CN102936245B - Prepared by photoelectric material - Google Patents
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- CN102936245B CN102936245B CN201110235857.8A CN201110235857A CN102936245B CN 102936245 B CN102936245 B CN 102936245B CN 201110235857 A CN201110235857 A CN 201110235857A CN 102936245 B CN102936245 B CN 102936245B
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- 0 *C1=C(*c([s]cc2*)c2I)S=C*1 Chemical compound *C1=C(*c([s]cc2*)c2I)S=C*1 0.000 description 14
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- 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
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Abstract
Disclose to receptor type oligo-thiophenes compound, its preparation method and purposes.Disclosed compound has accurate molecular weight, structure-controllable, easy purification, it is adaptable to preparation has high open circuit voltage, good stability, flexibility, large-area high-performance organic solar batteries.
Description
Field
The application relates to technical field of material chemistry.More specifically, the application relates to field of photovoltaic materials.
Background
Solar energy is that the mankind are inexhaustible, nexhaustible, the regenerative resource of cleanliness without any pollution.With inorganic solar cell
Comparing, organic solar batteries has light weight, inexpensive, solution-processible, high mechanical flexibility, can be made into flexible broad area device
Etc. advantage.
General introduction
On the one hand, the application relate to selected from formula (1) to formula (6) to receptor type oligo-thiophenes compound:
Formula (1)
Formula (2)
Formula (3)
Formula (4)
Formula (5)
Formula (6)
Wherein, n is the integer of 1 to 50,
R1And R2Separately selected from H, C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or its halogen substiuted
Derivant, wherein R1And R2Can be the same or different, but R1And R2Can not be H simultaneously,
D and D1It is separately the conjugated electrons donor monomer of bridging,
A and A1Be separately the conjugated electrons of bridging by body unit, and
A2For organic molecule dye groups.
On the other hand, the application relates to preparing formula (1) to the side to receptor type oligo-thiophenes compound of formula (6)
Method, wherein, the oligo-thiophenes containing small molecule dyes end group of donor bridging by the oligo-thiophenes of dialdehyde base donor bridging with have
Machine small molecule dyes monomer, in the presence of solvent and catalyst, carries out Ke Neifeinageer (Knoevenagel) condensation anti-
Should, obtain described compound.
Another further aspect, the application relates to formula (1) imitating to receptor type oligo-thiophenes compound to formula (6) in preparation field
Answer the purposes in transistor.
Another aspect, the application relates to formula (1) and is preparing photovoltaic to formula (6) to receptor type oligo-thiophenes compound
Purposes in device.
On the other hand, the application relate to comprising have formula (1) to formula (6) to receptor type oligo-thiophenes compound
The triode device of active layer.
Other aspects, the application relate to comprising have formula (1) to formula (6) to receptor type oligo-thiophenes compound
The photovoltaic device of active layer.
Accompanying drawing explanation
Fig. 1 shows the solution of compound and the ultraviolet-visible absorption spectroscopy of thin film in the embodiment of the present application 2.
Fig. 2 shows the solution of compound and the cyclic voltammetry curve of thin film in the embodiment of the present application 2.
Fig. 3 shows compound current density voltage curve under difference is to acceptor ratio in the embodiment of the present application 2.
Describe in detail
In the following description, comprehensively reason is provided including some concrete details with embodiment disclosed in each
Solve.But, those skilled in the relevant art are not it will be recognized that use these concrete details one or more, and use other
Embodiment can be realized in the case of method, parts, material etc..
Unless required in addition that in the application, in entire disclosure and claims thereafter, word " includes " and " bag
Contain " should be interpreted that open, to include formula meaning, i.e. " include but not limited to ".
" embodiment " that whole this specification is mentioned or " embodiment " or " in another embodiment " or
" in certain embodiments " mean at least one embodiment include relevant to described in this embodiment with specific reference to
Key element, structure or feature.Therefore, throughout the specification diverse location occur phrase " in one embodiment " or " in reality
Execute in scheme " or " in another embodiment " or " in certain embodiments " same embodiment need not be all referred to.Additionally,
Concrete key element, structure or feature can combine in any suitable manner in one or more embodiments.
Definition
By showing that the simplification symbol of the total number of carbon atoms found in shown chemical group is named herein above indicating
Some chemical group.Such as, C7-C12Alkyl describes has the alkyl being defined below that sum is 7 to 12 carbon atoms, and
C4-C12Cycloalkyl-alkyl describes has the cycloalkyl-alkyl being defined below that sum is 4 to 12 carbon atoms.Simplify carbon in symbol
Total atom number does not comprise the carbon in the substituent group being likely to be present in described group.
Therefore, non-separately have a contrary explanation, otherwise in description and claims following term used have with
Under the meaning:
In this application, term " alkyl " means and is made up of carbon and hydrogen atom, without unsaturated bond, has 1 to 30
Individual carbon atom, especially there is 1 to 12 carbon atom or 1 to 8 carbon atom, and by the remainder phase of singly-bound with molecule
Straight or branched hydrocarbon chain radical even, such as methyl, ethyl, n-pro-pyl, 1-Methylethyl (isopropyl), normal-butyl, n-pentyl,
1,1-dimethyl ethyl (tert-butyl group), octyl group etc..
In certain embodiments, alkyl is C1-C30Alkyl.In certain embodiments, alkyl is C1-C12Alkyl.?
In some embodiment, alkyl is C1-C8Alkyl.
Alkyl group can be the most substituted that is substituted or unsubstituted.When substituted, substituted radical is independent
Ground and independently selected from following one or more groups: cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxyl, alkoxyl,
Aryloxy group, sulfydryl, alkylthio group, arylthio, cyano group, halo, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl,
O-thiocarbamoyl, N-thiocarbamoyl, C-acylamino-, N-acylamino-, S-sulfonamido, N-sulfenyl ammonia
Base, C-carboxyl, O-carboxyl, isocyanato-, thiocyano, isothiocyanato, nitro, silicyl, three halide sulphonyl
Base ,-NR ' R " or amino including single-and di-substituted amino group, and protected derivant.
In certain embodiments, C1-C30Alkyl is optionally substituted by halogen.
In this application, term " cycloalkyl " refers to only to be made up of carbon and hydrogen atom, has three to ten five carbon atoms,
Especially there are 3 to 30 carbon atoms, and it is saturated, and steady with what the remainder of molecule was connected by singly-bound
Fixed non-aromatic monocyclic or bicyclic hydrocarbon radical, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, ring decyl etc..
In certain embodiments, cycloalkyl is C3-C30Cycloalkyl.In certain embodiments, cycloalkyl is C3-C12
Cycloalkyl.In certain embodiments, cycloalkyl is C3-C8Cycloalkyl.
Group of naphthene base can be the most substituted that is substituted or unsubstituted.When substituted, substituted radical is single
Solely and independently selected from following one or more groups: cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxyl, alcoxyl
Base, aryloxy group, sulfydryl, alkylthio group, arylthio, cyano group, halo, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamyl
Base, O-thiocarbamoyl, N-thiocarbamoyl, C-acylamino-, N-acylamino-, S-sulfonamido, N-sulfenyl
Amino, C-carboxyl, O-carboxyl, isocyanato-, thiocyano, isothiocyanato, nitro, silicyl, three halide sulphurs
Acyl group ,-NR ' R " or amino including single-and di-substituted amino group, and protected derivant.
In certain embodiments, C3-C30Cycloalkyl is optionally substituted by halogen.
In this application, term " alkoxyl " refers to formula-OR, and wherein R is alkyl defined above, as methoxyl group,
Ethyoxyl, positive propoxy, 1-methyl ethoxy (isopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, penta
Epoxide, tertiary amoxy etc..The moieties of alkoxy base can be as at random taken as abovementioned alkyl group definition
Generation.
In certain embodiments, alkoxyl is C1-C30Alkoxyl.In certain embodiments, alkoxyl is C1-C12Alkane
Epoxide.In certain embodiments, alkoxyl is C1-C8Alkoxyl.
In certain embodiments, C1-C30Alkoxyl is optionally substituted by halogen.
In this application, term " halogen " means bromine, chlorine, fluorine or iodine.
In this application, term " receptor " means the molecule with electron acceptability.
In this application, term " conjugated electrons donor " means that having electronics gives the conjugated molecule of ability.
In this application, term " conjugated electrons receptor " means the conjugated molecule with electron acceptability.
In this application, term " organic molecule dyestuff " mean can by fiber or other substance stain in visible region
There is the relatively strong organic micromolecule compound absorbed.
Detailed description of the invention
On the one hand, the application relate to selected from formula (1) to formula (6) to receptor type oligo-thiophenes compound:
Formula (1)
Formula (2)
Formula (3)
Formula (4)
Formula (5)
Formula (6)
Wherein, n is the integer of 1 to 50,
R1And R2Separately selected from H, C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or its halogen substiuted
Derivant, wherein R1And R2Can be the same or different, but R1And R2Can not be H simultaneously,
D and D1It is separately the conjugated electrons donor monomer of bridging,
A and A1Be separately the conjugated electrons of bridging by body unit, and
A2For organic molecule dye groups.
In certain embodiments, described formula (1) to formula (6) to D and D in receptor type oligo-thiophenes compound1
Separately selected from group 7 to group 17:
Wherein R3Selected from H, C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted.
In certain embodiments, described formula (1) to formula (6) to A and A in receptor type oligo-thiophenes compound1
Separately selected from group 18 to group 22:
Wherein R4Selected from C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted.
In certain embodiments, described formula (1) to formula (6) to A in receptor type oligo-thiophenes compound2It is selected from
Group 23 to group 46:
Wherein R5And R6Separately selected from C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or its halogen substiuted
Derivant, and
X-For A can be made2Form the anion of neutral group.
In certain embodiments, the structure of described compound is selected from:
Or
Wherein, n is the integer of 1 to 50,
R1And R2Separately selected from H, C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or its halogen substiuted
Derivant, wherein R1And R2Can be the same or different, but R1And R2Can not be H simultaneously,
R3Selected from H, C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted, and
R5Selected from C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted.
In certain embodiments, described formula (1) to formula (6) in receptor type oligo-thiophenes compound, A2Solely
On the spot selected from group 23, group 27, group 28, group 35 or group 36, wherein R5And R6Separately selected from C1-C30Alkyl,
C3-C30Cycloalkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted.
In certain embodiments, described formula (1) to formula (6) in receptor type oligo-thiophenes compound, D and D1
Separately selected from group 7, group 14, group 15 or group 17, wherein R3Selected from H, C1-C30Alkyl, C3-C30Cycloalkyl,
C1-C30Alkoxyl or the derivant of its halogen substiuted.
In certain embodiments, described formula (1) to formula (6) in receptor type oligo-thiophenes compound, A and A1
Separately selected from group 18.
In certain embodiments, described formula (1) to formula (6) in receptor type oligo-thiophenes compound, D and D1
Separately selected from group 7, group 14, group 15 or group 17, wherein R3Selected from H, C1-C30Alkyl, C3-C30Cycloalkyl,
C1-C30Alkoxyl or the derivant of its halogen substiuted, A2Independently selected from group 23, group 27, group 28, group 35 or group
36, wherein R5And R6Separately selected from C1-C30Alkyl, C3-C30Cycloalkyl, C1-C30Alkoxyl or its halogen substiuted derivative
Thing.
In certain embodiments, described formula (1) to formula (6) to n in receptor type oligo-thiophenes compound be 1 to
The integer of 30.In certain embodiments, described formula (1) is 1 to formula (6) to n in receptor type oligo-thiophenes compound
To the integer of 10.
In certain embodiments, described formula (1) to formula (6) to X in receptor type oligo-thiophenes compound-It is selected from
Halide ion, BF4 -、PF6 -、SO3 -Or CF3SO3 -。
In certain embodiments, described compound is selected from:
DCAO5T(OEH-BDT)
DRO5T(OEH-BDT)
DCAO3TTIN
BS3T
And
On the other hand, the application relates to preparing formula (1) to the side to receptor type oligo-thiophenes compound of formula (6)
Method, wherein, the oligo-thiophenes containing small molecule dyes end group of donor bridging by the oligo-thiophenes of dialdehyde base donor bridging with have
Machine small molecule dyes monomer, in the presence of solvent and catalyst, carries out Ke Neifeinageer (Knoevenagel) condensation anti-
Should, obtain described compound.
In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6)
The catalyst used in method is acidic catalyst.In certain embodiments, described prepare formula (1) to formula (6) give be subject to
The catalyst used in the method for build oligo-thiophenes compound is acidulous catalyst.
Can be used in herein described formula (1) of preparing to the method to receptor type oligo-thiophenes compound of formula (6)
In the example of exemplary acidulous catalyst include but not limited to ammonium acetate, propanoic acid ammonium and butanoic acid ammonium.
In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6)
The catalyst used in method is ammonium acetate.
In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6)
The solvent used in method is acid solution.In certain embodiments, described prepare formula (1) to formula (6) to receptor type
The solvent used in the method for oligo-thiophenes compound is weakly acidic solution.
Can be used in herein described formula (1) of preparing to the method to receptor type oligo-thiophenes compound of formula (6)
In the example of exemplary weakly acidic solution include but not limited to acetic acid, propanoic acid and butanoic acid.
In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6)
The solvent used in method is acetic acid.
In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6)
The consumption of catalyst described in method is excess.In certain embodiments, described prepare formula (1) to formula (6) to receptor
Described in the method for type oligo-thiophenes compound, the consumption of catalyst is 10-30mol%.In certain embodiments, described system
Described in the standby formula (1) method to receptor type oligo-thiophenes compound to formula (6), the consumption of catalyst is 20mol%.
In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (1) is as follows,
Step is the most anhydrous, anaerobic, under argon shield, and Ni (dppp) Cl2Catalyst, bromo-with 2-3 (and/or 4) alkylthrophene
Grignard reagent reflux 1-7 days in ether；
2. step first carries out bromination, the oligomerization of donor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid
Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Ni (dppp) Cl2Catalyst,
Catalyst amount 0.1-20mol%, the Grignard reagent of bromo-with 2-3 (and/or 4) alkylthrophene refluxes 1-7 days in ether；
3. step first carries out bromination, the oligomerization of donor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid
Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Ni (dppp) Cl2Catalyst,
Catalyst amount 0.1-20mol%, the Grignard reagent of bromo-with 2-3 (and/or 4) alkylthrophene refluxes 1-7 days in ether；
Step is the most first by POCl3Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to donor bridging
Oligo-thiophenes 1, in 2-dichloroethanes, Vilsmeier reagent excess, be heated to reflux 1-7 days；And
Step 5. acetic acid is solvent, and ammonium acetate is catalyst, catalyst amount 20mol%, receptor end monomers A* excess,
It is heated to reflux 24 hours.
In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (2) is as follows,
Step is the most anhydrous, anaerobic, under argon shield, and Pd (PPh3)4For catalyst, catalyst amount 0.1-20mol%, with
2-(tin trimethyl)-3 (and/or 4)-alkyl thiophene is in reflux in toluene 1-7 days；
2. step first carries out bromination, the oligomerization of receptor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid
Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Pd (PPh3)4For catalyst, urge
Agent consumption 0.1-20mol%, with 2-(tin trimethyl)-3 (and/or 4)-alkylthrophene or 2-(tributyl tin)-3 (and/or 4)
Alkylthrophene is in reflux in toluene 1-7 days；
3. step first carries out bromination, the oligomerization of receptor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid
Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Pd (PPh3)4For catalyst, urge
Agent consumption 0.1-20mol%, with 2-(tin trimethyl)-3 (and/or 4)-alkylthrophene or 2-(tributyl tin)-3 (and/or 4)
Alkylthrophene is in reflux in toluene 1-7 days；
Step is the most first by POCl3Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to receptor bridging
Oligo-thiophenes 1, in 2-dichloroethanes, Vilsmeier reagent excess, be heated to reflux 1-7 days；And
Step 5. acetic acid is solvent, and ammonium acetate is catalyst, catalyst amount 20mol%, receptor end monomers A* excess,
It is heated to reflux 24 hours.
In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (3) is as follows,
In formula, D and D1Can be the same or different,
Step is the most first by POCl3Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to donor bridging
Oligo-thiophenes 1, in 2-dichloroethanes, oligo-thiophenes is 1: 0.5 with the amount ratio of the material of Vilsmeier reagent, heats back
Flow 1-7 days；
Step 2. volume ratio be 1: 1 chloroform and glacial acetic acid in carry out bromination, the oligo-thiophenes of donor bridging with NBS
It is 1: 1 with the amount ratio of the material of NBS；
Step is the most anhydrous, anaerobic, and under argon shield, toluene is solvent, Pd (PPh3)4For catalyst, catalyst amount 0.1-
20mol%, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double stannum monomers of D, heating reflux reaction 1-7 days；
Under step 4. argon shield, toluene is solvent, Pd (PPh3)4For catalyst, catalyst amount 0.1-20mol%, add
Enter the K of appropriate 2mol/L2CO3Aqueous solution, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double pinacol borates of D, heating
Back flow reaction 1-7 days；And
Step 5. acetic acid is solvent, and ammonium acetate is catalyst, catalyst amount 20mol%, receptor end monomers A* excess,
It is heated to reflux 24 hours.
In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (4) is as follows,
Step is the most first by POCl3Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to receptor bridging
Oligo-thiophenes 1, in 2-dichloroethanes, the oligo-thiophenes of receptor bridging is 1 with the amount ratio of the material of Vilsmeier reagent:
0.5, it is heated to reflux 1-7 days；
Step 2. volume ratio be 1: 1 chloroform and glacial acetic acid in carry out bromination, the oligo-thiophenes of receptor bridging with NBS
It is 1: 1 with the amount ratio of the material of NBS；
Step is the most anhydrous, anaerobic, and under argon shield, toluene is solvent, Pd (PPh3)4For catalyst, catalyst amount 0.1-
20mol%, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double stannum monomers of D, heating reflux reaction 1-7 days；
Under step 4. argon shield, toluene is solvent, Pd (PPh3)4For catalyst, catalyst amount 0.1-20mol%, add
Enter the K of appropriate 2mol/L2CO3Aqueous solution, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double pinacol borates of D, heating
Back flow reaction 1-7 days；And
Step 5. acetic acid is solvent, and ammonium acetate is catalyst, catalyst amount 20mol%, receptor end monomers A* excess,
It is heated to reflux 24 hours.
In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (5) is as follows,
Under step 1. argon shield, toluene is solvent, Pd (PPh3)4For catalyst, catalyst amount 0.1-20mol%,
Add the K of appropriate 2mol/L2CO3Aqueous solution, bromo-derivative is 1 with the ratio of the amount of the material of double pinacol borate monomers of A1:
0.5, heating reflux reaction 1-7 days；And
Step 2. acetic acid is solvent, and ammonium acetate is catalyst, catalyst amount 20mol%, receptor end monomers A* excess,
It is heated to reflux 24 hours.
In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (6) is as follows,
In formula, A and A1Can be the same or different,
Under step 1. argon shield, toluene is solvent, Pd (PPh3)4For catalyst, catalyst amount 0.1-20mol%, add
Enter the K of appropriate 2mol/L2CO3Aqueous solution, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double pinacol borate monomers of A,
Heating reflux reaction 1-7 days；And
Step 2. acetic acid is solvent, and ammonium acetate is catalyst, catalyst amount 20mol%, receptor end monomers A* excess,
It is heated to reflux 24 hours.
Another further aspect, the application relates to formula (1) imitating to receptor type oligo-thiophenes compound to formula (6) in preparation field
Answer the purposes in transistor.
Another aspect, the application relates to formula (1) and is preparing photovoltaic to formula (6) to receptor type oligo-thiophenes compound
Purposes in device.
In certain embodiments, formula (1) to formula (6) to receptor type oligo-thiophenes compound may be used for preparation
Photovoltaic device is solar cell device.
In certain embodiments, formula (1) to formula (6) to receptor type oligo-thiophenes compound may be used for preparation
Photovoltaic device is the photoactive layer in solar cell device.
On the other hand, the application relate to comprising have formula (1) to formula (6) to receptor type oligo-thiophenes compound
The triode device of active layer.
Other aspects, the application relate to comprising have formula (1) to formula (6) to receptor type oligo-thiophenes compound
The photovoltaic device of active layer.
In certain embodiments, solar cell device comprise have formula (1) to formula (6) to receptor type oligomerization
The photoactive layer of thiophene compound.
The application relate to containing organic small molecule dyes receptor end group in receptor type oligo-thiophenes compound, due to
Oligo-thiophenes has higher hole mobility, and organic molecule dyestuff has high electron-withdrawing and molar absorption coefficient,
So this class involved by the application also has higher hole mobility and mole suction to receptor type oligo-thiophenes compound
Backscatter extinction logarithmic ratio.
What the application related to combines poly-containing organic small molecule dyes receptor end group to receptor type oligo-thiophenes compound
Compound and be conjugated the advantage of little molecule, has accurate molecular weight, controlled structure, the purest with conventional polymer phase ratio
Change process, has preferable dissolubility with common conjugation small molecular phase than again, makes solvation process be possibly realized, can be made into thin
Film, is conducive to preparing high performance organic field effect tube and the photovoltaic device including organic solar cell device.
Use the preparing to receptor type oligo-thiophenes compound containing organic small molecule dyes receptor end group that the application relates to
Organic thin film solar cell there is the feature of dye-sensitized cell material height molar absorption coefficient, withed a hook at the end organic simultaneously
Solaode can become the feature of fexible film.
Hereinafter, the present invention is explained in detail by below embodiment with reference to the accompanying drawings to be more fully understood that the present invention
Various aspects and advantage.It will be appreciated, however, that below example is nonrestrictive being simply used for, and the present invention is described
Some embodiment.
Embodiment
Embodiment 1
The synthesis of oligo-thiophenes precursor
1) synthesis of 2-bromo-3-octyl thiophene
60mL DMF is added in the 250mL bottle with two necks filling 3-octyl thiophene (10.00g, 50.93mmol).Cryosel is bathed
Under, instill the 60mL DMF solution of NBS (9.26g, 52.03mmol).Drip and finish, be slowly raised to room temperature, stirred overnight at room temperature.Stop
Reaction, pours in 200mL water, and dichloromethane (60mL × 4) extracts.Organic facies successively with potassium hydroxide aqueous solution (2M,
100mL), saturated aqueous common salt (100mL) and water (100mL × 2) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with oil
Ether is eluent, crosses post and separates, obtains 12.60g oily liquids, and productivity is 89%.
Its structural formula is as follows:
2) 3,3 "-dioctyl-2,2 ': 5 ', the 2 " synthesis of-three thiophene (3T)
20mL ether is added in the 100mL bottle with two necks filling magnesium chips (704mg, 28.96mmol), under argon shield, slow
Slow instillation 2-bromo-3-octyl thiophene (4.00g, 14.56mmol), glycol dibromide (1.37g, 7.28mmol) and 20mL ether
Mixed liquor.Drip and finish, be heated to reflux 4 hours, drop to room temperature.Gained Grignard reagent is slowly dropped into and fills Ni (dppp) Cl2
(177mg, 0.326mmol), 2,5-dibromo thiophene (1.40g, 5.56mmol) and the mixed liquor of 25mL ether.Drip and finish, heat back
Flow 18 hours.Dropping to room temperature, add 20mL dilute hydrochloric acid (2M), pour in 200mL water, dichloromethane (100mL × 3) extracts.Have
Aqueous sodium carbonate (2M, 100mL) used the most successively by machine, and saturated aqueous common salt (100mL) and water (100mL) are washed, and anhydrous sodium sulfate is done
Dry.Removal of solvent under reduced pressure, with petroleum ether as eluent, crosses post and separates, obtain 2.30g pale yellowish oil liquid, and productivity is 84%.
Its structural formula is as follows:
3) 5-tributyl tin-3,3 "-dioctyl-2,2 ': 5 ', the 2 " synthesis of-three thiophene (BS3T)
Under argon shield, in the 250mL there-necked flask filling three thiophene (3.65g, 7.72mmol), add 100mLTHF.
It is cooled to-78 DEG C, after the hexane solution (3.3ml, 2.4M, 2.92mmol) of dropping n-BuLi, is warming up to-40 DEG C of reaction 1h.
It is cooled to-78 DEG C again, instills tributyltin chloride (3.02g, 9.26mmol), stirred overnight at room temperature.Pour reactant into 100mL
In water, ethyl acetate (30mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL)
Washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, obtains orange-yellow oily liquids 4.83g, productivity 82%.
Its structural formula is as follows:
4) 5,5 "-two bromo-3,3 "-dioctyl-2,2 ': 5 ', 2 "-three thiophene (3TBr2) synthesis
In the 250mL bottle with two necks filling three thiophene 1 (1.20g, 2.54mmol), add 30mL chloroform and 30mL ice second
Acid, is cooled at 0 DEG C, is dividedly in some parts by NBS (0.96g, 5.39mmol), and about 20min adds.After stirring 3 hours under room temperature, will
Reactant is poured in 100mL water, and dichloromethane (100mL × 3) extracts.Organic facies successively with aqueous sodium carbonate (2M,
100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether be
Eluent, crosses post and separates, obtain 1.60g yellow oily liquid, and productivity is 100%.
Its structural formula is as follows:
5) 3,3 ', 3 " ', 3 " "-four octyl group-2,5 ': 2 ', 5 ": 2 ", 2 " ': 5 " ', the 2 " " synthesis of-five thiophene (5T)
20mL ether, argon shield, room temperature is added in the 100mL bottle with two necks filling magnesium powder (0.36g, 14.48mmol)
Lower instillation 2-bromo-3-octyl thiophene (2.00g, 7.28mmol), glycol dibromide (0.34g, 1.82mmol) and 20mL ether
Mixed liquor, drip finish, be heated to reflux 4 hours.It is added dropwise to gained Grignard reagent under argon shield fill dibromo three thiophene 2
(1.54g, 2.44mmol), Ni (dppp) Cl2In the mixed liquor of (90mg, 0.17mmol) and 20mL ether, about half an hour drips off.
It is heated to reflux 20 hours, after dropping to room temperature, adds dilute hydrochloric acid (20mL, 1M), stir 5 minutes, reactant liquor is poured into 100mL water
In, dichloromethane (100mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL)
Washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether as eluent, crosses post and separates, obtain 1.75g gold oil liquid
Body, productivity is 83%.
Its structural formula is as follows:
6) 5,5 " "-two bromo-3,3 ', 3 " ', 3 " "-four octyl group-2,5 ': 2 ', 5 ": 2 ", 2 " ': 5 " ', 2 " "-five thiophene
(5TBr2) synthesis
In the 250mL bottle with two necks filling five thiophene 3 (1.15g, 1.33mmol), add 30mL chloroform and 30mL ice second
Acid, is cooled at 0 DEG C, is dividedly in some parts by NBS (0.50g, 2.81mmol), and about 20min adds.After stirring 3 hours under room temperature, will
Reactant is poured in 100mL water, and dichloromethane (100mL × 3) extracts.Organic facies successively with aqueous sodium carbonate (2M,
100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether be
Eluent, crosses post and separates, obtain 1.22g yellow oily liquid, and productivity is 90%.
Its structural formula is as follows:
7) 3,3 ', 3 ", 3 " ", 3 " ", 3 " " "-six octyl group-2,5 ': 2 ', 5 ": 2 ", 2 " ': 5 " ', 2 " ": 5 " ", 2 " " ':
5 " " ', 2 " " " synthesis of-seven thiophene (7T)
In the 100mL bottle with two necks filling magnesium powder (0.18g, 7.24mmol), add 15mL ether, instill 2-under room temperature bromo-
3-octyl thiophene (1.00g, 3.64mmol), glycol dibromide (0.17g, 0.91mmol) and the mixed liquor of 15mL ether, drip
Finish, be heated to reflux 4 hours.Be added dropwise to gained Grignard reagent under argon shield to fill dibromo five thiophene 4 (1.24g,
1.22mmol), Ni (dppp) Cl2In the mixed liquor of (59mg, 0.11mmol) and 20mL ether, about half an hour drips off.Heat back
Flow 20 hours, after dropping to room temperature, add dilute hydrochloric acid (20mL, 1M), stir 5 minutes, reactant liquor is poured in 100mL water, dichloro
Methane (100mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous
Sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether as eluent, crosses post and separates, obtain 1.09g gold oil liquid, productivity
It is 72%.
Its structural formula is as follows:
8) 5,5 "-dicarbaldehyde-3,3 "-dioctyl-2,2 ': 5 ', the 2 " synthesis of-three thiophene (3T (CHO) 2)
At 0 DEG C, by POCl3(0.71mL, 7.74mmol) is slowly dropped in DMF (3.00mL, 38.70mmol), stirring
10 minutes, it is added dropwise to gained liquid under argon shield fill 3T (1.22g, 2.58mmol) and 30mL 1, mixing of 2-dichloroethanes
Close in mixed liquor.Being heated to 60 DEG C react 12 hours, be cooled to room temperature, pour in 200mL frozen water, sodium carbonate neutralizes, dichloromethane
(100mL × 3) extract.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous slufuric acid
Sodium is dried.Removal of solvent under reduced pressure, with the mixed liquor (volume ratio 1: 1) of petroleum ether and dichloromethane as eluent, crosses post and separates,
1.13g coral solid, productivity is 83%.
Its structural formula is as follows:
9) 5,5 " "-dicarbaldehyde-3,3 ', 3 " ', 3 " "-four octyl group-2,5 ': 2 ', 5 ": 2 ", 2 " ': 5 " ', 2 " "-five thiophene
(5T(CHO)2) synthesis
The same 3T of method (CHO)2Synthesis.Obtaining dark orange solid, productivity is 85%.
Its structural formula is as follows:
10) 5,5 " " "-diformazan aldehyde radical-3,3 ', 3 ", 3 " ", 3 " ", 3 " " "-six octyl group-2,5 ': 2 ', 5 ": 2 ", 2 " ': 5 " ',
2 " ": 5 " ", 2 " " ': 5 " " ', 2 " " "-seven thiophene (7T (CHO)2) synthesis
The same 3T of method (CHO)2Synthesis.Obtaining 1.13g brown solid, productivity is 81%.
Its structural formula is as follows:
11) synthesis of compound TBT
In the bottle with two necks of 250mL, addition 4,7-dibromo diazosulfide (6.00g, 20.4mmol), 2-tributyl tin-
4-octyl thiophene (55g, 113.3mmol), and Pd (PPh3)2Cl2(320mg, 0.46mmol).120mL is added under argon shield
Anhydrous new steaming oxolane.It is heated to reflux 24 hours, stopped reaction.Pour in 100mL water, extract with dichloromethane (100mL × 3)
Taking, organic phase washed with water (100mL) is washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, crosses post with petroleum ether for eluant and separates,
Obtaining 8.8g red solid, productivity is 82%.
Its structural formula is as follows:
12) synthesis of compound BrTBTBr
In the bottle with two necks of 100mL, add compound TBT (0.96g, 1.83mmol), 60 mL chloroforms.Cryosel bathes lower point
Criticize and add NBS (0.65g, 3.66mmol).Keep time thermotonus 1 hour, remove ice bath.Room temperature reaction is overnight.Pour 100mL into
In water, extracting with dichloromethane (100mL × 3), organic phase washed with water (100mL) is washed, and anhydrous sodium sulfate is dried.Decompression removes molten
Agent, crosses post with petroleum ether for eluant and separates, obtain 1.08g red solid, and productivity is 86%.
Its structural formula is as follows:
13) synthesis of compound 2TB2T
In the bottle with two necks of 100mL, add compound BrTBTBr (1.02g, 1.49mmol), 2-tributyl tin-4-octyl group
Thiophene (2.18g, 4.48mmol), and Pd (PPh3)2Cl2(105mg, 0.15mmol).65mL is added anhydrous newly under argon shield
Steam oxolane.It is heated to reflux 40 hours, stopped reaction.Pour in 100mL water, extract with dichloromethane (100mL × 3), have
Machine is washed with water (100mL) mutually, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, crosses post with petroleum ether for eluant and separates,
1.26g violet solid, productivity is 94%.
Its structural formula is as follows:
14) synthesis of compound Br2TB2TBr
In the bottle with two necks of 100mL, add compound 2TB2T (0.86g, 0.94mmol), 70mL chloroform.Cryosel bathes lower point
Criticize and add NBS (0.29g, 1.61mmol).Keep time thermotonus 1 hour, remove ice bath.Room temperature reaction is overnight.Pour 100mL into
In water, extracting with dichloromethane (100mL × 3), organic phase washed with water (100mL) is washed, and anhydrous sodium sulfate is dried.Decompression removes molten
Agent, crosses post with petroleum ether for eluant and separates, obtain 0.79g red solid, and productivity is 46%.
Its structural formula is as follows:
15) synthesis of compound 3TB3T
In the bottle with two necks of 250mL, add compound Br2TB2TBr (130mg, 0.12mmol), 3-butyl tin-4-octyl group
Thiophene (357mg, 0.36mmol), and Pd (PPh3)2Cl2(8.5mg, 0.01mmol).60mL is added anhydrous newly under argon shield
Steam oxolane.It is heated to reflux 40 hours, stopped reaction.Pour in 100mL water, extract with dichloromethane (100mL × 3), have
Machine is washed with water (100mL) mutually, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, crosses post with petroleum ether for eluant and separates,
139mg black solid, productivity is 89%.
Its structural formula is as follows:
16) synthesis of 5TCHO
At 0 DEG C, by POCl3(0.84mL, 9.2mmol) is slowly dropped in DMF (4.24mL, 55.0mmol), stirs 10
Minute, take the gained liquid of 1/10th under argon shield and be added dropwise to fill 5T (0.79g, 0.92mmol) and 30mL 1,2-dichloro
In the mixed liquor of ethane.Being heated to 70 DEG C react 24 hours, be cooled to room temperature, pour in 200mL frozen water, sodium carbonate neutralizes, dichloro
Methane (100mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous
Sodium sulfate is dried.Removal of solvent under reduced pressure, with the mixed liquor (volume ratio 1: 1) of petroleum ether and dichloromethane as eluent, crosses post and divides
From, obtaining 0.46g red solid, productivity is 56%.
Its structural formula is as follows:
17) synthesis of Br5TCHO
In the 100mL bottle with two necks filling 5TCHO (0.32g, 0.36mmol), add 30mL chloroform and 30mL glacial acetic acid,
Being dividedly in some parts by NBS (64mg, 0.36mmol), about 20min adds.After stirring 3 hours under room temperature, pour reactant into 100mL
In water, dichloromethane (100mL × 3) extracts.Organic facies is successively with aqueous sodium carbonate (2M, 100mL), saturated aqueous common salt
(100mL) washing with water (100mL), anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether as eluent, crosses post and separates,
0.31g red solid, productivity is 89%.
Its structural formula is as follows:
18) synthesis of compound 3TB3T (CHO)
Method is with the synthesis of 5TCHO.Obtaining 1.08g brown solid, productivity is 70%.
Its structural formula is as follows:
19) synthesis of compound Br3TB3T (CHO)
Method is with the synthesis of Br5TCHO.Obtaining 0.82g brown solid, productivity is 81%.
Its structural formula is as follows:
20) synthesis of compound D3TBT
Under argon shield, fill to dibromo bithiophene (0.40g, 1.34mmol), single tributyl tin three thiophene (2.46g,
The bottle with two necks of 40mL dry toluene 3.23mmol) and adds triphenylphosphine palladium (0.078g, 0.068mmol) 110 DEG C refluxed
Night.Being poured into by reactant liquor in 100mL water, dichloromethane (30mL × 3) extracts.Organic phase washed with water (50mL), saturated common salt
Water (50mL) and water (50mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-petroleum ether as eluant, mistake
Post separates, and obtains 0.60g Orange red solid, and productivity is 41%.
Its structural formula is as follows:
21) synthesis of compound DF3TBT
At 0 DEG C, by POCl3(0.76mL, 8.32mmol) is slowly dropped in DMF (3.19mL, 41.25mmol), stirring
10 minutes, it is added dropwise to gained liquid under argon shield fill D3TBT (0.60g, 0.55mmol) and 25mL 1,2-dichloroethanes
In mixing mixed liquor.Being heated to 60 DEG C react 12 hours, be cooled to room temperature, pour in 100mL frozen water, sodium carbonate neutralizes, dichloromethane
Alkane (30mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous slufuric acid
Sodium is dried.Removal of solvent under reduced pressure, with the mixed liquor (volume ratio 1: 1) of petroleum ether and dichloromethane as eluant, crosses post and separates,
0.40g black solid, productivity is 63%.
Its structural formula is as follows:
Embodiment 2
The synthesis of DERHD7T
Dialdehyde base seven thiophene 7T (CHO) is added in 50mL single port bottle2(50mg, 0.038mmol) and 30mL acetic acid, stirring
Make to be uniformly dispersed, add 3-ethyl Lip river tannin (20mg, 0.12mmol) and ammonium acetate (20mg, 0.12mmol), agitating heating
Backflow is overnight.Dropping to room temperature, pour in 200mL water, add the extraction of 50mL dichloromethane, organic facies adds 50mL washing (three
Secondary).Organic facies anhydrous magnesium sulfate is dried, and filters, is spin-dried for, and with dichloromethane and petroleum ether (1: 1) as eluent, column chromatography is divided
From, obtaining 60mg brown solid, productivity is 98.4%.1H NMR (400MHz, CHCl3): δ 7.764 (s, 2H) 7.209 (s,
2H), 7.100 (s, 4H), 7.011 (s, 2H), 4.21 (q, 4H, J=7.0Hz), 2.74 (t, 12H, J=6.7Hz), 1.709 (m,
12H), 1.300 (m, 60H), 0.882 (t, 18H, J=6.6Hz) .HRMS (MALDI-FTICR): C88H122N2O2S11[M]+, theoretical
Value: 1592.64；Measured value: 1591.10
Its structural formula is as follows:
Embodiment 3
The synthesis of DHFPD7T
Addition dialdehyde base seven thiophene (100mg, 0.077mmol) in 50mL single port bottle, hexafluoro acetylacetone,2,4-pentanedione (77mg,
0.37mmol), 20mL acetic acid, 5mL chloroform, stirring and dissolving are added.Under agitation heated overnight at reflux.Drop to room temperature, pour into
In 200mL water, adding the extraction of 50mL dichloromethane, organic facies adds 50mL washing (once), 50ml saturated sodium bicarbonate solution
Washing (once), 50mL washes (once).Organic facies anhydrous magnesium sulfate is dried, and filters, is spin-dried for, with dichloromethane and petroleum ether (2:
1) it is eluent, pillar layer separation, obtain 120mg dark green solid, productivity is 93.0%.1H NMR (400MHz, CHCl3): δ
7.878 (s, 2H) 7.396 (s, 2H), 7.155 (s, 4H), 6.976 (s, 2H), 2.757 (t, 12H, J=6.7Hz), 1.630 (m,
12H), 1.215 (m, 60H), 0.810 (t, 18H, J=6.6Hz) .HRMS (MALDI-FTICR): C88H112F12O4S7[M]+, reason
Opinion value: 1686.26；Measured value: 1685.32
Its structural formula is as follows:
Embodiment 4
The synthesis of DTFHD7T
Addition dialdehyde base seven thiophene (50mg, 0.038mmol) in 25mL bottle with two necks, n-butylamine (44mg,
0.6mmol), add 10mL dichloromethane stirring and dissolving, add anhydrous sodium sulfate (1g, 7ml), be stirred at room temperature 24 hours.Will
Reaction system is spin-dried for, and adds 15mL benzene and dissolves, adds trifluoroacetic ethyl acetoacetate (73mg, 0.4mmol), acetic anhydride (0.1g,
0.98mmol), after being heated to reflux 4 hours, being down to room temperature, be spin-dried for solvent, add 50mL dichloromethane and again dissolve, 50mL washes
(three times), organic facies anhydrous magnesium sulfate is dried, pillar layer separation, obtains dark green solid 32mg, productivity 52.6%.1H NMR
(400MHz, CHCl3): δ 7.853 (s, 2H) 7.409 (s, 1H), 7.342 (s, 1H) 7.134 (s, 4H), 7.021 (s, 2H),
4.32 (dd, 4H, J=6.9Hz, J=32.3Hz) 2.803 (t, 12H, J=6.7Hz), 1.685 (m, 18H), 1.259 (m,
60H), 0.878 (t, 18H, J=6.6Hz) .HRMS (MALDI-FTICR): C90H122F6O6S7[M]+, theoretical value: 1638.37；Real
Measured value: 1637.72
Its structural formula is as follows:
Embodiment 5
The synthesis of DMBA7T
Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)2(0.13g, 0.10mmol), 1,3-dimethyl-Ba Bi
Appropriate acid (0.156g, 1.00mmol) and 50mL are dried in chloroform bottle with two necks three piperidines of instillation, stirred overnight at room temperature.Pour into
In 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water
(50mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-ethyl acetate as eluant, crosses post and separates,
The black-and-blue solid of 0.12g, productivity is 79%.MALDI-TOF MS (m/z): C90H124N4O6S7[M]+, theoretical value: 1580.76；Real
Measured value: 1580.71
Its structural formula is as follows:
Embodiment 6
The synthesis of DCAEF7T
Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)2(0.13g, 0.10mmol), 2,2,2-trifluoroethyls
2-cyan-acetic ester (0.167g, 1.00mmol) and 50mL are dried in chloroform bottle with two necks three triethylamines of instillation, and room temperature is stirred
Mix overnight.Pouring in 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt
(50mL) washing with water (50mL), anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-petroleum ether as eluant, crosses post
Separating, obtain 0.11g dark green solid, productivity is 70%.MALDI-TOFMS (m/z): C88H116F6N2O4S7[M]+, theoretical value:
1603.69；Measured value: 1603.71
Its structural formula is as follows:
Embodiment 7
The synthesis of DCAPF7T
Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)2(0.13g, 0.10mmol), 2,2,3,3,3-five fluorine
Propyl group 2-cyan-acetic ester (0.217g, 1.00mmol) and 50mL are dried in chloroform bottle with two necks three triethylamines of instillation, room
Temperature is stirred overnight.Pouring in 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated common salt
Water (50mL) and water (50mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-petroleum ether as eluant, mistake
Post separates, and obtains 0.12g dark green solid, and productivity is 70%.MALDI-TOFMS (m/z): C90H116F10N2O4S7[M]+, theoretical value:
1702.68；Measured value: 1702.70
Its structural formula is as follows:
Embodiment 8
The synthesis of DCAOF7T
Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)2(0.13g, 0.10mmol), 2,2,3,3,4,4,5,
5,6,6,7,7,8,8,8-ten five fluorine octyl group 2-cyan-acetic ester (0.467g, 1.00mmol) and 50mL are dried chloroform twoport
Three triethylamines, stirred overnight at room temperature is instilled in Ping.Pouring in 100mL water, dichloromethane (20mL × 3) extracts.Organic facies depends on
Secondary water (50mL), saturated aqueous common salt (50mL) and water (50mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloro
Methane-petroleum ether is eluant, crosses post and separates, obtains 0.16g dark green solid, productivity 73%.MALDI-TOF MS (m/z):
C100H116F30N2O4S7[M]+, theoretical value: 2203.65；Measured value: 2203.71
Its structural formula is as follows:
Embodiment 9
The synthesis of 7T-2R-(8+2)
Under argon shield, filling dialdehyde base seven thiophene 7T (CHO) 2 (0.13g, 0.10mmol), (E)-5-(3-ethyl-
5-carbonyl thiazoline-2-ylide)-3-octyl group-2,4-dicarbapentaborane thiazoline (0.356g, 1.00mmol), ammonium acetate
In (0.077g, 1mmol) in 100mL bottle with two necks, add 30mL and be dried chlorobenzene and 20mL glacial acetic acid bottle with two necks, be stirred at room temperature
Night.Pouring in 100mL water, dichloromethane (30mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL)
Washing with water (50mL), anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-petroleum ether as eluant, crosses post and separates,
Obtaining the black-and-blue solid of 0.16g, productivity is 80%.MALDI-TOFMS (m/z): C110H156N4O4S13[M]+, theoretical value: 2013.85；
Measured value: 2013.83
Its structural formula is as follows:
Embodiment 10
The synthesis of DCAO3TBT
Under argon shield, fill the double thiophene three thienothiophene DFD3TBT (230mg, 0.20mmol) of dialdehyde base and
The 50mL bottle with two necks of 25mL chloroform adds 0.8mL cyanoacetic acid n-octyl, under argon shield, is stirred at reflux overnight.Fall
To room temperature, pouring in 100mL frozen water, dichloromethane (30mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt
(100mL) washing with water (100mL), anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether and the mixed liquor of dichloromethane
(volume ratio 2: 1) is eluant, crosses post and separates.1H NMR (400MHz, CDCl3): 8.21 (s, 2H), 7.60 (s, 2H), 7.31
(m, 4H), 7.14 (d, J=3.6Hz, 2H), 7.07 (s, 2H), 3.64 (t, J=6.4Hz, 4H), 2.84 (t, J=7.6Hz,
4H), 2.79 (t, J=7.6Hz, 4H), 1.68 (m, 12H), 1.28 (m, 60H), 0.89 (m, 18H).
Its structural formula is as follows:
Embodiment 11
The synthesis of DCAO3TSi
Under argon shield, cough up DCHO3TSi filling (147mg, 0.104mmol) double (aldehyde radical three thiophene) thiophene, ten times moles
The itrile group Caprylyl acetate of equivalent and 50mL are dried in chloroform bottle with two necks and instill several triethylamines, stirred overnight at room temperature.Pour into
In 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water
(50mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether-dichloromethane=1: 1 as eluant, crosses post and separates,
Obtaining brown solid, productivity is 90%.MALDI-TOF MS (m/z): C90H124N4O6S7[M]+, theoretical value: 1773.9；Actual measurement
Value: 1773.9.
Its structural formula is as follows:
Embodiment 12
The synthesis of DCAO3TBDT-1
Under argon shield, filling (1.0g, 0.71mmol) 3T (BDT) 3T (CHO) 2, the itrile group second of ten times of molar equivalents
Misery ester and 70mL are dried in chloroform bottle with two necks and instill several triethylamines, room temperature 40 hours.Pour in 100mL water, dichloro
Methane (50mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous sulfur
Acid sodium is dried.Removal of solvent under reduced pressure, with petroleum ether-dichloromethane=2: 3 as eluant, crosses post and separates, obtain black solid, produce
Rate is 70%.MALDI-TOF MS (m/z): C106H148N2O4S8[M]+, theoretical value: 1768.92；Measured value: 1768.93.
Its structural formula is as follows:
Embodiment 13
The synthesis of DCAO5T (OEH-BDT)
Under argon shield, filling (0.18g, 0.08mmol) 5T (OEH-BDT) 5T (CHO) 2, the nitrile of ten times of molar equivalents
Guanidine-acetic acid monooctyl ester and 60mL are dried in chloroform bottle with two necks and instill several triethylamines, are stirred at room temperature 48 hours.Pour 100mL water into
In, dichloromethane (50mL × 3) extracts.Organic phase washed with water (80mL), saturated aqueous common salt (80mL) and water (80mL) are washed,
Anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether-dichloromethane=2: 3 as eluant, crosses post and separates, obtain black
Solid, productivity is 76%.MALDI-TOF MS (m/z): C154H220N2O6S12[M]+, theoretical value: 2577.36；Measured value:
2577.35。
Its structural formula is as follows:
Embodiment 14
Testing to the uv-vis spectra of receptor oligomerization thiophene containing receptor end group in embodiment 2
DERHD7T is made into respectively 10-5With 10-2The chloroformic solution of mol/L, former solution measurement solution uv absorption, after
Person's solution, in 1200rpm rejection film on piezoid, measures the uv absorption of film, and sweep limits is 300-1000nm, measuring instrument
Device is Jasco V-570UV/VIS/NIR Spectrophotometer.Ultraviolet-visible absorption spectroscopy is as shown in Figure 1.
Embodiment 15
The solution of the DERHD7T in embodiment 2 and the cyclic voltammetry test of film
Molecular energy level structure is it will be seen that, to estimate highest occupied molecular orbital (HOMO) and minimum by cyclic voltammetry
The size of the value of unoccupied orbital (LUMO).We use LK98B II electrochemical workstation to carry out the test of electrochemical properties, electrolysis
Pond is three-electrode system (glass-carbon electrode is working electrode, and platinum electrode is auxiliary electrode, and calomel electrode is reference electrode), solution
Method does internal standard with ferrocene, and dried dichloromethane is solvent, the tetrabutyl hexafluorophosphoric acid amine (n-Bu of 0.1M4NPF6) for propping up
Holding electrolyte, scanning speed is 100mV s-1；The electrochemistry of film with dry acetonitrile as solvent, the tetrabutyl hexafluoro phosphorus of 0.1M
Acid amide (n-Bu4NPF6) it is supporting electrolyte, the solution of DERHD7T is dripped to film forming on glass-carbon electrode and measures.All in argon shield
Under, the cyclic voltammetry curve that scanning obtains is as shown in Figure 2.
By list of references (Li, Y.F.；Cao, Y.；Gao, J.；Wang, D.L.；Yu, G.；Heeger,
A.J.Synth.Met.1999,99,243.) converting obtains the solution of DERHD7T and the HOMO of film and lumo energy:
DERHD7T (in solution)
E (HOMO)=-5.00eV E (LUMO)=-3.28eV
DERHD7T (in film)
E (HOMO)=-5.21eV E (LUMO)=-3.74eV
Embodiment 16
The preparation of the solar cell device with the DERHD7T in embodiment 2 as electron donor
Device architecture is ITO/PEDOT:PSS/donor:PC61BM/LiF/Al, wherein donor is DERHD7T.Concrete system
Standby process is: first ITO (tin indium oxide, anode) glass is carried out pretreatment, specifically comprises the following steps that and first clean with abluent
Ito glass, deionized water rinsing is clean, and then ito glass is used acetone, isopropanol solvent ultrasonic cleaning each 20 minutes successively,
Put into after taking-up in baking oven and dry.One layer of PEDOT:PSS of spin coating (Baytron P VP on the most pretreated ito glass
Al 4083) as anode modification layer (40nm), until PEDOT:PSS after 140 DEG C of heating are completely dried for 20 minutes, will after cooling
DERHD7T∶PC61The chloroformic solution (DERHD7T: PC of BM mixture61BM mass ratio is respectively 1: 0.8, and 1: 0.5,1；0.3,
DERHD7T concentration is 8mg/mL) it is spin-coated on PEDOT:PSS surface as active layer (80nm), it is deposited with LiF (0.8nm) the most again
And metal electrode Al (60nm).Keep vacuum less than 3 × 10 during evaporation-4Pa.At standard sunlight (AM 1.5G) spoke
Under the conditions of according to, use computer-controlled Keithley 2400 digital sourcemeter that device performance is tested.The electric current of device is close
Degree-voltage curve is as it is shown on figure 3, performance parameter is listed in table 1.Table 1: in embodiment 2, compound is prepared to receptor ratio with difference
Solar cell properties compares
(light intensity is 100mW/cm2AM1.5G measures under the conditions of irradiating)
As shown in Table 1, the body heterojunction solar cell device that the solution utilizing the compound of the present invention to prepare processes
Ultravioletvisible absorption can reach 780nm, solar device open-circuit voltage reaches more than 0.90V, and short circuit current reaches 14mA/
cm2Above, maximum photoelectric transformation efficiency can reach more than 6%.
As can be seen here, the compound of the present invention has accurate molecular weight, structure-controllable, easy purification, it is adaptable to preparation tool
There are high open circuit voltage, good stability, flexibility, large-area high-performance organic solar batteries.
Although being appreciated that in order to the purpose of exemplary illustration describes specific embodiments of the present invention from the foregoing,
But under condit without departing from the spirit and scope of the present invention, technical staff described in this area may be made that various deformation or changes
Enter.These deformation or amendment all should fall into the application scope of the following claims.
Claims (19)
1. selected from formula (1) to formula (6) to receptor type oligo-thiophenes compound:
Wherein, n is the integer of 1 to 30；
R1And R2Separately selected from H, C1-C30Alkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted, wherein R1And R2
Can be the same or different, but R1And R2Can not be H simultaneously；
D and D1It is separately the conjugated electrons donor monomer of bridging, wherein D and D1Separately selected from group 7 and 8:
A and A1Be separately the conjugated electrons of bridging by body unit, wherein A and A1It is separately group 22:
A2For organic molecule dye groups, wherein A2Selected from group 23 to group 25:
Wherein R5Selected from C1-C30Alkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted.
2. compound as claimed in claim 1, the structure of wherein said compound is selected from:
Wherein, n is the integer of 1 to 30,
R1And R2Separately selected from H, C1-C30Alkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted, wherein R1And R2
Can be the same or different, but R1And R2Can not be H simultaneously, and
R5Selected from C1-C30Alkyl, C1-C30Alkoxyl or the derivant of its halogen substiuted.
3. compound as claimed in claim 1 or 2, wherein n is the integer of 1 to 10.
4. compound as claimed in claim 1, it is:
DERHD7T
5. the method for compound described in any claim in preparation claim 1-4, wherein, contaminating containing little molecule of donor bridging
The oligo-thiophenes of material end group is by the oligo-thiophenes of dialdehyde base donor bridging and organic molecule dye monomer, in solvent and catalysis
In the presence of agent, carry out Ke Neifeinageer (Knoevenagel) condensation reaction, obtain described compound.
6. method as claimed in claim 5, wherein said catalyst is acidic catalyst.
7. method as claimed in claim 6, wherein said acidic catalyst is acidulous catalyst.
8. method as claimed in claim 7, wherein said acidulous catalyst is ammonium acetate, propanoic acid ammonium or butanoic acid ammonium.
9. method as claimed in claim 5, wherein said solvent is acid solution.
10. method as claimed in claim 9, wherein said acid solution is weakly acidic solution.
11. methods as claimed in claim 10, wherein said weakly acidic solution is acetic acid, propanoic acid or butanoic acid.
12. methods as described in any claim in claim 5-11, the consumption of wherein said catalyst is excess.
13. claim 1-4 are preparing field effect transistor to receptor type oligo-thiophenes compound described in any claim
Purposes in pipe.
In 14. claim 1-4 described in any claim to receptor type oligo-thiophenes compound in preparing photovoltaic device
Purposes.
15. purposes as claimed in claim 14, wherein said photovoltaic device is solar cell device.
16. purposes as claimed in claim 15, wherein said compound is lived for the light preparing described solar cell device
Property layer.
17. triode devices, it comprises the active layer in claim 1-4 with the compound described in any claim.
18. photovoltaic devices, it comprises the active layer in claim 1-4 with the compound described in any claim.
19. photovoltaic devices as claimed in claim 18, wherein said photovoltaic device is solar cell device.
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| CN103588770B (en) * | 2013-11-27 | 2016-08-17 | 武汉尚赛光电科技有限公司 | 1,2,4-thiadiazoles derivative and the application as electroluminescent material thereof |
| CN104774200B (en) * | 2014-01-09 | 2018-01-23 | 南开大学 | It is prepared by organic photoelectrical material |
| CN104130252B (en) * | 2014-07-15 | 2016-09-14 | 南开大学 | Organic photoelectric compound and its preparation method and application |
| CN107163035B (en) * | 2017-04-07 | 2019-06-07 | 中南大学 | A kind of oligo-thiophenes organic micromolecule and its preparation method and application |
| WO2019137354A1 (en) * | 2018-01-10 | 2019-07-18 | The Hong Kong University Of Science And Technology | Thiophene-based fused aromatic systems |
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