CN104031096B - Isobutyl hydramine copper-rare earth hetero six core metal cluster compound and synthetic methods thereof - Google Patents
Isobutyl hydramine copper-rare earth hetero six core metal cluster compound and synthetic methods thereof Download PDFInfo
- Publication number
- CN104031096B CN104031096B CN201410300834.4A CN201410300834A CN104031096B CN 104031096 B CN104031096 B CN 104031096B CN 201410300834 A CN201410300834 A CN 201410300834A CN 104031096 B CN104031096 B CN 104031096B
- Authority
- CN
- China
- Prior art keywords
- mep
- thf
- iii
- cluster compound
- rare earth
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses class isobutyl hydramine copper-rare earth hetero six core metal cluster compound and synthetic methods thereof. Described cluster compound has following chemical formula composition: Ln2Cu4(Mep)8(NO3)6(THF), wherein, Ln represents rare earth metal, is selected from Tb (III) or Er (III); Mep represents isobutanol amine ligand; THF represents oxolane. Above-mentioned family compound is taking isobutyl hydramine as part, and it is reacted under corresponding conditions with rare-earth salts Ln (III) and obtained with certain Cu (II) salt. Synthetic method of the present invention is simple to operation, and productive rate is higher; Gained cluster compound is to utilize simple alcohols amine part cheap and easy to get to construct the assorted metallicl magnetic material of rare earth-transition metal, is having potential application prospect as a kind of novel molecular based magnetic material aspect information storage.
Description
Technical field
The present invention relates to isobutyl hydramine copper-rare earth hetero six core metal cluster compound and synthetic methods thereof, belong to organicMetallochemistry technical field.
Background technology
Multi-nuclear metal cluster compound has potential using value in fields such as magnetics, catalysis, optics and is sectionThe worker that grinds pays close attention to. Metal cluster compound (metalclusers) is defined as and contains two or two the earliestIndividual above metallic atom and a compounds that has Metal-Metal bond to exist. People are there is no metal in recent yearsThe limited multi-nuclear metal complexes that-metallic bond exists is also referred to as metal cluster compound, and this also makes metal cluster compoundThe definition of thing has obtained expansion. For the multinuclear cluster compound with different check figures, some has interesting skyBetween structure and special optical, electrical, magnetic property. For example, as the multi-nuclear metal cluster compound of single molecular magnets,Its size just in time within the scope of nanoscale, TBAt temperature, both showed the magnetic bi-stable of classical macroscopical magnet,Have again quantum tunneling magnetization effect, this is that classical macroscopical magnet is unexistent, and this makes metal clusterCompound has potential using value at aspects such as information storage and quantum calculations; And at some metal clustersIn compound, observed very large magnetothermal effect value, this is expected to be used to the magnetic refrigeration at ultralow temperature. ManyCore metal cluster compound is because of the diversity of its structure and some peculiar magnetic properties that show, Yi JiThe important function being risen in quantum and classical formalism, has made it to obtain the concern of researcher, becomes and joinsOne of study hotspot of position chemistry.
Existing published multi-nuclear metal cluster compound is more, as publication number be CN102087900A,CN103739628A, CN102982960A etc., disclose respectively a kind of dysprosium four core cluster compound type unimolecule magneticProperty material, three core ruthenium cluster compound crystal, three He Di family adduct molecule magnets, but there is not yet so far andIsobutyl hydramine is the relevant report of the assorted metal cluster compound of the Cu-Ln of part and synthetic method thereof.
Summary of the invention
The technical problem to be solved in the present invention is to provide isobutyl hydramine copper-rare earth hetero six core metals that a class is newCluster compound and synthetic method thereof.
Isobutyl hydramine copper-rare earth hetero six core metal cluster compounds of the present invention, have following chemical formula groupBecome:
Ln2Cu4(Mep)8(NO3)6(THF)
Wherein, Ln represents rare earth metal, is selected from Tb (III) or Er (III); Mep represents that isobutyl hydramine joinsBody; THF represents oxolane.
Mep in above-mentioned isobutyl hydramine copper-rare earth hetero six core metal cluster compounds-Part all adopts μ2-η3JoinBit pattern coordination, all Cu (II) ions are pentacoordinate tetragonal pyramid coordination geometric type, Ln (III) fromSon is the two cap triangular prism configurations of eight-coordinate distortion; Two Cu (II) ions and a Ln (III) in cluster compoundIon is by four μ2:η3The Mep of-bridging pattern-Part bridging forms assorted three core V-structure Cu2LnUnit, two this kind three core Cu2Ln unit obtains six nuclear structures by nitrate anion bridging.
Isobutyl hydramine copper-rare earth hetero six core metal cluster compounds shown in above-mentioned chemical formula, when Ln is Tb (III)Time, the chemical formula of described cluster compound is Tb2Cu4(Mep)8(NO3)6(THF), this cluster compound crystal belongs to monoclineCrystallographic system, space group is P21/ c, cell parameter is: α＝90.00°，β＝116.765(4)°，γ＝90.00°；Ferromagnetic coupling effect dominates status between the central metallic ions of this cluster compound; In the time that Ln is Er (III),The chemical formula of described cluster compound is Er2Cu4(Mep)8(NO3)6(THF), this cluster compound crystal belongs to monoclinic crystalSystem, space group is P21/ c, cell parameter is: α=90.00 °, β=113.384 (2) °, γ=90.00 °; This bunchBetween the central metallic ions of compound with antiferromagnetic coupling effect dominates status.
The present invention also comprises the synthetic method of above-mentioned isobutyl hydramine copper-rare earth hetero six core metal cluster compounds, itsIn:
In the time that Ln is Tb (III), cluster compound Tb2Cu4(Mep)8(NO3)6(THF) synthetic method comprise withLower step:
1) take in proportion Tb (NO3)3·5H2O、Cu(OAc)2·H2O and isobutyl hydramine, willTb(NO3)3·5H2O and Cu (OAc)2·H2O is dissolved in polar solvent, then adds isobutyl hydramine, mix,Obtain mixed liquor;
2) gained mixed liquor is placed in reaction vessel and under 10～45 DEG C of conditions, leaves standstill reaction to completely, has largeAmount crystal generates, and isolates crystal, and washing is dry, obtains cluster compound Tb2Cu4(Mep)8(NO3)6(THF)；
In the time that Ln is Er (III), cluster compound Er2Cu4(Mep)8(NO3)6(THF) synthetic method comprise withLower step:
A) take in proportion Er (NO3)3·5H2O、Cu(OAc)2·H2O, benzoic acid and isobutyl hydramine, willEr(NO3)3·5H2O、Cu(OAc)2·H2O and benzoic acid are dissolved in polar solvent, then add isobutyl hydramine,Mix, obtain mixed liquor;
B) gained mixed liquor is placed in container, is evacuated to vacuum after liquid nitrogen frozen, sealing by fusing, then in 40～Under 80 DEG C of conditions, reaction, to completely, is isolated crystal, and washing is dry, obtains cluster compoundEr2Cu4(Mep)8(NO3)6(THF)。
In above-mentioned synthetic method, described polar solvent is the combination of absolute ethyl alcohol and oxolane, described inThe ratio of absolute ethyl alcohol and oxolane can be any proportioning, preferably, and in the composition of polar solvent,The ratio of the volume ratio of absolute ethyl alcohol and oxolane is less than or equal at 1 o'clock, and the productive rate of gained object moreHigh. The consumption of described polar solvent can determine as required, under normal circumstances, can be by 1mmol rareEarth metal nitrate (Tb (NO3)3·5H2O or Er (NO3)3·5H2O) dissolve with 30～50mL polar solventCalculate the consumption of polar solvent.
Above-mentioned cluster compound Tb2Cu4(Mep)8(NO3)6(THF) in synthetic method, step 1) in,Tb(NO3)3·5H2O、Cu(OAc)2·H2The ratio of the amount of substance of O and isobutyl hydramine can be stoichiometryRatio, is preferably 1:1～3:3～5, more preferably 1:2:4; Step 2) in, reaction is to completely largeApproximately need the time of 5～30h; Reaction is more preferably under the condition of 20～35 DEG C to be carried out. This synthetic sideIn method, because polar solvent used easily volatilizees, and dust, carbon dioxide and steam etc. in airCan produce certain interference to reaction, therefore preferred reaction is to carry out in closeable container, asVial with a lid etc.
Above-mentioned cluster compound Er2Cu4(Mep)8(NO3)6(THF) in synthetic method, step a) in, described inEr(NO3)3·5H2O、Cu(OAc)2·H2The ratio of the amount of substance of O, benzoic acid and isobutyl hydramine can beingLearn metering ratio, be preferably 1:1～3:0.5～2:3～5, more preferably 1:2:1:4; Step b)In, reaction is to the time that completely approximately needs 12～72h; Reaction is more preferably at 50～60 DEG C to be carried out.
Compared with prior art, the invention provides the isobutyl hydramine taking isobutyl hydramine as part that a class is newCopper-rare earth hetero six core metal cluster compounds and their synthetic method, described synthetic method is simple and easy to behaviourDo, productive rate is higher; Gained cluster compound is to utilize simple alcohols amine part cheap and easy to get to construct rare earth-transitionThe metal metallicl magnetic material of mixing, as a kind of novel molecular based magnetic material aspect information storage, have potentialApplication prospect.
Brief description of the drawings
Fig. 1 is the molecular structure of the embodiment of the present invention 1 products therefrom;
Fig. 2 is the infrared spectrum spectrogram of the embodiment of the present invention 1 products therefrom;
Fig. 3 is the χ of the embodiment of the present invention 1 products therefromm，χmT-T and 1/ χm-T curve map;
Fig. 4 is the molecular structure of the embodiment of the present invention 2 products therefroms;
Fig. 5 is the infrared spectrum spectrogram of the embodiment of the present invention 2 products therefroms;
Fig. 6 is the χ of the embodiment of the present invention 2 products therefromsm，χmT-T and 1/ χm-T curve map;
Detailed description of the invention
With specific embodiment, the invention will be further described below, but the present invention is not limited to these in factExecute example.
MepH described in following embodiment is isobutyl hydramine.
Embodiment 1: cluster compound Tb2Cu4(Mep)8(NO3)6(THF) synthesize
Take Cu (OAc)2·H2O (0.1mmol, 0.0199g) and Tb (NO3)3·5H2O(0.05mmol,0.0222g) be placed in vial with a lid, and then add absolute ethyl alcohol and oxolane each 1.0ML, finally adds MepH (0.2mmol, 0.0178g), mixes and by the lid lid of vialGood, under room temperature condition, leave standstill after reaction 24h, on the bottom of vial and inwall, have a large amount of squareNavy blue crystal generate, isolate crystal, washing, dry, obtain navy blue product 0.0185g,Productive rate: 43% (based on Tb (NO3)3·6H2O)。
Above-mentioned gained navy blue product is carried out to structural characterization:
1) structural characterization:
Selected shape rule, the monocrystalline of above-described embodiment 1 gained that size is suitable, in 150 (2) K conditionsUnder, be placed in the Mo-K of SuperNova single crystal diffractometer graphite monochromatizationαRayDo incident light source, within the scope of certain θ, collect point diffraction for structure elucidation with φ-ω scan modeAnd correction. Non-hydrogen atom solves by direct method, and coordinate and anisotropy thermal parameter thereof to them carried outUse complete matrix least square refinement. Mixed hydrogenation, hydrogen atom adopts isotropism thermal parameter; Non-hydrogen is formerSon adopts anisotropy thermal parameter. The parsing of crystal structure and structural modifications are respectively by SHELX-97(Sheldrick, 1990) and SHELXL-97 (Sheldrick, 1997) program package completes. Detailed crystalline substanceBody and structural modifications data are as shown in table 1, and structure as shown in Figure 1.
Table 1:
aR1＝Σ||Fo|–|Fc||/Σ|Fo|；bwR2＝[Σw(Fo 2–Fc 2)2/Σw(Fo 2)2]1/2
From above-mentioned ray crystallographic analysis, cluster compound Tb2Cu4(Mep)8(NO3)6(THF) belong to monoclinic crystalSystem, P21/ c space group, cell parameter is: α=90.00 °, β=116.765 (4) °, γ=90.00 °; From itMolecular structure is known, and this cluster compound is assorted six core Cu4Tb2Complex. These assorted six caryogamy compounds canTo regard the assorted three core Cu that there is V-structure by two as2A little less than the O atom of Tb unit by nitrate anionCoordination is connected to form. Assorted three core Cu2Tb unit is the Cu (II) by two pentacoordinate tetragonal pyramid configurationsTb (III) ion of ion and the two cap triangular prism configurations of eight-coordinate distortion is by four μ2:η3-bridgingThe Mep of pattern-Oxygen atom bridging on part forms.
2) IR Characterization:
With U.S. Nicolet360FT-IR type Fourier transformation infrared spectrometer (KBr compressing tablet), take the photograph spectrumScope 400 – 4000cm-1, gained infrared spectrum spectrogram as shown in Figure 2, principal character infrared absorption peakAs follows:
IR(KBrpellet,cm-1):3422m,2968w,2874w,1593w,1468w,1404s,1310w,1186w，1078m,770w,622w,551w。
3) Magnetic Characterization:
With MPMSXL-7SQUID type magnetometer, under 1000Oe DC fields, in 2.0-300K temperatureWithin the scope of degree, collect the alternating temperature molar susceptibility of complex, sample is carried out to diamagnetic correction, and with χmT andχmDeng T is mapped. The χ of embodiment 1 products therefromm，χmT-T and 1/ χm-T curve map as shown in Figure 3.
As shown in Figure 3, cluster compound Tb2Cu4(Mep)8(NO3)6(THF) χ in the time of 300KmT value is 25.50cm3Kmol–1，χmT reduction along with temperature in 200-300K temperature range slowly reduces; In temperatureWhen being reduced to 190K from 200K, degree slightly a little increases again, afterwards when temperature drops to 8K by 190KProcess in, χmT value constantly increases, and the speed increasing accelerates rapidly in the time of 50K, and this shows that this joinsBetween (II) ion of Cu in compound and Tb (III) ion, there is stronger ferromagnetic coupling effect, when temperature continuesContinuous reduction, χmT value reduces rapidly again. From χm –1Known with the curve of T, between 2-300K, bunch closeThing Tb2Cu4(Mep)8(NO3)6(THF) observe Curie-Weiss law, according to χm＝C/(T–θ)Matching, obtains Curie constant C=25.34cm3Kmol–1, Weiss constant θ=0.76K.Curie constant and the theoretical value that there is no interactional four Cu (II) and two Tb (III) ion gained25.16cm3Kmol–1Close, positive Weiss constant declaration is at cluster compound Tb2Cu4(Mep)8(NO3)6(THF)Ferromagnetic coupling effect dominates effect between middle metal ion.
Embodiment 2: cluster compound Er2Cu4(Mep)8(NO3)6(THF) synthesize
Take Cu (OAc)2·H2O(0.1mmol,0.0199g)，Er(NO3)3·5H2O(0.05mmol,0.0222g) and benzoic acid (0.05mmol, 0.0061g) be placed in internal diameter be 10mm, long be 200mmThe horminess glass tube of an end closure in, and then add absolute ethyl alcohol and the each 0.5mL of oxolane,After add MepH (0.2mmol, 0.0178g), after mixing, after liquid nitrogen frozen, vacuumizing barUnder part, by its openend sealing by fusing, the glass tube of sealing is put in baking oven, under 60 DEG C of conditions, reacted 48h, slowSlowly be down to room temperature, on teat glass inwall, have a large amount of square navy blue crystal to generate, isolate crystalline substanceBody, washing, dry, obtain navy blue product 0.0185g, productive rate: 43% (based on Er (NO3)3·5H2O)。
Above-mentioned gained navy blue product is carried out to structural characterization:
1) structural characterization:
Selected shape rule, the monocrystalline of above-described embodiment 1 gained that size is suitable, in 150 (2) K conditionsUnder, be placed in the Mo-K of SuperNova single crystal diffractometer graphite monochromatizationαRayDo incident light source, within the scope of certain θ, collect point diffraction for structure elucidation with φ-ω scan modeAnd correction. Non-hydrogen atom solves by direct method, and coordinate and anisotropy thermal parameter thereof to them carried outUse complete matrix least square refinement. Mixed hydrogenation, hydrogen atom adopts isotropism thermal parameter; Non-hydrogen is formerSon adopts anisotropy thermal parameter. The parsing of crystal structure and structural modifications are respectively by SHELX-97(Sheldrick, 1990) and SHELXL-97 (Sheldrick, 1997) program package completes. Detailed crystalline substanceBody and structural modifications data are as shown in table 1, and structure as shown in Figure 4.
As shown in Figure 4, cluster compound Er2Cu4(Mep)8(NO3)6And cluster compound (THF)Tb2Cu4(Mep)8(NO3)6(THF) have similar crystal structure, belong to monoclinic system, space group isP21/ c, cell parameter is: α=90.00 °, β=113.384 (2) °, γ=90.00 °; From its molecular structure,This cluster compound is assorted six core Cu4Er2Complex. These assorted six caryogamy compounds can be regarded as by two toolsThere are the assorted three core Cu of V-structure2Er unit is connected to form by the weak coordination of the O atom of nitrate anion.Assorted three core Cu2Er unit is abnormal by Cu (II) ion of two pentacoordinate tetragonal pyramid configurations and an eight-coordinateBecome Er (III) ion of two cap triangular prism configurations by four μ2:η3The Mep of-bridging pattern-On partOxygen atom bridging forms.
2) IR Characterization:
With U.S. Nicolet360FT-IR type Fourier transformation infrared spectrometer (KBr compressing tablet), take the photograph spectrumScope 400 – 4000cm-1, gained infrared spectrum spectrogram as shown in Figure 5, principal character infrared absorption peakAs follows:
IR(KBrpellet,cm-1):3445m,3264m，2968w,2424w,1587w,1468w，1386s,1085m,771w,622w,546w。
3) Magnetic Characterization:
With MPMSXL-7SQUID type magnetometer, under 1000Oe DC fields, in 2.0-300K temperatureWithin the scope of degree, collect the alternating temperature molar susceptibility of complex, sample is carried out to diamagnetic correction, and with χmT andχmDeng T is mapped. The χ of embodiment 2 products therefromsm，χmT-T and 1/ χm-T curve map as shown in Figure 6.
As shown in Figure 6, cluster compound Er2Cu4(Mep)8(NO3)6(THF) χ in the time of 300KmT value is 24.11cm3Kmol–1, along with temperature drops to 30K by 300K, cluster compound Er2Cu4(Mep)8(NO3)6(THF)χmT value slowly reduces, the minimum of a value 7.97cm while quickly falling to 2K afterwards3Kmol–1, thisPlant χmThe trend that T value reduces along with the reduction of temperature shows cluster compound Er2Cu4(Mep)8(NO3)6(THF)Between (II) ion of Cu in system and Er (III) ion, exist obvious antiferromagnetic coupling effect; Fromχm –1Known with the curve of T, cluster compound Er between 50-300K2Cu4(Mep)8(NO3)6(THF) observeCurie-Weiss law, according to χm=C/ (T – θ) matching, obtains Curie (Curie) constant C＝25.52cm3Kmol–1, weiss (Weiss) constant θ=– 17.91K. Curie constant with do not haveThe theoretical value 24.48cm of interactional four Cu (II) and two Er (III) ion gained3Kmol–1Close, negative weiss (Weiss) constant declaration is at cluster compound Er2Cu4(Mep)8(NO3)6(THF) center gold inBelong to interionic antiferromagnetic coupling effect dominates status.
Embodiment 3: cluster compound Tb2Cu4(Mep)8(NO3)6(THF) synthesize
Repeat embodiment 1, different, wherein Tb (NO3)3·5H2O、Cu(OAc)2·H2O and isobutylThe ratio of the amount of substance of hydramine changes to 1:3:3, and by the volume ratio of absolute ethyl alcohol and oxolane moreChange 1:10 into, control reaction simultaneously and react 30h under 20 DEG C of conditions.
Products therefrom is carried out to IR Characterization, structural characterization and Magnetic Characterization, be defined as target productFor Tb2Cu4(Mep)8(NO3)6(THF)。
Embodiment 4: cluster compound Tb2Cu4(Mep)8(NO3)6(THF) synthesize
Repeat embodiment 1, different, wherein Tb (NO3)3·5H2O、Cu(OAc)2·H2O and isobutylThe ratio of the amount of substance of hydramine changes to 1:1:5, and by the volume ratio of absolute ethyl alcohol and oxolane moreChange 1:3 into, control reaction simultaneously and react 10h under 45 DEG C of conditions.
Products therefrom is carried out to IR Characterization, structural characterization and Magnetic Characterization, be defined as target productFor Tb2Cu4(Mep)8(NO3)6(THF)。
Embodiment 5: cluster compound Er2Cu4(Mep)8(NO3)6(THF) synthesize
Repeat embodiment 2, different, wherein Er (NO3)3·5H2O、Cu(OAc)2·H2O, benzene firstThe ratio of the amount of substance of acid and isobutyl hydramine changes to 1:1:2:3, and by absolute ethyl alcohol and oxolaneVolume ratio change to 5:1, simultaneously control reaction under 70 DEG C of conditions, react 24h.
Products therefrom is carried out to IR Characterization, structural characterization and Magnetic Characterization, be defined as target productFor Er2Cu4(Mep)8(NO3)6(THF)。
Embodiment 6: cluster compound Er2Cu4(Mep)8(NO3)6(THF) synthesize
Repeat embodiment 2, different, wherein Er (NO3)3·5H2O、Cu(OAc)2·H2O, benzene firstThe ratio of the amount of substance of acid and isobutyl hydramine changes to 1:3:0.5:5, and by absolute ethyl alcohol and tetrahydrochysene furanThe volume ratio of muttering changes to 1:3, controls reaction simultaneously and react 50h under 50 DEG C of conditions.
Products therefrom is carried out to IR Characterization, structural characterization and Magnetic Characterization, be defined as target productFor Er2Cu4(Mep)8(NO3)6(THF)。
Claims (5)
1. isobutyl hydramine copper-rare earth hetero six core metal cluster compounds, have following chemical formula composition:
Ln2Cu4(Mep)8(NO3)6(THF)
Wherein, Ln represents rare earth metal, is selected from Tb (III) or Er (III); Mep represents isobutanolAmine ligand; THF represents oxolane;
In the time that Ln is Tb (III), the chemical formula of described cluster compound is Tb2Cu4(Mep)8(NO3)6(THF)，This cluster compound crystal belongs to monoclinic system, and space group is P21/ c, cell parameter is: α＝90.00°，β＝116.765(4)°，γ＝90.00°；
In the time that Ln is Er (III), the chemical formula of described cluster compound is Er2Cu4(Mep)8(NO3)6(THF)，This cluster compound crystal belongs to monoclinic system, and space group is P21/ c, cell parameter is: α＝90.00°，β＝113.384(2)°，γ＝90.00°。
2. isobutyl hydramine copper-rare earth hetero six core metal cluster compounds according to claim 1, its spyLevy and be: Mep-Part all adopts μ2-η3Coordination mode coordination, all Cu (II) ions are fiveCoordination tetragonal pyramid coordination geometric type, Ln (III) ion is the two cap triangular prism configurations of eight-coordinate distortion;In cluster compound, two Cu (II) ions and a Ln (III) ion are by four μ2:η3-bridging patternMep-Part bridging forms assorted three core V-structure Cu2Ln unit, two this kind three core Cu2Ln unitObtain six nuclear structures by nitrate anion bridging.
3. the synthetic method of isobutyl hydramine copper-rare earth hetero six core metal cluster compounds described in claim 1,It is characterized in that:
In the time that Ln is Tb (III), cluster compound Tb2Cu4(Mep)8(NO3)6(THF) synthetic method comprise withLower step:
1) take in proportion Tb (NO3)3·5H2O、Cu(OAc)2·H2O and isobutyl hydramine, willTb(NO3)3·5H2O and Cu (OAc)2·H2O is dissolved in polar solvent, then adds isobutyl hydramine, mix,Obtain mixed liquor;
2) gained mixed liquor is placed in reaction vessel and under 10～45 DEG C of conditions, leaves standstill reaction to complete,There are a large amount of crystal to generate, isolate crystal, washing, dry, obtain cluster compoundTb2Cu4(Mep)8(NO3)6(THF)；
In the time that Ln is Er (III), cluster compound Er2Cu4(Mep)8(NO3)6(THF) synthetic method comprise withLower step:
A) take in proportion Er (NO3)3·5H2O、Cu(OAc)2·H2O, benzoic acid and isobutyl hydramine,By Er (NO3)3·5H2O、Cu(OAc)2·H2O and benzoic acid are dissolved in polar solvent, then add isobutylHydramine, mixes, and obtains mixed liquor;
B) gained mixed liquor is placed in container, is evacuated to vacuum after liquid nitrogen frozen, sealing by fusing, then inUnder 40～80 DEG C of conditions, reaction, to completely, is isolated crystal, and washing is dry, obtains cluster compoundEr2Cu4(Mep)8(NO3)6(THF)。
4. synthetic method according to claim 3, is characterized in that: described polar solventFor the combination of absolute ethyl alcohol and oxolane.
5. synthetic method according to claim 4, is characterized in that: in the group of polar solventCheng Zhong, the ratio of the volume ratio of absolute ethyl alcohol and oxolane is less than or equal to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410300834.4A CN104031096B (en) | 2014-06-27 | 2014-06-27 | Isobutyl hydramine copper-rare earth hetero six core metal cluster compound and synthetic methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410300834.4A CN104031096B (en) | 2014-06-27 | 2014-06-27 | Isobutyl hydramine copper-rare earth hetero six core metal cluster compound and synthetic methods thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104031096A CN104031096A (en) | 2014-09-10 |
| CN104031096B true CN104031096B (en) | 2016-05-25 |
Family
ID=51462113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410300834.4A Expired - Fee Related CN104031096B (en) | 2014-06-27 | 2014-06-27 | Isobutyl hydramine copper-rare earth hetero six core metal cluster compound and synthetic methods thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104031096B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402944A (en) * | 2014-11-15 | 2015-03-11 | 辽宁石油化工大学 | Neodymium-copper-glutamic acid-imidazole monocrystal complex and preparation method thereof |
| CN104530133B (en) * | 2014-12-29 | 2017-04-05 | 广西师范大学 | A kind of six core manganese cluster compounds and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120103913A1 (en) * | 2010-10-29 | 2012-05-03 | Hiroaki Kiyoto | Method for removing metallic ions from contaminated water by sorption onto magnetic particles coated with ligands |
| CN102516316A (en) * | 2011-11-04 | 2012-06-27 | 南开大学 | Preparation method of oxamide macrocyclic octanuclear complex [Cu6Ln2] (Ln=Gd, tb, dy, ho) |
| CN103310938A (en) * | 2013-06-27 | 2013-09-18 | 黑龙江大学 | Co-Dy type single molecule magnetic material and preparation method thereof |
-
2014
- 2014-06-27 CN CN201410300834.4A patent/CN104031096B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120103913A1 (en) * | 2010-10-29 | 2012-05-03 | Hiroaki Kiyoto | Method for removing metallic ions from contaminated water by sorption onto magnetic particles coated with ligands |
| CN102516316A (en) * | 2011-11-04 | 2012-06-27 | 南开大学 | Preparation method of oxamide macrocyclic octanuclear complex [Cu6Ln2] (Ln=Gd, tb, dy, ho) |
| CN103310938A (en) * | 2013-06-27 | 2013-09-18 | 黑龙江大学 | Co-Dy type single molecule magnetic material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| A 1D copper(II) chain featuring novel hexanuclear secondary building blocks:Synthesis, crystal structure and magnetic property;Suni Qin等，;《Inorganic Chemistry Communications》;20110316;第14卷;第784-787页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104031096A (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Tricarboxylate-based Gd III coordination polymers exhibiting large magnetocaloric effects | |
| Meihaus et al. | Dilution-induced slow magnetic relaxation and anomalous hysteresis in trigonal prismatic dysprosium (III) and uranium (III) complexes | |
| CN102136339B (en) | Dysprosium monomer magnet with dual functions of ferromagnetic and ferroelectric and preparation method thereof | |
| Li et al. | New 3d–4f heterometallic clusters built from mixed glycine and iminodiacetate acid: dioctahedron {La 2 Ni 9} and onion-like {Gd 5}⊂{Ni 12} with interesting magnetocaloric effect | |
| CN103833793A (en) | Nickel-coordination polymer and preparation method thereof | |
| Zhou et al. | Filling the Missing Links of M3 n Prototype 3d-4f and 4f Cyclic Coordination Cages: Syntheses, Structures, and Magnetic Properties of the Ni10Ln5 and the Er3 n Wheels | |
| Li et al. | Doping cobalt into a [Zn 7] cluster-based MOF to tune magnetic behaviour and induce fluorescence signal mutation | |
| Das et al. | pH dependent facile synthesis of di-and trinuclear oxime based Cu (II) complexes: antiferromagnetic coupling in the dinuclear cores and spin frustration in the triangular core | |
| CN104031096B (en) | Isobutyl hydramine copper-rare earth hetero six core metal cluster compound and synthetic methods thereof | |
| Long et al. | Coordination site manipulation of the annular growth mechanism to assemble chiral lanthanide clusters with different shapes and magnetic properties | |
| Zhang et al. | Hybrid materials based on metal–organic coordination complexes and cage-like polyoxovanadate clusters: Synthesis, characterization and magnetic properties | |
| CN103818971B (en) | A kind of preparation method of superparamagnetism ferrite nano particles | |
| Song et al. | Preparation, crystal structures and magnetic properties of 12-metallacrown-4 complexes with the donors on the organic periphery of molecule | |
| Sun et al. | Tricine-supported polyoxo (alkoxo) lanthanide cluster {Ln15}(Ln= Eu, Gd, Tb) with magnetic refrigerant and fluorescent properties | |
| CN104151365B (en) | Gd-Fe dissimilar metal compound with magnetic refrigerating function and preparation method thereof | |
| CN104332272B (en) | A kind of rareearth magnetic material and preparation method thereof | |
| CN104098612A (en) | 3d-4f heteronuclear metal magnetic complex and preparing method and application thereof | |
| Tarasenko et al. | A series of three-dimensional coordination polymers with general formula [{Ln (H2O) n}{Re6Te8 (CN) 6}]· xH2O (Ln= Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb; n= 3, 4, x= 0, 2.5) | |
| Langley et al. | Magnetic Exchange Effects in {CrIII2DyIII2} Single Molecule Magnets Containing Alcoholamine Ligands | |
| Khan et al. | Using the flexible ligand bis (2-hydroxyethyl) amino–tris (hydroxymethyl) methane (“bis–tris”) to access a family of 3d–4f Mn III 4 Ln 4 complexes | |
| Afrati et al. | Copper inverse-9-metallacrown-3 compounds showing antisymmetric magnetic behaviour | |
| An et al. | 3d Ion-driven hexanuclear heterometallic clusters with amazing structures and magnetic properties | |
| CN102030785A (en) | Method for preparing exoticmetal low-temperature magnetic material | |
| Zhou et al. | Lanthanide-ion-tuned magnetic properties in a series of three-dimensional cyano-bridged Ln III Wv assemblies | |
| 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 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160525 Termination date: 20190627 |