CN105070497B - Cobalt-based single molecular magnetses synthetic method - Google Patents
Cobalt-based single molecular magnetses synthetic method Download PDFInfo
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- CN105070497B CN105070497B CN201510524227.0A CN201510524227A CN105070497B CN 105070497 B CN105070497 B CN 105070497B CN 201510524227 A CN201510524227 A CN 201510524227A CN 105070497 B CN105070497 B CN 105070497B
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Abstract
The invention discloses a kind of cobalt-based single molecular magnetses synthetic method, using cobalt salt and 2 hydroxybenzimidazole parts, and participated in by azides ion, cobalt-based single molecular magnetses are prepared under the conditions of solvent hot system or microwave reaction.Experiment shows that present invention process is safe and simple, and cost of material is cheap, overcomes the shortcoming of conventional solwution method poor reproducibility, gained [Co12(L)15(N3)7](NO3)2·2(CH3OH)·2(H2O) single molecular magnetses of (L is 2 methylol benzimidazole parts) are the crystal of red hexagonal prism shape, and purity is high, crystalline size big (caning be controlled in 2 × 1 × 1.5mm), yield height (more than 50%).
Description
Technical field
The present invention relates to single molecular magnetses preparation field, more particularly to a kind of cobalt-based single molecular magnetses synthetic method.
Background technology
Single molecular magnetses are a kind of molecular magnet of truly nano-scale in fact, are that a class has identical chemistry knot
The aggregation of the molecule of structure, is generally arranged in lattice with the formal rule of crystal, weak because the magnetic between molecule exchanges very weak
To may typically only exist dipole-dipole effect (dipole-dipole interaction), it is believed that the magnetic behavior of macroscopic view
It is exactly the magnetic behavior only showed by individual molecule.There is the compound of " single molecular magnetses " behavior, they are in magnetic
Following two conditions must are fulfilled in property：First, with big spin ground states；Second, there is significantly negative anisotropy in molecule,
Namely magnetic anisotropy (the D of moleculemol) value be less than zero.Therefore, the energy barrier for how improving existing single molecular magnetses hinders in other words
Temperature is filled in, is just centered around and how to improve ground state spin values (ST) and anisotropy (D) on.The generation of big ground state spin is derived from
Intramolecular ferromagnetic interaction or the result lost one's head due to being spinned caused by specific topological structure.In the last few years, chemical work
Authors try to synthesize the multinuclear cluster basigamy adduct molecule that Spin multiplicity is tried one's best high, and them are then made again with Spin-Parallel
Mode is assembled.The single molecular magnetses (SMM) found at present mainly include Mn ion clusters, Fe ion clusters and its derivative etc.
Two classes, and to the fewer of cobalt cluster single molecular magnetses report, because divalence cobalt single ion magnetic anisotropy (Dion) usually big
Conclusive cause D in zero, and generallymol＞ 0.It is challenge for the control synthesis of cobalt cluster compound in itself, with solwution method
During synthesis cobalt-based cluster compound, often due to being influenceed compared with by conditions such as ambient temperature, air draughts, inconvenience control synthesis repeats to imitate
Really poor, so that being usually only capable of obtaining several test mono-crystalline structures, the consumption for being used in conjunction to do basic test property is all inadequate.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of process safety is simple, favorable reproducibility cobalt-based single molecular magnetses
Synthetic method, products obtained therefrom purity is high, crystalline size is big, yield is high.
In order to solve the above technical problems, the present invention uses following technical scheme：Cobalt-based single molecular magnetses synthetic method, is utilized
Cobalt salt and 2- hydroxybenzimidazole parts, and participated in by azides ion, prepare cobalt under the conditions of solvent hot system or microwave reaction
Base single molecular magnetses.
Above-mentioned cobalt-based single molecular magnetses synthetic method, is carried out according to the following steps：
(1) 8mL is contained into Co (NO3)2·6H2O 1mmol, NaN30.5mmol and 2- methylol benzimidazoles 0.5mmol
Absolute methanol solution, in atmosphere with magnetic stirrer 5 minutes；
(2) reactant solution is transferred in the container with polytetrafluoroethylsubstrate substrate, and adjusted with triethylamine after pH to 5-7
Closed, heating reacts it, then cools down at room temperature；
(3) reacted solution is filtered and washed with absolute methanol, produce the crystal of red hexagonal prism shape.
Container used is the hydrothermal reaction kettle of 15 milliliters of volume in step (2), and mode of heating makes instead to directly heat container
Answer thing solution to 140 DEG C~160 DEG C and kept for 72 hours.
Vessel volume 60mL used counteracting tank in step (2), mode of heating is that auxiliary is heated to 100 DEG C in micro-wave oven
And 1min is kept, it is then heated to 120 DEG C~140 DEG C and keeps 10min.
The power that heating is aided in micro-wave oven is that 300w, pressure are 3.2atm.
The molecular formula of gained cobalt-based single molecular magnetses is [Co12(L)15(N3)7](NO3)2·2(CH3OH)·2(H2O), R- is belonged to
3 space groups, wherein L are 2- methylol benzimidazole parts, and cell parameter is α=90 (deg), β=90 (deg), γ=90 (deg).
The problem of existing for the synthesis of current cobalt-based single molecular magnetses, inventor designs and establishes a kind of cobalt-based unimolecule
Magnet synthetic method, using cobalt salt and 2- hydroxybenzimidazole parts, and is participated in by azides ion, in solvent hot system or microwave
Cobalt-based single molecular magnetses are prepared under reaction condition.Its principle is：Under HTHP, strong basicity reaction system, 2- hydroxy benzos
Imidazole ligands slough a hydrogen atom on hydroxyl, so that hydroxyl oxygen atom can be with μ3- or μ2- wait a variety of bridging forms to construct cluster conjunction
Thing.Azides ion is as multi-functional minibridge part, and active promoting function is played in the formation to cluster compound, and two kinds of bridge ligands are in magnetic
Property cluster compound in can transmit very well ferromagnetic exchange effect, be single molecular magnetses structure play place mat effect.Experiment shows, this
Invented technology is safe and simple, and cost of material is cheap, overcomes the shortcoming of conventional solwution method poor reproducibility, gained [Co12(L)15
(N3)7](NO3)2·2(CH3OH)·2(H2O) single molecular magnetses of (L is 2- methylol benzimidazoles part) are red six prism
The crystal of shape, purity is high, crystalline size big (caning be controlled in 2 × 1 × 1.5mm), yield height (more than 50%).
Brief description of the drawings
Fig. 1 is the structure chart of the cobalt-based single molecular magnetses obtained by the present invention.
Fig. 2 is the χ of the cobalt-based single molecular magnetses obtained by the present inventionmT-T curves (a) and the M/H curves (b) in T=2K.
Fig. 3 is the direct current outfield of the cobalt-based single molecular magnetses obtained by the present invention to determine under 0Oe (a) and 1000Oe (b)
The alternating temperature ac magnetic susceptibility figure of different frequency.
Fig. 4 is that the frequency-changing AC magnetic susceptibility outside the different direct currents of 2.1K of the cobalt-based single molecular magnetses obtained by the present invention off field is bent
Cole-Cole curves under line (a figures) and different temperatures (b schemes, and solid line is debye models fittings result).
Embodiment
Embodiment 1
(1) 8mL is contained into Co (NO3)2·6H2O 1mmol, NaN30.5mmol and 2- methylol benzimidazoles 0.5mmol
Absolute methanol solution, in atmosphere with magnetic stirrer 5 minutes；
(2) reactant solution is transferred in the hydrothermal reaction kettle with polytetrafluoroethylsubstrate substrate (15 milliliters of volume), be used in combination
Closed after triethylamine regulation pH to 6, directly heating container makes reactant solution to 140 DEG C and is kept for 72 hours, then in room temperature
Lower cooling；
(3) reacted solution is filtered and washed with absolute methanol, produce red hexagonal prism shape crystal (2 × 1 ×
1.5mm)。
Embodiment 2
(1) 8mL is contained into Co (NO3)2·6H2O 1mmol, NaN30.5mmol and 2- methylol benzimidazoles 0.5mmol
Absolute methanol solution, in atmosphere with magnetic stirrer 5 minutes；
(2) reactant solution is transferred in the counteracting tank (volume 60mL) with polytetrafluoroethylsubstrate substrate, and uses triethylamine
Adjust closed after pH to 6, auxiliary heats (Power=300w, P=3.2atm) to 100 DEG C and keeps 1min in micro-wave oven, so
After be heated to 120 DEG C and keep 10min, then cool down at room temperature；
(3) reacted solution is filtered and washed with absolute methanol, produce red six rib of shape same as Example 1
The crystal of post shapes
Identify after testing, the molecular formula of cobalt-based single molecular magnetses obtained by Examples 1 and 2 is [Co12(L)15(N3)7]
(NO3)2·2(CH3OH)·2(H2O), R-3 space groups are belonged to, wherein L is 2- methylol benzimidazole parts, and cell parameter isα=90 (deg), β=90
(deg), γ=90 (deg).
As shown in figure 1, in the structure of gained cobalt-based single molecular magnetses, by 12 core cationic cobalts of a positive divalence disk like
Cluster [Co12(L)15(N3)7]2+With two counter anion NO3 -, and some solvent molecules composition in lattice, wherein 12 cores are positive
Ionic cobalt (II) has clustered round S4Symmetry.In " plate " of the cobalt-based cluster compound, cluster core [Co12(μ2-L)6(μ3-L)9(μ2-
N3)6(μ3-N3)]2+It is considered as using nitrine bridge as the bottom surface of the plate of template, 6 μ2Alcoxyl atom and 3 μ2Azide bridge 9
Cobalt ions is in the edge at dish bottom, and they pass through 9 μ respectively3- OR and 3 μ3-N33 cobalt ions bridgings at center get up, in
3 cobalt ions of the heart are by μ3-N3Template bridging, ultimately forms disk like compound as shown above.All cobalt ions are adopted
Take the pattern of hexa-coordinate, 3 CoIIIon takes CoN2O4, 3 CoIIIon takes CoN3O3, 3 CoIIIon takes CoN4O2、
3 CoIIIon takes CoN5The octahedra geometric configuration of O deformation.The distance between minimum cobalt cobalt is in clusterThe distance between most long cobalt cobalt is
As shown in Fig. 2 with the reduction of temperature, its χmT values slowly rise in 50K, then rapidly rise to 11K and reach
One sharp maximum 90.5cm3mol-1K, finally quickly falls to 2K.When H increases to 5T, M is 24.3N β, still without
Saturation is reached, also has the trend slowly risen.This shows that cobalt-based cluster compound has larger ground state spin values.
As shown in fig. 3, it was found that the increase of outer DC fields, promotes the real and imaginary parts value of ac magnetic susceptibility accordingly to increase, and
And slightly increase the corresponding temperature of imaginary part maximum under high frequency；And with the increase in direct current outfield, lower frequency area, imaginary part
Appearance, first and last, the peak value of the imaginary part of ac magnetic susceptibility are moved toward high frequency direction.
As shown in figure 4, low-temperature space, which tests out Cole-Cole curves, is significantly closer to semicircle, and by Debye models fittings
Go out Cole-Cole curves and obtain α=0.33-0.39.
Claims (5)
1. a kind of cobalt-based single molecular magnetses synthetic method, it is characterised in that using cobalt salt and 2- hydroxybenzimidazole parts, and have
Azides ion is participated in, and cobalt-based single molecular magnetses are prepared under the conditions of solvent hot system or microwave reaction；Specifically enter according to the following steps
OK：
(1) 8mL is contained into Co (NO3)2·6H2O 1mmol,NaN30.5mmol and 2- methylol benzimidazoles 0.5mmol nothing
Water beetle alcoholic solution, in atmosphere with magnetic stirrer 5 minutes；
(2) reactant solution is transferred in the container with polytetrafluoroethylsubstrate substrate, and adjusts close after pH to 5-7 with triethylamine
Close, heating reacts it, then cools down at room temperature；
(3) reacted solution is filtered and washed with absolute methanol, produce the crystal of red hexagonal prism shape.
2. cobalt-based single molecular magnetses synthetic method according to claim 1, it is characterised in that container used is in step (2)
The hydrothermal reaction kettle that 15 milliliters of volume, mode of heating makes reactant solution to 140 DEG C~160 DEG C and kept to directly heat container
72 hours.
3. cobalt-based single molecular magnetses synthetic method according to claim 1, it is characterised in that container used is in step (2)
Volume 60mL counteracting tank, mode of heating is that auxiliary is heated to 100 DEG C and keeps 1min in micro-wave oven, is then heated to 120
DEG C~140 DEG C and keep 10min.
4. cobalt-based single molecular magnetses synthetic method according to claim 3, it is characterised in that：Auxiliary adds in the micro-wave oven
The power of heat is that 300w, pressure are 3.2atm.
5. cobalt-based single molecular magnetses synthetic method according to claim 1, it is characterised in that：Gained cobalt-based single molecular magnetses
Molecular formula is [Co12(L)15(N3)7](NO3)2·2(CH3OH)·2(H2O), R-3 space groups are belonged to, wherein L is 2- methylol benzos
Imidazole ligands, cell parameter is
α=90 (deg), β=90 (deg), γ=90 (deg).
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| JP2006245313A (en) * | 2005-03-03 | 2006-09-14 | Tokyo Univ Of Science | METHOD OF MANUFACTURING SmCo-BASED MAGNETIC PARTICULATE |
| CN102641702A (en) * | 2012-05-14 | 2012-08-22 | 北京化工大学 | Ionic liquid functionalized magnetic nanoparticle and preparation method and application thereof |
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| CN104021911A (en) * | 2014-06-25 | 2014-09-03 | 桂林理工大学 | Magnetic material [Co2Na2(hmb)4(N3)2(CH3CN)2] (CH3CN)2 and synthetic method thereof |
| CN104130292A (en) * | 2014-07-04 | 2014-11-05 | 陈秀琼 | Three dimensional coordination polymer with double core structure and preparation method thereof |
| CN104356166A (en) * | 2014-11-22 | 2015-02-18 | 刘国政 | Cobalt-containing compound based on flexible nitrogen-containing and carboxylic acid-containing dual ligands and preparation method thereof |
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- 2015-08-25 CN CN201510524227.0A patent/CN105070497B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006245313A (en) * | 2005-03-03 | 2006-09-14 | Tokyo Univ Of Science | METHOD OF MANUFACTURING SmCo-BASED MAGNETIC PARTICULATE |
| CN102641702A (en) * | 2012-05-14 | 2012-08-22 | 北京化工大学 | Ionic liquid functionalized magnetic nanoparticle and preparation method and application thereof |
| CN102942527A (en) * | 2012-10-17 | 2013-02-27 | 西北工业大学 | Vinyl alkyl imidazole tetrathiocyanate cobalt (II) magnetic ionic liquids and synthetic methods thereof |
| CN103714932A (en) * | 2013-12-30 | 2014-04-09 | 北京工业大学 | Co zero-dimension single-molecular magnet material, preparation method and application of Co zero dimension single-molecular magnet material |
| CN104021911A (en) * | 2014-06-25 | 2014-09-03 | 桂林理工大学 | Magnetic material [Co2Na2(hmb)4(N3)2(CH3CN)2] (CH3CN)2 and synthetic method thereof |
| CN104130292A (en) * | 2014-07-04 | 2014-11-05 | 陈秀琼 | Three dimensional coordination polymer with double core structure and preparation method thereof |
| CN104356166A (en) * | 2014-11-22 | 2015-02-18 | 刘国政 | Cobalt-containing compound based on flexible nitrogen-containing and carboxylic acid-containing dual ligands and preparation method thereof |
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