CN105622579B - A kind of chiral covalent organic frame material and its synthetic method and application - Google Patents
A kind of chiral covalent organic frame material and its synthetic method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- C—CHEMISTRY; METALLURGY
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- C07B2200/07—Optical isomers
Abstract
The present invention discloses a kind of synthetic method of chiral covalent organic frame material, and this method comprises the following steps：（1）Under an inert atmosphere, chiral precursor obtains solid product with equal benzene trioxin by acetic acid catalytic reaction, and the structural formula of the chiral precursor is
Description
Technical field
The invention belongs to organofunctional Material Field, and in particular to a kind of chiral covalent organic frame material and its synthesis
Methods and applications.
Background technology
Chirality is the phenomenon of nature generally existing, and the life to origin of life and the mankind plays vital work
With.The different molecule of chiral configuration, its bioactivity may be significantly different, so it is one to obtain optically pure chipal compounds
Very great research field.Realize that asymmetric catalysis is that acquisition optical pure compound is maximally effective by chiral catalyst
Method.
Now there are some researches show L-Pro and its derivative have good catalysis to the asymmetric Aldol reaction of ketone and aldehyde
Effect（" the asymmetric aldol reaction of organocatalysis ", Jiang Lijuan etc.,Organic chemistry, 2006 volume 26 the 5th
Phase, the 618-626 pages）.But L-Pro and its derivative belong to homogeneous chiral catalyst, lacking of being not easy to separate with product be present
Point, limit its extensive use industrially.The heterogeneouss of homogeneous chiral catalyst are the main paths for solving this problem.
Inorganic molecule sieve is current most successful heterogeneous catalyst, it achieved in the field such as fine chemistry industry and petrochemical industry it is huge into
Work(.Scientist is inspired by this, it would be desirable to synthesis of chiral molecular sieve, and it is applied to multi-phase chiral catalytic field.Although pay
Very big effort, but up to the present, also it is successfully applied to chiral catalysis without chiral zeolite.
Covalent organic frame material (COFs) is a kind of emerging molecular sieve analog material, causes extensive pass in recent years
Note, at present in gas absorption/separation/storage, medicament slow release, photoelectricity（Device）, catalysis etc. the preliminary application in field.Covalently
The synthesis precursor of organic framework materials is various, can regulate and control its structure and performance by changing precursor；It has big simultaneously
Specific surface area and orderly duct, are easy to the transmission of reaction raw materials and product；Therefore covalent organic frame material is as multiphase
The ideal chose of chiral catalyst.It is contemplated that the development of chiral covalent organic frame material will greatly expand molecular sieve analog material
Expect the application in chiral catalysis field.
The content of the invention
The technical problem to be solved in the present invention is to overcome the defects of existing, there is provided a kind of chiral covalent organic frame material
And its synthetic method and application.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of synthetic method of chiral covalent organic frame material, comprises the following steps：
（1）Under an inert atmosphere, chiral precursor obtains solid product, the hand with equal benzene trioxin by acetic acid catalytic reaction
The structural formula of property precursor is, wherein Boc is tertbutyloxycarbonyl；
（2）Step（1）Gained solid product removes tertbutyloxycarbonyl, obtains the chiral covalent organic frame material.
Further, the mole of the acetic acid is 0.8-40 times, more preferably 6-12 times of equal benzene trioxin mole.
Further, step（1）Reaction temperature be 80-150 DEG C.
Step（1）Reaction system solvent is not specially required, make reactant dissolve, Isosorbide-5-Nitrae-dioxy can be used
Six rings, ethanol, tetrahydrofuran, mesitylene etc., it is preferred to use combinations thereof, such as Isosorbide-5-Nitrae-dioxane+mesitylene, second
Alcohol+mesitylene, tetrahydrofuran+mesitylene etc., the total concentration general control of reactant chiral precursor and equal benzene trioxin exist
1-100 g/L。
Further, step（2）The heating removing tertbutyloxycarbonyl under 180-300 DEG C and inert atmosphere.
Further, the mol ratio of equal benzene trioxin and chiral precursor is preferably 1:(1-2), more preferably 1:(1.5-2).
The synthetic method of the chiral precursor, comprises the following steps：
（1）In the presence of ethyl chloroformate and triethylamine, N- tertbutyloxycarbonyls-L-PROLINE and 3,6- bis- bromo- 1,2-
Phenylenediamine reacts, and reaction obtains compound 3 to obtained intermediate under acetic acid effect again：；
（2）In the presence of potassium carbonate and four triphenyl phosphorus palladiums, compound 3 obtains compound with p-nitrophenyl acid reaction
4：；
（3）Compound 4 obtains the chiral precursor through hydrogen reducing.
According to chiral covalent organic frame material made from any of the above-described method.
Application of the chiral covalent organic frame material as chiral catalyst.
Further, the chiral covalent organic frame material is used for the asymmetric Aldol reaction for being catalyzed ketone and aldehyde.
Further, the chiral covalent organic frame material is used to be catalyzed acetone and the asymmetric Aldol of aromatic aldehyde is anti-
Should.
Further, the aromatic aldehyde be benzaldehyde, paranitrobenzaldehyde, o-nitrobenzaldehyde, to cyanobenzaldehyde, 2- naphthalenes
Formaldehyde etc..
The present invention successfully synthesizes a kind of chiral covalent organic frame material, and it has larger specific surface area and rule
Pore passage structure, there is good catalytic activity and cyclical stability to the asymmetric Aldol reaction of ketone and aldehyde, be a kind of good
Multi-phase chiral catalyst, greatly expand application of the molecular sieve analog material in chiral catalysis field.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
Apply example to be used to explain the present invention together, be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the x-ray diffractogram of powder spectrum of the chiral covalent organic frame material of the present invention.
Fig. 2 is the solid state nmr spectrogram of the chiral covalent organic frame material of the present invention.
Fig. 3 is Fourier's infared spectrum of the chiral covalent organic frame material of the present invention.
Fig. 4 is the nitrogen Adsorption and desorption isotherms and pore size distribution curve of the chiral covalent organic frame material of the present invention.
Fig. 5 is the thermal gravimetric analysis curve of the chiral covalent organic frame material of the present invention.
Fig. 6 is powder x-ray diffraction spectrogram of the chiral covalent organic frame material of the present invention after use is catalyzed.
Embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that described herein preferred real
Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment 1
（1）The synthetic method of chiral precursor 1 is as follows：
The synthesis of compound 3：
A single port bottle is taken, adds N- tertbutyloxycarbonyls-L-PROLINE（5.17 g, 24.0 mmol）, anhydrous dichloromethane
Alkane（60 mL）, stirring and dissolving is simultaneously cooled to 0 DEG C.Ethyl chloroformate is slowly added dropwise（2.28 mL, 24.0 mmol）With anhydrous three
Ethamine（6.65 mL, 48.0 mmol）, then disposably add bromo- 1, the 2- phenylenediamines of 3,6- bis-（5.32 g, 20.0
mmol）.Allow reaction system to be warmed to room temperature, and 36 h of reaction are stirred at room temperature.After reaction terminates, water is added into reaction system
100 mL, are extracted with dichloromethane, and organic phase is with after saturated common salt water washing, and with anhydrous sodium sulfate drying, solvent evaporated obtains
Brown oil.Glacial acetic acid is added into the brown oil（25 mL）, the h of stirring reaction 12 at 65 DEG C.Reaction terminates
Afterwards, room temperature is cooled to, saturated sodium carbonate solution neutralization reaction is added into reaction system, until reaction system is alkalescence, uses second
Acetoacetic ester extracts, and organic phase uses anhydrous sodium sulfate drying with after saturated common salt water washing.After solvent evaporated, use column chromatography
（Petroleum ether：Ethyl acetate=8:1）, can obtain compound 3（White solid, 3.91 g）, yield 44%.1H NMR (400
MHz, CDCl3): δ = 11.18 (s, 1H), 7.19 (d, J = 36.2 Hz, 2H), 5.14 (m, 1H), 3.45
(m, 2H), 2.99 (m, 1H), 2.19 (m, 2H), 2.07 – 1.91 (m, 1H), 1.50 (s, 9H). 13C
NMR (100 MHz, CDCl3): δ = 156.5, 156.1, 141.2, 134.2, 125.7, 112.0, 102.3,
80.9, 54.7, 47.3, 28.5, 28.3, 24.7. HRMS: m/z calcd for C16H20Br2N3O2 [M+H]+:
443.9916, found: 443.9908。
The synthesis of compound 4：
A two-mouth bottle is taken, adds compound 3（886 mg, 2.0 mmol）, p-nitrophenyl boric acid（768 mg, 4.6
mmol）, potassium carbonate（828 mg, 6.0 mmol）, four triphenyl phosphorus palladiums（233 mg, 0.2 mmol）.System is replaced with argon gas
Three times, and with argon gas protect.By injecting 1,4 dioxane added into reaction bulb Jing Guo degassing process（16 mL）And water
（4 mL）Mixed solution.Reaction system is heated to reflux 8h at 100 DEG C.After reaction terminates, solvent evaporated, into residue
Water is added, is extracted with dichloromethane, merges organic phase, with using anhydrous sodium sulfate drying after saturated common salt water washing.Solvent evaporated
Afterwards, use column chromatography（Dichloromethane）, obtain compound 4（Yellow solid, 720 mg）, yield 72%.1H NMR (400
MHz, CDCl3): δ = 11.54 (s, 1H), 8.36 (d, J = 7.5 Hz, 6H), 7.80 (d, J = 8.2
Hz, 2H), 7.60 (d, J = 7.8 Hz, 1H), 7.46 (d, J = 7.8 Hz, 1H), 5.17 (m, 1H),
3.60 – 3.40 (m, 2H), 3.10 (m, 1H), 2.35 – 2.11 (m, 2H), 2.07 (m, 1H), 1.53
(s, 9H). 13C NMR (100 MHz, CDCl3): δ = 156.9, 156.6, 147.1, 146.9, 144.6,
140.9, 133.0, 129.8, 128.3, 124.4, 123.6, 122.8, 122.0, 81.0, 54.8, 47.4,
28.3, 27.9, 24.8. HRMS: m/z calcd for C28H28N5O6 [M+H]+: 530.2034, found:
530.2046。
The synthesis of chiral precursor 1：
A single port bottle is taken, adds compound 4（529 mg, 1.0 mmol）, 5% palladium carbon（212 mg, 0.1mmol）, nothing
Water tetrahydrofuran（40 mL）.Reaction system is replaced 5 times with hydrogen, and under an atmosphere of hydrogen（30℃）The h of stirring reaction 24.Reaction
After end, filtered with diatomite, n-hexane is added into filtrate（150 mL）, 24 h are then cooled down at -4 DEG C, are had a large amount of solid
Body separates out, and filtering, dries and can obtain chiral precursor 1（422 mg）, yield 90%.1H NMR (400 MHz, DMSO): δ =
11.93 (d, J = 21.7 Hz, 1H), 7.86 (d, J = 7.4 Hz, 2H), 7.30 (d, J = 7.7 Hz,
2H), 7.26 (m, 1H), 7.15 – 7.02 (m, 1H), 6.67 (dd, J = 32.0, 8.0 Hz, 4H), 5.19
(dd, J = 47.3, 7.4 Hz, 4H), 5.09 – 4.95 (m, 1H), 3.59 (m, 1H), 3.40 (m, 1H),
2.24 (m, 1H), 2.04 (m, 2H), 1.87 (m, 1H), 1.42 (s, 5H), 1.10 (s, 4H). 13C NMR
(150 MHz, DMSO): δ = 156.7, 155.9, 153.9, 153.4, 148.2, 148.1, 147.7, 147.6,
140.7, 140.4, 132.1, 132.0, 129.3, 129.2, 128.7, 128.6, 128.5, 128.5, 126.1,
126.0, 125.6, 125.5, 123.7, 123.6, 121.0, 120.9, 119.0, 118.9, 114.2, 113.6,
78.6, 78.1, 55.2, 54.7, 48.3, 46.6, 46.4, 33.1, 31.5, 28.1, 27.8, 23.7, 23.1.
HRMS: m/z calcd for C28H32N5O2 [M+H]+: 470.2550, found: 470.2565。
（2）The synthesis of chiral covalent organic frame material：
The equal benzene trioxins of 8.1 mg and 35.2 mg chiral precursors 1 are added in pressure pipe.Then 0.2 mL bis- is added
The ring of oxygen six and 0.8 mL mesitylene, the mol/L of 0.15 mL 3 acetum is added after shaking up.By pressure pipe rubber stopper
After sealing, with argon gas displacement three times, then quickly rubber stopper is removed, with Teflon stopper by the pressure-resistant seal of tube.By its
It is placed in baking oven, is reacted three days in 90 DEG C.After reaction terminates, there is solid generation in pressure-resistant bottom of the tube, solid is transferred to centrifugation
Guan Zhong, with acetone, tetrahydrofuran difference centrifuge washing 3 times.Solid is dried at 100 DEG C, obtains yellow solid powder（Will
Its life is CCOF-LZU72-Boc）29.8 mg, yield 73%.
By CCOF-LZU72-Boc（15.0 mg）It is placed in pressure pipe, is replaced 3 times with argon gas, then used polytetrafluoro
Ethene plug seal.It is placed on and is previously heated in 245 DEG C of baking oven, the min of heating response 15, you can obtain CCOF-
LZU72。
Fig. 1 is the X ray diffracting spectrum of product, and wherein Fig. 1 a correspond to CCOF-LZU72-Boc, and Fig. 1 b correspond to
CCOF-LZU-72, Fig. 1 c correspond to chiral precursor 1, and Fig. 1 d correspond to equal benzene trioxin.By contrast CCOF-LZU72-Boc and
The x-ray diffractogram of powder spectrum of raw material, it may be determined that the present invention successfully synthesizes a kind of new covalent organic frame material.
Fig. 2 is the solid state nmr spectrogram of product, and wherein Fig. 2 a correspond to CCOF-LZU72-Boc, and Fig. 2 b correspond to CCOF-
LZU-72。
Fig. 3 is the infrared spectrum of product, and wherein Fig. 3 a correspond to CCOF-LZU72-Boc, and Fig. 3 b correspond to CCOF-
LZU72, Fig. 3 c correspond to chiral precursor 1, and Fig. 3 d correspond to equal benzene trioxin.
Fig. 4 be product nitrogen adsorption desorption curve and pore size distribution curve, as shown by data CCOF-LZU72-Boc and
CCOF-LZU72 is respectively provided with the pore passage structure of larger specific surface area and rule, and its specific surface area is respectively：916 m2g-1With
1114 m2g-1。
By contrasting CCOF-LZU72 and CCOF-LZU72-Boc x-ray diffractogram of powder spectrum, solid state nmr spectrogram, red
Outer spectrogram, nitrogen adsorption desorption curve and pore size distribution curve, it can be found that CCOF-LZU72-Boc heats deprotection group
（Boc）Afterwards, the crystalline structure of material remains to be maintained.
Fig. 5 is the thermogravimetric curve of material, and wherein Fig. 5 a correspond to CCOF-LZU72, and Fig. 5 b correspond to CCOF-LZU72-
Boc, it can be seen that CCOF-LZU72-Boc has an obvious weightless process in 180 DEG C of -280 DEG C of sections, and the weightlessness comes from
The removing of the upper tertbutyloxycarbonyls of CCOF-LZU72-Boc.
（3）CCOF-LZU72 chiral catalysis performance
By taking the asymmetric Aldol reaction of common acetone and paranitrobenzaldehyde as an example, examination CCOF-LZU72 to ketone with
The asymmetric Aldol reaction catalytic activity of aldehyde.
By CCOF-LZU72（13.2 mg）, o-nitrobenzoic acid（5.0 mg）, acetone（1.0 mL）It is added to reaction tube
In, 5 min are stirred at room temperature.Then paranitrobenzaldehyde (45.3 mg) is added, 4 h of reaction are stirred at room temperature.Reaction terminates
Afterwards, the method by centrifuging or filtering and wash, liquid is collected, after removal of solvent under reduced pressure, residue is purified by column chromatography
（Petroleum ether:Ethyl acetate=3:1, V/V）It can obtain target product, yield 90%,eeFor 45%（Pass through high performance liquid chromatography
Measure）.
Above-mentioned centrifugation or the CCOF-LZU72 filtered out are washed with dichloromethane, are reused for after drying in catalysis
State reaction.
CCOF-LZU72 is substituted with CCOF-LZU72-Boc, does not find there is catalytic activity to above-mentioned reaction, because
CCOF-LZU72-Boc catalytic sites are protected by tertbutyloxycarbonyl.
Fig. 6 is the X x ray diffraction collection of illustrative plates after CCOF-LZU72 is reused, it can be seen that CCOF-LZU72 can be urged
Change and use four times, the order of material is kept.With increasing for cycle-index, the stereoselectivity of reaction is protected
Hold, but the reaction time gradually extends, this order for being primarily due to material gradually reduces, and hinders reaction raw materials and product
Transmission.
Embodiment 2
The equal benzene trioxins of 8.1 mg and 35.2 mg chiral precursors 1 are added in pressure pipe.Then add 0.2 mL without
Water-ethanol and 0.8 mL mesitylene, the mol/L of 0.10 mL 3 acetum is added after shaking up.By pressure pipe rubber stopper
After sealing, with argon gas displacement three times, then quickly rubber stopper is removed, with Teflon stopper by the pressure-resistant seal of tube.By its
It is placed in baking oven, is reacted three days in 100 DEG C.After reaction terminates, there is solid generation in pressure-resistant bottom of the tube, solid is transferred to centrifugation
Guan Zhong, with acetone, tetrahydrofuran difference centrifuge washing 3 times.Solid is dried at 100 DEG C, obtains CCOF-LZU72-Boc.
By CCOF-LZU72-Boc（15.0 mg）It is placed in pressure pipe, is replaced 3 times with argon gas, then used polytetrafluoro
Ethene plug seal.It is placed on and is previously heated in 235 DEG C of baking oven, the min of heating response 25, you can obtain CCOF-
LZU72。
Embodiment 3
The equal benzene trioxins of 16.2 mg and 70.4 mg chiral precursors 1 are added in pressure pipe.Then 0.2 mL is added
Tetrahydrofuran and 1.8 mL mesitylene, the mol/L of 0.4 mL 3 acetum is added after shaking up.By pressure pipe rubber
After plug sealing, with argon gas displacement three times, then quickly rubber stopper is removed, with Teflon stopper by the pressure-resistant seal of tube.Will
It is placed in baking oven, is reacted three days in 80 DEG C.Reaction terminate after, have solid generation in pressure-resistant bottom of the tube, by solid be transferred to from
In heart pipe, with acetone, tetrahydrofuran difference centrifuge washing 3 times.Solid is dried at 100 DEG C, obtains CCOF-LZU72-Boc.
By CCOF-LZU72-Boc（15.0 mg）It is placed in pressure pipe, is replaced 3 times with argon gas, then used polytetrafluoro
Ethene plug seal.It is placed on and is previously heated in 245 DEG C of baking oven, the min of heating response 15, you can obtain CCOF-
LZU72。
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (9)
1. a kind of synthetic method of chiral covalent organic frame material, comprises the following steps：
（1）Under an inert atmosphere, chiral precursor and equal benzene trioxin obtain solid product by acetic acid catalytic reaction, it is described it is chiral before
The structural formula of body is, wherein Boc is tertbutyloxycarbonyl；
（2）Step（1）Gained solid product removes tertbutyloxycarbonyl, obtains the chiral covalent organic frame material.
2. synthetic method according to claim 1, it is characterised in that：The mole of the acetic acid is equal benzene trioxin mole
0.8-40 times of amount.
3. synthetic method according to claim 1, it is characterised in that：Step（1）Reaction temperature be 80-150 DEG C.
4. synthetic method according to claim 1, it is characterised in that：Step（2）Under 180-300 DEG C and inert atmosphere
Heating removing tertbutyloxycarbonyl.
5. synthetic method according to claim 1, it is characterised in that：The mol ratio of equal benzene trioxin and chiral precursor is 1:
(1-2)。
6. according to chiral covalent organic frame material made from any methods describeds of claim 1-5.
7. application of the chiral covalent organic frame material as chiral catalyst described in claim 6, it is characterised in that the hand
Property covalent organic frame material be used to be catalyzed the asymmetric Aldol reaction of ketone and aldehyde.
8. application according to claim 7, it is characterised in that the chiral covalent organic frame material is used to be catalyzed acetone
With the asymmetric Aldol reaction of aromatic aldehyde.
9. application according to claim 8, it is characterised in that the aromatic aldehyde is benzaldehyde, paranitrobenzaldehyde, adjacent nitre
Benzaldehyde, to cyanobenzaldehyde or 2- naphthaldehydes.
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| CN103694469A (en) * | 2013-12-17 | 2014-04-02 | 兰州大学 | Sulfide functionalized covalent organic frame material and synthesis method thereof |
| CN103755588A (en) * | 2014-01-09 | 2014-04-30 | 兰州大学 | Synthetic method and application of covalent organic framework (COF) material |
| CN104761488A (en) * | 2015-03-10 | 2015-07-08 | 兰州大学 | Three-dimensional bipyridine functionalized covalent organic frame material synthesis method |
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