CN107118158A - A kind of magnetic switch material of near room temperature and preparation method thereof - Google Patents
A kind of magnetic switch material of near room temperature and preparation method thereof Download PDFInfo
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- CN107118158A CN107118158A CN201710299174.6A CN201710299174A CN107118158A CN 107118158 A CN107118158 A CN 107118158A CN 201710299174 A CN201710299174 A CN 201710299174A CN 107118158 A CN107118158 A CN 107118158A
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 5
- 150000002892 organic cations Chemical class 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 150
- 239000000243 solution Substances 0.000 claims description 93
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000012043 crude product Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012153 distilled water Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000009825 accumulation Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000002050 diffraction method Methods 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 21
- 108010053481 Antifreeze Proteins Proteins 0.000 abstract description 5
- 238000002390 rotary evaporation Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 5
- 230000008016 vaporization Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001144 powder X-ray diffraction data Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- -1 sulphur alkene Chemical class 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000005426 magnetic field effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of magnetic switch material [C of near room temperature3‑MIM][Ni(mnt)2] and preparation method thereof.The chemical formula of the material is C15H13N6NiS4, belong to anorthic system space group P 1, one of asymmetric cell includes an organic cation and [a Ni (mnt)2]‑Anion.The compound magnetic susceptibility presents obvious thermal hysteresis, is a kind of preferable room temperature magnetic switch material.
Description
Technical field
The invention belongs to magnetic switch Material Field, and in particular to a kind of magnetic switch material of near room temperature and its
Preparation method.
Background technology
Magnetic resistance material (magneto-resistance material) is a kind of magnetic with notable magneto-resistance effect
Material.Strong magnetic material caused resistance variations, referred to as magneto-resistance effect when being acted on by externally-applied magnetic field.No matter magnetic field and electricity
Flow direction parallel or vertical, will all produce magneto-resistance effect.The former (parallel) is referred to as vertical magnetic field effect, and the latter's (vertical) is referred to as
Transverse magnetic effect.
The magnetic resistivity (the ratio between resistance when resistance variations caused by magnetic field are not with adding magnetic field) of general strong magnetic material is in room
Temperature is lower to be less than 8%, and more than 10% is risen at low temperature.The magnetic resistance material used mainly has ferronickel system and Ni-Co series magnetic
Property alloy.The magnetic resistivity about 1%~3% of ferronickel system permalloy at room temperature, can if adding copper, chromium or manganese element in alloy
Increase resistivity；The resistivity of Ni-Co series alloy is higher, up to 6%.Compared with using other magnetic effects, imitated using magneto-resistor
The transducer and sensor that should be made, its device are simple, insensitive to speed and frequency.Magnetic resistance material has been used for manufacture magnetic note
Reader of record head, bubble detector and magnetic thin film memory etc..
With developing rapidly for microelectronics, the research of the electronic device material of molecular level is increasingly closed by people
Note.Increasing bistable system is used as the carrier of molecule sill device, in temperature sensor, photoswitch and information note
The field such as recall, store to be applied.
Double-(two sulphur alkene) metal complex has the advantages that chemical stability is good, is easy to modification, can be coordinated by changing
Central ion electron configuration, the molecular configuration of balance cation and ligand molecular configuration of thing etc. regulate and control the transformative of complex
Matter is so as to obtain more extensive molecule bistable system.For double-(two sulphur alkene) metal complex molecule sill, heat
Hysteresis characteristic can change particularly rare rapidly in room temperature.
The content of the invention
An object of the present invention is the magnetic switch material for providing a kind of near room temperature.The material of the present invention is spinning
Become double-(two sulphur alkene) metal complex, there is thermal hysteresis at room temperature.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：
A kind of magnetic switch material [C of near room temperature3-MIM][Ni(mnt)2], its chemical formula is C15H13N6NiS4, belong to three
Oblique system space group P-1, one of asymmetric cell includes an organic cation and [a Ni (mnt)2]-Anion.
Preferably, material [the C3-MIM][Ni(mnt)2] independent column accumulation is formed along crystallography a- direction of principal axis,
In [Ni (mnt)2]-Adjacent anion formation anion dimer in anion accumulation post.
Preferably, material [the C3-MIM][Ni(mnt)2] in [Ni (mnt)2]-Adjacent Ni ... Ni distances are in post
3.876-And 4.435-
Near room temperature of the present invention refers to 24 ± 30 DEG C of scope.
To the compound [C of the present invention3-MIM][Ni(mnt)2] magnetic property research in find, test interval in 2-400K
Interior, the compound there occurs absorbing magnetic phase transition near room temperature, and in temperature-fall period, the compound magnetic susceptibility is also in
Obvious thermal hysteresis is showed, heat stagnation returns wide about 70K.Therefore, compound of the invention is that a kind of preferable room temperature magnetic is opened
Close material.
An object of the present invention also resides in the magnetic switch material [C for providing near room temperature of the present invention3-MIM][Ni
(mnt)2] preparation method, comprise the following steps：
(1) to NiCl2·6H2Na is added in the O aqueous solution2mnt(C4N2S2Na obtain red molten after the aqueous solution), reaction
Liquid, is filtrated to get solution A；
(2) 1- methylimidazoles and 1- N-Propyl Bromides are dissolved in acetone, then reacted under heating, solution is layered, on
Layer is colourless transparent solution, and lower floor is a large amount of oily liquids, and lower floor's liquid is separated, and is extracted, and is evaporated rear soluble in water
Obtain solution B；
(3) added into solution A in solution B, adition process and produce a large amount of kermesinus precipitations, stirring, filtering precipitate,
Washing, is dried；After crude product dissolves and filtered, semi-hermetic, volatilization crystallization obtains red crystals C, yield is about 90%；
(4) by I2Methanol solution is added in C methanol solution, is added after stirring and the micro- of precipitation is filtered after methanol, standing
Crystalline substance, is washed, and is dried, and is volatilized after the crude product obtained after drying is dissolved, is obtained target product [C3-MIM][Ni(mnt)2]。
Above-mentioned magnetic switch material [C3-MIM][Ni(mnt)2] preparation method it is simple to operate, yield is high.
Preferably, NiCl in step (1)2·6H2NiCl in the O aqueous solution2·6H2O concentration is 5-20mol/mL, example
Such as it is 6mol/L, 8mol/L, 11mol/L, 13mol/L, 17mol/L, 19mol/L, preferably 10mol/mL.
Preferably, Na2Na in the mnt aqueous solution2Mnt concentration be 4-20mol/mL, for example, 4.8mol/L, 6mol/L,
8mol/L, 11mol/L, 13mol/L, 17mol/L, 19mol/L etc., preferably 8-10mol/mL.
Preferably, NiCl2·6H2The O aqueous solution and Na2The volume ratio of the mnt aqueous solution is 1:1-4, for example, 1:1.2、1:
1.6、1:2.5、1:3、1:3.5 etc., preferably 1:2.
NiCl2·6H2O and Na2Mnt molar ratio is preferably 1:0.4-8, for example, 1:0.5、1:0.6、1:0.7、1:
0.75 etc..If this ratio is less than 1:0.4, such as 1:0.2、1:0.1 etc., then the yield of product can be made very low, if this ratio is high
In 1:8, such as it is 1:10、1:15 etc., then it can greatly increase the cost of method.
Preferably, described add is carried out in the case where slightly heating and/or stirring.
Preferably, the temperature slightly heated is 30-60 DEG C.
Preferably, the time of the stirring is more than 5min, preferably 10min.
Preferably, the mol ratio of 1- methylimidazoles and 1- N-Propyl Bromides is 1 in step (2):0.5-3, for example, 1:0.8、
1:1.2、1:1.6、1:2.5、1:2.8 etc., preferably 1:1-1.5.
Preferably, the concentration of 1- methylimidazoles in acetone be 20-100mol/L, for example, 26mol/L, 38mol/L,
51mol/L, 63mol/L, 77mol/L, 89mol/L, 96mol/L etc., preferably 30-50mol/L.
Preferably, the temperature of the heating be 35-100 DEG C, for example, 38 DEG C, 45 DEG C, 52 DEG C, 59 DEG C, 64 DEG C, 68 DEG C,
75 DEG C, 82 DEG C, 89 DEG C, 93 DEG C, 98 DEG C etc., preferably 50-80 DEG C, the time of the reaction is more than 5 hours, for example, 5.2
Hour, 5.7 hours, 7.5 hours, 9.2 hours, 10.7 hours, 15.5 hours, 16 hours, 18 hours etc., preferably 12-18 is small
When.
Lower floor's liquid, which is separated, to be separated by technology well known in the art such as separatory funnel etc..
Preferably, the extraction is carried out using ethyl acetate, is preferably carried out multiple.This step has to the purity of final product
Important influence, if this step product is impure, is incorporated into rear single step reaction, final product can be caused not purify.
It is evaporated available techniques known in the art to carry out, such as rotary evaporation.
Preferably, the volume ratio of the water and acetone is 1:0.5-2, for example, 1:0.8、1:1.2、1:1.6、1:1.8 etc.,
Preferably 1:1.
Preferably, be incorporated as being slowly added dropwise in step (3) into.
Preferably, the volume ratio of solution A and solution B is 1:1-4, preferably 1:2.
Preferably, the time of the stirring is more than 15min, preferably 30-50min.
Preferably, the washing is carried out using distilled water.
Preferably, the washing is washing to filtrate in colourless.
Preferably, the drying is vacuum drying.
Preferably, the crude product dissolving uses methanol.
Preferably, volatilization crystallization is carried out in atmosphere.
Preferably, the time of the volatilization crystallization is more than 2 days, preferably 1 week or so.
Preferably, I in step (4)2Methanol solution in I2Concentration be 10-50mol/L, for example, 11mol/L,
13mol/L, 17mol/L, 19mol/L, 26mol/L, 35mol/L, 42mol/L, 47mol/L etc., preferably 20-30mol/L.
Preferably, I2Methanol solution and C methanol solution volume ratio be 1:1-5, preferably 1:2.
Methanol is aoxidized and I2Usage amount it is critically important to product qualities, preferably control I2Amount ratio with C material is 1:1-
1.5, for example, 1:1.1、1:1.2、1:1.3、1:1.4 etc., preferably 1:1.25 or so, it is no to ensure that it is complete that oxidation reaction is carried out
Divalence and trivalent mixture can then be obtained.
Preferably, the stirring is carried out at room temperature, and the time preferably stirred is more than 15min, preferably 30-50min.
Preferably, the volume ratio that methanol and C methanol solution are added after stirring is 1:5-20, preferably 1:10.
Preferably, the time of the standing is more than 5 hours, preferably 10-24 hours.
Preferably, the washing is carried out using methanol.
Preferably, the drying is vacuum drying.
Preferably, the crude product dissolves in methyl alcohol.
Preferably, the volatilization is carried out at room temperature.
Preferably, the time of the volatilization is more than 3 days, preferably 6 days.
Preferably, the preparation method of the present invention comprises the following steps：
(1) by NiCl2·6H2O (0.5mol) 50mL distilled water dissolves, and light blue solution is obtained, by Na2mnt(0.8-
1mol), after being dissolved with 100mL distilled water, above-mentioned NiCl is instilled under slightly heating and magnetic agitation2·6H2In O solution, obtain
Red solution, continues stir about 10min.Red solution is filtrated to get into solution A to continue to employ；
(2) 50mL acetone solutions are used after mixing 1- methylimidazoles (2mol) and 1- N-Propyl Bromides (2-3mol), and in 50-80
Reacted 12-18 hours at DEG C, solution is layered, upper strata is colourless transparent solution, lower floor is a large amount of oily liquids, is leaked with point liquid
Bucket separates lower floor's liquid, and is extracted several times with ethyl acetate, and rotary evaporation is dry rear and is dissolved in obtaining molten in 50mL water
Liquid B continues to employ；
(3) it is slowly added dropwise in solution A into solution B, a large amount of kermesinus precipitations, stir about 30- is produced during dropwise addition
After 50min, filtering precipitate is washed with distilled water to filtrate in after colourless, vacuum drying, crude product with methanol dissolving and mistake
Filter in clean beaker, semi-hermetic, crystallization of being volatilized in air.Red crystals C is obtained after about one week, yield is 90%；
(4) by I2The methanol solution (50mL) of (1-1.5mol) is slowly dropped to C methanol solution (100mL), at room temperature
30-50min is stirred, a large amount of methanol (1000mL) are added in obtained green solution, are stood overnight, next day is by the crystallite of precipitation
Filtering, is washed with methanol, and crude product is obtained after vacuum drying 5h, by crude product dissolving in methyl alcohol, at room temperature slow vaporization about 6
It obtains target product [C3-MIM][Ni(mnt)2]。
Compound [the C of the present invention3-MIM][Ni(mnt)2] magnetic susceptibility presents obvious thermo-lag and showed in temperature-fall period
As heat stagnation returns wide about 70K.Therefore, compound of the invention is a kind of preferable room temperature magnetic switch material.The preparation of the present invention
Method achieves higher yield (up to more than 86%).
Brief description of the drawings
Fig. 1 is compound [C3-MIM][Ni(mnt)2] molecular structure；
Fig. 2 is compound [C3-MIM][Ni(mnt)2] packed structures；
Fig. 3 is compound [C3-MIM][Ni(mnt)2] variable temperature magnetic susceptibility curve；
Fig. 4 is the powder xrd pattern of the resulting materials of embodiment 2；
Fig. 5 is the powder xrd pattern of the resulting materials of embodiment 3.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
A kind of magnetic switch material [C of near room temperature3-MIM][Ni(mnt)2] preparation method, comprise the following steps：
(1) NiCl is weighed2·6H2O (0.5mol) is dissolved with 50mL distilled water in 250mL beakers, obtains light blue solution.
Na is weighed again2Mnt (0.8mol), after being dissolved with 100mL distilled water, is instilled above-mentioned under slightly heating and magnetic agitation
NiCl2·6H2In O solution, red solution is obtained, continues stir about 10min.Red solution is filtrated to get into solution A to continue to employ；
(2) 1- methylimidazoles (2mol) and 1- N-Propyl Bromides (3mol) are weighed, both use 50mL acetone solutions after mixing, and
Reacted 12 hours at 80 DEG C, solution is layered, upper strata is colourless transparent solution, lower floor is a large amount of oily liquids, is leaked with point liquid
Bucket separates lower floor's liquid, and is extracted several times with ethyl acetate, and rotary evaporation is dry rear and is dissolved in obtaining molten in 50mL water
Liquid B continues to employ；
(3) it is slowly added dropwise in solution A into solution B, a large amount of kermesinus precipitations is produced during dropwise addition.Stir about
After 50min, filtering precipitate is washed with distilled water to filtrate in after colourless, vacuum drying.Crude product with methanol dissolves and filtered
In clean beaker, semi-hermetic, crystallization of being volatilized in air.Red crystals C is obtained after about one week, yield is 90%.
(4) by I2(1.5mol) methanol solution (50mL) is slowly dropped to C methanol solution (100mL), stirs at room temperature
50min.A large amount of methanol (1000mL) are added in obtained green solution, are stood overnight.Next day filters the crystallite of precipitation, uses
Methanol is washed, and crude product is obtained after vacuum drying 5h.By crude product dissolving in methyl alcohol, slow vaporization at room temperature is obtained for about 6 days
Target product [C3-MIM][Ni(mnt)2]。
Compound [C made from the present embodiment3-MIM][Ni(mnt)2] crystal data and structure refinement parameter be shown in Table 1, choosing
Selecting property bond distance is shown in Table 2 with bond angle.
Compound [the C of table 13-MIM][Ni(mnt)2] crystal data and structure refinement parameter
Compound [the C of table 23-MIM][Ni(mnt)2] selective bond distance and bond angle
Compound [C3-MIM][Ni(mnt)2] crystal structure
Compound [C3-MIM][Ni(mnt)2] crystal belong to anorthic system space group P-1, an asymmetric cell is included
One organic cation and [a Ni (mnt)2]-Anion (Fig. 1).Along crystallography a- the direction of principal axis, [C of compound3-MIM]
[Ni(mnt)2] independent column accumulation is formed, in [Ni (mnt)2]-Adjacent anion formation anion two in anion accumulation post
Aggressiveness.[Ni(mnt)2]-Adjacent Ni ... Ni distances are 3.928 Hes in post(Fig. 2).
Compound [C3-MIM][Ni(mnt)2] magnetic property research
To compound [C3-MIM][Ni(mnt)2] magnetic property research in it was found that testing interval in 2-400K
Interior, the compound there occurs absorbing magnetic phase transition (Fig. 3) in room temperature, the magnetic phase transition with higher than room temperature and in cooling
During, the compound magnetic susceptibility also presents obvious thermal hysteresis, and heat stagnation returns wide about 70K.Therefore, the compound is
A kind of preferable room temperature magnetic switch material.
Embodiment 2
A kind of magnetic switch material [C of near room temperature3-MIM][Ni(mnt)2] preparation method, comprise the following steps：
(1) NiCl is weighed2·6H2O (0.5mol) is dissolved with 50mL distilled water in 250mL beakers, obtains light blue solution.
Na is weighed again2Mnt (1mol), after being dissolved with 100mL distilled water, above-mentioned NiCl is instilled under slightly heating and magnetic agitation2·
6H2In O solution, red solution is obtained, continues stir about 10min.Red solution is filtrated to get into solution A to continue to employ；
(2) 1- methylimidazoles (2mol) and 1- N-Propyl Bromides (2mol) are weighed, both use 50mL acetone solutions after mixing, and
Reacted 18 hours at 50 DEG C, solution is layered, upper strata is colourless transparent solution, lower floor is a large amount of oily liquids, is leaked with point liquid
Bucket separates lower floor's liquid, and is extracted several times with ethyl acetate, and rotary evaporation is dry rear and is dissolved in obtaining molten in 50mL water
Liquid B continues to employ；
(3) it is slowly added dropwise in solution A into solution B, a large amount of kermesinus precipitations is produced during dropwise addition.Stir about
After 30min, filtering precipitate is washed with distilled water to filtrate in after colourless, vacuum drying.Crude product with methanol dissolves and filtered
In clean beaker, semi-hermetic, crystallization of being volatilized in air.Red crystals C is obtained after about one week, yield is 90%.
(4) by I2(1mol) methanol solution (50mL) is slowly dropped to C methanol solution (100mL), stirs at room temperature
30min.A large amount of methanol (1000mL) are added in obtained green solution, are stood overnight.Next day filters the crystallite of precipitation, uses
Methanol is washed, and crude product is obtained after vacuum drying 5h.By crude product dissolving in methyl alcohol, slow vaporization at room temperature is obtained for about 6 days
Target product [C3-MIM][Ni(mnt)2]。
Material manufactured in the present embodiment is tested in interval temperature-fall period in 2-400K, and the compound magnetic susceptibility is presented substantially
Thermal hysteresis, heat stagnation return it is wide about 70K.
Fig. 4 is the powder xrd pattern that material is made in the embodiment.It can be seen that material produced by the present invention has
The structure similar to material made from embodiment 1.Following line represents the powder diagram that sample is made in experiment, line generation above
Table is fitted obtained diffraction pattern by single crystal diffraction, and two curved diffraction peak positions are basically identical, illustrates the sample that we prepare
It is pure phase.
Embodiment 3
A kind of magnetic switch material [C of near room temperature3-MIM][Ni(mnt)2] preparation method, comprise the following steps：
(1) NiCl is weighed2·6H2O (0.25mol) is dissolved with 50mL distilled water in 250mL beakers, obtains light blue molten
Liquid.Na is weighed again2Mnt (2mol), after being dissolved with 100mL distilled water, is instilled above-mentioned under slightly heating and magnetic agitation
NiCl2·6H2In O solution, red solution is obtained, continues stir about 5min.Red solution is filtrated to get into solution A to continue to employ；
(2) 1- methylimidazoles (2mol) and 1- N-Propyl Bromides (1mol) are weighed, both use 100mL acetone solutions after mixing, and
Reacted 5 hours at 100 DEG C, solution is layered, upper strata is colourless transparent solution, lower floor is a large amount of oily liquids, with a point liquid
Funnel separates lower floor's liquid, and is extracted several times with ethyl acetate, and rotary evaporation is dry rear and is dissolved in obtaining in 50mL water
Solution B is continued to employ；
(3) it is slowly added dropwise in solution A into solution B, a large amount of kermesinus precipitations is produced during dropwise addition.Stir about
After 15min, filtering precipitate is washed with distilled water to filtrate in after colourless, vacuum drying.Crude product with methanol dissolves and filtered
In clean beaker, semi-hermetic, crystallization of being volatilized in air.Red crystals C is obtained after about one week, yield is 90%.
(4) by I2(0.5mol) methanol solution (50mL) is slowly dropped to C methanol solution (100mL), stirs at room temperature
15min.A large amount of methanol (500mL) are added in obtained green solution, 5 hours are stood.Next day filters the crystallite of precipitation, uses
Methanol is washed, and crude product is obtained after vacuum drying 5h.By crude product dissolving in methyl alcohol, slow vaporization at room temperature is obtained for about 3 days
Target product [C3-MIM][Ni(mnt)2]。
Fig. 5 is the powder xrd pattern that material is made in the embodiment.It can be seen that material produced by the present invention has
The structure similar to material made from embodiment 1.Following line represents the powder diagram that sample is made in experiment, line above
Represent and obtained diffraction pattern is fitted by single crystal diffraction, two curved diffraction peak positions are basically identical, illustrate the sample that we prepare
Product are pure phases.
Embodiment 4
A kind of magnetic switch material [C of near room temperature3-MIM][Ni(mnt)2] preparation method, comprise the following steps：
(1) NiCl is weighed2·6H2O (1mol) is dissolved with 50mL distilled water in 250mL beakers, obtains light blue solution.Again
Weigh Na2Mnt (0.4mol), after being dissolved with 100mL distilled water, above-mentioned NiCl is instilled under slightly heating and magnetic agitation2·
6H2In O solution, red solution is obtained, continues stir about 20min.Red solution is filtrated to get into solution A to continue to employ；
(2) 1- methylimidazoles (1mol) and 1- N-Propyl Bromides (3mol) are weighed, both use 50mL acetone solutions after mixing, and
Reacted 8 hours at 35 DEG C, solution is layered, upper strata is colourless transparent solution, lower floor is a large amount of oily liquids, uses separatory funnel
Lower floor's liquid is separated, and extracted several times with ethyl acetate, rotary evaporation is dry rear and is dissolved in obtaining solution B in 50mL water
Continue to employ；
(3) it is slowly added dropwise in solution A into solution B, a large amount of kermesinus precipitations is produced during dropwise addition.Stir about
After 20min, filtering precipitate is washed with distilled water to filtrate in after colourless, vacuum drying.Crude product with methanol dissolves and filtered
In clean beaker, semi-hermetic, crystallization of being volatilized in air.Red crystals C is obtained after about one week, yield is 90%.
(4) by I2(2.5mol) methanol solution (50mL) is slowly dropped to C methanol solution (250mL), stirs at room temperature
40min.A large amount of methanol (5000mL) are added in obtained green solution, are stood overnight.Next day filters the crystallite of precipitation, uses
Methanol is washed, and crude product is obtained after vacuum drying 5h.By crude product dissolving in methyl alcohol, slow vaporization at room temperature is obtained for about 8 days
Target product [C3-MIM][Ni(mnt)2]。
Shown through XRD, the material of structure similar to Example 1 has been made in the present embodiment.Following line represents experiment system
The powder diagram of sample is obtained, line above represents the diffraction pattern obtained by single crystal diffraction fitting, two curved diffraction peak positions
Put basically identical, illustrate that the sample that we prepare is pure phase.
Comparative example 1
It is identical with the step of embodiment 1, except NiCl2·6H2O and Na2Mnt molar ratio is 1:0.2.Yield is only
8%.
Comparative example 2
It is identical with the step of embodiment 1, except NiCl2·6H2O and Na2Mnt molar ratio is preferably 1:12.Greatly increase
Reaction cost, and reaction introduces impurity after giving, yield is only 15%.
Comparative example 3
It is identical with the step of embodiment 1, except I2Amount ratio with C material is 1:0.5.
A large amount of insoluble impurities generations are had, yield is only 32%, it is impossible to purified.
Comparative example 4
It is identical with the step of embodiment 1, except I2Amount ratio with C material is 1:2.
Oxidation is incomplete, has part divalence red product, yield is only 30%.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of magnetic switch material [C of near room temperature3-MIM][Ni(mnt)2], its chemical formula is C15H13N6NiS4, belong to three oblique
Crystallographic system space group P-1, one of asymmetric cell includes an organic cation and [a Ni (mnt)2]-Anion.
2. magnetic switch material [C according to claim 13-MIM][Ni(mnt)2], it is characterised in that the material [C3-
MIM][Ni(mnt)2] independent column accumulation is formed along crystallography a- direction of principal axis, in [Ni (mnt)2]-Phase in anion accumulation post
Adjacent anion formation anion dimer；
Preferably, the material [C3-MIM][Ni(mnt)2] in [Ni (mnt)2]-Adjacent Ni ... Ni distances are in postWith
3. the magnetic switch material [C of the near room temperature described in claim 1 or 23-MIM][Ni(mnt)2] preparation method, including
Following steps：
(1) to NiCl2·6H2Na is added in the O aqueous solution2Solution A is filtrated to get after the mnt aqueous solution, reaction；
(2) 1- methylimidazoles and 1- N-Propyl Bromides are dissolved in acetone, then reacted under heating, solution is layered, by lower floor
Liquid is separated, and is extracted, and is evaporated and rear soluble in water is obtained solution B；
(3) solution B is added into solution A, is stirred, filtering precipitate, is washed, is dried；After crude product dissolves and filtered, half is close
Close, volatilization crystallization obtains red crystals C；
(4) by I2Methanol solution is added in C methanol solution, and the crystallite that precipitation is filtered after methanol, standing is added after stirring, is washed
Wash, dry, volatilized after the crude product obtained after drying is dissolved, obtain target product [C3-MIM][Ni(mnt)2]。
4. preparation method according to claim 3, it is characterised in that NiCl in step (1)2·6H2In the O aqueous solution
NiCl2·6H2O concentration is 5-20mol/mL, preferably 10mol/mL；
Preferably, Na2Na in the mnt aqueous solution2Mnt concentration is 4-20mol/mL, preferably 8-10mol/mL；
Preferably, NiCl2·6H2The O aqueous solution and Na2The volume ratio of the mnt aqueous solution is 1:1-4, preferably 1:2；
Preferably, described add is carried out in the case where slightly heating and/or stirring；
Preferably, the temperature slightly heated is 30-60 DEG C；
Preferably, the time of the stirring is more than 5min, preferably 10min.
5. the preparation method according to claim 3 or 4, it is characterised in that 1- methylimidazoles and 1- N-Propyl Bromides in step (2)
Mol ratio be 1:0.5-3, preferably 1:1-1.5；
Preferably, the concentration of 1- methylimidazoles in acetone is 20-100mol/L, preferably 30-50mol/L；
Preferably, the temperature of the heating is 35-100 DEG C, and preferably 50-80 DEG C, the time of the reaction is more than 5 hours,
Preferably 12-18 hours；
Preferably, the extraction is carried out using ethyl acetate, is preferably carried out multiple；
Preferably, the volume ratio of the water and acetone is 1:0.5-2, preferably 1:1.
6. the preparation method according to claim any one of 3-5, it is characterised in that step is incorporated as being slowly added dropwise in (3)
Enter；
Preferably, the volume ratio of solution A and solution B is 1:1-4, preferably 1:2；
Preferably, the time of the stirring is more than 15min, preferably 30-50min；
Preferably, the washing is carried out using distilled water；
Preferably, the washing is washing to filtrate in colourless；
Preferably, the drying is vacuum drying.
7. the preparation method according to claim any one of 3-6, it is characterised in that in step (3), the crude product dissolving
Use methanol；
Preferably, volatilization crystallization is carried out in atmosphere；
Preferably, the time of the volatilization crystallization is more than 2 days, preferably 1 week or so.
8. the preparation method according to claim any one of 3-7, it is characterised in that I in step (4)2Methanol solution in I2
Concentration be 10-50mol/L, preferably 20-30mol/L；
Preferably, I2Methanol solution and C methanol solution volume ratio be 1:1-5, preferably 1:2.
9. the preparation method according to claim any one of 3-8, it is characterised in that step is stirred in room temperature described in (4)
Lower to carry out, the time preferably stirred is more than 15min, preferably 30-50min；
Preferably, the volume ratio that methanol and C methanol solution are added after stirring is 1:5-20, preferably 1:10；
Preferably, the time of the standing is more than 5 hours, preferably 10-24 hours.
10. the preparation method according to claim any one of 3-9, it is characterised in that washing uses first described in step (4)
Alcohol is carried out；
Preferably, the drying is vacuum drying；
Preferably, the crude product dissolves in methyl alcohol；
Preferably, the volatilization is carried out at room temperature；
Preferably, the time of the volatilization is more than 3 days, preferably 6 days.
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