CN102382141A - Preparation methods of sulfur atom bridging coordination compound with bimetal unit - Google Patents
Preparation methods of sulfur atom bridging coordination compound with bimetal unit Download PDFInfo
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- CN102382141A CN102382141A CN2010102688450A CN201010268845A CN102382141A CN 102382141 A CN102382141 A CN 102382141A CN 2010102688450 A CN2010102688450 A CN 2010102688450A CN 201010268845 A CN201010268845 A CN 201010268845A CN 102382141 A CN102382141 A CN 102382141A
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Abstract
Preparation methods of sulfur atom bridging coordination compound with a bimetal unit are disclosed. One of the preparation methods comprises the steps of: performing reaction of a tetrahydrofuran solution of a bimetal building unit M2(DAniF)3(OOCCH3) and an aqueous solution of a HS-ionic salt under an anaerobic condition without water to synthesize a coordination compound which is sensitive to moisture and air; and placing the obtained coordination compound in air for deprotonation coupling and oxidizing reaction to prepare the product. The other method comprises the steps of: performing reaction of a tetrahydrofuran solution of a bimetal building unit M2(DAniF)3(OOCCH3) and an aqueous solution of a S2-ionic salt in the air to prepare the product. The invention prepares the sulfur atom bridging coordination compound with a bimetal unit which is not sensitive to moisture and air and capable of presenting in air. Characterization research can be performed for the properties of the sulfur atom bridging coordination compound with a bimetal unit in air. The research result for the structural, optical and electric properties of the product shows that the electronic coupling and transferring abilities in the molecules of the prepared sulfur atom bridging coordination compound with double molybdenum units and the sulfur atom bridging coordination compound with a bimetal unit is a model compound for research of molecular and electronic apparatuses.
Description
Technical field
The present invention relates to a kind of preparation method of coordination compound, relate in particular to a kind of preparation method of sulphur atom bridging bi-metal element title complex.
Background technology
Along with the develop rapidly of information science and correlation technique, the computingmachine microprocessing systems is had higher requirement.The computingmachine of the ultraminiaturization of development and design a new generation, ultra-high speed, vast capacity, key is the high density integrated circuit of development of new.The complete processing that the tradition microelectronics industry utilizes photoetching technique on monocrystalline silicon piece, to make large-scale integrated circuit has been approached the limit.As far back as 1974, Aviram etc. just proposed the viewpoint of some molecular energy replacement silicon, but up to just getting along with in this field in recent years.Molecule electronic material can be on molecular scale the fast processing bulk information, its high-density, the high speed of response and high energy conversion efficiency have attracted numerous investigators' sight.Scientist thinks that following computingmachine should be a molecular computer, promptly through chemistry on the molecular level and physical action information is detected, handles, transmits and stores.Therefore, the research of relevant " molecular electronic device " becomes the international advanced subject and the hot fields that intersect at chemistry, material subject, and molecular wire and molecular switch are again emphasis wherein.In recent years proposed some and be expected to be used for actual system, the light-operated molecular wire of forming like the couplet multi-pyridine ligand that is connected with conjugation poly acetylene chain, has combined the automatically controlled molecular switch of oxidation-reduction type of composition with positively charged ion and with the nucleic acid based molecular wire of dna molecular composition etc. with anthraquinone lasso trick ether.But because the research of molecular wire and molecular switch relates to long-range light, electron-transfer reaction, many influence factors are unclear fully as yet, restricted the development in this field.And the intramolecularly electron-transfer reaction can take place in some bridging bi-metal element title complexs; Cause charge transfer process between valency (IVTC) and follow the variation of metal-metal length of covalent bond; Can control eaily and detect; Have the potential that becomes molecular device, caused numerous investigators' interest.And because its variety, relative stability and unique electricity and optical property thereof have become one of ideal model of research molecular wire, molecular switch and molecular rectifier equimolecular electron device.
The electron coupling in the bridging bi-metal element complex molecule and the research of electron transport are compared with the monokaryon metals ion, and the definition of metal-metal bonding monomer electronic structure is clear.The Mo that for example forms with the quadruple key
2, electronic configuration is σ
2π
4δ
2Its HOMO (δ) is different with HOMO-1 (π) symmetry; Energy level difference is bigger, and the redox reaction of metal center and the electronic coupling effect between the metal-metal are all only relevant with two δ valence electrons, and this brings great convenience for the analysis of electronic structure and rail effect.Secondly; The monomeric molecular structure of covalency bimetal, electronic configuration and spectral quality three are interrelated; The variation of electronic configuration is the variation of metal-metal key bond order, but shows as the variation of location parameter such as metal-metal key bond distance and visible region δ → δ * transition.With metal-metal key and the δ → δ * absorption spectrum probe as electronic structure, easy methods such as combined with electrochemical and magnetic property are explored the electron coupling character of title complex, and research means is easy, be prone to implement.
At present, relevant bridging bi-metal element title complex great majority are the bi-metal element title complex of organic ligand bridging, because this compounds is to air and moisture-sensitive, the research of its physicochemical property have been caused certain restriction.And during the bi-metal element title complex of synthetic organic ligand bridging, at first must design and synthesize suitable organic bridge part, with the reaction of bimetal construction unit, synthesis step is loaded down with trivial details again.Because this compounds to air and moisture-sensitive, exists synthesis condition harsh, the aftertreatment trouble, productive rate is low, problems such as monocrystalline culture system complicacy.
Summary of the invention
The object of the invention, exactly for provide a kind of existence stable in the air, and can be in practical study and the preparation method of the sulphur atom bridging bi-metal element title complex that be applied in producing.
In order to achieve the above object, the present invention has adopted following two kinds of technical schemes:
First kind of technical scheme is, under the anhydrous and oxygen-free condition, by bimetal construction unit M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution and HS
-The reactant aqueous solution of ion salt synthesizes the title complex to moisture and air-sensitive, places air to carry out the reaction of deprotonation coupled oxidation the gained title complex then, prepares sulphur atom bridging bi-metal element title complex;
Said bimetal construction unit M
2(DAniF)
3(OOCCH
3) and HS
-The ionic mol ratio is 1: 5;
Said bimetal construction unit M
2(DAniF)
3(OOCCH
3) in M represent Mo or W, DAniF represents N, N '-two-to anisole carbonamidine or N, N '-two-to the verivate of anisole carbonamidine.
Second kind of technical scheme is, in air, by bimetal construction unit M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution and S
2-The reactant aqueous solution of ion salt is prepared sulphur atom bridging bi-metal element title complex;
Said bimetal construction unit M2 (DAniF) 3 (OOCCH3) is 1: 5 with S2-ionic mol ratio;
M among the said bimetal construction unit M2 (DAniF) 3 (OOCCH3) represents Mo or W, and DAniF represents N, N '-two-to anisole carbonamidine or N, and N '-two-to the verivate of anisole carbonamidine.
The sulphur atom bridging bi-metal element title complex that utilizes method of the present invention to prepare, having can existence stable in the air and excellent physicochemical property, like optics and electrical properties, special magnetic property etc.
Method of the present invention is easy to operate, easy to control, and during to the property research of the product prepared, method is simple.
Composition, structure and character to the inventive method products therefrom characterize, can select for use respectively ultimate analysis, nuclear-magnetism (
1H NMR), X-ray single crystal structure diffraction, uv-vis spectra, cyclic voltammetric electrochemistry, susceptibility test etc.Results of elemental analyses shows the composition content of each element in the product; 1H NMR nuclear-magnetism and X-ray single crystal structure diffraction show the constructional feature of compound; Uv-vis spectra and cyclic voltammetric electrochemistry characterize the optics and the electrical properties of product respectively, and the susceptibility test result shows the magnetic property that product is special.
Method of the present invention also has the following advantages:
1. the sulphur atom bridging bi-metal element title complex that synthesizes of the present invention is insensitive to moisture and air, can stable existence in air, be convenient to its property research.
2. the preparation method who is adopted is simple, easy to operate, easy to control, and aftertreatment technology is simple, and productive rate is high, is easy to realize industriallization.
3. the test shows of optical property and electrical properties, electron coupling and electron transport in institute's synthetic sulphur atom bridging bi-metal element title complex are very capable, for the research of molecular wire, molecular switch equimolecular electron device provides the ideal model compound.
Description of drawings
Fig. 1 is synthetic title complex [Mo among the embodiment 1
2(DAniF)
3]
2(SH)
2X-ray single crystal diffraction crystalline structure figure.
Product-sulphur atom bridging bi-metal element title complex [the Mo of Fig. 2 for preparing among the embodiment 1 and 2
2(DAniF)
3]
2S
2X-ray single crystal diffraction crystalline structure figure.
Fig. 3 is for obtaining the UV, visible light electronic light spectrogram of product among the embodiment 2.
Fig. 4 is the cyclic voltammetric electrochemical properties test pattern of products therefrom among the embodiment 2.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
The first step, 10mL concentration are the configuration of the 0.2mol/L NaHS aqueous solution.In the Schlenk bottle, add 0.48g (2mmol) Na
2S9H
2O is dissolved in the 10mL zero(ppm) water, and measuring 0.2mL concentration is the hydrochloric acid soln adding Na of 10mol/L
2In the S aqueous solution, obtain the yellow clarifying NaHS aqueous solution.Logical nitrogen deoxygenation 3 hours, for use.
Second step is under the anhydrous and oxygen-free condition, with 0.2044g (0.2mmol) Mo
2(DAniF)
3(OOCCH
3) being dissolved in the 10mL THF, solid all dissolves, and obtains the glassy yellow settled solution.Stir down, slowly drip the first step and make NaHS aqueous solution 5mL, in the process that feeds intake, it is muddy that solution becomes gradually, color burn.Fed intake behind the 15min, had a large amount of yellow mercury oxides to generate, solution colour is brown.React 4h under the room temperature, do not have other considerable change.Filter, with washing with alcohol product 3 times, 15mL removes impurity at every turn, and decompressing and extracting gets yellow solid.Add the 10mL methylene dichloride, solid all dissolves, and is filtered in the reaction tubes, filtrates to be yellowish brown.Slowly add 30mL ethanol along the reaction tube wall.Adopt solvent diffusion method to cultivate monocrystalline, after the week, obtain blocky yellow crystals-title complex [Mo
2(DAniF)
3]
2(SH)
2It is carried out the X-ray single crystal structure characterize, figure is as shown in Figure 1 for its crystalline structure, and clear for structure iron, all that link to each other with N are omitted anisole.
The 3rd step with the yellow crystals of gained under the anhydrous and oxygen-free condition in second step, was exposed in the air 48 hours, and deprotonation coupled oxidation process takes place, and obtained required column black crystals product-title complex [Mo
2(DAniF)
3]
2S
2It is carried out the X-ray single crystal structure characterizes.Figure is as shown in Figure 2 for its crystalline structure, and clear for structure iron, all that link to each other with N are omitted anisole.
Embodiment 2:
Take by weighing 0.409g (0.4mmol) Mo
2(DAniF)
3(OOCCH
3) in 100mL Sehlenck bottle, add the 10mL THF, solid all dissolve the glassy yellow settled solution.Stir down, add the Na of 0.4mol/L
2S aqueous solution 5mL has a large amount of yellow mercury oxides to generate immediately, and open the Schlenk bottle in air this moment, reacts 24h under the room temperature, and the solid color slowly changes: yellow-yellowish brown-brown finally obtains a large amount of dark brown solids.Filter, with zero(ppm) water and alcoholic acid mixed solution (zero(ppm) water and alcoholic acid volume ratio are 2: 1) washed product, remove impurity, when pH=7, decompressing and extracting gets brown-black powder.Add the 10mL methylene dichloride, solid all dissolves, and is filtered in the reaction tubes, filtrates to be brownish black.Slowly add 30mL ethanol along the reaction tube wall.Adopt solvent diffusion method to cultivate crystal, after the week, obtain the black crystals product of column, its X-ray single crystal structure characterization result is with gained crystalline structure among the embodiment 1, and is as shown in Figure 2.Fig. 3 is the UV, visible light electronic spectrum of product, and characterization result shows at the 803nm place a very strong absorption peak to be arranged, and explains that the electron coupling between bi-metal element and electron transport ability are strong in the title complex, and energy required during transition of electron is very low.Fig. 4 is the cyclic voltammetric electrochemical properties test result of product; The result shows that title complex has two reversible one-electron oxidation reduction processes, the E1/2 of first redox processes (1)=-1.345V; The E1/2 of second redox processes (2)=0.365V; The difference of the two is Δ E1/2=1.71V, and this explains that also electron coupling and the electron transport ability between two molybdenum unit is strong in the title complex, is the model compound that is fit to the research molecular electronic device.
Claims (9)
1. the preparation method of a sulphur atom bridging bi-metal element title complex is characterized in that: under the anhydrous and oxygen-free condition, by bimetal construction unit M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution and HS
-The reactant aqueous solution of ion salt synthesizes the title complex to moisture and air-sensitive, places air to carry out the reaction of deprotonation coupled oxidation the gained title complex then, prepares sulphur atom bridging bi-metal element title complex;
Said bimetal construction unit M
2(DAniF)
3(OOCCH
3) and HS
-The ionic mol ratio is 1: 5;
Said bimetal construction unit M
2(DAniF)
3(OOCCH
3) in M represent Mo or W, DAniF represents N, N '-two-to anisole carbonamidine or N, N '-two-to the verivate of anisole carbonamidine.
2. the preparation method of a sulphur atom bridging bi-metal element title complex is characterized in that: in air, by bimetal construction unit M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution and S
2-The reactant aqueous solution of ion salt is prepared sulphur atom bridging bi-metal element title complex;
Said bimetal construction unit M
2(DAniF)
3(OOCCH
3) and S
2-The ionic mol ratio is 1: 5;
Said bimetal construction unit M
2(DAniF)
3(OOCCH
3) in M represent Mo or W, DAniF represents N, N '-two-to anisole carbonamidine or N, N '-two-to the verivate of anisole carbonamidine.
3. the preparation method of sulphur atom bridging bi-metal element title complex as claimed in claim 1 is characterized in that: described HS
-The aqueous solution of ion salt is by HS
-Ionic sodium salt or the preparation of other water-soluble salt, logical nitrogen deoxygenation is 3 hours in the preparation process, and ultimate density is 0.2mol/L.
4. the preparation method of sulphur atom bridging bi-metal element title complex as claimed in claim 2 is characterized in that: described S
2-The aqueous solution of ion salt is by S
2-Ionic sodium salt or the preparation of other water-soluble salt, concentration is 0.4mol/L.
5. according to claim 1 or claim 2 the preparation method of sulphur atom bridging bi-metal element title complex is characterized in that: described bimetal construction unit M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution by bimetal construction unit M
2(DAniF)
3(OOCCH
3) under the anhydrous and oxygen-free condition, be dissolved in the THF and be prepared from.
6. the preparation method of sulphur atom bridging bi-metal element title complex as claimed in claim 1 is characterized in that: the described concrete operations step that synthesizes the title complex of moisture and air-sensitive is, with M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution and HS
-The aqueous solution of ion salt is pressed M
2(DAniF)
3(OOCCH
3) and HS
-The ionic mol ratio is 1: 5 batching, under the anhydrous and oxygen-free condition, while stirring with HS
-The aqueous solution of ion salt slowly is added drop-wise to M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution in, stirring reaction is 3～5 hours under the room temperature, until the reaction no considerable change; Filter out throw out, throw out is removed impurity with washing with alcohol 3 times; Decompressing and extracting gets yellow solid, then yellow solid all is dissolved in the dichloromethane solution, and lysate is filtered in the reaction tubes; Slowly add ethanol along the reaction tube wall again, adopt solvent diffusion method to cultivate monocrystalline, obtain yellow crystals; Be the title complex to moisture and air-sensitive, the consumption volume ratio of above-mentioned ethanol and methylene dichloride is 3: 1.
7. the preparation method of sulphur atom bridging bi-metal element title complex as claimed in claim 2 is characterized in that: the described concrete operations step of preparing sulphur atom bridging bi-metal element title complex is, with M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution and S
2-The aqueous solution of ion salt is pressed M
2(DAniF)
3(OOCCH
3) and S
2-The ionic mol ratio is 1: 5 batching, in air, while stirring with S
2-The aqueous solution of ion salt slowly is added drop-wise to M
2(DAniF)
3(OOCCH
3) tetrahydrofuran solution in, stirring reaction is 24 hours under the room temperature, until the reaction no considerable change; Filter out throw out, throw out is removed impurity with zero(ppm) water and the washing of alcoholic acid mixed solution; When pH=7, decompressing and extracting obtains the brownish black solid, all is dissolved in the brownish black solid in the dichloromethane solution then; Lysate is filtered in the reaction tubes, slowly adds ethanol along the reaction tube wall again, adopt solvent diffusion method to cultivate monocrystalline; Obtain black crystals, be sulphur atom bridging bi-metal element title complex, the consumption volume ratio of above-mentioned ethanol and methylene dichloride is 3: 1.
8. like the preparation method of claim 1 or 6 described sulphur atom bridging bi-metal element title complexs, it is characterized in that: described anhydrous and oxygen-free condition comprises employing Schlenk vacuum line operative technique, and used solvent is the solvent of moisture-free and oxygen.
9. like the preparation method of claim 6 or 7 described sulphur atom bridging bi-metal element title complexs, it is characterized in that: described stirring is a magnetic agitation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788496A (en) * | 2015-04-14 | 2015-07-22 | 暨南大学 | Thiophene-2,5-dicarboamide fiber-bridged double-molybdenum metal unit complex and preparation method of crystal thereof |
| CN104926883A (en) * | 2014-03-18 | 2015-09-23 | 同济大学 | Preparation method of symmetric dithioacetic acid bridged dimolybdenum structural complex |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926883A (en) * | 2014-03-18 | 2015-09-23 | 同济大学 | Preparation method of symmetric dithioacetic acid bridged dimolybdenum structural complex |
| CN104926883B (en) * | 2014-03-18 | 2017-11-07 | 同济大学 | The preparation method of the symmetrical double molybdenum structure complexs of methyl-carbithionic acid bridging |
| CN104788496A (en) * | 2015-04-14 | 2015-07-22 | 暨南大学 | Thiophene-2,5-dicarboamide fiber-bridged double-molybdenum metal unit complex and preparation method of crystal thereof |
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Application publication date: 20120321 |