CN104844630B - A kind of coordination polymer of copper and preparation method thereof - Google Patents
A kind of coordination polymer of copper and preparation method thereof Download PDFInfo
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- CN104844630B CN104844630B CN201510182229.6A CN201510182229A CN104844630B CN 104844630 B CN104844630 B CN 104844630B CN 201510182229 A CN201510182229 A CN 201510182229A CN 104844630 B CN104844630 B CN 104844630B
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- Prior art keywords
- copper
- coordination polymer
- ethanol
- bib
- tricarboxylic acids
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- 239000010949 copper Substances 0.000 title claims abstract description 28
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 19
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 9
- MMHLSHSAOIJBHI-UHFFFAOYSA-N 5-(3-carboxyphenyl)benzene-1,3-dicarboxylic acid Chemical class OC(=O)C1=CC=CC(C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 MMHLSHSAOIJBHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000005291 magnetic effect Effects 0.000 claims description 14
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 150000002460 imidazoles Chemical class 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 150000004699 copper complex Chemical class 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005343 Curie-Weiss law Effects 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000002194 synthesizing effect 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- 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)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The present invention relates to a kind of coordination polymer of copper, its molecular formula is：[Cu(Hbpt)(1,4‑bib)]n, wherein H3Bpt and 1,4 bib represent 3,3', 5 biphenyl tricarboxylic acids and 1,4 pairs of imidazoles benzene respectively.The complex is obtained by hydrothermal method：By Cu (NO3)2·3H2O, 3,3', 5 biphenyl tricarboxylic acids and 1,4 pairs of imidazoles benzene are with 2:1:The ratio between 1 amount of material is dissolved in H2The mixed solution of O/ ethanol, is placed in polyfluortetraethylene pipe, after regulation pH is stirred at room temperature, is sealed in stainless steel cauldron, and 65 80h are reacted at 150 170 DEG C.Cooled down by room temperature, obtain blue flat crystal, after being washed with the mixed solution of water and ethanol, vacuum drying overnight.In the complex there is weak ferromagnetic interaction in Cu (II) interionic, can be used as molecularity magnet.
Description
Technical field
The present invention relates to a kind of coordination polymer of copper, more particularly to a kind of copper (II) ion and 3,3', 5- biphenyl tricarboxylic
Coordination polymer with ferromagnetic interaction that acid and the double imidazoles benzene of 1,4- are constructed and preparation method thereof.
Background technology
The magnetic partner that molecular magnetic materialses are made up of paramagnetic metal ion and organic ligand.Such material structure becomes
Change various, magnetic behavior to enrich, and be easy to adjust its 26S Proteasome Structure and Function by molecule cutting, therefore to molecular magnetic materialses
Research has turned into the study hotspot in the fields such as chemistry, physics and material science.Passed with traditional metal, metallic compound etc.
The inorganic magnetic material of system is compared, and molecular magnet has the advantages that proportion is small, transparency is high, solubility good, easy to process.Simultaneously
The diversity of organic bridge ligand is conducive to introducing the properties such as light, electricity, forms magneto-optic, magnetoelectricity with synergy etc. multi-functional
Molecular material.
The content of the invention
It is an object of the invention to be based on the above-mentioned state of the art, there is provided it is a kind of can matching somebody with somebody as the copper of molecular magnetic materialses
Position polymer and preparation method thereof.
A kind of coordination polymer of copper that the present invention is provided, its molecular formula is：[Cu(Hbpt)(1,4-bib)]n, wherein
H3Bpt and Isosorbide-5-Nitrae-bib represents 3,3', 5- biphenyl tricarboxylic acids and Isosorbide-5-Nitrae-bis- imidazoles benzene respectively, and its structural formula is：
The preparation method of the coordination polymer of the copper that the present invention is provided, comprises the following steps：
(1) it is 2 by mol ratio:1:1 Cu (NO3)2·3H20th, 3,3', 5- biphenyl tricarboxylic acids and Isosorbide-5-Nitrae-bis- imidazoles benzene, plus
Enter and contain volume ratio 5:1 H2In the polyfluortetraethylene pipe of the mixed solvent of O and ethanol, it is 5 to adjust pH with the KOH of 0.2mmol/L；
(2) this polyfluortetraethylene pipe is placed in stainless steel cauldron and is sealed, 65-80h is reacted at 150-170 DEG C, from
So cooling, it is overnight to separate out blue flat crystal, it is vacuum dried after being washed with the mixed solution of water and ethanol.
Reaction temperature is preferably 160 DEG C in step (2), and the reaction time is preferably 72h.
Advantages of the present invention and effect：
Copper coordination polymer of the invention is obtained under hydrothermal synthesizing condition, and reparation technology is simple, and the cycle is shorter, is produced
Rate, purity are higher.
The copper coordination polymer that the present invention is provided is that, based on 3,3', 5- biphenyl tricarboxylic acids and the double imidazoles benzene parts of 1,4- are constructed
, drawn in the coordination polymer by variable temperature magnetic susceptibility experimental data under 2000Oe external magnetic fields exist between copper ion it is weak ferromagnetic
Interact, can be as molecular magnetic materialses.
Brief description of the drawings
The crystal structure figure of the coordination polymer of Fig. 1 copper of the present invention
X-ray powder diffraction figure of the coordination polymer of Fig. 2 copper of the present invention in 298K
Variable temperature magnetic susceptibility curve map of the coordination polymer of Fig. 3 copper of the present invention under 2000Oe external magnetic fields
Specific embodiment
Embodiment 1
It is prepared by the coordination polymer of copper：
Weigh 0.2mmol Cu (NO3)2·3H2O, 0.1mmol 3,3', 5- biphenyl tricarboxylic acids and 0.1mmol Isosorbide-5-Nitraes-bis- miaows
Azoles benzene adds H containing 5ml2In the 13ml polyfluortetraethylene pipes of O/1ml ethanol, it is 5 to adjust pH with 0.2mmol/L KOH.By this poly- four
Fluoride tubes are sealed in stainless steel cauldron, after heating 72h at 160 DEG C, Temperature fall, precipitation blueness flake crystalline overnight
Body, is vacuum dried after being washed with the mixed solution of water and ethanol, and yield is 30%.Elementary analysis：Theoretical value：C 58.12,
H3.25, N 10.04；Experiment value:C 58.09,H 3.24,N 10.08.
The coordination polymer structure determination of copper：
Crystal structure determination uses X-ray single crystal diffraction, and graphite list is passed through with Bruker Smart Apex II detectors
The Mo-K alpha rays of color device monochromatization, scan mode ω, the temperature for collecting data is 100K.Initial data is through SAINT programe reductions
Afterwards, absorption correction is carried out using SADABS methods.Crystal structure is solved by SHELXL-97 program direct methods.Detailed crystal is surveyed
It is fixed to be shown in Table 1 with parsing data；Crystal structure is shown in Fig. 1.
The complex thing of table 1 [Cu (Hbpt) (1,4-bib)]nCrystallographic data
Powder diffraction：
X-ray powder diffraction result obtain experimental diffraction collection of illustrative plates with simulation collection of illustrative plates it is consistent, show copper complex of the invention
Crystal prototype thing is mutually homogeneous, sees Fig. 2.
The magnetic property of the complex material of copper：
Copper complex variable temperature magnetic susceptibility curve is as shown in figure 3, it can be seen that copper complex χ in room temperaturemT values
It is 0.50cm3·K·mol-1, higher than the room temperature magnetic moment (0.375cm that 1 independence does not couple Cu (II) ion3·K·mol-1)。
With the reduction of temperature, χmT values gradually rise,When reaching 25KWhenχmT values are raised rapidly, and maximum is reached in 1.79K
1.24cm3·K·mol-1, there is weak ferromagnetic interaction between showing copper ion in the phenomenon.Additionally, being utilized in the range of 2-290K
Curie-Weiss law is to χm -1- T (Fig. 3 illustrations) is fitted, and can obtain C=0.68cm3·mol-1, θ=3.45K, θ>0 demonstrate,proves again
There is weak ferromagnetic interaction between the bright coordination polymer copper ion.
Claims (1)
1. a kind of coordination polymer of copper is used as the purposes of molecular magnetic materialses, the coordination polymer of the copper, and molecular formula is [Cu
(Hbpt)(1,4-bib)]n, structural formula is：
The coordination polymer preparation method of copper, step is：
(1) it is 2 by mol ratio:1:1 Cu (NO3)2·3H2O, 3,3', 5- biphenyl tricarboxylic acids and Isosorbide-5-Nitrae-bis- imidazoles benzene, addition contain
There is volume ratio 5:1 H2In the polyfluortetraethylene pipe of the mixed solvent of O and ethanol, it is 5 to adjust pH with the KOH of 0.2mmol/L；
(2) this polyfluortetraethylene pipe is placed in stainless steel cauldron and is sealed, 72h is reacted at 160 DEG C, Temperature fall is overnight
Blue flat crystal is separated out, is vacuum dried after being washed with the mixed solution of water and ethanol.
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| CN201510182229.6A CN104844630B (en) | 2015-04-16 | 2015-04-16 | A kind of coordination polymer of copper and preparation method thereof |
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| Publication Number | Publication Date |
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| CN104844630A CN104844630A (en) | 2015-08-19 |
| CN104844630B true CN104844630B (en) | 2017-06-20 |
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| CN107663195B (en) * | 2016-07-28 | 2020-04-10 | 天津大学 | Alkyl imidazole tetrahalogenated iron salt substituted biphenyl type magnetic functional polymer and preparation method thereof |
| CN107099039B (en) * | 2017-05-18 | 2020-06-12 | 山西大学 | Trinuclear copper coordination polymer and preparation method thereof |
| CN109385270B (en) * | 2018-03-23 | 2019-07-30 | 南京晓庄学院 | A kind of white light emitting material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857604A (en) * | 2010-05-17 | 2010-10-13 | 天津师范大学 | Three-dimensional copper coordination polymer with hypoxanthine and pyromellitic benzoic acid mixed ligand and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857604A (en) * | 2010-05-17 | 2010-10-13 | 天津师范大学 | Three-dimensional copper coordination polymer with hypoxanthine and pyromellitic benzoic acid mixed ligand and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Metal ions and solvents ratio co-regulate four new magnetic coordination polymers based upon an unsymmetric tricarboxylate acid ligand;Yuan-Pu Li, et al.;《Dalton Trans》;20140515;第43卷;第10947-10955页 * |
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