CN108864211A - Ni-Ln isodigeranyl nuclear magnetism complex based on phthalocyanine and preparation method thereof - Google Patents
Ni-Ln isodigeranyl nuclear magnetism complex based on phthalocyanine and preparation method thereof Download PDFInfo
- Publication number
- CN108864211A CN108864211A CN201810617003.8A CN201810617003A CN108864211A CN 108864211 A CN108864211 A CN 108864211A CN 201810617003 A CN201810617003 A CN 201810617003A CN 108864211 A CN108864211 A CN 108864211A
- Authority
- CN
- China
- Prior art keywords
- phthalocyanine
- iii
- complex
- methanol
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- MFGOTAHWOBKNNU-XMHGGMMESA-N Isodigeranyl Chemical group CC(C)=CCC\C(C)=C\CC(C)(C=C)CCC=C(C)C MFGOTAHWOBKNNU-XMHGGMMESA-N 0.000 title claims description 17
- MFGOTAHWOBKNNU-FQEVSTJZSA-N Isodigeranyl Natural products CC(=CCCC(=CC[C@](C)(CCC=C(C)C)C=C)C)C MFGOTAHWOBKNNU-FQEVSTJZSA-N 0.000 title claims description 16
- 230000005311 nuclear magnetism Effects 0.000 title claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 73
- 230000005291 magnetic effect Effects 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- -1 rare earth ion Chemical class 0.000 claims abstract description 16
- GFSNBYBQKWNFTA-UHFFFAOYSA-N 2-[[3-[(2-hydroxyphenyl)methylideneamino]-2-[[(2-hydroxyphenyl)methylideneamino]methyl]-2-methylpropyl]iminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NCC(CN=CC=1C(=CC=CC=1)O)(C)CN=CC1=CC=CC=C1O GFSNBYBQKWNFTA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 238000013500 data storage Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 5
- 239000000696 magnetic material Substances 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 5
- 239000002262 Schiff base Substances 0.000 description 4
- 150000004753 Schiff bases Chemical class 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- FSVBAJHJVAWEID-UHFFFAOYSA-N 2-(propyliminomethyl)phenol Chemical compound CCCN=CC1=CC=CC=C1O FSVBAJHJVAWEID-UHFFFAOYSA-N 0.000 description 3
- 230000005283 ground state Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 241001269238 Data Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000010165 autogamy Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229940052810 complex b Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 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
- 238000010586 diagram Methods 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000010189 synthetic method Methods 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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)
Abstract
The present invention relates to neutral different binuclear complexs of Ni (the II)-Ln (III) based on phthalocyanine and preparation method thereof.The chemical formula of complex of the present invention is [(NiL) Ln (Pc) (CH3OH)], wherein Ln is rare earth ion Dy (III) or Tb (III)；L is the trivalent anion of 1,1,1- tri- [(salicylidene amino) methyl] ethane；Pc is the dianion of Phthalocyanine.For complex using substep synthesis, the preparation of ambient solvent method of diffusion, this method is simple and easy, controllability is high, repeated strong.There is stronger ferromagnetic interaction in prepared complex, its ac magnetic susceptibility shows apparent frequency in the presence of externally-applied magnetic field and relies on phenomenon, slow improved relaxation behavior with single molecular magnets can be used as molecule based magnetic materials and use in high density data storage equipment.
Description
Technical field
The invention belongs to organic and inorganic complexes and molecule based magnetic materials research field, and it is mixed to be related to transition-rare earth
Alloy category magnetic partner and preparation method thereof.The complex is Ni (the II)-Ln constructed jointly by phthalocyanine and schiff bases
(III) neutral different binuclear complex, the behavior with single molecular magnets can be used for novel magnetic memory materials, and method is simply easy
Row, controllability are high, repeatability is strong.
Background technique
Magnetic partner can be used as the information storage that molecular-based magnets realize ultra high density on a molecular scale, attract crowd
The interest of more researchers.This kind of material has the characteristics that small in size, relative density is low, easy modification is cut, they will likely
Represent the smallest of microelectronics industry.Mn12Ac is the complex that first case has single molecular magnets property, its ac magnetization
Rate have frequency dependence, and it is observed that multi-step formula hysteresis loop, superparamagnetic characteristic is shown, in ultrahigh density
The fields such as storage, molecular spin electronics have broad application prospects.
Single molecular magnets need to have two elements, big ground-state total spin value and strong negative magnetic anisotropy, but grind
Study carefully the result shows that, big ground state spin and negative magnetic anisotropy are difficult to obtain simultaneously.It is same that Matsumoto etc. reports first case
The heteronuclear single molecular magnets of Shi Hanyou rare earth (4f) and transition metal (3d) ion are reported.4f ion has stronger rotation rail coupling
Cooperation is used, and can produce stronger ferromagnetic interaction between 3d and 4f metal, this can not only increase the base of title complex
State spin, and be conducive to weaken quantum tunneling effect.In addition, this mixed metal system is easy to show single metal and be difficult to
The property of realization, for example big ground state spin and negative anisotropy are obtained simultaneously, and the presence of mixed metal is more advantageous to conjunction
Molecule can be effectively realized using properties such as the unique light of different paramagnetic rare earth ions, electricity, magnetic at the complex of structure novel
The multifunction of material.
Aspect is constructed in single molecular magnets, macrocyclic ligand phthalocyanine is by favor.Phthalocyanine has the rigidity knot of height conjugation
Structure not only has stronger coordination ability, but also this unique planar conjugate structure can be effectively controlled around rare earth ion
Crystalline field coordination environment, and then adjust its magnetic anisotropy.But the synthetic method of this kind of complex is generally more complex, often
Under the conditions of hydro-thermal or solvent heat, controllability is not high, and product purity and repeatability are difficult to ensure.Further investigate transition-
The controllable preparation strategy of rare-earth mixed metal single molecular magnets has a very important significance.
Summary of the invention
The preparation of it is an object of that present invention to provide a kind of Ni (II)-Ln (III) isodigeranyl nuclear magnetism complex based on phthalocyanine
Method can be used in the controlledly synthesis of mixed metal single molecular magnets, and method is simple and easy, and controllability is high, and repeatability is strong.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of Ni (II)-Ln (III) isodigeranyl nuclear magnetism complex based on phthalocyanine of the present invention：[(NiL)Ln(Pc)
(CH3OH)], wherein Ln is rare earth ion Dy (III) or Tb (III)；L is 1,1,1- tri- [(salicylidene amino) methyl] ethane
Trivalent anion；Pc is the dianion of Phthalocyanine.The structural formula of the complex is as follows：
With Ni (II)-Ln (III) isodigeranyl nuclear magnetism of the present invention constructed from phthalocyanine and tripod-type schiff bases
The preparation method of object, it is characterised in that substep synthesis gradually controls coordination site, and specific steps include：
One, 1,1,1- tri- [(salicylidene amino) methyl] ethane and six hydration Nickel Chlorides are mixed, dichloromethane is added
In the mixed solution of alkane and methanol, wherein the volume ratio of methylene chloride and methanol is 1：2, it is stirred at room temperature, obtains light green solid
Powder.Then obtained solid powder is dissolved in methanol solution, and triethylamine is added thereto, be stirred at room temperature to obtain clarify it is molten
Liquid.
Two, phthalocyanine acetylacetone,2,4-pentanedione rare-earth salts is stirred in the mixed solution of methanol and acetonitrile, wherein methanol and acetonitrile
Volume ratio is 1：1, obtain mixed solution.
Three, the solution that step 2 obtains slowly is layered in step 1 acquired solution, being stored at room temperature can be made described different
The green rhabdolith of double-core magnetic partner.Mixed solution through pure methanol and acetonitrile washs 2 times, air drying.
The purpose that substep synthesized and be added triethylamine is to make [(salicylidene amino) methyl] ethane of 1,1,1- tri- with physical efficiency
Enough to chelate Ni ion first, the coordination site for avoiding its excessive is occupied by rare earth ion, in three second after ligand sequestration Ni ion
Further deprotonation forms univalent anion with the help of amine, and then convenient for forming neutral molecule with phthalocyanine rare earth.
The chemical formula of the phthalocyanine acetylacetone,2,4-pentanedione rare-earth salts is LnPc (acac) (H2O)2, wherein Ln is rare earth ion Dy
(III) or Tb (III)；Acac is the univalent anion of acetylacetone,2,4-pentanedione.
Organic ligand 1,1,1- tri- [(salicylidene amino) methyl] ethane, six hydration Nickel Chlorides, triethylamine and
The molar ratio of phthalocyanine acetylacetone,2,4-pentanedione dysprosium salt is 1：1：1–2：1–2.
The volume ratio of methylene chloride and methanol is 1 in mixed solution described in step 1：2, in mixed solution described in step 2
The volume ratio of methanol and acetonitrile is 1：1.The solution of this ratio can be improved the solubility of reactant, and be easy that product is precipitated
Crystal.
Beneficial effects of the present invention：
(1) present invention substep synthesis, ambient solvent diffusion by way of by ligand, transition metal and rare earth metal into
Row ordered fabrication obtains the different binuclear complex of structure novel.Preparation method is simple and easy, controllability is high, repeated strong.
(2) Ni (II)-Ln (III) isodigeranyl caryogamy of the present invention constructed by phthalocyanine and Tripod schiff base ligand
Closing object is the single molecular magnets with ferromagnetic property, in terms of the preparation of novel molecular base magnetic material and high density data storage
Materials'use.
A kind of different binuclear complex [(NiL) Ln (Pc) (CH with single molecular magnets behavior can be made in the present invention3OH)]。
Detailed description of the invention
Fig. 1 is complex [(NiL) Ln (Pc) (CH3OH crystal structure figure)]；
Fig. 2 is complex [(NiL) Ln (Pc) (CH3OH powder diagram)]；
Fig. 3 is complex [(NiL) Ln (Pc) (CH3OH uv absorption spectra)]；
Fig. 4 is complex [(NiL) Ln (Pc) (CH3OH molar susceptibility (χ)]MT) the curve graph changed with temperature (T)；
Fig. 5 is complex [(NiL) Ln (Pc) (CH3OH the curve graph that the intensity of magnetization (M))] changes with magnetic field (H)；
Fig. 6 a, 6b are complex [(NiL) Ln (Pc) (CH respectively3OH real part (χ '))] exchanges a mole magnetic with imaginary part (χ ")
Rate curve graph.
Specific embodiment
The invention will be further described combined with specific embodiments below, and the present invention includes but is not limited to following embodiment.
The starting material for preparing complex of the present invention, such as Nickel dichloride hexahydrate, 1,1,1- tri- [(salicylidene amino) methyl] ethane with
Phthalocyanine acetylacetone,2,4-pentanedione rare-earth salts can directly be bought from the market.
Embodiment 1
The preparation method of Ni (II)-Dy (III) magnetic partner A：
One, by [(salicylidene amino) methyl] ethane (4.3mg, 0.01mmol) of 1,1,1- tri- and six hydration Nickel Chlorides
(2.4mg, 0.01mmol) mixing, is added in the mixed solution of methylene chloride (3.0mL) and methanol (1.5mL), is stirred at room temperature, obtains
To light green solid powder.Obtained solid powder is dissolved in methanol solution (1.5mL), and triethylamine is added thereto
(1.0mg, 0.01mmol) is stirred at room temperature to obtain clear solution.
Two, by phthalocyanine acetylacetone,2,4-pentanedione dysprosium salt (8.1mg, 0.01mmol) methanol (3.0mL) and acetonitrile (3.0mL) mixing
It is stirred in solution, obtains mixed solution.
Three, the solution that step 2 obtains slowly is layered in step 1 acquired solution, institute can be made by standing 3 days at room temperature
State the green rhabdolith of isodigeranyl nuclear magnetism complex A.Mixed solution (2.0mL) through pure methanol and acetonitrile washs 2 times,
Air drying.
The yield of magnetic partner A manufactured in the present embodiment is 52.6%.
Embodiment 2
The preparation method of Ni (II)-Tb (III) magnetic partner B：
One, by [(salicylidene amino) methyl] ethane (4.3mg, 0.01mmol) of 1,1,1- tri- and six hydration Nickel Chlorides
(2.4mg, 0.01mmol) mixing, is added in the mixed solution of methylene chloride (3.0mL) and methanol (1.5mL), is stirred at room temperature, obtains
To light green solid powder.Obtained solid powder is dissolved in methanol solution (1.5mL), and triethylamine is added thereto
(2.0mg, 0.02mmol) is stirred at room temperature to obtain clear solution.
Two, by phthalocyanine acetylacetone,2,4-pentanedione terbium salt (16.1mg, 0.02mmol) in the mixed of methanol (6.0mL) and acetonitrile (6.0mL)
It closes and is stirred in solution, obtain mixed solution.
Three, the solution that step 2 obtains slowly is layered in step 1 acquired solution, institute can be made by standing 5 days at room temperature
State the green rhabdolith of isodigeranyl nuclear magnetism complex.Mixed solution (2.0mL) through pure methanol and acetonitrile washs 2 times,
Air drying.
The yield of magnetic partner B manufactured in the present embodiment is 59.8%.
Complex A and B prepared by the embodiment of the present invention 1-2 is Ni (the II)-Ln constructed jointly by phthalocyanine and schiff bases
(III) isodigeranyl nuclear magnetism complex, chemical general formula NiLnC63H48N7O4, embodiments are as follows：
(1) crystal structure determination
The crystal of the complex A and B is measured using Bruker Smart Apex II CCD X-ray single crystal diffractometer
Structure.As shown in Figure 1, such complex is crystallized in monoclinic system, belong to P21/ c space group, cell parameter are β=113.265 (3)~113.641 (4) °, Z=4.It include double-core Ni (II)-Ln (III) different metal structural unit in one asymmetric cell,
Wherein Ni (II) is chelated by six atoms from tripod-type ligand L, takes { NiO3N3Octahedral coordination mode.Ln
(III) it is in { LnO3N4Seven coordination environments in, wherein four nitrogen-atoms come from macrocyclic ligand Pc, two oxygen atoms carry out autogamy
Body L, a remaining oxygen atom are attributed to the methanol molecules of coordination.
(2) uv-visible absorption spectra measures
Uv-visible absorption spectra (Fig. 2) is measured using Shimadzu UV-3600 ultraviolet specrophotometer.1-4 point of line
Not Wei ligand 1,1,1- tri- [(salicylidene amino) methyl] ethane, phthalocyanine, complex A and complex B is in dichloromethane solution
In UV-visible absorption spectrum.The complex shows the suction of very strong phthalocyanine metal complexes at 671nm
Receive peak.
(3) powder diffraction measures phase purity
Its phase purity is characterized with Bruker D8ADVANCE powder diffractometer to gained green rhabdolith.As shown in figure 3,
Simulation curve is simulated using Mercury 3.10.1 software and single crystal structural data.Prepared cooperation as the result is shown
Object A and B have reliable phase purity, provide safeguard for its application in molecule based magnetic materials.
(4) magnetic performance measures
Using superconducting quantum interference device (SQUID) magnetic measurement systems Quantum Design MPMS-SQUID-VSM to embodiment 1-
The performance of isodigeranyl nuclear magnetism the complex A and B of 2 preparations are measured.Molar susceptibility (χMT) the curve changed with temperature (T)
Such as Fig. 4, test temperature is 2-300K, DC fields 1000Oe.The intensity of magnetization (M) is with magnetic field (H) variation tendency such as Fig. 5, direct current
Field strength is 0-70kOe, and the test temperature of A is 1.8K, and the test temperature of B is 1.9K.Real part (χ ') exchanges mole with imaginary part (χ ")
Magnetic susceptibility such as Fig. 6, DC fields 1000Oe, the frequency of oscillation that ac magnetic susceptibility uses is 2Oe, and frequency range is 16-999Hz.
All susceptibility datas carry out diamagnetic correction through Pascal constant.
It is shown in Fig. 4, such complex molar susceptibility is slowly reduced with the reduction of temperature, when temperature is lower than 15K
When, χMT value rises rapidly again, illustrates that there are ferromagnetic interactions between nickel and rare earth ion dysprosium or terbium.Magnetisation curve
It has been shown that, in low field section, their intensity of magnetization increases rapidly with the increase in magnetic field, powerful when 10kOe on the spot, with field
The strong increase intensity of magnetization is slowly increased, and is not had in 70kOe and is reached saturation, illustrates that rare earth ion has strong anisotropy
(Fig. 5).Exchange molar susceptibility curve show, 1000Oe external dc off field, the complex A (Fig. 6 a) and B (scheme
Real and imaginary parts exchange molar susceptibility signal 6b) is presented apparent frequency in low-temperature space and relies on phenomenon, this illustrates this example
Prepared Ni (II)-Ln (III) complex has the slow relaxation behavior of field induction, has single molecular magnets feature.
In summary measurement result, Ni (II)-Ln (III) complex is that have ferromagnetic single molecular magnets, can
It is used as molecule based magnetic materials at novel high-density information storing device (such as CD, hard disc).
Claims (6)
1. a kind of Ni (II)-Ln (III) isodigeranyl nuclear magnetism complex based on phthalocyanine, which is characterized in that the complex be by
Phthalocyanine and 1, Ni (II)-Ln (III) neutral compound that 1,1- tri- [(salicylidene amino) methyl] ethane is constructed jointly, knot
Structure formula is as follows：
Wherein Ln is rare earth ion dysprosium or terbium；Such complex crystal belongs to P2 in monoclinic system1/ c space group, cell parameter
For Z=4；It include one in one asymmetric cell
Double-core Ni (II)-Ln (III) different metal structural unit, wherein Ni (II) takes { NiO3N3Octahedral coordination mode, Ln
(III) it is in { LnO3N4Seven coordination environments in.
2. the preparation method of the Ni based on phthalocyanine (II)-Ln (III) isodigeranyl nuclear magnetism complex as described in claim 1,
It is characterized in that including the following steps：
One, by 1,1,1- tri- [(salicylidene amino) methyl] ethane and six hydration Nickel Chlorides mix, be added methylene chloride and
In the mixed solution of methanol, wherein the volume ratio of methylene chloride and methanol is 1：2, it is stirred at room temperature, obtains light green solid powder.
Then obtained solid powder is dissolved in methanol solution, and triethylamine is added thereto, be stirred at room temperature to obtain clear solution；
Two, phthalocyanine acetylacetone,2,4-pentanedione rare-earth salts is stirred in the mixed solution of methanol and acetonitrile, wherein the volume of methanol and acetonitrile
Than being 1：1, obtain mixed solution；
Three, the solution that step 2 obtains slowly is layered in step 1 acquired solution, the isodigeranyl core can be made by being stored at room temperature
The green rhabdolith of magnetic partner.Mixed solution through pure methanol and acetonitrile washs 2 times, air drying.
3. the preparation method of the Ni based on phthalocyanine (II)-Ln (III) isodigeranyl nuclear magnetism complex as claimed in claim 2,
It is characterized in that in step 2 that the volume ratio of methanol and acetonitrile is 1：1.
4. the preparation method of the Ni based on phthalocyanine (II)-Ln (III) isodigeranyl nuclear magnetism complex as claimed in claim 2,
It is characterized in that being stored at room temperature in step 3 1-6 day.
5. the preparation method of the Ni based on phthalocyanine (II)-Ln (III) isodigeranyl nuclear magnetism complex as claimed in claim 2,
It is characterized in that reactant 1,1,1- tri- [(salicylidene amino) methyl] ethane, six hydration Nickel Chlorides, triethylamine and phthalein
The molar ratio of cyanines acetylacetone,2,4-pentanedione dysprosium salt is 1：1：1–2：1–2.
6. the Ni based on phthalocyanine (II)-Ln (III) isodigeranyl nuclear magnetism complex is as molecule-based magnetic as described in claim 1
Application of the material in high density data storage equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810617003.8A CN108864211A (en) | 2018-06-14 | 2018-06-14 | Ni-Ln isodigeranyl nuclear magnetism complex based on phthalocyanine and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810617003.8A CN108864211A (en) | 2018-06-14 | 2018-06-14 | Ni-Ln isodigeranyl nuclear magnetism complex based on phthalocyanine and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108864211A true CN108864211A (en) | 2018-11-23 |
Family
ID=64339321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810617003.8A Pending CN108864211A (en) | 2018-06-14 | 2018-06-14 | Ni-Ln isodigeranyl nuclear magnetism complex based on phthalocyanine and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108864211A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956297A (en) * | 2021-11-18 | 2022-01-21 | 江苏科技大学 | Co (III) -Co (II) binuclear cobalt monomolecular magnet and preparation method and application thereof |
-
2018
- 2018-06-14 CN CN201810617003.8A patent/CN108864211A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956297A (en) * | 2021-11-18 | 2022-01-21 | 江苏科技大学 | Co (III) -Co (II) binuclear cobalt monomolecular magnet and preparation method and application thereof |
| CN113956297B (en) * | 2021-11-18 | 2023-12-29 | 江苏科技大学 | Co (III) -Co (II) binuclear cobalt single-molecule magnet and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Toward heterometallic single-molecule magnets: Synthetic strategy, structures and properties of 3d–4f discrete complexes | |
| Zeng et al. | A single-molecule-magnetic, cubane-based, triangular Co12 supercluster | |
| Luneau et al. | Magnetism of metal-nitroxide compounds involving bis-chelating imidazole and benzimidazole substituted nitronyl nitroxide free radicals | |
| CN102136339B (en) | Dysprosium monomer magnet with dual functions of ferromagnetic and ferroelectric and preparation method thereof | |
| Fuller et al. | Magnetic properties of calixarene-supported metal coordination clusters | |
| Kou et al. | Crystal structure and magnetic properties of a new two-dimensional cyano-bridged bimetallic assembly [NiL′] 3 [Cr (CN) 5 (NO)] 2· 10H 2O (L′= 3, 10-dimethyl-1, 3, 5, 8, 10, 12-hexaazacyclotetradecane) | |
| CN104341460B (en) | Dy (III) Mn (II) mixed metal magnetic complex and preparation method and application | |
| Bera et al. | Investigation of the role of terminal ligands in magnetic relaxation in a series of dinuclear dysprosium complexes | |
| Ma et al. | Lanthanide hydroxide ribbons assembled in a 2D network: slow relaxation of the magnetization in the dysprosium (III) complex | |
| Nowicka et al. | A water sensitive ferromagnetic [Ni (cyclam)] 2 [Nb (CN) 8] network | |
| Du et al. | A centrosymmetric Dy2 compound derived from acylhydrazone Schiff base ligand exhibiting zero-field single-molecule magnet behavior | |
| CN108864211A (en) | Ni-Ln isodigeranyl nuclear magnetism complex based on phthalocyanine and preparation method thereof | |
| CN102982960B (en) | Trinuclear dysprosium cluster compound single-molecular magnet and preparation method thereof | |
| Antkowiak et al. | Generalized Heisenberg-Type Magnetic Phenomena in Coordination Polymers with Nickel–Lanthanide Dinuclear Units | |
| An et al. | 3d Ion-driven hexanuclear heterometallic clusters with amazing structures and magnetic properties | |
| Zhang et al. | Rare CH 3 O−/CH 3 CH 2 O−-bridged nine-coordinated binuclear Dy III single-molecule magnets (SMMs) significantly regulate and enhance the effective energy barriers | |
| Sun et al. | Bithiazole based polymer and its ferro complex containing hexacyanoferrate (III) group: synthesis and ferromagnetic property | |
| Li et al. | Two temperature-dependent 2D heterometallic Cd (II)–Dy (III) coordination polymers exhibiting slow magnetic relaxation and luminescence properties | |
| Doi et al. | Metal-Azide-Pyrimidine Complexes M (N3) 2 (pm) with a Three-Dimensional Network Showing Weak Ferromagnetism for M= Mn and Fe and Antiferromagnetism for M= Co and Ni | |
| CN108727251B (en) | Magnetic cobalt (II) complex based on 4, 4' -bipyridyl-itaconic acid derivative ligand and preparation method thereof | |
| CN105017294B (en) | A kind of thiadiazolyl group dicarboxylic acids terbium coordination compound and its preparation method and application | |
| Yakhmi | Magnetism as a functionality at the molecular level | |
| Vaz et al. | Synthesis and properties of new molecule-based magnets containing Mn (II), Cu (II) and nitronyl nitroxide radical cation | |
| CN103219148B (en) | A kind of preparation method of single molecular magnets | |
| Li et al. | A dual shell-like heptadecanuclearity [Gd5Ni12] cluster with ferromagnetic interaction and large magnetocaloric effect |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181123 |
|
| RJ01 | Rejection of invention patent application after publication |