CN102134308A - Aza-fluorenone conjugated polymer photoelectric material and preparation and application methods thereof - Google Patents
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Abstract
The invention discloses an aza-fluorenone conjugated polymer material and preparation and application methods thereof, relating to a polymer material containing a special aza-fluorene monomer, and the application of the material in the fields of organic solar cells, organic electroluminescence, organic field effect tubes, organic electric storage and the like. The conjugated polymer material has a 4, 5-biaza-fluorenone unit framework, and has the following advantages: (1) the 4, 5-biaza-fluorenone unit has strong electron acceptor characteristic, donor and acceptor low bandgap materials can be prepared by copolymerization; (2) the material has linear plane conformation, and crystallinity; and (3) the material can coordinate with metal ions. Solar cell devices prepared by the material of the invention achieves satisfying results in the aspect of energy conversion efficiency, and the material is expected to become a photoelectric material with low cost and commercial potential.
Description
Technical field
The invention belongs to the photoelectric material technical field.Be specifically related to a class and contain azepine Fluorenone class organic polymer semiconductor material, and relate to of the application of such material in fields such as organic electroluminescent, organic field-effect tube, organic solar batteries, nonlinear optics, bio-sensing, organic optical storage and organic lasers.
Background technology
From Tang research group of Kodak [Tang, C.W. in 1987; Van Slyke, S.A.Appl.Phys.Lett.1987,51,913.] and nineteen ninety univ cambridge uk [Burroughes, J.H.; Bradley, D.D.C.; Brown, A.B.; Marks, R.N.; Mackay, K.; Friend, R.H.; Burn, P.L.; Holmes, A.B.Nature 1990,347,539.] delivered respectively make film-type organic electroluminescence device (Organic Light-emitting Diodes) and polymer LED (PolymericLight-emitting Diodes) with organic and polymer fluorescent material since, organic flat pannel display becomes the demonstration product of the another generation marketization after liquid-crystal display.Meanwhile other organic electronics and photoelectronic industry comprise that field such as organic solar batteries, organic place effect pipe, organic optical storage, nonlinear optics, bio-sensing and organic laser and nonlinear optical material are also just moving towards the marketization.Organic and the advantage plastic electronic product is that the material preparation cost is low, technology simple, has the snappiness and the plasticity-of commodity polymer.Therefore, develop the novel organic photoelectric information material of market potential and attracted the scientist of the different subjects of many domestic and international universities and the concern and the input of research institution and company with practicality.Therefore, develop the novel organic photoelectric information material of market potential and attracted the scientist of the different subjects of many domestic and international universities and the concern and the input of research institution and company with practicality.
Up to the present, donor-receiver (D-A) compound causes concern widely at organic molecule and Solid State Electronics field, this mainly is because D-A type molecule has rectifying effect, its essence is similar with the intramolecularly p-n junction in the molecular device, especially Huang Wei professor seminar has proposed the band gap regulation and control notion of p-n block copolymerization in a creative way, realized that material band gap and spectrographic are adjustable in a big way, designed and developed line style, branching type p-n block conjugated polymer and the oligomer three-color light-emitting material of a series of different band gap.Transmit by can simply and effectively regulate and control electric charge and energy in conjunction with different structural units, thereby obtain efficient red light material and quadripole charge transfer material.Simultaneously, the p-n block can be regulated trap depth and trap density, can be used for developing polymkeric substance dynamic random storage (DRAM) unit, and the intramolecular charge in the D-A molecule shifts (ICT) transition can make the absorption spectrum of compound move to the long wave direction; In addition, can can reduce minimum occupied molecular orbital (LUMO) energy level by introducing strong electron-withdrawing group group (A), introduce strong electron-donating group (D) and can improve highest occupied molecular orbital (HOMO) energy level, this has the organic molecular device of particular requirement very favourable for the energy level with regard to material, especially in solar cell, the body heterojunction organic solar batteries requires material to have wide absorption, and promptly therefore low bandgap material needs to reduce the HOMO of donor material and the energy level difference between the LUMO; In addition, the open circuit voltage and the built in field of device are linear, built in field is meant the energy level difference between the LUMO of the HOMO of donor material and acceptor material, therefore, the HOMO energy level that reduces donor material is very useful for improving open circuit voltage, what but the reduction of HOMO energy level caused is wide bandgap material, is unfavorable for the absorption of material to sunlight.In organic semiconductor material, most compounds demonstrates the power supply sub-feature, promptly can be as giving body unit (D); In order to obtain organic assembly efficiently, explore that novel to be subjected to body unit (A) be crucial.Present pyridine, oxadiazole, benzothiazole, perylene diimides and C
60It is the acceptor of studying and being most widely used.Yet, azepine aromatic ring compounds is as part commonly used, its electron deficiency characteristic has been left in the basket to a great extent, its major cause may be because the restriction on the synthetic method, harsh reaction conditions, lower productive rate, its synthetic method is lacked the exploration of system and summary etc. has all greatly limited the application of this system in organic semiconductor material and device.Based on this, reaction rule, the structure of exploring the synthetic method of azepine aromatic ring compounds, the azepine aromatic ring that designs and synthesizes novelty and derivative thereof, summary azepine aromatic ring system are significant based on the D-A type organic semiconductor material and the device of azepine aromatic ring.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of azepine Fluorenone base polymer photoelectric material and methods for making and using same thereof, design 4,5-azepine Fluorenone class monomer prepares relevant photoelectric functional material.In addition, pointed out of the application of such material in organic electronic fields such as organic solar batteries, Organic Light Emitting Diode, organic field-effect tube, organic optical storage and organic lasers.
Technical scheme: of the present invention 4,5-diaza Fluorenone base polymer photoelectric material has following general structure:
Polymkeric substance I
In the formula: x is the natural number in 1～100, and y is the natural number in 0～100, and n is the natural number in 1～300,
R
1, R
2, R
3Identical or different during appearance, and be hydrogen or straight chain, side chain or cyclic alkyl chain with 1 to 22 carbon atom, one or more non-conterminous carbon atom can by-O-,-S-,-the CO-O-displacement, perhaps one or more hydrogen atom is replaced by fluorine, or for containing the kinds of aromatic ring conjugation structural unit;
Ar is for containing aromatic hydrocarbons conjugated structure unit, can have a kind of in the following structure of example:
In the described polymkeric substance I material, R
1, R
2, R
3Be selected from hydrogen or normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or positive certain herbaceous plants with big flowers base, n-octyloxy chain respectively or contain a kind of in the kinds of aromatic ring conjugation modular construction.
In the described polymkeric substance I material, get x, y all equal 1 and Ar get fluorenes, simultaneously, R
1And R
2All be n-octyl, R
3Be hydrogen atom, it is as follows then to constitute molecular structure:
Of the present invention 4, the preparation method of 5-diaza Fluorenone base polymer photoelectric material comprises 4, synthetic and this monomer of 5-diaza Fluorenone monomer is described 4 by the reaction of Suzuki coupling condensation polymerization or Yamamoto coupling condensation polymerization prepared in reaction, 5-diaza Fluorenone base polymer; Wherein Suzuki coupling condensation polymerization reaction conditions is triphenyl phosphorus palladium (Pd (PPh
3)
4, salt of wormwood K
2CO
3Or cesium fluoride CsF, toluene or 1,2-glycol dimethyl ether, triphenyl phosphorus Ph
3P; Yamamoto coupling condensation polymerization reaction conditions is two (1, the 5-cyclooctadiene) nickel, dipyridyl, 1,5-cyclooctadiene, NN-dimethyl formamide;
4,5-diaza Fluorenone monomer synthetic route is as follows:
Wherein, 1. step is included under the condition of n-propylcarbinyl chloride, sulfurous gas and carries out bromination reaction; 2. step is to carry out prepared in reaction azepine Fluorenone under the mixing acid-base function.
Yamamoto condensation polymerization reaction method is as follows:
Described 4,5-diaza Fluorenone base polymer photoelectric material is as organic solar batteries, LED device and fluorescence probe material, wherein the structure of organic solar batteries device is transparent anode, hole injection layer, electron donor material, electron acceptor material, the negative electrode that order is provided with, wherein, employing contains 4, and polymer semiconductor's material of 5-diaza Fluorenone monomeric unit is as electron acceptor material.
Beneficial effect: characterized oligomer and high polymer material structure, the thermostability of having tested material by thermogravimetric analysis and differential thermal analysis by infrared spectra (FTIR), nucleus magnetic resonance (NMR), gas chromatograph mass spectrometer (GCMS), ground substance assistant laser parsing time-of-fight mass spectrometry (MALDI-TOF-MS), gel chromatography (GPC).The wherein thermogravimetric analysis of such material and differential thermal analysis test has shown good thermostability.
Such polymer materials also can be applied to the organic electronic fields such as organic semiconductor layer, Organic Light Emitting Diode, organic optical storage, organic laser material and organic non linear optical material in the field effect transistor.Polymer materials I is suitable for and makes plastic electronic material, photoelectron material; The device in plastic electronic field or element comprise polymkeric substance and organic light emitting diode device, organic solar batteries, organic laser diode component, organic field-effect tube, OTFT, organic integration circuit, bio-sensing device, organic optical storage, nonlinear optical element etc.; Use transport material, interface injecting material, conductive material, the photoelectric material that comprises as luminescent material and hole as organic electronic material.
Description of drawings
Fig. 1 .2, the nmr spectrum of 7-dibromo azepine Fluorenone,
Fig. 2. the nmr spectrum of poly-{ (4,5-azepine Fluorenone)-copolymerization-(9,9-dioctyl fluorene-) },
Fig. 3. the ultraviolet-fluorescence emission spectrum of poly-{ (4,5-azepine Fluorenone)-copolymerization-(9,9-dioctyl fluorene-) }.
Embodiment
Azepine Fluorenone class monomer-polymer material of the present invention has following general structure (I):
In the formula: x is the numeral in 1～100, and y is the numeral in 0～100, and n is the numeral in 1～300,
R
1, R
2, R
3Identical or different during appearance, and be hydrogen; Or having straight chain, side chain or a cyclic alkyl chain of 1 to 22 carbon atom, one or more non-conterminous carbon atom can be by-NR
3-,-O-,-S-,-CO-O-,-CO-NR
3-displacement, perhaps one or more hydrogen atom is replaced by fluorine, perhaps is kinds of aromatic ring conjugation unit etc.;
Ar is for containing aromatic hydrocarbons conjugated structure unit, can have a kind of in the following structure of example:
In polymkeric substance I, when y equals zero, R
3=H, it is as follows then to constitute compound structure:
In polymkeric substance I, 2,7-dibromo azepine Fluorenone monomer synthesizes and this monomer prepares the aforesaid compound material by Suzuki and Yamamoto condensation reaction.Wherein the synthetic route of azepine fluorenes class monomeric unit is as follows:
Wherein, 1. step is included under the condition of n-propylcarbinyl chloride, sulfurous gas and carries out bromination reaction; 2. step is to carry out prepared in reaction azepine Fluorenone under the mixing acid-base function.
Wherein, the reactant of method (1) Suzuki linked reaction is aryl hypoboric acid and/or aryl dihalide and 2 equivalent aryl list halogenide and/or aryl list boric acid, and perhaps blended aromatic halides/boric acid is realized coupling with palladium catalyst; Catalyst consumption is 0.1 to 20mol%; Suitable solvent is low-pole or aprotic, polar organic solvent or its mixed solvent; Be reflected at 30 to 150 ℃ of temperature; Reaction times is 1 to 7 day; Reaction conditions as Suzuki is Ph (PPh
3)
4/ K
2CO
3/ toluene, or Ph (dba)
2/ CsF/Ph
3P/1, the 2-glycol dimethyl ether.
Method (2) is the Stille linked reaction: reactant is dihalide and/or two stannates and single stannate and/or single halogenide herein, perhaps corresponding single halogenide one single stannate derivatives monomer, linked reaction under alkaline condition and under the condition of palladium catalyst and solvent existence;
Method (3) is the Yamamoto linked reaction, and its reaction conditions is Ni (COD)
2/ bpy/1,5-cyclooctadiene/DMF.
In polymkeric substance I, Yamamoto condensation polymerization reaction method for preparing is as follows:
For example, 4,5-diaza Fluorenone class monomer homopolymer preparation feedback is as follows:
In order to understand the content of patent of the present invention better, further specify technical scheme of the present invention below by concrete example and legend, specifically comprise the preparation of synthetic, property testing and device.But these embodiments do not limit the present invention.
3,8-two bromo-1, the preparation of 10-phenanthroline (DiBrphen)
Get the single necked round bottom flask of a 500ml, add 1,10-phenanthroline (5.47g, 27.50mmol), get n-propylcarbinyl chloride 100ml, sulfur dichloride 7.3ml injection bottle and make the solid dissolving, inject pyridine 7.3ml, add liquid bromine 4.5ml again, controlled temperature (makes it to reflux and gets final product) about 90 ℃ and reacted 17 hours; Reaction finishes postcooling to room temperature, adds sodium hydroxide solution and chloroform washing gains, filters chloroform flushing dissolving and extraction; Anhydrous magnesium sulfate drying, column chromatography are purified, and (sherwood oil: ethyl acetate=4: 1) obtain white solid product 9.30g, productive rate is 50%.
GC-MS(EI-m/z)：338(M
+)。
2,7-two bromo-4, the preparation of 5-diaza Fluorenone (DiBrDAFO)
Get the single necked round bottom flask of a 100ml, with 2,7-two bromo-1,10-phenanthroline (8.72g, 25.80mmol) and Potassium Bromide (3.71g, 31.20mmol) add, add the concentrated nitric acid (31ml) and the vitriol oil (61ml) that mixes, heated and stirred then, reacted 24 hours down at 100 ℃, reaction is poured reaction solution in the water into after finishing cooling, is 7 with the NaOH solid with the solution PH that neutralizes, this moment, solution was black and bottom appearance precipitation, filter trichloromethane washing precipitation, chloroform extraction, the anhydrous magnesium sulfate drying organic layer, vacuum rotary steam, column chromatography are purified, and (sherwood oil: ethyl acetate=3: 1) obtain flaxen solid product 4.12g, productive rate is 47%.
GC-MS(EI-m/z)：340(M
+)。
2,7-two bromo-9, the preparation of 9-dioctyl fluorene
Get three mouthfuls of round-bottomed flasks of a 500ml, with 2 of 9.7g, 7-dibromo fluorenes and a spot of TBAB add, and the back adds DMSO (methyl-sulphoxide), stir the sodium hydroxide solution that adds preparation 50% down, heated and stirred to 70 ℃ is injected the 13ml bromooctane with syringe, reacts 24 hours, reaction finishes cooling, reaction solution is poured in the water, and in regulating with diluted acid and PH=7, this moment, solution was light brick yellow, and precipitation appears in the bottom, filter trichloromethane washing precipitation, chloroform extraction, the anhydrous magnesium sulfate drying organic layer, vacuum rotary steam, column chromatography purification (sherwood oil) obtains the solid product 16.4g of white, and productive rate is 90%.
GC-MS(EI-m/z)：548(M
+)。
Poly-{ (4,5-azepine Fluorenone)-alternately-copolymerization-(9, the 9-dioctyl fluorene) }
The careful purification (recrystallization or column chromatography are purified) monomer, under the nitrogen atmosphere with cyclooctadiene nickel 0.50g (2.6equiv), cyclooctadiene 0.24mL (2.6equiv) and 2,2 '-dipyridyl 0.28g (2.6equiv) joins in the round-bottomed flask of 100mL, vacuumizes logical nitrogen three times.Inject the anhydrous N of 6.0mL with syringe in round-bottomed flask, dinethylformamide obtains dark blue solution, stirs these navy blue solution 30 minutes down at 65 ℃.
In another flask, add 2,7-dibromo azepine Fluorenone 0.071g (0.21mmol) and 2,7-two bromo-9,9-dioctyl fluorene 0.27g (0.49mmol), vacuumize logical nitrogen three times, add the anhydrous N of 3mL, dinethylformamide to it, solid mixture is dissolved fully, then it is transferred in the navy blue solution.Reaction unit was 70 ℃ of following lucifuge reactions 96 hours.Syringe adds bromobenzene 0.1mL, and stirring reaction spends the night.Cooling adds 5mL tetrahydrofuran (THF) and 0.2mL hydrazine hydrate solution.The gained mixture was stirred 12 hours at normal temperatures.Mixture is filtered, and concentrates, and puts in the methyl alcohol of 500mL, and the suction filtration drying obtains yellow solid (128mg, 57%).
GPC：M
n＝5550；PDI＝1.9。
Embodiment 2,4,5-diaza Fluorenone and 2, and the preparation of 2 '-bithiophene unit copolymer material:
Careful purifying monomer 5,5 '-two (4,4,5,5-tetramethyl--[1,3,2] dioxo bora pentamethylene base)-2,2 '-bithiophene and monomer 2,7-two bromo-9,9-dioctyl-4 is behind the 5-diaza fluorenes Fluorenone, 1: 1 in molar ratio feed ratio mixed dissolution adds catalyzer (PPh under the atmosphere of high-purity argon gas in toluene solution
3)
4Pd (0) (0.5-2.0mol%) and drips several Aliquat 336, adds 2M Na simultaneously
2CO
3The aqueous solution.Be reflected under the vigorous stirring and refluxed 3 days.After reaction finished, cooling was also poured whole mixture in the methyl alcohol into.Filtration is also removed oligomer and small molecules and residual catalyzer with Soxhlet tubular type extraction plant extracting solid precipitation 48h in acetone.Obtain faint yellow solid (productive rate: 76%).
GPC：M
n＝16500；PDI＝1.9。
The photoluminescence spectra of embodiment 3, poly-(azepine Fluorenone class) semiconductor material is measured:
Product is made into the trichloromethane dilute solution of 1 μ M accurately, and removes oxygen by argon cleaning.Adopt Tianjin, island UV-3150 ultraviolet-visual spectrometer and RF-530XPC fluorescence spectrophotometer to carry out absorption spectrum and emission spectrometry, photoluminescence spectra is to measure under the maximum absorption wavelength of uv-absorbing.Solid film is by the preparation of solution spin-coating film technology, and thickness is 300nm.
The hot assay determination of embodiment 4, poly-(azepine Fluorenone class) semiconductor material:
Thermogravimetric analysis (TGA)) carry out on the DTG-60H of Tianjin, island company (Shimadzu) thermogravimetric analyzer, the heating sweep velocity is 10 ℃/min, and nitrogen flow rate is 20cm3/min.Differential scanning calorimetry (DSC) carries out on the DSC-60A of Tianjin, island company (Shimadzu) tester, sample at first is heated to the state of low ten degree of decomposed sample temperature with the speed of 10 ℃/min, then, the beginning temperature is got back in cooling under the liquid nitrogen condition, and the same second time is with the speed heat temperature raising scanning of 10 ℃/min.
The electrochemical gaging of embodiment 5, poly-(azepine Fluorenone class) semiconductor material:
Electrochemistry cyclic voltammetric (CV) experiment is finished on an Eco Chemie B.V.AUTOLAB potentiostat voltammetric analyzer, adopts three-electrode system, comprises platinum carbon working electrode, Ag/Ag
+For reference electrode, platinum filament are counter electrode.Oxidising process adopts methylene dichloride as solvent, and reduction process adopts tetrahydrofuran (THF) as solvent, hexafluoro phosphorus TBuA (Bu
4N
+PF
6 -) as supporting electrolyte, concentration is 0.1M.All electrochemistry experiments all are to carry out under the normal temperature condition nitrogen atmosphere, voltage sweep speed 0.1V/s.Use ferrocene (FOC) as benchmark, can calculate the HOMO and the lumo energy of material by the beginning voltage of measuring oxidation and reduction process.
A bi-layer devices, as luminescent layer, promptly device architecture is poly-{ (4,5-diaza Fluorenone)-copolymerization-(9,9-dioctyl fluorene-2,7-two bases) }/LiF of ITO/ with poly-{ (4,5-diaza Fluorenone)-copolymerization-(9,9-dioctyl fluorene-2,7-two bases) }
/ Al,, wherein ITO is the transparency electrode of square resistance 10-20 Ω/; Poly-{ (4,5-diaza Fluorenone)-copolymerization-(9,9-dioctyl fluorene-2,7-two bases) } adopt spin coating technique, evaporation LiF buffer layer again; At last, AM aluminum metallization negative electrode.
Claims (6)
1. one kind 4,5-diaza Fluorenone base polymer photoelectric material is characterized in that this material has following general structure:
Polymkeric substance I
In the formula: x is the natural number in 1～100, and y is the natural number in 0～100, and n is the natural number in 1～300,
R
1, R
2, R
3Identical or different during appearance, and be hydrogen or straight chain, side chain or cyclic alkyl chain with 1 to 22 carbon atom, one or more non-conterminous carbon atom can by-O-,-S-,-the CO-O-displacement, perhaps one or more hydrogen atom is replaced by fluorine, or for containing the kinds of aromatic ring conjugation structural unit;
Ar is for containing aromatic hydrocarbons conjugated structure unit, can have a kind of in the following structure of example:
2. according to claim 14,5-diaza Fluorenone base polymer photoelectric material is characterized in that in the described polymkeric substance I material R
1, R
2, R
3Be selected from hydrogen or normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or positive certain herbaceous plants with big flowers base, n-octyloxy chain respectively or contain a kind of in the kinds of aromatic ring conjugation modular construction.
3. according to claim 14,5-diaza Fluorenone base polymer photoelectric material is characterized in that in the described polymkeric substance I material, get x, y all equal 1 and Ar get fluorenes, simultaneously, R
1And R
2All be n-octyl, R
3Be hydrogen atom, it is as follows then to constitute molecular structure:
4. one kind as claimed in claim 14, the preparation method of 5-diaza Fluorenone base polymer photoelectric material, it is characterized in that this preparation method comprises 4, synthetic and this monomer of 5-diaza Fluorenone monomer is described 4 by the reaction of Suzuki coupling condensation polymerization or Yamamoto coupling condensation polymerization prepared in reaction, 5-diaza Fluorenone base polymer; Wherein Suzuki coupling condensation polymerization reaction conditions is triphenyl phosphorus palladium (Pd (PPh
3)
4, salt of wormwood K
2CO
3Or cesium fluoride CsF, toluene or 1,2-glycol dimethyl ether, triphenyl phosphorus Ph
3P; Yamamoto coupling condensation polymerization reaction conditions is two (1, the 5-cyclooctadiene) nickel, dipyridyl, 1,5-cyclooctadiene, NN-dimethyl formamide;
4,5-diaza Fluorenone monomer synthetic route is as follows:
Wherein, 1. step is included under the condition of n-propylcarbinyl chloride, sulfurous gas and carries out bromination reaction; 2. step is to carry out prepared in reaction azepine Fluorenone under the mixing acid-base function.
5. described 4 according to claim 4, the preparation method of 5-diaza Fluorenone base polymer photoelectric material is characterized in that Yamamoto condensation polymerization reaction method is as follows:
6. one kind as claimed in claim 14, the application method of 5-diaza Fluorenone base polymer photoelectric material, it is characterized in that described 4,5-diaza Fluorenone base polymer photoelectric material is as organic solar batteries, LED device and fluorescence probe material, wherein the structure of organic solar batteries device is transparent anode, hole injection layer, electron donor material, electron acceptor material, the negative electrode that order is provided with, wherein, employing contains 4, and polymer semiconductor's material of 5-diaza Fluorenone monomeric unit is as electron acceptor material.
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| CN105622901A (en) * | 2016-03-16 | 2016-06-01 | 南京邮电大学 | Interrupt conjugated type polymer semiconductor material and preparation method and application thereof |
| WO2020211140A1 (en) * | 2019-04-16 | 2020-10-22 | 武汉华星光电半导体显示技术有限公司 | Electroluminescent material, preparation method for electroluminescent material and light emitting device |
| CN113652705A (en) * | 2021-06-23 | 2021-11-16 | 北京工业大学 | Method for synthesizing fluorenone by catalyzing and electrolyzing N-hydroxyphthalimide |
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