CN103724355A - Porphyrin organic small molecular photovoltaic material and preparation method thereof - Google Patents
Porphyrin organic small molecular photovoltaic material and preparation method thereof Download PDFInfo
- Publication number
- CN103724355A CN103724355A CN201310670252.0A CN201310670252A CN103724355A CN 103724355 A CN103724355 A CN 103724355A CN 201310670252 A CN201310670252 A CN 201310670252A CN 103724355 A CN103724355 A CN 103724355A
- Authority
- CN
- China
- Prior art keywords
- porphyrin
- photovoltaic material
- organic molecule
- porphyrin organic
- preparation
- 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.)
- Pending
Links
- 0 C*C1=C(C=C2)*(C)=C2C(*)=C(*2C)C=CC2=C(C(*)*IIN)C(C=C2)=*(C)C2=C(*)C2=CC=C1*2C Chemical compound C*C1=C(C=C2)*(C)=C2C(*)=C(*2C)C=CC2=C(C(*)*IIN)C(C=C2)=*(C)C2=C(*)C2=CC=C1*2C 0.000 description 8
- DAJNVLLZSYCFBM-NSYFGSIISA-N C/C(/N)=C/C=N Chemical compound C/C(/N)=C/C=N DAJNVLLZSYCFBM-NSYFGSIISA-N 0.000 description 1
- YJTYJNDGWACTHT-UHFFFAOYSA-N CCC(C)CCC(C)NC Chemical compound CCC(C)CCC(C)NC YJTYJNDGWACTHT-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a porphyrin organic small molecular photovoltaic material and a preparation method thereof. The disclosed porphyrin organic small molecular photovoltaic material adopts a porphyrin ring as a framework, one radical is in each of four meso-position positions of the porphyrin ring, wherein two radicals are acceptor units, and the other two radicals are aromatic substituted radicals. The invention further discloses the preparation method of the above porphyrin organic small molecular photovoltaic material. Pyrrole is used as a primary reaction material, then subjected to a series of simple reactions, and finally coupled with different acceptor units under the catalysis of palladium to obtain the porphyrin organic small molecular photovoltaic material. Compared with the prior art, the porphyrin organic small molecular photovoltaic material, disclosed by the invention, is improved in the ability to absorb light, intramolecular electric charge transmission performance and Pi-Pi stacking of molecules in a film forming state; the film forming performance of the material is improved, an organic photovoltaic battery prepared by using the material and adopting a solution processing method has better device performance, and the highest conversion rate of solar energy reaches 7.2 percent, so that the porphyrin organic small molecular photovoltaic material has a very important application prospect in solar batteries.
Description
Technical field
The present invention relates to organic molecule photovoltaic material field, particularly a kind of porphyrin organic molecule photovoltaic material and preparation method thereof.
Background technology
Sun power is a kind of reproducible clean energy, is a huge energy treasure-house, the exploitation of sun power is more and more received to the mankind's concern.But the energy density of sun power is low, be difficult for directly utilization, need to change into other energy could well utilize.In effective utilization of sun power, utilizing photocell to convert solar energy into electrical energy is with fastest developing speed, most active in the last few years research field.
The organic polymer of solution-processible and organic small molecule material solar cell have low cost, be easy to processing (as can spin coating, spray ink Printing etc.), be suitable for preparing the potential advantages such as large area flexible device, not only can simplify the preparation process of device, also can greatly reduce preparation cost, thereby be subject to paying close attention to widely.Donor material in battery active material can be divided into conjugated polymers and organic molecule according to the size of molecular weight, the easy film forming of polymkeric substance, but product is not easy to purify, molecular weight distribution is wide, and every batch of product being synthesized causes the efficiency of solar cell usually to have larger difference because molecular weight and distribution thereof there are differences, and organic molecule does not exist these problems, so there is its unique advantage in organic molecule in organic solar batteries.
Photosynthesis is that green plants passes through after chlorophyll absorb light, carries out photochemical reaction and carrys out storage power, thereby provide food and the energy etc. for the mankind.The structure of porphyrin is similar with chlorophyll, there is large pi-conjugated system and high molar absorptivity, electronics can be rapidly from transferring to acceptor to body, easily the modification by peripheral group and cavity metal changes its physicochemical property, and Porphyrin and its derivative is to be used as the earliest light active material to be applied to one of material of organic solar batteries.Yet the photoelectric transformation efficiency based on Porphyrin and its derivative organic solar batteries is but very low.
Summary of the invention
In order to overcome the above-mentioned shortcoming and deficiency of prior art, the object of the present invention is to provide a kind of porphyrin organic molecule photovoltaic material, the pi-conjugated system and the intramolecular charge that have effectively increased molecule shift (ICT), have widened the absorption spectrum of material, have improved the carrier mobility of material; By changing the electron-withdrawing power of electron-withdrawing group, effectively regulated HOMO, the lumo energy of molecule simultaneously.
Another object of the present invention is to provide the preparation method of above-mentioned porphyrin organic molecule photovoltaic material.
Object of the present invention is achieved through the following technical solutions:
A porphyrin organic molecule photovoltaic material, has following chemical structure:
Wherein: A is for being subject to body unit; M is metal ion or protium; Ar is aromatic substituent group.
Described A is a kind of in following structural unit:
Wherein, R
1to be 0 to 20 alkyl or alkoxyl group containing carbon number.
Described Ar has a kind of in following structural unit:
Wherein, R
1to be 0 to 20 alkyl or alkoxyl group containing carbon number.
Described M is zine ion, cupric ion, magnesium ion, nickel ion or hydrogen ion.
The preparation method of above-mentioned porphyrin organic molecule photovoltaic material, comprises the following steps:
Adopt the preparation of Suzuki linked reaction: under argon gas atmosphere by 5, the two boric acid ester porphyrins of 10-, bromide are dissolved in and fill 1, in the reaction flask of 2-glycol dimethyl ether, add four (triphenyl phosphorus) to close palladium, heated and stirred reaction, after cooling, with methanol extraction, go out target product, by silica gel column chromatography and GPC HPLC purifying, be finally spin-dried for solvent, product is dry under vacuum, obtains porphyrin organic molecule photovoltaic material;
The molar weight of described bromide is 5,3～6 times of the molar weight of the two boric acid ester porphyrins of 10-, described 1, the molar weight of 2-glycol dimethyl ether is 5, the two boric acid ester porphyrins of 10-and bromide integral molar quantity 45～55 times, the molar weight that described four (triphenyl phosphorus) close palladium is 8～12% of the two boric acid ester porphyrin molar weights of 5,10-.
The preparation method of above-mentioned porphyrin organic molecule photovoltaic material, comprises the following steps:
Adopt the preparation of Sonogashira linked reaction: under argon gas atmosphere by 5, the two ethynyl porphyrins of 10-, bromide are dissolved in the reaction flask that fills toluene, add four (triphenyl phosphorus) to close palladium, heated and stirred reaction, cooling after, with methanol extraction, go out target product, by silica gel column chromatography and GPC HPLC purifying, finally be spin-dried for solvent, product is dry under vacuum, obtains porphyrin organic molecule photovoltaic material;
The molar weight of described bromide is 5,3～6 times of the molar weight of the two ethynyl porphyrins of 10-, described toluene molar weight be 5, the two ethynyl porphyrins of 10-and bromide integral molar quantity 45～55 times, the molar weight that described four (triphenyl phosphorus) close palladium is 8～12% of the two ethynyl porphyrin molar weights of 5,10-.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the donor-receiver porphyrin small molecules that porphyrin organic molecule photovoltaic material of the present invention is conjugation, the pi-conjugated system and the intramolecular charge that have effectively increased molecule shift (ICT), widen the absorption spectrum of material, improved the carrier mobility of material; By changing the electron-withdrawing power of electron-withdrawing group, effectively regulated HOMO, the lumo energy of molecule simultaneously.
(2) porphyrin organic molecule photovoltaic material of the present invention by introducing different metal ions in the cavity of porphyrin, because different metal ions has different outer shell electron distributions and give-electron-withdrawing power, further regulate HOMO, the lumo energy of synthetic materials, and the absorptive character of material to light.
(3) porphyrin organic molecule photovoltaic material of the present invention is introduced different alkyl or oxyalkyl chain by the periphery at porphyrin ring and on to body unit, optimizes solubleness, film-forming properties and under filminess the intermolecular bulk property of synthetic materials in organic solvent.
(4) porphyrin organic molecule photovoltaic material of the present invention has the wide high absorbing properties to 900nm near-infrared region, and good carrier mobility can spin-coating film, uses the efficiency of conversion of solar cell prepared by this material to reach 7%.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra of the dichloromethane solution of embodiments of the invention 7～9.
Fig. 2 is the porphyrin organic molecule photovoltaic material of embodiments of the invention 7～9 preparation uv-visible absorption spectra under filminess.
Fig. 3 is the J-V graphic representation of the SCLC device of embodiments of the invention 7～9 preparations, and in figure, SCLC fit is space charge limited current matched curve.
Fig. 4 be the photovoltaic cell of inventive embodiment 7～9 preparation at AM1.5,100mW/cm
2current-voltage curve figure under illumination.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Synthesizing of two (two (dodecyloxy) benzene of 3, the 5-) porphyrins of 5,15-
In two mouthfuls of round-bottomed flasks of 1000mL, add two (dodecyloxy) phenyl aldehyde (2.304g of 3,5-, 4.86mmol), the methylene dichloride of dipyrromethane (700mg, 4.86mmol) and 500mL, with nitrogen ventilation 30 minutes, then add the trifluoroacetic acid of 0.25mL, at room temperature stirring reaction is 12 hours, add again 1.8g2,3-bis-is chloro-5,6-dicyano-Isosorbide-5-Nitrae-benzoquinones (DDQ), continue stirring reaction 12 hours, after add the triethylamine cancellation reaction of 5mL.After reaction finishes, with silica gel/(methylene dichloride is eluent) column chromatography, after being spin-dried for, obtain crude product, then use chloroform/methanol recrystallization, obtain garnet solid.
1H?NMR(300MHz,CDCl
3):δ10.30(s,2H),9.39(d,J=4.6Hz,4H),9.18(d,J=4.6Hz,4H),7.42(s,4H),6.91(s,2H),4.15(t,J=6.6Hz,8H),1.93(m,8H),1.47(m,8H),1.24(m,64H),0.83(m,12H),-3.2(s,2H).
13C?NMR(75MHz,CDCl
3):δ158.67,147.02,145.31,143.16,131.46,131.13,119.07,114.64,105.16,101.12,68.47,67.94,31.92,29.68,29.62,29.47,29.45,29.34,26.16,25.60,22.68,14.09.Mass(MALDI-TOF):Obs.1200.2;Calcd.For?C
80H
118N
4O
4:1199.8。
Embodiment 2
5,15-is two bromo-10,20-two (two (dodecyloxy) benzene of 3,5-) zinc protoporphyrins synthetic
By 5,15-two (3, two (dodecyloxy) benzene of 5-) porphyrin (840mg, 0.7mmol) is dissolved in the chloroform of 700mL, adds the pyridine of 35mL, lucifuge, then add bromo-succinimide (NBS) (274mg, 1.54mmol), 0 ℃ of reaction 30 minutes, after at room temperature continue reaction 4 hours, finally with acetone cancellation reaction.React complete, add water, with chloroform extraction, anhydrous sodium sulfate drying, is dissolved in the chloroformic solution of 50mL after being spin-dried for solvent, after add the zinc acetate methanol solution (243mg of 12mL, the zinc acetate of 1.2mmol is dissolved in the methanol solvate of 12mL), lucifuge refluxes 2 hours.React complete, washing, and with anhydrous sodium sulfate drying, be spin-dried for solvent, after use purification by silica gel column chromatography, obtain the solid of shiny red.
1H?NMR(300MHz,CDCl
3):δ9.70(d,J=4.8Hz,4H),9.06(d,J=4.8Hz,4H),7.30(s,4H),6.86(s,2H),4.12(t,J=6.55Hz,8H),1.88(m,8H),1.46(m,8H),1.25(m,64H),0.85(m,12H).
13C?NMR(75MHz,CDCl
3):δ158.18,150.60,150.15,143.65,133.60,133.04,122.11,114.53,105.06,101.16,68.45,31.90,29.61,29.60,29.43,29.33,26.08,22.65,14.10,14.06.Mass(MALDI-TOF):Obs.1421.0;Calcd.ForC
80H
114Br
2N
4O
4Zn:1421.0。
Two (trimethylsilyl acetylene)-10 of 5,15-, 20-two (two (dodecyloxy) benzene of 3,5-) zinc protoporphyrins synthetic
In two mouthfuls of round-bottomed flasks of 100mL, add 5,15-two bromo-10,20-two (two (dodecyloxy) benzene of 3,5-) zinc protoporphyrin (710mg, 0.5mmol), 25mL tetrahydrofuran (THF) and 12.5mL triethylamine, logical nitrogen 30 minutes, then adds two (triphenylphosphine) palladium chloride (17.5mg, 0.025mmol), cuprous iodide (CuI) (5mg, o.o25mmol) and trimethylsilyl acetylene (200mg, 2mmol), lucifuge, reacts at room temperature stirring reaction three days.React complete, washing, with dichloromethane extraction, with anhydrous sodium sulfate drying, recycle silicon glue/(methylene dichloride/sherwood oil=1:1 is eluent) column chromatography, is spin-dried for and obtains green solid.
1H?NMR(300MHz,CDCl
3):δ9.68(d,J=4.6Hz,4H),9.04(d,J=4.6Hz,4H),7.33(s,4H),6.89(s,2H),4.10(t,J=6.4Hz,8H),1.82(m,8H),1.50(m,8H),1.23(m,64H),0.83(m,12H),0.60(s,18H).
13C?NMR(75MHz,CDCl
3):δ158.28,150.04,143.75,132.84,131.19,122.57,114.37,107.40,101.89,101.34,101.15,68.43,31.90,29.66,29.63,29.60,29.45,29.38,29.33,26.11,22.67,14.10.Mass(MALDI-TOF):Obs.1455.2;Calcd.For?C
90H
132N
4O
4Si
2Zn:1455.6。
Two (acetylene)-10 of 5,15-, 20-two (two (dodecyloxy) benzene of 3,5-) zinc protoporphyrins synthetic
By 5, two (trimethylsilyl acetylene)-10 of 15-, 20-two (3, two (dodecyloxy) benzene of 5-) zinc protoporphyrin (509mg, 0.35mmol) be dissolved in the tetrahydrofuran solution of 20mL, add tetrabutyl ammonium fluoride (0.72mL, 1M in THF), at room temperature stirring reaction is 5 minutes, adds the shrend reaction of going out.With chloroform extraction, anhydrous sodium sulfate drying, be spin-dried for, with silica gel/(methylene dichloride/sherwood oil=1:1 is eluent) column chromatography, be spin-dried for and obtain green solid.
1H?NMR(300MHz,CDCl
3):δ9.74(d,J=4.68Hz,4H),9.07(d,J=4.65Hz,4H),7.34(s,4H),6.89(s,2H),4.15(m,10H),1.83(m,8H),1.45(m,8H),1.24(m,64H),0.83(m,12H).
13C?NMR(75MHz,CDCl
3):δ158.35,152.37,150.20,133.04,131.19,114.30,68.42,31.88,29.63,29.58,29.43,29.38,29.30,26.11,22.64,14.05.Mass(MALDI-TOF):Obs.1311.2;Calcd.For?C
84H
116N
4O
4Zn:1311.2。
The bromo-7-of 4-(4-hexyl-2-thiophene)-2,1,3-diazosulfide synthetic
Under the protection of argon gas; by 4; 7-bis-bromo-2; 1,3-diazosulfide (882mg, 3mmol); tributyl (4-hexyl-2-thiophene)-Xi (458mg; 1mmol) add in the anhydrous tetrahydrofuran solution of 30mL with two (triphenylphosphine) palladium chlorides (42mg, 0.06mmol), 80 ℃ of reactions, stir 24 hours.React complete, washing, with dichloromethane extraction, anhydrous sodium sulfate drying, is spin-dried for, and with silica gel/(methylene dichloride/sherwood oil=1:15 is eluent) column chromatography, is spin-dried for and obtains yellow solid.
1H?NMR(300MHz,CDCl
3):δ7.95(s,1H),7.83(d,J=7.71Hz,1H),7.69(d,J=7.71Hz,1H),7.06(s,1H),2.71(t,J=7.68Hz,2H),1.73(m,2H),1.3(m,6H),0.92(m,3H).
13C?NMR(75MHz,CDCl
3):δ153.79,151.80,144.50,138.08,132.21,129.61,127.36,125.51,122.04,112.05,31.67,30.59,30.43,29.01,22.60,14.06.MS(ESI):m/z=382.8;Calcd.ForC
16H
17BrN
2S
2:381.4。
4-is bromo-5, the fluoro-7-of 6-bis-(4-octyl group-2-thiophene)-2,1,3-diazosulfide synthetic
Under the protection of argon gas; by 4; 7-bis-is bromo-5, and 6-bis-fluoro-2,1; 3-diazosulfide (1.08g; 3.27mmol), tributyl (4-octyl group-2-thiophene)-Xi (1.458g, 3mmol) and two (triphenylphosphine) palladium chloride (126mg; 0.18mmol) add in the anhydrous tetrahydrofuran solution of 90mL, 80 ℃ of reactions, stir 24 hours.React complete, washing, with dichloromethane extraction, anhydrous sodium sulfate drying, is spin-dried for, and with silica gel/(methylene dichloride/sherwood oil=1:15 is eluent) column chromatography, is spin-dried for and obtains lurid solid.
1H?NMR(300MHz,CDCl
3):δ8.11(s,1H),7.24(s,1H),2.74(t,J=7.68Hz,2H),1.72(m,2H),1.3(m,10H),0.92(m,3H).
13C?NMR(75MHz,CDCl
3):δ149.93,143.84,132.84,132.73,130.34,124.63,124.54,31.88,31.67,30.52,30.48,30.41,29.69,29.43,29.32，29.26,28.98,22.67,22.62，14.09.MS(ESI):m/z=445.09;Calcd.For?C
16H
17BrN
2S
2:445.39。
Embodiment 7
Two (7-(4-hexyl-2-thiophene)-2,1, the 3-diazosulfides)-10 of 5,15-, 20-two (two (dodecyloxy) benzene of 3,5-) zinc protoporphyrins synthetic
In the single necked round bottom flask of 50mL, add 5, 15-two (4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-)-10, 20-two (3, two (dodecyloxy) benzene of 5-) zinc protoporphyrin (303mg, 0.2mmol), the bromo-7-(4-hexyl-2-of 4-thiophene)-2, 1, 3-diazosulfide (228.6mg, 0.6mmol), barium hydroxide octahydrate (0.08g, 0.24mmol), tetrakis triphenylphosphine palladium (24mg, 0.02mmol), 1 of firm steaming, 2-glycol dimethyl ether (15mL) and water (0.3mL), after carry out the freezing-oxygen removed in system for three times of (freeze-pump-thaw) circulation of bleeding-melt, pass into again argon gas, lucifuge, and at 80 ℃ stirring reaction 72 hours.React complete, be cooled to room temperature, washing, with toluene extraction, anhydrous sodium sulfate drying, is spin-dried for, then uses gel permeation chromatography (GPC) column chromatography (toluene is eluent), obtains the solid of purple.
1H?NMR(300MHz,CDCl
3):δ9.02(d,J=5.5Hz,4H),8.75(d,J=6Hz,4H),8.49(d,J=7.3Hz,1H),8.42(d,J=7.2Hz,1H),8.34(d,J=7Hz,2H),8.29(s,2H),7.34(s,4H),7.20(s,2H),6.84(s,2H),4.09(t,J=5.0Hz,8H),2.85(t,J=7.6Hz,4H),1.84(m,12H),1.46(m,12H),1.25(m,72H),0.97(t,J=7.0Hz,3H),0.85(m,12H).
13C?NMR(75MHz,CDCl
3):δ158.87,158.18,151.50,150.28,150.18,144.62,144.36,139.12,134.35,132.63,131.15,129.73,127.81,124.49,122.03,121.53,115.37,114.29,101.12,68.37,31.86,31.76,30.77,30.59,29.60,29.57,29.54,29.39,29.36,29.28,29.08,26.07,22.67,22.62,14.11,14.04.Mass(MALDI-TOF):Obs.1862.8;Calcd.ForC
112H
148N
8O
4S
4Zn,1864.1。
Porphyrin organic molecule photovoltaic material prepared by the present embodiment is dissolved in methylene dichloride, and the uv-visible absorption spectra of the dichloromethane solution obtaining is shown in Fig. 1.
Porphyrin organic molecule photovoltaic material prepared by the present embodiment is prepared into film, and its uv-visible absorption spectra is shown in Fig. 2.
Utilize the porphyrin organic molecule photovoltaic material of the present embodiment to prepare SCLC device, device architecture: ITO/PEDOT:PSS (40nm)/active layer/MoO
3(10nm)/Al, its J-V curve is shown in Fig. 3.
Utilize photovoltaic cell prepared by the porphyrin organic molecule photovoltaic material of the present embodiment at AM1.5,100mW/
cm
2current-voltage curve under illumination is shown in Fig. 4, device architecture: ITO/PEDOT:PSS/ active coating/PFN/Al.
Embodiment 8
Two (7-(4-hexyl-2-thiophene)-2,1, the 3-diazosulfide-4-acetylene)-10 of 5,15-, 20-two (two (dodecyloxy) benzene of 3,5-) zinc protoporphyrins synthetic
Under the protection of argon gas; in two mouthfuls of round-bottomed flasks of 50mL, add 5; two (acetylene)-10 of 15-; 20-two (two (dodecyloxy) benzene of 3,5-) zinc protoporphyrin (262mg, 0.2mmol); the bromo-7-(4-hexyl-2-of 4-thiophene)-2; 1,3-diazosulfide (228.6mg, 0.6mmol); dry toluene (10mL); triethylamine (5mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium (24mg; 0; 02mmol), lucifuge, at 80 ℃, stirring reaction is three days.React complete, be cooled to room temperature, washing, with toluene extraction, anhydrous sodium sulfate drying, is spin-dried for, then uses gel permeation chromatography (Gel Permeation Chromatography, GPC) column chromatography (toluene is eluent), obtains atropurpureus solid.Mass(MALDI-TOF):Obs.1912.5;Calcd.for?C
116H
148N
8O
4S
4Zn,1912.1。
Porphyrin organic molecule photovoltaic material prepared by the present embodiment is dissolved in methylene dichloride, and the uv-visible absorption spectra of the dichloromethane solution obtaining is shown in Fig. 1.
Porphyrin organic molecule photovoltaic material prepared by the present embodiment is prepared into film, and its uv-visible absorption spectra is shown in Fig. 2.
Utilize the porphyrin organic molecule photovoltaic material of the present embodiment to prepare SCLC device, device architecture: ITO/PEDOT:PSS (40nm)/active layer/MoO
3(10nm)/Al, its J-V curve is shown in Fig. 3.
Utilize photovoltaic cell prepared by the porphyrin organic molecule photovoltaic material of the present embodiment at AM1.5,100mW/cm
2current-voltage curve under illumination is shown in Fig. 4, device architecture: ITO/PEDOT:PSS/ active coating/PFN/Al.
Embodiment 9
Two (the fluoro-7-of 5,6-bis-(4-octyl group-2-thiophene)-2,1, the 3-diazosulfide-4-acetylene)-10 of 5,15-, 20-two (two (dodecyloxy) benzene of 3,5-) zinc protoporphyrins synthetic
Coupled reaction condition condition is similar to Example 8, by the bromo-7-(4-hexyl-2-of the 4-of one of reaction raw materials thiophene)-2,1,3-diazosulfide changes 4-bromo-5 into, the fluoro-7-(4-octyl group-2-of 6-bis-thiophene)-2,1,3-diazosulfide, by obtaining target product after reaction, processing and purifying.Mass(MALDI-TOF):Obs.2038.24;Calcd.For?C
116H
148N
8O
4S
4Zn,2040.39。
Porphyrin organic molecule photovoltaic material prepared by the present embodiment is dissolved in methylene dichloride, and the uv-visible absorption spectra of the dichloromethane solution obtaining is shown in Fig. 1.
Porphyrin organic molecule photovoltaic material prepared by the present embodiment is prepared into film, and its uv-visible absorption spectra is shown in Fig. 2.
Utilize the porphyrin organic molecule photovoltaic material of the present embodiment to prepare SCLC device, device architecture: ITO/PEDOT:PSS (40nm)/active layer/MoO
3(10nm)/Al, its J-V curve is shown in Fig. 3.
Utilize photovoltaic cell prepared by the porphyrin organic molecule photovoltaic material of the present embodiment at AM1.5,100mW/cm
2current-voltage curve under illumination is shown in Fig. 4, device architecture: ITO/PEDOT:PSS/ active coating/PFN/Al.
In the following chemical structure of small molecules photovoltaic material of the present invention:
A also can be other and is subject to body unit, and M can also be cupric ion, magnesium ion, nickel ion etc., and Ar also can be other aromatic substituent groups, and the embodiment that its preparation principle and performance and the present invention provide is similar, does not repeat them here.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (6)
1. a porphyrin organic molecule photovoltaic material, is characterized in that, has following chemical structure:
Wherein: A is for being subject to body unit; M is metal ion or protium; Ar is aromatic substituent group.
2. porphyrin organic molecule photovoltaic material according to claim 1, is characterized in that, described A is a kind of in following structural unit:
Wherein, R
1to be 0 to 20 alkyl or alkoxyl group containing carbon number.
3. porphyrin organic molecule photovoltaic material according to claim 1, is characterized in that, described Ar has a kind of in following structural unit:
Wherein, R
1to be 0 to 20 alkyl or alkoxyl group containing carbon number.
4. porphyrin organic molecule photovoltaic material according to claim 1, is characterized in that, described M is zine ion, cupric ion, magnesium ion, nickel ion or hydrogen ion.
5. the preparation method of porphyrin organic molecule photovoltaic material described in claim 1～4 any one, is characterized in that, comprises the following steps:
Adopt the preparation of Suzuki linked reaction: under argon gas atmosphere by 5, the two boric acid ester porphyrins of 10-, bromide are dissolved in and fill 1, in the reaction flask of 2-glycol dimethyl ether, add four (triphenyl phosphorus) to close palladium, heated and stirred reaction, after cooling, with methanol extraction, go out target product, by silica gel column chromatography and GPC HPLC purifying, be finally spin-dried for solvent, product is dry under vacuum, obtains porphyrin organic molecule photovoltaic material;
The molar weight of described bromide is 5,3～6 times of the molar weight of the two boric acid ester porphyrins of 10-, described 1, the molar weight of 2-glycol dimethyl ether is 5, the two boric acid ester porphyrins of 10-and bromide integral molar quantity 45～55 times, the molar weight that described four (triphenyl phosphorus) close palladium is 8～12% of the two boric acid ester porphyrin molar weights of 5,10-.
6. the preparation method of porphyrin organic molecule photovoltaic material described in claim 1～4 any one, is characterized in that, comprises the following steps:
Adopt the preparation of Sonogashira linked reaction: under argon gas atmosphere by 5, the two ethynyl porphyrins of 10-, bromide are dissolved in the reaction flask that fills toluene, add four (triphenyl phosphorus) to close palladium, heated and stirred reaction, cooling after, with methanol extraction, go out target product, by silica gel column chromatography and GPC HPLC purifying, finally be spin-dried for solvent, product is dry under vacuum, obtains porphyrin organic molecule photovoltaic material;
The molar weight of described bromide is 5,3～6 times of the molar weight of the two ethynyl porphyrins of 10-, described toluene molar weight be 5, the two ethynyl porphyrins of 10-and bromide integral molar quantity 45～55 times, the molar weight that described four (triphenyl phosphorus) close palladium is 8～12% of the two ethynyl porphyrin molar weights of 5,10-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310670252.0A CN103724355A (en) | 2013-12-10 | 2013-12-10 | Porphyrin organic small molecular photovoltaic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310670252.0A CN103724355A (en) | 2013-12-10 | 2013-12-10 | Porphyrin organic small molecular photovoltaic material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103724355A true CN103724355A (en) | 2014-04-16 |
Family
ID=50448682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310670252.0A Pending CN103724355A (en) | 2013-12-10 | 2013-12-10 | Porphyrin organic small molecular photovoltaic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103724355A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017264A (en) * | 2015-06-29 | 2015-11-04 | 华南理工大学 | Organic small molecular photoelectric functional material, and preparation method thereof |
| CN105440044A (en) * | 2015-12-22 | 2016-03-30 | 南京邮电大学 | Preparation method for metalloporphyrin metal complexes with different structure frameworks and application |
| CN105837601A (en) * | 2016-05-03 | 2016-08-10 | 沈荣存 | Aromatic ring modified organic photovoltaic cell and preparation method thereof |
| CN105837600A (en) * | 2016-05-03 | 2016-08-10 | 沈荣存 | Aromatic ring modified organic photovoltaic material and preparation method thereof |
| CN105859729A (en) * | 2016-04-28 | 2016-08-17 | 华南理工大学 | Porphyrin small organic molecule cathode interface material and preparation method thereof |
| WO2018001330A1 (en) * | 2016-06-29 | 2018-01-04 | Hong Kong Baptist University | Design and synthesis of porphyrin materials for highly efficient organic photovoltaics |
| CN108658994A (en) * | 2018-04-17 | 2018-10-16 | 华南理工大学 | A kind of porphyrin organic molecule acceptor material and the preparation method and application thereof |
| CN110527107A (en) * | 2019-08-27 | 2019-12-03 | 深圳大学 | A kind of orderly two-dimentional electroconductive molecule monolayer array preparation method and photoelectric device |
| CN110544743A (en) * | 2019-08-08 | 2019-12-06 | 华南理工大学 | Efficient porphyrin material-based ternary organic solar cell and preparation method thereof |
| CN113105464A (en) * | 2021-03-09 | 2021-07-13 | 华南理工大学 | Single-component photovoltaic material based on porphyrin and fullerene, and preparation method and application thereof |
| CN116354971A (en) * | 2023-04-08 | 2023-06-30 | 湘潭大学 | Porphyrin compound and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011153680A1 (en) * | 2010-06-07 | 2011-12-15 | 海洋王照明科技股份有限公司 | Porphyrin copolymer containing thienothiadiazole units, preparation method and uses thereof |
| CN102295756A (en) * | 2010-06-25 | 2011-12-28 | 海洋王照明科技股份有限公司 | Carbazole porphyrin-thienothiadiazole copolymer as well as preparation method and application thereof |
| CN102344549A (en) * | 2010-07-30 | 2012-02-08 | 海洋王照明科技股份有限公司 | Porphyrin-pyrrolopyrrole copolymer containing carbazole, preparation method thereof and application thereof |
-
2013
- 2013-12-10 CN CN201310670252.0A patent/CN103724355A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011153680A1 (en) * | 2010-06-07 | 2011-12-15 | 海洋王照明科技股份有限公司 | Porphyrin copolymer containing thienothiadiazole units, preparation method and uses thereof |
| CN102295756A (en) * | 2010-06-25 | 2011-12-28 | 海洋王照明科技股份有限公司 | Carbazole porphyrin-thienothiadiazole copolymer as well as preparation method and application thereof |
| CN102344549A (en) * | 2010-07-30 | 2012-02-08 | 海洋王照明科技股份有限公司 | Porphyrin-pyrrolopyrrole copolymer containing carbazole, preparation method thereof and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| HUANG, YUYING等: "Solution processed small molecule bulk heterojunction organic photovoltaics based on a conjugated donor-acceptor porphyrin", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 22, no. 41, 7 September 2012 (2012-09-07) * |
| LI, LISHENG等: "Enhanced performance of solution-processed solar cells based on porphyrin small molecules with a diketopyrrolopyrrole acceptor unit and a pyridine additive", 《JOURNAL OF MATERIALS CHEMISTRY A: MATERIALS FOR ENERGY AND SUSTAINABILITY》, vol. 1, no. 6, 7 December 2012 (2012-12-07) * |
| 黄玉英: "基于卟啉的小分子和聚合物的合成及其光伏性能研究", 《华南理工大学博士学位论文》, 15 November 2013 (2013-11-15) * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017264B (en) * | 2015-06-29 | 2018-01-05 | 华南理工大学 | A kind of organic molecule photoelectric functional material and preparation method thereof |
| CN105017264A (en) * | 2015-06-29 | 2015-11-04 | 华南理工大学 | Organic small molecular photoelectric functional material, and preparation method thereof |
| CN105440044A (en) * | 2015-12-22 | 2016-03-30 | 南京邮电大学 | Preparation method for metalloporphyrin metal complexes with different structure frameworks and application |
| CN105440044B (en) * | 2015-12-22 | 2018-07-17 | 南京邮电大学 | The preparation method and application of different structure frame metal porphyrin metal complex |
| CN105859729A (en) * | 2016-04-28 | 2016-08-17 | 华南理工大学 | Porphyrin small organic molecule cathode interface material and preparation method thereof |
| CN105837601A (en) * | 2016-05-03 | 2016-08-10 | 沈荣存 | Aromatic ring modified organic photovoltaic cell and preparation method thereof |
| CN105837600A (en) * | 2016-05-03 | 2016-08-10 | 沈荣存 | Aromatic ring modified organic photovoltaic material and preparation method thereof |
| US10236457B2 (en) | 2016-06-29 | 2019-03-19 | Hong Kong Baptist University | Synthesis of porphyrin materials for highly efficient organic photovoltaics |
| WO2018001330A1 (en) * | 2016-06-29 | 2018-01-04 | Hong Kong Baptist University | Design and synthesis of porphyrin materials for highly efficient organic photovoltaics |
| CN108658994A (en) * | 2018-04-17 | 2018-10-16 | 华南理工大学 | A kind of porphyrin organic molecule acceptor material and the preparation method and application thereof |
| CN110544743A (en) * | 2019-08-08 | 2019-12-06 | 华南理工大学 | Efficient porphyrin material-based ternary organic solar cell and preparation method thereof |
| CN110544743B (en) * | 2019-08-08 | 2021-03-30 | 华南理工大学 | Efficient porphyrin material-based ternary organic solar cell and preparation method thereof |
| CN110527107A (en) * | 2019-08-27 | 2019-12-03 | 深圳大学 | A kind of orderly two-dimentional electroconductive molecule monolayer array preparation method and photoelectric device |
| CN113105464A (en) * | 2021-03-09 | 2021-07-13 | 华南理工大学 | Single-component photovoltaic material based on porphyrin and fullerene, and preparation method and application thereof |
| CN113105464B (en) * | 2021-03-09 | 2022-07-26 | 华南理工大学 | Single-component photovoltaic material based on porphyrin and fullerene, and preparation method and application thereof |
| CN116354971A (en) * | 2023-04-08 | 2023-06-30 | 湘潭大学 | Porphyrin compound and preparation method and application thereof |
| CN116354971B (en) * | 2023-04-08 | 2024-06-04 | 湘潭大学 | Porphyrin compound and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103724355A (en) | Porphyrin organic small molecular photovoltaic material and preparation method thereof | |
| CN105017264B (en) | A kind of organic molecule photoelectric functional material and preparation method thereof | |
| CN108864137B (en) | Receptor compound, preparation method and application thereof, and photovoltaic cell containing receptor compound | |
| CN104672434B (en) | A kind of organic semiconducting materials and preparation method and application | |
| JP5425338B2 (en) | Copolymer containing anthracene and pearselenol, its production method and its application | |
| CN103288848A (en) | Benzo terthiophene compound as well as preparation method and usage thereof | |
| CN101787020A (en) | Organic conjugated molecule capable of being processed by solution and application thereof in solar cells | |
| CN107383080A (en) | A kind of asymmetrical porphyrin organic molecule photovoltaic material and preparation method and application | |
| CN105859729B (en) | A kind of porphyrin organic molecule cathode interface material and preparation method thereof | |
| CN109517142B (en) | Star-shaped D-A structure conjugated molecule based on tri-indeno five-membered aromatic heterocycle, and preparation method and application thereof | |
| CN103483560A (en) | 2,1,3-benzothiadiazole thiophene derived bromide and carbazole conjugated polymer and synthesis method thereof | |
| CN107805254B (en) | Porphyrin micromolecular perovskite cathode buffer layer material and preparation method and application thereof | |
| CN101962380B (en) | Novel organic conjugated molecule and application thereof in organic solar cell | |
| CN102329418A (en) | 1,2,4,5-tetrazine based conjugated polymer and application thereof in preparing solar cells | |
| CN108516978B (en) | Asymmetric porphyrin organic micromolecule cathode interface material and preparation method and application thereof | |
| CN110577548A (en) | Asymmetric fused heterocycle micromolecule electron acceptor material based on dithienopyrrole and application thereof | |
| CN103601757A (en) | Low-bandgap ruthenium-containing complexes for solution-processed organic solar cells | |
| CN103467712B (en) | The semi-conducting polymer of two dimension conjugation naphtho-difuryl and preparation thereof, purposes | |
| KR101374070B1 (en) | Triphenylamine derivatives and organic photovoltaic cell comprising the derivatives | |
| CN114349771B (en) | Hexabenzocoronene-based non-fullerene acceptor material and preparation and application thereof | |
| CN102827357B (en) | Two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers | |
| CN103304781B (en) | Semiconductor polymer of naphtho-bifuran, and preparation method and use thereof | |
| CN105061435A (en) | Pyrrolo-pyrrolidone unit monomer and synthesizing method and polymers thereof | |
| CN102770476A (en) | Porphyrin copolymer containing quinoxaline unit, preparation method and uses thereof | |
| CN103897156A (en) | Dibenzothiophene two-dimensional conjugated polymer with thiophene side chain, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140416 |