CN108440574A - A kind of organic molecule and its preparation method and application containing thiazole - Google Patents
A kind of organic molecule and its preparation method and application containing thiazole Download PDFInfo
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- CN108440574A CN108440574A CN201810288440.XA CN201810288440A CN108440574A CN 108440574 A CN108440574 A CN 108440574A CN 201810288440 A CN201810288440 A CN 201810288440A CN 108440574 A CN108440574 A CN 108440574A
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- 0 CC#CC(*C(N1*)=S)C1=O Chemical compound CC#CC(*C(N1*)=S)C1=O 0.000 description 9
- QGNBNKAIDXSRNQ-SGAXSIHGSA-N C/C=C(/C(c1ccccc11)=C(C#N)C#N)\C1=O Chemical compound C/C=C(/C(c1ccccc11)=C(C#N)C#N)\C1=O QGNBNKAIDXSRNQ-SGAXSIHGSA-N 0.000 description 1
- WILGXDYWAUYSIP-SCZISCPTSA-N C/C=C(\C(\c1ccccc11)=C(/C)\C#N)/C1=C(C#N)C#N Chemical compound C/C=C(\C(\c1ccccc11)=C(/C)\C#N)/C1=C(C#N)C#N WILGXDYWAUYSIP-SCZISCPTSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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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
Abstract
The invention discloses a kind of organic molecule and its preparation method and application containing thiazole, utilizes high performance benzene thiophene unit（BDT）For daughter nucleus of powering, thiazole is as bridging unit, and the drawing electronic unit design for changing end has synthesized a series of completely new, dissolubility is good, thermal stability is good using thiazole as the A D A conjugated molecules of bridging unit, due to the oxidation stability of thiazole unit, the structure of flatness and pi accumulation, what electronic unit was drawn in high carrier mobility and end hales electronic capability, therefore this kind of molecule possesses strong visible light absorption capacity, high charge transport properties and suitable electron energy level, it is adapted as electron donor or electron acceptor material is applied to prepare organic solar batteries.
Description
Technical field
The present invention relates to molecular engineering fields, and in particular to a kind of organic molecule and preparation method thereof containing thiazole, with
And using the organic molecule containing thiazole as active layer electron donor or electron acceptor material at organic solar batteries (OPV)
In application.
Background technology
The organic solar batteries of solution processing are as a promising green energy resource technology due to having some uniquenesses
Advantage such as：It is inexpensive, light, broad area device preparation etc. can be carried out make great progress.Based on conjugated polymers
The energy conversion efficiency PCE for the organic solar batteries that object or organic molecule are donor, fullerene derivate is receptor is
Through be more than 10% (J.Wan, X.Xu, G.Zhang, Y.Li, K.Feng and Q.Peng, Energy Environ.Sci.,
2017,10,1739；B.Kan,M.Li,Q.Zhang,F.Liu,X.Wan,Y.Wang,W.Ni,G.Long,X.Yang and
H.Feng,J.Am.Chem.Soc.,2015,137,3886；D.Deng,Y.Zhang,J.Zhang,Z.Wang,L.Zhu,
J.Fang,B.Xia,Z.Wang,K.Lu and W.Ma,Nat.commun.,2016,7,13740；Y.Liu,C.-C.Chen,
Z.Hong,J.Gao,Y.M.Yang,H.Zhou,L.Dou,G.Li and Y.Yang,Sci.Rep.,2013,3,3356；
X.Ouyang,R.Peng,L.Ai,X.Zhang and Z.Ge,Nat.Photonics,2015,9,520；J.Zhao,Y.Li,
G.Yang,K.Jiang,H.Lin,H.Ade,W.Ma and H.Yan,Nature Energy,2016,1,15027.).However,
Some intrinsic defects, including high cost, solar spectrum visible region absorb weaker and energy level be difficult to still to deposit
It is in fullerene acceptor.Therefore non-fullerene acceptor material high performance in recent years obtain faster development (Y.Lin,
J.Wang,Z.G.Zhang,H.Bai,Y.F.Li,D.Zhu and X.W.Zhan,Adv.Mater.,2015,27,1170；
Y.Lin,Q.He,F.Zhao,L.Huo,J.Mai,X.Lu,C.-J.Su,T.Li,J.Wang,J.Zhu,Y.Sun,C.Wang and
X.W.Zhan,J.Am.Chem.Soc.,2016,138,2973；Y.Lin,Z.-G.Zhang,H.Bai,J.Wang,Y.Yao,
Y.F.Li,D.Zhu and X.W.Zhan,Energy Environ.Sci.,2015,8,610.W.Zhao,S.Li,H.Yao,
S.Zhang,Y.Zhang,B.Yang and J.H.Hou,J.Am.Chem.Soc.,2017,139,7148.)。
It is compared to polymer, organic molecule has distinctive advantage, such as：Be easily purified, with determining molecular weight, point
Sub- energy level be easy to difference between regulation and control and each batch it is smaller etc. (W.Ni, M.Li, B.Kan, F.Liu, X.Wan, Q.Zhang,
H.Zhang,T.P.Russellcd and Y.Chen,Chem.Commun.,2016,52,465；C.H.Cui,X.Guo,
J.Min,B.Guo,X.Cheng,M.J.Zhang,C.J.Brabec and Y.F.Li,Adv.Mater.,2015,27,7469；
B.Kan,Q.Zhang,M.Li,X.Wan,W.Ni,G.Long,Y.Wang,X.Yang,H.Feng and Y.Chen,
J.Am.Chem.Soc.,2014,136,15529.).Therefore, in the small molecule organic solar batteries based on PCBM, photovoltaic
Device has reached very high energy conversion efficiency (J.Wan, X.Xu, G.Zhang, Y.Li, K.Feng and Q.Peng, Energy
Environ.Sci.,2017,10,1739；B.Kan,M.Li,Q.Zhang,F.Liu,X.Wan,Y.Wang,W.Ni,G.Long,
X.Yang and H.Feng,J.Am.Chem.Soc.,2015,137,3886；D.Deng,Y.Zhang,J.Zhang,Z.Wang,
L.Zhu,J.Fang,B.Xia,Z.Wang,K.Lu and W.Ma,Nat.commun.,2016,7,13740.).However, when non-
When fullerene acceptor is combined together with organic molecule donor, organic solar batteries can obtain a relatively poor photovoltaic
Performance (W.Ni, M.Li, B.Kan, F.Liu, X.Wan, Q.Zhang, H.Zhang, T.P.Russellcd and Y.Chen,
Chem.Commun.,2016,52,465；L.Yang,S.Zhang,C.He,J.Zhang,H.Yao,Y.Yang,Y.Zhang,
W.Zhao,and J.H.Hou,J.Am.Chem.Soc.,2017,139,1958；G.Feng,Y.Xu,J.Zhang,Z.Wang,
Y.Zhou,Y.Li,Z.Wei,C.Li and W.Li,J.Mater.Chem.A,2016,4,6056.).Up to the present, non-lipid
The development for strangling the full small molecule organic solar batteries of alkene lags behind the organic solar batteries based on polymer or fullerene.It examines
Consider the advantage that the full small molecule organic solar batteries of non-fullerene combine both non-fullerene acceptor and small molecule donor, institute
With it with huge development potentiality, but low photovoltaic performance is an important problem for needing to solve.Above we
It has been noted that non-fullerene acceptor material high performance in recent years obtains development quickly.Thus, designing new and effective has
Machine small molecule donor material matches with it, and the photovoltaic performance to promoting full small molecule organic solar batteries has important meaning
Justice.
Design for active layer electron donor or electron acceptor material, some elements include：Dissolubility well, wide suction
It receives spectrum and has to consider and maintain one with high extinction coefficient, suitable energy level and high mobility
A good balance (B.Kan, M.Li, Q.Zhang, F.Liu, X.Wan, Y.Wang, W.Ni, G.Long, X.Yang and
H.Feng,J.Am.Chem.Soc.,2015,137,3886；B.Kan,Q.Zhang,M.Li,X.Wan,W.Ni,G.Long,
Y.Wang,X.Yang,H.Feng and Y.Chen,J.Am.Chem.Soc.,2014,136,15529.).It is given using receptor-
The skeleton of body-receptor (A-D-A) type is i.e. comprising an electron rich cells D as power supply daughter nucleus and two stronger lists of electrophilic
First A as end group, be a kind of adjusting absorption spectrum and molecular entergy level available strategy (Y.Chen, X.Wan and G.Long,
Acc.Chem.Res.,2013,46,2645；R.Fitzner,E.Mena-Osteritz,A.Mishra,G.Schulz,
E.Reinold,M.Weil,C.Korner,H.Ziehlke,C.Elschner,K.Leo,M.Riede,M.Pfeiffer,
C.Uhrich and P.Bauerle,J.Am.Chem.Soc.,2012,134,11064.).Past work has revealed that out base
In benzene thiophene (BDT) unit excellent photovoltaic has been shown as the photovoltaic small molecule active layer material of power supply daughter nucleus
Can (J.Wan, X.Xu, G.Zhang, Y.Li, K.Feng and Q.Peng, Energy Environ.Sci., 2017,10,
1739；Z.Wang,X.Xu,Z.Li,K.Feng,K.Li,Y.Li and Q.Peng,Adv.Electron.Mater.,2016,2,
1600061；H.Bin,Y.Yang,Z.G.Zhang,L.Ye,M.Ghasemi,S.Chen,Y.Zhang,C.Zhang,C.Sun,
L.Xue,C.Yang,H.Ade and Y.F.Li,J.Am.Chem.Soc.,2017,139,5085；B.Qiu,L.Xue,
Y.Yang,H.Bin,Y.Zhang,C.Zhang,M.Xiao,K.Park,W.Morrison,Z.G.Zhang,and Y.F.Li,
Chem.Mater.,2017,29,7543.)。
It is also to improve one of the key factor of photovoltaic performance using suitable bridging unit bridges.It is worth noting that, strong inhale
Electro thiazole unit causes huge concern, this, which has benefited from it, has such as：Oxidation stability, flatness and the π having had
The structure of accumulation and high carrier mobility (B.Guo, X.Guo, W.Li, X.Meng, W.Ma, M.Zhang, and Y.Li,
J.Mater.Chem.A,2016,4,13251；I.Osaka,M.Saito,T.Koganezawa,and K.Takimiya,
Adv.Mater.,2014,26,331.).Therefore, much the high-performance polymer system based on thiazole unit has obtained widely
Using (B.Guo, X.Guo, W.Li, X.Meng, W.Ma, M.Zhang, and Y.Li, J.Mater.Chem.A, 2016,4,
13251；B.Guo,W.B.Li,X.Guo,X.Y.Meng,W.Ma,M.J.Zhang,and Y.F.Li,Adv.Mater.,2017,
29,1702291.), but it is seldom applied in small molecule photovoltaic material.Since thiazole unit has huge application potential,
So being introduced into organic molecule it is desirable that efficient organic photovoltaic material can be obtained.
Invention content
It is an object of the present invention to provide a kind of organic molecule, preparation method and application containing thiazole.
The present invention a kind of technical solution be：
A kind of organic molecule containing thiazole, the organic molecule are to be as core, with thiazole using benzene thiophene unit
The A-D-A of bridging unit is conjugated organic molecule, including following general formula structure：
Wherein,
Any one of X in O, S or Se；
R1~R3Independently selected from hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls in it is any one
Kind；
Ar1And Ar2Independently represent any one in unsubstituted or following group containing substituent group：
Ethenylidene, ethynylene, monocycle arlydene, bicyclic arlydene, the arlydene containing at least three rings, the miscellaneous Asia of monocycle
Aryl, bicyclic heteroarylidene or the heteroarylidene containing at least three rings, the bicyclic arlydene, the Asia virtue containing at least three rings
In base, bicyclic heteroarylidene, the heteroarylidene containing at least three rings, condenses between ring and ring or connected by singly-bound；
Work as Ar1And Ar2In any one or two it is substituted simultaneously when, Ar1Or Ar2It is respectively provided with 1~2 substituent group,
The substituent group is aryl, has C1~C30Alkyl or have C1~C30Alkoxy in any one；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl in any one；
Alkyl in the 4- alkyl phenyls is C1~C8Alkyl in any one.
Further, the X=S；The R1~R3It independently is hydrogen, C1~C8Alkyl or 4- hexyl phenyl in appoint
Meaning is a kind of；R in the A structures4For C1~C8Alkyl in any one.
The present invention another technical solution be：
A kind of preparation method of the organic molecule containing thiazole, includes the following steps：
(1) compound 1 is dissolved in the in the mixed solvent of chloroform and glacial acetic acid, ice-water bath and under the conditions of being protected from light slowly plus
Enter N- bromo-succinimides, half an hour drops back after deicing water-bath carries out stirring at normal temperature 10 hours separating-purifyings of reaction and chemical combination is made
Object 2；
(2) phosphorus oxychloride and n,N-Dimethylformamide are stirred reaction 1~2 hour under the conditions of ice-water bath, later
Ice-water bath is removed, phosphorus oxychloride and N before the compound 2 is dissolved in chloroform and is added to syringe, N- dimethyl
In product after formamide, 70 DEG C are stirred at reflux obtained compound 3 after 12 hours separating-purifyings of reaction；
(3) make under the conditions of 110 DEG C the compound 3, compound 4 and catalyst tetrakis triphenylphosphine palladium in toluene into
Compound 5 is made after being stirred to react 20~30 hours separating-purifyings in row；
(4) compound 5, drawing electron group A and piperidines or pyridine is made to be stirred in chloroform under the conditions of 70 DEG C
Reaction 12 hours is mixed, it is core and thiophene based on benzene thiophene unit to be made after final separation purification with following general formula structure
Azoles is the A-D-A conjugated molecule product 6 of bridging unit：
Wherein,
Any one of X in O, S or Se；
R1~R3Independently selected from hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls in it is any one
Kind；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl in any one；
Alkyl in the 4- alkyl phenyls is C1~C8Alkyl in any one.
Further, the molar ratio of the addition of the piperidines or pyridine and compound 5 is 1:0.001~0.5.
Further, the step (2), (3) and (4) is stirred reaction under atmosphere of inert gases.
Further, the molar ratio of the addition Yu compound 4 of the tetrakis triphenylphosphine palladium is 1:10~100.
The active layer electron donor or electronics that the organic molecule containing thiazole prepared by aforesaid way is captured as light by
Body material is applied in preparing organic solar batteries.
The present invention provides a kind of organic molecule containing thiazole, major advantage is：
1, synthesis based on thiazole be bridging unit A-D-A conjugated molecules can solwution method processing, chloroform, tetrahydrochysene can be dissolved in
In the organic solvents such as furans and chlorobenzene；
2, synthesis is good based on the A-D-A conjugated molecules thermal stability that thiazole is bridging unit, and starting heat decomposition temperature is super
Cross 400 DEG C；
3, light absorptive of the synthesis based on the A-D-A conjugated molecules that thiazole is bridging unit is good, is suitble to do organic solar electricity
Pond material；
4, what is synthesized possesses suitable electron energy level based on the A-D-A conjugated molecules that thiazole is bridging unit, is suitable for
Electron donor material in organic solar batteries or electron acceptor material；
5, synthesis based on thiazole be bridging unit A-D-A conjugated molecules as electron donor material or electron acceptor material
Material shows high electricity conversion in organic solar batteries.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without having to pay creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein,
Fig. 1 is a kind of UV-visible absorption spectrum of the organic molecule containing thiazole of the present invention；
Fig. 2 is a kind of cyclic voltammetry curve figure of the organic molecule containing thiazole of the present invention；
Fig. 3 is a kind of thermal gravimetric analysis curve figure of the organic molecule containing thiazole of the present invention；
Fig. 4 is a kind of differential calorimetry curve figure of the organic molecule containing thiazole of the present invention；
Fig. 5 is a kind of organic molecule containing thiazole of the present invention in the J- applied to organic solar batteries
V curves；
Fig. 6 is a kind of synthetic route of organic molecule containing thiazole of the present invention；
Fig. 7 is a kind of BTTzR synthetic routes of organic molecule containing thiazole of the present invention.
Specific implementation mode
Organic molecule of the present invention is using benzene thiophene unit as core, using thiazole as the A-D-A of bridging unit
It is conjugated organic molecule, including following general formula structure：
Wherein,
Any one of X in O, S or Se；
R1~R3Independently selected from hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls in it is any one
Kind；
Ar1And Ar2Independently represent any one in unsubstituted or following group containing substituent group：
Ethenylidene, ethynylene, monocycle arlydene, bicyclic arlydene, the arlydene containing at least three rings, the miscellaneous Asia of monocycle
Aryl, bicyclic heteroarylidene or the heteroarylidene containing at least three rings, Ar1And Ar2Can be identical or differ the bicyclic sub- virtue
In base, the arlydene containing at least three rings, bicyclic heteroarylidene, the heteroarylidene containing at least three rings, condensed between ring and ring
Or it is connected by singly-bound；
Work as Ar1And Ar2In any one or two it is substituted simultaneously when, Ar1Or Ar2It is respectively provided with 1~2 substituent group,
The substituent group is aryl, has C1~C30Alkyl or have C1~C30Alkoxy in any one；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl in any one；
Alkyl in the 4- alkyl phenyls is C1~C8Alkyl in any one.
The preparation method of above structure, referring to Fig. 6, Fig. 6 is a kind of organic molecule containing thiazole of the present invention
Synthetic route.As shown in fig. 6, including below step：
(1) compound 1 is dissolved in the in the mixed solvent of chloroform and glacial acetic acid, ice-water bath and under the conditions of being protected from light slowly plus
Enter N- bromo-succinimides, half an hour drops back after deicing water-bath carries out stirring at normal temperature 10 hours separating-purifyings of reaction and chemical combination is made
Object 2；
(2) phosphorus oxychloride and N,N-dimethylformamide under ice-water bath and atmosphere of inert gases under the conditions of be stirred it is anti-
It answers 1~2 hour, removes ice-water bath later, trichlorine oxygen before the compound 2 is dissolved in chloroform and is added to syringe
In product after phosphorus and n,N-Dimethylformamide reaction, 70 DEG C are stirred at reflux obtained compound after 12 hours separating-purifyings of reaction
3；
(3) make the compound 3, compound 4 and catalyst four under 110 DEG C of temperature condition and atmosphere of inert gases
Compound 5 is made after being stirred 20~30 hours separating-purifyings of reaction in toluene in (triphenylphosphine) palladium, wherein described four
The addition of (triphenylphosphine) palladium and the tetrakis triphenylphosphine palladium catalyst and the benzene thiophene list for carrying Ar substituent groups
The molar ratio of first tin trimethyl compound, that is, compound 4 is 1:10~100；
(4) make the compound 5, drawing electron group A and piperidines under 70 DEG C of temperature condition and atmosphere of inert gases
Or pyridine is stirred reaction 12 hours in chloroform, is made with following general formula structure based on benzo after final separation purification
The A-D-A conjugated molecule product 6 that Dithiophene unit is core and thiazole is bridging unit, wherein the piperidines or pyridine plus
Enter amount with it is described carry R1, R2, R3 substituent groups using benzene thiophene unit as core and using thiazole as the aldehyde radical of bridging unit
The molar ratio of compound, that is, compound 5 is 1:0.001~0.5：
Wherein,
Any one of X in O, S or Se；
R1~R3Independently selected from hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls in it is any one
Kind；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl in any one；
Alkyl in the 4- alkyl phenyls is C1~C8Alkyl in any one.
The characteristic of the obtained organic molecule containing thiazole please refers to Fig.1-Fig. 4：
As shown in Figure 1, there is stronger absorption within the scope of 300-700nm, and film absorption have at 610nm it is one apparent
Acromion is absorbed, shows that intermolecular there are stronger interaction and aggregations；
As shown in Fig. 2, the initial oxidation current potential of small moleculeIt is 0.73V vs Ag/Ag+, initial reduction current potential
It is -1.14V vs Ag/Ag+.Pass through formula HOMO=- (Eox+ 4.73) (eV) and LUMO=- (Ere+ 4.73) (eV) can be calculated
It is respectively -5.46eV and -3.59eV to go out the HOMO energy levels of BTTzR and lumo energy；
As shown in figure 3, heat decomposition temperature (the T when small molecular weight loss 5%d) it is 402 DEG C, illustrate small molecule
BTTzR has good thermal stability；
As shown in figure 4, small molecule has a clear sharp melting endothermic peak (T at 315 DEG C during heatingm), it is corresponding
In exothermic process at 291 DEG C occur an apparent crystalline exotherm peak (Tc), it can be deduced that conclusion small molecule BTTzR has
Good crystal property.
The active layer electron donor or electricity that the above-mentioned organic molecule containing thiazole is captured as light is also claimed in the present invention
Sub- acceptor material is applied in preparing organic solar batteries.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawings and examples
The technical solution further illustrated the present invention.But the present invention is not limited to listed embodiments, should also be included in institute of the present invention
It is required that interest field in other any well known change.
First, " one embodiment " or " embodiment " referred to herein refers to that may be included at least one realization side of the present invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiment.
Secondly, the present invention is described in detail using structural schematic diagram etc., when describing the embodiments of the present invention, for ease of saying
Bright, schematic diagram can disobey general proportion and make partial enlargement, and the schematic diagram is example, should not limit the present invention herein
The range of protection.In addition, three dimensions that should be comprising length, width and depth in actual fabrication.
Embodiment 1
Referring to Fig. 7, Fig. 7 is a kind of BTTzR synthetic routes of organic molecule containing thiazole of the present invention.Such as figure
Shown in 7, the implementation case shows the synthetic route of the organic molecule containing thiazole as follows：
Note：R1Indicate 2- ethylhexyls, R2Indicate n-hexyl.
The detailed synthesis step of its each step product is as follows：
Step 1) synthesizes compound 2,2- (the bromo- 4- of 5- (2- ethylhexyls) thiophene -2- bases) -5- (4- (2- ethylhexyls)
Thiophene -2- bases) thiazole [5,4-d] and thiazole；
With compound 1, i.e. (4- (2- ethylhexyls) thiophene -2- bases) thiazoles [5,4-d] of 2,5- bis- and thiazole as raw material,
It is placed in the single necked round bottom flask of a 100ml, chloroform (25ml) and glacial acetic acid (25ml) is then added.It is protected from light in ice-water bath
Under the conditions of, N- bromo-succinimides (0.71g, 4.01mmol) are slowly added into single port bottle.Add N- bromos fourth two
After acid imide, plus the spherical drying tube with anhydrous magnesium sulfate in single port bottle, and react 10 hours under stirring conditions.
Later reaction mixture is poured into extract in water (60ml) and chloroform and be dried afterwards with anhydrous magnesium sulfate three times.It is revolved with revolving
Except crude product is obtained after organic solvent and use petroleum ether as eluant, eluent carry out column chromatography for separation obtain compound 2 (1.16g, production
Rate 50%) be crocus solid, i.e. 2- (the bromo- 4- of 5- (2- ethylhexyls) thiophene -2- bases) -5- (4- (2- ethylhexyls) thiophenes
Pheno -2- bases) thiazole [5,4-d] and thiazole.
Structural identification data is as follows：1H NMR(400MHz,CDCl3),δ(ppm):7.38(s,1H),7.21(s,1H),
7.04 (d, 1H), 2.56-2.55 (d, 2H), 2.52-2.50 (d, 2H), 1.35-1.29 (m, 18H), 0.93-0.88 (m, 12H),
(MALDI-TOF)MS:calcd.for C28H37BrN2S4M/z=609.77；found 611.23.
Step 2) synthesizes compound 3,5- (5- (the bromo- 4- of 5- (2- ethylhexyls) thiophene -2- bases) thiazoles [5,4-d] and thiophene
Azoles -2- bases) -3- (2- ethylhexyls) thiophene -2-formaldehyde；
In argon inert atmosphere, phosphorus oxychloride (1.32ml, 14.16mmol) is injected into a 100ml's with syringe
In two mouthfuls of round-bottomed flasks.Then under the conditions of ice-water bath, with syringe by n,N-Dimethylformamide (1.36ml, 17.7mmol)
It is slowly added drop-wise in two-mouth bottle and reacts one and a half hours under stirring conditions.By compound 2 (1.08g, 1.77mmol)
It is dissolved in chloroform (30ml).This chloroformic solution dissolved with compound 2 is injected into two-mouth bottle with syringe again.Later,
Reaction mixture is transferred in 70 DEG C of oil bath pan, under stirring conditions back flow reaction after 12 hours by this mixture with two
Chloromethanes (120ml) extracts.Solvent is removed with revolving rotation again after being dried with anhydrous magnesium sulfate, obtained crude product is with petroleum ether/bis-
Chloromethanes (1:1) eluant, eluent is used as to carry out column chromatography for separation to finally obtain compound 3 (0.99g, yield 88%) being Chinese red
Solid, i.e. 5- (5- (the bromo- 4- of 5- (2- ethylhexyls) thiophene -2- bases) thiazoles [5,4-d] and thiazol-2-yl) -3- (2- ethyl hexyls
Base) thiophene -2-formaldehyde.
Structural identification data is as follows：1H NMR(400MHz,CDCl3),δ(ppm):10.04(s,1H),7.40(s,1H),
7.24 (s, 1H), 2.90-2.88 (d, 2H), 2.52-2.51 (d, 2H), 1.38-1.25 (m, 18H), 0.93-0.89 (m, 12H),
(MALDI-TOF)MS:calcd.for C29H37BrN2OS4M/z=637.78；found 638.23.
Step 3) synthesizes (5,5'- (5,5'- (4,8- bis- (5- (2- the ethylhexyls) -4- hexyl thiophenes-of compound 5,5,5'-
2- yls) benzo [1,2-b:4,5-b'] Dithiophene -2,6- diyls) two (4- (2- ethylhexyls) thiophene -5,2- diyls)) two (thiophenes
Azoles [5,4-d] and thiazole -5,2- diyls)) two (3- (2- ethylhexyls) thiophene -2-formaldehydes)；
In two mouthfuls of round-bottomed flasks of a dried 100ml, by compound 3 (0.87g, 1.36mmol), compound 4
(4,8- bis- (5- (2- ethylhexyls) -4- hexyl thiophene -2- bases) benzo [1,2-b:4,5-b'] Dithiophene -2,6- diyls) two
(trimethyl-tin-radical) (0.59g, 0.55mmol) (compound 4 is bought from Na Kai companies) and catalyst tetrakis triphenylphosphine palladium
[Pd(PPh3)4] (0.047g, 0.04mmol) be dissolved in together in the toluene of dry purifying.The mixture of reaction is protected in argon gas
Be placed in oil bath pan under conditions of shield (temperature in oil bath pan slowly rises to 110 DEG C) and under stirring conditions reaction it is 24 small
When.After the completion of reaction, reactant is poured into the mixed liquor of water and dichloromethane (100ml) and extracted three times.Organic layer is with anhydrous
Magnesium sulfate is dried and is revolved to remove after solvent obtains crude product with revolving and detached with column chromatography silica gel method, column chromatography for separation
The specific polarity of eluant, eluent is petroleum ether：Chloroform=1:1, it is red solid (0.75g, yield 73%) to finally obtain compound 5,
That is 5,5'- (5,5'- (5,5'- (4,8- bis- (5- (2- ethylhexyls) -4- hexyl thiophene -2- bases) benzo [1,2-b:4,5-b']
Dithiophene -2,6- diyls) two (4- (2- ethylhexyls) thiophene -5,2- diyls)) two (thiazole [5,4-d] and thiazole -5,2- two
Base)) two (3- (2- ethylhexyls) thiophene -2-formaldehydes).
Structural identification data is as follows：1H NMR(400MHz,CD2Cl2),δ(ppm):9.98(s,2H),7.74(s,2H),
7.37-7.36(d,4H),7.32(s,2H),2.83-2.80(t,12H),2.69-2.66(t,4H),1.50-1.28(m,70H),
1.00-0.84 (m, 42H), (MALDI-TOF) MS:calcd.For C104H138N4O2S12M/z=1861.01；found
1860.03.
Step 4) synthesizes BTTzR, (5Z, 5'Z) -5,5'- ((5,5'- (5,5'- (5,5'- (4,8-bis (5- (2- ethyl hexyls
Base) -4- hexyl thiophene -2- bases) benzo [1,2-b:4,5-b'] Dithiophene -2,6- diyls) two (4- (2- ethylhexyls) thiophene -
5,2- diyls)) two (thiazole [5,4-d] and thiazole -5,2- diyls)) two (3- (2- ethylhexyls) thiophene -5,2- diyls)) two
(methyl subunit)) two (3- ethyls-rhodanine)；
Compound 5 (0.39g, 0.21mmol) is dissolved in the chloroform solvent (40ml) totally purified.Then it is added and draws
Electronics end group rhodanine (0.34g, 2.1mmol) and 5 drop piperidines.The reaction mixture is in the inert atmosphere that argon gas is protected later
Stirring 12 hours.After being stirred to react 12 hours, reaction mixture is extracted three times with chloroform.Organic layer is in washing three times afterwards with anhydrous
Magnesium sulfate is dried.It filters and removes organic solvent with revolving rotation after removing anhydrous magnesium sulfate, obtain crude product column chromatography silicon
Glue method is detached, and the specific polarity of column chromatography for separation eluant, eluent is petroleum ether：Chloroform=2:3, finally obtaining product BTTzR is
Black solid (0.32g, yield 71%).
Structural identification data is as follows：1H NMR(400MHz,CDCl3),δ(ppm):7.87(s,2H),7.77(s,2H),
7.38(d,2H),7.36(s,2H),7.28(s,2H),4.19-4.14(m,4H),2.84-2.76(m,8H),2.72-2.70(d,
4H), 2.67-2.63 (t, 4H), 1.38-1.25 (m, 70H), 1.00-0.84 (m, 48H), (MALDI-TOF) MS:calcd.For
C114H148N6O2S16M/z=2147.47；found 2145.56.
The preparation and performance test of solar photovoltaic device：
Commercially available tin indium oxide (ITO) glass is first cleaned with abluent, then successively water, deionized water, acetone,
Isopropanol is cleaned by ultrasonic, the Polyglycolic acid fibre of one layer of 40nm thickness of spin coating after drying：Poly styrene sulfonate PEDOT:PSS
(weight ratio 1:1) (AL 4083) anode modification layer, it is 15 minutes dry at 150 DEG C, it is spare.To be based on thiazole in embodiment
The A-D-A conjugated molecules BTTzR of bridging unit respectively with small molecule receptor material IT-4F (weight ratios 1.5:1,1:1 and 1:1.5)
Blend solution drop coating in PEDOT:The active layer of device, donor small molecule BTTzR are formed in PSS (AL4083) anode modification layer
Concentration be 10mg ml-1.The zinc oxide (ZnO-NPs) of spin coating nano particle is used as cathode interface layer on active layer later.Light
The effective area for lying prostrate each battery in device active layers is 0.2cm-2.Vacuum (1 × 10 on active layer-4Pa) evaporation thickness
Cathode of the metallic aluminium of 100nm or so as photovoltaic device.
With SS-F5-3A (Enli Technology CO., Ltd.) xenon lamp with 1.5 optical filters of AM as simulated solar
Light source, in 100mWcm-2Photovoltaic performance test is carried out to device under light intensity, light intensity is calibrated by standard monocrystalline silicon solar cell；
J-V curves are measured using Keithley 2450.
Referring to Fig. 5, Fig. 5 is a kind of organic molecule containing thiazole of the present invention applied to organic solar
The J-V curves of battery.As shown in figure 5, the short circuit current J of the device measuredscFor 17.84mA cm-1, open-circuit voltage VocFor
0.89V, fill factor FF are 66.45%, and energy conversion efficiency PCE is 10.59%.
The structure of small molecule receptor IT-4F used in the present invention is as follows：
Compared with prior art, the beneficial effects of the invention are as follows：Organic molecule of the present invention containing thiazole utilizes
High performance benzene thiophene unit (BDT) is power supply daughter nucleus, and thiazole changes the drawing electronics list of end as bridging unit
Meta design synthesized it is a series of it is completely new, dissolubility is good, thermal stability is good is divided using the A-D-A conjugation that thiazole is bridging unit
Son, since electricity is drawn in the structure of the oxidation stability of thiazole unit, flatness and pi accumulation, high carrier mobility and end
Subelement hales electronic capability, thus this kind of molecule possess strong visible light absorption capacity, high charge transport properties and
Suitable electron energy level, is adapted as electron donor or electron acceptor material is applied to prepare organic solar batteries.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to preferable
Embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the technology of the present invention
Scheme is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be covered in this hair
In bright right.
Claims (7)
1. a kind of organic molecule containing thiazole, the organic molecule is using benzene thiophene unit as core, using thiazole as bridge
Even the A-D-A of unit is conjugated organic molecule, which is characterized in that including following general formula structure：
Wherein,
Any one of X in O, S or Se；
R1~R3Independently selected from hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls in any one；
Ar1And Ar2Independently represent any one in unsubstituted or following group containing substituent group：
The miscellaneous sub- virtue of ethenylidene, ethynylene, monocycle arlydene, bicyclic arlydene, the arlydene containing at least three rings, monocycle
Base, bicyclic heteroarylidene or the heteroarylidene containing at least three rings, the bicyclic arlydene, the arlydene containing at least three rings,
In bicyclic heteroarylidene, the heteroarylidene containing at least three rings, condenses between ring and ring or connected by singly-bound；
Work as Ar1And Ar2In any one or two it is substituted simultaneously when, Ar1Or Ar2It is respectively provided with 1~2 substituent group, it is described
Substituent group is aryl, has C1~C30Alkyl or have C1~C30Alkoxy in any one；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl in any one；
Alkyl in the 4- alkyl phenyls is C1~C8Alkyl in any one.
2. the organic molecule according to claim 1 containing thiazole, it is characterised in that：The X=S；The R1~R3It is independent
Ground is hydrogen, C1~C8Alkyl or 4- hexyl phenyl in any one；R in the A structures4For C1~C8Alkyl in appoint
Meaning is a kind of.
3. a kind of preparation method of the organic molecule containing thiazole, which is characterized in that include the following steps：
(1) compound 1 is dissolved in the in the mixed solvent of chloroform and glacial acetic acid, ice-water bath and is slowly added to N- under the conditions of being protected from light
Bromo-succinimide, half an hour drop back after deicing water-bath carries out stirring at normal temperature 10 hours separating-purifyings of reaction and compound 2 are made；
(2) phosphorus oxychloride and n,N-Dimethylformamide are stirred reaction 1~2 hour under the conditions of ice-water bath, remove later
Ice-water bath, phosphorus oxychloride and N before the compound 2 is dissolved in chloroform and is added to syringe, N- dimethyl formyls
In product after amine reaction, 70 DEG C are stirred at reflux obtained compound 3 after 12 hours separating-purifyings of reaction；
(3) compound 3, compound 4 and catalyst tetrakis triphenylphosphine palladium is made to be stirred in toluene under the conditions of 110 DEG C
Compound 5 is made after mixing 20~30 hours separating-purifyings of reaction；
(4) compound 5, drawing electron group A and piperidines or pyridine is made to be stirred in chloroform anti-under the conditions of 70 DEG C
Answer 12 hours, final separation purification after be made with following general formula structure be core based on benzene thiophene unit and thiazole is
The A-D-A conjugated molecule product 6 of bridging unit：
Wherein,
Any one of X in O, S or Se；
R1~R3Independently selected from hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls in any one；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl in any one；
Alkyl in the 4- alkyl phenyls is C1~C8Alkyl in any one.
4. the preparation method of the organic molecule according to claim 3 containing thiazole, it is characterised in that：The piperidines or pyrrole
The addition of pyridine is 1 with the molar ratio of compound 5:0.001~0.5.
5. the preparation method of the organic molecule according to claim 3 containing thiazole, it is characterised in that：The step (2),
(3) and (4) are stirred reaction under atmosphere of inert gases.
6. the preparation method of the organic molecule according to claim 3 containing thiazole, it is characterised in that：Four (the triphen
Base phosphine) molar ratio of addition and the tetrakis triphenylphosphine palladium catalyst and compound 4 of palladium is 1:10~100.
7. active layer electron donor or electron acceptor material that a kind of organic molecule containing thiazole is captured as light have in preparation
It is applied in machine solar cell.
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| WO2023070569A1 (en) * | 2021-10-29 | 2023-05-04 | 武汉工程大学 | Ester group thiazole-type wide band-gap polymer and use thereof in photoelectric device |
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| CN104177380A (en) * | 2013-05-27 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing naphthodithiophene unit and preparation method thereof, and solar cell device |
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| BING GUO，等: "A wide-bandgap conjugated polymer for highly efficient inverted single and tandem polymer solar cells", 《J. MATER. CHEM. A》 * |
| CHENNAN YE，等: "High-performance organic solar cells based on a small molecule with thieno [3,2-b]thiophene as π-bridge", 《ORGANIC ELECTRONICS》 * |
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| WO2022091799A1 (en) * | 2020-10-30 | 2022-05-05 | 富士フイルム株式会社 | Photoelectric conversion element, imaging element, optical sensor, and compound |
| WO2023070569A1 (en) * | 2021-10-29 | 2023-05-04 | 武汉工程大学 | Ester group thiazole-type wide band-gap polymer and use thereof in photoelectric device |
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