CN104744495A - Chiral double-helix coordination polymer and preparation method thereof - Google Patents
Chiral double-helix coordination polymer and preparation method thereof Download PDFInfo
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- CN104744495A CN104744495A CN201510133513.4A CN201510133513A CN104744495A CN 104744495 A CN104744495 A CN 104744495A CN 201510133513 A CN201510133513 A CN 201510133513A CN 104744495 A CN104744495 A CN 104744495A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000013256 coordination polymer Substances 0.000 title abstract 7
- 229920001795 coordination polymer Polymers 0.000 title abstract 7
- 239000000126 substance Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 239000003446 ligand Substances 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 19
- 150000003217 pyrazoles Chemical class 0.000 claims description 10
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- -1 atoms metals Chemical class 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000373 single-crystal X-ray diffraction data Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to the field of coordination polymer, in particular to a chiral double-helix coordination polymer and a preparation method thereof. The chiral double-helix coordination polymer is characterized in that the chemical formula is C14H20ClCuN6O4, the chiral double-helix coordination polymer is of a hexagonal crystal system and P3j21 space group; the crystal unit cell parameters are as follows: a=12.4657(8)., b=12.466., c=11.0157(7)., alpha=beta=90 degrees, gamma=120 degrees, and V=1482.44(13).. The coordination polymer provided by the invention is of a chiral compound, and thus, the coordination polymer can be used as potential chiral catalytic and chiral separation materials.
Description
Technical field
The present invention relates to ligand polymer field, be specifically related to a kind of chirality duplex ligand polymer and preparation method thereof.
Background technology
Chirality is the essential characteristic of coenocorrelation, biomolecules and state of aggregation thereof.Molecular chiral has symmetrical structure by a pair but the special property that causes of the molecule do not overlapped each other, and it plays the part of very important role in host-guest interaction.In recent years, the design of chiral metal organic coordination compound and synthesis receive the very big concern of people, this is not only due to the extremely unique structure of chiral metal organic coordination compound and topological network, and is that they have potential application in all many-sides such as enantioselectivity separation and heterogeneous catalysts.
The maximum challenge of synthesis of chiral a metal-organic complex obtains homochiral target product, comprehensively previous research, mainly contain the following two kinds method to synthesize homochiral a metal-organic complex: (1) utilizes chirality thing to carry out enantioselective synthesis, such as adopt chiral ligand, chiral reactant, chiral solvent or other chiral physical environment; (2) adopt the achiral material not containing any chiral source to be split by oneself and synthesize target product.Up to the present, the first is the most frequently used method, but must adopt homochiral composition owing to can not comprise racemic modification in synthesis condition, thus has certain limitation.Will build chiral skeleton structure from achirality source, spirality may be transmit the carrier of chiral information, and the multiple tooth organic ligand of flexibility may improve spirality element effectively, thus contribute to forming chiral metal organic coordination compound.
Summary of the invention
Technical problem to be solved by this invention utilizes achirality source to prepare a kind of chirality duplex ligand polymer.
The preparation method of another object of the present invention above-mentioned chirality duplex ligand polymer.
Technical problem to be solved by this invention is achieved by the following technical programs:
A kind of chirality duplex ligand polymer, is characterized in that: chemical formula is C
14h
20clCuN
6o
4, described chirality duplex ligand polymer is hexagonal system,
p3 1 21spacer, unit cell parameters is
a=12.4657 (8),
b=12.466,
c=11.0157 (7),
α=β=90 o,
γ=120 o, V=1482.44 (13)
3.
Further, copper atom adopts four-coordination tetrahedral configuration, and join two nitrogen-atoms coordinations on pyrazoles respectively with two, the bond distance of Cu-N is 2.0198 (18), with two nitrogen-atoms coordinations on two molecule of acetonitrile, the bond distance of Cu-N is 2.017 (2).
The preparation method of described chirality duplex ligand polymer, is characterized in that: by Cu (ClO
4) 3CH
3cN is dissolved in the middle of acetonitrile, organic ligand being joined pyrazoles (Bpz) is dissolved in the middle of methyl alcohol, then will be dissolved with in the beaker of part containing slowly dropping in the solution of metal-salt, drips rear leaving standstill, allow it naturally volatilize, after 2 ~ 3 days, grow described chirality duplex ligand polymer.
Further, described Cu (ClO
4) 3CH
3the mol ratio of CN and connection pyrazoles is 0.8 ~ 1.2:0.8 ~ 1.2.
Further, described Cu (ClO
4) 3CH
3the mol ratio of CN and connection pyrazoles is preferably 1:1.
Further, the volume ratio of described acetonitrile and methyl alcohol is 0.8 ~ 1.2:0.8 ~ 1.2.
Further, the volume ratio of described acetonitrile and methyl alcohol is preferably 1:1.
The present invention has following beneficial effect:
Ligand polymer of the present invention is chipal compounds, can be used as potential chiral catalysis and chiral separation material.
Accompanying drawing explanation
Fig. 1 is chirality duplex ligand polymer C of the present invention
14h
20clCuN
6o
4with the coordination environment figure of metal center Cu.
Fig. 2 is chirality duplex ligand polymer C of the present invention
14h
20clCuN
6o
4duplex link composition.
Fig. 3 is chirality duplex ligand polymer C of the present invention
14h
20clCuN
6o
4solid CD spectrogram.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described in detail.
Cu (the ClO that the present invention is used
4) 3CH
3cN is prepared according to following steps:
By cupric perchlorate Cu (ClO
4)
2with copper powder when acetonitrile solvent, under anhydrous and oxygen-free, backflow obtains, and separates out anhydrous transparent Cu (ClO after cooling
4) 3CH
3cN crystal.
embodiment 1:
By the Cu (ClO of preparation
4) 3CH
3cN (0.10 mmol) is dissolved in 5 mL acetonitriles, Bpz (0.10 mmol) is dissolved in 5mL methyl alcohol, then be dissolved with in the beaker of part by slowly dropping in metal salt solution to join, drip rear leaving standstill, allow it naturally volatilize, after 3 days, grow the crystal of colourless hexa-prism.Filter and use water, methanol wash respectively, obtain clear crystal after drying, productive rate is about 73.9%(based on Cu).
Then above-mentioned chirality duplex ligand polymer is carried out structural characterization
Crystal X-ray diffraction data acquisition Burkcer Smart CCD single crystal diffractometer measures.MoKa radiation (λ=0.71073), graphite monochromator, collects data with ω scan mode, and carries out Lp factor correction and empirical absorption correction.First with direct method determination atoms metal and part other non-hydrogen atoms position, then all the other whole non-hydrogen atom coordinates are obtained by difference functions method and method of least squares, and obtain hydrogen atom position with theoretical hydrogenation method or find from difference Fourier figure, by complete matrix method of least squares, structure is revised.Crystallographic parameter is in table 1, and structure is shown in Fig. 1, Fig. 2.
the crystallographic parameter of table 1. chirality duplex ligand polymer and structure elucidation
Single crystal X-ray diffraction data show that this ligand polymer belongs to hexagonal system,
p3 1 21spacer, it to contain in a crystallography independently Cu (I) atom (as shown in Figure 1), it joins N (Cu-N 2.0198 (18)) coordination on pyrazoles respectively with 2 two, and N (Cu-N 2.017 (2)) coordination on 2 molecule of acetonitrile.Neutral connection Pyrazole Ligands adopts the linear coordination mode of similar 4,4'-Bipyridine, and namely, each part bridging two atoms metals, wherein, the distance between two atoms metals is 9.624.In addition, because two pyrazole rings in connection pyrazoles can rotate around C-C key, and interfacial angle is 95.716
o, therefore, the spirality of whole skeleton may be the flexibility coming from part.Can confirm that this ligand polymer is made up of (as shown in Figure 2) one dimension left hand helix chain from single crystal structural data.
The most outstanding feature of this ligand polymer is the duplex chain with same chirality.Each in duplex chain is all 3
1screw shaft, pitch is 22.03.More what is interesting is, duplex chain is not simple simple helix chain, but two duplex chains have the identical hand of spiral, i.e. left (as shown in Figure 3).
embodiment 2:
By the Cu (ClO of preparation
4) 3CH
3cN (0.12 mmol) is dissolved in 5 mL acetonitriles, Bpz (0.09 mmol) is dissolved in 5mL methyl alcohol, then be dissolved with in the beaker of part by slowly dropping in metal salt solution to join, drip rear leaving standstill, allow it naturally volatilize, after 3 days, grow the crystal of colourless hexa-prism.Filter and use water, methanol wash respectively, obtain clear crystal after drying, productive rate is about 62.3%(based on Cu).
embodiment 3:
By the Cu (ClO of preparation
4) 3CH
3cN (0.1 mmol) is dissolved in 5 mL acetonitriles, Bpz (0.08 mmol) is dissolved in 4.5mL methyl alcohol, then be dissolved with in the beaker of part by slowly dropping in metal salt solution to join, drip rear leaving standstill, allow it naturally volatilize, after 3 days, grow the crystal of colourless hexa-prism.Filter and use water, methanol wash respectively, obtain clear crystal after drying, productive rate is about 68.4%(based on Cu).
embodiment 4:
By the Cu (ClO of preparation
4) 3CH
3cN (0.09 mmol) is dissolved in 4.5 mL acetonitriles, Bpz (0.1 mmol) is dissolved in 5mL methyl alcohol, then be dissolved with in the beaker of part by slowly dropping in metal salt solution to join, drip rear leaving standstill, allow it naturally volatilize, after 3 days, grow the crystal of colourless hexa-prism.Filter and use water, methanol wash respectively, obtain clear crystal after drying, productive rate is about 64.8%(based on Cu).
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.
Claims (7)
1. a chirality duplex ligand polymer, is characterized in that: chemical formula is C
14h
20clCuN
6o
4, described chirality duplex ligand polymer is hexagonal system,
p3 1 21spacer, unit cell parameters is
a=12.4657 (8),
b=12.466,
c=11.0157 (7),
α=β=90 o,
γ=120 o, V=1482.44 (13)
3.
2. a kind of chirality duplex ligand polymer according to claim 1, it is characterized in that: copper atom adopts four-coordination tetrahedral configuration, two nitrogen-atoms coordinations on pyrazoles are joined respectively with two, the bond distance of Cu-N is 2.0198 (18), with two nitrogen-atoms coordinations on two molecule of acetonitrile, the bond distance of Cu-N is 2.017 (2).
3. the preparation method of chirality duplex ligand polymer according to claim 1, is characterized in that: by Cu (ClO
4) 3CH
3cN is dissolved in the middle of acetonitrile, organic ligand being joined pyrazoles is dissolved in the middle of methyl alcohol, then will be dissolved with in the beaker of part containing slowly dropping in the solution of metal-salt, drips rear leaving standstill, allow it naturally volatilize, after 2 ~ 3 days, grow described chirality duplex ligand polymer.
4. preparation method according to claim 3, is characterized in that, described Cu (ClO
4) 3CH
3the mol ratio of CN and connection pyrazoles is 0.8 ~ 1.2:0.8 ~ 1.2.
5. preparation method according to claim 4, is characterized in that, described Cu (ClO
4) 3CH
3the mol ratio of CN and connection pyrazoles is preferably 1:1.
6. preparation method according to claim 3, is characterized in that, the volume ratio of described acetonitrile and methyl alcohol is 0.8 ~ 1.2:0.8 ~ 1.2.
7. preparation method according to claim 6, is characterized in that, the volume ratio of described acetonitrile and methyl alcohol is preferably 1:1.
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|---|---|---|---|---|
| CN103626788A (en) * | 2013-09-24 | 2014-03-12 | 广东工业大学 | Hybrid material with function of adsorbing and desorbing iodine and synthetic methods thereof |
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|---|---|---|---|---|
| CN103626788A (en) * | 2013-09-24 | 2014-03-12 | 广东工业大学 | Hybrid material with function of adsorbing and desorbing iodine and synthetic methods thereof |
Non-Patent Citations (2)
| Title |
|---|
| ISHTVAN BOLDOG ET AL.: "One- and two-dimensional coordination polymers of 3,3,5,5-tetramethyl-4,4-bipyrazolyl,a new perspective crystal engineering module", 《POLYHEDRON》 * |
| 何军: "吡唑类配体的Cu/Zn金属配位聚合物合成、结构、荧光和热性质研究", 《工程科技1辑》 * |
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Application publication date: 20150701 |