CN105037405A - Single molecular magnet Dy2 (salen) 2 (tta) 4 (OAc) 2 and preparation method of single molecular magnet - Google Patents
Single molecular magnet Dy2 (salen) 2 (tta) 4 (OAc) 2 and preparation method of single molecular magnet Download PDFInfo
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- CN105037405A CN105037405A CN201510363035.6A CN201510363035A CN105037405A CN 105037405 A CN105037405 A CN 105037405A CN 201510363035 A CN201510363035 A CN 201510363035A CN 105037405 A CN105037405 A CN 105037405A
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- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 81
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 126
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 52
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- QSYBHIGFOMLLBD-UHFFFAOYSA-N dysprosium 4,4,4-trifluoro-1-thiophen-2-ylbutane-1,3-dione Chemical compound [Dy].C1(=CC=CS1)C(=O)CC(=O)C(F)(F)F QSYBHIGFOMLLBD-UHFFFAOYSA-N 0.000 claims description 20
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 18
- 238000009792 diffusion process Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 6
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 claims description 6
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 abstract description 10
- 238000010189 synthetic method Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 24
- -1 Rare earth ion Chemical class 0.000 description 8
- 238000013329 compounding Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 101100321817 Human parvovirus B19 (strain HV) 7.5K gene Proteins 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 150000000914 Dysprosium Chemical class 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 230000005303 antiferromagnetism Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention relates to a single molecular magnet and a preparation method of the single molecular magnet, namely to a single molecular magnet Dy2 (salen) 2 (tta) 4 (OAc) 2 and the preparation method of the single molecular magnet. The invention aims to solve the problems that the synthetic yield of rare earth complex single molecular magnet is relatively low, the synthetic method of the complex is complex, the batch production cannot be carried out and the like, which are faced at present. The molecular formula of the single molecular magnet Dy2 (salen) 2 (tta) 4 (OAc) 2 is C84H56Dy2F12N4O16S4, and the crystal system is a triclinic system. The preparation method comprises the following steps: Carrying out heating reflux on a mixed solution C, then cooling to the room temperature, and filtering to obtain a solution D; dispersing a mixed solution E into the solution D in a solution dispersal mode, and standing to obtain the single molecular magnet Dy2 (salen) 2 (tta) 4 (OAc) 2. The method is used for obtaining the single molecular magnet Dy2 (salen) 2 (tta) 4 (OAc) 2.
Description
Technical field
The present invention relates to a kind of single molecular magnets and preparation method thereof.
Background technology
Single molecular magnets (Single-MolecularMagnets, SMMs) be type material between molecular-based magnets and nano magnetic material, refer to that those can be magnetized under magnetic field, after magnetic field is removed, still can keep the unit molecule of magnetic, the curve of its specific magnetising moment external magnetic field there will be magnetic hysteresis loop.GatteschiD in 1993 etc. find first single molecular magnets [Mn
12o
12(OCMe)
16(H
2o)
4], thus hew out a new magnetic fields.Rare earth ion (the especially Tb that single electron number is many, have strong Spin-orbit coupling interaction is introduced in molecule
3+and Dy
3+) be the important channel of preparing high energy barrier single molecular magnets.The preparation of single molecular magnets can be obtained and be easy to purifying by solution methods by relatively simple reagent, and its solvability is good, dissolves in conventional organic reagent, and this point has just in time catered to the requirement of following application, such as, be applied on film.But these single molecular magnetses present temperature (the blocking temperature T of magnetic relaxation effect
b) general lower, this makes it apply to be very limited.So investigators expect to improve blocking temperature by synthesis other types single molecular magnets, therefore, introducing single electron number rare earth ion that is many, that have strong Spin-orbit coupling interaction in molecule becomes the important channel of preparing high energy barrier single molecular magnets.And in all rare earth metals, Dy (III) becomes form the most important rare earth ion of single molecular magnets owing to having high-torque and high coordination environment.The application of metal complexes single molecular magnets in various fields of 3d structure causes the extensive concern of all circles scholar, and in rare earth compounding single molecular magnets, because 4f electronics in rare earth ion is by the shielding of 5s and 5p electronics, the intensity and rare earth ion ubiquity specific magnetising moment quantum tunnelling (QTM) effect that are difficult to the magnetic interaction of raising interionic cause magneticanisotropy energy barrier to reduce, therefore its report is relatively less, in addition, Schiff bases, beta-diketon class rare earth compounding synthetic method is complicated, productive rate is lower, general productive rate only has 20% ~ 30%, these become the ultimate challenge of this field face.
Summary of the invention
It is lower that the present invention will solve the rare earth compounding single molecular magnets synthetic yield faced at present, and the synthetic method of title complex is complicated, the problem such as can not to produce in batches, and provide a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2and preparation method thereof.
A kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2, it is characterized in that a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2molecular formula be C
84h
56dy
2f
12n
4o
16s
4, crystallographic system is triclinic(crystalline)system, and spacer is P-1, and unit cell parameters is
α=95.80 (3) °, β=100.18 (3) °, γ=90.38 (3) °, V=1967.8 (7), Z=1.
A kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2preparation method, prepare according to the following steps:
One, quadrol salicylaldehyde is dissolved in methylene dichloride, obtains solution A; Cadmium acetate is dissolved in methyl alcohol, obtains solution B; Then by solution A and solution B mixing, mixed solution C is obtained;
The amount of substance of the quadrol salicylaldehyde described in step one and the volume ratio of methylene dichloride are (0.125mol ~ 0.13mol): 1L;
The amount of substance of the cadmium acetate described in step one and the volume ratio of methyl alcohol are (0.125mol ~ 0.13mol): 1L;
In mixed solution C described in step one, the mol ratio of quadrol salicylaldehyde and cadmium acetate is 1:1;
Two, by the mixed solution C obtained in step one reflux 1h ~ 1.5h at temperature is 70 DEG C ~ 80 DEG C, then be cooled to room temperature, then filter, obtain solution D;
Three, 2-thenoyltrifluoroacetone dysprosium is dissolved in methyl alcohol, obtains solution E; Solution E is added drop-wise in solution D with the rate of addition of 5/min ~ 10 droplet/min, obtains the precast body prepared by solution diffusion mode;
The amount of substance of 2-thenoyltrifluoroacetone dysprosium described in step 3 and the volume ratio of methyl alcohol are (0.031mol ~ 0.035mol): 1L;
In the precast body prepared by solution diffusion mode described in step 3, the ratio of the amount of quadrol salicylaldehyde, cadmium acetate and 2-thenoyltrifluoroacetone dysprosium is 2:2:1;
Four, the precast body prepared by solution diffusion mode obtained in step 3 is at room temperature left standstill 7 days ~ 8 days, obtain single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.
Advantage of the present invention:
One, rare earth ion and part are carried out coordination by the mode of solution diffusion by the present invention, obtain the rare earth compounding of good properties after crystallization;
Two, the Dy for preparing of the present invention
2(salen)
2(tta)
4(OAc)
2for single molecular magnets, energy barrier is higher, and the productive rate of preparation method of the present invention is high, can reach more than 57.26%, and the synthetic method of single molecular magnets is simple, and repeatability is strong.
The present invention can obtain a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.
Accompanying drawing explanation
Fig. 1 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2molecular structure;
Fig. 2 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2dC magnetic susceptibility figure;
Fig. 3 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2ac magnetic susceptibility real part thetagram, wherein
for ac magnetic susceptibility real part temperature curve under the condition of 10Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 30Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 100Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 300Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 400Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 600Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 800Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 1000Hz;
Fig. 4 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2ac magnetic susceptibility imaginary part thetagram, wherein
for ac magnetic susceptibility imaginary part temperature curve under the condition of 10Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 30Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 100Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 300Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 400Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 600Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 800Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 1000Hz;
Fig. 5 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2frequency-changing AC susceptibility imaginary part real part is mapped, wherein
for the distribution of relaxation times figure at 2K temperature,
for the distribution of relaxation times figure at 2.5K temperature,
for the distribution of relaxation times figure at 3K temperature,
for the distribution of relaxation times figure at 3.5K temperature,
for the distribution of relaxation times figure at 4K temperature,
for the distribution of relaxation times figure at 4.5K temperature,
for the distribution of relaxation times figure at 5K temperature,
for the distribution of relaxation times figure at 5.5K temperature,
for the distribution of relaxation times figure at 6K temperature,
for the distribution of relaxation times figure at 6.5K temperature,
for the distribution of relaxation times figure at 7K temperature,
for the distribution of relaxation times figure at 7.5K temperature.
Embodiment
Embodiment one: present embodiment is a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2molecular formula be C
84h
56dy
2f
12n
4o
16s
4, crystallographic system is triclinic(crystalline)system, and spacer is P-1, and unit cell parameters is
α=95.80 (3) °, β=100.18 (3) °, γ=90.38 (3) °, V=1967.8 (7), Z=1.
The advantage of present embodiment:
One, rare earth ion and part are carried out coordination by the mode of solution diffusion by present embodiment, obtain the rare earth compounding of good properties after crystallization;
Two, the Dy for preparing of present embodiment
2(salen)
2(tta)
4(OAc)
2for single molecular magnets, energy barrier is higher, and the productive rate of preparation method of the present invention is high, can reach more than 57.26%, and the synthetic method of single molecular magnets is simple, and repeatability is strong.
Present embodiment can obtain a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.
Embodiment two: present embodiment is a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2preparation method prepare according to the following steps:
One, quadrol salicylaldehyde is dissolved in methylene dichloride, obtains solution A; Cadmium acetate is dissolved in methyl alcohol, obtains solution B; Then by solution A and solution B mixing, mixed solution C is obtained;
The amount of substance of the quadrol salicylaldehyde described in step one and the volume ratio of methylene dichloride are (0.125mol ~ 0.13mol): 1L;
The amount of substance of the cadmium acetate described in step one and the volume ratio of methyl alcohol are (0.125mol ~ 0.13mol): 1L;
In mixed solution C described in step one, the mol ratio of quadrol salicylaldehyde and cadmium acetate is 1:1;
Two, by the mixed solution C obtained in step one reflux 1h ~ 1.5h at temperature is 70 DEG C ~ 80 DEG C, then be cooled to room temperature, then filter, obtain solution D;
Three, 2-thenoyltrifluoroacetone dysprosium is dissolved in methyl alcohol, obtains solution E; Solution E is added drop-wise in solution D with the rate of addition of 5/min ~ 10 droplet/min, obtains the precast body prepared by solution diffusion mode;
The amount of substance of 2-thenoyltrifluoroacetone dysprosium described in step 3 and the volume ratio of methyl alcohol are (0.031mol ~ 0.035mol): 1L;
In the precast body prepared by solution diffusion mode described in step 3, the ratio of the amount of quadrol salicylaldehyde, cadmium acetate and 2-thenoyltrifluoroacetone dysprosium is 2:2:1;
Four, the precast body prepared by solution diffusion mode obtained in step 3 is at room temperature left standstill 7 days ~ 8 days, obtain single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.
The advantage of present embodiment:
One, rare earth ion and part are carried out coordination by the mode of solution diffusion by present embodiment, obtain the rare earth compounding of good properties after crystallization;
Two, the Dy for preparing of present embodiment
2(salen)
2(tta)
4(OAc)
2for single molecular magnets, energy barrier is higher, and the productive rate of preparation method of the present invention is high, can reach more than 57.26%, and the synthetic method of single molecular magnets is simple, and repeatability is strong.
Present embodiment can obtain a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.
Embodiment three: the difference of present embodiment and embodiment two is: the amount of substance of the quadrol salicylaldehyde described in step one and the volume ratio of methylene dichloride are 0.125mol:1L.Other are identical with embodiment two.
Embodiment four: the difference of present embodiment and embodiment two or three is: the amount of substance of the cadmium acetate described in step one and the volume ratio of methyl alcohol are 0.125mol:1L.Other are identical with embodiment two or three.
Embodiment five: the difference of present embodiment and embodiment two to four is: by the mixed solution C obtained in step one reflux 1h at temperature is 70 DEG C ~ 75 DEG C in step 2, then be cooled to room temperature, then filter, obtain solution D.Other are identical with embodiment two to four.
Embodiment six: the difference of present embodiment and embodiment two to five is: the amount of substance of 2-thenoyltrifluoroacetone dysprosium described in step 3 and the volume ratio of methyl alcohol are 0.031mol.Other are identical with embodiment two to five.
Embodiment seven: the difference of present embodiment and embodiment two to six is: in step 4, the precast body obtained in step 3 is at room temperature left standstill 7 days, obtain single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.Other are identical with embodiment two to six.
Embodiment eight: present embodiment with the difference of embodiment two to seven is: the preparation method of the quadrol salicylaldehyde described in step one is: mixed with salicylic aldehyde methanol solution by quadrol methanol solution, reflux 1h at temperature is 70 DEG C ~ 80 DEG C again, naturally cool to room temperature again, 2h is stirred again under room temperature and stirring velocity are the condition of 500r/min ~ 1000r/min, filter again, obtain yellow needles solid and be quadrol salicylaldehyde; Described quadrol methanol solution and the volume ratio of salicylic aldehyde methanol solution are 2:1; In described quadrol methanol solution, the amount of substance of quadrol and the volume ratio of methyl alcohol are 1mol:2mL; In described salicylic aldehyde methanol solution, the amount of substance of salicylic aldehyde and the volume ratio of methyl alcohol are 2mol:1mL.Other are identical with embodiment two to seven.
Embodiment nine: the difference of present embodiment and embodiment two to eight is: the 2-thenoyltrifluoroacetone dysprosium described in step 3 is prepared according to the following steps:
1., by 2-thenoyltrifluoroacetone and sodium hydroxide join in methyl alcohol, then stir 1h under room temperature and stirring velocity are the condition of 500r/min, obtain solution I;
Step 1. described in 2-thenoyltrifluoroacetone and the mol ratio of sodium hydroxide be 1:1;
Step 1. described in the amount of substance of 2-thenoyltrifluoroacetone and the volume ratio of methyl alcohol be 6mmol:10mL;
2., by Dysprosium trichloride join in solution I, then stir 24h under room temperature and stirring velocity are 500r/min, then self-heating is cooled to room temperature, obtains solution II;
Step 2. described in the amount of substance of Dysprosium trichloride and the volume ratio of solution I be 2mmol:10mL;
3., by solution II low whipping speed be stir under 500r/min, in solution II, add distilled water no longer increases to precipitation simultaneously, and stopped reaction, obtains reaction solution; Reaction solution is filtered, is precipitated material; Sedimentable matter is carried out dry 10h at temperature is 80 DEG C, obtains 2-thenoyltrifluoroacetone dysprosium.Other are identical with embodiment two to eight.
Embodiment ten: the difference of present embodiment and embodiment two to nine is: the amount of substance of 2-thenoyltrifluoroacetone dysprosium described in step 3 and the volume ratio of methyl alcohol are (0.031mol ~ 0.033mol): 1L.Other are identical with embodiment two to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2preparation method prepare according to the following steps:
One, quadrol salicylaldehyde is dissolved in methylene dichloride, obtains solution A; Cadmium acetate is dissolved in methyl alcohol, obtains solution B; Then by solution A and solution B mixing, mixed solution C is obtained;
The amount of substance of the quadrol salicylaldehyde described in step one and the volume ratio of methylene dichloride are 0.125mol:1L;
The amount of substance of the cadmium acetate described in step one and the volume ratio of methyl alcohol are 0.125mol:1L;
In mixed solution C described in step one, the mol ratio of quadrol salicylaldehyde and cadmium acetate is 1:1;
Two, by the mixed solution C obtained in step one reflux 1h at temperature is 75 DEG C, then be cooled to room temperature, then filter, obtain solution D;
Three, 2-thenoyltrifluoroacetone dysprosium is dissolved in methyl alcohol, obtains solution E; Solution E is added drop-wise in solution D with the rate of addition of 5, obtains the precast body prepared by solution diffusion mode;
The amount of substance of 2-thenoyltrifluoroacetone dysprosium described in step 3 and the volume ratio of methyl alcohol are 0.031mol:1L;
In the precast body prepared by solution diffusion mode described in step 3, the ratio of the amount of quadrol salicylaldehyde, cadmium acetate and 2-thenoyltrifluoroacetone dysprosium is 2:2:1;
Four, the precast body prepared by solution diffusion mode obtained in step 3 is at room temperature left standstill 7 days ~ 8 days, obtain single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.
The single molecular magnets Dy of test one preparation
2(salen)
2(tta)
4(OAc)
2for title complex;
Single molecular magnets Dy is prepared in test one
2(salen)
2(tta)
4(OAc)
2productive rate be 57.26%.
Single molecular magnets Dy is prepared in test one
2(salen)
2(tta)
4(OAc)
2sign as follows:
(1) the single molecular magnets Dy that RigakuRaxis-RapidX-x ray diffractometer x is prepared test one is utilized
2(salen)
2(tta)
4(OAc)
2crystalline structure measure, as shown in Figure 1, Fig. 1 be test one prepare single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2molecular structure;
(2) table 1 is single molecular magnets Dy prepared by test one
2(salen)
2(TTA)
4(OAc)
2crystalline structure refine data:
Table 1
To single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2magnetic performance research as follows:
Utilize the single molecular magnets Dy that MPMS-5 type superconducting quantum interference device (SQUID) (SQUID) is prepared test one
2(salen)
2(tta)
4(OAc)
2magnetic performance measure; Variable temperature magnetic susceptibility condition determination: field intensity is 0Oe, temperature is 0K ~ 300K, survey data and correct through the anti-magnetic of Pascl constant.
As Figure 2-Figure 5;
Fig. 2 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2dC magnetic susceptibility figure;
Fig. 3 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2ac magnetic susceptibility real part thetagram, wherein
for ac magnetic susceptibility real part temperature curve under the condition of 10Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 30Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 100Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 300Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 400Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 600Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 800Hz,
for ac magnetic susceptibility real part temperature curve under the condition of 1000Hz;
Fig. 4 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2ac magnetic susceptibility imaginary part thetagram, wherein
for ac magnetic susceptibility imaginary part temperature curve under the condition of 10Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 30Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 100Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 300Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 400Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 600Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 800Hz,
for ac magnetic susceptibility imaginary part temperature curve under the condition of 1000Hz;
Fig. 5 is single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2frequency-changing AC susceptibility imaginary part real part is mapped, wherein
for the distribution of relaxation times figure at 2K temperature,
for the distribution of relaxation times figure at 2.5K temperature,
for the distribution of relaxation times figure at 3K temperature,
for the distribution of relaxation times figure at 3.5K temperature,
for the distribution of relaxation times figure at 4K temperature,
for the distribution of relaxation times figure at 4.5K temperature,
for the distribution of relaxation times figure at 5K temperature,
for the distribution of relaxation times figure at 5.5K temperature,
for the distribution of relaxation times figure at 6K temperature,
for the distribution of relaxation times figure at 6.5K temperature,
for the distribution of relaxation times figure at 7K temperature,
for the distribution of relaxation times figure at 7.5K temperature.
The single molecular magnets Dy of test one preparation
2(salen)
2(tta)
4(OAc)
2dC magnetic susceptibility figure as shown in Figure 3, the value of this dysprosium title complex χ mT is at ambient temperature 30.93cm
3kmol
-1, slowly decline with the reduction of temperature, χ when being reduced to 70K
mt value declines rapidly, finally reaches minimum value 14.20cm when 2K
3kmol
-1.For proving that it is single molecular magnets further, it is tested, to the variable temperature magnetic susceptibility curve (Fig. 3-4) under the Plotting data different frequency obtained under field intensity is 0Oe temperature range 1.8 – 16K vibrational frequency 1 – 1000Hz.By observing the real part χ ' (Fig. 3) of ac magnetization rate curve and imaginary part χ, " (Fig. 4) can find that curve does not have overlap at different frequencies, proves the phenomenon that there is frequency dependent.Imaginary part χ " (Fig. 4) ac magnetic susceptibility; have obvious peak at more than 600Hz; its temperature range is at 6K-8K place; occur that single peak proves there is a kind of relaxation modes; a kind of relaxation modes proof central rare earth exists the generation that a kind of coordination configuration causes identical Ligand Field; our backspace structure goes the coordination configuration having a look Dy (III) ion also just in time to demonstrate this conclusion, two Dy1 (III) coordination configurations are eight-coordinate, and theoretical and experiment conclusion matches.Prove single molecular magnets Dy prepared by test one
2(salen)
2(tta)
4(OAc)
2.In conjunction with above-mentioned phenomenon, the title complex single molecular magnets Dy of test one preparation
2(salen)
2(tta)
4(OAc)
2for single molecular magnets.
Test the single molecular magnets Dy of a preparation as can be seen from Figure 2
2(salen)
2(tta)
4(OAc)
2in the temperature range of 2-100K, the product of mole DC magnetic susceptibility and temperature significantly increases along with the rising of temperature, and arrived in the scope of 100-300K, the slope of upcurve reduces gradually; When 300K, the product of mole DC magnetic susceptibility and temperature reaches maximum value 30.8cm
3mol
-1k, thus the single molecular magnets Dy demonstrating test one preparation
2(salen)
2(tta)
4(OAc)
2for antiferromagnetism rare earth compounding.
Test the single molecular magnets Dy of a preparation as can be seen from Figure 5
2(salen)
2(tta)
4(OAc)
2distribution of relaxation times figure corresponding under illustrating differing temps; As can be seen from Figure 5, curve presents the shape close to semicircle, is consistent with relaxation model, and proves that it is single molecular magnets further.
Claims (10)
1. a single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2, it is characterized in that a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2molecular formula be C
84h
56dy
2f
12n
4o
16s
4, crystallographic system is triclinic(crystalline)system, and spacer is P-1, and unit cell parameters is
α=95.80 (3) °, β=100.18 (3) °, γ=90.38 (3) °, V=1967.8 (7), Z=1.
2. a single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that a kind of single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2preparation method prepare according to the following steps:
One, quadrol salicylaldehyde is dissolved in methylene dichloride, obtains solution A; Cadmium acetate is dissolved in methyl alcohol, obtains solution B; Then by solution A and solution B mixing, mixed solution C is obtained;
The amount of substance of the quadrol salicylaldehyde described in step one and the volume ratio of methylene dichloride are (0.125mol ~ 0.13mol): 1L;
The amount of substance of the cadmium acetate described in step one and the volume ratio of methyl alcohol are (0.125mol ~ 0.13mol): 1L;
In mixed solution C described in step one, the mol ratio of quadrol salicylaldehyde and cadmium acetate is 1:1;
Two, by the mixed solution C obtained in step one reflux 1h ~ 1.5h at temperature is 70 DEG C ~ 80 DEG C, then be cooled to room temperature, then filter, obtain solution D;
Three, 2-thenoyltrifluoroacetone dysprosium is dissolved in methyl alcohol, obtains solution E; Solution E is added drop-wise in solution D with the rate of addition of 5/min ~ 10 droplet/min, obtains the precast body prepared by solution diffusion mode;
The amount of substance of 2-thenoyltrifluoroacetone dysprosium described in step 3 and the volume ratio of methyl alcohol are (0.031mol ~ 0.035mol): 1L;
In the precast body prepared by solution diffusion mode described in step 3, the ratio of the amount of quadrol salicylaldehyde, cadmium acetate and 2-thenoyltrifluoroacetone dysprosium is 2:2:1;
Four, the precast body prepared by solution diffusion mode obtained in step 3 is at room temperature left standstill 7 days ~ 8 days, obtain single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.
3. a kind of single molecular magnets Dy according to claim 2
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that the amount of substance of the quadrol salicylaldehyde described in step one and the volume ratio of methylene dichloride are 0.125mol:1L.
4. a kind of single molecular magnets Dy according to claim 2
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that the amount of substance of the cadmium acetate described in step one and the volume ratio of methyl alcohol are 0.125mol:1L.
5. a kind of single molecular magnets Dy according to claim 2
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that by the mixed solution C obtained in step one reflux 1h at temperature is 70 DEG C ~ 75 DEG C in step 2, then be cooled to room temperature, then filter, obtain solution D.
6. a kind of single molecular magnets Dy according to claim 2
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that the amount of substance of 2-thenoyltrifluoroacetone dysprosium described in step 3 and the volume ratio of methyl alcohol are 0.031mol.
7. a kind of single molecular magnets Dy according to claim 2
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that, in step 4, the precast body that obtains in step 3 is at room temperature left standstill 7 days, obtain single molecular magnets Dy
2(salen)
2(tta)
4(OAc)
2.
8. a kind of single molecular magnets Dy according to claim 2
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that the preparation method of the quadrol salicylaldehyde described in step one is: mixed with salicylic aldehyde methanol solution by quadrol methanol solution, reflux 1h at temperature is 70 DEG C ~ 80 DEG C again, naturally cool to room temperature again, 2h is stirred again under room temperature and stirring velocity are the condition of 500r/min ~ 1000r/min, filter again, obtain yellow needles solid and be quadrol salicylaldehyde; Described quadrol methanol solution and the volume ratio of salicylic aldehyde methanol solution are 2:1; In described quadrol methanol solution, the amount of substance of quadrol and the volume ratio of methyl alcohol are 1mol:2mL; In described salicylic aldehyde methanol solution, the amount of substance of salicylic aldehyde and the volume ratio of methyl alcohol are 2mol:1mL.
9. a kind of single molecular magnets Dy according to claim 2
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that the 2-thenoyltrifluoroacetone dysprosium described in step 3 is prepared according to the following steps:
1., by 2-thenoyltrifluoroacetone and sodium hydroxide join in methyl alcohol, then stir 1h under room temperature and stirring velocity are the condition of 500r/min, obtain solution I;
Step 1. described in 2-thenoyltrifluoroacetone and the mol ratio of sodium hydroxide be 1:1;
Step 1. described in the amount of substance of 2-thenoyltrifluoroacetone and the volume ratio of methyl alcohol be 6mmol:10mL;
2., by Dysprosium trichloride join in solution I, then stir 24h under room temperature and stirring velocity are 500r/min, then self-heating is cooled to room temperature, obtains solution II;
Step 2. described in the amount of substance of Dysprosium trichloride and the volume ratio of solution I be 2mmol:10mL;
3., by solution II low whipping speed be stir under 500r/min, in solution II, add distilled water no longer increases to precipitation simultaneously, and stopped reaction, obtains reaction solution; Reaction solution is filtered, is precipitated material; Sedimentable matter is carried out dry 10h at temperature is 80 DEG C, obtains 2-thenoyltrifluoroacetone dysprosium.
10. a kind of single molecular magnets Dy according to claim 2
2(salen)
2(tta)
4(OAc)
2preparation method, it is characterized in that the volume ratio of the amount of substance of the 2-thenoyltrifluoroacetone dysprosium described in step 3 and methyl alcohol is for (0.031mol ~ 0.033mol): 1L.
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| JP2019031446A (en) * | 2017-08-04 | 2019-02-28 | 日亜化学工業株式会社 | Rare earth metal complex and light-emitting device using the same |
| CN109705151A (en) * | 2019-01-28 | 2019-05-03 | 黑龙江大学 | The preparation method of Metallacrown single molecular magnets |
| CN110729090A (en) * | 2018-11-19 | 2020-01-24 | 仝佳平 | Multi-core single-molecule magnet |
| JP2022075722A (en) * | 2017-08-04 | 2022-05-18 | 日亜化学工業株式会社 | Rare earth metal complex and light-emitting device using the same |
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| CN103219148A (en) * | 2013-04-27 | 2013-07-24 | 黑龙江大学 | Preparation method of single-molecule magnetic body |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019031446A (en) * | 2017-08-04 | 2019-02-28 | 日亜化学工業株式会社 | Rare earth metal complex and light-emitting device using the same |
| JP7034624B2 (en) | 2017-08-04 | 2022-03-14 | 日亜化学工業株式会社 | Rare earth metal complex and light emitting device using it |
| JP2022075722A (en) * | 2017-08-04 | 2022-05-18 | 日亜化学工業株式会社 | Rare earth metal complex and light-emitting device using the same |
| JP7335377B2 (en) | 2017-08-04 | 2023-08-29 | 日亜化学工業株式会社 | Rare earth metal complex and light emitting device using the same |
| CN110729090A (en) * | 2018-11-19 | 2020-01-24 | 仝佳平 | Multi-core single-molecule magnet |
| CN110729090B (en) * | 2018-11-19 | 2023-08-29 | 中国人民解放军陆军勤务学院 | Polynuclear single-molecule magnet |
| CN109705151A (en) * | 2019-01-28 | 2019-05-03 | 黑龙江大学 | The preparation method of Metallacrown single molecular magnets |
| CN109705151B (en) * | 2019-01-28 | 2020-12-29 | 黑龙江大学 | Preparation method of metal crown ether monomolecular magnet |
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