CN101157757B - Polymer based on perylene diimide and aromatic alkyne and preparation method thereof - Google Patents
Polymer based on perylene diimide and aromatic alkyne and preparation method thereof Download PDFInfo
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- CN101157757B CN101157757B CN2007100459455A CN200710045945A CN101157757B CN 101157757 B CN101157757 B CN 101157757B CN 2007100459455 A CN2007100459455 A CN 2007100459455A CN 200710045945 A CN200710045945 A CN 200710045945A CN 101157757 B CN101157757 B CN 101157757B
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Abstract
The present invention pertains to the technical field of organic photoelectric materials, in particular to a preparation method and the application of a novel polymer which is based on perylene diimide and aromatic acetylene. The functional materials of the present invention are that benzyne or rluoreneethynylene which is taken as an electron donor is connected on the amide or the bay position of perylene diimide which is taken as an electron acceptor, including the synthesis of various intermediates and polymers, wherein, the synthesis of the polymers adopts a Sonogasira coupling reaction in the presence of the palladium catalyst. The materials can be widely used in organic solar cells, organic/polymer electroluminescent diodes, molecular self-assembly and other fields.
Description
Technical field
The invention belongs to the organic photoelectric functional material technical field, be specially new polymers of a kind of Ji Yu perylene diimide and aromatic alkyne and preparation method thereof, and this polymkeric substance is in the application of aspects such as organic solar batteries, organic/polymer electroluminescent diode, molecule self-assembly.
Technical background
The perylene diimide based compound is the novel organic photoelectric functional dye of a class, because characteristics such as its absorption spectrum ranges is wide, fluorescence quantum efficiency is high, photo-thermal stability is good have been subjected to numerous investigators' attention in photoelectron molecular device fields such as organic solar batteries, organic/polymer electroluminescent diode, molecule self-assemblies; Especially in the Conversion of energy research direction, bigger progress is arranged in recent years.The perylene diimide analog derivative has big common phenyl ring two dimensional structure and two imide ring structures, so molecule has higher electron affinity, is a kind of extraordinary n section bar material.1997, R.H.Friend group is incorporated into the perylene diimide derivative in the heterojunction organic solar batteries first, Tong Guo reaches 4.9% Jiang the perylene diimide evaporation to the photovoltaic cell photoelectric transformation efficiency (IPCE) under the monochromatic irradiation of 490nm that vinylbenzene support (PPV) is gone up preparation, packing factor reaches 0.6, open circuit voltage 1V (Synthetic metal, 1997,85 (1-3): 1307-1308).The ， perylene diimide is widely used in fields such as organic solar batteries as a kind of n section bar material at present.The photogenerated charge efficient of perylene diimide derivative can reach 95%, under the prerequisite that keeps compound photogenerated charge efficient, how to widen life-span ， Shi perylene diimide derivative that light in its spectral absorption scope Ti Gao perylene diimide derivative molecular system swashs the dispersion of electric charge and molecule charge separation body and need in the Conversion of energy research to be applied to the key issue that solves.
Summary of the invention
But the object of the present invention is to provide a kind of Tuo Kuan perylene diimide derivative spectral absorption scope, improve polymkeric substance of sharp electric charge of its light and molecule charge separation body life time and its production and application.
Study emphasis organic photoelectric functional material intramolecularly of the present invention or studies on Intermolecular Energy Transfer are started with from novel material structure design, explore the new way that overcomes the above problems.The present invention is with electron donor(ED) (Donor)---benzyne or fluorenes alkynes are connected to electron acceptor(EA) by the Sonogasira linked reaction (acid amides or " bay " position of Acceptor) — — perylene diimide obtain the alternating copolymer of Donor-Acceptor structure.Introduce the aromatic alkyne structure simultaneously and help widening the spectral absorption scope of material and the transmission of photogenerated charge.Fluorescence spectrum and excitation spectrum show and have intramolecularly or intermolecular transmission ofenergy really.
Core of the present invention is electron donor(ED)---benzyne or fluorenes alkynes obtain the alternating copolymer of Donor-Acceptor structure by linked reaction with electron acceptor(EA) — — perylene diimide monomer.In addition, introduce the transmission that the aromatic alkyne structure helps widening the photogenerated charge of the spectral absorption scope of material and generation.Difference according to the coupling position, also there is difference in interaction between the Donor-Acceptor: there is node in (1) charge distribution of You Yu perylene diimide when in the coupling of acid amides position at the nitrogen-atoms place, so there is not interaction between the Donor-Acceptor when ground state; (2) when in the coupling of " bay " position, owing to a certain degree distortion can take place in sterically hindered reason ， perylene ring, and between the Donor-Acceptor be exist interactional.
The Ji Yu perylene diimide that the present invention proposes and the novel polymer material of benzyne or fluorenes alkynes are acid amides or " bay " positions that electron donor(ED) benzyne or fluorenes alkynes is connected to Dian Shou Ti perylene diimide, and its molecular structure is as follows:
In the formula: X is the monomeric length of oligomerization benzyne; R1, R2 are a kind of in hydrogen atom or the following group:
Wherein * represents R1, and R2 and R5 are Yu the tie point of perylene ring; R3 is the oxyalkyl chain of random length; R4 is the alkyl chain of random length.R5 is a kind of of straight chained alkyl or following group:
In the alternating copolymer material of the present invention, as follows in common 22:
(1) R1 and R2 are hydrogen atom; R3 is a hexyloxy, X=1, and 3,5 o'clock, its structural formula:
(2) R1 is a hydrogen atom; R2 is respectively phenoxy group, to tertiary butyl phenoxy group and pyrrolidyl; R3 is a hexyloxy, X=1, and 3,5 o'clock, its structural formula:
(3) R1 and R2 are respectively phenoxy group, to tertiary butyl phenoxy group; R3 is a hexyloxy, X=1, and 3,5 o'clock, its structural formula:
(4) R1 and R2 are hydrogen atom; When R4 is n-hexyl, its structural formula:
(5) R1 is a hydrogen atom; R2 is respectively phenoxy group, to tertiary butyl phenoxy group and pyrrolidyl; When R4 is n-hexyl, its structural formula:
(6) R1 and R2 are respectively phenoxy group, to tertiary butyl phenoxy group; When R4 is n-hexyl, its structural formula:
(7) R3 is a hexyloxy, X=1,3,5; R5 is respectively n-octyl, the 7-tridecyl, and 1, the 3-diisopropyl phenyl, 3,4,5-three hexyloxy phenyl and alkoxy chains, its structural formula:
(8) R4 is a n-hexyl; R5 is respectively n-octyl, the 7-tridecyl, and 1, the 3-diisopropyl phenyl, 3,4,5-three hexyloxy phenyl and alkoxy chains, its structural formula:
The synthetic method of the polymer materials that the present invention proposes is as follows: adopt compd A or B in the following structural formula; with Compound C or D; press and wait molar ratio in toluene and Diisopropylamine solution; make catalyzer with inferior ketone of iodate and triphenyl phosphorus palladium; under nitrogen protection, carry out the Sonogasira polyreaction; the gained crude product repeatedly precipitates with the acetone Soxhlet through methyl alcohol and extracts, and promptly obtains described polymkeric substance.
Characterize through test, its spectral absorption scope of polymkeric substance that the present invention obtains, the characteristics such as transmission of photogenerated charge all are enhanced, and promptly its photoelectric properties have had very big improvement.Therefore, this polymer materials can be widely used in organic solar batteries, fields such as organic/polymer electroluminescent diode and molecule self-assembly.
Description of drawings
Fig. 1: the absorption spectrum of polymkeric substance 6 (x=5) in methylene dichloride.
Fig. 2: the fluorescence spectrum of polymkeric substance 6 (x=5) in methylene dichloride.The fluorescence spectrum that obtains as excitation wavelength with 434nm and 583nm among the figure is exaggerated 5 times and 2 times respectively.
Fig. 3: absorption and the excitation spectrum (λ em=609nm) of polymkeric substance 6 (x=5) in dichloromethane solution.
Fig. 4: the ultraviolet-visible absorption spectroscopy of polymkeric substance 18 (x=1) in trichloromethane.
Fig. 5: the cyclic voltammetric spectrogram of polymkeric substance 18 (x=1).
Embodiment
Further specify technical scheme of the present invention below by embodiment, so that understand content of the present invention better.
(1) monomeric preparation:
Synthesizing of monomer A:
With Si Lv perylene acid anhydrides (2.6g, 5mmol) and paraiodoaniline (4.7g 21.5mmol) joins in the propionic acid (100mL), be heated to 160 ℃ under nitrogen protection the reaction 24 hours.Behind the cool to room temperature, filter, the worry slag washes repeatedly with methyl alcohol and obtains the wine-colored crude product of 3.7g (productive rate 80%).Crude product directly carries out next step reaction without purifying.
(2.3g, 2.4mmol), (2.5g, 18mmol) (3.6g 24mmol) joins in the N-N-methyl-2-2-pyrrolidone N-(100mL) salt of wormwood the crude product that previous step is obtained, and is heated to 90 ℃ of reaction 24h under nitrogen protection with the 4-tert.-butyl phenol.Behind the cool to room temperature, reaction solution is poured in 10% the dilute hydrochloric acid solution (100mL).Filter, water and methyl alcohol wash the worry slag repeatedly.Carry out column chromatography for separation with methylene dichloride and sherwood oil (2: 3) and obtain 1.3g monomer A (productive rate 41%).
Synthesizing of monomers B:
Jiang the perylene acid anhydrides (15.65g, 40mmol) be dissolved in 98% vitriol oil (128.3mL, p=1.84g/mL), at room temperature stir 12h after, add iodine (0.385g, 1.5mmol).Be warmed up to 85 ℃, slowly (4.52mL), whole process continues 8h to the dropping liquid bromine for 14.1g, 88mmol.After continuing under maintaining 85 ℃ after dripping to stir 10h, cool to room temperature is with the excessive bromine of nitrogen gas stream derivation slowly.Carefully add 30mL water then, continue to stir and remove HBr gas.Filter with the G4 funnel, filter cake washes with 86% sulfuric acid (150mL) and a large amount of water.Drying obtains red solid.Crude product is insoluble to organic solvent.
With the top bromination De perylene acid anhydrides crude product (2.85g that arrives; about 5.16mmol) be dissolved in the N-N-methyl-2-2-pyrrolidone N-(60mL), add Glacial acetic acid (1.43mL, 24.99mmol) and n-octyl amine (2.5ml; 15.21mmol), be heated to 85 ℃ and under nitrogen protection, stir 6h.Cool to room temperature filters, with methyl alcohol flush cake repeatedly.Drying obtains the crude product of black.Use methylene dichloride: sherwood oil (3: 1) carries out column chromatography and obtains red monomers B.
Monomer C's is synthetic:
With 1,4-two hexyloxy-2, the 5-diiodo-benzene (7.95g, 0.015mol), cuprous iodide (CuI, 0.14g, 0.75mol) and Pd (PPh
3)
2Cl
2(0.53g 0.75mol) joins in the round-bottomed flask, adds Diisopropylamine (100mL) again and stirs, drip then trimethyl silicane alkynes (1.47g, 0.015mol).15h is at room temperature stirred in reaction, revolves steaming, carries out silica gel column chromatography with normal hexane and methylene dichloride (20: 1) and separates and obtain yellow oily liquid (3.30g, 44%).
With 1,4-two hexyloxy-2,5-diiodo-benzene (7.95g, 0.015mol), cuprous iodide (0.14g, 0.75mol) and Pd (PPh3) 2Cl2 (0.53g, 0.75mol) join in the round-bottomed flask, (2.94g 0.03mol) stirs successively to add Diisopropylamine (100mL) and trimethyl silicane alkynes again.Mixture reacts 1h under the condition that refluxes.The cooling back adds methylene dichloride (100mL), removes by filter the throw out of white.As elutriant, silica gel column chromatography separates, and obtains white crystal (6.3g, 89%) with ethyl alcohol recrystallization then with the mixed solution (4: 1) of normal hexane and methylene dichloride.
With the aqueous solution of NaOH (2mL, 5mol/L) and ethanol (20mL) join 1 in the stirring, 4-two (trimethylsilyl acetylene base)-2, (2.82g is in tetrahydrofuran (THF) 0.006mol) (20mL) solution for 5-two hexyloxy benzene.After the reaction 2h, revolve steaming, extraction, anhydrous magnesium sulfate drying is used in water and saturated common salt water washing then, and the target product that obtains behind the rotary evaporation is lurid solid.Be monomer C (x=1).
With 1,4-diynyl-2,5-two hexyloxy benzene (1.63g, 5mmol), 1-iodo-4-trimethylsilyl acetylene base-2,5-two hexyloxy benzene (6.25g, 12.5mmol), cuprous iodide (0.095g, 0.5mmol) and Pd (PPh3) 2Cl2 (0.35g, 0.5mmol) add in the round-bottomed flask, successively add Diisopropylamine (60mL) and THF (30mL) again.Mixing solutions is 70 ℃ of following 1h that stir again, revolve steaming, and the mixed solution of using normal hexane and methylene dichloride is as elutriant, and the silica gel column chromatography separation obtains glassy yellow solid (4.82g, 90%).
(2mL, mixing solutions 5M) join above-mentioned crude product in the stirring, and (2.64g in THF 2.47mmol) (100mL) solution, reacted two hours with ethanol (45mL) and NaOH.Revolve steaming, extraction, anhydrous magnesium sulfate drying is used in water and saturated common salt water washing then.Obtain light yellow solid target product (2.02g, 87%) behind the rotary evaporation.Be monomer C (x=3).
Synthetic method obtains flaxen crystal at last with reference to the synthesis step of monomer C (x=3).
Monomer D's is synthetic:
With 2,7-two bromo-9,9-dihexyl fluorenes (2.74g, 5.0mmol) and Pd (PPh
3)
4(290mg, 0.25mmol), (0.047g 0.25mmol) is dissolved in the Diisopropylamine (50mL) cuprous iodide, and (1.08g, Diisopropylamine 11mmol) (20mL) solution also at room temperature stirs 30min to inject trimethyl silicane alkynes with syringe.Under nitrogen protection, be warmed up to 70 ℃ of reaction 8h then.Cool to room temperature, extraction back rotary evaporation obtain solid with being to obtain yellow solid after the elutriant separation with the normal hexane with silica gel column chromatography.Then this yellow solid is dissolved in tetrahydrofuran (THF) (50mL) and stirring, in the process that stirs, slowly drips KOH solution (6mL, 20%), use methyl alcohol (25mL) dilution afterwards.6h is at room temperature stirred in reaction, adds the deionized water termination reaction.Anhydrous sodium sulfate drying is used in extraction, revolves the steaming back and separates on silica gel column chromatography as eluent with normal hexane, obtains yellow crystals (1.43g, 65%) with the normal hexane recrystallization then.Be monomer D.
(2) preparation of polymkeric substance
The general synthesis step of polymkeric substance:
Monomer A or B; with monomer C or D; press and wait molar ratio in toluene and Diisopropylamine solution; with the inferior ketone of iodate and triphenyl phosphorus palladium as catalyzer; under nitrogen protection, carry out the Sonogasira polyreaction; the gained crude product repeatedly precipitates with the acetone Soxhlet through methyl alcohol and extracts, and promptly gets described compound.
Synthesizing of polymkeric substance 6 (x=5):
(69.35mg, 0.05mmol), (76.4mg, 0.05mmol), Pd (PPh3) 4 (4mg), cuprous iodide (2mg) join in the mixed solvent of toluene (5mL) and Diisopropylamine (5mL) monomer C (x=5) with monomer A.Under nitrogen protection, be heated to 50 ℃ of reaction 48h.Cool to room temperature revolves steaming, and solid dissolves in a spot of chloroform, and sedimentation is three times in a large amount of methyl alcohol, uses acetone extraction 48h then in apparatus,Soxhlet's, and drying obtains the solid of black.It is polymkeric substance 6.Infrared signature peak: 2360cm
-1, v
(C=O): 1705,1605cm
-1Ultraviolet absorption peak: 434,541,583nm; Fluorescence emission peak: 609nm; Oxidizing potential: 0.8 volt, reduction potential :-0.99 ,-2.13 volts.Heat decomposition temperature is at 353 ℃.
Synthesizing of polymkeric substance 18:
With monomer D (219.34mg; 0.5mmol); monomers B (386.28mg; 0.5mmol); cuprous iodide (14mg; 0.075mmol) and Pd (PPh3) 4 (29mg 0.025mmol) adds in the mixed solvent of toluene (10mL) and Diisopropylamine (10mL), is warmed up to 70 ℃ and reacts 48h under nitrogen protection.But arrive room temperature, revolve steaming, solid dissolves in a spot of chloroform again, and sedimentation is three times in a large amount of methyl alcohol, uses acetone extraction 48h then in apparatus,Soxhlet's, and drying obtains the solid of black.It is polymkeric substance 18.Ultraviolet absorption peak: 388,634,710nm; Almost detect less than fluorescent emission, promptly fluorescence basically by fully the collection go out; Oxidizing potential: 0.98 volt, reduction potential :-0.85 ,-2.33 volts.
The synthetic synthesis step preparation of other polymkeric substance with reference to polymkeric substance 6 and 18.
Claims (1)
1. a base is in the polymkeric substance of perylene diimide and aromatic alkyne, it is characterized in that molecular structural formula is one of following:
Wherein, n is the multiplicity of polymkeric substance, and * is the point of contact of polymkeric substance, and X is the monomeric length of oligomerization benzyne, X=1,3,5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2280972A1 (en) | 2008-03-26 | 2011-02-09 | Yeda Research And Development Company Ltd. | Doubly reduced perylene-diimides and supramolecular polymers derived from perylene-diimides |
| US9701784B2 (en) | 2008-03-26 | 2017-07-11 | Yeda Research And Development Co. Ltd. | Supramolecular polymers derived from perylene-diimides |
| EP2518788A4 (en) * | 2010-01-13 | 2013-05-29 | Sumitomo Chemical Co | Organic electroluminescent element and light-emitting polymer composition |
| CN102134307B (en) * | 2010-01-22 | 2013-01-16 | 海洋王照明科技股份有限公司 | Perylene diimide-fluorene-thiophene and (3, 4-b) pyrazine conjugated polymer and preparation method and application thereof |
| CN102344550B (en) * | 2010-07-30 | 2013-03-27 | 海洋王照明科技股份有限公司 | Perylenetetracarboxylic diimide copolymer containing thiophenepyrrole dione unit, preparation method thereof and application thereof |
| US9623381B2 (en) | 2010-08-27 | 2017-04-18 | Yeda Research And Development Co. Ltd. | Separation of nanoparticles |
| EP2608874A1 (en) | 2010-08-27 | 2013-07-03 | Yeda Research and Development Co. Ltd. | Separation of nanoparticles |
| CN102070771A (en) * | 2010-11-30 | 2011-05-25 | 南京邮电大学 | Perylene diimide photoelectric functional materials and preparation method thereof |
| CN102504213B (en) * | 2011-11-15 | 2013-08-28 | 上海交通大学 | Soluble benzenetetracarboxylic diimide group-containing full-conjugated polymer and preparation method thereof |
| CN104152137A (en) * | 2014-05-06 | 2014-11-19 | 上海大学 | Fluorine-perylene bisimide molecule internal-energy transferring fluorescence split compound and preparation method thereof |
| CN105085756B (en) * | 2014-05-20 | 2017-12-22 | 华东师范大学 | One kind is containing imido conjugation polyacetylene and preparation method thereof |
| CN107098919B (en) * | 2017-03-13 | 2019-08-20 | 华南理工大学 | The molten conjugation small molecule of A-D-A type water/alcohol and its application in organic electronic device |
| CN106986982A (en) * | 2017-04-12 | 2017-07-28 | 华南理工大学 | The molten conjugated polymer of water alcohol of three keys connection and its application in organic electro-optic device |
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| US6084099A (en) * | 1996-08-09 | 2000-07-04 | Basf Aktiengesellschaft | Preparation of N,N'-dialkylperylene-3,4,9,10-tetracarboxylic acid diimides |
| CN1764652A (en) * | 2003-04-15 | 2006-04-26 | 3M创新有限公司 | Ethynyl containing electron transport agents and their use in organic luminescent devices |
| CN1827664A (en) * | 2006-02-23 | 2006-09-06 | 复旦大学 | Fluorescent sensing materials made of conjugated polymer and process for preparing same |
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Patent Citations (3)
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| US6084099A (en) * | 1996-08-09 | 2000-07-04 | Basf Aktiengesellschaft | Preparation of N,N'-dialkylperylene-3,4,9,10-tetracarboxylic acid diimides |
| CN1764652A (en) * | 2003-04-15 | 2006-04-26 | 3M创新有限公司 | Ethynyl containing electron transport agents and their use in organic luminescent devices |
| CN1827664A (en) * | 2006-02-23 | 2006-09-06 | 复旦大学 | Fluorescent sensing materials made of conjugated polymer and process for preparing same |
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