CN105131045A - Salicylaldehyde schiff base ligand nickel metallic complex, and preparation method and application thereof - Google Patents
Salicylaldehyde schiff base ligand nickel metallic complex, and preparation method and application thereof Download PDFInfo
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- CN105131045A CN105131045A CN201510580013.5A CN201510580013A CN105131045A CN 105131045 A CN105131045 A CN 105131045A CN 201510580013 A CN201510580013 A CN 201510580013A CN 105131045 A CN105131045 A CN 105131045A
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- schiff base
- base ligand
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Abstract
The invention relates to a salicylaldehyde schiff base ligand nickel metallic complex, and a preparation method and application thereof. The method comprises the following steps: dissolving adamantanamine hydrochloride and potassium hydroxide into ethyl alcohol, stirring at 25 to 35 DEG C to enable the raw materials to react for 10-20 minutes, and performing suction filtration to obtain a solution A; dissolving 5-nitrosalicylaldehyde into ethyl alcohol to be mixed with the solution A, stirring at 60-70 DEG C to enable the raw materials to react for 1-2 hours, and performing filtering to obtain precipitate; mixing the precipitate with sodium hydroxide, dissolving the precipitate and sodium hydroxide into methyl alcohol, stirring at 25 to 35 DEG C to enable the raw materials to react for 10-20 minutes, adding nickel chloride hexahydrate, keeping the temperature unchanged, and stirring for 2-3 hours to obtain precipitate; dissolving the precipitate into methyl alcohol and methylene dichloride to obtain a target product. The salicylaldehyde schiff base ligand nickel metallic complex is simple in technology, low in cost, and high in yield and reproducibility, and the prepared complex has molecular magnetism and high anti-ferromagnetic coupling effect, and can serve as a molecular-based magnetic material and can be widely applied in the fields of information storage, molecular switch and electromagnetic imaging.
Description
Technical field
The present invention relates to molecular magnetic materials field, particularly bigcatkin willow aldehydes schiff base ligand nickel metal complexes and its preparation method and application.
Background technology
In the middle of single molecular magnets, each molecule is an independently small magnet, and the size of molecule is that particle diameter is unique simultaneously for Nano grade.It has small-size effect and quantum effect, also in the consumption etc. of the time of signal response, the efficiency of transmission and energy, there is advantage simultaneously, this also causes single molecular magnets to have very huge potential using value, particularly in the high-density city and quantum computer etc. of information.Meanwhile, single molecular magnets magnetic is produced by individual molecule, but not long-range order, so no matter make it also dissolve or be distributed in the middle of colloid also can not cause large change to magnetic.Single molecular magnets is a metal-organic complex normally, and its character in dissolving and dispersion is all very good.So single molecular magnets has incomparable advantage with other magneticsubstances in device fabrication etc.
Information age to promote magneticsubstance to a great extent and advances, and it all has not replaceable effect in process and storing information etc.Particularly in recent years, magneticsubstance and theory of magnetism have had darker development, make molecular structure become focus with the research of magnetic communication.Study from molecular level become a current chemical important field already to having special magnetic function molecular material.This also makes molecular magnetic materials will can occupy very important status in the middle of the electricity in future, magnetic, light and optical device.
Summary of the invention
The object of the present invention is to provide a kind of single molecular magnets magneticsubstance bigcatkin willow aldehydes schiff base ligand nickel metal complexes and preparation method thereof.
The technical solution used in the present invention is: a kind of bigcatkin willow aldehydes schiff base ligand nickel metal complexes, its chemical formula is [Ni
4l
4(μ
3-OMe)
4(MeOH)
4], structural formula is as follows:
Wherein, L is organic ligand 2-imino--4-oil of mirbane negative oxygen ion.
Described bigcatkin willow aldehydes schiff base ligand nickel metal complexes, crystal is green, triclinic(crystalline)system, spacer P ī; Unit cell parameters:
α=104.591 (6) °, β=104.687 (5) °, γ=117.084 (7) °,
f (000)=1184, R
1=0.1422, ω R
2=0.3015.
The preparation method of bigcatkin willow aldehydes schiff base ligand nickel metal complexes of the present invention, comprises the steps:
1) be dissolved in dehydrated alcohol by adamantanamine hydrochloride and potassium hydroxide, stirring reaction 10-20 minute at 25-35 DEG C, suction filtration obtains pure transparent solution A;
2) take 5-nitrosalicylaldehyde, and be dissolved in dehydrated alcohol, then the solution A that this solution and step (1) obtain is mixed, stirring reaction 1-2 hour at 60-70 DEG C, filter to obtain precipitation;
3) precipitation of step (2) gained mixed with sodium hydroxide, be dissolved in anhydrous methanol, at 25-35 DEG C, stirring reaction 10-20 minute, then adds Nickel dichloride hexahydrate, keeps temperature-resistant, stirs 2-3 hour, is precipitated;
4) get gained precipitation in step (3), be dissolved in anhydrous methanol and methylene dichloride, obtain target product.
The preparation method of above-mentioned bigcatkin willow aldehydes schiff base ligand nickel metal complexes, in molar ratio, adamantanamine hydrochloride: potassium hydroxide: 5-nitrosalicylaldehyde: sodium hydroxide: Nickel dichloride hexahydrate=1:1:1:1:1.
The preparation method of above-mentioned bigcatkin willow aldehydes schiff base ligand nickel metal complexes, in step 4, the volume ratio of anhydrous methanol and methylene dichloride is 1:1.
The invention has the beneficial effects as follows: present invention process is simple, with low cost, productive rate is high, reproducibility is high; Title complex of the present invention has molecular magnetism, and anti-ferromagnetic coupling interaction is very strong, can be used as molecule based magnetic materials, and can store in information, the field such as molecular switch, magnetography is used widely.
Accompanying drawing explanation
Fig. 1 is [Ni
4l
4(μ
3-OMe)
4(MeOH)
4] infrared detection figure.
Fig. 2 is [Ni
4l
4(μ
3-OMe)
4(MeOH)
4] crystalline structure figure.
Fig. 3 is [Ni
4l
4(μ
3-OMe)
4(MeOH)
4] variable temperature magnetic susceptibility graphic representation.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1 one kinds of bigcatkin willow aldehydes schiff base ligand nickel metal complexess
(1) preparation method is as follows:
1) be dissolved in 10 milliliters of analytical pure dehydrated alcohols by 0.08 mmole analytical pure adamantanamine hydrochloride and 0.08 mmole analytical pure potassium hydroxide, stirring reaction 10-20 minute at 30 DEG C, suction filtration obtains pure transparent solution A;
2) take 0.08 mmole 5-nitrosalicylaldehyde, and be dissolved in 10 milliliters of analytical pure dehydrated alcohols, then this solution is mixed with the solution A finally obtained in step (1), stirring reaction 1-2 hour at 60-70 DEG C, filter to obtain pure precipitation;
3) by the pure precipitation of step (2) gained and 0.08 mmole analytical pure sodium hydroxide mixed dissolution in 20 milliliters of analytical pure anhydrous methanols, stirring reaction 10-20 minute at 30 DEG C, and 0.08 mmole analytical pure Nickel dichloride hexahydrate is joined in above-mentioned reaction, keep temperature-resistant, stir 2-3 hour, be precipitated;
4) in the step that takes a morsel (3), gained is precipitated and dissolved in the analytical pure anhydrous methanol and analytical pure methylene dichloride that 5-8 ml volumes ratio is 1:1, and obtain crystal, productive rate is 47%.
(2) relevant characterization of bigcatkin willow aldehydes schiff base ligand nickel metal complexes and crystal structure determination:
Infrared detection figure as shown in Figure 1 shows, at 1603cm
-1place is the stretching vibration peak of C=N in title complex, at 1244cm
-1the absorption peak at place is attributed to the stretching vibration peak of the C-O key that phenyl ring in title complex is connected with phenolic hydroxyl group, at 450cm
-1stretching vibration peak belong to the absorption of vibrations of Ni-O, in part, O atom and Ni ion carry out coordination.
Get sizeable monocrystalline under the microscope, at room temperature carry out X-ray diffraction experiment.On BrukerSMARTAPEXIICCD single crystal diffractometer, with the Mo-K of graphite monochromator monochromatization
αradiation
under 296 (2) K, use ω scanning technique to collect crystal data.Carry out reduction of data by SAINT program, by SADABS program, absorption correction is carried out to diffraction data.Whole non-hydrogen atom coordinate and anisotropic parameters carry out complete matrix least-squares refinement, and hydrogen atom position is determined by theoretical mode computation.As shown in Figure 2, detailed crystal data is in table 1 for crystalline structure.
The crystallographic data of table 1 title complex
By showing the x-ray crystal structure analysis of Fig. 2, title complex is triclinic(crystalline)system, with P ī for spacer structure.In its each structure cell, average packet contains 2 independently molecules.In the middle of molecule, Ni is hexa-coordinate, coordination is carried out respectively with the O atom in the O atom on the phenolic hydroxyl group of Schiff's base and the atom N on C=N and four methanol molecules, and with the O atom in four Ni atoms and four methanol molecules for summit constitutes a hexahedron title complex, its core is [Ni
4(μ
3-OMe)
4].Angle between Ni-O-Ni from 94.9 (2) ° to 98.9 (2) ° not etc., the bond distance of Ni-O from
arrive
not etc., Ni-N bond distance from
arrive
not etc., Ni-Ni bond distance from
arrive
not etc.Because do not have obvious intermolecular hydrogen bonding to interact or pi-pi accumulation effect in title complex, so complex molecule is by being present in the orderly arrangement of weak Van der Waals force between reticulated structure.
Fig. 3 is title complex [Ni
4l
4(μ
3-OMe)
4(MeOH)
4] variable temperature magnetic susceptibility, test under the condition of outfield 100Oe, temperature range 2-300K, its χ
mtvsT curve as shown in upper graph in Fig. 3, wherein χ
mfor molar susceptibility.For title complex, along with the reduction curve entirety of temperature presents downward trend, χ during 300K
mt value is 2.46cm
3kmol
-1, the process that first half term declines is comparatively slow, reaches 1.99cm when 100K
3kmol
-1, then the downtrending of the second half accelerates, the χ when 2K
mt reaches minimum value 0.20cm
3kmol
-1.The χ of title complex
mt value reduces with temperature and reduces, and there is antiferromagnetic interaction between the paramagnetic ion in this display compound.At 300K to 100K, it is fine that experimental data and curieweisslaw meet, as in Fig. 3 below shown in curve.The Curie constant that matching obtains and Weiss constant are respectively: C=2.79cm
3kmol
-1, θ=-45.88K.
So, title complex [Ni can be drawn by above data
4l
4(μ
3-OMe)
4(MeOH)
4] there is molecular magnetism, and there is strong anti-ferromagnetic coupling interaction.And as nano level molecular magnet, from application, effectively can break through the restriction of the size aspect suffered by traditional magneton performance, single molecular magnets has quantum magnetic effect, molecular device can be made into, the Electricity Functionals such as excellent switch and conduction can be shown in microscale, and the magnetic memory materials of super-high density can be made into.Bigcatkin willow aldehydes schiff base ligand nickel metal complexes synthesized by the present invention, dimensional effect caused by the specific surface area that it is huge and quantum effect, also has its advantage in the consumption of the time of signal response, the efficiency of transmission and energy etc., make bigcatkin willow aldehydes schiff base ligand nickel metal complexes be expected to become the material realizing Ultrahigh-Density Data Storage, simultaneously in quantum computer etc., there is huge potential using value.
Embodiment 2 one kinds of bigcatkin willow aldehydes schiff base ligand nickel metal complexess
Preparation method is as follows:
1) be dissolved in 10 milliliters of analytical pure dehydrated alcohols by 0.13 mmole analytical pure adamantanamine hydrochloride and 0.13 mmole analytical pure potassium hydroxide, stirring reaction 10-20 minute at 30 DEG C, suction filtration obtains pure transparent solution A;
2) take 0.13 mmole 5-nitrosalicylaldehyde, and be dissolved in 10 milliliters of analytical pure dehydrated alcohols, then this solution is mixed with the solution A finally obtained in step (1), stirring reaction 1-2 hour at 60-70 DEG C, filter to obtain pure precipitation;
3) by the pure precipitation of step (2) gained and 0.13 mmole analytical pure sodium hydroxide mixed dissolution in 20 milliliters of analytical pure anhydrous methanols, stirring reaction 10-20 minute at 30 DEG C, and 0.13 mmole analytical pure Nickel dichloride hexahydrate is joined in above-mentioned reaction, keep temperature-resistant, stir 2-3 hour, be precipitated;
4) in the step that takes a morsel (3), gained is precipitated and dissolved in the analytical pure anhydrous methanol and analytical pure methylene dichloride that 5-8 ml volumes ratio is 1:1, and obtain crystal, productive rate is 47%.
Claims (6)
1. a bigcatkin willow aldehydes schiff base ligand nickel metal complexes, is characterized in that, its chemical formula is [Ni
4l
4(μ
3-OMe)
4(MeOH)
4], structural formula is as follows:
Wherein, L is organic ligand 2-imino--4-oil of mirbane negative oxygen ion.
2. a kind of bigcatkin willow aldehydes schiff base ligand nickel metal complexes according to claim 1, is characterized in that, described bigcatkin willow aldehydes schiff base ligand nickel metal complexes, and crystal is green, triclinic(crystalline)system, spacer P ī; Unit cell parameters:
α=104.591 (6) °, β=104.687 (5) °, γ=117.084 (7) °,
f (000)=1184, R
1=0.1422, ω R
2=0.3015.
3. a preparation method for the bigcatkin willow aldehydes schiff base ligand nickel metal complexes described in claim 1 or 2, is characterized in that comprising the steps:
1) be dissolved in dehydrated alcohol by adamantanamine hydrochloride and potassium hydroxide, stirring reaction 10-20 minute at 25-35 DEG C, suction filtration obtains pure transparent solution A;
2) take 5-nitrosalicylaldehyde, and be dissolved in dehydrated alcohol, then the solution A that this solution and step (1) obtain is mixed, stirring reaction 1-2 hour at 60-70 DEG C, filter to obtain precipitation;
3) precipitation of step (2) gained mixed with sodium hydroxide, be dissolved in anhydrous methanol, at 25-35 DEG C, stirring reaction 10-20 minute, then adds Nickel dichloride hexahydrate, keeps temperature-resistant, stirs 2-3 hour, is precipitated;
4) get gained precipitation in step (3), be dissolved in anhydrous methanol and methylene dichloride, obtain target product.
4. preparation method according to claim 3, is characterized in that: in molar ratio, adamantanamine hydrochloride: potassium hydroxide: 5-nitrosalicylaldehyde: sodium hydroxide: Nickel dichloride hexahydrate=1:1:1:1:1.
5. preparation method according to claim 3, is characterized in that: in step 4, and the volume ratio of anhydrous methanol and methylene dichloride is 1:1.
6. the bigcatkin willow aldehydes schiff base ligand nickel metal complexes described in claim 1 or 2 is as the application of magneticsubstance.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796478A (en) * | 2019-01-10 | 2019-05-24 | 广西师范大学 | Monokaryon dysprosium complex based on double schiff base ligand and its preparation method and application |
| CN111592660A (en) * | 2020-06-15 | 2020-08-28 | 平顶山学院 | One-dimensional coordination polymer of nickel, preparation method thereof and application thereof in proton conducting membrane of fuel cell |
| CN113105499A (en) * | 2021-04-16 | 2021-07-13 | 河北民族师范学院 | Schiff base vanadyl complex and preparation method thereof |
| CN113461741A (en) * | 2021-06-02 | 2021-10-01 | 昆明学院 | Saldmpn type nickel (II) halide complex and preparation method and application thereof |
| CN116178353A (en) * | 2023-05-04 | 2023-05-30 | 四川省产品质量监督检验检测院 | Cantilever macrocyclic binuclear nickel metal complex, preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796478A (en) * | 2019-01-10 | 2019-05-24 | 广西师范大学 | Monokaryon dysprosium complex based on double schiff base ligand and its preparation method and application |
| CN109796478B (en) * | 2019-01-10 | 2021-03-02 | 广西师范大学 | Mononuclear dysprosium complex based on bis-Schiff base ligand and preparation method and application thereof |
| CN111592660A (en) * | 2020-06-15 | 2020-08-28 | 平顶山学院 | One-dimensional coordination polymer of nickel, preparation method thereof and application thereof in proton conducting membrane of fuel cell |
| CN113105499A (en) * | 2021-04-16 | 2021-07-13 | 河北民族师范学院 | Schiff base vanadyl complex and preparation method thereof |
| CN113461741A (en) * | 2021-06-02 | 2021-10-01 | 昆明学院 | Saldmpn type nickel (II) halide complex and preparation method and application thereof |
| CN116178353A (en) * | 2023-05-04 | 2023-05-30 | 四川省产品质量监督检验检测院 | Cantilever macrocyclic binuclear nickel metal complex, preparation method and application thereof |
| CN116178353B (en) * | 2023-05-04 | 2023-08-01 | 四川省产品质量监督检验检测院 | Cantilever macrocyclic binuclear nickel metal complex, preparation method and application thereof |
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Application publication date: 20151209 |