CN105859729B - A kind of porphyrin organic molecule cathode interface material and preparation method thereof - Google Patents
A kind of porphyrin organic molecule cathode interface material and preparation method thereof Download PDFInfo
- Publication number
- CN105859729B CN105859729B CN201610281315.7A CN201610281315A CN105859729B CN 105859729 B CN105859729 B CN 105859729B CN 201610281315 A CN201610281315 A CN 201610281315A CN 105859729 B CN105859729 B CN 105859729B
- Authority
- CN
- China
- Prior art keywords
- bis
- organic molecule
- porphyrin
- cathode interface
- mole
- 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.)
- Expired - Fee Related
Links
- UOIWOHLIGKIYFE-UHFFFAOYSA-N CCCCCNC Chemical compound CCCCCNC UOIWOHLIGKIYFE-UHFFFAOYSA-N 0.000 description 1
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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- 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
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
-
- 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)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a kind of porphyrin organic molecule cathode interface materials, using porphyrin ring as core, connect a group respectively in four bit positions of porphyrin ring, two of which is the conjugate unit with polar group, and two are aromatic substituent group.The invention also discloses the preparation methods of above-mentioned porphyrin organic molecule cathode interface material, using pyrroles as initial reaction raw materials, by a series of reaction, it is coupled from the different conjugate units with polar group to obtain porphyrin organic molecule cathode interface material finally by palladium chtalyst.Compared with prior art, porphyrin organic molecule cathode interface material of the invention improves π pi accumulations of the material between molecule under film-forming state, and then improves electronic transmission performance；The solubility property of material in methyl alcohol is improved, using the material of the present invention, the photoelectric conversion efficiency of solar cell can be further improved.
Description
Technical field
The present invention relates to organic photoelectrical material field, more particularly to a kind of porphyrin organic molecule cathode interface material and its
Preparation method.
Background technology
With the development of the social economy, energy-output ratio is increasing, traditional fossil energy increasingly depleted, exploitation can be again
The raw energy has become the important subject of current researcher.Solar energy is a kind of reproducible clean energy resource, has storage
The advantages such as amount is big, distribution is wide, are a huge energy treasure-houses, have become various countries' extensive concern to the utilization of solar energy
Hot spot.Electric energy is converted the solar into using photovoltaic cell become most effective utilize one of technology of solar energy.
The photovoltaic cell of the comparative maturity for the research that initial development is got up is based on inorganic material, although having been commercialized,
Because of its high processing costs, using being limited by very large.In comparison, the organic polymer of solution-processible and small point organic
Sub- materials for solar cells has the characteristics that at low cost, easy processing (such as can spin coating, inkjet printing), and its is light-weight, has
The defects of potential advantage such as large area flexible device is made, inorganic photovoltaic cell can be overcome well, so as to receive extensively
Concern.
Organic photovoltaic battery structure is simpler, i.e., forms light active material folder between electrodes, one of electrode
It is transparent, is conducive to light and is absorbed through electrode by active layer, and then carries out opto-electronic conversion.In order to obtain higher opto-electronic conversion
Efficiency can generally be inserted into a bed boundary material between electrode and active layer, be divided into anodic interface material and cathode interface material,
For cathode interface, most widely used for a long time is the molten polymer material of water/alcohol, such polymer easily forms a film, but
Do not allow to be easily purified, molecular weight distribution is wide, and the product that every batch of is synthesized is had differences and caused too due to molecular weight and its distribution
The efficiency of positive energy battery is usually present difference, and these problems are not present in organic molecule, therefore organic molecule is organic
There are its unique advantages in solar cell.
Porphyrin is to be obtained from the natural products containing porphyrin compound by the methods of extracting and developing, purifying, it
Structure is similar with chlorophyll, has big pi-conjugated system, is conducive to electron-transport, and easily pass through peripheral groups and cavity
The modification of metal changes its physicochemical properties, and Porphyrin and its derivative is because of its molar extinction coefficient height, in photovoltaic device
Active layer can be generally used as.Porphyrin has also been used in cathode interface gradually in recent years, but since it is with structural rigidity etc. one
A little characteristics so that it is difficult to dissolve in polar solvent, there are problems that when as boundary material, later some scientific researches
Worker is modified porphyrin, improves its dissolubility in polar solvent, only drawback is that, up to the present,
Porphyrin material does not play the role of extraordinary modifying interface.
Invention content
In order to overcome the disadvantages mentioned above of the prior art with insufficient, organic small point the purpose of the present invention is to provide a kind of porphyrin
Sub- cathode interface material by modifying porphyrin, makes it have extraordinary dissolubility in polar solvent, effectively increases
The big electronic transmission performance of organic electro-optic device.
Another object of the present invention is to provide a kind of preparation method of porphyrin organic molecule cathode interface material.
The purpose of the present invention is achieved through the following technical solutions：A kind of porphyrin organic molecule cathode interface material, has
Following chemical constitution：
Wherein, A is the conjugate unit with polar group；M is metal ion or protium；Ar is aromatic substituent group；
A is one kind in following structural unit：
Wherein, R is containing the alkyl or oxyalkyl chain with polar group that carbon number is 0 to 20.
The polar group have the following structure in one kind：Amido, diethanol amido, phosphate-based, carboxyl, quaternary ammonium
Salt, carboxylate radical, sulfonate radical, amphoteric ion group.
The M is zinc ion, copper ion, magnesium ion, nickel ion or hydrogen ion.
The Ar has the following structure one kind in unit：
Wherein, R1It is containing the alkyl or alkoxy that carbon number is 0 to 20.
The preparation method of the porphyrin organic molecule cathode interface material, includes the following steps：
It is prepared using Suzuki coupling reactions：The bis- borate porphyrins of 5,10-, bromide are dissolved in Sheng under an argon atmosphere
It in the reaction bulb for having 1,2- dimethoxy-ethanes, adds in four (triphenyl phosphorus) and closes palladium, add in aqueous slkali, heating stirring reaction is cold
But after, target product is extracted with chloroform, is purified by silica gel column chromatography and GPC, is finally spin-dried for solvent, product is done under vacuum
It is dry, obtain porphyrin organic molecule cathode interface material；
3~6 times of mole for the bis- borate porphyrins of 5,10- of the mole of the bromide, 1, the 2- dimethoxies
45~55 times for the bis- borate porphyrins of 5,10- and bromide integral molar quantity of the mole of base ethane, four (triphenyl phosphorus)
The mole for closing palladium is the 8~12% of the bis- borate porphyrin moles of 5,10-.
The preparation method of the porphyrin organic molecule cathode interface material, includes the following steps：
It is prepared using Sonogashira coupling reactions：It is under an argon atmosphere that the bis- ethynyl porphyrins of 5,10-, bromide is molten
Solution adds in four (triphenyl phosphorus) and closes palladium and cuprous iodide, heating stirring reaction is cold in the reaction bulb of toluene and triethylamine is filled
But after, target product is extracted with chloroform, is purified by silica gel column chromatography, be finally spin-dried for solvent, product is dried under vacuum, and obtains
To porphyrin organic molecule cathode interface material；
3~6 times of mole for the bis- ethynyl porphyrins of 5,10- of the mole of the bromide, mole of the toluene
45~55 times for the bis- ethynyl porphyrins of 5,10- and bromide integral molar quantity are measured, the triethylamine is 1/3rd of toluene amount,
The mole that four (triphenyl phosphorus) close palladium is the 8~12% of the bis- ethynyl porphyrins moles of 5,10-, the cuprous iodide
Mole is the 8~12% of the bis- ethynyl porphyrins moles of 5,10-.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) porphyrin organic molecule cathode interface material of the invention is using porphyrin as core, by connecting other conjugated radicles
Group effectively increases the pi-conjugated system and electron transport ability of molecule；Simultaneously by connecting polar group and other side chains,
So that molecule has extraordinary water/alcohol-soluble.
(2) porphyrin organic molecule cathode interface material of the invention in the cavity of porphyrin by introducing different metals
Ion since different metal ions has different outer shell electron distributions and to-electron-withdrawing ability, further adjusts synthesis material
HOMO, the lumo energy of material so that the boundary material can effectively reduce the work content of metal electrode, further improve photovoltaic device
The photoelectric conversion efficiency of part.
(3) porphyrin organic molecule cathode interface material extinction of the invention is relatively narrow, and partially blue, uses interface during the material
With good photopermeability so that sunlight is absorbed to greatest extent by active layer, so as to further improve photovoltaic device
Photoelectric conversion efficiency.
Description of the drawings
Fig. 1 is the uv-visible absorption spectra of the dichloromethane solution of the embodiment of the present invention 1,2.
Fig. 2 is ultraviolet-visible of the porphyrin organic molecule boundary material of the embodiment of the present invention 1,2 under filminess
Absorption spectrum.
Photovoltaic cell prepared by Fig. 3 the embodiment of the present invention 1,2 is in AM 1.5,100mW/cm2Current-voltage under illumination
Curve graph.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
The synthesis of bis- (3,4- bis- (3, the 6- dioxoethyl methyl) benzene) porphyrins of (1) 5,15-
In 500mL three neck round bottom flask, bis- (3, the 6- dioxoethyl methyl) benzaldehydes of 3,4- of addition (1.19g,
3.48mmol), the dichloromethane of dipyrromethane (508mg, 3.48mmol) and 350mL is ventilated 30 minutes with nitrogen, Ran Houjia
Enter the trifluoroacetic acid of 0.035mL, reaction 12 hours is stirred at room temperature, adds 1.18g 2, bis- chloro- 5,6- dicyano -1 of 3-,
4- benzoquinones (DDQ) continues to be stirred to react 12 hours.After reaction, with silica gel/(dichloromethane is eluant, eluent) column chromatography, rotation
Crude product is obtained, then recrystallized with chloroform/methanol after dry, obtain dark red solid.1H NMR (500MHz, CDCl3)：δ 10.30 (s,
2H), 9.38 (d, J=4.6Hz, 4H), 9.11 (d, J=4.6Hz, 4H), 7.87 (t, J=1.7Hz, 2H), 7.79 (d, J=
8.1Hz, 2H), 7.34 (d, J=8.1Hz, 2H), 4.51 (dd, J=5.7,4.5Hz, 4H), 4.40-4.34 (m, 4H), 4.11
(dd, J=5.7,4.5Hz, 4H), 3.99-3.94 (m, 4H), 3.93-3.88 (m, 4H), 3.80-3.74 (m, 4H), 3.72-
3.66 (m, 4H), 3.57-3.51 (m, 4H), 3.49 (s, 6H), 3.29 (s, 6H), -3.10 (s, 2H)
The synthesis of bis- bromo- bis- (3,4- bis- (3, the 6- dioxoethyl methyl) benzene) zinc protoporphyrins of 10,20- of (2) 5,15-
Bis- (3,4- bis- (3, the 6- dioxoethyl methyl) benzene) porphyrins (500mg, 0.54mmol) of 5,15- are dissolved in 250mL
Chloroform in, add in the pyridine of 2.5mL, after being protected from light fully dissolving, then add in bromo-succinimide (NBS) (211mg,
1.19mmol), 0 DEG C react 30 minutes, after at room temperature the reaction was continued overnight, reaction finally is quenched with acetone.Reaction finishes,
Water is added in, is extracted with chloroform, anhydrous sodium sulfate drying is dissolved in the chloroformic solution of 50mL after being spin-dried for solvent, adds in 10mL afterwards
Zinc acetate methanol solution (zinc acetate of 273mg, 1.35mmol are dissolved in the methanol solvate of 10mL), be protected from light reflux 2 hours.
Reaction finishes, washing, and is dried with anhydrous sodium sulfate, is spin-dried for solvent, obtains consolidating for shiny red after purification using silica gel column chromatography
Body.1H NMR (500MHz, CDCl3)：δ 9.69 (d, J=4.5Hz, 4H), 8.95 (d, J=4.5Hz, 4H), 7.68 (d, J=
5.9Hz, 2H), 7.63 (t, J=7.3Hz, 2H), 7.12 (dd, J=11.4,8.0Hz, 2H), 4.24 (d, J=6.0Hz, 4H),
4.10 (d, J=21.8Hz, 4H), 3.76 (t, J=5.0Hz, 4H), 3.70-3.53 (m, 8H), 3.50-3.36 (m, 8H),
3.32-3.16 (m, 10H), 3.07 (d, J=21.6Hz, 6H).
Bis- (3,4- bis- (3, the 6- dioxoethyl methyl) benzene) zinc protoporphyrins of bis- (trimethylsilyl acetylene) -10, the 20- of (3) 5,15-
Synthesis
In two mouthfuls of round-bottomed flasks of 100mL, it is bis- (3,5- bis- (dodecyloxy) benzene) to add in bis- bromo- 10, the 20- of 5,15-
Zinc protoporphyrin (400mg, 0.346mmol), 40mL tetrahydrofurans and 20mL triethylamines, lead to nitrogen 30 minutes, then add in bis- (triphens
Base phosphine) palladium chloride (25mg, 0.036mmol), cuprous iodide (CuI) (7.05mg, 0.036mmol) and trimethylsilyl acetylene
(169mg, 1.73mmol), is protected from light, and reaction three days is stirred at room temperature in reaction.Reaction finishes, and with chloroform extraction, washes,
It is dried with anhydrous sodium sulfate, then with silica gel/(methylene chloride/methanol=30/1 be eluant, eluent) column chromatography, is spin-dried for obtaining green
Solid.1H NMR (500MHz, CDCl3)：δ 9.69 (dd, J=4.6,1.6Hz, 4H), 8.93 (dd, J=4.5,1.5Hz, 4H),
7.70 (dd, J=6.5,2.0Hz, 2H), 7.65 (m, 2H), 7.14 (dd, J=11.5,8.0Hz, 2H), 4.32-4.22 (m,
4H), 4.15 (d, J=22.1Hz, 4H), 3.83 (d, J=6.6Hz, 4H), 3.71 (d, J=29.2Hz, 4H), 3.61-3.64
(m, 4H), 3.53-3.40 (m, 8H), 3.33-3.21 (m, 10H), 3.11 (d, J=20.1Hz, 6H), 0.62 (s, 18H).
The synthesis of bis- (3,4- bis- (3, the 6- dioxoethyl methyl) benzene) zinc protoporphyrins of bis- (acetylene) -10, the 20- of (4) 5,15-
By bis- (3,5- bis- (dodecyloxy) benzene) zinc protoporphyrins of bis- (trimethylsilyl acetylene) -10, the 20- of 5,15- (165mg,
It 0.14mmol) is dissolved in the tetrahydrofuran solution of 20mL, tetrabutyl ammonium fluoride (0.3mL, 1M in THF) is added in, in room temperature
Under be stirred to react 5 minutes, water quenching is added to go out reaction.It is extracted with chloroform, anhydrous sodium sulfate drying is spin-dried for, miscellaneous by gel post separation
Matter is spin-dried for obtaining the solid of green.1H NMR (500MHz, CDCl3)：δ 9.71 (dd, J=4.7,1.2Hz, 4H), 8.96 (dd, J
=4.6,1.1Hz, 4H), 7.73 (t, J=2.6Hz, 2H), 7.67 (dd, J=7.8,2.9Hz, 2H), 7.19 (t, J=7.2Hz,
2H), 4.35 (s, 4H), 4.18 (d, J=9.4Hz, 4H), 3.91 (d, J=9.9Hz, 4H), 3.76 (d, J=31.8Hz, 8H),
3.56 (d, J=26.9Hz, 8H), 3.39-3.31 (m, 12H), 3.16 (d, J=13.5Hz, 6H).
(5) synthesis of bromo- 9, the 9- bis- of 2- (3 '-(N, N- dimethyl amido) propyl) fluorenes
Under the protection of argon gas, 2- bromines fluorenes (2.94g, 12mmol) is dissolved in 60ml dimethyl sulfoxides (DMSO), is added
80mg tetrabutylammonium bromide is subsequently added into 8ml sodium hydroxide solutions (50wt%), after stirring a little while, by 3- (N, N- diformazans
Base) amino-n-propyl chloride hydrochloride (5g, 32mmol) is dissolved in 20mlDMSO, be added drop-wise in the system, after adding at room temperature after
Continuous reaction 6h.50ml water is added in after reaction with the salt in dissolution system, is extracted with ether, successively with sodium hydroxide solution,
Water, saturated common salt water washing, anhydrous magnesium sulfate drying are spin-dried for, and repeated recrystallize obtains white solid, and room temperature is in viscous liquid.1H
NMR (500MHz, DMSO-d6)：δ 7.67-7.63 (m, 1H), 7.54 (d, J=8.1Hz, 1H), 7.48 (d, J=1.8Hz, 1H),
7.44 (dd, J=8.0,1.8Hz, 1H), 7.36-7.28 (m, 3H), 2.08-1.92 (m, 20H), 0.84-0.68 (m, 4H).
Bis- (9,9- bis- (3 '-(N, N- dimethyl amido) propyl) fluorenes -2- acetylene) -10, the 20- of (6) 5,15- are bis-, and (3,4- is bis-
(3,6- dioxoethyl methyl) benzene) zinc protoporphyrin synthesis
Under the protection of argon gas, bis- (acetylene) -10, the 20- bis- (3,4- of 5,15- are added in into two mouthfuls of round-bottomed flasks of 50mL
Bis- (3,6- dioxoethyl methyl) benzene) zinc protoporphyrin (133mg, 0.13mmol), bromo- 9, the 9- bis- of 2- (3 '-(N, N- dimethyl amidos)
Propyl) fluorenes (158mg, 0.38mmol), dry toluene (20mL), triethylamine (10mL), cuprous iodide (2.5mg, 0.01mmol)
With tetrakis triphenylphosphine palladium (14.6mg, 0.01mmol), reaction system is protected from light, and is stirred to react at 80 DEG C three days.Reaction finishes,
It is cooled to room temperature, water is added to quench, extracted with chloroform, washed, anhydrous sodium sulfate drying is spin-dried for, and is crossed silica gel post separation crude product and (is washed
De- agent：Methylene chloride/methanol/triethylamine=10/1/0.5), then with gel permeation chromatography (Gel Permeation
Chromatography, GPC) column chromatography (tetrahydrofuran is eluant, eluent), obtain blackish green solid.Mass(MALDI-TOF)：
Obs.1713.6；Calcd.for C102H120N8O12Zn, 1712.8.
Porphyrin organic molecule boundary material manufactured in the present embodiment is dissolved in dichloromethane, obtained dichloromethane solution
Uv-visible absorption spectra see Fig. 1.
Porphyrin organic molecule boundary material manufactured in the present embodiment is prepared into film, uv-visible absorption spectra
See Fig. 2.
The photovoltaic cell prepared using the porphyrin organic molecule boundary material of the present embodiment is in AM 1.5,100mW/cm2
Current -voltage curve under illumination is shown in Fig. 3, device architecture：ITO/PEDOT：PSS/PTB7：PC71BM/ interfaces/Al.In figure simultaneously
Give no cathode interface layer battery and using typical cathodic boundary material poly [(9,9-bis (3 '-(N, N-
Dimethylamino) propyl) -2,7-fluorene)-alt-2,7- (9,9-dioctylfluorene)] and (PFN) be cathode
The battery of decorative layer, to compare.
Embodiment 2
5,15- bis- (9,9- bis- (3 '-(N, N- dimethyl amido) propyl) fluorenes) -10,20- bis- (3,5- di-tert-butyl-phenyls)
The synthesis of zinc protoporphyrin
Under the protection of argon gas, added in into the single necked round bottom flask of 25mL 5,15- it is bis- (4,4,5,5- tetramethyls -1,3,
2- di (hetero) oxygen pentaborane) bis- (3, the 5- dual-tert-butyl benzene) zinc protoporphyrins (40mg, 0.04mmol) of -10,20-, bromo- 9, the 9- bis- of 2- (3 ' -
(N, N- dimethyl amido) propyl) fluorenes (50mg, 0.12mmol), barium hydroxide octahydrate (27mg, 0.08mmol), four (triphens
Base phosphine) palladium (9.6mg, 0.008mmol), 1, the 2- dimethoxy-ethanes (3mL) and water (0.1mL) just steamed, after freeze-take out
Gas-thawing (freeze-pump-thaw) recycles the oxygen in removing system three times, then is passed through argon gas, is protected from light, and stirred at 90 DEG C
Mix reaction 72 hours.Reaction finishes, and is cooled to room temperature, and water is added to quench, and is extracted with chloroform, washing, anhydrous sodium sulfate drying, rotation
It is dry, cross silica gel post separation crude product (eluant, eluent：Methylene chloride/methanol/triethylamine=100/1/1), then use gel permeation chromatography
(GPC) column chromatography (tetrahydrofuran is eluant, eluent), obtains the solid of aubergine.Mass(MALDI-TOF)：Obs.1417.8；
Calcd.for C94H112N8Zn, 1416.8.
Porphyrin organic molecule boundary material manufactured in the present embodiment is dissolved in dichloromethane, obtained dichloromethane solution
Uv-visible absorption spectra see Fig. 1.
Porphyrin organic molecule boundary material manufactured in the present embodiment is prepared into film, uv-visible absorption spectra
See Fig. 2.
The photovoltaic cell prepared using the porphyrin organic molecule boundary material of the present embodiment is in AM 1.5,100mW/cm2
Current -voltage curve under illumination is shown in Fig. 3, device architecture：ITO/PEDOT：PSS/PTB7：PC71BM/ interfaces/Al.
Embodiment 3
5,15- bis- (9,9- bis- (3 '-(N, N- dimethyl amido) propyl) fluorenes) bis- (3,4- bis- (3,6- dioxy second of -10,20-
Ylmethyl) benzene) zinc protoporphyrin synthesis
Under the protection of argon gas, added in into the single necked round bottom flask of 25mL 5,15- it is bis- (4,4,5,5- tetramethyls -1,3,
2- di (hetero) oxygen pentaborane) bis- (3,4- bis- (3, the 6- dioxoethyl methyl) benzene) zinc protoporphyrins (41mg, 0.04mmol) of -10,20-, 2-
Bromo- 9,9- bis- (3 '-(N, N- dimethyl amido) propyl) fluorenes (50mg, 0.12mmol), barium hydroxide octahydrate (27mg,
0.08mmol), tetrakis triphenylphosphine palladium (9.6mg, 0.008mmol), 1, the 2- dimethoxy-ethanes (3mL) and water just steamed
(0.1mL), after freeze-pump-thaw (freeze-pump-thaw) the cycle oxygen in removing system, then be passed through argon three times
Gas is protected from light, and is stirred to react at 90 DEG C 72 hours.Reaction finishes, and is cooled to room temperature, and water is added to quench, and is extracted with chloroform, water
It washes, anhydrous sodium sulfate drying is spin-dried for, crosses silica gel post separation crude product (eluant, eluent：Methylene chloride/methanol/triethylamine=100/1/
1), then with gel permeation chromatography (Gel Permeation Chromatography, GPC) column chromatography (tetrahydrofuran is elution
Agent), obtain the solid of aubergine.Mass(MALDI-TOF)：Calcd.for C98H120N8O12Zn, 1667.4, Obs.1667.8.
In the following chemical constitution of small molecule boundary material of the present invention：
A can also be other conjugate units, and its polar group for being connected also there are many kinds of, M can also be copper ion, magnesium
Ion, nickel ion etc., Ar can also be the embodiment phase that other aromatic substituent groups, preparation principle and performance are provided with the present invention
It is similar, no longer add to tell about herein.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, letter
Change, should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (4)
1. a kind of porphyrin organic molecule cathode interface material, which is characterized in that there is following chemical constitution：
Wherein, M is zinc ion, copper ion, magnesium ion or nickel ion；
A is following structural unit：
The Ar structures are with lower structure：
Wherein, R1It is containing the alkyl that carbon number is 0 to 20.
2. a kind of porphyrin organic molecule cathode interface material, which is characterized in that there is one kind in following chemical constitution：
3. the preparation method of claim 1~2 any one of them porphyrin organic molecule cathode interface material, feature exist
In including the following steps：
It is prepared using Suzuki coupling reactions：The bis- borate porphyrins of 5,10-, bromide are dissolved in and fill 1 under an argon atmosphere,
It in the reaction bulb of 2- dimethoxy-ethanes, adding in four (triphenyl phosphorus) and closes palladium, add in aqueous slkali, heating stirring is reacted, after cooling,
Target product is extracted with chloroform, is purified by silica gel column chromatography and GPC, is finally spin-dried for solvent, product is dried under vacuum, and obtains
To porphyrin organic molecule cathode interface material；
3~6 times of mole for the bis- borate porphyrins of 5,10- of the mole of the bromide, 1, the 2- dimethoxys second
The mole of alkane is 45~55 times of the bis- borate porphyrins of 5,10- and bromide integral molar quantity, and four (triphenyl phosphorus) close palladium
Mole be the bis- borate porphyrin moles of 5,10- 8~12%.
4. the preparation method of claim 1~2 any one of them porphyrin organic molecule cathode interface material, feature exist
In including the following steps：
It is prepared using Sonogashira coupling reactions：The bis- ethynyl porphyrins of 5,10-, bromide are dissolved under an argon atmosphere
In the reaction bulb for filling toluene and triethylamine, add in four (triphenyl phosphorus) and close palladium and cuprous iodide, heating stirring reaction, cooling
Afterwards, target product is extracted with chloroform, is purified by silica gel column chromatography, be finally spin-dried for solvent, product is dried under vacuum, and obtains
Porphyrin organic molecule cathode interface material；
The mole of the bromide is 3~6 times of the mole of the bis- ethynyl porphyrins of 5,10-, and the mole of the toluene is
45~55 times of 5,10- bis- ethynyl porphyrins and bromide integral molar quantity, the triethylamine is 1/3rd of toluene amount, described
The mole that four (triphenyl phosphorus) close palladium is the 8~12% of the bis- ethynyl porphyrins moles of 5,10-, mole of the cuprous iodide
Measure 8~12% for the bis- ethynyl porphyrins moles of 5,10-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610281315.7A CN105859729B (en) | 2016-04-28 | 2016-04-28 | A kind of porphyrin organic molecule cathode interface material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610281315.7A CN105859729B (en) | 2016-04-28 | 2016-04-28 | A kind of porphyrin organic molecule cathode interface material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105859729A CN105859729A (en) | 2016-08-17 |
| CN105859729B true CN105859729B (en) | 2018-06-19 |
Family
ID=56629900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610281315.7A Expired - Fee Related CN105859729B (en) | 2016-04-28 | 2016-04-28 | A kind of porphyrin organic molecule cathode interface material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105859729B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107805254B (en) * | 2017-09-18 | 2020-08-18 | 华南理工大学 | Porphyrin micromolecular perovskite cathode buffer layer material and preparation method and application thereof |
| CN109939735B (en) * | 2017-12-20 | 2022-02-18 | 湖南科技大学 | Phase transfer catalyst and synthesis method thereof |
| CN108516978B (en) * | 2018-04-04 | 2020-01-14 | 华南理工大学 | Asymmetric porphyrin organic micromolecule cathode interface material and preparation method and application thereof |
| CN110993797B (en) * | 2019-12-20 | 2022-06-21 | 储天新能源科技（长春）有限公司 | Non-lead double perovskite solar cell and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4561069B2 (en) * | 2003-09-10 | 2010-10-13 | ソニー株式会社 | Method for manufacturing photoelectric conversion element and method for manufacturing electronic device |
| JP4752269B2 (en) * | 2004-12-28 | 2011-08-17 | ソニー株式会社 | Porphyrin compound and method for producing the same, organic semiconductor film, and semiconductor device |
| US7501508B2 (en) * | 2005-07-29 | 2009-03-10 | North Caroline State University | Methods and intermediates for the synthesis of porphyrins |
| CN103588960A (en) * | 2013-10-29 | 2014-02-19 | 南京邮电大学 | Non-labeled ionic conjugated polyelectrolyte, synthetic method thereof and application to biological detection |
| CN103724355A (en) * | 2013-12-10 | 2014-04-16 | 华南理工大学 | Porphyrin organic small molecular photovoltaic material and preparation method thereof |
-
2016
- 2016-04-28 CN CN201610281315.7A patent/CN105859729B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105859729A (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105859729B (en) | A kind of porphyrin organic molecule cathode interface material and preparation method thereof | |
| CN105017264B (en) | A kind of organic molecule photoelectric functional material and preparation method thereof | |
| CN103724355A (en) | Porphyrin organic small molecular photovoltaic material and preparation method thereof | |
| CN101525334B (en) | Organic solar cell material and preparation thereof | |
| CN107286178B (en) | A kind of gear type heterocycle trimerization imide compound and its preparation method and application | |
| CN103547582B (en) | For the compound containing fused thiophene ring and the polymkeric substance thereof of electronic application | |
| CN107383080A (en) | A kind of asymmetrical porphyrin organic molecule photovoltaic material and preparation method and application | |
| CN105753851B (en) | Tetrafluoride Benzoquinoxalines compound and tetrafluoride Benzoquinoxalines based polyalcohol and its preparation method and application | |
| CN104744675B (en) | Conjugated polymer and its application containing 6H-pyrrolo- [3,4-f] BTA-5,7-diketone | |
| CN108658994A (en) | A kind of porphyrin organic molecule acceptor material and the preparation method and application thereof | |
| CN107814807A (en) | A kind of organic semiconducting materials containing porphyrin being applied in photoelectric device and preparation method thereof | |
| Qian et al. | Stabilization of the film morphology in polymer: Fullerene heterojunction solar cells with photocrosslinkable bromine‐functionalized low‐bandgap copolymers | |
| Qiu et al. | An asymmetric small molecule based on thieno [2, 3-f] benzofuran for efficient organic solar cells | |
| Gu et al. | Synthesis and characterization of a novel solid–solid phase change luminescence material | |
| CN107805254A (en) | A kind of porphyrin small molecule perovskite cathode cushioning layer material and preparation method and application | |
| CN105914298B (en) | Using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer | |
| CN107311975A (en) | A kind of derivative of dibenzothiophenes and its application | |
| Liu et al. | Sulfur-rich benzodithieno [3, 2-b] thiophene-cored hole transporting materials for long-time stability of perovskite solar cells | |
| CN107674183B (en) | Containing naphthalene [1,2-c；5,6-c] two [1,2,5] thiadiazoles conjugated polymer and preparation method and application | |
| CN109535420A (en) | A kind of dark red smooth high molecular material of thermal activation delayed fluorescence and preparation method thereof | |
| CN108516978A (en) | A kind of asymmetrical porphyrin organic molecule cathode interface material and its preparation method and application | |
| CN108659002A (en) | The conjugation small molecule electron-acceptor material and preparation method thereof in active layer is blended in polymer solar battery | |
| CN106700039A (en) | FPP (fluoropyridine [3,4-b] pyrazine) compound, fPP-based copolymer material and application of fPP-based copolymer material | |
| CN106750193A (en) | Even tripyrrole and pyrroledione polymer and its synthetic method and application | |
| KR101374070B1 (en) | Triphenylamine derivatives and organic photovoltaic cell comprising the derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180619 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |