CN102127100A - Cadmium complex of 1,5-di(1-H-benzimidazolyl)pentane, and preparation method and application thereof - Google Patents
Cadmium complex of 1,5-di(1-H-benzimidazolyl)pentane, and preparation method and application thereof Download PDFInfo
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- CN102127100A CN102127100A CN2010100301710A CN201010030171A CN102127100A CN 102127100 A CN102127100 A CN 102127100A CN 2010100301710 A CN2010100301710 A CN 2010100301710A CN 201010030171 A CN201010030171 A CN 201010030171A CN 102127100 A CN102127100 A CN 102127100A
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- benzimidazolyl
- pentane
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Abstract
The invention discloses a cadmium complex of 1,5-di(1-H-benzimidazolyl)pentane. The cadmium complex of the 1,5-di(1-H-benzimidazolyl)pentane has the following chemical formula: {[Cd(pbbm)2]2(ClO4)4(H2O)2}positive infinite, wherein pbbm is the 1,5-di(1-H-benzimidazolyl)pentane. The cadmium complex of the 1,5-di(1-H-benzimidazolyl)pentane has a double helix structure and multiple cation exchange functions; when soaked in aqueous solution of perchlorate comprising Cu<2+>, Co<2+>, Ni<2+> and Zn<2+>, the complex can replace Cd<2+> metal ions in a skeleton; the complex serving as a multi-ion exchanger has a wide application prospect in the field of material science; and a preparation method can be performed at normal temperature and normal pressure, and is mild in condition, high in yield and high in reproducibility.
Description
Technical field
The invention belongs to the transition metal complex technical field, be specifically related to is a kind of cadmium complex and preparation method thereof and application, described cadmium ligand polymer has the Cd (II)-1 of spirane structure, 5-two (1-H-benzimidazolyl-) pentane one dimension cadmium ligand polymer has represented cation exchange property.
Background technology
Spiral is a kind of geometricdrawing of grace, has axial chirality, and it extensively exists in nature, human art product and living things system.Nineteen fifty-three, Watson and Crick have proved that according to X-ray diffraction pattern and various chemical analysis data DNA is double-spiral structure, and this is extremely one of significant achievement that contemporary bio-science obtains.Also all there is spirality in many natural polymers in the living things system as polyose, nucleic acid class and some polypeptide compounds.The important biomolecule meaning of spiral that these exist naturally and spiral thereof impels the chemist to simulate relevant biological structure with the material supply section scholar, synthetic compound with spirane structure, and develop their potential application aspect asymmetry catalysis, chemical fractionation, nonlinear optics, biomimetic chemistry and structure biology.
In recent years, the spiral title complex is because its special constitutional features and functions peculiar characteristic and the potential application foreground at aspects such as a plurality of fields optics, asymmetry catalysis, biomimetic material, transmitters have become one of research focus direction of coordination chemistry and Materials science.Under the promotion of outstanding work such as chemist Jean-Marie Lehn and Zubieta, many study group are obtaining the achievement in research that attracts people's attention aspect the design of spiral title complex, the synthetic and Study on functional properties.Some spiral title complexs with novel structure, excellent functional performance are in the news in succession.These are indicating that all the research for the spiral title complex still will be one of focus that coordination chemistry is man and the material supply section scholars pay close attention in future.Yet design and rational and synthetic spiral title complex remain a huge challenge in the current synthetic chemistry field, and the research of spiral title complex is scarcely out of swaddling-clothes, and are fields that has research potential.
As a kind of new type functional molecular material, metal-organic coordination polymer has been subjected to all circles' scientists in the huge potential application of ion-exchange and adsorbing domain and has more and more paid close attention to.But at present the research of ion-exchange aspect is anionic exchange mostly, and exchange also only appears between the object negatively charged ion usually, this be because the interaction force between object negatively charged ion and the positively charged ion framework a little less than, make this class exchange be easy to carry out.By contrast, the exchange of frame center's metal ion, because the formation of the fracture of the coordinate bond that it has formed around existing simultaneously in exchange process and new coordinate bond exists very big restriction, to a certain extent so the report of correlative study is comparatively rare.We think that under appropriate condition promptly cationic exchange is likely a kind of very effective strategy of regulation and control crystalline material performance by changing frame center's metal ion.Understand this brand-new field in order to explore, must be revealed about the structure and the relation between the ion-exchange performance of metal one organic coordination polymer, guide people's design and rational and synthetic type material with this with high-effect ionic exchange capacity.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of material with cationic exchange, be specially a kind of 1, cadmium complex of 5-two (1-H-benzimidazolyl-) pentane and preparation method thereof and application.
Technical scheme of the present invention is: a kind of 1, and the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane, this title complex has following chemical formula: { [Cd (pbbm)
2]
2(ClO
4)
4(H
2O)
2}
∞, wherein, pbbm=1,5-two (1-H-benzimidazolyl-) pentane, its molecular formula is as follows:
The secondary building unit of described cadmium complex is: crystal belongs to tetragonal system, and spacer is P-42 (1) c, and unit cell parameters is:
α=β=γ=90 °,
Described title complex has the 1-D double-spiral structure, and its basic structural unit is by two Cd
IIIon and two nuclear species that end to end pbbm part forms, each Cd
IIIon is formed the tetrahedral coordination geometric configuration of a distortion by four nitrogen-atoms coordinations of the suitable pbbm part of four symmetries.
1, the preparation method of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane comprises the steps:
(1) respectively with 1,5-two (1-H-benzimidazolyl-) pentane and Cd (ClO
4)
26H
2O is dissolved in the acetonitrile, makes 1,5-two (1-H-benzimidazolyl-) pentane acetonitrile solution and Cd (ClO
4)
26H
2The O acetonitrile solution;
(2) with 1,5-two (1-H-benzimidazolyl-) pentane acetonitrile solution is added drop-wise to Cd (ClO
4)
26H
2In the O acetonitrile solution, stir, left standstill under the room temperature 10～20 days, obtain colourless bright monocrystalline, successively with distilled water, acetonitrile washing, be drying to obtain then.
Described 1,5-two (1-H-benzimidazolyl-) pentane and Cd (ClO
4)
26H
2The ratio of the amount of substance of O is 1～1.5: 1.
Described 1, the concentration of 5-two (1-H-benzimidazolyl-) pentane acetonitrile solution is 0.01～0.03molL
-1
Described Cd (ClO
4)
26H
2The concentration of O acetonitrile solution is 0.01～0.03molL
-1
Described 1, the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane aspect material as the application of ion-exchanger.
1 of the present invention's preparation, the main infrared absorption peak of cadmium complex of 5-two (1-H-benzimidazolyl-) pentane is 3423cm
-1, 3102cm
-1, 2938cm
-1, 1614cm
-1, 1515cm
-1, 1462cm
-1, 1393cm
-1, 1102cm
-1, 923cm
-1, 743cm
-1, 623cm
-1
1 of the present invention's preparation, the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane has the polyion function of exchange.When being immersed in, title complex contains Cu
2+, Co
2+, Ni
2+And Zn
2+The perchlorate aqueous solution in the time, can substitute skeleton central metallic ions Cd
2+, this title complex can be used as ion-exchanger, is with a wide range of applications at material science.
The invention has the beneficial effects as follows: 1 of the present invention's preparation, the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane has double-spiral structure, has multiple cationic exchange function, contains Cu when title complex is immersed in
2+, Co
2+, Ni
2+And Zn
2+The perchlorate aqueous solution in the time, can substitute Cd in the skeleton
2+Metal ion, this title complex is with a wide range of applications at material science as the polyion exchanger, and the preparation method can carry out at normal temperatures and pressures, and mild condition, productive rate height, reproducibility are good.
Description of drawings
Fig. 1 is 1, the Cd of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane
IICoordination environment figure;
Fig. 2 is 1, the one dimension double-spiral structure figure of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane;
Fig. 3 is 1, the SEM phenogram of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane;
Fig. 4 is 1, the EDS phenogram of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane;
Fig. 5 is 1, powdery diffractometry phenogram in the ion-exchange test of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane.
Embodiment
Take by weighing the Cd (ClO of 0.0156g (0.05mmol)
4)
26H
2O is dissolved in the 4mL acetonitrile, and the 4mL acetonitrile solution that will be dissolved with 0.0152g (0.05mmol) pbbm then dropwise splashes into and obtains a clear soln in the above-mentioned solution, leaves standstill 14 days, obtains colorless single-crystal.Successively with distilled water, acetonitrile washing, drying obtains again.Productive rate is about 60% (based on 1,5-two (1-H-benzimidazolyl-) pentane calculates).
Take by weighing the Cd (ClO of 0.0156g (0.05mmol)
4)
26H
2O is dissolved in the 2.5mL acetonitrile, and the 6mL acetonitrile solution that will be dissolved with 0.0182g (0.06mmol) pbbm then dropwise splashes into and obtains a clear soln in the above-mentioned solution, leaves standstill 18 days, obtains colorless single-crystal.Successively with distilled water, acetonitrile washing, drying obtains again.Productive rate is about 57% (based on 1,5-two (1-H-benzimidazolyl-) pentane calculates).
Take by weighing the Cd (ClO of 0.0156g (0.05mmol)
4)
26H
2O is dissolved in the 5mL acetonitrile, and the 3mL acetonitrile solution that will be dissolved with 0.0228g (0.075mmol) pbbm then dropwise splashes into and obtains a clear soln in the above-mentioned solution, leaves standstill 20 days, obtains colorless single-crystal.Successively with distilled water, acetonitrile washing, drying obtains again.
Take by weighing the Cd (ClO of 0.0156g (0.05mmol)
4)
26H
2O is dissolved in the 2mL acetonitrile, and the 2mL acetonitrile solution that will be dissolved with 0.0182g (0.06mmol) pbbm then dropwise splashes into and obtains a clear soln in the above-mentioned solution, leaves standstill 10 days, obtains colorless single-crystal.Successively with distilled water, acetonitrile washing, drying obtains again.
In the foregoing description, in the structure of the title complex that makes, exist independently cadmium atom (Cd (1) and Cd (2)) of two kinds of crystallography.The pbbm part of distortion connects two Cd
IIIon has formed 24 yuan of rings, and wherein the distance between the Cd...Cd is
The contiguous shared same metal center of bimetal ring has produced this unidimensional duplex.
The sign of title complex:
(1) structure determination of title complex
The monocrystalline of choosing suitable size at microscopically at room temperature carries out the X-ray diffraction experiment.On Bruker Smart 1000CCD diffractometer, use Mo-K through the graphite monochromator monochromatization
αRay
With
Mode is collected diffraction data.Use Bruker SAINT (Bruker AXS respectively, SAINT Software Reference Manual, Madison, WI, 1998) and SHELXTL (G.M.Sheldrick, G.M.SHELXTL NT Version 5.1.Program for Solution andRefinemen of Crystal Structures.University of
Germany, l997) program is carried out reduction of data and structure elucidation.The diffraction data of part-structure carries out absorption correction with the SADABS program.Crystalline structure is solved in conjunction with difference Fourier is synthetic by direct method.All non-hydrogen atom coordinate and anisotropic parameters carry out the complete matrix least-squares refinement, and the hydrogen atom position is determined by theoretical mode computation.Hydrogen atom on partial solvent water and the methyl alcohol is handled with the method for difference Fourier peak-seeking.Detailed axonometry data see Table 1 and table 2.Structure is seen Fig. 1 and Fig. 2.Fig. 1 is the CdII coordination environment figure of title complex; Fig. 2 is the one dimension double-spiral structure figure of title complex.
(2) ion-exchange performance of title complex
{ [Cd (pbbm) with 5mg
2]
2(C1O
4)
4(H
2O)
2)
∞Crystal is immersed in respectively and contains Cu
2+, Co
2+, Ni
2+And Zn
2+Perchlorate aqueous solution (80mgmL
-1) in, leave standstill 7 days under the room temperature after, products obtained therefrom is filtered out, distilled water wash repeatedly, and is to be identified behind air drying.Identification of means is energy spectrum analysis, infrared spectra and powder x-ray diffraction analysis.
EDAX results: the Cd of frame center in the title complex
2+Can be by Cu
2+, Co
2+, Ni
2+And Zn
2+Part replaces, above-mentioned ion-exchange Cd
2+Percentage amounts be respectively Cu
2+(91.9%), Co
2+(70.3%), Ni
2+(85.4%), Zn
2+(94.3%), this may be since metal ion to be exchanged to due to the difference of the coordination ability of nitrogen proton and their ionic radius.With Cu
2+Replace Cd
2+The SEM of product and EDS the results are shown in Figure 3 and Fig. 4.
The results of FT-IR: the product after the ion-exchange and the infrared spectra of cadmium complex are roughly the same, and the infrared spectra of exchange product has produced the new peak of discrete, and main peaks is only sent out the dirt offset slightly, illustrate that the skeleton structure of exchange front and back polymkeric substance does not change.
(3) the XPRD phase purity of title complex characterizes
The XPRD of title complex characterizes and shows that it has reliable phase purity, for its application as the absorption exchange material provides assurance.See Fig. 5 (instrument model: Bruker/D8 Advance).
The main crystallographic data of table 1 title complex
aR＝∑(||F
0|-|F
C||)/∑F
0|
bwR＝[∑w(|F
0|
2-F
C|
2)
2/∑w(F
0 2)]
1/2
The main bond distance of table 2 title complex
And bond angle [°] *
* symmetrical code: #1-x+2 ,-y, z #2-y+1, x-1 ,-z #3y+1 ,-x+1 ,-z#4-y+1, x-1 ,-z+1 #5y+1 ,-x+1 ,-z+1
Claims (7)
1. the cadmium complex of a 5-two (1-H-benzimidazolyl-) pentane, it is characterized in that: this title complex has following chemical formula: { [Cd (pbbm)
2]
2(ClO
4)
4(H
2O)
2}
∞, wherein, pbbm=1,5-two (1-H-benzimidazolyl-) pentane.
2. according to claim 11, the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane, it is characterized in that: the secondary building unit of described cadmium complex is: crystal belongs to tetragonal system, and spacer is P-42 (1) c, and unit cell parameters is: a=14.160 (2)
B=14.160 (2)
C=20.245 (4)
α=β=γ=90 °, V=4059.0 (11)
Described title complex has the 1-D double-spiral structure, and its basic structural unit is by two Cd
IIIon and two nuclear species that end to end pbbm part forms, each Cd
IIIon is formed the tetrahedral coordination geometric configuration of a distortion by four nitrogen-atoms coordinations of the suitable pbbm part of four symmetries.
3. as claimed in claim 11, the preparation method of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane, it is characterized in that: it comprises the steps:
(1) respectively with 1,5-two (1-H-benzimidazolyl-) pentane and Cd (ClO
4)
26H
2O is dissolved in the acetonitrile, makes 1,5-two (1-H-benzimidazolyl-) pentane acetonitrile solution and Cd (ClO
4)
26H
2The O acetonitrile solution;
(2) with 1,5-two (1-H-benzimidazolyl-) pentane acetonitrile solution is added drop-wise to Cd (ClO
4)
26H
2In the O acetonitrile solution, stir, left standstill under the room temperature 10～20 days, obtain colourless bright monocrystalline, successively with distilled water, acetonitrile washing, be drying to obtain then.
4. according to claim 31, the preparation method of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane is characterized in that: described 1, and 5-two (1-H-benzimidazolyl-) pentane and Cd (ClO
4)
26H
2The ratio of the amount of substance of O is 1～1.5: 1.
5. according to claim 31, the preparation method of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane is characterized in that: described 1, the concentration of 5-two (1-H-benzimidazolyl-) pentane acetonitrile solution is 0.01～0.03molL
-1
6. described 1 according to claim 3, the preparation method of the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane is characterized in that: described Cd (ClO
4)
26H
2The concentration of O acetonitrile solution is 0.01～0.03molL
-1
7. as claimed in claim 11, the cadmium complex of 5-two (1-H-benzimidazolyl-) pentane aspect material as the application of ion-exchanger.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665008A (en) * | 2013-11-22 | 2014-03-26 | 河南工程学院 | 1,5-di-(1-H-benzimidazolyl) pentane-silver(I) complex and preparation method thereof. |
| CN103864826A (en) * | 2014-04-03 | 2014-06-18 | 哈尔滨工业大学 | Trinuclear cadmium coordination polymer with fluorescence thermochromic property and containing four pore paths with different sizes and synthetic method thereof |
| CN104370821A (en) * | 2014-11-21 | 2015-02-25 | 岭南师范学院 | Benzimidazole ligand and preparation method and application of dinuclear complexes of benzimidazole ligand |
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| CN101016292A (en) * | 2007-02-14 | 2007-08-15 | 南开大学 | 9-(1-Benzimidazolyl)acridine CuI complex, preparing method and application thereof |
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2010
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| CN101016292A (en) * | 2007-02-14 | 2007-08-15 | 南开大学 | 9-(1-Benzimidazolyl)acridine CuI complex, preparing method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665008A (en) * | 2013-11-22 | 2014-03-26 | 河南工程学院 | 1,5-di-(1-H-benzimidazolyl) pentane-silver(I) complex and preparation method thereof. |
| CN103665008B (en) * | 2013-11-22 | 2016-04-20 | 河南工程学院 | 1,5-bis-(1-H-benzimidazolyl-) pentane-Yin (I) title complex and preparation method |
| CN103864826A (en) * | 2014-04-03 | 2014-06-18 | 哈尔滨工业大学 | Trinuclear cadmium coordination polymer with fluorescence thermochromic property and containing four pore paths with different sizes and synthetic method thereof |
| CN103864826B (en) * | 2014-04-03 | 2016-01-20 | 哈尔滨工业大学 | A kind of three core cadmium coordination polymer and synthetic methods thereof containing four kinds of different size ducts with heat induced fluorescence variable color character |
| CN104370821A (en) * | 2014-11-21 | 2015-02-25 | 岭南师范学院 | Benzimidazole ligand and preparation method and application of dinuclear complexes of benzimidazole ligand |
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