CN105753797B - A kind of high core manganese cluster compound based on sulfur-bearing Triazole ligand and preparation method thereof - Google Patents
A kind of high core manganese cluster compound based on sulfur-bearing Triazole ligand and preparation method thereof Download PDFInfo
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- CN105753797B CN105753797B CN201610185604.7A CN201610185604A CN105753797B CN 105753797 B CN105753797 B CN 105753797B CN 201610185604 A CN201610185604 A CN 201610185604A CN 105753797 B CN105753797 B CN 105753797B
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- cluster compound
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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
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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 discloses a kind of high core manganese cluster compounds based on sulfur-bearing Triazole ligand and preparation method thereof, it is a kind of 5 mercapto methyl 1 of 3 thioketones that high core manganese cluster compound is learnt from its molecular structure, 2,4 triazole, 24 core manganese cluster compound, using the method for adding in second of metal salt cadmium nitrate during preparation, the dissolubility of indissoluble sulfur-bearing triazole cluster compound is improved.The manganese cluster compound has potential application value in the selection absorption of modern medicine, optics, magnetics and ion with detaching aspect, and this method has wide application prospects in terms of the preparation of slightly solubility cluster compound monocrystalline.
Description
Technical field
The present invention relates to the synthetic methods of complex, and in particular to the preparation method of slightly solubility cluster compound monocrystalline especially relates to
And a kind of high core manganese cluster compound based on sulfur-bearing Triazole ligand and preparation method thereof.
Technical background
The type of triazole derivative is various, and as important function base, triazole ligand complex metal from
The ability of son and formation hydrogen bond is stronger, so as to receive the concern of many researchers in chemical field.In biosystem, by
It is present in around the metal center of metalloproteinases in the compound of sulfur-bearing, there is potential application value in disease treatment,
Metalloproteinases is also served as in pharmaceutical chemistry applies raw material, also can be as the original of synthesis semi-conducting material in materials chemistry
Material, application are relatively broad.In terms of the synthesis of complex, the sulphur atom for belonging to soft base can be easily with belonging to the mistake of soft acid
It crosses metal and forms 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 as semiconductor, fluorescence and biomimetic material, arouse great concern.Sulphur atom is due to containing
Multipair lone pair electrons, coordination is undersaturated, and there are μ2- S, μ3- S, μ4- S, μ5- S, μ6More 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
It is enough to be easily and rapidly coordinated with transition metal ions, and bridge ligand is alternatively arranged as because size is smaller, make coordination mode more
Diversification is more easy to generate high core metal cluster compound.But the solubility of complex that sulfur-bearing triazole is formed with transition metal is very
Small, easily generation precipitates, it is difficult to obtain the monocrystalline measured needed for crystal structure.
Invention content
In order to obtain new sulfur-bearing 1,2,4-triazole complex, the particularly cluster compound with 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, the preparation side of such indissoluble cluster compound is on the other hand also provided
Method using the method for adding in second of metal salt cadmium nitrate, improves the dissolubility of indissoluble sulfur-bearing triazole cluster compound.
The high core manganese cluster compound based on sulfur-bearing Triazole ligand of the present invention, chemical formula are [Mn24(HL)24(H2O)6]·
NO3, wherein HL is 3- thioketones -5- mercapto methyls -1,2, and 4- triazoles, which 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, which is by 24 manganese ions, and 24 cores that 24 ligands are formed are double-deck
Cyclic annular cluster compound, also there are a nitrate ions at center.
The preparation method of high core manganese cluster compound of the present invention, includes the following steps：
(1) by 0.2mmol (0.0294g) 3- thioketones -5- mercapto methyl -1,2,4- triazoles (H3L)、0.2mmol
(0.0724g) Manganese perchlorate Mn (ClO4)2·6H2O, 0.2mmol (0.0617g) cadmium nitrate Cd (NO3)2·4H2O in 10mL N,
It is mixed in dinethylformamide (DMF)；
(2) after reaction is stirred at room temperature 5-7 hours in mixed liquor, colourless solution is filtered to obtain；
(3) filtrate is stood into slowly volatilization, there are light yellow cube of bulk crystals to be precipitated from mother liquor after 25 days, separation is washed
It washs, drying obtains cluster compound, yield 29%.
As a further preference, in the step (2), after reaction is stirred at room temperature 6 hours in mixed liquor, filtering.
The present invention is based on the high core manganese cluster compounds of sulfur-bearing Triazole ligand, learn it is a kind of 3- sulphur from its molecular structure
Ketone -5- mercapto methyls -1,2,24 core manganese cluster compound of 4- triazoles, using the side for adding in second of metal salt cadmium nitrate during preparation
Method improves the dissolubility of indissoluble sulfur-bearing triazole cluster compound.The high core manganese cluster compound modern medicine, optics, magnetics and
The selection absorption of ion has potential application value with detaching aspect, and this method is in terms of the preparation of slightly solubility cluster compound monocrystalline
Have wide application prospects.
Description of the drawings
Fig. 1 is the molecular structure (solvent molecule omission) of the high core manganese cluster compound of the present invention；
Fig. 2 is the simplification structure of Mn skeletons in the high core manganese cluster compound of the present invention；
Fig. 3 is the high core manganese cluster compound minimum asymmetric cell figure of the present invention.
Specific embodiment
The content of present invention is further described with reference to embodiment, but is not limitation of the invention.
Embodiment
The synthesis of high core manganese cluster compound based on sulfur-bearing Triazole ligand：
0.2mmol (0.0294g) H is weighed respectively3L、0.2mmol(0.0724g)Mn(ClO4)2·6H2O、0.2mmol
(0.0617g)Cd(NO3)2·4H2O is mixed in 10mL N, N-DMF；Reaction 6 hours is stirred at room temperature in obtained mixed liquor
Afterwards, colourless solution is filtered to obtain.Filtrate is stood into slowly volatilization, has light yellow cube of block-like crystal to be analysed from mother liquor after 25 days
Go out, separating, washing, it is dry.Its yield is 29%.
Referring to the molecular structure of the high core manganese cluster compound of Fig. 1 present invention, for the ease of observation, the object for deleting periphery is molten
Agent molecule.Apparent it is observed that the high core manganese cluster compound of the present invention is by 24 manganese ions from figure, 24 are matched
The 24 core double-layer circular cluster compounds that body and six water of coordination molecule are formed, also there are a nitrate ions at center.Cluster unit
Ring center is in equilateral triangular shape, and all there are two water of coordination molecule in each edge.The manganese cluster compound is asymmetric single by three
Member composition, there are one the centers that crystallography triad passes through the structure.
Referring to the simplified structure diagram of Mn skeletons in the high core manganese cluster compound of Fig. 2 present invention, can more intuitively find out from figure,
The metallic framework is that the hexagon being made of six manganese ions is composed.
Referring to the minimum asymmetric cell figure of the high core manganese cluster compound of Fig. 3 present invention, it can be seen from the figure that each asymmetric
Unit includes eight manganese ions, eight ligand moleculars and two water of coordination molecule, then by sulfydryl bridging on ligand, forms one
A Metallomacrocycle structure.It can be seen from the figure that the distortion tetragonal pyramid configuration of Mn1, Mn2, Mn3, Mn5 presentation pentacoordinate, Mn4,
The trigonal biyramid geometric configuration of pentacoordinate is presented in Mn6, and the distortion tetrahedral configuration of four-coordination is presented in Mn7, Mn8.
The crystal structure determination of the high core manganese cluster compound of the present invention：
The all proper manganese cluster compound monocrystalline of size and shape is selected, is placed on SuperNova single crystal diffractometers, is used
Graphite monochromatised Mo-K α radiationUnder the conditions of 153 (2) K respectively in the range of certain θ with
Scan mode collects point diffraction and is used for structure elucidation and amendment.Non-hydrogen atom is solved with direct method, and to their coordinate and its
Anisotropy thermal parameter corrected with complete matrix least square method.Mixed hydrogenation, hydrogen atom use isotropism thermal parameter；It is non-
Hydrogen atom uses anisotropy thermal parameter.The parsing of crystal structure and structural modifications respectively by SHELX-97 (Sheldrick,
1990) it is completed with SHELXL-97 (Sheldrick, 1997) program bag.1 is shown in Table in relation to crystallography and structural modifications data.
The crystallography of 1. cluster compound of table 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 (2)
1. a kind of high core manganese cluster compound based on sulfur-bearing Triazole ligand, it is characterized in that：The high core manganese cluster compound chemical formula is
[Mn24(HL)24(H2O)6]·NO3, wherein HL be 3- thioketones -5- mercapto methyls -1,2,4- triazoles；
The cluster compound crystal belongs to trigonal system,R Space group,Z =4；Cell parameter is：a=33.8212 (5),b =
33.8212 (5),c=56.1370 (9),α=90.00o,β=90.00o,γ=120.00o,V = 55610.6(14)
Å3；
X-ray crystal structure analysis shows, which is the 24 core double-layer circulars that 24 ligands are formed by 24 manganese ions
Cluster compound, also there are a nitrate ions at center.
2. the preparation method of high core manganese cluster compound according to claim 1, it is characterized in that including the following steps：
（1）By 0.2 mmol (0.0294g) 3- thioketones -5- mercapto methyl -1,2,4- triazoles, 0.2 mmol (0.0724g)
Manganese perchlorate Mn (ClO4)2·6H2O, 0.2 mmol (0.0617g) cadmium nitrate Cd (NO3)2·4H2O is in 10 mL N, N- diformazans
It is mixed in base formamide；
（2）After reaction is stirred at room temperature 6 hours in mixed liquor, colourless solution is filtered to obtain；
（3）Filtrate is stood into slowly volatilization, there are light yellow cube of bulk crystals to be precipitated from mother liquor after 25 days, separating, washing is done
It is dry to obtain cluster compound.
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| CN109942604B (en) * | 2019-04-22 | 2021-05-14 | 广西师范大学 | Macrocyclic pentacoordinate copper (II) complex containing sulfur-sulfur bond and in-situ synthesis method thereof |
| 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 |
| 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 |
Citations (2)
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|---|---|---|---|---|
| CN104844657A (en) * | 2015-04-09 | 2015-08-19 | 山西大学 | Manganese metal polymer and preparation method and application thereof |
| CN105732719A (en) * | 2016-04-25 | 2016-07-06 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole two-dimensional manganese complex single crystal and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844657A (en) * | 2015-04-09 | 2015-08-19 | 山西大学 | Manganese metal polymer and preparation method and application thereof |
| CN105732719A (en) * | 2016-04-25 | 2016-07-06 | 天津师范大学 | 1,4-dimethyl-2,5-di-1H-1,2,4-ditriazole two-dimensional manganese complex single crystal and application |
Non-Patent Citations (3)
| Title |
|---|
| Coordination geometries of bis(4-amino-3-ethyl-1,2,4-triazole-5-thione) complexes of Mn, Fe, Co, Ni, Cu and Zn: relationship to the 3-methyl analogs;Todd W. Kajdan等;《Inorganica Chimica Acta》;20000420;第300-302卷;第1082页左栏第1段，第1083页第2.2节 * |
| Structural trends in a series of divalent transition metal triazole complexes;Robert W. Clark等;《Inorganica Chimica Acta》;19991002;第293卷(第1期);第61-69页，尤其是第61页左栏第1段，第62页第2.3节 * |
| 新型1,2,4-三唑重金属离子荧光淬灭剂的合成、表征与性能;陈连清，等;《中南民族大学学报( 自然科学版)》;20150930;第34卷(第3期);第15-21页 * |
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