CN102453233B - Organic semiconductor material containing metalloporphyrin-triphenylamine and preparation method and application thereof - Google Patents
Organic semiconductor material containing metalloporphyrin-triphenylamine and preparation method and application thereof Download PDFInfo
- Publication number
- CN102453233B CN102453233B CN 201010523782 CN201010523782A CN102453233B CN 102453233 B CN102453233 B CN 102453233B CN 201010523782 CN201010523782 CN 201010523782 CN 201010523782 A CN201010523782 A CN 201010523782A CN 102453233 B CN102453233 B CN 102453233B
- Authority
- CN
- China
- Prior art keywords
- benzene
- triphenylamine
- organic
- porphyrin
- semiconductor material
- 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.)
- Active
Links
- 0 CCCCCCCC[Si]1(*)c2cc(C([C@@]3NC(C=C4N=C5C=C4)=CC3)=C(C=C3)N=C3C=C(C=C3)NC3=C5c(cc3)cc4c3-c(cccc3)c3[Si]4(*)CCCCCCCC)ccc2-c2ccccc12 Chemical compound CCCCCCCC[Si]1(*)c2cc(C([C@@]3NC(C=C4N=C5C=C4)=CC3)=C(C=C3)N=C3C=C(C=C3)NC3=C5c(cc3)cc4c3-c(cccc3)c3[Si]4(*)CCCCCCCC)ccc2-c2ccccc12 0.000 description 5
Images
Classifications
-
- 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
Abstract
The invention belongs to the field of optoelectronic materials and discloses an organic semiconductor material containing metalloporphyrin-triphenylamine and a preparation method and application thereof. The organic semiconductor material containing metalloporphyrin-triphenylamine has a structural formula (I) shown in the specification, wherein in the formula, n is an integer from 1 to 100; R1, R2, R3 and R4 are H, C1-C32 alkyl, phenyl and alkylbenzene or alkoxy benzene containing one or more C1-C32; and M is a metal ion. The organic semiconductor material containing metalloporphyrin-triphenylamine has a wide light absorption range, thus improving the sunlight use ratio of the material. The material also has better heat stability and environmental stability. Besides, the preparation method is simple in process and easy to operate and control.
Description
Technical field
The present invention relates to a kind of organic semiconductor material, relate to a kind of containing metal porphyrin-triphenylamine organic semiconductor material more specifically.
The invention still further relates to preparation method and the application thereof of containing metal porphyrin-triphenylamine organic semiconductor material.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is research focus and the difficult point in photovoltaic field always.Be used for the silicon wafer battery on ground at present owing to complex manufacturing, cost height, its application is restricted.In order to reduce the battery cost, expand range of application, people are seeking novel solar cell material always for a long time.Organic semiconductor material with its raw material be easy to get, cheap, preparation technology is simple, environmental stability good, have good advantages such as photovoltaic effect to receive much concern.Go up report conjugated polymers and C from N.S.Sariciftci in 1992 etc. at SCIENCE (N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474)
60Between photoinduction transfer transport phenomenon after, people have dropped into big quantity research aspect polymer solar battery, and have obtained development at full speed, but still much lower than the efficiency of conversion of inorganic solar cell.The main restricting factor that limiting performance improves has: the spectral response of organic semiconductor material and solar radiation spectrum do not match, the electrode collection effciency of the carrier mobility that organic semiconductor is relatively low and lower current carrier etc.In order to make polymer solar battery obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
The porphyrin molecule is the general name that is connected with a substituent class macrocylc compound at porphin ring, and porphines is the big ring delocalized of the two dimensional structure conjugated system that is replaced by the Dan Shuanjian that four pyrrole rings and four methyne bridgings get up.The quantum yield of their charge transfer and energy transfer reaction is higher, has good electron resiliency and photoelectric magnetic property, good hard and soft property and better thermostability and environmental stability.Therefore, porphyrin class organic semiconductor material is the up-and-coming material of a class, and its application in the photovoltaic field has obtained broad research.Metal and some non-metallic elements nearly all in the periodic table of elements can form title complex with the porphyrin effect.In these compounds, comprised most main group and subgroup metallic element, some lanthanide series metals (Pr, Eu, Yb etc.) also oneself warp are synthetic.Because porphyrin is the big rail system altogether with 18 πDian Zis, the electronics flowability is very good in its ring, and therefore, most of containing metal porphyrin compounds have photoelectric property preferably.
The triphenylamine compounds is because having the good optical performance and the p-type carrier transmission performance is widely used fields such as organic photoelectric.Have the hole mobile material of specific HOMO energy level or introduce on the current material basis to/electron-withdrawing group by design and change effective coupling that the HOMO energy level can be realized transport material and charge generating material.The triphenylamine compounds can form amine ion free radical under electric field action, have higher hole mobility.Introduce the solvability that alkyl, alkoxyl group or other substituting groups can improve the triphenylamine compounds, make things convenient for film forming, reduce the device preparation cost.In addition, because the steric interaction between the phenyl ring, triphenylamine presents nonplanar geometric configuration, and the sterie configuration of triphenylamine and derivative thereof is between plane configuration and isotropic tetrahedral configuration.This accurate three-dimensional steric configuration can stop intermolecular pi accumulation closely, and then has reduced the possibility of this analog derivative formation crystal.Therefore, the triphenylamine compounds with its give the higher hole mobility of electronics, lower ionization potential preferably, solvability and amorphous film-forming and light stability become one of focus of research preferably.
In recent years, siliceous conjugated polymers also is subjected to increasing attention in the research of photoelectric functional material.On the one hand be because Siliciumatom is attached in traditional conjugated polymers based on carbon hydrogen nitrogen sulfur with the chemical bond form, can significantly change electronic structure and the molecularity of polymkeric substance, thus the photoelectric properties of regulation and control polymkeric substance; On the other hand, silicon is a kind of inorganic functional material that is widely used in industry such as hyundai electronics electrical equipment, and siliceous conjugated polymers has very high research and development as a kind of hybrid inorganic-organic materials and is worth.The silicon fluorenes is good photoelectricity group, has good thermostability, and lower minimum not occupied orbital (LUMO) and higher triplet, thereby have higher electron affinity and higher electronics injection and transmittability, and can be used as material of main part.
Yet the organic semiconductor material that contains the containing metal porphyrin-triphenylamine of silicon fluorenes does not still have document and patent report so far, and this has just limited the range of application of organic semiconductor material greatly.。
Summary of the invention
The object of the present invention is to provide a kind of containing metal porphyrin-triphenylamine organic semiconductor material, it can address the above problem.
The present invention also aims to provide preparation method and the application thereof of this containing metal porphyrin-triphenylamine organic semiconductor material.
Containing metal porphyrin-triphenylamine organic semiconductor material involved in the present invention has following structure (I):
In the formula: n is the integer between 1-100, R
1, R
2, R
3, R
4Be H identical or inequality, C
1-C
32Alkyl, phenyl, contain one or more C identical or inequality
1-C
32Alkylbenzene or alkoxy benzene; M is metal ion, can but be not limited to Zn
2+, Cu
2+, Fe
2+, Co
2+, Cd
2+, Pt
2+, Zr
2+, Mn
2+, Ni
2+, Pb
2+, Sn
2+Deng metal ion.
Containing metal porphyrin of the present invention-triphenylamine organic semiconductor material is to adopt following steps to make:
Step S1, dibromo triphenylamine (Y) is joined in first organic solvent, be cooled to-78 ℃ with liquid nitrogen/Virahol, drip n-Butyl Lithium (n-BuLi, down with), then in-78 ℃ of reaction 0.5-5h, property adding 2-isopropoxy-4,4 again, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (X) react 0.5-5h down at-78 ℃, naturally be warming up to room temperature then, behind the reaction 1-48h, obtain 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) triphenylamine (G); Reaction formula is as follows:
Step S2, with two pyrroles's methane (A), the first silicon fluorene derivatives (B) and the second silicon fluorene derivatives (C) in molar ratio i: j: k be dissolved in second organic solvent that contains oxygenant and first catalyzer, and under 20-100 ℃, reacted 1-24 hour, obtain silicon fluorenes derivatives of porphyrin (D), wherein, i: j: k=1: 1～100: 1～100, and i=j+k, i 〉=j＞0; Reaction formula is as follows:
In the formula, R
1, R
2, R
3, R
4Be H identical or inequality, C
1-C
32Alkyl, phenyl, contain one or more C
1-C
32Alkylbenzene or alkoxy benzene;
Step S3, the silicon fluorenes derivatives of porphyrin (D) that obtains among the step S1 and bromizating agent were added in the 3rd organic solvent in 1: 2 in molar ratio～1: 5, in 0～120 ℃ of reaction 1～72 hour down, obtain dibromo silicon fluorenes derivatives of porphyrin (E); Reaction formula is as follows:
Step S4, the dibromo silicon fluorenes derivatives of porphyrin (E) that obtains among the step S2 is dissolved in the 4th organic solvent, then add and contain the M metal ion solution, stirred 0.5-24 hour down in 0-30 ℃, obtain dibromo silicon fluorenes metalloporphyrin containing metal derivatives of porphyrin (F), wherein, the mol ratio of described dibromo silicon fluorenes derivatives of porphyrin (E) and M metal ion is 1: 1～1: 5; Reaction formula is as follows:
In step S5, the oxygen-free environment, with obtain among the dibromo silicon fluorenes metal porphyrin derivative (F) that obtains among the step S3 and the step S1 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) triphenylamine (G) was dissolved in the 5th organic solvent that contains second catalyzer in 1: 2 in molar ratio～2: 1, carried out the Suzuki coupling reaction 12～72 hours under 50-120 ℃, obtained described containing metal porphyrin-triphenylamine organic semiconductor material (I); Reaction formula is as follows:
In the formula, n is the integer between 1-100.
Above-mentioned containing metal porphyrin-triphenylamine organic semiconductor material can be widely used in organic solar batteries, organic electroluminescent, and organic field effect tube, organic optical storage is in the fields such as organic non-linear device and organic laser apparatus.
The organic semiconductor material of the containing metal porphyrin-triphenylamine of the siliceous fluorenes of the present invention's exploitation, such material is by introducing the silicon fluorene group to the porphyrin framework, and the coordination by metal ion, adjusted the band gap of porphyrin polymer, and then the better stability of acquisition and good film-forming properties, widened the visible spectrum absorption region, make its absorption region extend to the near-infrared region, improve it to the utilization ratio of sunlight, improve carrier mobility simultaneously, enlarged them in the range of application in fields such as organic solar batteries.
Compared with prior art, the present invention has following advantage:
1. the silicon fluorenes unit that contains in the organic semiconductor material molecule among the present invention has good thermostability, and higher electron affinity and higher electronics injection and transmittability;
2. also contain the porphyrin unit simultaneously, have the big ring delocalized conjugated system of two dimensional structure, the quantum yield of charge transfer and energy transfer reaction is higher, has good hard and soft property and better thermostability and environmental stability.
3. also contain triphenylamine units simultaneously, have good optical performance and p-type carrier transmission performance, and give electronics, lower ionization potential and solvability preferably preferably.
4. organic semiconductor material of the present invention is owing to comprised silicon fluorene structural units, porphyrin unit and triphenylamine units simultaneously, taken into account their performance advantage, and expanded the absorption region of this organic semiconductor material to sunlight, increased the matching degree with solar radiation spectrum, thus effectively expanded this organic semiconductor material at polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device or/and the application in the organic laser apparatus;
5. the preparation technology of described organic semiconductor material is simple, is easy to operate and control.
Description of drawings
Fig. 1 is with the structural representation of the organic semiconductor material among the present invention as the organic solar batteries device of active coating.
Fig. 2 is with the structural representation of the organic semiconductor material among the present invention as the organic electroluminescence device of luminescent layer.
Fig. 3 is with the structural representation of the organic semiconductor material among the present invention as the organic field effect tube device of organic semiconductor layer.
Embodiment
Containing metal porphyrin-triphenylamine organic semiconductor material involved in the present invention has following structure (I):
In the formula: n is the integer between 1-100, R
1, R
2, R
3, R
4Be H identical or inequality, C
1-C
32Alkyl, phenyl, contain one or more C identical or inequality
1-C
32Alkylbenzene or alkoxy benzene; M is metal ion, can but be not limited to Zn
2+, Gu
2+, Fe
2+, Co
2+, Cd
2+, Pt
2+, Zr
2+, Mn
2+, Ni
2+, Pb
2+, Sn
2+Deng metal ion.
The preparation method of containing metal porphyrin-triphenylamine organic semiconductor material that the present invention is designed, step is as follows: step S1, dibromo triphenylamine (Y) is joined in first organic solvent, be cooled to-78 ℃ with liquid nitrogen/Virahol, drip n-BuLi, then at-78 ℃ of reaction 0.5-5h, property adding 2-isopropoxy-4,4 again, 5,5-tetramethyl--1, the assorted oxygen pentaboranes (X) of 3,2-two (its mole dosage is 2～4 times of molar weight of dibromo triphenylamine (Y)) perhaps for structural formula are
Two tetramethyl ethylene ketones close two boron), at-78 ℃ of following reaction 0.5-5h, be warming up to room temperature then naturally, (4,4,5,5-tetramethyl--1,3,2-two the mix oxygen pentaboranes) triphenylamine (G) that behind the reaction 1-48h, obtains 4,4 '-two; Wherein, first organic solvent is at least a in anhydrous tetrahydro furan, ether or the dioxane, and reaction formula is as follows:
Step S2, with two pyrroles's methane (A), the first silicon fluorene derivatives (B) and the second silicon fluorene derivatives (C) in molar ratio i: j: k be dissolved in second organic solvent that contains oxygenant and first catalyzer, and under 20-100 ℃, reacted 1-24 hour, obtain silicon fluorenes derivatives of porphyrin (D), wherein, i: j: k=1: 1～100: 1～100, and i=j+k, i 〉=j＞0; Wherein, first catalyzer is at least a in propionic acid or the trifluoroacetic acid; Second organic solvent is one or both in trichloromethane, the methylene dichloride; Reaction formula is as follows:
In the formula, R
1, R
2, R
3, R
4Be H identical or inequality, C
1-C
32Alkyl, phenyl, contain one or more C
1-C
32Alkylbenzene or alkoxy benzene;
Step S3, with the silicon fluorenes derivatives of porphyrin (D) and the bromizating agent that obtain among the step S2, as N-bromo-succinimide (NBS, added in 1: 2 in molar ratio～1: 5 in the 3rd organic solvent down together), reacted 1～72 hour down in 0～120 ℃, obtain dibromo silicon fluorenes derivatives of porphyrin (E); The 3rd organic solvent is at least a in tetrahydrofuran (THF), chloroform, dimethylformamide or the orthodichlorobenzene; Reaction formula is as follows:
Step S4, the dibromo silicon fluorenes derivatives of porphyrin (E) that obtains among the step S3 is dissolved in the 4th organic solvent, then add and contain the M metal ion solution, stirred 0.5-24 hour down in 0-30 ℃, obtain dibromo silicon fluorenes metal porphyrin derivative (F), wherein, the mol ratio of described dibromo silicon fluorenes derivatives of porphyrin (E) and M metal ion is 1: 1～1: 5; The 4th organic solvent is at least a in trichloromethane, tetrahydrofuran (THF), benzene, toluene or the methylene dichloride; Described containing in the M metal ion solution, the M metal ion that contains in the M metal ion solution is selected from Zn
2+, Cu
2+, Fe
2+, Co
2+, Cd
2+, Pt
2+, Zr
2+, Mn
2+, Ni
2+, Pb
2+Or Sn
2+In a kind of, contain solvent in the M metal ion solution and be at least a in methyl alcohol, ethanol or the water; Reaction formula is as follows:
(its oxygen-free atmosphere is nitrogen atmosphere for step S5, oxygen-free environment, also can be other inert gas atmospheres, at this not to its restriction) in, with obtain among the dibromo silicon fluorenes metal porphyrin derivative (F) that obtains among the step S4 and the step S1 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) triphenylamine (G) was dissolved in the 5th organic solvent that contains second catalyzer in 1: 2 in molar ratio～2: 1, carried out the Suzuki coupling reaction 12～72 hours under 50-120 ℃, obtained described containing metal porphyrin-triphenylamine organic semiconductor material (I); Wherein, second catalyzer is that organic palladium or organic palladium are (as, Pd
2(dba)
3, Pd (PPh
3)
4, Pd (OAc)
2Or Pd (PPh
3)
2Cl
2) and organophosphor ligand (as, P (o-Tol)
3, tricyclohexyl phosphine) mixture; The mole dosage of described second catalyzer is the 0.01%-20% of 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) triphenylamine (G) mole dosage; The 5th organic solvent is at least a in tetrahydrofuran (THF), methylene dichloride, chloroform, dioxane, dimethylformamide, glycol dimethyl ether, dimethyl sulfoxide (DMSO), benzene, chlorobenzene or the toluene; Reaction formula is as follows:
In the formula, n is the integer between 1-100.
2-bromo-9-replaces the silicon fluorenes and makes (reference: Macromolecules 2002 by 2-bromine silicon fluorenes and corresponding bromide under the catalyst/solvent condition, 35,3474), 2-aldehyde-9-replaces the silicon fluorenes and makes (reference: Macromolecules 2006 by 2-bromo-9-replacement silicon fluorenes in n-Butyl Lithium/dimethyl formamide/tetrahydrofuran (THF) system, 39,456), two pyrroles's methane make (reference: Tetrahedron 1994 by formaldehyde and pyrroles under catalyst action, 39,11427).
Above-mentioned containing metal porphyrin-triphenylamine organic semiconductor material can be widely used in organic solar batteries, organic electroluminescent, and organic field effect tube, organic optical storage is in the fields such as organic non-linear device and organic laser apparatus.
The organic semiconductor material of the silicon fluorenes containing metal porphyrin-triphenylamine of the present invention's exploitation, such material is by introducing the silicon fluorene group to the porphyrin framework, and the coordination by metal ion, adjusted the band gap of porphyrin polymer, and then the better stability of acquisition and good film-forming properties, widened the visible spectrum absorption region, make its absorption region extend to the near-infrared region, improve it to the utilization ratio of sunlight, improve carrier mobility simultaneously, enlarged them in the range of application in fields such as organic solar batteries.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
Present embodiment disclose a kind of structure following 10,20-two (9 ', 9 '-dioctyl) silicon fluorenes zinc protoporphyrin-triphenylamine organic semiconductor material (n=40):
Above-mentioned organic semiconductor material preparation process is as follows:
One, synthesizing of 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) triphenylamines
Under protection of nitrogen gas, in there-necked flask, add to 44 '-dibromo triphenylamine (8.0g; 0.02mol), the tetrahydrofuran solvent of adding 150ml slowly injects n-Butyl Lithium (16.8mL with syringe again under-78 ℃ of conditions; 2.5M, 0.04mol), continue stirring reaction 2h; under-78 ℃ of conditions, inject 2-isopropoxy-4,4,5 with syringe; 5-tetramethyl--1,3,2-two assorted oxygen pentaborane (8.7mL; 0.04mol), stir under the room temperature and spend the night.Add saturated sodium-chloride water solution (30ml) termination reaction, use chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve steaming and fall solvent.At last crude product is separated for leacheate carries out silica gel column chromatography with petrol ether/ethyl acetate (15/1), obtain product 9.1g, productive rate 92%.GC-MS(EI-m/z)：497(M
+)
Two, 5,15-two (9 ', 9 '-dioctyl) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9, (0.44g is 1mmol) with two pyrroles's methane (0.15g for 9-dioctyl silicon fluorenes, 1mmol), be dissolved in the 250ml methylene dichloride, feed nitrogen 30min, syringe adds propionic acid 1ml, 20 ℃ are stirred 24h down, (0.91g 4mmol), continues at room temperature to stir 30min to add DDQ (DDQ) then, add 1ml triethylamine cancellation reaction then, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, to product 0.49g, productive rate is about 88% with ether/recrystallizing methanol.GC-MS(EI-m/z)：1120(M
+)
Three, 5,15-two bromo-10,20-two (9 ', 9 '-dioctyl) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing 10,20-two (9 ', 9 '-dioctyl) (0.23g 0.2mmol) is dissolved in the 80ml chloroform silicon fluorenes porphyrin, adds the 1ml pyridine, reactant is dropped to 0 ℃, and adding N-bromo-succinimide (0.07g, 0.4mmol), after stirring 72h, mixture returns to room temperature, continues to stir 4h then, add 5ml acetone termination reaction, desolventizing is carried out recrystallization with ether/methyl alcohol and is obtained product 0.22g, productive rate 86%.GC-MS(EI-m/z)：1278(M
+)
Four, 5,15-two bromo-10,20-two (9 ', 9 '-dioctyl) silicon fluorenes zinc protoporphyrin synthetic
Take by weighing intermediate 5,15-two bromo-10,20-two (9,9-dioctyl fluorene) porphyrin (0.25g, 0.2mmol) be dissolved in the 50ml methylene dichloride, add contain zinc acetate (0.11g, methanol solution 0.5mmol) (5ml) stirs 5h under the room temperature, be spin-dried for solvent, use methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collect and be spin-dried for solvent and obtain product 0.25g, productive rate 95%.GC-MS(EI-m/z)：1340(M
+)
Five, 10, synthetic (n=40) of 20-two (9 ', 9 '-dioctyl) silicon fluorenes zinc protoporphyrin-triphenylamine organic semiconductor material
Under nitrogen protection, add 4,4 '-two (4; 4,5,5-tetramethyl--1; the assorted oxygen pentaboranes of 3,2-two) basic triphenylamine (0.10g, 0.2mmol), 5; 15-two bromo-10; (0.27g is 0.2mmol) with toluene solvant 50ml for 20-two (9 ', 9 '-dioctyl) silicon fluorenes zinc protoporphyrin; vacuumize deoxygenation and charge into nitrogen, add 5mg Pd (PPh then
3)
2Cl
2With 2mlNaHCO
3(50%) solution is heated to 100 ℃ of reaction 56h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 300ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product 0.21g, and productive rate 74%.Molecular weight (GPC, THF, R.I): Mn=56900, Mw/Mn=3.44; )
Embodiment 2
Present embodiment discloses the following 10-of a kind of structure (9 '-methyl-9 '-hexadecyl) silicon fluorenes-20-(9 '-dotriacontyl) silicon fluorenes iron porphyrin-triphenylamine organic semiconductor material (n=56)
Above-mentioned organic semiconductor material preparation process is as follows:
One, synthesizing of 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic triphenylamines
Its preparation sees embodiment 1. for details
Two, 5-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-15-(9 '-dotriacontyl) silicon fluorenes porphyrin is synthetic
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9-methyl-9-hexadecyl silicon fluorenes (0.45g, 1mmol), 2-aldehyde-9-dotriacontyl silicon fluorenes (0.66g, 1mmol), two pyrroles's methane (0.30g, 2mmol), be dissolved in the 250ml methylene dichloride, feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml, 100 ℃ are stirred 1h down, (1.8g 8mmol), continues at room temperature to stir 30min to add DDQ (DDQ) then, add 2ml pyridine cancellation reaction then, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, to product 1.1g, productive rate is about 78% with ether/recrystallizing methanol.GC-MS(EI-m/z)：1359(M
+)
Three, 5,15-two bromo-10-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-20-(9 '-dotriacontyl) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, (0.27g 0.2mmol) is dissolved in the 80ml chloroform to take by weighing 5-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-15-(9 '-dotriacontyl) silicon fluorenes porphyrin, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide (0.07g, 0.4mmol), after stirring 0.5h, mixture is warming up to 120 ℃, after continuing then to stir 1h, add 5ml acetone termination reaction, desolventizing is carried out recrystallization with ether/methyl alcohol and is obtained product 0.24g, productive rate 79%.GC-MS(EI-m/z)：1516(M
+)
Four, 5,15-two bromo-10-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-20-(9 '-dotriacontyl) silicon fluorenes iron porphyrin synthetic
N
2Under the condition, take by weighing intermediate 5, (0.31g 0.2mmol) is dissolved in the 50ml methylene dichloride 15-two bromo-10-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-20-(9 '-dotriacontyl) silicon fluorenes porphyrin, adds to contain the ferrous (0.12g of chlorination, methanol solution 1mmol) (5ml), stir 8h under the room temperature, be spin-dried for solvent, use methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collect and be spin-dried for solvent and obtain product 0.30g, productive rate 96%.GC-MS(EI-m/z)：1569(M
+)
Five, synthetic (n=56) of 10-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-20-(9 '-dotriacontyl) silicon fluorenes iron porphyrin-triphenylamine organic semiconductor material
Under nitrogen protection, add 4,4 '-two (4; 4; 5,5-tetramethyl--1,3; 2-two assorted oxygen pentaboranes) basic triphenylamine (0.1g; 0.2mmol), 5,15-two bromo-10-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-20-(9 '-dotriacontyl) silicon fluorenes iron porphyrin (0.32g, 0.2mmol) and toluene solvant 120ml; vacuumize deoxygenation and charge into nitrogen, add Pd (OAc) then
2(2.5mg)/tricyclohexyl phosphine (7mg) and 2ml 20% (wt) tetraethyl ammonium hydroxide (Et
4NOH) solution is heated to 120 ℃ of reaction 24h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 200ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product 0.26g, and productive rate 79%.Molecularweight (GPC, THF, R.I): Mn=92500, Mw/Mn=3.76; )
Embodiment 3
Present embodiment disclose a kind of structure following 10,20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) silicon fluorenes copper porphyrin-triphenylamine organic semiconductor material (n=100):
Above-mentioned organic semiconductor material preparation process is as follows:
One, synthesizing of 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic triphenylamines
Its preparation sees embodiment 1. for details
Two, 10,20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9-hexadecyl-9-(3 '-hexadecyl-4 '-n-Hexadecane oxygen base) benzene) silicon fluorenes (2.0g, 2mmol) (0.30g 2mmol), is dissolved in the 300ml methylene dichloride with two pyrroles's methane, feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml, stirs 3h under the room temperature, adds DDQ (DDQ) (1.8g then, 8mmol), continue at room temperature to stir 30min, add 2ml triethylamine cancellation reaction then, concentrated solvent, filter, collect filtrate and be spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, to product 1.9g, productive rate is about 85% with ether/recrystallizing methanol.GC-MS(EI-m/z)：2201(M
+)
Three, 5,15-two bromo-10,20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing 10,20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) silicon fluorenes porphyrin (0.44g, 0.2mmol) be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, adding N-bromo-succinimide (0.07g, 0.4mmol), behind the stirring 0.5h, mixture is warming up to 30 ℃, continue to stir 48h then, add 5ml acetone termination reaction, desolventizing, carry out recrystallization with ether/methyl alcohol and obtain product 0.36g, productive rate 76%.GC-MS(EI-m/z)：2360(M
+)
Four, 5,15-two bromo-10,20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) silicon fluorenes copper porphyrin synthetic
Take by weighing intermediate 5,15-two bromo-10,20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) (0.47g 0.2mmol) is dissolved in the 50ml methylene dichloride silicon fluorenes porphyrin, adds CuSO
45H
2(0.05g, 0.2mmol) solution (5ml) stirs 5h under the room temperature to O, is spin-dried for solvent, uses methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collects and is spin-dried for solvent and obtain product 0.47g, productive rate 97%.GC-MS(EI-m/z)：2416(M
+)
Five, 10,20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) synthetic (n=100) of silicon fluorenes copper porphyrin-triphenylamine organic semiconductor material
Under nitrogen protection, add 4,4 '-two (4; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaboranes of 2-two) basic triphenylamine (0.1g, 0.2mmol), 5,15-two bromo-10; 20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) silicon fluorenes copper porphyrin (0.48g; 0.2mmol) and toluene solvant 100ml, vacuumize deoxygenation and charge into nitrogen, add 10mg Pd (PPh then
3)
2Cl
2With 2ml KHCO
3(30%) solution is heated to 50 ℃ of reaction 72h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 300ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product 0.36g, productive rate 72%.Molecular?weight(GPC，THF，R.I)：Mn＝250400，Mw/Mn＝4.28；)
Embodiment 4
Present embodiment disclose the following 10-of a kind of structure (9 '-to eicosyl benzene-9 '-(3 ", 5 "-two dodecyloxy benzene)) silicon fluorenes-20-(9 '-to n-Hexadecane oxygen base benzene-9 '-decyl benzene) silicon fluorenes cadmium porphyrin-triphenylamine organic semiconductor material (n=10)
Above-mentioned organic semiconductor material preparation process is as follows:
One, synthesizing of 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic triphenylamines
Its preparation sees embodiment 1. for details
Two, 5-(9 '-to eicosyl benzene-9 '-(3 ", 5 "-two dodecyloxy benzene)) silicon fluorenes-15-(9 '-to n-Hexadecane oxygen base benzene-9 '-decyl benzene) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing the eicosyl benzene-9-(3 ' of intermediate 2-aldehyde-9-, 5 '-two dodecyloxy benzene) silicon fluorenes (1.0g, 1mmol), decyl benzene silicon fluorenes (0.74g between the n-Hexadecane oxygen of 2-aldehyde-9-base benzene-9-, 1mmol) (0.30g 2mmol), is dissolved in the 250ml methylene dichloride with two pyrroles's methane, feed nitrogen 30min, syringe adds acetic acid 1ml, and 20 ℃ are stirred 24h down, add DDQ (DDQ) (0.91g then, 4mmol), continue at room temperature to stir 30min, add 1ml triethylamine cancellation reaction then, concentrated solvent, filter, collect filtrate and be spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, to product 1.7g, productive rate is about 84% with ether/recrystallizing methanol.GC-MS(EI-m/z)：2205(M
+)
Three, 5,15-two bromo-10-(9 '-to eicosyl benzene-9 '-(3 ", 5 "-two dodecyloxy benzene)) silicon fluorenes-20-(9 '-to n-Hexadecane oxygen base benzene-9 '-decyl benzene) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing 5,15-two bromo-10-(9 '-to eicosyl benzene-9 '-(3 "; 5 "-two dodecyloxy benzene)) silicon fluorenes-20-(9 '-to n-Hexadecane oxygen base benzene-9 '-decyl benzene) silicon fluorenes porphyrin (0.44g, 0.2mmol) be dissolved in 80ml N, in the dinethylformamide (DMF, down together), reactant is dropped to 0 ℃, adding N-bromo-succinimide (0.07g, 0.4mmol), behind the stirring 72h, mixture returns to room temperature, continue to stir 4h then, add 5ml acetone termination reaction, desolventizing, carry out recrystallization with ether/methyl alcohol and obtain product 0.36g, productive rate 83%.GC-MS(EI-m/z)：2162(M
+)
Four, 5,15-two bromo-10-(9 '-to eicosyl benzene-9 '-(3 ", 5 "-two dodecyloxy benzene)) silicon fluorenes-20-(9 '-to n-Hexadecane oxygen base benzene-9 '-decyl benzene) silicon fluorenes cadmium porphyrin synthetic
Take by weighing intermediate 5,15-two bromo-10-(9 '-to eicosyl benzene-9 '-(3 "; 5 "-two dodecyloxy benzene)) (0.43g 0.2mmol) is dissolved in the 50ml methylene dichloride silicon fluorenes-20-(9 '-to n-Hexadecane oxygen base benzene-9 '-decyl benzene) silicon fluorenes porphyrin, adds Cd (NO
3)
24H
2(0.31g, methanol solution 1mmol) (5ml) stirs 5h under the room temperature to O, is spin-dried for solvent, uses methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collects and is spin-dried for solvent and obtain product 0.43g, productive rate 95%.GC-MS(EI-m/z)：2271(M
+)
Five, 10-(9 '-to eicosyl benzene-9 '-(3 ", 5 "-two dodecyloxy benzene)) synthetic (n=10) of silicon fluorenes-20-(9 '-to n-Hexadecane oxygen base benzene-9 '-decyl benzene) silicon fluorenes cadmium porphyrin-triphenylamine organic semiconductor material
Under nitrogen protection, add 4,4 '-two (4; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaboranes of 2-two) basic triphenylamine (0.1g, 0.2mmol), 5,15-two bromo-10-(9 '-to eicosyl benzene-9 '-(3 "; 5 "-two dodecyloxy benzene)) silicon fluorenes-20-(9 '-to n-Hexadecane oxygen base benzene-9 '-decyl benzene) silicon fluorenes porphyrin (0.45g; 0.2mmol) and dioxane solvent 60ml, vacuumize deoxygenation and charge into nitrogen, add Pd then
2(dba)
3(5mg)/P (o-Tol)
3(8mg) with 15% Na
2CO
3(3ml) solution is heated to 80 ℃ of reaction 36h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product 0.35g, and productive rate 74%.Molecular weight (GPC, THF, R.I): Mn=23500, Mw/Mn=2.93;
Embodiment 5
Present embodiment disclose the following 10-of a kind of structure (9 '-(3 "; 4 ", 5 "-three the last of the ten Heavenly stems alkoxyl group) benzene-9 '-to hexadecyl benzene) silicon fluorenes-20-(9 '-(3 "-dodecyl-5 "-eicosane oxygen base) benzene-9 '-(3 "-dotriacontyl-4 "-laccerane oxygen base) benzene) silicon fluorenes cobalt porphyrin-triphenylamine organic semiconductor material (n=28)
Above-mentioned organic semiconductor material preparation process is as follows:
One, synthesizing of 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic triphenylamines
Its preparation sees embodiment 1. for details
Two, 5-(9 '-(3 ", 4 ", 5 "-three the last of the ten Heavenly stems alkoxyl group) benzene-9 '-to hexadecyl benzene) silicon fluorenes-15-(9 '-(3 "-dodecyl-5 "-eicosane oxygen base) benzene-9 '-(3 "-dotriacontyl-4 "-laccerane oxygen base) benzene) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9-(3 ', 4 ', 5 '-three the last of the ten Heavenly stems alkoxyl group) the hexadecyl benzene of benzene-9-silicon fluorenes (and 1.1g, 1mmol), 2-aldehyde-9-(3 '-dodecyl-5 '-eicosane oxygen base)-9-(3 '-dotriacontyl-4 '-laccerane oxygen base) benzene silicon fluorenes (1.7g, 1mmol), two pyrroles's methane (0.30g, 2mmol), be dissolved in the 250ml methylene dichloride, feed nitrogen 30min, syringe adds propionic acid 2ml, 100 ℃ are stirred 1h down, (1.8g 8mmol), continues at room temperature to stir 30min to add DDQ (DDQ) then, add 2ml pyridine cancellation reaction then, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, to product 2.4g, productive rate is about 79% with ether/recrystallizing methanol.GC-MS(EI-m/z)：3047(M
+)
Three, 5,15-two bromo-10-(9 '-(3 "; 4 ", 5 "-three the last of the ten Heavenly stems alkoxyl group) benzene-9 '-to hexadecyl benzene) silicon fluorenes-20-(9 '-(3 "-dodecyl-5 "-eicosane oxygen base) benzene-9 '-(3 "-dotriacontyl-4 "-laccerane oxygen base) benzene) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing 5-(9 '-(3 "; 4 "; 5 "-three the last of the ten Heavenly stems alkoxyl group) benzene-9 '-to hexadecyl benzene) silicon fluorenes-15-(9 '-(3 "-dodecyl-5 "-eicosane oxygen base) benzene-9 '-(3 "-dotriacontyl-4 "-laccerane oxygen base) benzene) silicon fluorenes porphyrin (0.61g, 0.2mmol) be dissolved in the 40ml tetrahydrofuran (THF), add the 0.5ml triethylamine, reactant is dropped to 0 ℃, add N-bromo-succinimide (0.07g, 0.4mmol), after stirring 0.5h, mixture is warming up to backflow, after continuing then to stir 1h, add 5ml acetone termination reaction, desolventizing is carried out recrystallization with ether/methyl alcohol and is obtained product 0.53g, productive rate 83%.GC-MS(EI-m/z)：3204(M
+)
Four, 5-(9 '-(3 "; 4 ", 5 "-three the last of the ten Heavenly stems alkoxyl group) benzene-9 '-to hexadecyl benzene) silicon fluorenes-15-(9 '-(3 "-dodecyl-5 "-eicosane oxygen base) benzene-9 '-(3 "-dotriacontyl-4 "-laccerane oxygen base) benzene) silicon fluorenes cobalt porphyrin synthetic
Take by weighing intermediate 5-(9 '-(3 "; 4 "; 5 "-three the last of the ten Heavenly stems alkoxyl group) benzene-9 '-to hexadecyl benzene) silicon fluorenes-15-(9 '-(3 "-dodecyl-5 "-eicosane oxygen base) benzene-9 '-(3 "-dotriacontyl-4 "-laccerane oxygen base) benzene) silicon fluorenes porphyrin (0.64g, 0.2mmol) be dissolved in the 50ml methylene dichloride, add CoCl
26H
2(0.12g, 0.5mmol) solution (5ml) stirs 12h under the room temperature to O, is spin-dried for solvent, uses methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collects and is spin-dried for solvent and obtain product 0.63g, productive rate 97%.GC-MS(EI-m/z)：3257(M
+)
Five, 10-(9 '-(3 "; 4 ", 5 "-three the last of the ten Heavenly stems alkoxyl group) benzene-9 '-to hexadecyl benzene) silicon fluorenes-20-(9 '-(3 "-dodecyl-5 "-eicosane oxygen base) benzene-9 '-(3 "-dotriacontyl-4 "-laccerane oxygen base) benzene) synthetic (n=28) of silicon fluorenes cobalt porphyrin-triphenylamine organic semiconductor material
Under nitrogen protection; add 4; 4 '-two (4; 4; 5; 5-tetramethyl--1; the assorted oxygen pentaboranes of 3,2-two) basic triphenylamine (0.1g, 0.2mmol), 5; 15-two bromo-10-(9 '-(3 "; 4 ", 5 "-three the last of the ten Heavenly stems alkoxyl group) benzene-9 '-to hexadecyl benzene) silicon fluorenes-20-(9 '-(3 "-dodecyl-5 "-eicosane oxygen base) benzene-9 '-(3 "-dotriacontyl-4 "-laccerane oxygen base) benzene) silicon fluorenes cobalt porphyrin (0.65g, 0.2mmol) and DMF solvent 80ml; vacuumize deoxygenation and charge into nitrogen, add Pd (OAc) then
2(2.5mg)/tricyclohexyl phosphine (6.5mg) and 2ml 20% (wt) Et
4NOH solution is heated to 80 ℃ of reaction 48h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product 0.51g, and productive rate 76%.Molecular weight (GPC, THF, R.I): Mn=93600, Mw/Mn=3.61;
Embodiment 6
Present embodiment disclose the following 10-of a kind of structure (9 '-hexadecyl-9 '-(3 "-methyl-4 "-laccerane oxygen base) benzene) silicon fluorenes-20-(9 '-(3 ", 5 "-two decyls) benzene-9 '-(3 "-octyl group-4 "-dodecyloxy) benzene) silicon fluorenes tin porphyrin-triphenylamine organic semiconductor material (n=78)
Above-mentioned organic semiconductor material preparation process is as follows:
One, synthesizing of 4,4 '-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic triphenylamines
Its preparation sees embodiment 1. for details
Two, 5-(9 '-hexadecyl-9 '-(3 "-methyl-4 "-laccerane oxygen base) benzene) silicon fluorenes-15-(9 '-(3 ", 5 "-two decyls) benzene-9 '-(3 "-octyl group-4 "-dodecyloxy) benzene) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9-hexadecyl-9-(3 '-methyl-4 '-laccerane oxygen base) benzene silicon fluorenes (1.0g, 1mmol), 2-aldehyde-9-(3 ', 5 '-two decyls) benzene-9-(3 '-octyl group-4 '-dodecyloxy) benzene silicon fluorenes (0.94g, 1mmol), (0.30g 2mmol), is dissolved in the 250ml methylene dichloride two pyrroles's methane, feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml, and 100 ℃ are stirred 1h down, add DDQ (DDQ) (1.8g then, 8mmol), continue at room temperature to stir 30min, add 2ml triethylamine cancellation reaction then, concentrated solvent, filter, collect filtrate and be spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, to product 1.7g, productive rate is about 75% with ether/recrystallizing methanol.GC-MS(EI-m/z)：2179(M
+)
Three, 5,15-two bromo-10-(9 '-hexadecyl-9 '-(3 "-methyl-4 "-laccerane oxygen base) benzene) silicon fluorenes-20-(9 '-(3 ", 5 "-two decyls) benzene-9 '-(3 "-octyl group-4 "-dodecyloxy) benzene) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing 5-(9 '-hexadecyl-9 '-(3 "-methyl-4 "-laccerane oxygen base) benzene) silicon fluorenes-15-(9 '-(3 "; 5 "-two decyls) benzene-9 '-(3 "-octyl group-4 "-dodecyloxy) benzene) silicon fluorenes porphyrin (0.44g, 0.2mmol) be dissolved in the 80ml orthodichlorobenzene, add the 1ml pyridine, reactant is dropped to 0 ℃, adding N-bromo-succinimide (0.07g, 0.4mmol), behind the stirring 0.5h, mixture is warming up to 120 ℃, after continuing then to stir 1h, add 5ml acetone termination reaction, desolventizing, carry out recrystallization with ether/methyl alcohol and obtain product 0.31g, productive rate 86%.GC-MS(EI-m/z)：2337(M
+)
Four, 5,15-two bromo-10-(9 '-hexadecyl-9 '-(3 "-methyl-4 "-laccerane oxygen base) benzene) silicon fluorenes-20-(9 '-(3 ", 5 "-two decyls) benzene-9 '-(3 "-octyl group-4 "-dodecyloxy) benzene) silicon tin porphyrin synthetic
N
2Under the atmosphere, take by weighing intermediate 5,15-two bromo-10-(9 '-hexadecyl-9 '-(3 "-methyl-4 "-laccerane oxygen base) benzene) silicon fluorenes-20-(9 '-(3 "; 5 "-two decyls) benzene-9 '-(3 "-octyl group-4 "-dodecyloxy) benzene) silicon fluorenes porphyrin (0.47g, 0.2mmol) be dissolved in the 50ml methylene dichloride, add and contain SnCl
2(0.11g, ethanolic soln 0.6mmol) (5ml) stirs 24h under the room temperature, is spin-dried for solvent, uses methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collects and is spin-dried for solvent and obtain product 0.25g, productive rate 96%.GC-MS(EI-m/z)：2451(M
+)
Five, 10-(9 '-hexadecyl-9 '-(3 "-methyl-4 "-laccerane oxygen base) benzene) silicon fluorenes-20-(9 '-(3 ", 5 "-two decyls) benzene-9 '-(3 "-octyl group-4 "-dodecyloxy) benzene) synthetic (n=78) of silicon fluorenes tin porphyrin-triphenylamine organic semiconductor material
Under nitrogen protection; add 4; 4 '-two (4; 4; 5; 5-tetramethyl--1; 3; the assorted oxygen pentaboranes of 2-two) basic triphenylamine (0.1g, 0.2mmol), 5,15-two bromo-10-(9 '-hexadecyl-9 '-(3 "-methyl-4 "-laccerane oxygen base) benzene) silicon fluorenes-20-(9 '-(3 "; 5 "-two decyls) benzene-9 '-(3 "-octyl group-4 "-dodecyloxy) benzene) silicon fluorenes tin porphyrin (0.49g; 0.2mmol) and glycol dinitrate ether solvents 80ml, vacuumize deoxygenation and charge into nitrogen, add 10mgPd (PPh then
3)
4With 4ml K
2CO
3(5%) solution is heated to 80 ℃ of reaction 24h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product 0.37g, and productive rate 73%.Molecular weight (GPC, THF, R.I): Mn=197900, Mw/Mn=3.98;
The present invention also provides structural formula to be
(in the formula: n is the integer between 1-100, R
1, R
2, R
3, R
4Be H identical or inequality, C
1-C
32Alkyl, phenyl, contain one or more C
1-C
32Alkylbenzene or alkoxy benzene; M is metal ion, can but be not limited to Zn
2+, Cu
2+, Fe
2+, Co
2+, Cd
2+, Pt
2+, Zr
2+, Mn
2+, Ni
2+, Pb
2+, Sn
2+Deng) containing metal porphyrin-triphenylamine organic semiconductor material at organic solar batteries, organic electroluminescent, organic field effect tube, organic optical storage, Application for Field such as organic non-linear device and organic laser apparatus.
Following examples be containing metal porphyrin-triphenylamine organic semiconductor material at organic solar batteries, organic field effect tube, the application in the organic electroluminescence device.
Embodiment 7
Be the organic solar batteries device of active layer material with the porphyrin of the containing metal among the embodiment 1-triphenylamine organic semiconductor material
A kind of organic solar batteries device, its structure as shown in Figure 1.Wherein, the substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic solar batteries device is: glass 11/ITO layer 12/PEDOT:PSS layer 13/ active coating 14/Al layer 15; Wherein, the material of active coating is mixture, comprises electron donor material, and PCBM is electron acceptor material; Electron donor material is material with the porphyrin of the containing metal among the embodiment 1-triphenylamine organic semiconductor material, and electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate (being called for short PCBM); ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid); Preferred square resistance is the ITO of 10 Ω/mouths.
This organic solar batteries preparation of devices process is: ito glass is through after the ultrasonic cleaning, handle with oxygen-Plasma, being coated with last layer at the ITO layer is the decorative layer of material with PEDOT:PSS, to be coated on the decorative layer after the organic semiconductor material among the present invention and the PCBM dissolving blend then, form active coating, evaporating Al layer on active coating again, obtain solar cell device, at last with after the epoxy encapsulation, place under 110 ℃ of air tight conditions and annealed 1.5 hours, drop to room temperature again, obtain the organic solar batteries device.Because after device was annealed, the chemical structure of material was more regular in order, has improved transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.The thickness of preferred ITO, PEDOT:PSS layer, active coating, A1 layer is respectively 150nm, 40nm, 110nm, 100nm.
Embodiment 8
Be the organic electroluminescence devices of material with the porphyrin of the containing metal among the embodiment 1-triphenylamine organic semiconductor material
A kind of organic electroluminescence device, its structure is as shown in Figure 2; Substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic electroluminescence device is: glass 21/ITO layer 22/ luminescent layer 23/LiF buffer layer 24/Al layer 25; Wherein: luminescent layer is material with the porphyrin of the containing metal among the embodiment 1-triphenylamine organic semiconductor material.
The preparation process of this organic electroluminescence device is:
Tin indium oxide (ITO) layer 22 in that surface deposition one deck square resistance of glass substrate 21 is 10-20 Ω/mouth forms the conductive layer as anode, and thickness is 50-300nm; Preferred square resistance is the ITO of 10 Ω/mouths.
Be the luminescent layer 23 of material at ITO surface preparation one deck with the porphyrin of the containing metal among the embodiment 1-triphenylamine organic semiconductor material by spin coating technique, thickness is about 50-300nm;
Vacuum evaporation LiF on luminescent layer, as buffer layer 14, thickness is about 0.3-2nm;
Vacuum evaporation metallic aluminium on described luminescent layer forms the metal aluminium lamination 25 as negative electrode, obtains described organic electroluminescence device.
Embodiment 9
Be the organic field effect tube of material with containing metal porphyrin-triphenylamine organic semiconductor material of containing among the embodiment 1
A kind of organic field effect tube, its structure is as shown in Figure 3; Substrate in the present embodiment adopts doped silicon wafer (Si) as substrate.
The structure of this organic field effect tube is: the SiO that Si 31/480nm is thick
2Insulation layer 32/ is used for modifying SiO
2Octadecyl trichlorosilane (OTS) layer 33/ organic semiconductor layer 34/ be source electrode (S) 35 and the drain electrode (D) 36 of material with the gold; Wherein, organic semiconductor layer is material with the porphyrin of the containing metal among the embodiment 1-triphenylamine organic semiconductor material; Wherein, source electrode (S) and drain electrode (D) material also can be selected copper material for use.
The preparation process of this organic field effect tube is:
At first, apply the thick SiO of one deck 480nm on a surface cleaning doped silicon wafer 31 later
2Insulation layer 32; Secondly, at described SiO
2Apply the octadecyl trichlorosilane layer 33 that one deck plays modification on the insulation layer, thickness is 10-200nm; Then, spin coating one deck is the organic semiconductor layer 34 of material with the porphyrin of the containing metal among the embodiment 1-triphenylamine organic semiconductor material on described octadecyl trichlorosilane layer, and thickness is about 50-300nm; At last, described organic semiconductor layer be arranged at intervals with the gold but be not limited only to source electrode (S) 35 and the drain electrode (D) 36 that gold is material, obtain described organic field effect tube.
Should be understood that above-mentioned statement at preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (3)
1. containing metal porphyrin-triphenylamine organic semiconductor material with following general formula (I):
In the formula: n is the integer between 1-100, R
1, R
2, R
3, R
4Be H identical or inequality, C
1-C
32Alkyl, phenyl, contain one or more C
1-C
32Alkylbenzene or alkoxy benzene; M is metal ion.
2. containing metal porphyrin according to claim 1-triphenylamine organic semiconductor material is characterized in that, described metal ion is Zn
2+, Cu
2+, Fe
2+, Co
2+, Cd
2+, Pt
2+, Zr
2+, Mn
2+, Ni
2+, Pb
2+, Sn
2+
3. the described containing metal porphyrin of claim 1-triphenylamine organic semiconductor material is at organic solar batteries, organic electroluminescence device, organic field effect tube, organic optical storage, organic non-linear device and organic laser apparatus Application for Field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010523782 CN102453233B (en) | 2010-10-28 | 2010-10-28 | Organic semiconductor material containing metalloporphyrin-triphenylamine and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010523782 CN102453233B (en) | 2010-10-28 | 2010-10-28 | Organic semiconductor material containing metalloporphyrin-triphenylamine and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102453233A CN102453233A (en) | 2012-05-16 |
| CN102453233B true CN102453233B (en) | 2013-10-02 |
Family
ID=46036951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010523782 Active CN102453233B (en) | 2010-10-28 | 2010-10-28 | Organic semiconductor material containing metalloporphyrin-triphenylamine and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102453233B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965448A (en) * | 2013-01-31 | 2014-08-06 | 海洋王照明科技股份有限公司 | Organic semiconductor material, preparation method thereof and electroluminescent device |
| CN111208125B (en) * | 2020-01-21 | 2022-02-22 | 陕西师范大学 | Dual-mode sensor array and application thereof in distinguishing and identifying hydrazine and organic amine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1808739A (en) * | 2006-02-06 | 2006-07-26 | 友达光电股份有限公司 | Organic electroluminescence device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1329955A3 (en) * | 2002-01-18 | 2006-06-14 | E.I. Du Pont De Nemours And Company | Process for forming a multicolor display |
-
2010
- 2010-10-28 CN CN 201010523782 patent/CN102453233B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1808739A (en) * | 2006-02-06 | 2006-07-26 | 友达光电股份有限公司 | Organic electroluminescence device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102453233A (en) | 2012-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102906152B (en) | Polymer containing units of fluorene, anthracene and benzothiadiazole, preparation method and uses thereof | |
| CN101665563B (en) | Donor-acceptor conjugated polymer and application thereof in solar cells | |
| JP5425338B2 (en) | Copolymer containing anthracene and pearselenol, its production method and its application | |
| CN101787020A (en) | Organic conjugated molecule capable of being processed by solution and application thereof in solar cells | |
| CN102344549B (en) | Porphyrin-pyrrolopyrrole copolymer containing carbazole, preparation method thereof and application thereof | |
| CN112375079A (en) | Micromolecular receptor material based on naphthalene diimide unit derivative, preparation method and application | |
| CN109517142B (en) | Star-shaped D-A structure conjugated molecule based on tri-indeno five-membered aromatic heterocycle, and preparation method and application thereof | |
| CN102453229B (en) | Metalloporphyrin-thienopyrazine organic semiconductor material, preparation method thereof and application thereof | |
| CN102417584B (en) | Metal porphyrin-anthracene organic semiconductor material as well as preparation method and application thereof | |
| CN102453233B (en) | Organic semiconductor material containing metalloporphyrin-triphenylamine and preparation method and application thereof | |
| CN114621276B (en) | Benzothiadiazole boron nitrogen derivative and application thereof | |
| EP2573124A1 (en) | Porphyrin copolymer containing quinoxaline unit, preparation method and uses thereof | |
| CN102417586B (en) | Metal porphyrin-diazosulfide organic semiconductor material as well as preparation method and application thereof | |
| CN102453234B (en) | Metalloporphyrin-thienothiadiazole organic semiconductor material and preparation method and application thereof | |
| CN103025737B (en) | Silafluorene metalloporphyrin- benzene organic semiconductor material and preparing method and uses thereof | |
| CN102295756B (en) | Carbazole porphyrin-thienothiadiazole copolymer as well as preparation method and application thereof | |
| CN102453232B (en) | Metalloporphyrin-pyrrolopyrrole organic semiconductor material and preparation method and application thereof | |
| CN102295750B (en) | Carbazole porphyrin-paranaphthalene copolymer and preparation method and application thereof | |
| CN102276800B (en) | Triphenylamine unit porphyrin copolymer as well as preparation method and application thereof | |
| CN102206330B (en) | Bi-thiophene silole-containing conjugated polymer and preparation method and application thereof | |
| CN102443141B (en) | Metalloporphyrin-quinoxaline organic semiconductor material and preparation method and application thereof | |
| CN103435616A (en) | D(A-Ar)n type compound and application thereof | |
| CN102295757B (en) | Carbazolyl porphyrin-thienopyrazine-containing copolymer and preparation method as well as application thereof | |
| CN102329417B (en) | Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof | |
| CN102311538B (en) | Copolymer material containing carbazole porphyrin-triphenylamine and 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |