CN109772459A - A kind of chirality polyacid Base Metal organic framework materials and its preparation method and application - Google Patents
A kind of chirality polyacid Base Metal organic framework materials and its preparation method and application Download PDFInfo
- Publication number
- CN109772459A CN109772459A CN201910209209.1A CN201910209209A CN109772459A CN 109772459 A CN109772459 A CN 109772459A CN 201910209209 A CN201910209209 A CN 201910209209A CN 109772459 A CN109772459 A CN 109772459A
- Authority
- CN
- China
- Prior art keywords
- dpndi
- znw
- pyi1
- organic framework
- pyi2
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention provides a kind of chiral polyacid Base Metal organic framework materials, the chemical formulas of the polyacid Base Metal organic framework materials are as follows: C74H101B2Zn2N22O84W24, ZnW DPNDI PYI1 and ZnW DPNDI PYI2 is denoted as according to chirality respectively, wherein DPNDI is N, and N '-two (4- picoline) naphthalimide, as bridging ligand and photosensitizer, PYI is L pyrrolidines -2- imidazoles, and PYI is as chiral ligand and electron donor；Affiliated crystal belongs to monoclinic system, and the space group of the ZnW DPNDI PYI1 and ZnW DPNDI PYI2 is (1) P2.Chiral polyacid Base Metal organic framework materials of the invention belong to multifunctional inorganic porous material, it has asymmetric photocatalysis oxidation technique, and the technology is by occurring redox with substrate after visible optical drive light-sensitive catalyst to excitation state to complete reacting for related free-radical type.
Description
Technical field
The invention belongs to polyoxometallate functional material preparation technical fields, and in particular to a kind of chirality polyacid Base Metal
Organic framework materials and its preparation method and application.
Background technique
Epoxide is the important intermediate and industrial chemicals of organic synthesis, and Eleventh Five-Year Plan is China's propylene oxide industry
It flourishes, becomes the propylene oxide whole world maximum production and marketing state, 2010 annual capacities reach 154.5 ten thousand tons, 143.76 ten thousand tons of yield.With
Polyether Polyol Industry, high-quality electronic product, Aerospace Products manufacture wilderness demand, China's product propylene need
It asks still in fast development, it is predicted that the year two thousand twenty consumption figure can reach 275.6 ten thousand tons quickly.Epoxy especially with optical activation
Compound is the important intermediate of chiral drug synthesis, can by the reaction such as the selective opening of epoxides and functional group's conversion
To synthesize many valuable medicine, pesticide.The industrial chemicals such as the hydrocarbon of petroleum fossil resource will be derived from through selecting
The oxidation of selecting property is converted into the corresponding chiral oxygenatedchemicals with high added value, is used as it and prepares polymer monomer and agriculture
The base stock of medicine and pharmaceuticals is one of key reaction process of modern petrochemical industry.Sharpless epoxidation (AE)
Reaction is the important breakthrough of chiral technology, but there is certain limitation to be such as only applicable to allyl alcohol substrate and use for the reaction
Oxidant TBHP less stable.Then, different chiral catalysts developed to Sharpless system carried out supplement and it is complete
It is kind, as Jacobsen catalyst using NaOCl be oxidant for non-functional group alkene epoxidation (J.Am.Chem.Soc.,
1990,112,2801), Groves chirality porphyrin complex catalyst is used for phenylethylene substrate by oxidant of PhIO
The Catalyzed by Chiral Ketones agent of (J.Am.Chem.Soc., 1991,113,6865), Yang Dan and Shi Yian is with KHSO5 and HClO4 respectively
Oxidant for substituted olefine (J.Am.Chem.Soc., 1996,118,491；1996,118,11311；J.Am.Chem.Soc.,
1997,119,11224), Julia-Colonna catalyst is oxidant for-beta-unsaturated ketone using urea element hydrogen peroxide complex object
(aldehyde) (Chem.Commun., 1997,739).Although the above homogeneous chiral catalysis has efficient, high enantioselectivity and reaction item
The features such as part is mild, but to realize these applications of catalysis reaction industrially, it is necessary to time of solution expensive catalyst first
It receives and utilizes this serious problem, and these catalyst systems are mainly based upon heat catalysis process, need organic peracid, have
Machine peroxide etc. makees oxidant, and there are process cost height, corrosivity, risk, toxicity, serious environmental pollution and harshness are anti-
Answer the drawbacks such as condition.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of chiral polyacid base
Metal-organic framework material, the material belong to multifunctional inorganic porous material, have asymmetric photocatalysis oxidation technique, the skill
Art is a kind of related free to complete by the way that redox occurs to substrate after visible optical drive light-sensitive catalyst to excitation state
The reaction of base type, and chiral polyacid Base Metal organic framework materials of the invention can provide for asymmetric photocatalysis oxidation reaction
Superior technique.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a pair has the chirality of photo-catalysis function more
Acidic group metal-organic framework material, which is characterized in that the chemical formula of the polyacid Base Metal organic framework materials are as follows:
C74H101B2Zn2N22O84W24, it is denoted as ZnW-DPNDI-PYIs, is denoted as ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2 respectively,
Wherein DPNDI is N, N '-two (4- picoline) naphthalimide, as bridging ligand and photosensitizer；PYI is L- pyrrolidines -2-
Imidazoles, as chiral ligand and electron donor；Polyoxoanion (POMs) conduct of the polyacid Base Metal organic framework materials
Oxidation catalysis functional group；Affiliated crystal belongs to monoclinic system, the ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2's
Space group is (1) P2；The single cell structure chart of ZnW-DPNDI-PYI1 is as shown in Figure 1.
The present invention also provides the preparation method of polyacid Base Metal organic framework materials, the system of the ZnW-DPNDI-PYI1
Preparation Method are as follows: weigh the Zn (NO of 45mg, 0.15mmol respectively3)2·6H2The K of O, 157.8mg, 0.05mmol5[BW12O40]·
5H2The DPNDI of O, 23.4mg, 0.15mmol and the L-BCIP (L-N- tertbutyloxycarbonyl -2- imidazoles -1- of 24.5mg, 0.1mmol
Pyrrolidines) in vial, 4.0mL distilled water, the dissolution of 2.0mL methanol is added, is stirred overnight, obtains suspension solution, by institute
It states suspension solution to be transferred in the autoclave of 25mL, is put into baking oven, be heated to 120 DEG C and react five days, after being cooled to room temperature
Reaction product is taken out, is washed repeatedly with distilled water, obtains white yellow rhabdolith ZnW-DPNDI-PYI1, the ZnW-DPNDI-
The yield of PYI1 is 60%；
The ZnW-DPNDI-PYI2's the preparation method comprises the following steps: weighing the Zn (NO of 45mg, 0.15mmol respectively3)2·6H2O,
The K of 157.8mg, 0.05mmol5[BW12O40]·5H2The DPNDI of O, 23.4mg, 0.15mmol and the D- of 24.5mg, 0.1mmol
BCIP is added 4.0mL distilled water, the dissolution of 2.0mL methanol, is stirred overnight, obtains suspension solution in vial, will be described outstanding
Turbid solution is transferred in the autoclave of 25mL, is put into baking oven, is heated to 120 DEG C and is reacted four days, takes out after being cooled to room temperature
Reflect product, is washed repeatedly with distilled water, obtain white yellow rhabdolith ZnW-DPNDI-PYI2, the ZnW-DPNDI-PYI2
Yield be 60%.
Raw material L-BCIP is L-N- tertbutyloxycarbonyl -2- imidazoles -1- pyrrolidines or D-BCIP is D-N- tertbutyloxycarbonyl -
2- imidazoles -1- pyrrolidines, reference literature (S.Luo, Mi, X.L.Zhang, S.Liu, H.Xu, J.P.Cheng,
Angew.Chem.Int.Ed.2006,45,3093-3097) disclosed in method synthesize to obtain.
Raw material DPNDI be N, N '-two (4- picoline) naphthalimide, reference literature (G.B.Li, J.M.Liu,
Z.Q.Yu, W.Wang, C.Y.Su, Inorg.Chem.2009,48,8659-8661) disclosed in method synthesize to obtain.
Raw material K5BW12O40For Keggin-type multi-acid salt K5BW12O40, reference literature (C.Rocchiccioli-
Deltcheff, M.Fournier, R.Franck, R.Thouvenot, Inorg.Chem.1983,22,207-216) disclosed in
Method synthesizes to obtain.
The present invention also provides C-N coupling and alkene rings that a kind of chiral polyacid Base Metal organic framework materials are applied to amine
The light-catalyzed reaction of oxidation, concrete application are as follows: using ZnW-DPNDI-PYIs as catalyst, under the conditions of radiation of visible light, with O2
For single oxidation source, the C-N applied to amine is coupled in the light-catalyzed reaction with alkene epoxidation.
The principle of the present invention: DPNDI is the derivative of naphthalimide, be it is a kind of there is photochemistry, optical physics, electrochemistry and
It is catalyzed multi-functional π-electron deficient organic ligand of special ability, due in the Modulatory character and naphthalene nucleus of the N atom on its imidodicarbonic diamide
The reducibility of electronics transfer, so that naphthalimide becomes a kind of splendid multi-function metal-organic framework materials (Metal-
Organic frameworks, MOFs) constructing block.Polyoxometallate (polyacid, Polyoxometalates, POMs) has
The features such as high proton acidity, low temperature high activity, good thermal stability and heteropoly acid unique " false liquid phase " reacting field.Wherein, more
Acid has redox site abundant and photocatalytic activity, has the potential of Photo-induced electron transfer, and then generate photochromic
Phenomenon.Proline is a kind of most commonly seen chiral ligand, can realize efficient asymmetry catalysis by hydrogen bond action, this is close
Another bright spot of year organocatalysis, while electrically make PYI also can be used as a kind of electron donor to the richness of its nitrogen-atoms.I
By [the BW with good catalyzing expoxidation of olefines function12O40]5-Polyoxoanion, the DPNDI that may act as photosensitizer and have
The chiral ligand PYI of stereoselectivity is introduced into well-designed MOFs simultaneously, obtains a pair of of enantiomer catalyst Z nW-
DPNDI-PYI1 and ZnW-DPNDI-PYI2.After DPNDI absorbs visible light, it can be produced by continuous Photo-induced electron transfer process
Raw DPNDI·-And DPNDI·-*, then electronics transfer gives [BW12(VI)O40]5-Form the weed seedbank [BW with reproducibility11W(V)
O40]6-, DPNDI of the PYI offer electronics to excitation state·-, while chirality PYIs will be used as concerted catalysis site, form driving multiphase
The key reaction center of asymmetric reaction.POMs, chiral ligand are introduced into MOF structure simultaneously, constructed with multi-catalytic
The chiral polyacid Base Metal organic framework materials MOFs in site, the advantages of can playing each component and realizes catalytic site
Concerted catalysis.
Compared with the prior art, the present invention has the following advantages:
1, ZnW-DPNDI-PYIs provided by the invention is polyacid Base Metal organic framework materials, and it is more to belong to multifunctional inorganic
Porous materials, have asymmetric photocatalysis oxidation technique, which is a kind of by visible optical drive light-sensitive catalyst to excitation
Redox occurs to complete reacting for related free-radical type with substrate after state.Multifunctional inorganic porous material ZnW-
DPNDI-PYIs can provide superior technique for asymmetric photocatalysis oxidation reaction.
2, polyacid Base Metal organic framework materials of the invention can accurately understand its structure by X-ray single crystal diffraction
Feature.
3, the present invention is prepared as core objective with the Controllable assembly and orientation that develop the chiral catalyst that function is guiding, closes
Reason utilizes coordination guiding role, building stereochemical structure stabilization, Multifunctional chiral metal-organic framework of good performance reaction
Platform.By playing the special space limitation of metal-organic framework internal gutter, the association between multi-catalytic site is utilized
Same-action realizes the process that complicated chiral epoxy compound is efficiently constructed from simple hydrocarbon raw material.Moreover, China's tungsten,
The reserves of molybdenum occupy first place in the world, and provide development space for later practical application.
4, preparation method and application of the invention have the characteristics that high efficiency, Atom economy and greenization, photocatalytic synthesis
At strategy, catalyst system is studied in control kinetically, to select with peak optimization reaction time, conversion ratio and maximum
The reaction condition of yield；By three-dimensional between regulation " catalytic site-substrate ", electronic effect matching, the vertical of chiral catalysis is realized
Body selectively controls.
Invention is further described in detail with reference to the accompanying drawings and examples.
Detailed description of the invention
Fig. 1 is ZnW-DPNDI-PYI1 single cell structure figure prepared by the embodiment of the present invention 1.
Fig. 2 is the synthesis and the signal of asymmetry catalysis site of ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2 of the present invention
Figure.
Fig. 3 is the CD spectrum of ZnW-DPNDI-PYI1 (a) prepared by the embodiment of the present invention 1 and ZnW-DPNDI-PYI2 (b)
Figure.
Fig. 4 is three-dimensional accumulation graph of the ZnW-DPNDI-PYI1 along c-axis direction of the preparation of the embodiment of the present invention 1.
Fig. 5 be absorbable spectrogram outside the solid violet of ZnW-DPNDI-PYI1 prepared by the embodiment of the present invention 1, fluorogram and
XPS spectrum figure, (a) are outside the solid violet of ZnW-DPNDI-PYI1；(b) the XPS spectrum figure for being ZnW-DPNDI-PYI1 with (d)；(c) it is
The fluorogram of ZnW-DPNDI-PYI1.
Fig. 6 is aryl olefin epoxidation reaction expression formula.
Fig. 7 is EPOXIDATION OF ALKENES CATALYZED BY expression formula.
Fig. 8 is that catalytic mechanism speculates figure.
Specific embodiment
Embodiment 1
The chemical formula of the present embodiment chirality polyacid Base Metal organic framework materials are as follows: C74H101B2Zn2N22O84W24, it is denoted as
ZnW-DPNDI-PYIs is denoted as ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2 according to material is chiral respectively again.
The present embodiment ZnW-DPNDI-PYI1's the preparation method comprises the following steps: weighing the Zn (NO of 45mg, 0.15mmol respectively3)2·
6H2The K of O, 157.8mg, 0.05mmol5[BW12O40]·5H2The DPNDI and 24.5mg, 0.1mmol of O, 23.4mg, 0.15mmol
L-BCIP in vial, be added 4.0mL distilled water, 2.0mL methanol dissolution, be stirred overnight, obtain suspension solution, by institute
It states suspension solution to be transferred in the autoclave of 25mL, is put into baking oven, be heated to 120 DEG C and react five days, after being cooled to room temperature
Reaction product is taken out, is washed repeatedly with distilled water, obtains white yellow rhabdolith ZnW-DPNDI-PYI1, the ZnW-DPNDI-
The yield of PYI1 is 60%；
The present embodiment ZnW-DPNDI-PYI2's the preparation method comprises the following steps: weighing the Zn (NO of 45mg, 0.15mmol respectively3)2·
6H2The K of O, 157.8mg, 0.05mmol5[BW12O40]·5H2The DPNDI and 24.5mg, 0.1mmol of O, 23.4mg, 0.15mmol
D-BCIP in vial, be added 4.0mL distilled water, 2.0mL methanol dissolution, be stirred overnight, obtain suspension solution, by institute
It states suspension solution to be transferred in the autoclave of 25mL, is put into baking oven, be heated to 120 DEG C and react four days, after being cooled to room temperature
Reflection product is taken out, is washed repeatedly with distilled water, obtains white yellow rhabdolith ZnW-DPNDI-PYI2, the ZnW-DPNDI-
The yield of PYI2 is 60%.
In the present embodiment, raw material L-BCIP is L-N- tertbutyloxycarbonyl -2- imidazoles -1- pyrrolidines or D-BCIP is D-N-
Tertbutyloxycarbonyl -2- imidazoles -1- pyrrolidines, reference literature (S.Luo, Mi, X.L.Zhang, S.Liu, H.Xu,
J.P.Cheng, Angew.Chem.Int.Ed.2006,45,3093-3097) disclosed in method synthesize to obtain.
In the present embodiment, raw material DPNDI be N, N '-two (4- picoline) naphthalimide, reference literature (G.B.Li,
J.M.Liu, Z.Q.Yu, W.Wang, C.Y.Su, Inorg.Chem.2009,48,8659-8661) disclosed in method synthesize
It arrives.
In the present embodiment, raw material K5BW12O40For Keggin-type multi-acid salt K5BW12O40, reference literature
(C.Rocchiccioli-Deltcheff,M.Fournier,R.Franck,R.Thouvenot,Inorg.Chem.1983,22,
207-216) method disclosed in synthesizes to obtain.
In the present embodiment, raw material Zn (NO3)2Selected from the commercially available pure Zn (NO of analysis3)2。
The structure of the polyacid Base Metal organic framework materials of preparation is analyzed as follows:
Fig. 3 is the CD spectrogram of ZnW-DPNDI-PYI1 (a) prepared by the present embodiment 1 and ZnW-DPNDI-PYI2 (b), right
Fig. 3 is analyzed the result shows that ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2 are a pair of of enantiomer-specific structures.With ZnW-DPNDI-
Crystal structure is discussed in detail for PYI1.Mutually independent two zinc atoms of crystallography show identical coordination environment, are
The tetrahedral configuration of distortion is connected by 1 bridge ligand DPNDI, and respectively with 3 from chiral ligand L-PYI's
Atom is matched, two [BW12O40]5–It is in free state (as shown in Figure 1).One of them [BW12O40]5-Just DPNDI is fallen within
The surface of naphthalene nucleus, centre distance areGenerate anion π effect.These anion π effect pushes away significantly
Moved the center DPNDIs and the electron transmission on the surface POMs with exchange, improve the efficient catalytic ability of POMs.Valence link calculates knot
Fruit shows that atom is+6 valences in all compounds, as a result consistent with single crystal diffraction result.Boc in reaction process on BCIP
It removes and generates PYI, exposed pyrroles's nitrogen-atoms is protonated.N atom and [BW in PYI12O40]5-Oxygen is held to form hydrogen bond, N
(10) O (41) and N (22) O (57) distance are respectivelyWithIt is presumed that due to
Chiral PYIs activates W=O by hydrogen bond, and chiral pyrrolidine molecule will be used as concerted catalysis site, the not only oxidation of very high POMs
Activity, additionally it is possible to which additional stereoselectivity is provided.Meanwhile being less than at a distance from PYIs and DPNDI molecule Pi-pi accumulation act on (as shown in Figure 4), promote PYIs and
DPNDIs can carry out electron transmission, not need to introduce additional electronics sacrifice agent (as shown in Figure 2).It is analyzed by PLATON, hole
Rate is(10.3%), it is ensured that reaction substrate and product can freely enter and leave the duct.anion···π,π-π
With N-HO hydrogen bond, the synergistic effect of three has not only promoted the POMOFs, and (POMOFs indicates that chiral polyacid Base Metal has
Machine frame frame material) formation, while improving its stability, also enhance the interaction in POMOFs between different component.
This promotes electron transmissions and charge-exchange to produce the longer fluorescence longevity so that the free radical charge-separated state time increases
Life, finally ensure that efficient catalytic.By that can monitor the formation of DPNDI free radical outside solid violet with fluorometric investigation, simultaneously
XPS the result shows that in During Illumination reduction-state weed seedbank generation (as shown in Figure 5).
The application of polyacid Base Metal organic framework materials of the invention is explained in detail by 2~embodiment of embodiment 4
It states.
Embodiment 2
The present embodiment is using styrene as substrate, O2For oxidant, the ZnW-DPNDI-PYI1 or ZnW- of 0.1%mol is added
DPNDI-PYI2 reacts 12h under visible light illumination, realizes heterogeneous asymmetry catalysis epoxidation reaction of olefines, reaction side
As shown in fig. 6, reaction condition and reaction result are as shown in table 1, the selective oxidation yield of styrene is converted into formula up to 92%
Product styrene oxide, while ee value is up to 45%, substrate can extend to styrene derivative, such as 4- chloro styrene, 2-
Chlorostyrene, 4- methyl styrene.
Embodiment 3
As selected a variety of substrates to carry out catalytic oxidation in table 1, wherein 3 are selected, 5- di-t-butyl -4- vinyl biphenyl
When (t-butyl styrene i.e. in table 1) is used as substrate, under the conditions of same as Example 2, Asymmetric catalytic epoxidation reaction
Yield is less than 10%.It is presumed that this is because the substrate volume is excessive, cannot be introduced into the duct of ZnW-DPNDI-PYI1 into
Row reaction, only a small amount of substrate are adsorbed on the reaction of the surface ZnW-DPNDI-PYI1.It is shape-selective that this phenomenon not only embodies POMOFs
The advantage of catalysis, the Asymmetric catalytic epoxidation reaction also demonstrated in this experiment is strictly to occur among the duct POMOFs,
Efficiently highly selective is the result of multiple catalytic site synergistic effects in the duct POMOFs.
The conversion ratio and selectivity of 1 aryl olefin epoxidation reaction of table
Reaction equation can be indicated by Fig. 6 in table 1, reaction condition: substrate olefin 5mmol, ZnW-DPNDI-PYI1
(10mg, 12.5 μm of ol, 0.02mol%), CH3CN 3mL；Under air atmosphere, 10W white led lamps, room temperature, reaction time 12h.
Conversion ratio and to the selectivity of epoxides by the nuclear magnetic resonance hydrogen spectruming determining of crude product.
Embodiment 4
The present embodiment selects different oxidants as control experiment, N2Under the conditions of do not react.By introducing a series of captures
Agent, investigated oxygen be mainly activated for singlet oxygen (1O2) and superoxide radical (O2-), it is further formed hydroxyl radical free radical
(OH).The reaction mechanism is speculated, as shown in Figure 7.The result shows that in this configuration, each catalysis group passes through association
Same-action high efficiency and highly selective catalyzed alkene asymmetric Epoxidation process.
The conversion ratio and selectivity of the different oxidants of table 2, catalyst and free radical scavenger photochemical catalytic oxidation styrene
This product is not measured in "-" expression.
Reaction equation in table 2 is as shown in fig. 7, reaction condition: substrate: styrene, 5mmol, CH3CN,3mL；10W white
LED light, room temperature, 12h, (entry 1-6:ZNW-DPNDI-PYI1,12.5 μm of ol；Air, 1 atmospheric pressure O2Or N2；Entry 4-6:
Air and 5mg DABCO, 5mg BQ or 0.5ml IPA.Entry 7-8, DPND, 10mg；K5[BW12O40], 10mg ,/K5
[BW12O40]/DPNDI/PYI, 10mg.Conversion ratio and to the selectivity of epoxides by the nuclear magnetic resonance hydrogen spectruming determining of crude product.
Using ZnW-DPNDI-PYIs as catalyst, under the conditions of radiation of visible light, with O2For single oxidation source, it is applied to amine
C-N coupling and the light-catalyzed reaction of alkene epoxidation in, catalytic mechanism speculate as shown in figure 8, DPNDI be it is a kind of have it is photochemical
It learns, optical physics, electrochemistry and the multi-functional π-electron deficient organic ligand for being catalyzed special ability, due to the N atom on its imidodicarbonic diamide
Modulatory character and naphthalene nucleus in electronics transfer reducibility so that naphthalimide becomes a kind of splendid multi-function metal-
The constructing block of organic framework materials.The richness of the nitrogen-atoms of PYI electrically makes it as a kind of electron donor, [BW12O40]5-Polyacid yin
Ion has the function of that good catalyzing expoxidation of olefines, DPNDI may act as photosensitizer, and PYI has the chiral ligand of stereoselectivity,
After DPNDI absorbs visible light, DPNDI can be generated by continuous Photo-induced electron transfer process·-And DPNDI·-*, then electronics
It is transferred to [BW12(VI)O40]5-Form the weed seedbank [BW with reproducibility11W(V)O40]6-, PYI offer electronics is to excitation state
DPNDI·-, while chirality PYIs will be used as concerted catalysis site, form the key reaction center of driving multiphase asymmetric reaction.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (3)
1. the chiral polyacid Base Metal organic framework materials that a pair has photo-catalysis function, which is characterized in that the polyacid fund
Belong to the chemical formula of organic framework materials are as follows: C74H101B2Zn2N22O84W24, it is denoted as ZnW-DPNDI-PYIs, according to the chirality of material
It is denoted as ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2 respectively again, wherein DPNDI is N, and N '-two (4- picoline) naphthoyl is sub-
Amine, as bridging ligand and photosensitizer, PYI is L- pyrrolidines -2- imidazoles, and PYI is described more as chiral ligand and electron donor
The polyoxoanion of acidic group metal-organic framework material is as oxidation catalysis functional group；Affiliated crystal belongs to monoclinic system,
The space group of the ZnW-DPNDI-PYI1 and ZnW-DPNDI-PYI2 is (1) P2；
The cell parameter of the ZnW-DPNDI-PYI1 are as follows: a=15.7431 (10), b=24.2207 (16), c=19.2219
(12), β=97.0620 (10), unit cell volume areThe ZnW-DPNDI-PYI2 cell parameter are as follows: a=
15.7383 (12), b=24.2051 (19), c=19.2483 (15), β=97.0450 (10), unit cell volume are
2. a kind of method for preparing polyacid Base Metal organic framework materials as described in claim 1, which is characterized in that described
ZnW-DPNDI-PYI1's the preparation method comprises the following steps: weigh the Zn (NO of 45mg, 0.15mmol respectively3)2·6H2O, 157.8mg,
The K of 0.05mmol5[BW12O40]·5H2The DPNDI of O, 23.4mg, 0.15mmol and the L-BCIP of 24.5mg, 0.1mmol are in small
In vial, 4.0mL distilled water, the dissolution of 2.0mL methanol is added, is stirred overnight, obtains suspension solution, the suspension solution is turned
It moves in the autoclave of 25mL, is put into baking oven, be heated to 120 DEG C and react five days, take out reaction product after being cooled to room temperature,
It is washed repeatedly with distilled water, obtains yellow rhabdolith ZnW-DPNDI-PYI1, the yield of the ZnW-DPNDI-PYI1 is
60%；
The ZnW-DPNDI-PYI2's the preparation method comprises the following steps: weighing the Zn (NO of 45mg, 0.15mmol respectively3)2·6H2O,
The K of 157.8mg, 0.05mmol5[BW12O40]·5H2The DPNDI of O, 23.4mg, 0.15mmol and the D- of 24.5mg, 0.1mmol
BCIP is added 4.0mL distilled water, the dissolution of 2.0mL methanol, is stirred overnight, obtains suspension solution in vial, will be described outstanding
Turbid solution is transferred in the autoclave of 25mL, is put into baking oven, is heated to 120 DEG C and is reacted four days, takes out after being cooled to room temperature
Reflect product, is washed repeatedly with distilled water, obtain yellow rhabdolith ZnW-DPNDI-PYI2, the ZnW-DPNDI-PYI2's
Yield is 60%.
3. a kind of application of chirality polyacid Base Metal organic framework materials, which is characterized in that with ZnW-DPNDI-PYIs be catalysis
Agent, under the conditions of radiation of visible light, with O2For single oxidation source, the photocatalysis of C-N coupling and alkene epoxidation applied to amine
In reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910209209.1A CN109772459B (en) | 2019-03-19 | 2019-03-19 | Chiral polyacid-based metal organic framework material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910209209.1A CN109772459B (en) | 2019-03-19 | 2019-03-19 | Chiral polyacid-based metal organic framework material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109772459A true CN109772459A (en) | 2019-05-21 |
| CN109772459B CN109772459B (en) | 2021-10-12 |
Family
ID=66488627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910209209.1A Active CN109772459B (en) | 2019-03-19 | 2019-03-19 | Chiral polyacid-based metal organic framework material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109772459B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848974A (en) * | 2020-08-24 | 2020-10-30 | 河南大学 | Polyacid-based metal-organic framework material, synthesis method thereof and application thereof in coupling of photocatalytic oxidation benzylamine |
| CN112608493A (en) * | 2020-12-31 | 2021-04-06 | 济宁学院 | Polyacid crystalline molecule with zinc complex and preparation method and application thereof |
| CN113845666A (en) * | 2021-10-18 | 2021-12-28 | 郑州轻工业大学 | Porous material of metal organic framework based on naphthalimide, preparation method and application |
| CN114292414A (en) * | 2022-01-06 | 2022-04-08 | 河南大学 | Vacancy type polyacid-based metal organic framework molecular material and application thereof in selective catalytic reduction of nitrobenzene |
| CN116693868A (en) * | 2023-05-10 | 2023-09-05 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306383A (en) * | 2007-05-14 | 2008-11-19 | 中国科学院化学研究所 | Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof |
| CN103301885A (en) * | 2013-06-16 | 2013-09-18 | 大连理工大学 | Preparation method of chiral POM/MOFs (Polyoxometalates/Metal-organic Frameworks) with asymmetric catalytic action |
| CN105148997A (en) * | 2015-07-12 | 2015-12-16 | 大连理工大学 | Preparation method of chiral POMOFs |
| CN105642355A (en) * | 2015-12-29 | 2016-06-08 | 上海大学 | Crystalline polyacid complex-based composite Fischer-Tropsch catalyst and preparation method thereof |
| CN107739443A (en) * | 2017-11-03 | 2018-02-27 | 福建师范大学 | A kind of homogeneous metal-organic framework material and its production and use |
-
2019
- 2019-03-19 CN CN201910209209.1A patent/CN109772459B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306383A (en) * | 2007-05-14 | 2008-11-19 | 中国科学院化学研究所 | Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof |
| CN103301885A (en) * | 2013-06-16 | 2013-09-18 | 大连理工大学 | Preparation method of chiral POM/MOFs (Polyoxometalates/Metal-organic Frameworks) with asymmetric catalytic action |
| CN105148997A (en) * | 2015-07-12 | 2015-12-16 | 大连理工大学 | Preparation method of chiral POMOFs |
| CN105642355A (en) * | 2015-12-29 | 2016-06-08 | 上海大学 | Crystalline polyacid complex-based composite Fischer-Tropsch catalyst and preparation method thereof |
| CN107739443A (en) * | 2017-11-03 | 2018-02-27 | 福建师范大学 | A kind of homogeneous metal-organic framework material and its production and use |
Non-Patent Citations (2)
| Title |
|---|
| JIAN-ZHEN LIAO ET AL.: "Exceptional Photosensitivity of the Polyoxometalate-based Charge Transfer Hybrid Material", 《CHEMICAL COMMUNICATIONS》 * |
| 赫光生著: "《非线性光学与光电子》", 30 December 2018, 上海科学技术出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848974A (en) * | 2020-08-24 | 2020-10-30 | 河南大学 | Polyacid-based metal-organic framework material, synthesis method thereof and application thereof in coupling of photocatalytic oxidation benzylamine |
| CN111848974B (en) * | 2020-08-24 | 2021-06-29 | 河南大学 | Polyacid-based metal-organic framework material, synthesis method thereof and application thereof in coupling of photocatalytic oxidation benzylamine |
| CN112608493A (en) * | 2020-12-31 | 2021-04-06 | 济宁学院 | Polyacid crystalline molecule with zinc complex and preparation method and application thereof |
| CN113845666A (en) * | 2021-10-18 | 2021-12-28 | 郑州轻工业大学 | Porous material of metal organic framework based on naphthalimide, preparation method and application |
| CN113845666B (en) * | 2021-10-18 | 2023-02-24 | 郑州轻工业大学 | Porous material of metal organic framework based on naphthalimide, preparation method and application |
| CN114292414A (en) * | 2022-01-06 | 2022-04-08 | 河南大学 | Vacancy type polyacid-based metal organic framework molecular material and application thereof in selective catalytic reduction of nitrobenzene |
| CN116693868A (en) * | 2023-05-10 | 2023-09-05 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
| CN116693868B (en) * | 2023-05-10 | 2024-05-10 | 苏州大学 | Singlet oxygen capturing or releasing material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109772459B (en) | 2021-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109772459A (en) | A kind of chirality polyacid Base Metal organic framework materials and its preparation method and application | |
| Wasson et al. | Metal–organic frameworks: A tunable platform to access single-site heterogeneous catalysts | |
| Wei et al. | Selective photooxidation of amines and sulfides triggered by a superoxide radical using a novel visible-light-responsive metal–organic framework | |
| Suzuki et al. | Polyoxometalate photocatalysis for liquid-phase selective organic functional group transformations | |
| Rachuri et al. | Adenine-based Zn (II)/Cd (II) metal–organic frameworks as efficient heterogeneous catalysts for facile co2 fixation into cyclic carbonates: A DFT-supported study of the reaction mechanism | |
| Cao et al. | Lewis acid dominant windmill-shaped V8 clusters: a bifunctional heterogeneous catalyst for CO2 cycloaddition and oxidation of sulfides | |
| Lu et al. | A polyoxovanadate–resorcin [4] arene-based porous metal–organic framework as an efficient multifunctional catalyst for the cycloaddition of CO2 with epoxides and the selective oxidation of sulfides | |
| Yuan et al. | Modified polyoxometalates: hydrothermal syntheses and crystal structures of three novel reduced and capped Keggin derivatives decorated by transition metal complexes | |
| Zhao et al. | State-of-the-art advances in the structural diversities and catalytic applications of polyoxoniobate-based materials | |
| Li et al. | Highly stable chiral zirconium–metallosalen frameworks for CO2 conversion and asymmetric C–H azidation | |
| Ayla et al. | Alkene epoxidations with H2O2 over groups 4–6 metal-substituted BEA zeolites: reactive intermediates, reaction pathways, and linear free-energy relationships | |
| Tan et al. | Cluster-organic framework materials as heterogeneous catalysts for high efficient addition reaction of diethylzinc to aromatic aldehydes | |
| CN103301885B (en) | Preparation method of chiral POM/MOFs (Polyoxometalates/Metal-organic Frameworks) with asymmetric catalytic action | |
| Li et al. | A giant Mo/Ta/W ternary mixed-addenda polyoxometalate with efficient photocatalytic activity for primary amine coupling | |
| CN101433854B (en) | Hydrotalcite-like in situ assembled nano multiple-metal oxygen-containing cluster catalyst and application | |
| Chen et al. | Highly efficient epoxidation of allylic alcohols with hydrogen peroxide catalyzed by peroxoniobate-based ionic liquids | |
| Chen et al. | Visible light-driven photoreduction of CO2 to CH4 over TiO2 using a multiple-site ionic liquid as an absorbent and photosensitizer | |
| Liu et al. | Cobalt (II)-based metal–organic framework as bifunctional materials for Ag (I) detection and proton reduction catalysis for hydrogen production | |
| Adão et al. | Vanadium-salen and-salan complexes: Characterization and application in oxygen-transfer reactions | |
| Somekh et al. | Selective visible light aerobic photocatalytic oxygenation of alkanes to the corresponding carbonyl compounds | |
| Huang et al. | Decavanadate‐based Transition Metal Hybrids as Bifunctional Catalysts for Sulfide Oxidation and C—C Bond Construction | |
| Kulawiec et al. | Modeling the oxygen-evolving center of photosystem II: synthesis and characterization of a tetranuclear manganese carboxylate complex | |
| CN106694050A (en) | Preparation method of visible-light-induced photocatalyst with core-shell structure | |
| Amarante et al. | Crystal structure and catalytic behavior in olefin epoxidation of a one-dimensional tungsten oxide/bipyridine hybrid | |
| Karmalkar et al. | Deeper Understanding of Mononuclear Manganese (IV)–Oxo Binding Brønsted and Lewis Acids and the Manganese (IV)–Hydroxide Complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |