CN102453229A - Metalloporphyrin-thienopyrazine organic semiconductor material, preparation method thereof and application thereof - Google Patents
Metalloporphyrin-thienopyrazine organic semiconductor material, preparation method thereof and application thereof Download PDFInfo
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Abstract
The invention which belongs to the photoelectron material field discloses a metalloporphyrin-thienopyrazine organic semiconductor material, a preparation method thereof and an application thereof. The structural formula of the metalloporphyrin-thienopyrazine organic semiconductor material is represented by formula (I). In the formula (I), n is an integer between 1 and 100; R1, R2, R3 and R4 are H, C1-C32 alkyl, phenyl and alkylbenzene or alkoxybenzene containing one or more C1-C32 respectively; and M is a metallic ion. The metalloporphyrin-thienopyrazine organic semiconductor material provided in the invention, which has a wide light absorption range, allows the utilization rate to sunlight to be improved and has the advantages of good thermal stability and good environment stability. In addition, the preparation method of the material has the advantages of simple process, easy operation and easy control.
Description
Technical field
The present invention relates to a kind of organic semiconductor material, relate to a kind of metalloporphyrin-thieno-pyrazine organic semiconductor material more specifically.
The invention still further relates to the preparation method and the application thereof of metalloporphyrin-thieno-pyrazine organic semiconductor material.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is photovoltaic hot research fields and difficult point always.The silicon wafer battery that is used for ground at present is restricted its application owing to complex manufacturing, cost are high.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 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 on porphin ring, is connected with substituent one type of macrocylc compound, and porphines is by four pyrrole rings and four the big ring delocalized of Dan Shuanjian alternative two dimensional structure conjugated systems that the methyne bridging gets 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 one type of up-and-coming material, and its application in the photovoltaic field has obtained broad research.Metal nearly all in the periodic table of elements can form title complex with the porphyrin effect with some non-metallic elements.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, the most metal porphyrin compound all has photoelectric property preferably.
Thieno-[3,4-b] pyrazine is a kind of good two dimensional structure that has, and contains the body unit that receives of a five-ring and six-ring skeleton, has intramolecular charge and shifts character and excellent electrochemical reduction character; Thieno-[3,4-b] pyrazine unit also has stronger modifiability, can utilize easy method to introduce electron-donating group and electron-accepting group, regulates its electrophilic performance.The LUMO value of thieno-[3,4-b] pyrazine is-1.41eV to compare unit such as thieno-commonly used [3,4-b] pyrazine and have stronger electron-withdrawing power.Therefore; It is often as be incorporated in the photovaltaic material to regulate bandwidth and reduction potential by body unit; With thieno-[3; 4-b] pyrazine be incorporated into form in the porphyrin unit to electronics have electron donor(ED) and a unitary donor material of receptor structure, and have high hole mobility and wide sunshine absorption spectrum ranges simultaneously.
In recent years, siliceous conjugated polymers also receives increasing attention in the research of photoelectric functional material.Be because Siliciumatom is attached in the traditional conjugated polymers based on carbon hydrogen nitrogen sulfur with the chemical bond form on the one hand, can significantly change the 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 metalloporphyrin-thieno-pyrazine of silicon fluorenes does not still have document and patent report so far, this just big limitations the range of application of organic semiconductor material.。
Summary of the invention
The object of the present invention is to provide a kind of metalloporphyrin-thieno-pyrazine organic semiconductor material, it can address the above problem.
The present invention also aims to provide the preparation method and the application thereof of this metalloporphyrin-thieno-pyrazine organic semiconductor material.
Metalloporphyrin involved in the present invention-thieno-pyrazine organic semiconductor material 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
32Korenyl or alkoxy benzene; M is a metals 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 metals ion.
Metalloporphyrin of the present invention-thieno-pyrazine organic semiconductor material is to adopt following steps to make:
Step S1: 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 first organic solvent that contains the 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; First catalyzer adopts organic acid, like propionic acid, trifluoroacetic acid etc.; Oxygenant can adopt DDQ (DDQ), and first organic solvent can be in trichloromethane or the methylene dichloride one or both; Reaction formula is following:
Step S2: be dissolved in silicon fluorenes derivatives of porphyrin (D) that obtains among the step S1 and bromizating agent in second organic solvent in 1: 2 in molar ratio～1: 5; Reacted 1～72 hour down in 0～120 ℃; Obtain dibromo silicon fluorenes derivatives of porphyrin (E); Wherein, the consumption mol ratio of silicon fluorenes derivatives of porphyrin (D) and bromizating agent is 1: 2～1: 5; Bromizating agent can be N-bromo-succinimide (NBS), and second organic solvent is THF (THF), chloroform (CHCl
3), at least a in dimethylformamide (DMF) or the orthodichlorobenzene; Reaction formula is following:
Step S3: the dibromo silicon fluorenes derivatives of porphyrin (E) that obtains among the step S2 is dissolved in the 3rd organic solvent; At least a as in trichloromethane, THF, benzene, toluene or the methylene dichloride; 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); Reaction formula is following:
Wherein, the mol ratio of said dibromo silicon fluorenes derivatives of porphyrin (E) and M metals ion is 1: 1～1: 5, the M metals 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, the M metallic salt can comprise M (OAc)
2, MCl
2, MSO
4, M (NO
3)
2Deng;
Step S4: in oxygen-free environment, with the dibromo silicon fluorenes metal porphyrin derivative (F) and 5 that obtains among the step S3,7-two (4; 4,5,5-tetramethyl--1; 3, assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazines (G) were dissolved in the having ideals, morality, culture, and discipline machine solvent that contains second catalyzer in 1: 2 in molar ratio～2: 1; Under 50-120 ℃, carry out the Stille coupling reaction 12～72 hours, and obtained said metalloporphyrin-thieno-pyrazine organic semiconductor material (I); Reaction formula is following:
In the formula, n is the integer between 1-100;
Wherein, second catalyzer can for the mixture of organic palladium or organic palladium and organophosphor ligand (mol ratio of organic palladium and organophosphor ligand is 1: 1-20), like Pd
2(dba)
3, Pd (OAc)
2, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2, P (o-Tol)
3, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (OAc)
2/ tricyclohexyl phosphine etc.; The mole dosage of second catalyzer is 5,8-two (tributyl tin)-2, the 0.01%-20% of two (phenyl) thieno-pyrazine (G) molar weights of 3-; Said having ideals, morality, culture, and discipline machine solvent is at least a in THF, methylene dichloride, chloroform, dioxane, dimethylformamide, DMSO 99.8MIN., glycol dimethyl ether, chlorobenzene, benzene or the toluene etc.
Among above-mentioned preparing method's the step S4,5,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazines (G) adopt following steps to make:
With 5,7-dibromo thiophene also [3,4-b] pyrazine adds (Y) and is dissolved in the 5th organic solvent, is cooled to-78 ℃ with liquid helium/Virahol subsequently; Drip n-Butyl Lithium, at-78 ℃ of reaction 1-5h, add the 2-isopropoxy-4,4 of structural formula more then for
; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (X); At-78 ℃ of reaction 0.5-5h, the room temperature of intensification was naturally reacted 1-48 hour then, obtained said 5; 7-two (4,4,5,5-tetramethyl--1; 3,2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazines (G); Reaction formula is following:
Wherein, said the 5th organic solvent is at least a in THF, ether or the dioxane; Said 2-isopropoxy-4,4,5,5-tetramethyl--1,3, the molar weight of the assorted oxygen pentaboranes (X) of 2-two is 5, the 7-dibromo thiophene is 2～4 times of molar weight of [3,4-b] pyrazines (Y) also.
Above-mentioned metalloporphyrin-thieno-pyrazine 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 metalloporphyrin-thieno-pyrazine of the siliceous fluorenes of the present invention's exploitation; Said material is through introducing the silicon fluorene group to the porphyrin framework, and the coordination through metals ion, adjusted the band gap of porphyrin polymer; And then acquisition is better stable and good film-forming properties; Widened the visible spectrum absorption region, made its absorption region extend to the near-infrared region, improved its utilization ratio sunshine; Improved carrier mobility simultaneously, enlarged their ranges 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 thieno-pyrazine unit simultaneously; Have good two dimensional structure, have the electrochemical reduction character of intramolecular charge transfer character and excellence etc., it also has strong electrophilic characteristic; It is a kind of good body unit that receives; Itself and electron donor material are mated, can reduce the energy gap of material, widen absorption region sunshine.
4. organic semiconductor material of the present invention is owing to comprised silicon fluorene structural units, porphyrin unit and thieno-pyrazine unit simultaneously; Taken into account their performance advantage; And expanded the absorption region of this organic semiconductor material to sunshine; Increased and solar radiation spectrographic matching degree, 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 said 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
Metalloporphyrin involved in the present invention-thieno-pyrazine organic semiconductor material 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
32Korenyl or alkoxy benzene; M is a metals 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 metals ion.
The preparation method of the metalloporphyrin that the present invention designed-thieno-pyrazine organic semiconductor material, step is following:
Step S1: 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 first organic solvent that contains the oxygenant and first catalyzer; In said first organic solvent, add oxygenant, first catalyzer, and reacted 1-24 hour down, obtain silicon fluorenes derivatives of porphyrin (D) in 20-100 ℃; Wherein, I: j: k=1: 1～100: 1～100, and i=j+k, i >=j＞0; First catalyzer adopts organic acid, like propionic acid, trifluoroacetic acid; Oxygenant can adopt DDQ (DDQ), and first organic solvent can be in trichloromethane or the methylene dichloride one or both; Reaction formula is following:
Step S2: silicon fluorenes derivatives of porphyrin (D) that obtains among the step S1 and bromizating agent were dissolved in second organic solvent in 1: 2 in molar ratio～1: 5, reacted 1～72 hour down, obtain dibromo silicon fluorenes derivatives of porphyrin (E) in 0～120 ℃; Reaction formula is following:
Wherein, the consumption mol ratio of silicon fluorenes derivatives of porphyrin (D) and bromizating agent is 1: 2～1: 5; Bromizating agent can be N-bromo-succinimide (NBS), and second organic solvent is THF (THF), chloroform (CHCl
3), at least a in dimethylformamide (DMF) or the orthodichlorobenzene;
Step S3: the dibromo silicon fluorenes derivatives of porphyrin (E) that obtains among the step S2 is dissolved in the 3rd organic solvent; At least a as in trichloromethane, THF, benzene, toluene or the methylene dichloride; 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); Reaction formula is following:
Wherein, the mol ratio of said dibromo silicon fluorenes derivatives of porphyrin (E) and M metals ion is 1: 1～1: 5, the M metals 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, the M metallic salt can comprise M (OAc)
2, MCl
2, MSO
4, M (NO
3)
2Deng;
Step S4: in oxygen-free environment, (comprise the protection of inert gas atmosphere that nitrogen and/or argon gas etc. constitute), with the dibromo silicon fluorenes metal porphyrin derivative (F) and 5 that obtains among the step S3,7-two (4; 4; 5,5-tetramethyl--1,3; 2-two assorted oxygen pentaboranes) basic thieno-[3; 4-b] pyrazine (G) was dissolved in the having ideals, morality, culture, and discipline machine solvent that contains second catalyzer in 1: 2 in molar ratio～2: 1, under 50-120 ℃, carried out the Stille coupling reaction 12～72 hours, obtained said metalloporphyrin-thieno-pyrazine organic semiconductor material (I); Reaction formula is following:
In the formula, n is the integer between 1-100;
Wherein, second catalyzer can for the mixture of organic palladium or organic palladium and organophosphor ligand (mol ratio of organic palladium and organophosphor ligand is 1: 1-20), like Pd
2(dba)
3/ P (o-Tol)
3, Pd (OAc)
2/ tricyclohexyl phosphine, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2Deng; The mole dosage of second catalyzer is 55, the 0.01%-20% of 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazines (G) molar weight; Said having ideals, morality, culture, and discipline machine solvent is at least a in THF, methylene dichloride, chloroform, dioxane, dimethylformamide, DMSO 99.8MIN., glycol dimethyl ether, chlorobenzene, benzene or the toluene etc.
Among above-mentioned preparing method's the step S4,5,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazines (G) adopt following steps to make;
With 5,7-dibromo thiophene also [3,4-b] pyrazine adds (Y) and is dissolved in the 5th organic solvent; Be cooled to-78 ℃ with liquid nitrogen/Virahol subsequently, drip n-Butyl Lithium, then at-78 ℃ of reaction 1-5h; Add the 2-isopropoxy-4,4 of structural formula again, 5 for
; 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (X) or the two tetramethyl ethylene ketones of structural formula for
close two boron; At-78 ℃ of reaction 0.5-5h, the room temperature of intensification was naturally reacted 1-48 hour then; Obtain saidly 5,7-two (4,4; 5,5-tetramethyl--1,3; 2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazines (G); Reaction formula is following:
Wherein, said the 5th organic solvent is at least a in THF, ether or the dioxane; Said 2-isopropoxy-4,4,5,5-tetramethyl--1,3, the molar weight that the assorted oxygen pentaboranes (X) of 2-two or two tetramethyl ethylene ketone close two boron is 5, the 7-dibromo thiophene is 2～4 times of molar weight of [3,4-b] pyrazines (Y) also.
2-bromo-9-replaces the silicon fluorenes and under the catalyst/solvent condition, makes (reference: Macromolccules 2002,35,3474) by 2-bromine silicon fluorenes and corresponding bromide; 2-aldehyde-9-replaces the silicon fluorenes and in n-Butyl Lithium/N/THF system, makes (reference: Macromolecules 2006 by 2-bromo-9-replacement silicon fluorenes; 39,456), two pyrroles's methane make (reference: Tetrahedron 1994 by formaldehyde and pyrroles under catalyst action; 39,11427).
Above-mentioned metalloporphyrin-thieno-pyrazine 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 metalloporphyrin-thieno-pyrazine of the siliceous fluorenes of the present invention's exploitation; Said material is through introducing the silicon fluorene group to the porphyrin framework, and the coordination through metals ion, adjusted the band gap of porphyrin polymer; And then acquisition is better stable and good film-forming properties; Widened the visible spectrum absorption region, made its absorption region extend to the near-infrared region, improved its utilization ratio sunshine; Improved carrier mobility simultaneously, enlarged their ranges of application in fields such as organic solar batteries.
Below in conjunction with accompanying drawing, further explain is done in preferred embodiment of the present invention.
Embodiment 1
Present embodiment discloses the following silicon fluorenes zinc protoporphyrin of a kind of structure-thieno-pyrazine organic semiconductor material
In the following formula, n=10;
Above-mentioned organic semiconductor material preparation process is following:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
Under the protection of argon gas, add in the there-necked flask 5, the 7-dibromo thiophene also [3,4-b] pyrazine (8.8g, 0.03mol); The tetrahydrofuran solvent that adds 200ml, (25.2mL, 2.5M 0.06mol), continue stirring reaction 2h under-78 ℃ of conditions, slowly to inject n-Butyl Lithium with syringe again; Under-78 ℃ of conditions, inject 2-isopropoxy-4,4,5,5-tetramethyl--1 with syringe; 3, and 2-two assorted oxygen pentaboranes (13mL, 0.06mol), stirred overnight under the room temperature.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, productive rate 93%.
GC-MS(EI-m/z)：388(M
+)
Two, 5,15-two (9 ', 9 '-dioctyl) silicon fluorenes porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing midbody 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 argon gas 30min, syringe adds propionic acid 1ml; 20 ℃ are stirred 24h down, and (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 filtrating and revolves dried solvent; With methylene dichloride drip washing fast on silicagel column, revolve dried solvent, to product, productive rate is about 85% 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) silicon fluorenes porphyrin (0.23g; 0.2mmol) be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide (0.07g; 0.4mmol), behind the stirring 72h, mixture returns to room temperature, continues to stir 4h then; Add 5ml acetone termination reaction, remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 81%.
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 midbody 5,15-two bromo-10,20-two (9; The 9-dioctyl fluorene) (0.25g 0.2mmol) is dissolved in the 50ml methylene dichloride porphyrin, adds to contain zinc acetate (0.11g; 0.5mmol) methanol solution (5ml), stir 5h under the room temperature, revolve dried solvent; Use methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collect and revolve dried solvent and obtain product, productive rate 94%.
GC-MS(EI-m/z)：1340(M
+)
Five, silicon fluorenes zinc protoporphyrin-thieno-pyrazine organic semiconductor material is synthetic
Under argon shield, add 5,7-two (4,4; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3; 4-b] and pyrazine (78mg, 0.2mmol), 5,15-two bromo-10,20-two (9 '; 9 '-dioctyl) (268mg 0.2mmol) with toluene solvant 50ml, vacuumizes deoxygenation and charges into argon gas silicon fluorenes zinc protoporphyrin, adds 5mgPd (PPh then
3)
2Cl
2With 2ml NaHCO
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, add eight in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight.With the column chromatography of organic phase through 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, and productive rate 75%.Molecular weight (GPC, THF, R.I): Mn=13100, Mw/Mn=2.76; )
Embodiment 2
Present embodiment discloses the following silicon fluorenes iron porphyrin of a kind of structure-thieno-pyrazine organic semiconductor material
In the following formula, n=28;
Above-mentioned organic semiconductor material preparation process is following:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
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 midbody 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, logical eight helium 30min, syringe adds trifluoroacetic acid 2ml; 100 ℃ are stirred 1h down, and (1.82g 8mmol), continues at room temperature to stir 30min to add DDQ (DDQ) then; Add 2ml pyridine cancellation reaction then, concentrated solvent filters, and collects filtrating and revolves dried solvent; With methylene dichloride drip washing fast on silicagel column, revolve dried solvent, to product, 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, adds the 1ml pyridine to take by weighing 5-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-15-(9 '-dotriacontyl) silicon fluorenes porphyrin; Reactant is dropped to 0 ℃, and 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, adds 5ml acetone termination reaction; Remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 72%.
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 midbody 5,15-two bromo-10-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-20-(9 '-dotriacontyl) silicon fluorenes porphyrin (0.31g; 0.2mmol) be dissolved in the 50ml methylene dichloride, add and contain chlorination ferrous (0.12g, methanol solution 1mmol) (5ml); Stir 8h under the room temperature, revolve dried solvent, use methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then; Collect and revolve dried solvent and obtain product, productive rate 95%.
GC-MS(EI-m/z)：1569(M
+)
Five, silicon fluorenes iron porphyrin-thieno-pyrazine organic semiconductor material is synthetic
Under nitrogen protection, add 5,7-two (4,4; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3; 4-b] and pyrazine (78mg, 0.2mmol), 5,15-two bromo-10-(9 '-methyl-9 '-hexadecyl) silicon fluorenes-20-(9 '-dotriacontyl) silicon fluorenes iron porphyrin (314mg; 0.2mmol) and toluene solvant 120ml, take out very to deoxygenation and charge into nitrogen, add Pd (OAc) then
2(2.5mg)/tricyclohexyl phosphine (6.5mg) and 2ml 20% (wt) tetraethyl ammonium hydroxide (Et
4NOII, down together) solution, be heated to 120 ℃ of reaction 12h.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 stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, and productive rate 80%.Molecular weight (GPC, THF, R.I): Mn=43200, Mw/Mn=2.88; )
Embodiment 3
Present embodiment discloses the following silicon fluorenes copper porphyrin of a kind of structure-thieno-pyrazine organic semiconductor material
In the following formula, n=40;
Above-mentioned organic semiconductor material preparation process is following:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
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 midbody 2-aldehyde-9-hexadecyl-9-(3 '-hexadecyl-4 '-n-Hexadecane oxygen base) benzene) the silicon fluorenes (1.95g, 2mmol) with two pyrroles's methane (0.30g, 2mmol); Be dissolved in the 300ml methylene dichloride, feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml, stirs 3h under the room temperature; (1.82g 8mmol), continues at room temperature to stir 30min, adds 2ml triethylamine cancellation reaction then to add DDQ (DDQ) then; Concentrated solvent filters, and collects filtrating and revolves dried solvent, with methylene dichloride drip washing fast on silicagel column; Revolve dried solvent, to product, 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) (0.44g 0.2mmol) is dissolved in the 80ml chloroform silicon fluorenes porphyrin; Add the 1ml pyridine, reactant is dropped to 0 ℃, and adding N-bromo-succinimide (0.07g, 0.4mmol); After stirring 0.5h, mixture is warming up to 30 ℃, continues to stir 48h then, adds 5ml acetone termination reaction; Remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 72%.
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 midbody 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, revolves dried solvent, uses methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collects and revolve dried solvent to obtain product, productive rate 93%.
GC-MS(EI-m/z)：2416(M
+)
Five, silicon fluorenes copper porphyrin-thieno-pyrazine organic semiconductor material is synthetic
Under nitrogen protection, add 5,7-two (4,4; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3; 4-b] pyrazine (78mg, 0.2mmol), 5,15-two bromo-10,20-two (9 '-hexadecyl-9 '-(3 "-hexadecyl-4 "-n-Hexadecane oxygen base) benzene) silicon fluorenes copper porphyrin (483mg; 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 stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 73%.Molecular?weight(GPC，THF，R.I)：Mn＝958100，Mw/Mn＝3.29；)
Embodiment 4
Present embodiment discloses the following silicon fluorenes cadmium porphyrin-thieno-pyrazine organic semiconductor material of a kind of structure
In the following formula, n=56;
Above-mentioned organic semiconductor material preparation process is following:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
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 midbody 2-aldehyde-9-to eicosyl benzene-9-(3 ', 5 '-two dodecyloxy benzene) silicon fluorenes (1.02g, 1mmol), 2-aldehyde-9-is to decyl benzene silicon fluorenes (0.74g between n-Hexadecane oxygen base benzene-9-; 1mmol) (0.30g 2mmol), is dissolved in the 250ml methylene dichloride, feeds nitrogen 30min with two pyrroles's methane; Syringe adds acetate 1ml, and 20 ℃ are stirred 24h down, add then DDQ (DDQ) (0.91g, 4mmol); Continue at room temperature to stir 30min, add 1ml triethylamine cancellation reaction then, concentrated solvent; Filter, collect filtrating and revolve dried solvent, with methylene fluoride drip washing fast on silicagel column; Revolve dried solvent, to product, productive rate is about 83% 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), reactant is dropped to 0 ℃; Add eight N-bromo-succinimides (0.07g, 0.4mmol), stir 72h after; Mixture returns to room temperature, continues to stir 4h then, adds 5ml acetone termination reaction; Remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 82%.
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 midbody 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, revolves dried solvent, uses methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collects and revolve dried solvent to obtain product, productive rate 94%.
GC-MS(EI-m/z)：2271(M
+)
Five, silicon fluorenes cadmium porphyrin-thieno-pyrazine organic semiconductor material is synthetic
Under nitrogen protection, add 85,7-two (4,4; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3; 4-b] pyrazine (78mg, 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 (454mg; 0.2mmol) and dioxane solvent 60ml, vacuumize deoxygenation and fill eight 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 stirred overnight.With the column chromatography of organic phase through 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, and productive rate 71%.Molecular weight (GPC, THF, R.I): Mn=125800, Mw/Mn=3.83;
Embodiment 5
Present embodiment discloses the following silicon fluorenes cobalt porphyrin-thieno-pyrazine organic semiconductor material of a kind of structure
In the following formula, n=78;
Above-mentioned organic semiconductor material preparation process is following:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
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 midbody 2-aldehyde-9-(3 ', 4 ', 5 '-three last of the ten Heavenly stems alkoxyl group) benzene-9-hexadecyl benzene silicon fluorenes (1.06g; 1mmol), 2-aldehyde-9-(3 '-dodecyl-5 '-eicosane oxygen base)-9-(3 '-dotriacontyl-4 '-laccerane oxygen base) benzene silicon fluorenes (1.74g, 1mmol), two pyrroles's methane (0.30g, 2mmol), dissolving is done in the 250ml methylene dichloride; Feed nitrogen 30min, syringe adds propionic acid 2ml, and 100 ℃ are stirred 1h down, add DDQ (DDQ) (1.82g then; 8mmol), continue at room temperature to stir 30min, add 2ml pyridine cancellation reaction then, concentrated solvent; Filter, collect filtrating and revolve dried solvent, with methylene dichloride drip washing fast on silicagel column; Revolve dried solvent, to product, productive rate is about 74% 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 THF adds the 0.5ml triethylamine, and reactant is dropped to 0 ℃; add the N-bromo-succinimide (0.07g, 0.4mmol), stir 0.5h after; mixture is warming up to backflow, after continuing then to stir 1h, adds 5ml acetone termination reaction; remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 82%.
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 midbody 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, revolves dried solvent, uses methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collects and revolve dried solvent to obtain product, productive rate 96%.
GC-MS(EI-m/z)：3257(M
+)
Five, silicon fluorenes cobalt porphyrin-thieno-pyrazine organic semiconductor material is synthetic
Under the helium protection, add 5,7-two (4,4; 5,5-tetramethyl--1,3; The assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine (78mg, 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 (650mg; 0.2mmol), vacuumize deoxygenation and charge into nitrogen, add Pd (OAc) then with DMF solvent 80ml
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 stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, and productive rate 79%.Molecular weight (GPC, THF, R.I): Mn=252400.Mw/Mn=4.25;
Embodiment 6
Present embodiment discloses the following silicon fluorenes tin porphyrin-thieno-pyrazine organic semiconductor material of a kind of structure
In the following formula, n=100;
Above-mentioned organic semiconductor material preparation process is following:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
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 midbody 2-aldehyde-9-hexadecyl-9-(3 '-methyl-4 '-laccerane oxygen base) benzene silicon fluorenes (0.99g, 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, feeds helium 30min; Syringe adds trifluoroacetic acid 2ml, and 100 ℃ are stirred 1h down, add then DDQ (DDQ) (1.82g, 8mmol); Continue at room temperature to stir 30min, add 2ml triethylamine cancellation reaction then, concentrated solvent; Filter, collect filtrating and revolve dried solvent, with methylene dichloride drip washing fast on silicagel column; Revolve dried solvent, to product, productive rate is about 74% 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, adds 5ml acetone termination reaction; Remove and desolvate, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 85%.
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 midbody 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) (0.47g 0.2mmol) is dissolved in the 50ml methylene dichloride silicon fluorenes porphyrin, adds to contain SnCl
2(0.11g, ethanolic soln 0.6mmol) (5ml) stirs 24h under the room temperature, revolves dried solvent, uses methylene dichloride/sherwood oil (1/1) drip washing on silicagel column then, collects and revolve dried solvent to obtain product productive rate 95%.
GC-MS(EI-m/z)：2451(M
+)
Five, silicon fluorenes tin porphyrin-thieno-pyrazine organic semiconductor material is synthetic
Under nitrogen protection, add 5,7-two (4; 4,5,5-tetramethyl--1; 3,2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazine (78mg; 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 (490mg; 0.2mmol) and glycol dinitrate ether solvents 80ml, vacuumize deoxygenation and fill eight chlorine, add 10mg Pd (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 stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, and productive rate 72%.Molecular weight (GPC, THF, R.I): Mn=242800, Mw/Mn=4.33;
The present invention also provides structural formula to do
(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
32Korenyl or alkoxy benzene; M is a metals 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) metalloporphyrin-thieno-pyrazine 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 metalloporphyrin-thieno-pyrazine organic semiconductor material at organic solar batteries, organic field effect tube, the application in the organic electroluminescence device.
Embodiment 7
With the metalloporphyrin among the embodiment 1-thieno-pyrazine organic semiconductor material is the organic solar batteries device of active layer material
A kind of organic solar batteries device, its structure is 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 a mixture, comprises electron donor material, and PCBM is an electron acceptor material; Electron donor material is a material with the metalloporphyrin among the embodiment 1-thieno-pyrazine 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 for gathering (3, the 4-Ethylenedioxy Thiophene), and PSS is for gathering (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 handled with oxygen-Plasma through after the ultrasonic cleaning, and on the ITO layer, being coated with last layer is the decorative layer of material with PEDOT:PSS; Then with being coated on the decorative layer after organic semiconductor material among the present invention and the PCBM dissolving blend; Form active coating, evaporating Al layer on active coating obtains solar cell device again; 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 the 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, Al layer is respectively 150nm, 50mm, 120nm, 100nm.
Embodiment 8
With the metalloporphyrin among the embodiment 1-thieno-pyrazine organic semiconductor material is the organic electroluminescence devices of 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 impact plies 24/Al layer 25; Wherein: luminescent layer is a material with the metalloporphyrin among the embodiment 1-thieno-pyrazine 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 as the anodic conductive layer, and thickness is 50-300nm; Preferred square resistance is the ITO of 10 Ω/mouths.
Is the luminescent layer 23 of material at ITO surface preparation one deck with the metalloporphyrin among the embodiment 1-thieno-pyrazine organic semiconductor material through spin coating technique, and thickness is about 50-300nm;
Vacuum evaporation LiF on luminescent layer, as impact plies 14, thickness is about 0.3-2nm;
Vacuum evaporation metallic aluminium on said luminescent layer forms the metal aluminium lamination 25 as negative electrode, obtains said organic electroluminescence device.
Embodiment 9
Metalloporphyrin-thieno-pyrazine organic semiconductor material to contain among the embodiment 1 is the organic field effect tube of material
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 31/450nm is thick
2Insulation layer 32/ is used to modify 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 a material with the metalloporphyrin among the embodiment 1-thieno-pyrazine 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, on a surface cleaning doped silicon wafer 31, apply the thick SiO of one deck 450nm later
2 Insulation layer 32; Secondly, at said 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 metalloporphyrin among the embodiment 1-thieno-pyrazine organic semiconductor material on said octadecyl trichlorosilane layer, and thickness is about 50-300nm; At last, on said 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 a material, obtain said organic field effect tube.
Should be understood that above-mentioned statement to 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 accompanying claims.
Claims (10)
1. metalloporphyrin-thieno-pyrazine 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
32Korenyl or alkoxy benzene; M is a metals ion.
2. metalloporphyrin according to claim 1-thieno-pyrazine organic semiconductor material is characterized in that said metals 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 preparation method of metalloporphyrin-thieno-pyrazine organic semiconductor material is characterized in that said preparation method comprises the steps:
Step S1, 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 first organic solvent that contains the 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 following:
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
32Korenyl or alkoxy benzene;
Step S2, silicon fluorenes derivatives of porphyrin (D) that obtains among the step S1 and bromizating agent were dissolved in second organic solvent in 1: 2 in molar ratio～1: 5,, obtain dibromo silicon fluorenes derivatives of porphyrin (E) in 0～120 ℃ of reaction 1～72 hour down; Reaction formula is following:
Step S3, the dibromo silicon fluorenes derivatives of porphyrin (E) that obtains among the step S2 is dissolved in the 3rd 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 said dibromo silicon fluorenes derivatives of porphyrin (E) and M metals ion is 1: 1～1: 5; Reaction formula is following:
In step S4, the oxygen-free environment, with the dibromo silicon fluorenes metal porphyrin derivative (F) and 5 that obtains among the step S3,7-two (4; 4,5,5-tetramethyl--1; 3, assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazines (G) were dissolved in the having ideals, morality, culture, and discipline machine solvent that contains second catalyzer in 1: 2 in molar ratio～2: 1; Under 50-120 ℃, carry out the Stille coupling reaction 12～72 hours, and obtained said metalloporphyrin-thieno-pyrazine organic semiconductor material (I); Reaction formula is following:
In the formula, n is the integer between 1-100.
4. preparation method according to claim 3 is characterized in that, among the said step S1, said first catalyzer is at least a in propionic acid or the trifluoroacetic acid; Said oxygenant is a DDQ; To connect first organic solvent be in trichloromethane, the methylene dichloride one or both.
5. preparation method according to claim 3 is characterized in that, among the said step S2, said bromizating agent is the N-bromo-succinimide; Said second organic solvent is at least a in THF, chloroform, dimethylformamide or the orthodichlorobenzene.
6. preparation method according to claim 3 is characterized in that, among the said step S3, said the 3rd organic solvent is at least a in trichloromethane, THF, benzene, toluene or the methylene dichloride; Said containing in the M metal ion solution, the M metals ion 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, solvent is at least a in methyl alcohol, ethanol or the water.
7. preparation method according to claim 3 is characterized in that, among the said step S4, said second catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand; The mole dosage of said second catalyzer is 5, the 0.01%-20% of 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazines (G) mole dosage;
Said organic palladium is Pd
2(dba)
3, Pd (PPh
3)
4, Pd (OAc)
2Or Pd (PPh
3)
2Cl
2
Said organophosphor ligand is P (o-Tol)
3, tricyclohexyl phosphine;
Said having ideals, morality, culture, and discipline machine solvent is at least a in THF, methylene dichloride, chloroform, dioxane, dimethylformamide, glycol dimethyl ether, DMSO 99.8MIN., benzene, chlorobenzene or the toluene.
8. preparation method according to claim 3 is characterized in that, and is said 5 among the said step S4, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazines (G) adopt following steps to make:
With 5,7-dibromo thiophene also [3,4-b] pyrazine adds (Y) and is dissolved in the 5th organic solvent, is cooled to-78 ℃ with liquid nitrogen/Virahol subsequently; Drip n-Butyl Lithium, at-78 ℃ of reaction 1-5h, add the 2-isopropoxy-4,4 of structural formula more then for
; 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (X); At-78 ℃ of reaction 0.5-5h, the room temperature of intensification was naturally reacted 1-48 hour then, obtained said 5; 7-two (4,4,5,5-tetramethyl--1; 3,2-two assorted oxygen pentaboranes) basic thieno-[3,4-b] pyrazines (G); Reaction formula is following:
9. preparation method according to claim 8 is characterized in that, said the 5th organic solvent is at least a in THF, ether or the dioxane; Said 2-isopropoxy-4,4,5,5-tetramethyl--1,3, the molar weight of the assorted oxygen pentaboranes (X) of 2-two is 5, the 7-dibromo thiophene is 2～4 times of molar weight of [3,4-b] pyrazines (Y) also;
10. metalloporphyrin-thieno-pyrazine the organic semiconductor material with formula (I) is at organic solar batteries; Organic electroluminescence device; Organic field effect tube, organic optical storage, Application for Field such as organic non-linear device and organic laser apparatus:
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
32Korenyl or alkoxy benzene; M is a metals ion.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105914297A (en) * | 2016-04-27 | 2016-08-31 | 扬州鑫晶光伏科技有限公司 | Organic photovoltaic cell and a preparation method thereof |
| CN108219791A (en) * | 2018-01-26 | 2018-06-29 | 温州大学 | A kind of fluorescent crystal material and its preparation process flow based on rare earth oxide |
| CN110294838A (en) * | 2019-07-03 | 2019-10-01 | 江南大学 | Polyhydroxyl porphyrin polymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631890A (en) * | 2004-12-10 | 2005-06-29 | 吉林大学 | Tetraphenyl porphyrin derivative and its application in organic electroluminescent device |
| WO2007051947A1 (en) * | 2005-11-03 | 2007-05-10 | Biomerieux | Novel electropolymerisable monomers which are soluble in an aqueous solution and comprise a metalloporphyrine |
-
2010
- 2010-10-19 CN CN 201010513294 patent/CN102453229B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631890A (en) * | 2004-12-10 | 2005-06-29 | 吉林大学 | Tetraphenyl porphyrin derivative and its application in organic electroluminescent device |
| WO2007051947A1 (en) * | 2005-11-03 | 2007-05-10 | Biomerieux | Novel electropolymerisable monomers which are soluble in an aqueous solution and comprise a metalloporphyrine |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105914297A (en) * | 2016-04-27 | 2016-08-31 | 扬州鑫晶光伏科技有限公司 | Organic photovoltaic cell and a preparation method thereof |
| CN108219791A (en) * | 2018-01-26 | 2018-06-29 | 温州大学 | A kind of fluorescent crystal material and its preparation process flow based on rare earth oxide |
| CN110294838A (en) * | 2019-07-03 | 2019-10-01 | 江南大学 | Polyhydroxyl porphyrin polymer and preparation method thereof |
| CN110294838B (en) * | 2019-07-03 | 2021-11-02 | 江南大学 | Polyhydroxy porphyrin polymer and preparation method thereof |
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