecule nano magnet with 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-molecularmagnets, SMMs) and single-chain magnets (single-chainmagnets, SCMs).These Novel magnetic bodies may finally for highdensity information reservation equipment, and molecule nano magnet contributes to people and understands nano-scale magnetic ion physical performance, thus explain that macroscopical Magnetic behavior is provided fundamental basis from macro-scale.
Nitroxyl free radical refers to the organic free radical containing N-O group, and it is a part with paramagnetic center, and the title complex obtained after itself and paramagnetic metallic ion coordination may demonstrate magnetic and light, the uncommon character that magnetic is associated with electricity etc.Italian Gatteschi in 1989 etc. obtain the title complex of nitroxyl free radical-metal first, and experiment proves 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 double-core four spin.Magnetic Measurement shows Dy in system
3+and be ferromagnetic interaction between free radical, this title complex shows specific magnetising moment relaxation phenomena slowly [G.Poneti etc., Chem.Commun., 2007,1807] at low temperatures.Compared with single nitroxyl free radical part, dinitrogen oxyradical part has following two advantages: the first, has more spin center, adds the quantity of spin plasmid in list of coordination units with metallic ion coordination, thus can strengthen magnetic interaction further; The second, there are more ligating atom and coordination mode, during with metal-complexing, different structures can be obtained at different conditions, eventually through the position and the experiment condition that control 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, provide the synthetic method of a kind of dinitrogen oxyradical and title complex thereof, this title complex is the title complex that the monokaryon three be assembled into by hexafluoroacetylacetone conjunction dysprosium and dinitrogen oxyradical spins.It is a kind of single molecular magnets title complex with potential using value.
For this reason, the invention discloses following technical scheme:
The present invention's object is to disclose a kind of rare earth metal-bis-nitroxyl free radical complex, it is characterized in that: be monokaryon three spin structure, 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-is oxidized-1-oxygen base free radical) pyridine.
Another object of the present invention is the crystal disclosing rare earth metal-bis-nitroxyl free radical 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) °: containing two dysprosium ions in minimum repeating unit, respectively with six Sauerstoffatoms from three hfac with from a NITPy
mbistwo Atomic coordinates, define monokaryon three spin title complex, axonometry data are as follows:.
Further object of the present invention is the preparation method disclosing 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 DEG C of reactions 6 hours, after reaction solution is down to room temperature, filter, wash 3-5 time with chloroform, collect filtrate, concetrated under reduced pressure, 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, after 3-dimethyl-2,3-dihydroxyl butane and 2,6-pyridine dicarbaldehyde mix, room temperature reaction 2 days, suction filtration, washs with a small amount of anhydrous methanol, obtain 2,6-, bis--(1,3-dihydroxyl-4,4,5,5-tetramethyl-imidazolidine) pyridine;
(3) NITPy
mthe synthesis of bis: 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), after stirring 20 minutes, separatory, collects organic phase, washing is once, dry, filters, decompression backspin steams, and obtains blue solid;
(4) [Dy (hfac)
3nITPy
mbis]
2the synthesis of title complex: by Dy (hfac)
32H
2o is dissolved in normal heptane, and backflow 1-2 hour, drops to 50 DEG C by the temperature of solution, then simultaneously to dinitrogen oxyradical (NITPy in solution
mbis) dichloromethane solution, reaction is carried out by reactant cool to room temperature after 0.5-1 hour, filters, finally filtrate is sealed in the refrigerator of 0-4 DEG C, 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, preferred 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, defines with the hexafluoroacetylacetone salt binding of rare earth metal Dy (II) [the Dy (hfac) that monokaryon three spins
3nITPymbis]
2title complex, for free radical synthesis single molecular magnets provides important channel.And it is few, simple to operate that this diradical part also has synthesis step, productive rate high.
The present invention further discloses synthesis and the magnetic characteristic of dinitrogen oxyradical rare earth metal complex crystal, strong ferromagnetic magnetic interaction can be there is between rare earth metal dysprosium and free radical, likely become 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 greatly can improve the store content of computer, in 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-bis-nitroxyl free radical complex, be monokaryon three spin structure, 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-is oxidized-1-oxygen base free radical); Containing two dysprosium ions in minimum repeating unit, respectively with six Sauerstoffatoms from three hfac with from a NITPy
mbistwo Atomic coordinates, define monokaryon three spin title complex, Fig. 1 is [Dy (hfac)
3(NITPy
mbis)]
2structural representation, its preparation process is as follows:
(1) active MnO
2synthesis
In the large beaker of 1L, add 48gKMnO
4with 300mL water, under oil bath 90 DEG C of conditions, drip the aqueous sodium hydroxide solution of manganese sulfate solution (42.25g manganous sulfate is dissolved in 75mL water), 58.5mL40% simultaneously, after dripping off, reaction 1h.After reaction terminates, suction filtration, with washing with water, till filtrate clarification.The brown solid obtained dries 60h at 110 DEG C.Then with benzene and water trap backflow 2h, a small amount of water is removed, filters, obtain the active MnO of brownish black
218.2g, productive rate is 88%
The synthesis of (2) 2,6-pyridine dicarbaldehyde
Under nitrogen protection, in 100mL anhydrous chloroform, add 1g2,6-pyridine dimethanol and 12.5g activated manganese dioxide, backflow 10h.After reaction terminates, filter, wash repeatedly with chloroform, 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
mthe synthesis of bis
By 2 of 5.92g (40mmol), 3-dimethyl-2,3-dihydroxyl butane adds in 150ml anhydrous methanol to all dissolving, 1.35g (10mmol) 2,6-pyridine dicarbaldehyde is added, room temperature reaction 3 days under stirring, adularescent powdery product is formed, suction filtration, washs with a small amount of anhydrous methanol, obtains white powder; Be dissolved in by white powder in 100ml chloroform, under cryosel bath, slowly drip the solution that 1g sodium periodate is dissolved in 20ml water, react 10 minutes, separatory at 0 DEG C, collect organic phase, dry, filter, the lower rotary evaporated to dryness of decompression, obtains blue solid; With sherwood oil: ethyl acetate=1:1 (volume) does leacheate and crosses post, collect strong blue bands, obtain blue solid and be NITPy
mbis, productive rate 23%.
Reaction formula:
(4) [Dy [(hfac)
3nITPy
mbis]
2synthetic method: by 82mg (0.1mmol) Dy (hfac)
32H
2o is dissolved in 20mol normal heptane, after the hours that refluxes, the temperature of solution is dropped to 60 DEG C, in above-mentioned solution, then adds the NITPy of 38.9mg (0.1mmol)
mbis is dissolved in the solution of 10mL methylene dichloride, and 0.5h is carried out in reaction, by reactant cool to room temperature, filters, finally filtrate is sealed in the refrigerator of 0-4 DEG C.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 BrukerSmartApexIICCD type X-ray single crystal diffraction instrument, uses through graphite monochromatised Mo-K
aray (l=0.71073) is incident radiation, collects point diffraction, obtain unit cell parameters, utilize SHELXL-97 direct method to solve crystalline structure from difference Fourier electron density map through least-squares refinement with ω-φ scan mode.All H atom are synthesized by difference Fourier and are determined 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 RigakuD/Max-2500 diffractometer and completes, and instrumentation voltage is 40KV, and electric current is 100mA, uses graphite monochromatised copper target X-ray.Density data is collected and is used 2q/q scan pattern, and within the scope of 3 ° to 60 °, continuous sweep completes, and sweep velocity is 8 °/per second, and span is 0.02 °/each.Data fitting uses Cerius2 program, and the simulation of single crystal structure powdery diffractometry transforms and uses Mercury1.42.
Fig. 2 is title complex [Dy (hfac)
3nITPy
mbis]
2powder diagram.
3) magnetic measurement:
Magnetic Test uses QuantumDesignMPMSXL-7SQUID device to complete.
Fig. 3 is the molar susceptibility of this magneticsubstance and the product variation with temperature graphic representation of temperature.Show in figure: 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 greatly can improve the store content of computer, in computer miniaturization, has potential using value.
Embodiment 2
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 DEG C of reactions 6 hours, after reaction solution is down to room temperature, filters, wash 3 times with chloroform, collect filtrate, concetrated under reduced pressure, 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; 2,6-wherein said pyridine dimethanols and the mol ratio of activated manganese dioxide are 1:15; The concentration of described 2,6-pyridine dimethanols 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, after 3-dimethyl-2,3-dihydroxyl butane and 2,6-pyridine dicarbaldehyde mix, room temperature reaction 2 days, suction filtration, washs with a small amount of anhydrous methanol, 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-is oxidized-1-oxygen base free radical) pyridine (NITPy
mbis) synthesis: 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, stirring after 20 minutes, separatory, collects organic phase, and washing once, dry, filter, decompression backspin steams, and obtains blue 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]
2the synthesis of title complex: by Dy (hfac)
32H
2o is dissolved in normal heptane, and backflow 1-2 hour, drops to 50 DEG C by the temperature of solution, then simultaneously to dinitrogen oxyradical (NITPy in solution
mbis) dichloromethane solution, reaction is carried out by reactant cool to room temperature after 0.5-1 hour, filters, finally filtrate is sealed in the refrigerator of 0-4 DEG C, 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 DEG C of reactions 6 hours, after reaction solution is down to room temperature, filters, wash 5 times with chloroform, collect filtrate, concetrated under reduced pressure, 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; 2,6-wherein said pyridine dimethanols and the mol ratio of activated manganese dioxide are 1:30, and the concentration of described 2,6-pyridine dimethanols 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, after 3-dimethyl-2,3-dihydroxyl butane and 2,6-pyridine dicarbaldehyde mix, room temperature reaction 2 days, suction filtration, washs with a small amount of anhydrous methanol, 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-is oxidized-1-oxygen base free radical) pyridine (NITPy
mbis) synthesis: 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, stirring after 20 minutes, separatory, collects organic phase, and washing once, dry, filter, decompression backspin steams, and obtains blue 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]
2the synthesis of title complex: by Dy (hfac)
32H
2o is dissolved in normal heptane, and backflow 1-2 hour, drops to 50 DEG C by the temperature of solution, then simultaneously to dinitrogen oxyradical (NITPy in solution
mbis) dichloromethane solution, reaction is carried out by reactant cool to room temperature after 0.5-1 hour, filters, finally filtrate is sealed in the refrigerator of 0-4 DEG C, after two weeks, separates out bluish voilet crystal; Described dinitrogen oxyradical (NITPy
mthe concentration of dichloromethane solution bis) is 0.072 mol/L.
Claims (3)
1. a dinitrogen oxyradical rare earth metal complex crystal, this complex crystal belongs to triclinic(crystalline)system, spacer is P-1, and unit cell parameters is: a=12.223 (2), b=12.935 (3), c=31.349 (6), α=89.49 (3)
o,
β =80.03 (3)
o,
γ=75.48 (3)
o: containing two dysprosiums in minimum repeating unit, respectively with six Sauerstoffatoms from three hfac with from a NITPy
mbistwo Atomic coordinates, define monokaryon three spin title complex, crystal data is as follows:
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-is oxidized-1-oxygen base free radical) pyridine.
2. the preparation method of dinitrogen oxyradical rare earth metal complex crystal described in claim 1, 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 DEG C of reactions 6 hours, after reaction solution is down to room temperature, filters, wash 3-5 time with chloroform, collect filtrate, concetrated under reduced pressure, 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-diamino-N, after N'-dihydroxyl-2,3-dimethylbutane and 2,6-pyridine dicarbaldehyde mix, room temperature reaction 2 days, suction filtration, washs with a small amount of anhydrous methanol, 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-is oxidized-1-oxygen base free radical) synthesis of pyridine: 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 add the sodium periodate aqueous solution again, stir after 20 minutes, separatory, collect organic phase, washing is once, dry, filter, decompression backspin steams, and obtains blue solid; The described sodium periodate aqueous solution refers to: 1 gram of sodium periodate is dissolved in 20 ml waters;
(4) [Dy (hfac)
3nITPymbis]
2the synthesis of title complex: by Dy (hfac)
32H
2o is dissolved in normal heptane, and backflow 1-2 hour, drops to 50 DEG C by the temperature of solution, then in solution, adds NITPy simultaneously
mthe dichloromethane solution of bis, reaction is carried out by reactant cool to room temperature after 0.5-1 hour, filters, finally filtrate is sealed in the refrigerator of 0-4 DEG C, after two weeks, separates out bluish voilet crystal; Wherein
The mol ratio of 2,6-pyridine dimethanols described in step (1) and activated manganese dioxide is 1:15-30, and the concentration of described 2,6-pyridine dimethanols is 0.072 mol/L;
2,3-diamino-Ns described in step (2), the mol ratio of N'-dihydroxyl-2,3-dimethylbutane and pyridine dicarbaldehyde is 4:1-3;
NITPy described in step (4)
mthe concentration of the dichloromethane solution of bis is 0.072 mol/L.
3. described in claim 1, dinitrogen oxyradical rare earth metal complex crystal is preparing the application in computer memory device.
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| CN104341460B (en) * | 2014-10-08 | 2017-06-16 | 天津师范大学 | Dy (III) Mn (II) mixed metal magnetic complex and preparation method and application |
| CN104332272B (en) * | 2014-10-16 | 2016-08-24 | 广西师范大学 | A kind of rareearth magnetic material and preparation method thereof |
| CN105237481B (en) * | 2015-10-20 | 2018-07-13 | 复旦大学 | A kind of method of rare earth catalyst synthesis 1,4,5,6- tetrahydropyrimidinederivatives derivatives |
| CN105218451A (en) * | 2015-10-20 | 2016-01-06 | 复旦大学 | A kind of method of narrowing of rare earth catalyst ring Reactive Synthesis imidazolidine derivatives |
| 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 |
| 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 |
| 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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