CN107098921B - The dysprosium complex and its synthetic method constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand and application - Google Patents
The dysprosium complex and its synthetic method constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand and application Download PDFInfo
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- hydroxyquinoline
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 22
- 239000005725 8-Hydroxyquinoline Substances 0.000 title claims abstract description 20
- 229960003540 oxyquinoline Drugs 0.000 title claims abstract description 20
- -1 8-hydroxyquinoline acyl hydrazone derivative Chemical class 0.000 title claims abstract description 17
- 239000003446 ligand Substances 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- AYQCIXVFXMKKCA-UHFFFAOYSA-N N-[(8-hydroxyquinolin-2-yl)methylideneamino]benzamide Chemical compound N1=C2C(O)=CC=CC2=CC=C1C=NNC(=O)C1=CC=CC=C1 AYQCIXVFXMKKCA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012046 mixed solvent Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000696 magnetic material Substances 0.000 claims description 7
- 230000006698 induction Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 19
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 17
- 239000005297 pyrex Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 10
- 229920000742 Cotton Polymers 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 241000736199 Paeonia Species 0.000 description 6
- 235000006484 Paeonia officinalis Nutrition 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- SLBPIHCMXPQAIQ-UHFFFAOYSA-N 8-hydroxyquinoline-2-carbaldehyde Chemical compound C1=C(C=O)N=C2C(O)=CC=CC2=C1 SLBPIHCMXPQAIQ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000010365 information processing Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 description 1
- 229910018162 SeO2 Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005641 tunneling Effects 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of dysprosium complex constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand and its synthetic method and applications.The chemical formula of the complex is [Dy (HL) (L)] 2H2O, wherein L is that 2- Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs a hydrogen atom on hydroxyl hydrogen atom and acylhydrazone nitrogen, the negative electrical charge of two units of band;HL is that 2- Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs hydroxyl hydrogen atom, one unit negative charge of band.The synthetic method of the complex are as follows: take Dy (NO3)3·6H2O and 2- Formyl-8-hydroxyquinoline benzoyl hydrazone, is dissolved with mixed solvent, adjusts pH=7.5~8.1 of acquired solution, and gained mixed liquor reacts under heating condition, and reactant is cooling, there is crystal to be precipitated to get;Wherein, the mixed solvent is the composition of first alcohol and water.Complex of the present invention shows as the slow relaxation magnetic behavior of field induction at low temperature.
Description
Technical field
The present invention relates to a kind of dysprosium complex constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand and its synthetic methods
And application, belong to technical field of magnetic materials.
Background technique
In recent years, with the fast development of quantum calculation and information technology revolution, nano magnetic material has been subjected to more next
The more concern of polyvoltine researcher.Derived from single molecular magnets in high density information processing and storage, quantum computer, molecular spin
The potential application of electronics etc., the design and synthesis of single molecular magnets have become physics, chemistry, material in the latest 20 years
The primary study object in the fields such as science.The wherein rare-earth base single molecular magnets single electron number relatively more because rare earth ion has and aobvious
The magnetic anisotropy of work becomes the research hotspot in current single molecular magnets field.By development in more than 20 years, single molecular magnets
Research also make great progress.But the research in relation to rare earth single molecular magnets still suffers from many challenges: how gram
Rare earth ion quantum tunneling effect due to caused by magnetization is taken, effective energy barrier of rare earth single molecular magnets how is improved, illustrates
The relaxation mechanism etc. of rare earth single molecular magnets.The energy barrier of rare earth single molecular magnets not only with the ground state spin values of metal ion itself
It is closely related with magnetic anisotropy and closely related with the symmetry of the entirety of molecule and part.
Single molecular magnets are because high density information processing is with storage, quantum calculation, molecular spin in terms of
Potential application becomes the research hotspot in the fields such as chemistry, physics, material science.Research finds the change by organic ligand structure
Change or the variation of substituent group can play the purpose for effectively regulating and controlling single molecular magnets property.Although relevant research has taken
Very big progress is obtained, but there is presently no unified explanation, single molecular magnets knots for the magnetic action mechanism of single molecular magnets
Relationship between structure and magnetism is still the mainstream of single molecular magnets research field at this stage.With the rapid development of information technology,
Scientists have researched and proposed higher requirement to nano magnetic material and its various performance parameters, it is more and more have it is real
It is synthesized with the magnetic material of value, but has not yet to see point constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand
Minor is C34H27DyN6O6Dysprosium complex relevant report.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of structure novel with 8-hydroxyquinoline acyl hydrazone derivative be with
The dysprosium complex and its synthetic method and application that body is constructed.
The dysprosium complex of the present invention constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand, the chemistry of the complex
Formula are as follows: [Dy (HL) (L)] 2H2O, wherein L is that 2- Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs hydroxyl hydrogen atom and acylhydrazone
A hydrogen atom on nitrogen, the negative electrical charge of two units of band;HL is that 2- Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs hydroxyl hydrogen
Atom, one unit negative charge of band.
The complex belongs to anorthic system, P-1 space group, cell parameter are as follows: α=83.966 (8) °, β=88.751 (9) °, γ=82.244 (9) °.
The Formyl-8-hydroxyquinoline of 2- involved in above-mentioned technical proposal-benzoyl hydrazone can refer to existing literature (Liu
Yong-chun, Yang Zheng-yin, Eur.J.Med.Chem., 2009,44 (12), 5080-5089) it is synthesized, it ties
Structure formula is shown below:
The molecular formula of the dysprosium complex of the present invention constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand is
C34H27DyN6O6, molecular weight 778.13.
The crystal structural data of the dysprosium complex of the present invention constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand
As described in Table 1, part bond distance bond angle data are as described in Table 2.
Table 1:[Dy (HL) (L)] 2H2The crystallographic parameter of O
aR1=Σ | | Fo|–|Fc||/Σ|Fo|.bwR2=[Σ w (| Fo 2|–|Fc 2|)2/Σw(|Fo 2|)2]1/2
Table 2:[Dy (HL) (L)] 2H2The part bond distance of OBond angle (°) table
Applicants have found that the dysprosium complex of the present invention constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand
Magnetic property show as slow relaxation magnetic behavior.Therefore, the invention also includes it is above-mentioned with 8-hydroxyquinoline acyl hydrazone derivative be with
The dysprosium complex that body is constructed is preparing the application in magnetic material.
The synthetic method of the above-mentioned dysprosium complex constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand are as follows: take Dy
(NO3)3·6H2O and 2- Formyl-8-hydroxyquinoline-benzoyl hydrazone, is dissolved with mixed solvent, adjusts the pH=of acquired solution
7.5~8.1, gained mixed liquor reacts under heating condition, and reactant is cooling, has crystal to be precipitated to get target product;Wherein,
The mixed solvent is the composition of first alcohol and water.
In above-mentioned synthetic method, the Dy (NO3)3·6H2The molar ratio of O and 2- Formyl-8-hydroxyquinoline benzoyl hydrazone
Usually 1~3:1, preferably 1:1.
In above-mentioned synthetic method, the in the mixed solvent, the volume ratio of first alcohol and water can be any proportion, preferably
1~3:1~3 are preferably selected as 1:1,1:2 or 1:3.The dosage of the mixed solvent can determine as needed, usually with energy
The raw material that reaction is participated in dissolution is advisable.Specifically, it is counted on the basis of the 2- of 0.1mmol Formyl-8-hydroxyquinoline-benzoyl hydrazone
It calculates, total dosage of mixed solvent used in whole raw materials is generally 2~3mL.It, can be by Dy (NO in specific the step of dissolving3)3·
6H2O and 2- Formyl-8-hydroxyquinoline-benzoyl hydrazone uses one of mixed solvent ingredient to dissolve respectively, remixes together
Reaction, can also be by Dy (NO3)3·6H2Add mixed solvent dissolution again after O and 2- Formyl-8-hydroxyquinoline-benzoyl hydrazone mixing.
In above-mentioned synthetic method, the pH value of solution can be adjusted using existing common alkaline matter, is preferably used
The pH value of triethylamine adjusting solution.In technical solution of the present invention, pH=7.7~7.9 of solution are preferably adjusted.
In above-mentioned synthetic method, resulting mixed liquor is placed in container after will usually adjusting pH value, after liquid nitrogen frozen
It is evacuated to vacuum, is sealed, is placed under heating condition reacts again later.The reaction preferably carries out under the conditions of 60~120 DEG C,
The time reacted under the conditions of above-mentioned temperature is usually 30~80h, can also be greater than 80h;It will preferably control in the reaction time
In 60~80h.Reaction more preferably carries out under the conditions of 80~100 DEG C.Generally use heavy wall horminess glass tube closed at one end
To contain resulting mixed liquor after adjusting pH value.
Compared with prior art, the present invention provides a kind of structure novels using 8-hydroxyquinoline acyl hydrazone derivative as ligand
The dysprosium complex and its synthetic method constructed, synthetic method are simple, low in cost, reproducible;Applicant also sends out under study for action
Slow relaxation magnetic behavior now is shown as under the complex low temperature, can be used for preparing magnetic material.
Detailed description of the invention
Fig. 1 is ligand 2- Formyl-8-hydroxyquinoline-benzoyl hydrazone infrared spectroscopy that various embodiments of the present invention use
Figure;
Fig. 2 is the infrared spectrogram of final product made from the embodiment of the present invention 1;
Fig. 3 is the structure chart of final product made from the embodiment of the present invention 1;
Fig. 4 is the χ of final product made from the embodiment of the present invention 1m-T,χmT-T curve graph;
Fig. 5 is the M-H curve graph of final product made from the embodiment of the present invention 1;
Fig. 6 is the exchange curve graph of final product made from the embodiment of the present invention 1;
Fig. 7 is the thermal multigraph of final product made from the embodiment of the present invention 1.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, content to better understand the invention, but
The present invention is not limited to following embodiments.
The Formyl-8-hydroxyquinoline of 2- involved in following embodiment-benzoyl hydrazone is synthesized using following methods, is closed
It is as follows at route:
1) 2- aldehyde radical -8-hydroxyquinoline synthesis: 2- methyl -8-hydroxyquinoline (50mmol, 8g) is weighed, pours into and is equipped with
In the round-bottomed flask of the mixed solution of 150mL Isosorbide-5-Nitrae-dioxane and 6mL water composition, being placed in 70 DEG C of oil baths keeps it completely molten
Solution, by pre-prepared dissolved with SeO2The mixed solution of 4mL water and the 100mL Isosorbide-5-Nitrae-dioxane of (63mmol, 7g) is slow
Ground is added dropwise in above-mentioned mixed solution, after temperature is increased to 100 DEG C, is continued heated at constant temperature reflux 3h, is stopped reaction, be cooled to
After room temperature, decompression filters abstraction solvent, then is repeatedly extracted for (minimum 3 times) with ethyl acetate, finally extract liquor is spin-dried for obtaining red
Hexamethylene is added into Red oil substance, gently vibrates for color oily mater, can generate flaxen flocculent substance at this time, molten
Liquid also becomes light yellow, and flaxen flocculent substance, which is put into togerther freezing in refrigerator together with light yellow clear liquid, keeps it slowly cold
But it crystallizes, places it in room temperature thaw again later, 2- aldehyde radical -8-hydroxyquinoline can be obtained after filtration drying, yield is about
52%.
2) 1.360g (10mmol) methyl benzoate and 50mL ethyl alcohol the synthesis of benzoyl hydrazine: are added to round-bottomed flask
In, the ethanol solution 10mL for containing 1.000g (20mmol) hydrazine hydrate is added dropwise in the side Bian Jiare, rises to 80 DEG C of continuation constant temperature to temperature
Stop reaction after being heated to reflux 6h, be cooled to room temperature, decompression abstraction partial solvent is put into refrigerator freezing, makes it that crystalline substance slowly be precipitated
Body is filtered, washed and dried, and obtains benzoyl hydrazine, and yield is about 85%.
3) 2- Formyl-8-hydroxyquinoline-benzoyl hydrazone (L) synthesis:
Benzoyl hydrazine (2mmol, 0.2723g) and 2- aldehyde radical -8-hydroxyquinoline (2mmol, 0.34g) are dissolved in 30mL respectively
In the ethyl alcohol of 70mL, 6 drop glacial acetic acid are added into the round-bottomed flask equipped with benzoyl hydrazine, heating is increased to 80 DEG C to temperature
When, aldehyde radical containing 2- -8-hydroxyquinoline ethanol solution is slowly added dropwise, continues heating reflux reaction 6h, stops reaction, is cooled to room
Temperature after decompression extracts solvent, is successively washed several times with ethyl alcohol, ether, dry, obtains target product L, yield is about 60%.Member
Element analysis (%) (C17H13N3O2), experiment value: C, 70.88, H, 4.46, N, 14.41;Theoretical value: C, 70.9, H, 4.50, N,
14.42.Infrared spectroscopy is as shown in Figure 1, data are as follows: IR (KBr, cm-1): 3450 (w), 1564 (s), 1483 (m), 1358 (m),
1105 (s), 1063 (w), 840 (w), 715 (w).
Embodiment 1
Take ligand 2- Formyl-8-hydroxyquinoline benzoyl hydrazone (0.025mmol, 7.3mg) and Dy (NO3)3·6H2O
(0.025mmol, 11.4mg) is added in the Pyrex pipe for being about 18cm closed at one end, and 0.6mL CH is added3OH and 0.6mL
H2O is added dropwise triethylamine 2 and drips, and gently oscillation shakes up (pH=7.8 of solution at this time), by the pipe other end under conditions of vacuumizing
Sealing is taken out, Pyrex pipe is tightly wrapped up with cotton-wool makes it be slowly dropped to room later as insulation reaction 72h under the conditions of 80 DEG C
Peony web crystal is precipitated in temperature, and yield is about 25% (being calculated with Dy).Elemental analysis (%) (C34H27DyN6O6), experiment value:
C, 52.42, H, 3.62, N, 10.81;Theoretical value: C, 52.48, H, 3.50, N, 10.80.
1 products therefrom of embodiment is characterized:
1) IR Characterization:
With U.S. Nicolet 360FT-IR type Fourier transformation infrared spectrometer (KBr tabletting), the present embodiment is made
Product carry out infrared analysis, take the photograph 4000~400cm of spectral limit-1, gained infrared spectrum spectrogram is as shown in Fig. 2, data are as follows:
IR(KBr,cm-1): 3650 (w), 1557 (s), 1482 (m), 1353 (m), 1104 (s), 1061 (s), 837 (w),
713 (s), 494 (w).
2) crystal structure analysis:
The intact peony web crystal of surface texture is measured by agilent company SuperNova single crystal diffractometer
To determine its mono-crystalline structures, resulting structures data are shown in aforementioned table 1, and bond distance's bond angle data are shown in that aforementioned table 2, the dark red color strip-shaped of gained are brilliant
The chemical structure of body is as shown in figure 3, determine that resulting peony web crystal is of the present invention with 8-hydroxyquinoline acylhydrazone
Derivative is dysprosium complex [Dy (HL) (L)] 2H that ligand is constructed2O, wherein L is 2- Formyl-8-hydroxyquinoline benzoyl
Hydrazone sloughs a hydrogen atom on hydroxyl hydrogen atom and acylhydrazone nitrogen, the negative electrical charge of two units of band;HL is 2- formoxyl -8- hydroxyl
Quinoline benzoyl hydrazone sloughs hydroxyl hydrogen atom, one unit negative charge of band.The molecular formula of the complex is C34H27DyN6O6, molecule
Amount is 778.13.
3) magnetic property measures:
Take dysprosium complex made from 31.6mg the present embodiment [Dy (HL) (L)] 2H2O pulverize after on Magnetic Test instrument
Magnetic Test is carried out, the χ of complex is obtainedM-T,χMT-T curve graph as shown in figure 4, M-H curve graph as shown in figure 5, complex magnetic
The real and imaginary parts of rate exchange are as shown in Figure 6 to the curve graph of temperature.
By Fig. 4 and Fig. 5 it is found that dysprosium complex of the present invention [Dy (HL) (L)] 2H2O is the area 2-300K in temperature
In, under the conditions of direct current external magnetic field is 1000Oe, in 300K, χMThe value of T is maximum, is 13.98cm3K mol-1, one only certainly
Dy (III) ion of rotation, theoretical value 14.17cm3K mol-1, (6H15/2, S=5/2, L=5, g=4/3, C=14.17cm3K
mol-1), the experiment value and theoretical value of dysprosium complex of the present invention coincide substantially.With the reduction of temperature, χMThe value of T is gradually
It reduces, later χMT value declines rapidly suddenly, when temperature reaches 2K, χMThe value of T is minimized, and is 10.52cm3K mol-1。
It will be appreciated from fig. 6 that the real and imaginary parts of exchange have apparent frequency dependent behavior, it was demonstrated that this hair in low temperature part
Bright described dysprosium complex [Dy (HL) (the L)] 2H constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand2O table at low temperature
It is now slow relaxation magnetic behavior.
4) thermogravimetric characterizes:
With French C1-esteraseremmer-N La Mu Instrument Ltd. Labsys evo TG-DSC/DTA, dysprosium made from the present embodiment is matched
Close object [Dy (HL) (L)] 2H2O carries out thermogravimetric analysis.By thermogravimetric analysis it is found that from room temperature to 102 DEG C, weightlessness 4.65% is right
Answer two object hydrones (theoretical value 4.63%).Main body frame starts gradually to disintegrate when 425 DEG C, rises to temperature
At 1000 DEG C, the 71.6% of gross mass is lost.Residue 24.5%, residue may be the oxide Dy of dysprosium2O3(theoretical value is
23.9%).Gained thermogravimetric analysis spectrogram is as shown in Figure 7.
Comparative example 1
Embodiment 1 is repeated, unlike: mixed solvent is changed to be made of second alcohol and water, the volume ratio of second alcohol and water
Total dosage for 1:1, mixed solvent is constant.
Pyrex pipe is taken out, Pyrex pipe is tightly wrapped up with cotton-wool makes it be slowly dropped to room temperature, no solid product or crystal analysis
Out, it is still precipitated without solid product or crystal after standing 10 days, i.e., no target product generates.
Comparative example 2
Embodiment 1 is repeated, unlike: mixed solvent is changed to be made of acetonitrile and water, the volume ratio of acetonitrile and water
Total dosage for 1:1, mixed solvent is constant.
Pyrex pipe is taken out, Pyrex pipe is tightly wrapped up with cotton-wool makes it be slowly dropped to room temperature, no solid product or crystal analysis
Out, it is still precipitated without solid product or crystal after standing 10 days, i.e., no target product generates.
Comparative example 3
Embodiment 1 is repeated, unlike: mixed solvent is changed to be made of chloroform and water, chloroform and water
Volume ratio be 1:3, total dosage of mixed solvent is constant.
Pyrex pipe is taken out, Pyrex pipe is tightly wrapped up with cotton-wool makes it be slowly dropped to room temperature, no solid product or crystal analysis
Out, it is still precipitated without solid product or crystal after standing 10 days, i.e., no target product generates.
Embodiment 2
Embodiment 1 is repeated, unlike:
It 1) is 2:1 by the ratio of in the mixed solvent first alcohol and water, total dosage of mixed solvent is constant;
3) pH value of solution is adjusted to 7.9.
Pyrex pipe is taken out, Pyrex pipe is tightly wrapped up with cotton-wool makes it be slowly dropped to room temperature, and Pyrex bottom of the tube has peony
Web crystal is precipitated.Yield 27%.
Structural characterization is carried out to products therefrom, determines that product is target product [Dy (HL) (L)] 2H2O, wherein L is 2-
Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs a hydrogen atom on hydroxyl hydrogen atom and acylhydrazone nitrogen, and two units of band are born
Charge, HL are that 2- Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs hydroxyl hydrogen atom, one unit negative charge of band.Gained is produced
Products therefrom known to the Magnetic Characterization of object shows as the slow relaxation magnetic behavior of field induction at low temperature.
Embodiment 3
Embodiment 1 is repeated, unlike:
It 1) is 1:3 by the ratio of in the mixed solvent first alcohol and water, total dosage of mixed solvent is constant;
2) pH value of solution is adjusted to 8.0;
3) reaction temperature is changed to 60 DEG C, the reaction time is changed to 80h.
Pyrex pipe is taken out, Pyrex pipe is tightly wrapped up with cotton-wool makes it be slowly dropped to room temperature, and Pyrex bottom of the tube has peony
Web crystal is precipitated.Yield 26%.
Structural characterization is carried out to products therefrom, determines that product is target product [Dy (HL) (L)] 2H2O, wherein L is 2-
Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs a hydrogen atom on hydroxyl hydrogen atom and acylhydrazone nitrogen, and two units of band are born
Charge, HL are that 2- Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs hydroxyl hydrogen atom, one unit negative charge of band.Gained is produced
Products therefrom known to the Magnetic Characterization of object shows as the slow relaxation magnetic behavior of field induction at low temperature.
Embodiment 4
Embodiment 1 is repeated, is different from:
1) pH value of solution is adjusted to 8.1;
2) reaction temperature is changed to 120 DEG C, the reaction time is changed to 30h.
Pyrex pipe is taken out, Pyrex pipe is tightly wrapped up with cotton-wool makes it be slowly dropped to room temperature, and Pyrex bottom of the tube has peony
Web crystal is precipitated.Yield 23%.
Structural characterization is carried out to products therefrom, determines that product is target product [Dy (HL) (L)] 2H2O, wherein L is 2-
Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs a hydrogen atom on hydroxyl hydrogen atom and acylhydrazone nitrogen, and two units of band are born
Charge, HL are that 2- Formyl-8-hydroxyquinoline benzoyl hydrazone sloughs hydroxyl hydrogen atom, one unit negative charge of band.Gained is produced
Products therefrom known to the Magnetic Characterization of object shows as the slow relaxation magnetic behavior of field induction at low temperature.
Claims (7)
1. the dysprosium complex constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand, it is characterised in that:
The chemical formula of the complex are as follows: [Dy (HL) (L)] 2H2O, wherein L is de- for 2- Formyl-8-hydroxyquinoline benzoyl hydrazone
Remove a hydrogen atom on hydroxyl hydrogen atom and acylhydrazone nitrogen, the negative electrical charge of two units of band;HL is 2- Formyl-8-hydroxyquinoline
Benzoyl hydrazone sloughs hydroxyl hydrogen atom, one unit negative charge of band;
The complex belongs to anorthic system, P-1 space group, cell parameter are as follows: α=83.966 (8) °, β=88.751 (9) °, γ=82.244
(9)°。
2. the synthetic method of dysprosium complex described in claim 1, it is characterised in that: take Dy (NO3)3·6H2O and 2- formoxyl -8-
Oxyquinoline-benzoyl hydrazone, is dissolved with mixed solvent, adjusts pH=7.5~8.1 of acquired solution, gained mixed liquor is in heating
Under the conditions of react, reactant is cooling, has crystal to be precipitated to get target product;Wherein, the mixed solvent is first alcohol and water
Composition.
3. synthetic method according to claim 2, it is characterised in that: the in the mixed solvent, the volume of first alcohol and water
Than for 1~3:1~3.
4. synthetic method according to claim 2, it is characterised in that: reaction carries out under the conditions of 60~120 DEG C.
5. synthetic method according to claim 2, it is characterised in that: the time of reaction is 30~80h or is greater than 80h.
6. synthetic method according to claim 2, it is characterised in that: adjust the pH value of solution with triethylamine.
7. the dysprosium complex described in claim 1 constructed using 8-hydroxyquinoline acyl hydrazone derivative as ligand is preparing magnetic material
In application.
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CN108069992B (en) * | 2018-01-19 | 2019-10-01 | 广西师范大学 | A kind of Trinuclear dysprosium cluster compound and its synthetic method and application |
CN108191895B (en) * | 2018-01-19 | 2019-10-11 | 广西师范大学 | Based on four core dysprosium cluster compounds of 2- aldehyde radical -8-hydroxyquinoline contracting trihydroxy aminomethane schiff bases and its synthetic method and application |
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CN108840880B (en) * | 2018-05-29 | 2019-10-01 | 广西师范大学 | 2- aldehyde radical -8-hydroxyquinoline contracting four core dysprosium cluster compound of -1,3 diamino -2- propyl alcohol schiff bases and its synthetic method |
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