CN105749978A - Preparation method and application of perylene bisimide based organometallic polymer with visible-light photocatalytic performance - Google Patents

Preparation method and application of perylene bisimide based organometallic polymer with visible-light photocatalytic performance Download PDF

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CN105749978A
CN105749978A CN201610144664.4A CN201610144664A CN105749978A CN 105749978 A CN105749978 A CN 105749978A CN 201610144664 A CN201610144664 A CN 201610144664A CN 105749978 A CN105749978 A CN 105749978A
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pdi
reaction
visible
preparation
imide
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段春迎
曾乐
何成
史岽瑛
张飞利
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The invention relates to the technical field of photocatalytic materials, in particular to a preparation method and application of a perylene bisimide based organometallic polymer with visible-light photocatalytic performance.The preparation method includes the steps: 1, adding transition metal salt Tm and perylene bisimide derivative H2PDI in the molar ratio of 1:1.0-1.5 into a mixed solvent of N,N-dimethylformamide and water in the volume ratio of 1:2-2.5, and regulating the solution to alkalescence with NaOH; 2, putting the reaction solution prepared in the step 1 in an oven with the temperature controlled between 90 DEG C and 110 DEG C and time controlled between 60h and 80h, closing the oven, cooling to room temperature, crystallizing out, filtering and drying to obtain the target material Zn-PDI.The catalyst is simple to synthesize and easy to operate, the catalyst and the raw materials for catalytic reaction are low in cost, yield is high, visible-light photocatalysis can be realized under mild conditions, and convenience is brought to widespread popularization and application.

Description

A kind of preparation side of the imide organometallic polymer with visible light photocatalysis performance Method and application
Technical field
The present invention relates to a kind of imide organometallic polymer with visible light photocatalysis performance Preparation method and application, belongs to catalysis material technical field.
Background technology
Solar energy is a kind of cleaning, sustainable, abundant energy source, but its dispersibility, discontinuity With the difficulty that unstability causes utilization.Visible light photocatalysis can utilize most energy in solar energy And solar energy is converted into the chemical energy beneficially storing and transporting, therefore obtain the pass of numerous scientist Note.Compare with traditional chemosynthesis, it is seen that the reaction condition of light photocatalysis organic synthesis is gentle, the most all Being normal temperature and pressure, and avoid the use of strong oxidizer or reducing agent, side reaction is relatively fewer, is former Subeconomy and the representative of Green Chemistry.But, the most widely used photocatalyst tris (bipyridine) ruthenium or Person's titanium dioxide has respective limitation.Tris (bipyridine) ruthenium absorbs in visible region owing to having, excited state The advantages such as life-span length, are widely used in the reduction of all kinds of organic light-catalyzed reaction such as alkene, the dehalogenation of halogenated hydrocarbons, The oxidation of alcohol, the acylation reaction of amine.But ruthenium belongs to noble metal, source is rare expensive, it is difficult to To promoting widely, and it is difficult to separate with product as homogeneous catalyst, heavy metal pollution can be caused. Titanium dioxide is due to harmless, and the raw material reason such as be easy to get is the best photocatalyst of commercialization, but it Structures shape it is the most weak to the absorption of visible ray, thus to the utilization rate of solar energy relatively low.Accordingly, it is capable to There is strong absorption in visible region, excited state can be carried out to the conversion of charge-separated state and the most honest and the cleanest with high efficiency The photocatalyst of valency has huge market potential.
Imide analog compounds, due to its big aromatic conjugated structure, has good chemistry, thermodynamics with And optical stability.They not only absorption region in visible region wide (typically 400～600nm), tool There is big molar extinction coefficient, and big conjugated system is conducive to flowing and the transmission of electronics, therefore acyl The redox property of imines is the most outstanding.The combination of these features makes imide analog compounds as one Class Functional dye is at DSSC, organic electroluminescent LED, organic effect crystal The fields such as pipe are widely used.And in basic research, imide analog compounds also through frequently as Ingredient is used for building artificial light synthesis system, but seldom has research using this compounds as photocatalysis Agent is studied.Reason is that big conjugated system and high flatness make imide analog compounds exist Being difficult in general organic solvent dissolve, the most often there is uncontrollable gathering in that part of dissolving.For Increase dissolubility, the most all can introduce long alkyl on the position, gulf of imido nitrogen-atoms or ring Chain or big steric group, and this is generally required for the synthetic schemes of numerous and diverse harshness.
The end of the year in 2014, Germanization scholar Burkhard" science " magazine reports acyl sub- Amine derivative is catalyzed the reduction reaction of halogenated hydrocarbons under visible light as photocatalyst.This report have draw time The meaning in generation, because which proposing continuous print this concept of photoinduced electron transmittance process, and this concept is broken The historical limitation of visible light photocatalysis.All the time, it is seen that light photocatalysis all relies on single light and sends a telegraph Sub-transmittance process, may be restricted to the light of that visible ray that catalyst absorbs for carrying out the energy of chemical conversion Son.And the transmission of continuous print photoinduced electron can accumulate the energy of two photons, thus expand visible light catalytic Range of application.But due to the solubility problem of imide analog compounds, the application of this process is subject to Limit.
It is thoroughly to solve its dissolubility and gather problem thus efficient by imide analog compounds heterogeneousization Utilize the good method of its excellent spectrochemical property.In numerous heterogeneousization means, acid imide chemical combination Thing is incorporated in organometallic polymer the most attractive as skeleton.Organometallic polymer is by gold The crystalline state with periodic network structure that genus ion (bunch) and multiple tooth organic ligand are assembled by coordinate bond Material, the application at catalytic field receives scientists and favors greatly, be a kind of great development prospect, Programmable functional material.The porous of organometallic polymer can obtain highdensity separate The space that acid imide and catalytic substrate interact is provided, it is ensured that catalyst while acid imide molecule High activity.The more important thing is, organometallic polymer, can be by filtration etc. as a kind of crystalline material Simple means realize and the high efficiency separation of reactant mixture, thus realize purification and the catalyst of product Recycling.
The present invention, according to the demand of high-efficiency cleaning visible light photocatalysis, is successfully incorporated into acid imide molecule In organometallic polymer, solve imido low solubility and gather problem；By acid imide/metal Organic polymer is successfully applied to the reduction reaction of the aromatic halohydrocarbon under visible ray, it is to avoid high activity halogen For hydrocarbon precursor and the use of strong basicity high pressure-temperature condition, it is achieved that continuously photoinduced electron transfer process non-all Xiang Hua；Acid imide/organometallic polymer is successfully applied to the aromatic alcohol under visible ray, the oxidation of amine Reaction, its catalytic effect can be compared with titanium-porphyrin metal organic frame or titanium dioxide.Acid imide It is a business-like dyestuff of class already, and after the metallic zinc synthesis organometallic polymer of nontoxic and rich content Can under the effect of visible ray high-efficiency cleaning carry out important oxidation and reduction reaction, this photocatalyst should This has good practical value and market prospect.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the present invention to provide one and there is visible ray light urge Change the preparation method and application of the imide organometallic polymer of performance.Having good photochemistry property Matter but the acid imide that is difficult to dissolve in usual vehicle are assembled in organometallic polymer.Use this system The imide organometallic polymer target material that Preparation Method obtains has wide visible absorption scope, Stereochemical structure is stable, has high temperature resistant, the stability of Acidity of Aikalinity, before providing for heterogeneous visible light photocatalysis Carry；Utilizing its indissolubility in multi-solvents, the recycling that easy separation is catalyst provides may； The more important thing is that the imide organometallic polymer target material that the present invention relates to also has preparation letter Single, the advantage such as cheaper starting materials.
In order to realize foregoing invention purpose, solving the problem in the presence of prior art, the present invention takes Technical scheme is: the preparation of a kind of imide organometallic polymer with visible light photocatalysis performance Method, with imide derivative H2PDI for constructing block, the Zn in transition metal salt Tm2+Lead to as node Cross hydrothermal synthesis method and prepare the two-dimensional metallic organic polymer Zn-PDI with pore passage structure, its synthetic route As follows:
H2PDI+Tm→Zn-PDI；
Described transition metal salt Tm is selected from Zn (ClO4)2·6H2O；
Described H2PDI is C selected from molecular formula28H14N2O8Imide derivative；
Described preparation method specifically includes following steps:
Step one, by transition metal salt Tm, imide derivative H2PDI is according to the mol ratio of 1:1.0～1.5 Join in the mixed solvent of DMF that volume ratio is 1:2～2.5 and water, and use NaOH Regulation solution is to alkalescence；
Step 2, by step one prepare reactant liquor be placed in baking oven, temperature controls at 90～110 DEG C, time Between control 60～80h, close baking oven, be cooled to room temperature, have crystal to separate out, filter, be dried, prepared mesh Mark material Zn-PDI.
Described target material Zn-PDI obtains aryl radical at visible light photocatalysis aryl halides dehalogenation And free radical is used for the reaction of C-H arylation, the oxidation of aromatic alcohol to aldehyde and the virtue with N-methylpyrrole Application in the coupling reaction of fragrant amine.
The medicine have the advantages that a kind of imide metal with visible light photocatalysis performance is organic The preparation method of polymer, specifically includes following steps: step one, by sub-to transition metal salt Tm, acyl Amine derivative H2PDI joins the N that volume ratio is 1:2～2.5, N-dimethyl methyl according to the mol ratio of 1:1.0～1.5 In the mixed solvent of amide and water, and with NaOH regulation solution to alkalescence；Step 2, step one is made The reactant liquor obtained is placed in baking oven, and temperature controls at 90～110 DEG C, and the time controls 60～80h, closes and dries Case, is cooled to room temperature, has crystal to separate out, and filters, and is dried, and prepares target material Zn-PDI.With Zn-PDI For photocatalyst, can the high efficiency reduction being catalyzed aryl halides especially aryl chloride complex under visible light And aromatic alcohol and the oxidation of aromatic amine.Constructing of Zn-PDI has effectively regulated and controled imido gathering, and solves Determine imido difficult problems of dissolution, continuous print photo induced electron transfer mistake can have been realized under heterogeneous conditions Journey, thus the gentle reduction of multiple aryl halides particularly aryl chloride complex can be catalyzed under visible light, and The aryl radical obtained has been used the formation of carbon-carbon bond the most crucial in organic synthesis.Acid imide Between conjugation and Zn-acid imide between coordination mutually coordinated, obtain having catalysis activity Zn metallic site, it is possible to and imido photolytic activity is combined with under visible ray aromatic alcohol to fragrant The selective oxidation of aldehyde and the oxidative coupling reaction of aromatic amine.Compared with the prior art, the present invention relates to urges Agent synthesis is simple to operation, catalyst and the low in raw material price of catalytic reaction, and productivity is high, and can be Visible light photocatalysis is realized, it is easy to large-area popularization and application under conditions of gentleness.By by under homogeneous phase condition Have the imide derivative of good spectrochemical property be incorporated in organometallic polymer realize heterogeneous Change so that catalyst keep highly active while can simply and reactant mixture carry out isolated and purified and Do not cause residual, be suitable for the demand of industrialization large-scale production, there is extraordinary industrial prospect.
Accompanying drawing explanation
Fig. 1 is the two-dimensional structure schematic diagram of embodiment 1 target material Zn-PDI.
Fig. 2 be embodiment 1 target material Zn-PDI PXRD figure (a-simulate, b-test, c-catalysis three-wheel after Reclaim and surveyed).
Fig. 3 is the thermal analysis curue of embodiment 1 target material Zn-PDI.
Fig. 4 is the visible absorption spectrogram of embodiment 1 target material Zn-PDI.
Fig. 5 is the electrochemistry spectrogram of embodiment 1 target material Zn-PDI.
Fig. 6 is the reduction reaction result that the material Zn-PDI of embodiment 1 is catalyzed fragrance halides under visible light Figure
Fig. 7 be embodiment 1 material Zn-PDI under visible light be catalyzed reduction fragrance halides obtain free radical It is applied to the result figure of carbon carbon coupling reaction.
Fig. 8 be embodiment 1 material Zn-PDI visible ray under be catalyzed aromatic alcohol to the reaction result figure of aromatic aldehyde
Fig. 9 be embodiment 1 material Zn-PDI visible ray under be catalyzed the result of oxidative coupling reaction of aromatic amine Figure.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
By imide derivative C28H14N2O8(5mg, 0.01mmol), Zn (ClO4)2·6H2O(3.7 Mg, 0.01mmol) it is dissolved in the mixed solvent of 3mL DMF and 7mL water, and add NaOH (6mg, 0.1mmol) regulation solution is to alkalescence.Again the mixture obtained is placed in baking oven, Fire 72h for 100 DEG C, close baking oven, be cooled to room temperature, have the rhombus bulk crystals of redness～black to separate out, Filter, be dried, prepare target material Zn-PDI, productivity about 44%.Elementary analysis (%) for C45H29N4O15Zn: C,58.05；H,3.14；N,6.02.Found:C,58.58；H,3.08；The target material two that N, 6.23. obtain Dimension structural representation is as shown in Figure 1.
Embodiment 2
The reaction of catalysis aryl halides dehalogenation under Zn-PDI visible ray: aryl halides (0.05mmol), Zn-PDI (5mol%), the DMF solution 3mL being dried join in the dry transparent glass tube of 10mL, Logical nitrogen (N in glass tubing2) oxygen that about 20 minutes removes in reaction tube and solvent.At logical N2Cross Journey adds electronics sacrifice agent triethylamine (3.6mmol).With the blue LED lamp of 455nm under the conditions of 40 DEG C Irradiate reaction.Reaction process is monitored by gas phase.After completion of the reaction by catalyst centrifugal filtration, after filtrate dilution The internal standard method of direct gas phase obtains productivity, as shown in Figure 6.
Embodiment 3
Aryl halides dehalogenation it is catalyzed and for the C-H arylation with N-methylpyrrole under Zn-PDI visible ray Reaction: aryl halides (0.1mmol), Zn-PDI (5mol%), the DMF solution 3mL being dried add In the dry transparent glass tube of 10mL, logical nitrogen (N in glass tubing2) about 20 minutes remove reaction Oxygen in pipe and solvent.At logical N2During add electronics sacrifice agent triethylamine (0.8mmol) and N- Methylpyrrole (2.5mmol or 5.0mmol).With the blue LED lamp of 455nm under the conditions of 40 DEG C Irradiate reaction.Reaction process is monitored by gas phase.After completion of the reaction reactant mixture is transferred in separatory funnel, Add deionized water and the saturated aqueous common salt of 2mL of 10mL.Extract by ethyl acetate (3 × 10mL) The organic layer obtained also is dried by this mixed liquor, filters, is concentrated in vacuo.By ethyl acetate/petroleum ether it is finally Eluant is crossed post isolated pure products and calculates separation productivity, as shown in Figure 7.
Embodiment 4
Being catalyzed aromatic alcohol selective oxidation under Zn-PDI visible ray is the reaction of aromatic aldehyde: aromatic alcohol (5 Mmol), Zn-PDI (0.1mol%), deuterated acetonitrile 0.5mL join the dry transparent glass tube of 5mL In, logical oxygen (O in glass tubing2) about 20 minutes remove other gases after keep reaction to exist with oxygen ball In oxygen atmosphere.Under room temperature with the xenon lamp of 500W (before the filter elimination 400nm of 400nm is installed Light) irradiate reaction 24 hours.After completion of the reaction by catalyst centrifugal filtration, filtrate directly carries out core The test of magnetic spectrum is also obtained reaction yield, as shown in Figure 8 by the characteristic peak of reaction substrate and product.
Embodiment 5
The oxidative coupling reaction of aromatic amine it is catalyzed: aromatic amine (1mmol), Zn-PDI (1 under Zn-PDI visible ray Mol%), acetonitrile 5mL joins in the dry transparent glass tube of 10mL, and glass tubing opening is exposed to sky In gas.With the xenon lamp (filter being provided with 400nm filters off the light before 400nm) of 500W under room temperature Irradiate reaction.Reaction process thin layer chromatography detects, and developing solvent is dichloromethane: petroleum ether=1:1 (volume Than).After completion of the reaction by catalyst centrifugal filtration, it is (interior that filtrate dilutes laggard row gas chromatographic detection productivity Mark method), as shown in Figure 9.
Embodiment 6
Catalyst recycle experiment: for 4-bromoacetophenone under light being reduced to 1-Phenylethanone., benzene first Alcohol is oxidized to benzaldehyde, and the coupling of benzylamine has all carried out recovery and the circulation catalytic reaction of Zn-PDI, and Productivity for these three reaction third time catalysis and catalysis for the first time reduces less than 10%.Before be once catalyzed After completion of the reaction, catalyst is separated with reactant liquor by centrifugal method, then with clean DMF or Person's acetonitrile washs 3 times, then washs three times with ether, carries out catalytic reaction next time after natural air drying.Enter Repeatedly the Zn-PDI after circulation remains in that preferable crystal structure, as shown in Figure 2.

Claims (2)

1. the preparation side of an imide organometallic polymer with visible light photocatalysis performance Method, it is characterised in that: with imide derivative H2PDI for constructing block, the Zn in transition metal salt Tm2+ Prepared the two-dimensional metallic organic polymer Zn-PDI with pore passage structure by hydrothermal synthesis method as node, Its synthetic route is as follows:
H2PDI+Tm→Zn-PDI；
Described transition metal salt Tm is selected from Zn (ClO4)2·6H2O；
Described H2PDI is C selected from molecular formula28H14N2O8Imide derivative；
Described preparation method specifically includes following steps:
Step one, by transition metal salt Tm, imide derivative H2PDI is according to the mol ratio of 1:1.0～1.5 Join in the mixed solvent of DMF that volume ratio is 1:2～2.5 and water, and use NaOH Regulation solution is to alkalescence；
Step 2, by step one prepare reactant liquor be placed in baking oven, temperature controls at 90～110 DEG C, time Between control 60～80h, close baking oven, be cooled to room temperature, have crystal to separate out, filter, be dried, prepared mesh Mark material Zn-PDI.
2. the target material Zn-PDI described in claim 1 obtains at visible light photocatalysis aryl halides dehalogenation Free radical is also used for the reaction of C-H arylation with N-methylpyrrole, aromatic alcohol to aldehyde by aryl radical Application in the coupling reaction of oxidation and aromatic amine.
CN201610144664.4A 2016-03-14 2016-03-14 Preparation method and application of perylene bisimide based organometallic polymer with visible-light photocatalytic performance Pending CN105749978A (en)

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CN109092362A (en) * 2018-07-25 2018-12-28 大连理工大学 The organic preparation method and application with polymers of triphenylamine base metal with visible light catalytic heteroaromatic compounds trifluoromethylation performance
CN110642745A (en) * 2019-10-25 2020-01-03 中山大学 Method for preparing imine through oxidative coupling of amine by photocatalysis
CN111393663A (en) * 2020-04-07 2020-07-10 曲靖师范学院 Perylene bisimide base coordination polymer, preparation method and application thereof
CN111514934A (en) * 2020-04-08 2020-08-11 四川大学 Petal-shaped zinc perylenetetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof
CN113540480A (en) * 2021-08-17 2021-10-22 北京化工大学 Regularly coordinated cobalt or iron doped cobalt-based electrocatalyst and preparation and use thereof
CN115611915A (en) * 2022-10-13 2023-01-17 上海理工大学 Preparation method and application of perylene metal compound and composite material thereof

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CN109092362A (en) * 2018-07-25 2018-12-28 大连理工大学 The organic preparation method and application with polymers of triphenylamine base metal with visible light catalytic heteroaromatic compounds trifluoromethylation performance
CN109092362B (en) * 2018-07-25 2021-07-06 大连理工大学 Preparation method and application of triphenylamine-based metal organic coordination polymer with visible light catalytic aromatic heterocyclic compound trifluoromethyl performance
CN110642745A (en) * 2019-10-25 2020-01-03 中山大学 Method for preparing imine through oxidative coupling of amine by photocatalysis
CN110642745B (en) * 2019-10-25 2023-06-06 中山大学 Method for preparing imine by photo-catalytic amine oxidative coupling
CN111393663A (en) * 2020-04-07 2020-07-10 曲靖师范学院 Perylene bisimide base coordination polymer, preparation method and application thereof
CN111514934A (en) * 2020-04-08 2020-08-11 四川大学 Petal-shaped zinc perylenetetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof
CN111514934B (en) * 2020-04-08 2023-04-25 四川大学 Petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof
CN113540480A (en) * 2021-08-17 2021-10-22 北京化工大学 Regularly coordinated cobalt or iron doped cobalt-based electrocatalyst and preparation and use thereof
CN115611915A (en) * 2022-10-13 2023-01-17 上海理工大学 Preparation method and application of perylene metal compound and composite material thereof

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