CN107973913A - Frame material with spin crossover property and its preparation method and application - Google Patents
Frame material with spin crossover property and its preparation method and application Download PDFInfo
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Abstract
Frame material with spin crossover property and its preparation method and application, the chemical formula of the material is C91H72Fe2N16O24S4, Mr=2013.63gmol‑1, tetragonal system, space group P42During/n.T=250K, cell parameter is a=13.9160 (17), b=13.9160 (17),During T=106K, cell parameter is a=13.8547 (4), b=13.8547 (4),Not only the advantages of structure diversity of MOFs had been remained in the material, but also the electron transfer capacity with SCO systems, have obvious spin crossover performance；The material is more sensitive for ambient pressure, is a kind of preferable functional material, has the potential using value as materials such as information storage, molecular switch or pharmaceutical diagnosis.
Description
Technical field
The present invention relates to feature crystalline material and its preparation and use.
Background technology
In in the past few decades, there is 3d4-3d7The spin-spin intersection of height of the transition metal ions of electron configuration
(spin-crossover, SCO) phenomenon has been subjected to widely paying close attention in field of coordinative chemistry.Electroactive spin crossover chemical combination
Thing (generally octahedral Fe (II) and Fe (III) compound) can be used as bistable material, its structure, color, optics or magnetic
Property such as hot, pressure and the change in magnetic field or light exciting significant change occur because of environmental stimuli.Therefore chiasmate
Compound is a kind of preferable functional material, has the potential application as materials such as information storage, molecular switch or pharmaceutical diagnosis
Value.
In extension system by between the active coordination site of bridge ligand be directly connected to promote SCO centers it
Between interaction, therefore more and more higher-dimension complex is concerned by people.More it is noted that this class framework
Material not only includes different short distance or long range interaction, more embodies some charming properties, such as：Modularity, choosing
Selecting property and reversible adsorption and desorption.However, the formation of the complex of higher dimensionality is influenced by many factors,
It is even more a huge challenge to obtain expected topological structure.In this regard, design and select suitably to have and can repair
The organic linking ligand of the trunk of decorations and more tie point is a kind of preferable acquisition expected structure and the novel frame of property
The method of structure.
The content of the invention
It is an object of the invention to provide a kind of feature crystalline material.
First, the present invention discloses a kind of frame material with spin crossover property, and the chemical formula of the material is
C91H72Fe2N16O24S4, Mr=2013.63gmol-1, tetragonal system, space group P42During/n.T=250K, cell parameter a
=13.9160 (17), b=13.9160 (17),During T=106K, cell parameter a=13.8547
(4), b=13.8547 (4),
Further, the present invention discloses the preparation method of the above-mentioned frame material with spin crossover property, including following step
Suddenly：Ferrous salt, potassium rhodanide and ascorbic acid are added into methanol, agitation and filtration removes precipitation；Gained filtrate exists with TINM
Red crystals are obtained in reaction under room temperature in methanol, i.e., the described frame material with spin crossover property.
It is wherein described and TINM (tetrakis (isonicotinoxymethyl) methane) there is Formulas I structure
Organic ligand：
The frame material with spin crossover property of above-mentioned acquisition is synthesized with flexible multiple tooth bridging ligand TINM
SCOFs (spin-crossover complexes with metal-organic frameworks) compound.Obtained
Not only the advantages of structure diversity of MOFs (metal-organic frameworks) had been remained in new material compound, but also tool
There is the electron transfer capacity of SCO systems, there is obvious spin crossover performance in alternating temperature section；Meanwhile pressure test shows this
Material is more sensitive for ambient pressure, is a kind of preferable functional material, has as information storage, molecular switch or pharmacy
The potential using value of the materials such as diagnosis.And the product obtained has extremely strong stability, heat endurance is good.Mutually should chemical combination
The preparation method of thing utilizes Fe2+And TINM, three-dimensional spin crossover frame compound is made by simple technique.Synthetic method
Simple and efficient, easily operated, equipment of less demanding need to have excellent industrial application prospect.
Brief description of the drawings
4 width of attached drawing of the present invention：
Fig. 1 is the dissymmetrical structure unit figure of material of the present invention.
Fig. 2 is the three dimensional topology figure of material of the present invention, wherein：
Fig. 2 (a) is the coordination mode figure of material center ferrous ion, and can be reduced to square constructs module.
Fig. 2 (b) is material ligand structure figure, and can be reduced to tetrahedroid constructs module.
Fig. 2 (c) and (d) are by the three-dimensional PtS structures of the square compound constructed with tetrahedral modules, wherein Fig. 2 (c)
It is to be obtained along a axis, Fig. 2 (d) along b axis.
Fig. 2 (e) is the interspersed structure chart of compound
Fig. 3 is the magnetic chart of material of the present invention.
Fig. 4 is the thermal multigraph of material of the present invention.
Embodiment
The present invention is to adjust Fe2+Coordination with TINM is means, prepares the three-dimensional framework material with spin crossover property.
The preparation method includes adding ferrous salt, potassium rhodanide and ascorbic acid into methanol, and agitation and filtration removes precipitation；Gained
Filtrate and TINM in methyl alcohol in react the step of under room temperature.Red crystals obtained by reaction is completed, i.e. tool of the invention
There is the frame material of spin crossover property.
Wherein described TINM is the organic ligand for having Formulas I structure
More specifically, in the preparation process, ferrous salt, potassium rhodanide, the molar ratio of ascorbic acid and TINM
According to ferrous ion:Potassium rhodanide:Ascorbic acid:TINM=1:2~4：0.025~0.1:0.2~0.35.
More specifically in embodiment, the preparation method includes the following steps：
(1) molysite, potassium rhodanide, ascorbic acid are added in methanol solution, agitation and filtration removes precipitation；
Ferrous salt preferably sulfuric acid ferrous iron, ferrous perchlorate or its mixture therein.
(2) liquid layer i, liquid layer ii and liquid layer iii are slowly injected into container successively from bottom to up, stands 2-3 days until liquid layer
Ii has red bright crystal to be separated out along chamber wall：Wherein：
Liquid layer i is filtrate and the water of step (1) according to volume ratio 1:0.5~2 mixture；It is preferred that according to ferrous salt and liquid
Layer i is 1mmol than it:20~40ml sets the usage amount of material；
Liquid layer ii is methanol；
Liquid layer iii is the methanol solution of TINM, preferably using TINM and methanol according to 1mmol:60~120ml mixing gained
Solution.
The volume ratio of liquid layer i, ii and iii are 1:0.5~1:1~2.
As an example, above-mentioned preparation method of the present invention can be specifically described but is not limited to：
By FeSO4·7H2O (0.2mmol) and KSCN (0.4mmol) and a small amount of ascorbic acid (5mg) add 4ml's
5min is stirred in methanol solution, is filtered to remove precipitation, is added in the colorimetric cylinder of 20ml, then adds the deionized water mixing of 4ml
Uniformly.The methanol of 5ml is spread as transition zone in centre, and the superiors spread methanol solutions of the 4ml dissolved with 0.05mmol TINM.Through
After spending 2-3 days, the mid layer section of test tube has red bright crystal and is separated out along tube wall.
Crystal structure test carried out with X-ray powder diffraction instrument to the red crystals that are obtained, test temperature for 106K and
250K.It is known that its chemical formula is C from crystal structure analysis91H72Fe2N16O24S4, Mr=2013.63gmol-1, just
Prismatic crystal system, space group P42/ n, Z=2.T=250K, cell parameter are a=13.9160 (17), b=13.9160 (17),T=106K, cell parameter are a=13.8547 (4), b=13.8547
(4),Crystal data shows that this is that first case has the two of PtS configurations
Intert three-dimensional intersection compound again.As shown in Figure 1, each asymmetric cell contains an independent Fe atom, two SCN-
The half (N1, N2) of group (N3, N3C) and bridging ligand TINM, the in addition also free ligand of a quarter.Fe atoms position
In octahedral coordination center, the pyridine ring of four TINM ligands is respectively from four N positioned at equatorial plane of Fe coordinations,
And two axial N come from SCN-.Bond distance of the compound at 250 and 106K is as shown in table 1, under the line the bond distance of plane (it is respectively
106K and 250K)] than axial locationIt is long.
Both is respectively in the change of different temperatures average bond lengthWith
Bond distance of 1 compound of table at 250 and 106KWith bond angle [°]
In table 1：
*：-x+3/2,-y-1/2,z；**：y+1/2,-x,z+1/2；***：-y+1,x-1/2,z+1/2.
<dFe-N>bRepresent average Fe-N bond distance.
S-H cRepresent in S and interspersed structure close to the distance between H.
O-H dRepresent the O-H distances between Subjective and Objective.
O-H eThe distance between O-H in representational framework
Further, to the red crystals material that is obtained in Quantum Design MPMS XL-7 magnetometer
On carried out spin crossover property research, research approach is as follows：
Magnetic data carries out on Quantum Design MPMS XL-7 magnetometer, in temperature range 2-
300K, 5000Oe outfield, 1K/min-1Received under sweeping rate patterns, the application of pressure relies primarily on EasyLab
Mcell 10hydrostatic pressure cell.In 2-300K, applied field strengths 5kOe, carries out under different pressures
Magnetization curve is tested, such as Fig. 3, it is illustrated that show that the compound embodies intersection property in alternating temperature section.Meanwhile pressure test shows
Intersection is more sensitive for the ambient pressure changed with molecular size and volume change.χMT values are with ambient pressure
Increase and increase, while transition temperature is also correspondingly moved towards high-temperature region.Transition temperature in cooling procedure under different temperatures
Parameter and flex point be listed in shown in Fig. 3 illustrations.According to ligand field theory, when external pressure is below or above 7Kbar, T1/2And P
Show good linear relationship.During starting, external pressure increase can cause volume contraction, because the structure of the compound compares
It is soft.It is not only volume contraction caused by pressure effect when impressed pressure is more than 7Kbar, and is probably to change FeIIIn
Crystalline field field strength around the heart.
The structure of obtained red crystals material uses Mo K radiation on Oxford diffractometer
sourceCollection obtains.Test temperature is 106K and 250K, its chemical formula is
C91H72Fe2N16O24S4, Mr=2013.63gmol-1, tetragonal system, space group P42/ n, Z=2.T=250K, cell parameter
For a=13.9160 (17), b=13.9160 (17),T=106K, structure cell
Parameter is a=13.8547 (4), b=13.8547 (4),
Magnetic Test is carried out to the red crystals material obtained, magnetic data is in Quantum Design MPMS XL-
Carried out on 7magnetometer, in temperature range 2-300K, 5000Oe outfield, 1K/min-1Received under sweeping rate patterns
, the application of pressure relies primarily on EasyLab Mcell 10hydrostatic pressure cell.Fig. 3 is compound
χMT values correspond to the mapping of T at various pressures.Illustration is T1/2With the graph of a relation of P.
Fig. 3 shows that the compound embodies intersection property in alternating temperature section.Under normal pressure, the χ of room temperatureMT values are
4.23cm3K mol-1, corresponding to ferrous high spin state.As temperature reduces, χMT values are almost unchanged until temperature drops
To 170K, then gradually decrease up to and a new new platform from 60 to 17.5K occur, this process indicates compound
Not exclusively transformation.χ after 17.5KMT is worth reducing rapidly the zero-field splitting that be attributed to remaining divalence high ferro.At this
Hysteresis is not occurred in the heating and cooling process of a circulation.Meanwhile pressure test shows cross-pair in big with molecule
Small and volume change and the ambient pressure that changes is more sensitive.χMT values increase with the increase of ambient pressure, while change temperature
Degree is also correspondingly moved towards high-temperature region.The parameter and flex point of transition temperature in cooling procedure under different temperatures are listed in Fig. 3 and insert
Shown in figure.According to ligand field theory, when external pressure is below or above 7Kbar, T1/2Good linear relationship is showed with P.
Thermal gravimetric analysis results such as attached drawing 4 to the red crystals material obtained.It can be seen from the figure that it is with extremely strong
Stability, heat endurance is good.
Claims (10)
1. the frame material with spin crossover property, it is characterised in that the chemical formula of the material is C91H72Fe2N16O24S4,
Mr=2013.63gmol-1, tetragonal system, space group P42During/n.T=250K, cell parameter is a=13.9160 (17), b
=13.9160 (17),During T=106K, cell parameter is a=13.8547 (4), b=13.8547 (4),
2. the frame material according to claim 1 with spin crossover property, it is characterised in that the structure cell of the material
In Molecules Z=2；Unit cell volume in 250K,In 106K,
3. the frame material according to claim 1 with spin crossover property, it is characterised in that the material is that have
The two-fold penetration three-dimensional compound of PtS configurations.
4. the frame material according to claim 1 with spin crossover property, it is characterised in that the thermogravimetric of the material
Analysis curve has weightless peak at 300 ± 10 DEG C.
5. the preparation method of the frame material with spin crossover property described in claim 1, includes the following steps：
Ferrous salt, potassium rhodanide and ascorbic acid are added into methanol, agitation and filtration removes precipitation；Gained filtrate exists with TINM
Red crystals are obtained in reaction under room temperature in methanol, i.e., the described frame material with spin crossover property.
6. preparation method according to claim 5, it is characterised in that the ferrous salt, potassium rhodanide, ascorbic acid and
TINM's feeds intake mole according to ferrous ion:Potassium rhodanide:Ascorbic acid:TINM=1:2~4：0.025~0.1:0.2~
0.35。
7. preparation method according to claim 6, it is characterised in that include the following steps：
(1) ferrous salt, potassium rhodanide, ascorbic acid are added in methanol solution, agitation and filtration removes precipitation；
(2) liquid layer i, liquid layer ii and liquid layer iii are slowly injected into container successively from bottom to up, is stood until liquid layer ii has red thoroughly
Bright crystal separates out：Wherein：
Liquid layer i is filtrate and the water of step (1) according to volume ratio 1:0.5~2 mixture；
Liquid layer ii is methanol；
Liquid layer iii is the methanol solution of TINM；
The volume ratio of liquid layer i, ii and iii are 1:0.5~1:1~2.
8. preparation method according to claim 7, it is characterised in that the ratio of ferrous salt and the liquid layer i is 1mmol:
20~40ml；The ratio of TINM and methanol is 1mmol in the liquid layer iii:60~120ml.
9. preparation method according to claim 5, it is characterised in that the ferrous salt is selected from ferrous sulfate, perchloric acid
Ferrous or its mixture.
10. the frame material with spin crossover property described in claim 1 is preparing information storage material, molecular switch material
Application in material or pharmaceutical diagnosis material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912339A (en) * | 2018-06-28 | 2018-11-30 | 江汉大学 | A kind of ferrous metal organic framework materials and preparation method thereof |
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|---|---|---|---|---|
| CN101712695A (en) * | 2009-11-27 | 2010-05-26 | 南开大学 | Two-dimensional Fe(II) complex pressure-caused spin conversion materials, preparation method and application thereof |
| CN103145765A (en) * | 2013-03-21 | 2013-06-12 | 新疆大学 | Preparation method of spin-crossover nanometer materials of mononuclear Fe (II) complexes |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101712695A (en) * | 2009-11-27 | 2010-05-26 | 南开大学 | Two-dimensional Fe(II) complex pressure-caused spin conversion materials, preparation method and application thereof |
| CN103145765A (en) * | 2013-03-21 | 2013-06-12 | 新疆大学 | Preparation method of spin-crossover nanometer materials of mononuclear Fe (II) complexes |
Non-Patent Citations (2)
| Title |
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| KALLE I. NA1TTINEN ET AL.: "《Ligand Entrapment in Twofold Interpenetrating PtS Matrixes by Metallo-Organic Frameworks》", 《INORGANIC CHEMISTRY》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912339A (en) * | 2018-06-28 | 2018-11-30 | 江汉大学 | A kind of ferrous metal organic framework materials and preparation method thereof |
| CN108912339B (en) * | 2018-06-28 | 2021-04-30 | 江汉大学 | Iron metal organic framework material and preparation method thereof |
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