CN104230963A - Dual-core coordination polymer and preparation method of dual-core coordination polymer - Google Patents
Dual-core coordination polymer and preparation method of dual-core coordination polymer Download PDFInfo
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- CN104230963A CN104230963A CN201410435390.5A CN201410435390A CN104230963A CN 104230963 A CN104230963 A CN 104230963A CN 201410435390 A CN201410435390 A CN 201410435390A CN 104230963 A CN104230963 A CN 104230963A
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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 System
- C07F1/08—Copper compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention relates to the field of inorganic chemistry, and particularly relates to a dual-core coordination polymer and a preparation method of the dual-core coordination polymer. The chemical formula of the dual-core coordination polymer is CHNOSCu; the coordination polymer is a triclinic system; and cell parameters of a P-1 space group are as follows: a=9.9698(6)A, b=10.1748(6)A, c=20.8022(8)A, alpha=99.428(4) degrees, beta=100.826(4) degrees, gamma=99.970(5) degrees, V=1998.85(19)A<3>. The coordination polymer disclosed by the invention is easy to prepare; and the synthesized material is few in defects, and high in degree of crystallinity, and has good potential application prospects in the fields such as catalysis, sensing, molecular recognition, molecular luminescence and the like.
Description
Technical field
The present invention relates to domain of inorganic chemistry, be specifically related to a kind of double-core ligand polymer and preparation method thereof.
Background technology
Ligand polymer refers to the type material with periodic network structure formed by coordinate bond by metal ion or metal cluster and organic bridge ligand, and be otherwise known as Inorganic-Organic Hybrid Material or metal organic framework compound.Metal ion or metal cluster and organic ligand are functional unit, determine again the topological framework of ligand polymer.Therefore, the molecular designing of ligand polymer not only needs the good functional unit of selecting properly, and needs to control the interaction between these unit, to realize aligning and assembling of molecule.Due to the easy coordination of copper atom, its metal-salt is cheap and easy to get, is subject to widely using of people in recent years; Thioether Carboxylic acid ligand has the functional group of two kinds of character, according to hsab theory, thioether is softer, carboxylic acid is harder, this part is easy and soft metal ions coordination both, again easy and hard metal ion coordination, or wherein a kind of functional group is exposed in duct, for further performance study provides foundation, thus be subject to the favor of people.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of ligand polymer of double-core cupric coordination.
Another object of the present invention is to provide the preparation method of above-mentioned ligand polymer.
Technical problem to be solved by this invention is achieved by the following technical programs:
A kind of double-core ligand polymer, chemical formula is CHNOSCu, and this ligand polymer is triclinic(crystalline)system,
p-1spacer, unit cell parameters is
a=9.9698 (6),
b=10.1748 (6),
c=20.8022 (8),
α=99.428 (4) o,
β=100.826 (4) o,
γ=99.970 (5) o, V=1998.85 (19)
3.
In this ligand polymer, copper atom takes the mode of pentacoordinate, each copper atom respectively with four 4-(thiomethyls) the O atom on phenylformic acid and the N coordination in a molecule of acetonitrile, Cu-O bond distance is 1.973 (4), Cu-N bond distance is 2.143 (6), distance between Cu1Cu2 is 2.6402 (17), defines unique dual-core architecture.
A kind of preparation method of double-core ligand polymer: by soluble copper salt and 4-(thiomethyl) phenylformic acid is added in acetonitrile solution, and reacting by heating under solvent thermal condition, obtains described double-core ligand polymer.
Further, described soluble copper salt and 4-(thiomethyl) benzoic mol ratio is 6 ~ 3:0.5 ~ 1.5.
Further preferred, described soluble copper salt and 4-(thiomethyl) benzoic mol ratio is preferably 4:1.
Further, described Heating temperature is 80 ~ 120 DEG C.
Preferred further, described Heating temperature is 100 DEG C.
Further, adding the reaction times described in is 12 ~ 72 hours.
Further preferably, adding the reaction times described in is 48 hours.
Further, described soluble copper salt is the wherein one in cupric nitrate, cupric chloride, cupric bromide.
The present invention has following beneficial effect:
Double-core ligand polymer of the present invention is easy to preparation, and the fault in material be synthesized is few, and degree of crystallinity is high, has extraordinary potential application prospect in fields such as catalysis, sensing, molecular recognition, molecular luminescences.
Accompanying drawing explanation
Fig. 1 is the coordination environment figure of the double-core ligand polymer of the embodiment of the present invention 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described in detail.
embodiment 1
By 80 μm of ol cupric nitrates and 20 μm of ol4-(thiomethyls) phenylformic acid is dissolved in 1mL acetonitrile solution, being placed in external diameter is 8mm, internal diameter is 6mm, in the long Glass tubing for 10cm, add hot-seal, react 48 hours at being placed in constant temperature oven 100 DEG C, obtain described double-core ligand polymer crystal CHNOSCu, productive rate is 62.8% (based on Cu).
Then above-mentioned polymkeric substance 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.
the crystallographic parameter of table 1. double-core ligand polymer and structure elucidation
In this ligand polymer, copper atom takes the mode (as shown in Figure 1) of pentacoordinate, each copper atom respectively with four 4-(thiomethyls) the O atom on phenylformic acid and the N coordination in a molecule of acetonitrile, Cu-O bond distance is 1.973 (4), Cu-N bond distance is 2.143 (6), distance between Cu1Cu2 is 2.6402 (17), defines unique dual-core architecture.
embodiment 2
By 120 μm of ol cupric nitrates and 20 μm of ol4-(thiomethyls) phenylformic acid is dissolved in 1mL acetonitrile solution, being placed in external diameter is 8mm, internal diameter is 6mm, in the long Glass tubing for 10cm, add hot-seal, react 48 hours at being placed in constant temperature oven 100 DEG C, obtain described double-core ligand polymer crystal CHNOSCu, productive rate is 40.3% (based on Cu).
embodiment 3
By 70 μm of ol cupric chlorides and 20 μm of ol4-(thiomethyls) phenylformic acid is dissolved in 1mL acetonitrile solution, being placed in external diameter is 8mm, internal diameter is 6mm, in the long Glass tubing for 10cm, add hot-seal, react 48 hours at being placed in constant temperature oven 110 DEG C, obtain described yellow cubic crystal CHNOSCu, productive rate is 53.1% (based on Cu).
embodiment 4
By 160 μm of ol cupric bromides and 40 μm of ol4-(thiomethyls) phenylformic acid is dissolved in 2mL acetonitrile solution, being placed in external diameter is 8mm, internal diameter is 6mm, in the long Glass tubing for 10cm, add hot-seal, react 32 hours at being placed in constant temperature oven 100 DEG C, obtain described double-core ligand polymer crystal CHNOSCu, productive rate is 59.2% (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 (8)
1. a double-core ligand polymer, is characterized in that: chemical formula is CHNOSCu.
2. a kind of double-core ligand polymer according to claim 1, is characterized in that: this ligand polymer belongs to triclinic(crystalline)system,
p-1spacer, unit cell parameters is
a=9.9698 (6),
b=10.1748 (6),
c=20.8022 (8),
α=99.428 (4) o,
β=100.826 (4) o,
γ=99.970 (5) o, V=1998.85 (19)
3.
3. a kind of double-core ligand polymer according to claim 2, it is characterized in that: in this ligand polymer, copper atom takes the mode of pentacoordinate, each copper atom respectively with four 4-(thiomethyls) the O atom on phenylformic acid and the N coordination in a molecule of acetonitrile.
4. a preparation method for double-core ligand polymer according to claim 1, is characterized in that: by soluble copper salt and 4-(thiomethyl) phenylformic acid is added in acetonitrile solution, and reacting by heating under solvent thermal condition, obtains described double-core ligand polymer.
5. the preparation method of a kind of double-core ligand polymer according to claim 4, is characterized in that: described soluble copper salt and 4-(thiomethyl) benzoic mol ratio is 6 ~ 3:0.5 ~ 1.5.
6. the preparation method of a kind of double-core ligand polymer according to claim 4, is characterized in that: described Heating temperature is 80 ~ 120 DEG C.
7. the preparation method of a kind of double-core ligand polymer according to claim 4, is characterized in that: the described reaction times is 12 ~ 72 hours.
8. the preparation method of a kind of double-core ligand polymer according to claim 4, is characterized in that: described soluble copper salt is at least one in cupric nitrate, cupric chloride, cupric bromide.
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| CN201410435390.5A CN104230963A (en) | 2014-08-31 | 2014-08-31 | Dual-core coordination polymer and preparation method of dual-core coordination polymer |
| CN201510133974.1A CN104744496B (en) | 2014-08-31 | 2015-03-26 | A kind of double-core coordination polymer and preparation method thereof |
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| CN201410435390.5A CN104230963A (en) | 2014-08-31 | 2014-08-31 | Dual-core coordination polymer and preparation method of dual-core coordination polymer |
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| CN201410435390.5A Withdrawn CN104230963A (en) | 2014-08-31 | 2014-08-31 | Dual-core coordination polymer and preparation method of dual-core coordination polymer |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3206466A (en) * | 1962-06-27 | 1965-09-14 | Dow Chemical Co | Catalyzed method of preparing cuprous mercaptides |
| JP4058579B2 (en) * | 1999-04-28 | 2008-03-12 | 学校法人神奈川大学 | Gas adsorbents using organometallic complexes |
| EP1914263B1 (en) * | 2005-06-09 | 2012-12-05 | Yokohama City University | Single-crystalline organic carboxylic acid metal complex, process for producing the same, and use thereof |
| JP2010082544A (en) * | 2008-09-30 | 2010-04-15 | Ngk Insulators Ltd | Gas adsorbent |
| CN102964364B (en) * | 2012-12-04 | 2015-05-27 | 南昌航空大学 | Transition metal copper 4-(imidazole-1-yl) benzoic acid complex and preparation method thereof |
-
2014
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Application publication date: 20141224 |