CN110229336B - Di (polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compound and preparation method thereof - Google Patents
Di (polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compound and preparation method thereof Download PDFInfo
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Abstract
The di (polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compound is prepared from two polyoxometallates and one cage type silsesquioxaneThe hemisiloxane is a hybrid cluster compound covalently linked by organic chains, and is prepared by reacting two polyoxometallates (Bu) in six steps4N)6[H3P2W15V3O62]And a cage type silsesquioxane POSS-NH2And connecting to obtain the organic-inorganic hybrid material. The hybrid cluster compound is connected in a covalent bond mode through organic chains, and has accurately fixed molecular weight and molecular shape; in the solution self-assembly study, it was dissolved in acetone and n-decane was added and evaporated at 25 ℃. In the acetone volatilization process, the di (polyoxometallate) -organic chain-cage type silsesquioxane molecules are self-assembled, and a striped plate structure can be observed in a high-angle annular dark field image-scanning transmission mode through a high-power transmission microscope.
Description
Technical Field
The invention belongs to the technical field of preparation of di (polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compounds, and particularly relates to a preparation method of a di (Wells-Dawson type polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compound.
Background
Polyoxometalates (POMs) are clusters of early transition metal atoms (e.g., vanadium, molybdenum, tungsten, etc.) and central atoms (e.g., phosphorus, silicon, etc.) bridged by oxygen coordination. Polyoxometalates are further classified into isopoly acids and heteropoly acids according to the kind of the oxolate they contain. Polyoxometalates synthesized from one kind of oxoacid salt are called isopoly acids, and polyoxometalates synthesized from two or more kinds of oxoacid salts are called heteropoly acids. The isopoly acid can be thought of as being formed by condensation of two or more simple oxyacid molecules of the same kind, vanadium, molybdenum, tungsten, chromium and the like can form the isopoly acid in the transition metal, and silicon, phosphorus and other elements can also form the isopoly acid. The heteropoly acid is formed by bridging heteroatom and coordination atom through oxygen atom according to a certain proportion, and has higher catalytic activity.
The size of the polyoxometalate cluster is generally between 0.5 and 5nm, and the polyoxometalate cluster is fixed in geometric shape, so that the molecular topological structure plays a great role in the process of assembling the nano material. The polyoxometallate also has various topological structures and physical and chemical properties, so that the polyoxometallate has wide application prospects in the fields of light, electricity, magnetism, catalysis and medicine. And the polyoxometallate has stable chemical properties and mature synthesis technology, and can be synthesized in a large amount at one time in a laboratory.
Polyoxometallate also has disadvantages due to its own structure and properties, such as being present in the form of inorganic crystals or powders, poor thermal stability, poor solubility, etc. These disadvantages lead to poor processability and poor compatibility with other materials, which greatly limits their application in the field of materials. In order to improve the self-defects of polyoxometallates, researchers have developed various methods of organic modification.
Polyhedral Oligomeric Silsesquioxanes (POSS) are composed of an inorganic skeleton core with alternating Si-O connections and reactive or inert groups R connected with eight apex Si atoms, and the molecular formula is (RSiO)1.5)8. According to different types of R groups, the polyhedral oligomeric silsesquioxane can be divided into monofunctional group polyhedral oligomeric silsesquioxane and polyfunctional group polyhedral oligomeric silsesquioxane. The monofunctional group cage type silsesquioxane is characterized in that only one of R groups at eight vertex angles is a reactive group, and the others are inert groups, and the type is mainly linear pendant cage type silsesquioxane, wherein the cage type silsesquioxane with a highly symmetrical T8 structure has the most wide application value. The cage type silsesquioxane with the T8 structure has the advantages that the glass transition temperature and the degradation temperature can be increased by the inorganic framework inner core, the compatibility with other materials can be improved by changing the inert R group, and the cage type silsesquioxane can be used for preparing a composite material with a certain function. The multifunctional cage type silsesquioxane means that R groups at eight vertex angles have two or more than two reactive groups.
By means of organic chains in covalent bond form: connecting a polyoxometallate and a cage type silsesquioxane and assembling into a bicontinuous cubic structure and a honeycomb structure. One polyoxometallate is connected with two cage-type silsesquioxane and self-assembled into the 2D nano crystal, and one polyoxometallate is connected with four cage-type silsesquioxane and self-assembled into the single-layer 2D honeycomb-shaped superlattice similar to graphene. However, the connection of two polyoxometallates and one cage-type silsesquioxane is not realized so far, and the research of the self-assembly behavior is not related.
Disclosure of Invention
The invention aims to solve the problems of connection of two polyoxometallates and one cage-type silsesquioxane and research on self-assembly behavior of the two polyoxometallates, and provides a preparation method of a di (polyoxometallate) -organic chain-cage-type silsesquioxane hybrid cluster compound.
In order to explore the influence of two polyoxometallate cluster compounds on the formation of a solution self-assembly structure, the invention connects two polyoxometallates with a single cage-type silsesquioxane in a covalent bond mode by changing an organic connecting chain. The two polyoxometallate-cage silsesquioxane hybrid cluster compounds obtained by the invention can be assembled to obtain a striped plate structure, and the self-assembled material has regular structure period and great potential application value in the field of molecular etching.
Technical scheme of the invention
A di (polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compound is a cluster compound formed by connecting two polyoxometallates and one cage type silsesquioxane through a covalent bond, has accurate molecular weight and T-shaped molecular shape, has the molecular weight of 12079.43 and has the chemical formula of { [ (n-Bu)4N]6P2W15V3O59(OCH2)3CNHCO}2C6H3CONHCH2CH2CONH(C31H69Si8O12) The chemical structural formula is as follows:
a synthetic method of the di (polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compound comprises the following steps:
1) di-tert-butyl-amino (2-t-BuO-NH)2) Synthesis of (2)
Dissolving 5-nitroisophthalic acid di-tert-butyl ester, zinc powder and ammonium chloride (the molar ratio is 1:10:10) in a mixed solvent of tetrahydrofuran/methanol/water (the volume ratio is 1:2:2) at room temperature, reacting and refluxing for 4-6 hours, filtering after reaction, concentrating the filtrate, performing column chromatography, and eluting with ethyl acetate: petroleum ether 1:5, and the receiving liquid was removed by spinning to obtain a white solid powder of di-tert-butyl ester-amino compound.
2) Synthesis of di-tert-butyl ester-carboxyl (2-t-BuO-COOH)
Dissolving the di-tert-butyl ester-amino compound obtained in the previous step in chloroform, adding excessive succinic anhydride, wherein the molar ratio of the di-tert-butyl ester-amino to the succinic anhydride is 1:1.76, refluxing the reaction system for 3-5 hours, removing the solvent by spinning, and performing column separation, wherein an eluent is ethyl acetate: and (3) drying the product receiving solution by using anhydrous sodium sulfate, and concentrating to obtain light wine red solid di-tert-butyl ester-carboxyl.
3) Synthesis of di-tert-butyl ester-cage type silsesquioxane (2-t-BuO-POSS)
Under the protection of argon, dissolving di-tert-butyl-carboxyl and polyhedral oligomeric silsesquioxane (the molar ratio of which is 1:1.2) obtained in the step 2) in trichloromethane, sequentially adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI), 1-Hydroxybenzotriazole (HOBT) and N, N-Diisopropylethylamine (DIEA) in a molar ratio of 1.4:1.3:3, reacting and refluxing for 1-2 days, and after the reaction is completed, concentrating and carrying out column chromatography, wherein an eluent is dichloromethane: methanol 20: 1, concentrating the product receiving solution to obtain white solid di-tert-butyl ester-cage type silsesquioxane.
4) Synthesis of dicarboxylic acid-cage type silsesquioxane (2-COOH-POSS)
Dissolving the di-tert-butyl ester-cage type silsesquioxane obtained in the step 3) in dichloromethane, and adding excessive trifluoroacetic acid, wherein the molar ratio of the di-tert-butyl ester-cage type silsesquioxane to the trifluoroacetic acid is 1: 3. reacting at room temperature for 12-14 hours, concentrating after the reaction is finished, and eluting with 200 ml of dichloromethane, then dichloromethane: and (3) concentrating the receiving solution to obtain white powdery dicarboxylic acid-polyhedral oligomeric silsesquioxane, wherein the methanol is 10: 1.
5) Synthesis of di (trihydroxymethyl methylamine) -cage type silsesquioxane (2-Tris-POSS)
Under the protection of argon, dissolving the dicarboxy-cage type silsesquioxane obtained in the step 4) in dry acetonitrile, and sequentially adding 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline (EEDQ) and trimethylol methylamine, wherein the molar ratio of the dicarboxy-cage type silsesquioxane, the 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline (EEDQ) and the trimethylol methylamine is 1: 4: 4. And (3) refluxing for 2-3 days, and after the reaction is finished, concentrating a reaction system and carrying out column chromatography to obtain a white solid di (trihydroxymethyl methylamine) -cage type silsesquioxane.
6) Synthesis of di (polyoxometallate) -cage type silsesquioxane (2POM-POSS)
Under the protection of argon, dissolving di (trihydroxymethyl methylamine) -cage type silsesquioxane in N, N-dimethylformamide, and adding Wells-Dawson type polyoxometallate, wherein the molar ratio of the di (trihydroxymethyl methylamine) -cage type silsesquioxane to the Wells-Dawson type polyoxometallate is 1: 2.5. reacting for 4-6 days at 80 ℃, after the reaction is finished, adding the dried residue into trichloromethane, partially dissolving, centrifuging to remove precipitates, drying the supernatant, adding acetonitrile, dropwise adding into ether, sealing overnight, separating out solids, centrifuging to obtain tsukudani, washing the solids with water, and drying in vacuum to obtain light yellow solid powder, namely the final product of di (polyoxometallate) -cage type silsesquioxane.
The invention has the advantages and beneficial effects that:
the di (polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compound is a target product obtained by taking 5-tert-butyl nitroisophthalate as an initial raw material through six-step reaction, mainly relates to reaction types such as reduction hydrogenation, amidation and esterification of polyoxometallate, and finally connects two polyoxometallates and two inorganic compounds of cage type silsesquioxane to form the hybrid cluster compound in a covalent bond mode. And the cluster is confirmed by various chemical characterization methods.
Drawings
FIG. 1 is a structural formula of a di (polyoxometallate) -organic chain-silsesquioxane hybrid cluster compound (2 POM-POSS).
FIG. 2 is a time-of-flight mass spectrum of a bis (polyoxometallate) -organic chain-silsesquioxane hybrid cluster (2 POM-POSS).
FIG. 3 is a phosphorus spectrum of a building block Polyoxometalate (POM) and a hybrid compound bis (polyoxometalate) -organic chain-cage silsesquioxane.
FIG. 4 shows di-tert-butyl-amino (2-t-BuO-NH)2) The structural formula (1).
FIG. 5 shows the structural formula of di-tert-butyl ester-carboxyl (2-t-BuO-COOH).
FIG. 6 is a structural formula of di-tert-butyl ester-cage silsesquioxane (2-t-BuO-POSS).
FIG. 7 is a structural formula of dicarboxylic acid-cage silsesquioxane (2-COOH-POSS).
FIG. 8 is a structural formula of di (trimethylolmethylamine) -cage silsesquioxane (2-Tris-POSS).
FIG. 9 shows the synthesis route of di (polyoxometallate) -organic chain-cage silsesquioxane hybrid cluster compound (2 POM-POSS).
FIG. 10 is a self-assembly striped plate structure of hybrid cluster compound 2 POM-POSS.
FIG. 11 is an enlarged view of the self-assembled striped plate structure of the hybrid cluster compound 2 POM-POSS.
FIG. 12 is an energy spectrum of a hybrid cluster compound 2POM-POSS self-assembled striped plate structure.
FIG. 13 is an energy spectrum of self-assembly of hybrid cluster 2POM-POSS with a striped plate structure.
Detailed Description
Example 1:
a hybrid compound of di (polyoxometallate) -organic chain-cage type silsesquioxane is a hybrid compound formed by two polyoxometallates and one cage type silsesquioxane through organic chains in a covalent bond mode, and the formed compound has an accurate molecular weight of 12079.43 and has a chemical formula of { [ (n-Bu)4N]6P2W15V3O59(OCH2)3CNHCO}2C6H3CONHCH2CH2CONH(C31H69Si8O12) The chemical structural formula of bis (polyoxometallate) -organic chain-cage silsesquioxane (2POM-POSS) is as follows:
the preparation method comprises the following step of reducing the nitro group of the tert-butyl 5-nitroisophthalate into amino group by zinc powder to obtain (2-t-BuO-NH)2) The amino is connected with succinic anhydride to obtain (2-t-BuO-COOH), the exposed carboxyl and the amino of a reactive group on the cage-type silsesquioxane are subjected to dehydration condensation to obtain (2-t-BuO-POSS), tert-butyl ester is removed by trifluoroacetic acid to obtain (2-COOH-POSS), two carboxyl groups on a benzene ring react with trimethylolmethylamine to obtain 2-Tris-POSS, and the 2-Tris-POSS is subjected to esterification with polyoxometallate V3POM to obtain a hybrid compound 2-POM-POSS, wherein the specific synthetic steps are as follows:
1) di-tert-butyl-amino (2-t-BuO-NH)2) Synthesis of (2)
5.5 g of di-tert-butyl 5-nitroisophthalate (17mmol, 1eq) was added to a 250 ml round-bottom flask at room temperature and dissolved in 120 ml of a mixed solvent of tetrahydrofuran/methanol/water in a volume ratio of tetrahydrofuran: methanol: water 1:2:2, adding 11.3 g zinc powder (170mmol,10eq) and 9.2 g ammonium chloride (170mmol,10eq) and heating and refluxing for 4 hours, filtering, concentrating the filtrate and carrying out column chromatography, wherein the eluent is petroleum ether: ethyl acetate 5:1, the desired product receiver from this step was concentrated and dried to give 4.0 g of di-tert-butyl-amino compound as a white solid powder in 81% yield.
2) Synthesis of di-tert-butyl ester-carboxyl (2-t-BuO-COOH)
To a 100 ml round bottom flask was added 4.0 g of di-tert-butyl-amino (2-t-BuO-NH) at room temperature2) (17mmol, 1eq) is dissolved in 50 ml of trichloromethane, then 3.0 g of succinic anhydride (30mmol, 1.76eq) is added, the reaction is refluxed for 3 hours, the reaction system is concentrated and purified by column chromatography, and the eluent is acetic acidEthyl ester: petroleum ether 1:3, concentrated and dried to give 5.0 g of di-tert-butyl-carboxy as a pale wine red solid in 94% yield.
3) Synthesis of di-tert-butyl ester-cage type silsesquioxane (2-t-BuO-POSS)
Under argon protection, 1.6 g of di-tert-butyl ester-carboxyl (2-t-BuO-COOH) (4mmol, 1eq) was dissolved in 40 ml of chloroform, 4.37 g of polyhedral oligomeric silsesquioxane (5mmol, 1.2eq) was added, after stirring and dissolution, 1.08 g of 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride (EDCI) (5.6mmol, 1.4eq), 725 mg of 1-Hydroxybenzotriazole (HOBT) (5.3mmol, 1.3eq), 2.0 ml of N, N-Diisopropylethylamine (DIEA) (12mmol, 3eq) were added, the reaction was refluxed for 1 day, and after completion of the reaction, column chromatography was concentrated, eluent dichloromethane: methanol 20: 1, concentrating the product receiving solution to obtain 4.9 g of white solid di-tert-butyl ester-cage type silsesquioxane, wherein the yield is 96%.
4) Synthesis of dicarboxylic acid-cage type silsesquioxane (2-COOH-POSS)
Under argon protection, 4.8 g of di-tert-butyl ester-cage silsesquioxane (2-t-BuO-POSS) (3.9mmol, 1eq) was dissolved in 50 ml of chloroform, and 8 ml of trifluoroacetic acid (107mmol, 27eq) was added and reacted overnight at room temperature, after completion of the reaction, concentrated with eluent of 200 ml of dichloromethane, followed by dichloromethane: methanol 10:1, 4.3 g of dicarboxylic acid-polyhedral oligomeric silsesquioxanes was obtained as a white solid in 89% yield.
5) Synthesis of di (trihydroxymethyl methylamine) -cage type silsesquioxane (2-Tris-POSS)
Under the protection of argon, 4.2 g of dicarboxylic acid-polyhedral oligomeric silsesquioxane (2-COOH-POSS) (3.7mmol, 1eq) is dissolved in 80 ml of dry acetonitrile, 3.65 g of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline (EEDQ) (14.8mmol, 4eq) is added, after stirring and dissolution, 1.8 g of trimethylolmethylamine (14.8mmol, 4eq) is added, the reaction is refluxed for 2 days, after the reaction is finished, the crude product is concentrated, and the crude product is purified by column chromatography, wherein an eluent is dichloromethane: methanol 25: 1, concentration gave 1.0 g of ditrimethylaminomethane-caged silsesquioxane as a white solid in 20% yield.
6) Synthesis of di (polyoxometallate) -cage type silsesquioxane (2POM-POSS)
Under the protection of argon, 0.27 g of bis (trihydroxymethyl methylamine) -cage type silsesquioxane (2-Tris-POSS) (0.2mmol, 1eq) is dissolved in N, N-dimethylformamide, 2.7 g of Wells-Dawson type polyoxometallate (0.5 mmol, 2.5eq) is added, the reaction is carried out for 4 days at 80 ℃, after the reaction is finished, the dried residue is added into trichloromethane, partial dissolution is carried out, the precipitate is removed by centrifugation, the supernatant is dried by spinning, acetonitrile is added, the mixture is dripped into ether, the mixture is sealed overnight, the solid is separated out, the precipitate is obtained by centrifugation, the solid is washed by water, and light yellow solid powder, namely the final product of bis (polyoxometallate) -cage type silsesquioxane 569 mg is obtained by vacuum drying, and the yield is 19.2%.
The structural formulas of the six compounds of the di-tert-butyl-amino, the di-tert-butyl-carboxyl, the di-tert-butyl-cage silsesquioxane, the dicarboxylic acid-cage silsesquioxane, the di (trihydroxymethyl methylamine) -cage silsesquioxane and the di (polyoxometallate) -cage silsesquioxane are shown in the figures 4 to 9 in sequence.
FIG. 10 shows the synthesis route of di (polyoxometallate) -organic chain-cage silsesquioxane hybrid cluster compound (2 POM-POSS).
FIG. 1 is a hydrogen spectrum of a hybrid cluster compound 2 POM-POSS. From the hydrogen spectra we were able to determine the hydrogen on the hybrid corresponding to each peak, which is the first evidence we confirmed to obtain a di (polyoxometallate) -organic chain-cage silsesquioxane hybrid cluster.
FIG. 2 is a time-of-flight mass spectrum of a hybrid cluster compound 2 POM-POSS. In the time-of-flight mass spectrum we obtained 12080.81 (molecule gets one proton hydrogen), 12321.41 (molecule gets one peak of tetrabutylammonium cation), 11839.01 (molecule gets two proton hydrogens and loses one tetrabutylammonium cation), 11598.34 (molecule gets three proton hydrogens and loses two tetrabutylammonium cations), which is the second evidence that we synthesized di (polyoxometallate) -organic chain-cage silsesquioxane hybrid clusters of fixed molecular weight.
FIG. 3 is a comparison of the phosphorus spectra of the building block Polyoxometallate (POM) cluster and the hybrid cluster bis (polyoxometallate) -organic chain-cage silsesquioxane (2POM-POSS), and we found that the phosphorus spectra has a shift of 0.33ppm and no other hetero peaks, indicating that the building block Polyoxometallate (POM) has been completely reacted, which is the third evidence that we synthesized the fixed molecular weight bis (polyoxometallate) -organic chain-cage silsesquioxane hybrid cluster.
FIGS. 11 and 12 show the self-assembly of hybrid cluster 2POM-POSS with striped plate structure. Dissolving di (polyoxometallate) -organic chain-cage type silsesquioxane in a certain amount of acetone, adding a certain proportion of n-decane, volatilizing at 25 ℃, and carrying out self-assembly on molecules in the volatilizing process of the acetone to obtain a strip-shaped plate structure.
FIG. 13 is an energy spectrum of self-assembly of hybrid cluster 2POM-POSS with a striped plate structure. From the energy spectrum, it was observed that the region contained phosphorus, tungsten, and vanadium elements contained in polyoxometallate and silicon elements contained in cage-type silsesquioxane, which confirmed that the assembly structure consisted of di (polyoxometallate) -organic chain-cage-type silsesquioxane
Solution self-assembly process monitoring
In a 20 ml glass bottle, 2 mg of di (polyoxometallate) -organic chain-cage silsesquioxane is dissolved in 6 ml of acetone, 4 ml of n-decane is rapidly added to obtain 0.2 g/ml of solution, the solution is volatilized at the room temperature of 25 ℃ for 48 hours, and when a laser pen is used for irradiating the solution, a significant Tyndall phenomenon is caused, aggregates are generated in the system, and light rays are scattered.
We pipetted a drop onto an ultra-thin carbon film, left to stand for one minute, blotted the surface solution with filter paper, and dried the ultra-thin carbon film in a drying tower for 12 hours. Observing in a high-angle annular dark field phase-scanning transmission mode by using a high-power transmission electron microscope, wherein a plate structure with light and dark alternate stripes can be seen, in the scanning transmission mode, the contrast in an electron microscope picture is in direct proportion to the square of an atomic coefficient, the atomic coefficient of tungsten contained in polyoxometallate is 74, the quadratic of the tungsten is 5476, the atomic coefficient of silicon contained in cage-type silsesquioxane is 14, and the quadratic of the tungsten is 196, so that bright stripes in the electron microscope picture self-service structure are formed by arraying the polyoxometallate in two (polymetallic hydrochloride) -organic chain-cage-type silsesquioxane, dark stripes are arrayed in the cage-type silsesquioxane, and an energy spectrum experiment is carried out on the area to obtain the area containing phosphorus, tungsten and vanadium which are peculiar to the polyoxometallate and the silicon contained in the cage-type silsesquioxane, this also confirms that the assembled structure is composed of di (polyoxometallate) -organic chain-cage silsesquioxane.
Claims (8)
1. A di (polyoxometallate) -organic chain-cage type silsesquioxane hybrid cluster compound is a cluster compound formed by connecting two polyoxometallates and one cage type silsesquioxane through a covalent bond, has accurate molecular weight and T-shaped molecular shape, has the molecular weight of 12079.43 and has the chemical formula { [ (n-Bu)4N]6P2W15V3O59(OCH2)3CNHCO}2C6H3CONHCH2CH2CONH(C31H69Si8O12) The chemical structural formula is as follows:
2. a method for preparing the di (polyoxometallate) -organic chain-cage silsesquioxane hybrid cluster compound of claim 1 is characterized by comprising the following steps:
1) di-tert-butyl-amino (2-t-BuO-NH)2) Synthesis of (2)
Dissolving 5-nitroisophthalic acid di-tert-butyl ester, zinc powder and ammonium chloride in a tetrahydrofuran/methanol/water mixed solvent at room temperature, reacting and refluxing for 4-6 hours, filtering after reaction, concentrating the filtrate and performing column chromatography, wherein an eluent is ethyl acetate: removing the receiving liquid by spinning to obtain white solid powder of di-tert-butyl ester-amino compound, wherein the petroleum ether is 1: 5;
2) synthesis of di-tert-butyl ester-carboxyl (2-t-BuO-COOH)
Dissolving the di-tert-butyl ester-amino compound obtained in the previous step into chloroform, adding excessive succinic anhydride, refluxing a reaction system for 3-5 hours, removing the solvent by spinning, and performing column separation, wherein an eluent is ethyl acetate: petroleum ether is 1:3, and a product receiving solution is dried by anhydrous sodium sulfate and concentrated to obtain light wine red solid di-tert-butyl ester-carboxyl;
3) synthesis of di-tert-butyl ester-cage type silsesquioxane (2-t-BuO-POSS)
Under the protection of argon, dissolving the di-tert-butyl ester-carboxyl and amino substituted cage-type silsesquioxane obtained in the step 2) in chloroform, sequentially adding 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride (EDCI), 1-Hydroxybenzotriazole (HOBT) and N, N-Diisopropylethylamine (DIEA), carrying out reaction reflux for 1-2 days, and after the reaction is completed, concentrating column chromatography, wherein an eluent is dichloromethane: methanol 20: 1, concentrating the product receiving solution to obtain white solid di-tert-butyl ester-cage type silsesquioxane;
4) synthesis of dicarboxylic acid-cage type silsesquioxane (2-COOH-POSS)
Dissolving the di-tert-butyl ester-cage type silsesquioxane obtained in the step 3) in dichloromethane, adding excessive trifluoroacetic acid, reacting at room temperature for 12-14 hours, concentrating after the reaction is finished, and eluting with 200 ml of dichloromethane, and then dichloromethane: concentrating the receiving solution with methanol at a ratio of 10:1 to obtain white powdery dicarboxylic acid-polyhedral oligomeric silsesquioxane;
5) synthesis of di (trihydroxymethyl methylamine) -cage type silsesquioxane (2-Tris-POSS)
Under the protection of argon, dissolving the dicarboxyl-cage type silsesquioxane obtained in the step 4) in dry acetonitrile, sequentially adding 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline (EEDQ) and trimethylol methylamine, refluxing for 2-3 days, and after the reaction is finished, concentrating a reaction system and carrying out column chromatography to obtain white solid di (trimethylol methylamine) -cage type silsesquioxane;
6) synthesis of di (polyoxometallate) -cage type silsesquioxane (2POM-POSS)
Under the protection of argon, dissolving di (trihydroxymethyl methylamine) -cage type silsesquioxane in N, N-dimethylformamide, adding Wells-Dawson type polyoxometallate, reacting at 80 ℃ for 4-6 days, after the reaction is finished, adding the spin-dried residue into trichloromethane, partially dissolving, centrifuging, removing the precipitate, spin-drying the supernatant, adding acetonitrile, dropwise adding to diethyl ether, sealing overnight, separating out a solid, centrifuging to obtain a precipitate, washing the solid with water, and vacuum-drying to obtain light yellow solid powder, namely the final product, i.e. di (polyoxometallate) -cage type silsesquioxane.
3. The method as claimed in claim 2, wherein the molar ratio of the di-tert-butyl 5-nitrom-toluate, the zinc powder and the ammonium chloride in the step 1) is 1:10: 10; the volume ratio of the tetrahydrofuran to the methanol to the water is 1:2: 2.
4. The method according to claim 2, wherein the molar ratio of the di-tert-butyl ester-amino compound to succinic anhydride in step 2) is 1: 1.76.
5. The process according to claim 2, wherein the molar ratio of di-tert-butyl-carboxy, amino-substituted cage-type silsesquioxane, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDCI), 1-Hydroxybenzotriazole (HOBT), N, N-Diisopropylethylamine (DIEA) in step 3) is 1: 1.2: 1.4:1.3: 3.
6. the method according to claim 2, wherein the molar weight ratio of di-tert-butyl ester-cage silsesquioxane to trifluoroacetic acid in step 4) is 1: 3.
7. the method of claim 2, wherein the molar ratio of dicarboxy-cage silsesquioxane, 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline (EEDQ), and trimethylolmethylamine in step 5) is 1: 4: 4.
8. the method of claim 2, wherein the molar ratio of bis (trimethylolmethylamine) -cage silsesquioxane to the polyoxometalate of Wells-Dawson type in step 6) is 1: 2.5.
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