CN105440061A - Right-handed 4<1> helix coordination polymer and its preparation method and use - Google Patents
Right-handed 4<1> helix coordination polymer and its preparation method and use Download PDFInfo
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- CN105440061A CN105440061A CN201510924604.XA CN201510924604A CN105440061A CN 105440061 A CN105440061 A CN 105440061A CN 201510924604 A CN201510924604 A CN 201510924604A CN 105440061 A CN105440061 A CN 105440061A
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- ligand polymer
- spiral
- right hand
- cdmp
- helix
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Abstract
The invention discloses a right-handed 4<1> helix coordination polymer and its preparation method and use. The right-handed 4<1> helix coordination polymer has a chemical formula of {[Cu(R, R-cdmp)(H2O)]. 2NO3. 2H2O}n. The preparation method comprises adding Cu(NO3)2. 3H2O and R, R-cdmp into 4mL of a methanol solution, carrying out mixing to obtain a light blue solution and carrying out standing at a room temperature to obtain the right-handed 4<1> helix coordination polymer. The one-dimensional helix coordination polymer is prepared from double chelate ligands such as R, R-cdmp and Cu(II) of the chiral cyclohexanediamine and has a right-handed 4<1> helix structure and second order nonlinear optical activity. The preparation method has simple processes, is free of a complex synthesis device and reduces a production cost. The prepared coordination polymer can be used for an asymmetric Henry reaction of aromatic aldehyde and nitromethane.
Description
Technical field
The invention belongs to chemical field, particularly relate to a kind of right hand 4
1spiral ligand polymer and preparation method thereof and application.
Background technology
Chirality ligand polymer/chiral metal-organic backbone has very large development potentiality in asymmetry catalysis, this is because they there is structure diversification, do not need external load, avtive spot is homogeneous, reusable edible and provide the advantages such as crystalline structure.In recent years, lot of domestic and international seminar has made a large amount of fruitful work in the asymmetry catalysis of chirality ligand polymer/chiral metal-organic backbone, but mainly concentrate on the ligand polymer of higher dimensionality (two and three dimensions), particularly there is the metal-organic framework materials of pore passage structure.Meanwhile, as a kind of stand-in of DNA coiled strand, one dimension chiral helical ligand polymer has potential using value in asymmetry catalysis, but does not also have the research of this respect to report in document.
In addition, spirane structure is widespread in nature, and can as the basis of gene-code.In supramolecular chemistry and Materials science, the process that the synthesis of spirane structure can allow people understand supramolecule better to construct.Research shows, the chirality of spirane structure is determined by coordination instead of metal ion, and the spiral element that the polydentate ligand of two chelating contributes to chirality ligand polymer is formed.Meanwhile, in document, the adducts of existing chirality cyclohexanediamine and Cu (II) salt is applied in the report of asymmetric Henle reaction aspect.
Summary of the invention
Goal of the invention: that the first object of the present invention is to provide a kind of one dimension and there is the right hand 4
1the ligand polymer of spirane structure; The second object of the present invention is to provide the preparation method of this ligand polymer; The third object of the present invention is to provide the application of this ligand polymer.
Technical scheme: the right hand 4 of the present invention
1the chemical formula of spiral ligand polymer is { [Cu (R, R-cdmp) (H
2o)] .2NO
3.2H
2o}
n, wherein, R, R-cdmp are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (3-methyl-2-pyridine anilide), and it be chirality pair chelated organic ligands.Furtherly, this ligand polymer belongs to tetragonal system, and spacer is P4
12
12, its crystallization parameters is
wherein, to be respectively the rib of three ribs of structure cell long for a, b, c.
Furtherly, R in ligand polymer of the present invention, R-cdmp part adopts trans pair of chelating pattern and the coordination of two Cu (II), and the tetragonal pyramid structure that Cu (II) is pentacoordinate, the base plane of tetragonal pyramid is occupied by two nitrogen-atoms of two chelating ligands and two Sauerstoffatoms, and the vertex position of tetragonal pyramid is occupied by a water molecules, bottom tetragonal pyramid, four atoms of coordination are in same plane, wherein, the structural formula of R, R-cdmp part is:
The right hand 4 of the present invention
1the preparation method of spiral ligand polymer comprises the steps: the Cu (NO of 0.1mmol
3)
23H
2the R of O and 0.1mmol, R-cdmp add 4mL methanol solution and mix, and obtain homogeneous, transparent light blue solution, stirring at room temperature 0.5 ~ 1h, and filtered by solution, filtrate at room temperature leaves standstill, and naturally volatilize, and within 3 ~ 7 days, obtain the right hand 4 afterwards
1spiral ligand polymer.
The right hand 4 of the present invention
1spiral ligand polymer is applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min..
Beneficial effect: compared with prior art, its remarkable advantage is that the present invention adopts two chelating ligand R, R-cdmp and Cu (II) based on chirality cyclohexanediamine to construct a kind of one dimension spiral ligand polymer, and it has the right hand 4
1spirane structure, and there is second order non-linear optical active; Meanwhile, preparation technology of the present invention is simple, without the need to the synthesis device of complexity, reduces production cost; In addition, the ligand polymer of preparation can be applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min., thus thus explores and feasibility study for chiral helical title complex provides originality as the application of heterogeneous catalyst in asymmetry catalysis.
Accompanying drawing explanation
Fig. 1 a is the molecular structure of the ligand polymer that the present invention obtains;
Fig. 1 b is the one-dimensional linear topological diagram of the ligand polymer that the present invention obtains.
Embodiment
The right hand 4 of the present invention
1the chemical formula of spiral ligand polymer is { [Cu (R, R-cdmp) (H
2o)] .2NO
3.2H
2o}
n, wherein, R, R-cdmp are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (3-methyl-2-pyridine anilide), and it be chirality pair chelated organic ligands.Furtherly, this ligand polymer belongs to tetragonal system, and spacer is P4
12
12, its crystallization parameters is
wherein, to be respectively the rib of three ribs of structure cell long for a, b, c.
Furtherly, R in ligand polymer of the present invention, R-cdmp part adopts trans pair of chelating pattern and the coordination of two Cu (II), and the tetragonal pyramid structure that Cu (II) is pentacoordinate, the base plane of tetragonal pyramid is occupied by two nitrogen-atoms of two chelating ligands and two Sauerstoffatoms, and the vertex position of tetragonal pyramid is occupied by a water molecules, bottom tetragonal pyramid, four atoms of coordination are in same plane, wherein, the structural formula of R, R-cdmp part is:
The right hand 4 of the present invention
1the preparation method of spiral ligand polymer comprises the steps: the Cu (NO of 0.1mmol
3)
23H
2the R of O and 0.1mmol, R-cdmp add 4mL methanol solution and mix, and obtain homogeneous, transparent light blue solution, stirring at room temperature 0.5 ~ 1h, and filtered by solution, filtrate at room temperature leaves standstill, and naturally volatilize, and within 3 ~ 7 days, obtain the right hand 4 afterwards
1spiral ligand polymer.
The right hand 4 of the present invention
1spiral ligand polymer is applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min..Furtherly, aromatic aldehyde is that (substituting group is H, 2-/3-/4-NO for 1-naphthaldehyde and single-substituted formaldehyde
2, 2-/3-/4-F, 2-/4-Cl, 2-/3-/4-Br, 4-OCH
3or 4-Ph).
Embodiment 1
By the Cu (NO of 0.1mmol (0.0242g)
3)
23H
2the R of O and 0.1mmol (0.035g), R-cdmp adds 4mL methanol solution and mixes, and obtains homogeneous, transparent light blue solution, stirring at room temperature 0.5h, and filtered by solution, filtrate at room temperature leaves standstill, and naturally volatilizees, and within 3 days, obtains the right hand 4 afterwards
1spiral ligand polymer, as shown in Figure 1a, its one-dimensional linear topology is as shown in 1b, and from Fig. 1 a, this ligand polymer, compared with urea, has second order non-linear optical activity and asymmetry catalysis activity for the molecular structure obtained.
Embodiment 2
By the Cu (NO of 0.1mmol (0.0242g)
3)
23H
2the R of O and 0.1mmol (0.035g), R-cdmp adds 4mL methanol solution and mixes, and obtains homogeneous, transparent light blue solution, stirring at room temperature 1h, and filtered by solution, filtrate at room temperature leaves standstill, and naturally volatilizees, and within 7 days, obtains the right hand 4 afterwards
1spiral ligand polymer.
Embodiment 3
0.5mmol ligand polymer is added in the small test tube of 4mL, 1mL Virahol (i-PrOH) and 5mmolN, N-diisopropylethylamine (DIPEA) obtains a blue suspension, then in suspension, the aromatic aldehyde of 0.5mmol and the Nitromethane 99Min. of 5mmol is added, test tube is put into low-temp reaction device, filter react 168h under-20 DEG C of conditions after, filtrate is crossed column purification, wherein, weighting agent is silica gel, moving phase is sherwood oil and the ethyl acetate mixed solvent of volume ratio 4:1, gained solution is concentrated, after vacuum-drying, namely catalysate is obtained, its catalyzed reaction equation is shown below.
By the high-performance liquid chromatogram determination e.e. value of the catalysate of gained with chiral column.Wherein, chiral column used and liquid-phase condition, and the e.e. value of products therefrom is as shown in table 1.
The e.e. value of table 1 catalysate
As shown in Table 1, this right hand 4
1the asymmetric Henle reaction of Helical Complex to aromatic aldehyde and Nitromethane 99Min. has good catalytic effect.
Claims (8)
1. a right hand 4
1spiral ligand polymer, is characterized in that: the chemical formula of this ligand polymer is { [Cu (R, R-cdmp) (H
2o)] .2NO
3.2H
2o}
n, wherein, R, R-cdmp are (-)-N, N'-(1R, 2R)-1,2-diamino hexahydroaniline two base two (3-methyl-2-pyridine anilide), and it be chirality pair chelated organic ligands.
2. the right hand 4 according to claim 1
1spiral ligand polymer, is characterized in that: described ligand polymer belongs to tetragonal system, and spacer is P4
12
12.
3. the right hand 4 according to claim 1
1spiral ligand polymer, is characterized in that: the crystallization parameters of described ligand polymer is
wherein, to be respectively the rib of three ribs of structure cell long for a, b, c.
4. the right hand 4 according to claim 1
1spiral ligand polymer, is characterized in that: the structural formula of described R, R-cdmp part is:
5. the right hand 4 according to claim 4
1spiral ligand polymer, is characterized in that: the R in described ligand polymer, R-cdmp part adopts trans pair of chelating pattern and the coordination of two Cu (II).
6. the right hand 4 according to claim 5
1spiral ligand polymer, it is characterized in that: the tetragonal pyramid structure that described Cu (II) is pentacoordinate, the base plane of tetragonal pyramid is occupied by two nitrogen-atoms of two chelating ligands and two Sauerstoffatoms, the vertex position of tetragonal pyramid is occupied by a water molecules, and bottom tetragonal pyramid, four atoms of coordination are in same plane.
7. prepare the right hand 4 according to claim 1 for one kind
1the method of spiral ligand polymer, is characterized in that comprising the steps: the Cu (NO by 0.1mmol
3)
23H
2the R of O and 0.1mmol, R-cdmp add 4mL methanol solution and mix, and obtain homogeneous, transparent light blue solution, stirring at room temperature 0.5 ~ 1h, and filtered by solution, filtrate at room temperature leaves standstill, and naturally volatilize, and within 3 ~ 7 days, obtain the right hand 4 afterwards
1spiral ligand polymer.
8. a right hand 4 according to claim 1
1spiral ligand polymer is applied to the asymmetric Henle reaction of aromatic aldehyde and Nitromethane 99Min..
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265703A (en) * | 2018-11-20 | 2019-01-25 | 东南大学 | It is a kind of three-dimensional containing zinc/copper chiral metal organic framework material and preparation method thereof |
| CN114213470A (en) * | 2021-12-27 | 2022-03-22 | 郑州轻工业大学 | Crystalline molecular base material generated by chiral mononuclear cobalt second-order harmonic and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531672A (en) * | 2008-03-12 | 2009-09-16 | 安徽大学 | Metal-organic framework material with nano pores and preparation method and application thereof |
| CN104892515A (en) * | 2014-10-09 | 2015-09-09 | 广东工业大学 | Coordination polymer with copper spiral structure and method for preparing same |
-
2015
- 2015-12-14 CN CN201510924604.XA patent/CN105440061A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531672A (en) * | 2008-03-12 | 2009-09-16 | 安徽大学 | Metal-organic framework material with nano pores and preparation method and application thereof |
| CN104892515A (en) * | 2014-10-09 | 2015-09-09 | 广东工业大学 | Coordination polymer with copper spiral structure and method for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| 张秀英: ""手性配位聚合物的合成、表征及其在不对称催化反应中的应用"", 《万方数据 东南大学硕士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265703A (en) * | 2018-11-20 | 2019-01-25 | 东南大学 | It is a kind of three-dimensional containing zinc/copper chiral metal organic framework material and preparation method thereof |
| CN114213470A (en) * | 2021-12-27 | 2022-03-22 | 郑州轻工业大学 | Crystalline molecular base material generated by chiral mononuclear cobalt second-order harmonic and preparation method thereof |
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