CN108840880A - 2- aldehyde radical -8-hydroxyquinoline contracting four core dysprosium cluster compound of -1,3 diamino -2- propyl alcohol schiff bases and its synthetic method - Google Patents
2- aldehyde radical -8-hydroxyquinoline contracting four core dysprosium cluster compound of -1,3 diamino -2- propyl alcohol schiff bases and its synthetic method Download PDFInfo
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- CN108840880A CN108840880A CN201810534060.XA CN201810534060A CN108840880A CN 108840880 A CN108840880 A CN 108840880A CN 201810534060 A CN201810534060 A CN 201810534060A CN 108840880 A CN108840880 A CN 108840880A
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- cluster compound
- diamino
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- aldehyde radical
- hydroxyquinoline
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 239000005725 8-Hydroxyquinoline Substances 0.000 title claims abstract description 26
- 229960003540 oxyquinoline Drugs 0.000 title claims abstract description 26
- -1 diamino -2- propyl Chemical group 0.000 title claims abstract description 25
- 239000002262 Schiff base Substances 0.000 title claims abstract description 21
- 238000010189 synthetic method Methods 0.000 title claims abstract description 20
- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 19
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 19
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 title claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000019441 ethanol Nutrition 0.000 claims abstract description 20
- 239000012046 mixed solvent Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 239000000696 magnetic material Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 8
- 230000006698 induction Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 35
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 229910002651 NO3 Inorganic materials 0.000 description 17
- 230000005291 magnetic effect Effects 0.000 description 17
- 229960004756 ethanol Drugs 0.000 description 14
- 239000003446 ligand Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000005641 tunneling Effects 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 4
- 238000002050 diffraction method Methods 0.000 description 4
- 230000005283 ground state Effects 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000012675 alcoholic extract Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 150000000914 Dysprosium Chemical class 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- CGUXYKPTTSTGQV-UHFFFAOYSA-N acetic acid;dysprosium Chemical compound [Dy].CC(O)=O CGUXYKPTTSTGQV-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
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 2- aldehyde radical -8-hydroxyquinoline contracting four core dysprosium cluster compound of -1,3 diamino -2- propyl alcohol schiff bases and its synthetic methods.The cluster compound belongs to monoclinic system, P21/ n space group, chemical formula are：[Dy4(C23H17N4O3)2(μ3‑OH)2(NO3)4(H2O)2].The synthetic method of the cluster compound is：Take 2- aldehyde radical -8-hydroxyquinoline, 1,3- diamino -2- propyl alcohol and Dy (NO3)3·6H2O is dissolved in the mixed solvent, adjusts pH=9.4~10.0 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 ethyl alcohol and acetonitrile.Cluster compound of the present invention has the single molecular magnets behavior of field induction, can be used for preparing magnetic material；And its synthetic method is simple to operation.
Description
Technical field
The present invention relates to a kind of 2- aldehyde radical -8-hydroxyquinoline contracting four core dysprosium cluster compounds of -1,3 diamino -2- propyl alcohol schiff bases
And its synthetic method, belong to technical field of magnetic materials.
Background technique
The features such as rare earth compounding is due to its structure and rare earth ion itself unique property, have excellent light, electricity,
Magnetic property has broad application prospects in fields such as magnetic material, optical sensor, molecular recognitions.It is dilute compared with transition metal
Native ion is often used in since itself has big anisotropy and constructs single molecular magnets, complex often has excellent
Good magnetic property, in view of the excellent magnetic performance of its complex, scientific research personnel, which has reported to have synthesized at present, much has unimolecule
The rare earth compounding of magnet behavior, from monokaryon to high core.High core complex often has complicated and beautiful structure, influences height
The factor of core complex magnetism is too many, is not easy to Modeling Calculation.And low core complex is since its structure is simple, convenient for passing through magnetism
Relevant calculation study its magnetic behavior, by the extensive concern of scientific research personnel, especially rare earth binuclear complex.But at present still
There are no with 2- aldehyde radical -8-hydroxyquinoline and 1,3- diamino -2- propyl alcohol after the spontaneous assembling of reaction in-situ forms ligand again with
Dy(NO3)3·6H2O reacts to obtain 2- aldehyde radical -8-hydroxyquinoline contracting four core dysprosium cluster compound of -1,3 diamino -2- propyl alcohol schiff bases
Relevant report.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of 2- of structure novel aldehyde radical -8-hydroxyquinoline -1,3 diaminos of contracting
Four core dysprosium cluster compound of base -2- propyl alcohol schiff bases and its synthetic method.
2- aldehyde radical of the present invention -8-hydroxyquinoline contracting four core dysprosium cluster compound of -1,3 diamino -2- propyl alcohol schiff bases,
Chemical formula is：[Dy4(C23H17N4O3)2(μ3-OH)2(NO3)4(H2O)2]；The cluster compound belongs to monoclinic system, P21/ n space group,
Cell parameter is： α=90.00 °, β=
106.186 (2) °, γ=90.00 °.
Less stable, water-soluble, methanol, DMF, DMSO equal solvent do not dissolve in above-mentioned double-core dysprosium cluster compound in air
Methylene chloride, chloroform, ether, hexamethylene equal solvent.
The present invention also provides above-mentioned 2- aldehyde radical -8-hydroxyquinoline contracting four core dysprosium clusters of -1,3 diamino -2- propyl alcohol schiff bases to close
The synthetic method of object, specially：Take 2- aldehyde radical -8-hydroxyquinoline, 1,3- diamino -2- propyl alcohol and Dy (NO3)3·6H2O dissolution
In in the mixed solvent, pH=9.4~10.0 of acquired solution are adjusted, gained mixed liquor reacts under heating condition, and reactant is cold
But, crystal is precipitated to get target product；Wherein, the mixed solvent is the composition of ethyl alcohol and acetonitrile.
The aldehyde radical of 2- involved in synthetic method of the present invention -8-hydroxyquinoline with reference to existing literature (M.Hassani,
W.Cai,D.C.Holley,J.P.Lineswala,B.R.Maharjan,G.R.Ebrahimian,H.Seradj,
M.G.Stocksdale,F.Mohammadi,C.C.Marvin,J.M.Gerdes,H.D.Beall,M.Behforouz,
J.Med.Chem.48 (2005) 7733.) it is synthesized.
In above-mentioned synthetic method, the 2- aldehyde radical -8-hydroxyquinoline, 1,3-diamino-2-propanol and Dy (NO3)3·6H2O
Molar ratio be stoichiometric ratio, in the actual operation process, Dy (NO3)3·6H2The dosage of O can be relatively excessive, specifically
, 2- aldehyde radical -8-hydroxyquinoline, 1,3-diamino-2-propanol and Dy (NO3)3·6H2The molar ratio of O can be 5：1：1~5.
In above-mentioned synthetic method, the volume ratio of the in the mixed solvent, ethyl alcohol and acetonitrile is preferably 1：2~5, more preferably
It is 1：3~4, most preferably 1：3.The dosage of the mixed solvent can determine as needed, usually participate in reaction can dissolve
Raw material is advisable.Specifically, calculated on the basis of the 2- of 1mmol aldehyde radical -8-hydroxyquinoline, mixed solvent used in whole raw materials it is total
Dosage is generally 4~6mL.In the specific dissolution the step of, can by 2- aldehyde radical -8-hydroxyquinoline, 1,3-diamino-2-propanol and
Dy(NO3)3·6H2O uses one of mixed solvent ingredient to dissolve respectively, remixes and reacts together, can also be by 2- aldehyde radical -8-
Oxyquinoline, 1,3- diamino -2- propyl alcohol and Dy (NO3)3·6H2Add mixed solvent dissolution after O mixing again；Preferably by 2- aldehyde
Base -8-hydroxyquinoline and 1,3-diamino-2-propanol are first dissolved in the mixed solvent, and Dy is then added into acquired solution again
(NO3)3·6H2O reacts in a heated condition later.
In above-mentioned synthetic method, existing common alkaline matter (such as ammonium hydroxide, sodium bicarbonate, triethylamine, carbonic acid can be used
Sodium, potassium carbonate etc.) adjust the pH value of solution, the pH value of solution is preferably adjusted using triethylamine.It is excellent in above-mentioned synthetic method
It recruits and saves pH=9.5~9.7 of solution, more preferably adjust the pH=9.6 of solution.
In above-mentioned synthetic method, reaction is preferably carried out under the conditions of 50~120 DEG C, is carried out under the conditions of above-mentioned temperature anti-
The time answered is usually 12~72h, can also be in 72h or more.It will preferably control in 24~48h in the reaction time.It reacts into one
Step preferably carries out under the conditions of 60~100 DEG C.
Applicant is to 2- aldehyde radical of the present invention -8-hydroxyquinoline contracting four core dysprosium of -1,3 diamino -2- propyl alcohol schiff bases
The magnetism of cluster compound is the study found that the magnetic property of the cluster compound shows as the single molecular magnets behavior of field induction.Therefore, this hair
Bright further includes that above-mentioned four core dysprosium cluster compound is preparing the application in magnetic material.
Compared with prior art, the method have the characteristics that：
1, a kind of 2- aldehyde radical -8-hydroxyquinoline contracting four core of -1,3 diamino -2- propyl alcohol schiff bases of structure novel is provided
Dysprosium cluster compound and its synthetic method can be used for making it is found by the applicant that the cluster compound has the single molecular magnets behavior of field induction
Standby magnetic material；
2, cluster compound of the present invention is obtained using reaction in-situ and solvent structure, and synthetic method is simple to operation.
Detailed description of the invention
Fig. 1 is the chemical structural drawing of final product made from the embodiment of the present invention 1；
Fig. 2 is the powder diagram of final product made from the embodiment of the present invention 1；
Fig. 3 is χ of the final product under 1000Oe DC fields made from the embodiment of the present invention 1mT-T curve graph；
Fig. 4 is the M-H curve graph of final product at different temperatures made from the embodiment of the present invention 1；
Fig. 5 is hysteresis loop of final product at a temperature of 2K made from the embodiment of the present invention 1；
Fig. 6 is ac magnetic susceptibility of the final product outside zero direct current off field made from the embodiment of the present invention 1 to temperature curve
Figure；
Fig. 7 is Cole-Cole figure of the final product made from the embodiment of the present invention 1 under 0Oe DC fields..
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.
Embodiment 1
1) it weighs 2- aldehyde radical -8-hydroxyquinoline 0.173g (1mmol) to be dissolved in 5mL anhydrous acetonitrile, 0.0456g
(0.05mmol) 1,3-diamino-2-propanol is dissolved in 5mL ethyl alcohol, after being completely dissolved, by 2- aldehyde radical -8-hydroxyquinoline
Acetonitrile solution is slowly added into the ethanol solution of 1,3-diamino-2-propanol, is uniformly mixed, is obtained mixed liquor, spare；
2) metal salt Dy (NO is weighed3)3·6H2Volume is added in O (0.1mmol, 45.6mg),
1mL above-mentioned aldehyde amine mixed liquor is drawn with liquid-transfering gun to be added in vial, then the ethyl alcohol and 2.5mL of 0.5mL are added thereto
Acetonitrile, so that the volume ratio of ethyl alcohol and acetonitrile is 1 in vial：3 (respectively 1mL and 3mL), are then added 15 μ L thereto again
Triethylamine shakes up (pH=9.6 of solution at this time)；Then vial bottleneck is sealed with aluminium-foil paper, covers bottle cap, vial is set
It reacts for 24 hours, takes out under the conditions of 60 DEG C in baking oven, be placed in bubble chamber with cotton-wool package and be down to room temperature, obtain red strip
Shape crystal.Yield is about 23.6% (being calculated with the amount of Dy).Elemental analysis (%) (C46H40Dy4N12O22), theoretical value：C,
31.34, H, 2.28, N, 9.53；Experiment value：C, 31.40, H, 2.45, N, 9.68.
The present embodiment products therefrom is characterized：
1) IR Characterization：
With the Spectrum Two FT-IR Spectrometer Fourier Transform Infrared Spectroscopy of Perkin-Klmer company
Instrument (KBr tabletting) carries out infrared analysis to product made from the present embodiment, and gained ir data is as follows：
IR (KBr, cm-1)：3698 (m), 2927 (s), 1507 (s), 1456 (s), 1383 (s), 1103 (m), 761 (m),
515(w)。
2) crystallographic structural analysis
The red strip crystal for choosing moderate dimensions is placed on agilent company SuperNova single crystal diffractometer, is used
Graphite monochromatised Mo-Kα Ray carries out monocrystalline test.The primary crystalline knot of the present embodiment products therefrom
Structure is all made of SHELXS-97 direct method and solves, and geometry adds hydrogen, and non-hydrogen atom coordinate and anisotropy thermal parameter use SHELXL-
97 through complete matrix least square method refine.Gained crystallography and structure refinement data are as described in Table 1, part bond distance's bond angle
Data are respectively as shown in following table 2 and table 3, and the chemical structure of gained red strip crystal is as shown in Figure 1, determination is resulting red
Color strip crystal is 2- aldehyde radical of the present invention -8-hydroxyquinoline contracting four core dysprosium cluster of -1,3 diamino -2- propyl alcohol schiff bases
Close object [Dy4(C23H17N4O3)2(μ3-OH)2(NO3)4(H2O)2]。
As shown in Figure 1, cluster compound is the four core symmetrical structures using double-core dysprosium as separate building blocks, be by two ligands,
Four DyIIIIon, two hydrones and four NO3 -What ion collectively constituted.Adjacent DyIIIPass through μ between ion3- OH oxygen is former
Son is connected with the alcoholic extract hydroxyl group O atom on schiff base ligand, three on ligand hydroxyl whole deprotonation, each schiff base ligand
In-trivalent, entire complex is in charge balance state.The coordination environment of Dy1 with Dy2 ion in cluster compound is different, Dy1 from
Son is the triangular lattices configuration of nine coordinations, and Dy2 ion is the trigondodecahedron configuration of eight-coordinate.Dy1 ion is by an alcohol
Hydroxyl O atom, a μ3- OH oxygen atom, two N atoms in a schiff base ligand, a phenolic hydroxyl group O atom and adjacent seat
A phenolic hydroxyl group O atom on husband's aar ligand, a NO3 -Two O atoms and a hydrone on ion participate in coordination,
The middle atom for participating in coordination has O1, O2, O4, O4a, O5, O6, O8, N1 and N2.Dy2 ion is by a μ3- OH oxygen atom, one
A alcoholic extract hydroxyl group O atom, two N atoms in a schiff base ligand, on a phenolic hydroxyl group O atom and adjacent schiff base ligand
One phenolic hydroxyl group O atom, a NO3 -Two O atoms on ion participate in coordination, wherein participating in the atom of coordination has O1a, O2,
O3, O4, O9, O11, N3 and N4.Four center DyIIIIon and the oxygen atom of bridging constitute the double cubanes of two coplanar defects
Configuration.Using Dy1, Dy2 as representative, bond distance is respectively：Dy1-O1：2.402 Dy1-O2：2.285 Dy1-O4：2.393 Dy1-
O41：2.383 Dy1-O5：2.461 Dy1-O6：2.531 Dy1-O8：2.642 Dy1-N1：2.446 Dy1-N2：2.518
Dy2-O11：2.309 Dy2-O2：2.279 Dy2-O3：2.340 Dy2-O4：2.340 Dy2-O9：2.474 Dy2-O11：
2.450 Dy2-N3：2.496 Dy2-N4：2.458.Bond distance between Dy atom and coordination atom N, O is all in normal Dy-N
Within the scope of key and Dy-O key bond distance
The ligands mode of cluster compound is analyzed it is found that 2- aldehyde radical -8-hydroxyquinoline contracting 1,3- diamino -2- third
7 coordination atoms (N1, N2, N3, N4, O1, O2 and O3 atom) on alcohol schiff base ligand have been involved in coordination, and in complex
Two schiff base ligands all use μ2-η1:η1:η1:η2:η1:η1:η1Mode and two DyIIIIon coordination bonding.Wherein Dy1-
The angle of O2-Dy2 is 110.0 °, four DyIIIIon and μ3The angle that the O atom of-OH is formed is respectively：Dy1-O4-Dy2：
104.4 °, Dy1-O4-Dy11：111.9 °, Dy2-O4-Dy11：105.9°.In addition, the μ3Alcoholic extract hydroxyl group in the O atom and ligand of-OH
O atom has played very important connection function, four Dy in complex structureIIIBetween ion magnetic can be carried out by them
Exchange interaction.
Table 1：The data of crystallography and structural modifications
Table 2：Part bond distance's data
11-X,1-Y,1-Z
Table 3：Part bond angle data
11-X,1-Y,1-Z
3) powder diffraction analysis：
Using the D/max-2500V/PC diffractometer of Rigaku electric machine industry Co., Ltd. to the present embodiment products therefrom
Diffraction analysis is carried out, powder diagram at normal temperature is as shown in Figure 2.In Fig. 2, the curve of top is single crystal structural data mould
Quasi- XRD curve, the curve of lower section are actually measured XRD curve, and as shown in Figure 2, theoretical value and actual test value are relatively coincide,
Show that products therefrom is pure phase.
4) magnetic property is studied：
After taking product made from appropriate the present embodiment to pulverize Magnetic Test instrument (Quantum Design company
MPMS-XL-5-SQUID generator) on carry out Magnetic Test.
χ of the present embodiment products therefrom outside 1000Oe direct current off fieldmT-T curve is as shown in Figure 3.From the figure 3, it may be seen that
When 300K, complex 10 tests the χ measuredMThe value of T is 52.00cm3K mol-1, experiment value is slightly below four and only spins
DyIIIThe theoretical value 56.68cm of ion3K mol-1, (free a DyIIIIon：14.17cm3K mol-1,6H15/2, S=5/
2, L=5, g=4/3), from 300K to 20K, χmT value is reduced with temperature and is reduced, χ when 20KMT value is 43.90cm3K mol-1,
20-2K, reduction is extremely obvious, and minimum value 24.96cm is reached in 2K3K mol-1.This phenomenon is attributable to two factors：
(1) with the reduction of temperature, the Stark sublevel m of excitation stateJReduction.(2) two DyIIIThere may be weak between ion
Antiferromagnetic reaction.
The present embodiment products therefrom between 2-5K, 0-70kOe external dc M-H curve graph off field as shown in figure 4, by
Fig. 4 is it is found that the present embodiment products therefrom is under the conditions of low field, and the M-H curve of each temperature is not overlapped, it may be possible to because in system
There are strong magnetic anisotropy and low excited states with the increase of externally-applied magnetic field, and the intensity of magnetization of complex increases rapidly, finally
The intensity of magnetization of each temperature tends to be overlapped.Such as at 2K, 70kOe, the intensity of magnetization is 21.36 μB, this numeric ratio theory
40 μ of saturation valueB(DyIIIThe intensity of magnetization of ion is 10 μB) want low, causing this species diversity may be due to DyIIIIon
Crystal field effects leads to the division of Stark energy level, eliminates6H15/2The heavy degeneracy in the 16 of ground state.
Loop curve of the present embodiment products therefrom at 2K is as shown in figure 5, experimental data shows to produce obtained by the present embodiment
The hysteresis loop of object is not obvious, it may be possible to caused by the strong quantum tunneling effect of rare earth ion.
Between 2-15K, vibration frequency tests obtained by the present embodiment temperature off field between 10-969Hz outside zero direct current
The ac magnetic susceptibility of product, as shown in fig. 6, the present embodiment products therefrom is lower than 12K in temperature, outside zero direct current off field, AC magnetism
The imaginary part of rate has frequency dependence, shows slow relaxation behavior, and regrettably there is no go out for the imaginary signals outside zero direct current off field
Existing maximum value, illustrates that its energy barrier is smaller, blocking temperature may be in 2K or less.Its reason may be that strong quantum tunneling effect is led
Cause us that can not observe the peaks of imaginary signals in 2K or more.Relaxation phenomena at this time derives from quantum tunneling, due to quantum tunneling
Occur between the ground state of degeneracy, so χM' and χM" value it is directly proportional to the quantity of ground state.With the reduction of temperature, ground state number
Amount increases therewith, so leading to χM' and χM" value increase, in χM'-T and χM"-T curve in, it is observed that its value is with temperature
The reduction of degree and increase, all there is frequency dependence in real part, imaginary part, and complex has typical single molecular magnets behavior.
Cole-Cole curve of the present embodiment products therefrom outside zero direct current off field is as shown in fig. 7, as shown in Figure 7, this reality
Applying a products therefrom, there are a relaxation processes in 2-5K, may be quantum tunneling process.
Comparative example 1
Embodiment 1 is repeated, unlike, mixed solvent is changed to water, methanol, ethyl alcohol, acetonitrile, DMF or methylene chloride etc.
Single solvent.
As a result cluster compound crystal is not obtained, wherein using water, anhydrous methanol, dehydrated alcohol after reaction terminates cooling
What is obtained is all colourless clear liquid, is still generated without crystal after standing 10 days；And acetonitrile, DMF, methylene chloride are to rare earth metal
The dissolubility of salt is bad, and the metal salt for being difficult to dissolve all has been remained after reaction.
Comparative example 2
Embodiment 1 is repeated, unlike, the ethyl alcohol of in the mixed solvent is replaced with methanol.As a result crystal is not obtained.
Comparative example 3
Embodiment 1 is repeated, unlike, dysprosium nitrate Dy (NO is replaced with four water of acetic acid dysprosium3)3·6H2O, it is desirable to CH3COO-From
Son can replace the NO for participating in being coordinated3 -Ion also or by acetate bridging obtains the dysprosium cluster compound of new structure, but does not obtain
To crystal, explanation is unable to reach the thermodynamic condition to form dysprosium cluster compound and crystallization with acetate.
Embodiment 2
Embodiment 1 is repeated, unlike：
1) after 1mL aldehyde amine mixed liquor is added into vial, then 0.5mL ethyl alcohol and 3.5mL acetonitrile are added thereto, make
The volume ratio of in the mixed solvent ethyl alcohol and acetonitrile is 1：4；
2) pH=9.8 of triethylamine regulation system is used；
3) reaction carries out under the conditions of 50 DEG C, and the time of reaction is 48h.
Obtain red strip crystal, yield 21.7%.Structural characterization is carried out to products therefrom, determines that product is target
Product [Dy4(C23H17N4O3)2(μ3-OH)2(NO3)4(H2O)2].To products therefrom tool known to the Magnetic Characterization of products therefrom
There is single molecular magnets behavior.
Embodiment 3
Embodiment 1 is repeated, unlike：
1) after 1mL aldehyde amine mixed liquor is added into vial, then 0.5mL ethyl alcohol and 4.5mL acetonitrile are added thereto, make
The volume ratio of in the mixed solvent ethyl alcohol and acetonitrile is 1：5；
2) pH=9.5 of triethylamine regulation system is used；
3) reaction carries out under the conditions of 80 DEG C, and the time of reaction is 30h.
Obtain red strip crystal, yield 23.9%.Structural characterization is carried out to products therefrom, determines that product is target
Product [Dy4(C23H17N4O3)2(μ3-OH)2(NO3)4(H2O)2].To products therefrom tool known to the Magnetic Characterization of products therefrom
There is single molecular magnets behavior.
Embodiment 4
Embodiment 1 is repeated, unlike：
1) after 1mL aldehyde amine mixed liquor is added into vial, then 0.5mL ethyl alcohol and 1.5mL acetonitrile are added thereto, make
The volume ratio of in the mixed solvent ethyl alcohol and acetonitrile is 1：2；
2) pH=10.0 of triethylamine regulation system is used；
3) reaction carries out under the conditions of 100 DEG C, and the time of reaction is 20h.
Obtain red strip crystal, yield 22.3%.Structural characterization is carried out to products therefrom, determines that product is target
Product [Dy4(C23H17N4O3)2(μ3-OH)2(NO3)4(H2O)2].To products therefrom tool known to the Magnetic Characterization of products therefrom
There is single molecular magnets behavior.
Embodiment 5
Embodiment 1 is repeated, unlike：
1) pH=9.4 of triethylamine regulation system is used；
2) reaction carries out under the conditions of 120 DEG C, and the time of reaction is 20h.
Obtain red strip crystal, yield 21.6%.Structural characterization is carried out to products therefrom, determines that product is target
Product [Dy4(C23H17N4O3)2(μ3-OH)2(NO3)4(H2O)2].To products therefrom tool known to the Magnetic Characterization of products therefrom
There is single molecular magnets behavior.
Claims (8)
1.2- aldehyde radical -8-hydroxyquinoline contracting four core dysprosium cluster compound of -1,3 diamino -2- propyl alcohol schiff bases, it is characterised in that：
The chemical formula of the cluster compound is：[Dy4(C23H17N4O3)2(μ3-OH)2(NO3)4(H2O)2]；
The cluster compound belongs to monoclinic system, P21/ n space group, cell parameter are： α=90.00 °, β=106.186 (2) °, γ=90.00 °.
2. the conjunction of the aldehyde radical of 2- described in claim 1-8-hydroxyquinoline contracting four core dysprosium cluster compound of-1,3 diamino-2- propyl alcohol schiff bases
At method, it is characterised in that：Take 2- aldehyde radical -8-hydroxyquinoline, 1,3- diamino -2- propyl alcohol and Dy (NO3)3·6H2O is dissolved in
In the mixed solvent adjusts pH=9.4~10.0 of acquired solution, and gained mixed liquor reacts under heating condition, and reactant is cooling,
There is crystal to be precipitated to get target product；Wherein, the mixed solvent is the composition of ethyl alcohol and acetonitrile.
3. synthetic method according to claim 2, it is characterised in that：The body of the in the mixed solvent, ethyl alcohol and acetonitrile
Product is than being 1：2~5.
4. synthetic method according to claim 2, it is characterised in that：The body of the in the mixed solvent, ethyl alcohol and acetonitrile
Product is than being 1：3~4.
5. synthetic method according to claim 2, it is characterised in that：Adjust pH=9.5~9.7 of acquired solution.
6. synthetic method according to claim 2, it is characterised in that：The reaction carries out under the conditions of 50~120 DEG C.
7. synthetic method according to claim 2, it is characterised in that：The reaction carries out under the conditions of 60~100 DEG C.
8. 2- aldehyde radical described in claim 1-8-hydroxyquinoline contracting four core dysprosium cluster compound of-1,3 diamino-2- propyl alcohol schiff bases exists
Prepare the application in magnetic material.
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| 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 |
| CN111039990A (en) * | 2019-12-23 | 2020-04-21 | 广西师范大学 | Low-toxicity iridium complex and synthesis method and application thereof |
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| CN107098921A (en) * | 2017-05-19 | 2017-08-29 | 广西师范大学 | The dysprosium complex constructed using 8 oxyquinoline acyl hydrazone derivatives as part and its synthetic method and application |
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| 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 |
| CN111039990A (en) * | 2019-12-23 | 2020-04-21 | 广西师范大学 | Low-toxicity iridium complex and synthesis method and application thereof |
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