CN105753797A - High-nuclear manganese cluster compound based on sulfur-containing triazole ligand and preparation method thereof - Google Patents

High-nuclear manganese cluster compound based on sulfur-containing triazole ligand and preparation method thereof Download PDF

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CN105753797A
CN105753797A CN201610185604.7A CN201610185604A CN105753797A CN 105753797 A CN105753797 A CN 105753797A CN 201610185604 A CN201610185604 A CN 201610185604A CN 105753797 A CN105753797 A CN 105753797A
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cluster compound
manganese
preparation
sulfur
triazole
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CN105753797B (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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Abstract

The invention discloses a high-nuclear manganese cluster compound based on a sulfur-containing triazole ligand and a preparation method thereof. According to the molecular structural graph, the high-nuclear manganese cluster compound is the 3-thioketone-5-mercapto methyl-1,2,4-triazole 24-nuclear manganese cluster compound. In the preparation process, by the adoption of the method of adding the second kind of metal salt cadmium nitrate, the solubleness of the indissolvable sulfur-containing triazole cluster compound is improved; the manganese cluster compound has the potential application value in the aspects of modern medicine, optics, magnetics, and ion selective absorption and separation. The method has the wide application prospect in the aspect of preparation of indissolvable cluster compound monocrystals.

Description

A kind of high core manganese cluster compound based on sulfur-bearing Triazole ligand and preparation method thereof
Technical field
The present invention relates to the synthetic method of complex, be specifically related to the preparation method of slightly solubility cluster compound monocrystalline, relate to especially And a kind of high core manganese cluster compound based on sulfur-bearing Triazole ligand and preparation method thereof.
Technical background
Triazole derivative of a great variety, and as important function base, triazole ligand complex metal from The ability of son and formation hydrogen bond is stronger, thus receives the concern of many researchers at chemical field.In living things system, by Compound in sulfur-bearing is present in around the metal center of metalloproteinases, has potential using value in disease treatment, The application raw material of metalloproteinases is also served as in pharmaceutical chemistry, also can be as synthesizing the former of semi-conducting material in materials chemistry Material, applies relatively broad.In terms of the synthesis of complex, belong to soft base sulphur atom can easily with the mistake belonging to soft acid Cross metal and form stable complex.People have synthesized many sulfur-bearing 1,2,4-triazole complexes with superperformance in recent years, this A little complexs can be used to, as semiconductor, 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 bonding mode and design feature.And sulfur-bearing Triazole ligand, it is not only due to containing multiple strong coordination atom sulphur and nitrogen, energy The most easily and rapidly it is coordinated with transition metal ions, and is alternatively arranged as bridge ligand because size is less, make coordination mode more Diversification, is more easy to generate high core metal cluster compound.But, the solubility of complex that sulfur-bearing triazole and transition metal are formed is very Little, easily generate precipitation, be 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 having the cluster compound of high check figure, one aspect of the present invention carries For a kind of high core manganese cluster compound based on sulfur-bearing Triazole ligand, on the other hand also provide for the preparation side of such indissoluble cluster compound Method, uses the method adding the second slaine cadmium nitrate, improves the dissolubility of indissoluble sulfur-bearing triazole cluster compound.
Based on sulfur-bearing Triazole ligand the high core manganese cluster compound of the present invention, chemical formula is [Mn24(HL)24(H2O)6]· NO3, wherein HL is 3-thioketones-5-mercapto methyl-1,2,4-triazoles, and this cluster compound crystal belongs to trigonal system,Space Group, Z=4；Cell parameter is: α= 90.00 °, β=90.00 °, γ=120.00 °,
X-ray crystal structure analysis shows, this cluster compound is by 24 manganese ions, the 24 cores bilayers that 24 parts are constituted Circular cluster compound, center there is also a nitrate ion.
The preparation method of high core manganese cluster compound of the present invention, comprises the steps:
(1) by 0.2mmol (0.0294g) 3-thioketones-5-mercapto methyl-1,2,4-triazole (H3L)、0.2mmol (0.0724g) Manganese perchlorate Mn (ClO4)2·6H2O, 0.2mmol (0.0617g) cadmium nitrate Cd (NO3)2·4H2O in 10mL N, Mixing in dinethylformamide (DMF)；
(2), after mixed liquor is stirred at room temperature reaction 5-7 hour, colourless solution is filtered to obtain；
(3) filtrate standing slowly volatilization, have light yellow cube of bulk crystals to separate out from mother liquor after 25 days, separation is washed Washing, be dried and i.e. prepare cluster compound, its productivity is 29%.
As the most preferably, in described step (2), after mixed liquor is stirred at room temperature reaction 6 hours, filter.
The present invention high core manganese cluster compound based on sulfur-bearing Triazole ligand, learns it is a kind of 3-sulphur from its molecular structure Ketone-5-mercapto methyl-1,2,4-triazole 24 core manganese cluster compounds, use the side adding the second slaine cadmium nitrate during preparation Method, improves the dissolubility of indissoluble sulfur-bearing triazole cluster compound.This high core manganese cluster compound modern medicine, optics, magnetics and The selecting absorption and separate aspect and have potential using value of ion, the method is in terms of the preparation of slightly solubility cluster compound monocrystalline Have wide application prospects.
Accompanying drawing explanation
Fig. 1 is the molecular structure (solvent molecule omission) of height core manganese cluster compound of the present invention；
Fig. 2 is the simplification structure of Mn skeleton in height core manganese cluster compound of the present invention；
Fig. 3 is height core manganese cluster compound minimum asymmetric cell figure 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
The synthesis of high core manganese cluster compound based on sulfur-bearing Triazole ligand:
Weigh 0.2mmol (0.0294g) H respectively3L、0.2mmol(0.0724g)Mn(ClO4)2·6H2O、0.2mmol (0.0617g)Cd(NO3)2·4H2O, in 10mL N, mixes in N-DMF；The mixed liquor obtained is stirred at room temperature reaction 6 hours After, filter to obtain colourless solution.Filtrate is stood slowly volatilization, after 25 days, has light yellow cube of block crystal to analyse from mother liquor Go out, separating, washing, be dried.Its productivity is 29%.
Seeing the molecular structure of Fig. 1 height of the present invention core manganese cluster compound, for the ease of observing, the object deleting periphery is molten Agent molecule.Significantly it is observed that height core manganese cluster compound of the present invention is by 24 manganese ions from figure, join for 24 Body and 24 core double-layer circular cluster compounds of six water of coordination molecular compositions, center there is also a nitrate ion.Cluster unit Ring center is equilateral triangular shape, and each edge has two water of coordination molecules.This manganese cluster compound is by three asymmetric lists Unit's composition, has the crystallography triad center through this structure.
See the simplified structure diagram of Mn skeleton in Fig. 2 height of the present invention core manganese cluster compound, can more intuitively find out from figure, This metallic framework is that the hexagon being made up of six manganese ions combines.
See the minimum asymmetric cell figure of Fig. 3 height of the present invention core manganese cluster compound, it can be seen that each asymmetric Unit comprises eight manganese ions, eight ligand moleculars and two water of coordination molecules, then by sulfydryl bridging on part, defines one Individual Metallomacrocycle structure.It can be seen that Mn1, Mn2, Mn3, Mn5 present the distortion tetragonal pyramid configuration of pentacoordinate, Mn4, Mn6 presents the trigonal biyramid geometric configuration of pentacoordinate, and Mn7, Mn8 present the distortion tetrahedral configuration of four-coordination.
The crystal structure determination of height core manganese cluster compound of the present invention:
Select the manganese cluster compound monocrystalline that size and shape is the most proper, be placed on SuperNova single crystal diffractometer, use Graphite monochromatised Mo-K α radiatesUnder the conditions of 153 (2) K respectively in the range of certain θ with Scan mode collects point diffraction for structure elucidation and correction.Non-hydrogen atom direct method solves, and to their coordinate and Anisotropy thermal parameter carries out using complete matrix least square refinement.Mixed hydrogenation, hydrogen atom uses isotropism thermal parameter；Non- Hydrogen atom uses anisotropy thermal parameter.The parsing of crystal structure and structural modifications respectively by SHELX-97 (Sheldrick, 1990) complete with SHELXL-97 (Sheldrick, 1997) program bag.It is shown in Table 1 about crystallography and structural modifications data.
The crystallography of table 1. cluster compound and structural modifications data
aR1=Σ | | Fo|–|Fc||/Σ|Fo|；bwR2=[Σ w (Fo 2–Fc 2)2/Σw(Fo 2)2]1/2。

Claims (3)

1. a high core manganese cluster compound based on sulfur-bearing Triazole ligand, is characterized in that: this high core manganese cluster compound chemical formula is [Mn24(HL)24(H2O)6]·NO3, wherein HL is 3-thioketones-5-mercapto methyl-1,2,4-triazoles；
This cluster compound crystal belongs to trigonal system,Space group, Z=4；Cell parameter is: α=90.00 °, β=90.00 °, γ=120.00 °,
X-ray crystal structure analysis shows, this cluster compound is by 24 manganese ions, the 24 core double-layer circulars that 24 parts are constituted Cluster compound, center there is also a nitrate ion.
The preparation method of high core manganese cluster compound the most according to claim 1, is characterized in that comprising the steps:
(1) by 0.2mmol (0.0294g) 3-thioketones-5-mercapto methyl-1,2,4-triazole, 0.2mmol (0.0724g) high chlorine Acid manganese Mn (ClO4)2·6H2O, 0.2mmol (0.0617g) cadmium nitrate Cd (NO3)2·4H2O is in 10mLN, dinethylformamide Middle mixing；
(2), after mixed liquor is stirred at room temperature reaction 5-7 hour, colourless solution is filtered to obtain；
(3) filtrate is stood slowly volatilization, after 25 days, have light yellow cube of bulk crystals to separate out from mother liquor, separating, washing, dry Dry i.e. prepare cluster compound.
The preparation method of high core manganese cluster compound the most according to claim 2, is characterized in that: in described step (2), mixed liquor After being stirred at room temperature reaction 6 hours, filter.
CN201610185604.7A 2016-03-29 2016-03-29 A kind of high core manganese cluster compound based on sulfur-bearing Triazole ligand and preparation method thereof Expired - Fee Related CN105753797B (en)

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CN109867689A (en) * 2019-04-22 2019-06-11 广西师范大学 A kind of double-core Cd (II) complex and its in-situ synthetic method of sulfur-bearing-sulfide linkage
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
CN109942604A (en) * 2019-04-22 2019-06-28 广西师范大学 A kind of big ring pentacoordinate copper (II) complex and its in-situ synthetic method of sulfur-bearing-sulfide linkage
CN113831368A (en) * 2021-08-16 2021-12-24 山东交通学院 Mixed-valence ten-core manganese cluster compound protected by organosilane ligand and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN109867689A (en) * 2019-04-22 2019-06-11 广西师范大学 A kind of double-core Cd (II) complex and its in-situ synthetic method of sulfur-bearing-sulfide linkage
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
CN109942604A (en) * 2019-04-22 2019-06-28 广西师范大学 A kind of big ring pentacoordinate copper (II) complex and its in-situ synthetic method of sulfur-bearing-sulfide linkage
CN109867689B (en) * 2019-04-22 2021-05-14 广西师范大学 Binuclear Cd (II) complex containing sulfur-sulfur bond and in-situ synthesis method thereof
CN113831368A (en) * 2021-08-16 2021-12-24 山东交通学院 Mixed-valence ten-core manganese cluster compound protected by organosilane ligand and preparation method thereof

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