CN105884676B - The preparation method of fullerene-polyoxometallate hybrid molecule - Google Patents
The preparation method of fullerene-polyoxometallate hybrid molecule Download PDFInfo
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- CN105884676B CN105884676B CN201610259221.XA CN201610259221A CN105884676B CN 105884676 B CN105884676 B CN 105884676B CN 201610259221 A CN201610259221 A CN 201610259221A CN 105884676 B CN105884676 B CN 105884676B
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Abstract
The invention discloses a kind of preparation method of fullerene polyoxometallate hybrid molecule, the technical solution of the preparation method is：First, using bromine alkyl tert-butyl acrylate and hydroxy benzaldehyde as raw material, under potassium carbonate effect, the benzaldehyde of synthetic intermediate alkyl tert-butyl acrylate substitution；Then using benzaldehyde, sarcosine and the fullerene of alkyl tert-butyl acrylate substitution as raw material, chlorobenzene is solvent, by [3+2] cycloaddition reaction, prepares the fullerene derivate containing the tert-butyl ester；By the fullerene derivate containing the tert-butyl ester, further hydrolysis obtains the fullerene derivate containing carboxyl, and then be covalently joined together by amidation process with the polyoxometallate containing amino.The present invention is easy to operate, and the type and number of fullerene and polyoxometallate are adjustable in target molecule.
Description
Technical field
The invention belongs to field of new materials, are related to the preparation method of fullerene-polyoxometallate hybrid molecule.
Background technology
Polyoxometallate is by transition metal element（Mainly molybdenum, tungsten, vanadium）The metal formed with oxygen atom bridging
Oxygen cluster compound.The basic unit for forming metal oxygen cluster is mainly MO4Tetrahedron and MO6Octahedron leads between different polyhedrons
It crosses side, corner-sharing or coplanar further connection altogether and forms complicated and diversified polyacid structure.Polyoxometallate has many peculiar
Property, such as oxidisability, highly acid, big size, with higher negative electrical charge, nucleophilic performance, in catalysis, medicine, electrification
It learns, the photochromic various fields to magnetism show huge application potential, therefore cause the great interest of people with closing
Note.However, due to polyoxometallate lattice energy height, pH stability is low, and structure of modification is difficult with modification, it is difficult to according to
It is actually needed to control its size, shape and physicochemical characteristics, therefore polyoxometallate is a kind of not easy to be processed again
Material.These shortcomings limit it as the development and application of material devices.
There is excellent molecule to cut out and modification for organic compound, the especially organic compound with pi-conjugated structure
Function.The performance of both polyoxometallate and organic compound complementation is combined, is constructed plastic, stable, firm new
Type hybrid inorganic-organic materials have become synthesis chemistry and the important subject in materials science field.Fullerene is peculiar
The spherical cluster containing pi-conjugated structure, it has, and many remarkable property such as free radical captures, DNA are affine, electronics by
Body, efficient absorption etc..There is very important theoretical and reality to modify polyoxometallate by the use of fullerene as organic component
Meaning.Firstly, since fullerene is hydrophobic components, and polyoxometallate tends to big organic molten of hydrophilic or close polarity
Agent, so the novel amphiphile, amphiphilic molecule that can obtain that a kind of hydrophilic, hydrophobic part is nanoscale that the two is connected.Next, as
Be respectively provided with good photoelectric property constructs primitive, by polyoxometallate and fullerene carry out hydridization be expected to obtain with it is new,
The material of more excellent photoelectric properties.Again, magnetic fullerene-based material has many peculiar performances, and prepares magnetic fowler at present
The method of alkene also compares shortcoming, and with high costs.To have magnetic polyoxometallate with fullerene to be connected, and can obtain one kind
New magnetic material has huge potential application in fields such as information storage, organic photovoltaics.
Although fullerene-polyoxometallate hybrid molecule has so tempting application prospect, presently relevant grinds
Study carefully few.This is mainly due to such material preparation difficulties.First, fullerene and polyoxometallate are all nanoscale rigid bone
Frame, to the difficult of its chemical modification.Secondly, fullerene is easily soluble in non-polar organic solvent（Especially benzene class or naphthalenes
Solvent）, and polyoxometallate is then easily soluble in polar organic solvent such as acetonitrile, the selection of solvent is also to compare in building-up process
Stubborn problem.One group of scientist of Italy utilizes and is connected with silylating reagent（-Si(OEt)3）Fullerene derivate with
Polyoxometallate [γ-SiW10O36]8-Effect, is prepared for a fullerene-polyoxometallate hydridization unique so far
Molecule（Adv. Synth. Catal. 2004, 346, 648-654）.It is various in view of polyoxometallate type, develop it
It facilitate it is feasible, available for multiple types polyoxometallate（Such as Dawson types, Anderson types and Lindqvist types）
Fullerene-polyoxometallate hybrid molecule preparation method it is extremely urgent.
Invention content
The present invention provides a kind of preparation methods of fullerene-polyoxometallate hybrid molecule, and this method is easy to operate,
The type and number of fullerene and polyoxometallate are adjustable in target molecule.
To achieve the above object, the present invention adopts the following technical scheme that：First, with bromine alkyl tert-butyl acrylate and hydroxy benzenes first
Aldehyde is raw material, under potassium carbonate effect, the benzaldehyde of synthetic intermediate alkyl tert-butyl acrylate substitution；Then with alkyl tert-butyl acrylate
Substituted benzaldehyde, sarcosine and fullerene is raw material, and chlorobenzene is solvent, by [3+2] cycloaddition reaction, is prepared containing the tert-butyl ester
Fullerene derivate；By the fullerene derivate containing the tert-butyl ester, further hydrolysis obtains the fullerene derivative containing carboxyl
Object, and then be covalently joined together with the polyoxometallate containing amino by amidation process.
The preparation method of fullerene-polyoxometallate hybrid molecule, it is characterised in that the preparation method includes following step
Suddenly：
1）The preparation of the benzaldehyde of alkyl tert-butyl acrylate substitution
Under inert gas shielding, to containing K2CO3N,N-dimethylformamide（DMF）It is middle addition bromine alkyl tert-butyl acrylate and
Hydroxy benzaldehyde, 50-150 DEG C is stirred to react 10-100 hours, then adds in water and ethyl acetate extracts 3-5 times, merge organic
Phase, anhydrous MgSO4It is dry, it filters, takes filtrate, silica gel column chromatography is carried out up to the substitution of alkyl tert-butyl acrylate after solvent is removed under reduced pressure
Benzaldehyde；
2）The preparation of fullerene derivate containing the tert-butyl ester
Under inert gas shielding, the benzene of alkyl tert-butyl acrylate substitution is added in into the chlorobenzene solution containing sarcosine and fullerene
Formaldehyde flows back 10-24 hours under the conditions of being protected from light, and filters, takes filtrate, and chlorobenzene is removed under reduced pressure, and carries out silica gel column chromatography, takes brown group
Point, solvent is removed under reduced pressure, product is redissolved in toluene, gel size exclusion chromatography separation is carried out, takes the second component to obtain the final product
Fullerene derivate of single addition containing the tert-butyl ester；
3）The preparation of the fullerene derivate containing carboxyl
By the fullerene derivate containing the tert-butyl ester in the in the mixed solvent of dichloromethane and trifluoroacetic acid, 10-100 DEG C of stirring
10-48 hours, solvent is removed under reduced pressure up to carboxylic fullerene derivate；
4）The preparation of fullerene-polyoxometallate hybrid molecule
Under inert gas shielding, the in the mixed solvent of acetonitrile and tetrahydrofuran to the fullerene derivate containing carboxyl adds in ammonia
The polyoxometallate of base modification, with the help of amidation reagent, 10-100 DEG C is stirred 1-10 days, is filtered, is taken filtrate, is depressurized
Solvent is removed, solid is redissolved in THF, filters, takes solid；Solid is dissolved in acetonitrile and then it is added dropwise to second dropwise
In ether, filtering takes solid, repeats this process；Obtained solid is washed with acetone up to fullerene-polyoxometallate hydridization point
Son.
The molar ratio of the hydroxy benzaldehyde and bromine alkyl tert-butyl acrylate is 0.5-1.5:1-3；The K2CO3With bromine alkyl
The molar ratio of tert-butyl acrylate is 1-3:0.5-1.5.
The hydroxy benzaldehyde is 4- hydroxy benzaldehydes, 2,4- 4-dihydroxy benzaldehydes, 2,5- 4-dihydroxy benzaldehydes, 3,4-
4-dihydroxy benzaldehyde, 3,5- 4-dihydroxy benzaldehydes, 3,4,5- tri hydroxybenzaldehydes, 2,3,4- tri hydroxybenzaldehydes or 2,4,6- tri-
Hydroxy benzaldehyde；The bromine alkyl tert-butyl acrylate is bromo-acetic acid tert-butyl, the bromo-propionic acid tert-butyl ester or the bromo-butyric acid tert-butyl ester.
Step 1）Eluant, eluent selected by middle silica gel column chromatography is n-hexane/ethyl acetate, wherein ethyl acetate volume hundred
It is 10%-50% to divide content.
Step 2）Described in alkyl tert-butyl acrylate substitution benzaldehyde and fullerene molar ratio be 0.5-1.5:1-4；Institute
The molar ratio of benzaldehyde and sarcosine for stating the substitution of alkyl tert-butyl acrylate is 0.5-1.5:1-3.
Step 2）Described in fullerene be C60、C70、C76Or C84。
Step 2）Eluant, eluent selected by middle silica gel column chromatography is ethyl acetate/toluene Mixed Solvent, wherein ethyl acetate
Volumn concentration is 10%-50%.
Step 3）Described in the molar ratio of dichloromethane and trifluoroacetic acid be 1-5:0.5-1.5.
Step 4）In fullerene derivate containing carboxyl, amido modified polyoxometallate and amidation reagent molar ratio
0.5-1.5：0.5-4：0.5-4.
The amido modified polyoxometallate is Dawson type polyoxometallates（[N(C4H9)4]6[P2W15V3O59
(OCH2)3CNH2], it is abbreviated as Dawson-NH2）, Anderson type polyoxometallates（[N(C4H9)4]3[FeMo6O18
{(OCH2)3CNH2}2], it is abbreviated as Anderson-NH2）Or Lindqvist type polyoxometallates（[N(C4H9)4]2[V6O13
{(OCH2)3CNH2}2], it is abbreviated as Lindqvist-NH2）.
Step 4）Described in the molar ratio of acetonitrile and tetrahydrofuran be 0.5-1.5:1-8.
The amidation reagent is dicyclohexylcarbodiimide（DCC）, 4-dimethylaminopyridine（DMAP）Or 2- ethyoxyls-
1- ethoxy carbonic acyl radical -1,2- dihydroquinoline（EEDQ）.
In terms of technical key point of the present invention has following four：1）In K2CO3In the presence of, utilize disappearing for halogenated hydrocarbons and phenolic hydroxyl group
Dereaction makes bromine alkyl tert-butyl acrylate be reacted with hydroxy benzaldehyde；2）Modify fullerene, sarcosine, alkyl tert-butyl acrylate
[3+2] cycloaddition reaction occurs for benzaldehyde, prepares the fullerene derivate containing the tert-butyl ester；3）Fullerene containing the tert-butyl ester is derived
Object hydrolyzes to obtain carboxylic fullerene derivate；4）Carboxylic fullerene derivate is more by amidation process and amino
Oxometallate is connected.
The present invention outstanding characteristic be：1) preparation method is simple and feasible, designability is strong, yield is higher and is easy to scale
Change；2) fullerene-polyoxometallate hybrid molecule structure novel prepared by, functional；3) hydridization point prepared by
Sub- solubility is adjustable, dissolves in dimethyl sulfoxide (DMSO)（DMSO）, N,N-dimethylformamide (DMF), acetonitrile and they formed
A variety of mixed solvents.
Advantage of the invention is that：Target product only needs the reaction of 4 steps that can be prepared, involved organic reaction operation
Easy, yield height；Fullerene substitution number, type and the number of polyoxometallate substitution, type can be mostly golden by changing
The structure for belonging to the type of oxygen hydrochlorate, the type of fullerene and hydroxy benzaldehyde is easily adjusted.
Description of the drawings
Fig. 1 is the molecular structure of 1 gained fullerene-Dawson type polyoxometallate hybrid molecules of the embodiment of the present invention
With1H nmr spectrums.
Fig. 2 is the molecular structure of 1 gained fullerene-Dawson type polyoxometallate hybrid molecules of the embodiment of the present invention
With13C nmr spectrums.
Fig. 3 is 1 gained fullerene-Dawson type polyoxometallates hybrid molecule of the embodiment of the present invention, before two kinds of reactions
Drive body and the infrared absorption spectrum of their mechanical impurity.
Fig. 4 for 1 gained fullerene-Dawson type polyoxometallate hybrid molecules of the embodiment of the present invention in different solvents and
The uv-visible absorption spectra of in the mixed solvent（Concentration：100 every liter of micromoles）.
Fig. 5 is molten for 1 gained fullerene-Dawson type polyoxometallate hybrid molecule dimethyl sulfoxide (DMSO)s of the embodiment of the present invention
Liquid（20 milligrams every milliliter）Transmission electron microscopy observation result.
Fig. 6 is 1 gained fullerene-Dawson type polyoxometallate hybrid molecule N, N- dimethyl methyls of the embodiment of the present invention
Amide solution（20 milligrams every milliliter）Transmission electron microscopy observation result.
Fig. 7 is 1 gained fullerene-Dawson type polyoxometallate hybrid molecule acetonitrile solutions of the embodiment of the present invention（20
Every milliliter of milligram）Transmission electron microscopy observation result.
Fig. 8 is 1 gained fullerene-Dawson type polyoxometallates hybrid molecule of the embodiment of the present invention, before two kinds of reactions
The cyclic voltammetry curve of body is driven, using ferrocene as internal standard, tetrabutyl ammonium hexafluorophosphate is supporting electrolyte（Concentration：0.1 mole every
It rises）, glass-carbon electrode is working electrode, and platinized platinum is to electrode, and platinum filament is reference electrode.
Fig. 9 is 1 gained fullerene-Dawson type polyoxometallate hybrid molecules of the embodiment of the present invention（Solid）And
Dawson-NH2（Solid）ESR electron paramagnetic resonance collection of illustrative plates.
Specific embodiment
Embodiment 1
（1）Take 9.87 mMs of parahydroxyben-zaldehydes, 14.88 mMs of anhydrous Ks2CO3In 100 milliliters of two-mouth bottles, take out
Vacuum leads to argon gas, and in triplicate, n,N-Dimethylformamide of the injection containing 12.84 mMs of bromo-acetic acid tert-butyls is molten thereto
Liquid (40 milliliters), 70oIt is stirred overnight under C.Filtering, removes potassium carbonate, and concentrate is transferred in separatory funnel, uses second by concentration
Acetoacetic ester extracts three times, merges organic phase, and anhydrous magnesium sulfate drying filters, takes filtrate, organic solvent is removed under reduced pressure.It will slightly produce
Object is dissolved in a small amount of n-hexane/ethyl acetate in the mixed solvent（Volume ratio shared by ethyl acetate is 30%）, and as elution
Agent carries out silica gel column chromatography, obtains the benzaldehyde of tert-butyl acetate substitution.Faint yellow solid, yield 70.39%.
（2）Into 2 liters of two-mouth bottles, 2.54 mMs of C are added in60It with 8.50 mMs of sarcosines, vacuumizes, leads to argon gas, weight
Again three times, 600 milliliters of chlorobenzenes are injected thereto, treat C60After dissolving, the benzene first that will replace containing 1.69 mMs of tert-butyl acetates
(200 milliliters) of the chlorobenzene solution of aldehyde injects wherein, and 140 oIt is stirred overnight under C.Reaction mixture is cooled to room temperature, filters, takes
Filtrate；Chlorobenzene is removed under reduced pressure, crude product is dissolved in a small amount of ethyl acetate/toluene Mixed Solvent（Body shared by ethyl acetate
Product ratio is 20%）, and carry out silica gel column chromatography as eluant, eluent.Organic solvent is removed under reduced pressure, product is dissolved in a small amount of first
In benzene, and gel size exclusion chromatography separation is carried out as eluant, eluent.Toluene is removed under reduced pressure, product is dissolved in a small amount of first
Benzene adds in excessive methanol recrystallization.It filters, obtains solid, be dried in vacuo to obtain target product.Yellow-brown solid, yield 53.34
%。
（3）Take 0.94 mM of the C containing the tert-butyl ester60Derivative is dissolved in 100 milliliters of dichloromethane/trifluoroacetic acid mixing
In solvent（Volume ratio shared by dichloromethane is 75%）, it is stirred at room temperature 24 hours, organic solvent is removed under reduced pressure, obtains brown color and consolidate
Body, yield 93.38%.
（4）Into 500 milliliters of two-mouth bottle, 0.32 mM of carboxylic C is added in60Derivative, the two of 0.33 mM
Carbodicyclo hexylimide and 0.33 mM of 4-dimethylaminopyridine, vacuumize, and lead to argon gas, in triplicate, add thereto
Enter the mixed solvent of 200 milliliters of tetrahydrofuran/acetonitriles.It is stirred 1 hour at 45 DEG C, adds in 100 milliliters and contain 0.26 mM
Dowson-NH2Tetrahydrofuran/acetonitrile mixed solvent.It is stirred 7 days at 45 DEG C, filters, take filtrate.Organic solvent is removed under reduced pressure,
Tetrahydrofuran is added in, fully after dissolving, filtering washs solid with THF.Solid is dissolved in a small amount of acetonitrile, is added dropwise to dropwise a large amount of
In ether, filtering takes solid, this process is repeated twice.Obtained solid with acetone is repeatedly washed, obtains target molecule.
The molecular structure of above-mentioned gained target molecule and1H nuclear magnetic resoance spectrums are illustrated in Fig. 1,13C nuclear magnetic resoance spectrums are illustrated in
Fig. 2, infrared absorption spectrum are shown in Fig. 3, and uv-visible absorption spectra is shown in Fig. 4, the transmission electron microscopy of dimethyl sulphoxide solution
Mirror observed result is shown in Fig. 5, and the transmission electron microscopy observation result of n,N-Dimethylformamide solution is shown in Fig. 6, and acetonitrile is molten
The transmission electron microscopy observation result of liquid is shown in Fig. 7.
Fig. 1 1H nmr spectrums, the chemical position of main hydrogen can correspond to.The reason of spectrogram peak shape is bad be mainly
Because molecule is assembled in deuterated solvent, this is also confirmed by following experimental result.
Fig. 213C nmr spectrums, spectrogram chemical shift further prove that target molecule successfully synthesizes.
It can therefrom find out amido bond in Fig. 3 infrared spectrums, the corresponding characteristic absorption peak such as C-N and polyoxometallate,
Further demonstrate that the successful preparation of target molecule.
Fig. 4 uv-visible absorption spectras, there is no occur single addition C at 431nm for molecule60The characteristic absorption of derivative
Peak, it was demonstrated that target molecule is assembled in selected solvent.This conclusion is demonstrate,proved by the result of follow-up transmission electron microscope
It is real.
Fig. 5 dimethyl sulphoxide solutions transmission electron microscopy observation the result shows that, aggregation is formed therein in target molecule
Body（Vesica）, further demonstrate the conclusion that uv-visible absorption spectra measure obtains.
Fig. 6 n,N-Dimethylformamide solution transmission electron microscopy observations the result shows that, target molecule also shape wherein
Into aggregation（Vesica）, further demonstrate the conclusion that uv-visible absorption spectra measure obtains.
Fig. 7 acetonitrile solutions transmission electron microscopy observation the result shows that, aggregation is formed therein in target molecule（Capsule
Bubble）, further demonstrate the conclusion that uv-visible absorption spectra measure obtains.
Fig. 8 cyclic voltammetries the results show that presoma carboxylated C60Contain 3 pairs of reversible redox in derivative
Peak, and reaction product C60There is no 3 pairs of reversible reduction peaks occur in-Dawson, the reason is that reaction product occurs in DMF solution
Aggregation, side demonstrate the conclusion that uv-visible absorption spectra measures and transmission electron microscopy observation obtains.
Fig. 9 ESR electron paramagnetic resonance collection of illustrative plates, presoma Dawson-NH2And C60- Dawson is paramagnet, and
Unmodified fullerene is without magnetism.Meanwhile compared to Dawson-NH2, C60The spectrogram of-Dawson, which is split, point to be become apparent from,
Should be due to C60The access of molecule, hybrid molecule is compared to Dawson-NH2Move slack-off reason.
Embodiment 2
On the basis of embodiment 1, by step（1）In parahydroxyben-zaldehyde replace with 2,4- 4-dihydroxy benzaldehydes, bromine
The addition of tert-butyl acetate is adjusted to 25.68 mMs, anhydrous K2CO3Addition be adjusted to 20 mMs；In step 4
Dawson-NH2Addition be adjusted to 0.80 mM, other conditions are constant.
Embodiment 3
On the basis of embodiment 2, by step（1）In parahydroxyben-zaldehyde replace with 2,5- 4-dihydroxy benzaldehydes,
Its condition is constant.
Embodiment 4
On the basis of embodiment 2, by step（1）In parahydroxyben-zaldehyde replace with 3,4- 4-dihydroxy benzaldehydes,
Its condition is constant.
Embodiment 5
On the basis of embodiment 2, by step（1）In parahydroxyben-zaldehyde replace with 3,5- 4-dihydroxy benzaldehydes,
Its condition is constant.
Embodiment 6
On the basis of embodiment 1, by step（1）In parahydroxyben-zaldehyde replace with 3,4,5- tri hydroxybenzaldehydes,
The addition of bromo-acetic acid tert-butyl is adjusted to 38.52 mMs, anhydrous K2CO3Addition be adjusted to 30 mMs；In step 4
Dawson-NH2Addition be adjusted to 1.20 mMs, other conditions are constant.
Embodiment 7
On the basis of embodiment 6, by step（1）In parahydroxyben-zaldehyde replace with 2,3,4- tri hydroxybenzaldehydes,
Other conditions are constant.
Embodiment 8
On the basis of embodiment 6, by step（1）In parahydroxyben-zaldehyde replace with 2,4,6- tri hydroxybenzaldehydes,
Other conditions are constant.
Embodiment 9
On the basis of embodiment 1, by step（1）In bromo-acetic acid tert-butyl replace with the bromo-propionic acid tert-butyl ester, other
Part is constant.
Embodiment 10
On the basis of embodiment 1, by step（1）In bromo-acetic acid tert-butyl replace with the bromo-butyric acid tert-butyl ester, other
Part is constant.
Embodiment 11
On the basis of embodiment 1, by step（2）In fullerene C60Replace with fullerene C70, other conditions are constant.
Embodiment 12
On the basis of embodiment 1, by step（2）In fullerene C60Replace with fullerene C76, other conditions are constant.
Embodiment 13
On the basis of embodiment 1, by step（2）In fullerene C60Replace with fullerene C84, other conditions are constant.
Embodiment 14
On the basis of embodiment 1, by step（4）In Dawson-NH2Replace with Anderson-NH2, addition adjustment
It it is 0.13 mM, other conditions are constant.
Embodiment 15
On the basis of embodiment 14, by step（4）In Dawson-NH2Replace with Lindqvist-NH2, addition tune
Whole is 0.13 mM, and other conditions are constant.
Claims (11)
1. the preparation method of fullerene-polyoxometallate hybrid molecule, it is characterised in that the preparation method includes the following steps：
1）The preparation of the benzaldehyde of alkyl tert-butyl acrylate substitution
Under inert gas shielding, to containing K2CO3N,N-dimethylformamide in add in bromine alkyl tert-butyl acrylate and hydroxy benzenes first
Aldehyde, 50-150 DEG C is stirred to react 10-100 hours, then adds in water and ethyl acetate extracts 3-5 times, merge organic phase, anhydrous
MgSO4It is dry, it filters, takes filtrate, the benzene first that silica gel column chromatography replaces up to alkyl tert-butyl acrylate is carried out after solvent is removed under reduced pressure
Aldehyde；
2）The preparation of fullerene derivate containing the tert-butyl ester
Under inert gas shielding, the benzene first of alkyl tert-butyl acrylate substitution is added in into the chlorobenzene solution containing sarcosine and fullerene
Aldehyde flows back 10-24 hours under the conditions of being protected from light, and filters, takes filtrate, and chlorobenzene is removed under reduced pressure, and carries out silica gel column chromatography, takes brown group
Point, solvent is removed under reduced pressure, product is redissolved in toluene, gel size exclusion chromatography separation is carried out, takes the second component to obtain the final product
Fullerene derivate of single addition containing the tert-butyl ester；
3）The preparation of the fullerene derivate containing carboxyl
By the fullerene derivate containing the tert-butyl ester in the in the mixed solvent of dichloromethane and trifluoroacetic acid, 10-100 DEG C of stirring 10-
48 hours, solvent is removed under reduced pressure up to carboxylic fullerene derivate；
4）The preparation of fullerene-polyoxometallate hybrid molecule
Under inert gas shielding, the in the mixed solvent of acetonitrile and tetrahydrofuran to the fullerene derivate containing carboxyl adds in amino and repaiies
The polyoxometallate of decorations, with the help of amidation reagent, 10-100 DEG C is stirred 1-10 days, is filtered, is taken filtrate, be removed under reduced pressure
Solid is redissolved in THF by solvent, and filtering takes solid；Solid is dissolved in acetonitrile and then it is added dropwise to ether dropwise
In, filtering takes solid, repeats this process；Obtained solid is washed with acetone up to fullerene-polyoxometallate hydridization point
Son；The amido modified polyoxometallate for Dawson types polyoxometallate, Anderson types polyoxometallate or
Lindqvist type polyoxometallates.
2. preparation method as described in claim 1, it is characterised in that the hydroxy benzaldehyde rubs with bromine alkyl tert-butyl acrylate
You are than being 0.5-1.5:1-3；The K2CO3Molar ratio with bromine alkyl tert-butyl acrylate is 1-3:0.5-1.5.
3. preparation method as claimed in claim 1 or 2, it is characterised in that the hydroxy benzaldehyde for 4- hydroxy benzaldehydes, 2,
4- 4-dihydroxy benzaldehydes, 2,5- 4-dihydroxy benzaldehydes, 3,4- 4-dihydroxy benzaldehydes, 3,5- 4-dihydroxy benzaldehydes, tri- hydroxyls of 3,4,5-
Benzaldehyde, 2,3,4- tri hydroxybenzaldehydes or 2,4,6- tri hydroxybenzaldehydes；The bromine alkyl tert-butyl acrylate is bromoacetic acid uncle
Butyl ester, the bromo-propionic acid tert-butyl ester or the bromo-butyric acid tert-butyl ester.
4. preparation method as described in claim 1, it is characterised in that step 1）Eluant, eluent selected by middle silica gel column chromatography is
N-hexane/ethyl acetate, wherein ethyl acetate volumn concentration are 10%-50%.
5. preparation method as described in claim 1, it is characterised in that step 2）Described in alkyl tert-butyl acrylate substitution benzene first
The molar ratio of aldehyde and fullerene is 0.5-1.5:1-4；The benzaldehyde of the alkyl tert-butyl acrylate substitution and the molar ratio of sarcosine
For 0.5-1.5:1-3.
6. the preparation method as described in claim 1 or 5, it is characterised in that step 2）Described in fullerene be C60、C70、C76Or
C84。
7. preparation method as described in claim 1, it is characterised in that step 2）Eluant, eluent selected by middle silica gel column chromatography is
Ethyl acetate/toluene Mixed Solvent, wherein ethyl acetate volumn concentration are 10%-50%.
8. preparation method as described in claim 1, it is characterised in that step 3）Described in dichloromethane and trifluoroacetic acid rub
You are than being 1-5:0.5-1.5.
9. preparation method as described in claim 1, it is characterised in that step 4）In fullerene derivate containing carboxyl, amido modified
Polyoxometallate and amidation reagent molar ratio 0.5-1.5：0.5-4：0.5-4.
10. preparation method as described in claim 1, it is characterised in that step 4）Described in the molar ratio of acetonitrile and tetrahydrofuran
For 0.5-1.5:1-8.
11. the preparation method as described in claim 1 or 9, it is characterised in that the amidation reagent is sub- for dicyclohexyl carbon two
Amine, 4-dimethylaminopyridine or 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline.
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| CN113600240B (en) * | 2021-07-16 | 2022-08-19 | 清华大学 | Amino acid or derivative modified polyoxometallate and preparation method and application thereof |
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