CN105693639A - High nuclear nickel cluster based on sulphur-containing triazole ligand and preparation method thereof - Google Patents

High nuclear nickel cluster based on sulphur-containing triazole ligand and preparation method thereof Download PDF

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CN105693639A
CN105693639A CN201610185682.7A CN201610185682A CN105693639A CN 105693639 A CN105693639 A CN 105693639A CN 201610185682 A CN201610185682 A CN 201610185682A CN 105693639 A CN105693639 A CN 105693639A
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cluster compound
nickel
preparation
cluster
high core
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CN105693639B (en
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蒋毅民
郑云云
黄富平
张晓强
王慧
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Guangxi Normal University
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Guangxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a high nuclear nickel cluster based on a sulphur-containing triazole ligand and a preparation method thereof. The high nuclear nickel cluster can be known as a 3-thioketone-5-mercaptomethyl-1,2,4-triazole 24 nuclear nickel cluster from a molecular graph thereof. A method of adding second metal salt cadmium nitrate is adopted during preparation, so that the solubility of the insoluble sulphur-containing triazole cluster is improved. The nickel cluster has potential application values in the aspects of modern medicine, optics, magnetics and selective adsorption and separation of ions, and the preparation method has broad application prospects in preparation of insoluble cluster single crystals.

Description

A kind of high core nickel cluster compound based on sulfur-bearing Triazole ligand and preparation method thereof
Technical field
The present invention relates to the synthetic method of coordination compound, the preparation method being specifically related to slightly solubility cluster compound monocrystalline, particularly to a kind of high core nickel cluster compound based on sulfur-bearing Triazole ligand and preparation method thereof。
Technical background
Triazole derivant of a great variety, and as important function base, triazole ligand complex metal ion and to form the ability of hydrogen bond stronger, thus receiving the concern of many researcheres at chemical field。In living things system, owing to the compound of sulfur-bearing is present in around the metal center of metalloproteases, disease treatment has potential using value, pharmaceutical chemistry also serves as the application raw material of metalloproteases, materials chemistry also can, as the raw material of synthesis semi-conducting material, be applied relatively broad。In the synthesis of coordination compound, the sulphur atom belonging to soft base can form stable coordination compound with the transition metal belonging to soft acid easily。People have synthesized many sulfur-bearing 1,2,4-triazole complexes with superperformance in recent years, and these coordination compounds can be used to, as quasiconductor, fluorescence and biomimetic material, arouse great concern。Sulphur atom is owing to containing multipair lone pair electrons, its coordination is undersaturated, and there is μ2-S, μ3-S, μ4-S, μ5-S, μ6Many kinds of bridging patterns of-S, show abundant one-tenth key mode and construction features。And sulfur-bearing Triazole ligand, it is not only due to containing multiple strong coordination atom sulfur and nitrogen, it is possible to easily and rapidly with transition metal ions coordination, and because of the smaller bridge ligand that is alternatively arranged as, makes coordination mode diversification more, be more easy to the high core metal cluster compound of generation。But, the solubility of complex that sulfur-bearing triazole is formed with transition metal is only small, very easily generates precipitation, is difficult to obtain the monocrystalline measured needed for crystal structure。
Summary of the invention
In order to obtain new sulfur-bearing 1,2,4-triazole complex, particularly there is the cluster compound of high check figure, one aspect of the present invention provides a kind of high core nickel cluster compound based on sulfur-bearing Triazole ligand, the preparation method also providing for such indissoluble cluster compound on the other hand, adopt the method adding the second slaine cadmium nitrate, improve the dissolubility of indissoluble sulfur-bearing triazole cluster compound。
The high core nickel cluster compound based on sulfur-bearing Triazole ligand of the present invention, chemical formula is [Ni24(HL)24]·NO3, wherein HL is 3-thioketone-5-mercapto methyl-1, and 2,4-triazoles, this cluster compound crystal belongs to hexagonal crystal system, P6mn space group, Z=8；Cell parameter is: α=90.00 °, β=90.00 °, γ=120.00 °,
X-ray crystal structure analysis shows, this cluster compound is that the 24 core double-layer circular cluster compounds that 24 parts are constituted, center there is also a nitrate ion by 24 nickel ions。
The preparation method of high core nickel cluster compound of the present invention, comprises the steps:
(1) by 0.2mmol (0.0294g) 3-thioketone-5-mercapto methyl-1,2,4-triazole (H3L), 0.2mmol (0.0581g) perchloric acid nickel (NO3)2·6H2O, 0.2mmol (0.0617g) cadmium nitrate Cd (NO3)2·4H2O is mixing in 10mLN, dinethylformamide (DMF)；
(2) mixed liquor stirring reaction at 40-60 DEG C, after 5-7 hour, filters to obtain green solution；
(3) filtrate standing slow volatilization, have green block crystal to precipitate out from mother solution after 15 days, separating, washing, dry i.e. prepared cluster compound, its productivity is 38%。
As further preferably, in described step (2), mixed liquor stirring reaction at 40 DEG C, after 6 hours, filters。
The present invention is based on the high core nickel cluster compound of sulfur-bearing Triazole ligand, learn it is a kind of 3-thioketone-5-mercapto methyl-1 from its molecular structure, 2,4-triazole 24 core nickel cluster compounds, adopt the method adding the second slaine cadmium nitrate during preparation, improve the dissolubility of indissoluble sulfur-bearing triazole cluster compound。This nickel cluster compound has potential using value in the selection of modern medicine, optics, magnetics and ion is adsorbed and separated, and the method has wide application prospects in the preparation of slightly solubility cluster compound monocrystalline。
Accompanying drawing explanation
Fig. 1 is the molecular structure (solvent molecule omission) of height core nickel cluster compound of the present invention；
Fig. 2 is the simplified structure diagram of Ni skeleton in height core nickel cluster compound of the present invention；
Fig. 3 is the asymmetric cell figure of height core nickel cluster compound of the present invention。
Detailed description of the invention
Below in conjunction with embodiment, present invention is further described, but is not limitation of the invention。
Embodiment
Synthesis based on the high core nickel cluster compound of sulfur-bearing Triazole ligand:
Weigh 0.2mmol (0.0294g) H respectively3L、0.2mmol(0.0581g)Ni(NO3)2·6H2O、0.2mmol(0.0617g)Cd(NO3)2·4H2O mixes in 10mLDMF；Mixed liquor after stirring reaction 6h, filters to obtain green solution at 40 DEG C；Filtrate stands slow volatilization, and within about 15 days, green block crystal precipitates out from mother solution, separating, washing, and dry i.e. prepared cluster compound, its productivity is 38%。
Referring to the molecular structure of Fig. 1 height of the present invention core nickel cluster compound, for the ease of observing, delete the object solvent molecule of periphery。Significantly it can be observed that there is the nickel ion of six hexa-coordinates, the nickel ion of six pentacoordinate nickel ions and 12 four-coordinations in a cluster unit from figure。Triazole ring in 24 parts has both participated in coordination, have 30 nitrogen-atoms and participate in coordination, wherein there are 4 nitrogen-atoms on 18 triazole rings individually and nickel ion coordination, on six triazole rings 1 and 2 nitrogen-atoms simultaneously participate in coordination, what is interesting is these six triazole rings three angle relative positions just at center nitrate ion O-N-O, upper and lower two rings are corresponding。
Referring to the simplified structure diagram of Ni skeleton in Fig. 2 height of the present invention core nickel cluster compound, the skeleton of this high core nickel cluster compound, there is crystallography hexagonal axis center through this structure, it is possible to regard as and be made up of six minimum asymmetric cell containing four center nickel ions, with the μ of sulphur atom2-S and μ3-S bridging makes these six asymmetric cell couple together, and constitutes the 20 four-core metal macro ring that is repetitive with [Ni-S-Ni]。
Each asymmetric cell of asymmetric cell figure referring to Fig. 3 height of the present invention core nickel cluster compound comprises four nickel ions, the different nickel ion of these four coordination environment is respectively, Ni1 is the distorted octahedron configuration of hexa-coordinate, Ni2 is the distortion tetrahedral configuration of four-coordination, Ni3 is the distortion tetragonal pyramid configuration of pentacoordinate, and Ni4 is the tetrahedral configuration of the distortion of four-coordination。Each asymmetric cell, again through sulfydryl bridging on part, defines a Metallomacrocycle structure。
The crystal structure determination of height core nickel cluster compound of the present invention:
Select size and all proper nickel cluster compound monocrystalline of shape, be placed on SuperNova single crystal diffractometer, adopt graphite monochromatised Mo-K α to radiateWhen 153 (2) K respectively within the scope of certain θ withScan mode collects point diffraction for structure elucidation and correction。Non-hydrogen atom direct method solves, and the coordinate and anisotropy thermal parameter thereof to them carries out using complete matrix least square refinement。Mixed hydrogenation, hydrogen atom adopts isotropism thermal parameter；Non-hydrogen atom adopts anisotropy thermal parameter。The parsing of crystal structure and structural modifications are completed by SHELX-97 (Sheldrick, 1990) and SHELXL-97 (Sheldrick, 1997) program package respectively。About crystallography and structural modifications data in Table 1。
1. the crystallography of cluster compound and structural modifications data
Σ||Fo|–|Fc||/Σ|Fo|；bwR2=[Σ w (Fo 2–Fc 2)2/Σw(Fo 2)2]1/2。

Claims (3)

1. based on a high core nickel cluster compound for sulfur-bearing Triazole ligand, it is characterized in that: this high core nickel cluster compound chemical formula is [Ni24(HL)24]·NO3, wherein HL is 3-thioketone-5-mercapto methyl-1,2,4-triazoles,
This cluster compound crystal belongs to hexagonal crystal system, P6mn space group, Z=8；Cell parameter is: α=90.00 °, β=90.00 °, γ=120.00 °,
X-ray crystal structure analysis shows, this cluster compound is that the 24 core double-layer circular cluster compounds that 24 parts are constituted, center there is also a nitrate ion by 24 nickel ions。
2. the preparation method of high core nickel cluster compound according to claim 1, it is characterized in that comprising the steps: that (1) is by 0.2mmol (0.0294g) 3-thioketone-5-mercapto methyl-1,2,4-triazoles, 0.2mmol (0.0581g) perchloric acid nickel (NO3)2·6H2O, 0.2mmol (0.0617g) cadmium nitrate Cd (NO3)2·4H2O mixes in 10mLN, dinethylformamide；
(2) mixed liquor stirring reaction at 40-60 DEG C, after 5-7 hour, filters to obtain green solution；
(3) filtrate standing slow volatilization, after 15 days, green block crystal precipitates out from mother solution, separating, washing, dry i.e. prepared cluster compound。
3. the preparation method of high core nickel cluster compound according to claim 2, is characterized in that: in described step (2), and mixed liquor stirring reaction at 40 DEG C, after 6 hours, filters to obtain green solution。
CN201610185682.7A 2016-03-29 2016-03-29 A kind of high core nickel cluster compound and preparation method thereof based on sulfur-bearing Triazole ligand Expired - Fee Related CN105693639B (en)

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CN106905376A (en) * 2017-02-21 2017-06-30 广西师范大学 A kind of core mixed valence cobalt cluster compound of micropore 20 and its synthetic method
CN106928284A (en) * 2017-02-21 2017-07-07 广西师范大学 A kind of core mixed valence nickel cluster compound of micropore 20 and its synthetic method
CN109912627A (en) * 2019-04-22 2019-06-21 广西师范大学 A kind of big ring four-coordination copper (II) complex and its in-situ synthetic method of sulfur-bearing-sulfide linkage
CN109912628A (en) * 2019-04-22 2019-06-21 广西师范大学 A kind of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage and its in-situ synthetic method
CN109970767A (en) * 2019-04-22 2019-07-05 广西师范大学 The four of a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex and its in-situ synthetic method

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Publication number Priority date Publication date Assignee Title
CN106905376A (en) * 2017-02-21 2017-06-30 广西师范大学 A kind of core mixed valence cobalt cluster compound of micropore 20 and its synthetic method
CN106928284A (en) * 2017-02-21 2017-07-07 广西师范大学 A kind of core mixed valence nickel cluster compound of micropore 20 and its synthetic method
CN109912627A (en) * 2019-04-22 2019-06-21 广西师范大学 A kind of big ring four-coordination copper (II) complex and its in-situ synthetic method of sulfur-bearing-sulfide linkage
CN109912628A (en) * 2019-04-22 2019-06-21 广西师范大学 A kind of big ring nickel (II) complex of the dimerization of sulfur-bearing-sulfide linkage and its in-situ synthetic method
CN109970767A (en) * 2019-04-22 2019-07-05 广西师范大学 The four of a kind of sulfur-bearing-sulfide linkage gather big ring trinuclear iron complex and its in-situ synthetic method

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