CN108440574B - Thiazole-containing organic small molecule and preparation method and application thereof - Google Patents

Thiazole-containing organic small molecule and preparation method and application thereof Download PDF

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CN108440574B
CN108440574B CN201810288440.XA CN201810288440A CN108440574B CN 108440574 B CN108440574 B CN 108440574B CN 201810288440 A CN201810288440 A CN 201810288440A CN 108440574 B CN108440574 B CN 108440574B
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张茂杰
叶陈男
国霞
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Abstract

The invention discloses a thiazole-containing organic micromolecule and a preparation method and application thereof, wherein a high-performance benzodithiophene unit (BDT) is used as an electron donor core, thiazole is used as a bridging unit, and a series of brand-new A-D-A conjugated molecules which take thiazole as the bridging unit and have good solubility and good thermal stability are synthesized by changing the design of an electron pulling unit at the tail end.

Description

Thiazole-containing organic small molecule and preparation method and application thereof
Technical Field
The invention relates to the technical field of molecules, in particular to a thiazole-containing organic micromolecule, a preparation method thereof and application of the thiazole-containing organic micromolecule as an active layer electron donor or electron acceptor material in an organic solar cell (OPV).
Background
Solution processed organic solar cells as a promising green energy technology have some unique advantages such as: the preparation method has the advantages of low cost, light weight, capability of preparing large-area devices and the like. Energy conversion efficiencies based on organic solar cells with conjugated polymers or small organic molecules as donors and fullerene derivatives as acceptors have exceeded 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.com., 7, U.S. 40, Y.Yang.40, Y.Yang.C, J.Yang, J.F.F.Wang, J.F.Wang, J.J.F.Wang, W.Ni, G.Long, X.Yang and H.F.J.F.Wang, J.Wang, J.J.J.J.Zong, B.Wang, Z.Wang, K.Lu.Lu.Lu.Wang, K.J.F.F.F.F.F.J.F.F.F.J.F.F.F.F.Wang, J.Wang, J.C.C.C.C.Wang, J.S.J.F.F.C.Wang, J.F.F.F.F.F.F.Wang, J.F.F.F.Wang, J.Wang, J.F.F.F.F.F.F.F.F.F.F.F.Wang. However, some inherent drawbacks, including high cost, poor absorption in the visible region of the solar spectrum, and difficult energy level control, still exist in fullerene acceptors. Thus, in recent years, high performance non-fullerene acceptor materials have been developed (Y.Lin, J.Wang, Z.G.Zhang, H.Bai, Y.F.Li, D.Zhu and X.W.Zhang, 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.Zhang, J.Am.Chem. Soc, 2016,138,2973; Y.Lin, Z.Zhang, H.Bai, J.Wang, Y.Yao, Y.F.Li, D.Zhu X.W.Zhang, Energy.Yang, H.Zhu, J.Zhang, H.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.H.J.J.J.J.J.J.J.J.J.H.H.J.J.J.J.H.J.J.H.H.J.J.J.H.J.J.H.H.H.H.J.H.H.H.H.H.H.J.H.J.J.J.J.J..
Small organic molecules have specific advantages over polymers, such as: easy purification, defined molecular weight, easily controllable molecular energy levels and small batch-to-batch variation (W.Ni, M.Li, B.Kan, F.Liu, X.Wan, Q.Zhang, H.Zhang, T.P.Russelcdd 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.n, J.Am.Chen, 2014,136,15529). Thus, in PCBM-based small molecule organic solar cells, photovoltaic devices achieve very high Energy conversion efficiencies (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, organic solar cells achieve a relatively poor photovoltaic performance when non-fullerene acceptors are combined with small organic molecule donors (W.Ni, M.Li, B.Kan, F.Liu, X.Wan, Q.Zhang, H.Zhang, T.P.Russelcdd 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.and Z.Li, C.Li, J.chem.A, Mater.A, 2016, 56, 2016). To date, the development of non-fullerene all small molecule organic solar cells lags behind polymer or fullerene based organic solar cells. Considering that a non-fullerene all-small molecule organic solar cell combines the advantages of both a non-fullerene receptor and a small molecule donor, the non-fullerene all-small molecule organic solar cell has great development potential, but low photovoltaic performance is an important problem to be solved. In the foregoing we have mentioned that high performance non-fullerene acceptor materials have evolved very rapidly in recent years. Therefore, the design of a novel efficient organic small molecule donor material matched with the organic small molecule donor material has important significance for improving the photovoltaic performance of the all-small molecule organic solar cell.
For the design of the active layer electron donor or electron acceptor material, some elements include: good solubility, broad absorption spectrum and with high extinction coefficient, suitable energy levels and high mobility have to be taken into account and maintained in 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.). The use of a framework of the acceptor-donor-acceptor (a-D-a) type, i.e. comprising one electron-rich unit D as electron donor core and two electron-strongly withdrawing units a as end groups, is an effective strategy for tuning the absorption spectrum and the molecular energy levels (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. ziehlne, c.elscher, k.leo, m.riede, m.eipffer, c.uhrick and p.bauuerle, j.am.chem.sac. 2012,134,11064.). Past work has revealed that photovoltaic small molecule active layer materials based on Benzodithiophene (BDT) units as donor cores have exhibited excellent photovoltaic performance (j.wan, x.xu, g.zhang, y.li, k.feng and q.pen, Energy environ.sci.,2017,10, 1739; z.wang, x.xu, z.li, k.feng, k.li, y.li and q.pen, adv. electron.mater.,2016,2, 1600061; h.bin, y.yang, z.g.zhang, l.ye, m.ghasemii, s.n, y.zhang, c.zhang, c.sun, l.xue, c.yang, h.ad, y.j.am.m.m.m, par.zhang, c.zhang, c.su, l.xue, c.yang, h.ad, h.j.am.m.m.m.m.m.m.n, qi.s.n, y.zhang, y.z.z.g., qin, y.7, y.zhang, y.g, y.k.k.7, z.
The use of suitable bridging unit bridges is also one of the key factors in improving photovoltaic performance. It is noteworthy that thiazole units, which are strongly electron withdrawing, have attracted a great deal of attention, which is benefited from having properties such as: has good oxidation stability, planarity and structure of pi 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.). Thus, many high performance polymer systems based on thiazole units are widely used (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 they are rarely used in small molecule photovoltaic materials. Due to the huge application potential of the thiazole unit, the thiazole unit is introduced into organic small molecules, so that high-efficiency organic photovoltaic materials can be expected.
Disclosure of Invention
The invention aims to provide a thiazole-containing organic micromolecule, a preparation method and application thereof.
The invention has a technical scheme that:
the organic micromolecule containing thiazole is an A-D-A conjugated organic micromolecule which takes a benzodithiophene unit as a core and takes thiazole as a bridging unit and comprises the following general structure:
Figure BDA0001616687860000041
wherein,
x is selected from any one of O, S or Se;
R1～R3independently selected from hydrogen, C1～C30Alkyl of (C)1～C30Any one of alkoxy or 4-alkylphenyl;
Ar1and Ar2Independently represents any one of the following unsubstituted or substituted groups:
an ethenylene group, an ethynylene group, a monocyclic arylene group, a bicyclic arylene group, an arylene group containing at least three rings, a monocyclic heteroarylene group, a bicyclic heteroarylene group or a heteroarylene group containing at least three rings, wherein in the bicyclic arylene group, the arylene group containing at least three rings, the bicyclic heteroarylene group or the heteroarylene group containing at least three rings, the rings are fused with each other or connected through a single bond;
when Ar is1And Ar2When any one or two of them are substituted at the same time, Ar1Or Ar2Respectively has 1 to 2 substituents which are aryl and have C1～C30Or with C1～C30Any one of the alkoxy groups of (a);
the electron withdrawing group A is selected from one of the following structures:
Figure BDA0001616687860000042
r in the above A structure4Is C1～C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1～C8Any one of the alkyl groups of (1).
Further, X ═ S; the R is1～R3Independently of one another is hydrogen, C1～C8Any one of alkyl or 4-hexylphenyl; r in the structure of A4Is C1～C8Any one of the alkyl groups of (1).
The other technical scheme of the invention is as follows:
a preparation method of thiazole-containing organic micromolecules comprises the following steps:
Figure BDA0001616687860000051
(1) dissolving the compound 1 in a mixed solvent of chloroform and glacial acetic acid, slowly adding N-bromosuccinimide in an ice-water bath under the condition of keeping out of the sun, removing the ice-water bath after half an hour, carrying out normal-temperature stirring reaction for 10 hours, and separating and purifying to obtain a compound 2;
(2) stirring phosphorus oxychloride and N, N-dimethylformamide to react for 1-2 hours under the condition of ice-water bath, removing the ice-water bath, dissolving the compound 2 in chloroform, adding the chloroform into the product obtained by the reaction of the phosphorus oxychloride and the N, N-dimethylformamide by using an injector, stirring at 70 ℃, refluxing for 12 hours, separating and purifying to obtain a compound 3;
(3) stirring and reacting the compound 3, the compound 4 and a catalyst tetrakis (triphenylphosphine) palladium in toluene at 110 ℃ for 20-30 hours, and separating and purifying to obtain a compound 5;
(4) and (2) carrying out stirring reaction on the compound 5, an electron withdrawing group A and piperidine or pyridine in chloroform at 70 ℃ for 12 hours, and finally separating and purifying to obtain an A-D-A conjugated molecular product 6 which has the following general structure and takes a benzodithiophene unit as a core and thiazole as a bridging unit:
Figure BDA0001616687860000061
wherein,
x is selected from any one of O, S or Se;
R1～R3independently selected from hydrogen, C1～C30Alkyl of (C)1～C30Any one of alkoxy or 4-alkylphenyl;
the electron withdrawing group A is selected from one of the following structures:
Figure BDA0001616687860000062
r in the above A structure4Is C1～C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1～C8Any one of the alkyl groups of (1).
Furthermore, the molar ratio of the added piperidine or pyridine to the compound 5 is 1: 0.001-0.5.
Further, the steps (2), (3) and (4) are stirred and reacted under the inert gas atmosphere.
Further, the molar ratio of the added tetrakis (triphenylphosphine) palladium to the compound 4 is 1: 10-100.
The thiazole-containing organic micromolecules prepared in the mode are used as an electron donor or electron acceptor material of an active layer for light capture and applied to preparation of organic solar cells.
The invention provides a thiazole-containing organic micromolecule, which has the main advantages that:
1. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit can be processed by a solution method and can be dissolved in organic solvents such as chloroform, tetrahydrofuran, chlorobenzene and the like;
2. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit has good thermal stability, and the initial thermal decomposition temperature exceeds 400 ℃;
3. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit has good light absorption and is suitable for being used as an organic solar cell material;
4. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit has a proper electron energy level and is suitable for an electron donor material or an electron acceptor material in an organic solar cell;
5. the synthesized A-D-A conjugated molecule based on thiazole as a bridging unit is used as an electron donor material or an electron acceptor material to show high photoelectric conversion efficiency in an organic solar cell.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein,
FIG. 1 is a diagram of an ultraviolet-visible absorption spectrum of a thiazole-containing small organic molecule according to the present invention;
FIG. 2 is a cyclic voltammogram of a thiazole-containing small organic molecule of the present invention;
FIG. 3 is a thermogravimetric analysis graph of a thiazole-containing small organic molecule according to the present invention;
FIG. 4 is a differential scanning calorimetry trace of a thiazole-containing small organic molecule according to the present invention;
FIG. 5 is a J-V curve of a thiazole-containing organic small molecule in an organic solar cell according to the present invention;
FIG. 6 is a synthetic route of a thiazole-containing small organic molecule according to the present invention;
FIG. 7 shows the synthetic route of BTTzR of a thiazole-containing small organic molecule according to the invention.
Detailed Description
The organic micromolecule is an A-D-A conjugated organic micromolecule which takes a benzodithiophene unit as a core and takes thiazole as a bridging unit, and comprises the following general structure:
Figure BDA0001616687860000081
wherein,
x is selected from any one of O, S or Se;
R1～R3independently selected from hydrogen, C1～C30Alkyl of (C)1～C30Any one of alkoxy or 4-alkylphenyl;
Ar1and Ar2Independently represents any one of the following unsubstituted or substituted groups:
vinylene, ethynylene, monocyclic arylene, bicyclic arylene, arylene containing at least three rings, monocyclic heteroarylene, bicyclic heteroarylene or heteroarylene containing at least three rings, Ar1And Ar2The bicyclic arylene, arylene containing at least three rings, bicyclic heteroarylene, heteroarylene containing at least three rings may be the same or different, and the rings are fused with each other or connected by a single bond;
when Ar is1And Ar2Any ofWhen one or two are substituted at the same time, Ar1Or Ar2Respectively has 1 to 2 substituents which are aryl and have C1～C30Or with C1～C30Any one of the alkoxy groups of (a);
the electron withdrawing group A is selected from one of the following structures:
Figure BDA0001616687860000082
r in the above A structure4Is C1～C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1～C8Any one of the alkyl groups of (1).
Referring to fig. 6, fig. 6 is a synthetic route of a thiazole-containing small organic molecule according to the present invention. As shown in fig. 6, the method comprises the following steps:
Figure BDA0001616687860000091
(1) dissolving the compound 1 in a mixed solvent of chloroform and glacial acetic acid, slowly adding N-bromosuccinimide in an ice-water bath under the condition of keeping out of the sun, removing the ice-water bath after half an hour, carrying out normal-temperature stirring reaction for 10 hours, and separating and purifying to obtain a compound 2;
(2) stirring phosphorus oxychloride and N, N-dimethylformamide under the conditions of an ice water bath and an inert gas atmosphere for reacting for 1-2 hours, then removing the ice water bath, dissolving the compound 2 in chloroform, adding the chloroform into the product obtained by the reaction of the phosphorus oxychloride and the N, N-dimethylformamide by using an injector, stirring at 70 ℃, refluxing for 12 hours, and separating and purifying to obtain a compound 3;
(3) stirring and reacting the compound 3, the compound 4 and a catalyst tetrakis (triphenylphosphine) palladium in toluene at the temperature of 110 ℃ under an inert gas atmosphere for 20-30 hours, and separating and purifying to obtain a compound 5, wherein the molar ratio of the added amount of the tetrakis (triphenylphosphine) palladium to the molar ratio of the tetrakis (triphenylphosphine) palladium catalyst to a benzodithiophene unit trimethyltin compound with Ar substituent, namely the compound 4, is 1: 10-100;
(4) stirring the compound 5, an electron withdrawing group A and piperidine or pyridine in chloroform at 70 ℃ for 12 hours, and finally separating and purifying to obtain an A-D-A conjugated molecular product 6 which has the following general structure and takes a benzodithiophene unit as a core and thiazole as a bridging unit, wherein the molar ratio of the added piperidine or pyridine to the aldehyde compound which has R1, R2 and R3 substituents and takes the benzodithiophene unit as the core and the thiazole as the bridging unit, namely the compound 5, is 1: 0.001-0.5:
Figure BDA0001616687860000101
wherein,
x is selected from any one of O, S or Se;
R1～R3independently selected from hydrogen, C1～C30Alkyl of (C)1～C30Any one of alkoxy or 4-alkylphenyl;
the electron withdrawing group A is selected from one of the following structures:
Figure BDA0001616687860000102
r in the above A structure4Is C1～C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1～C8Any one of the alkyl groups of (1).
The characteristics of the prepared thiazole-containing organic micromolecules refer to the figures 1 to 4:
as shown in FIG. 1, the absorption is stronger in the range of 300-700nm, and the film absorption has a distinct absorption shoulder at 610 nm, indicating that stronger interaction and aggregation exist among molecules;
as shown in FIG. 2, the initial oxidation potential of the small molecule
Figure BDA0001616687860000103
Is 0.73V vs Ag/Ag+Initial reduction potential
Figure BDA0001616687860000104
is-1.14V vs Ag/Ag+. By the formula HOMO ═ Eox+4.73) (eV) and LUMO ═ Ere+4.73) (eV) the HOMO and LUMO levels of BTTzR can be calculated to be-5.46 eV and-3.59 eV, respectively;
as shown in FIG. 3, the thermal decomposition temperature (T) when the weight loss of the small molecule is 5%d) The temperature is 402 ℃, which shows that the small molecule BTTzR has good thermal stability;
as shown in FIG. 4, the small molecule has a sharp melting endothermic peak (T) at 315 ℃ during heatingm) Correspondingly, a distinct exothermic crystallization peak (T) occurs at 291 ℃ during the exothermc) It can be concluded that the small molecule BTTzR has good crystallization properties.
The invention also claims application of the thiazole-containing organic micromolecules as an electron donor or electron acceptor material of an active layer for light capture in preparation of organic solar cells.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
First, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The present invention will be described in detail by using structural schematic and the like, and in the detailed description of the embodiments of the present invention, the schematic is not partially enlarged in general proportion for convenience of description, and the schematic is only an example, which should not limit the scope of the present invention. In addition, the actual fabrication process should include three-dimensional space of length, width and depth.
Example 1
Referring to fig. 7, fig. 7 is a synthesis route of BTTzR of a thiazole-containing small organic molecule according to the present invention. As shown in FIG. 7, the present embodiment shows the synthetic route of thiazole-containing small organic molecules as follows:
Figure BDA0001616687860000121
note: r1Represents 2-ethylhexyl, R2Represents n-hexyl.
The detailed synthesis steps of the product in each step are as follows:
step 1) synthesizing a compound 2,2- (5-bromo-4- (2-ethylhexyl) thiophen-2-yl) -5- (4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazole;
starting with compound 1, i.e., 2, 5-bis (4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazole, in a 100ml single neck round bottom flask, chloroform (25ml) and glacial acetic acid (25ml) were added. N-bromosuccinimide (0.71g,4.01mmol) was slowly added to the single-necked flask in an ice-water bath protected from light. After the addition of N-bromosuccinimide was completed, a spherical drying tube with anhydrous magnesium sulfate was attached to the single-necked flask, and reacted for 10 hours with stirring. The reaction mixture was then poured into water (60ml) and chloroform and extracted three times and dried over anhydrous magnesium sulfate. After removal of the organic solvent by rotary evaporation, the crude product was isolated by column chromatography using petroleum ether as eluent to give compound 2 (1.16g, 50% yield) as an orange solid, i.e. 2- (5-bromo-4- (2-ethylhexyl) thiophen-2-yl) -5- (4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazole.
The structure validation 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) synthesizing a compound 3, 5- (5- (5-bromo-4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazolo-2-yl) -3- (2-ethylhexyl) thiophene-2-carbaldehyde;
phosphorus oxychloride (1.32ml,14.16mmol) was injected into a 100ml two-necked round bottom flask with a syringe under an inert atmosphere of argon. N, N-dimethylformamide (1.36ml,17.7mmol) was then slowly added dropwise to the two-necked flask with a syringe under ice-water bath conditions and reacted for one and a half hours with stirring. Compound 2(1.08g,1.77mmol) was dissolved in chloroform (30 ml). The chloroform solution containing compound 2 dissolved therein was injected into a two-necked flask by a syringe. Thereafter, the reaction mixture was transferred to a 70 ℃ oil bath, and after refluxing the reaction for 12 hours with stirring, the mixture was extracted with methylene chloride (120 ml). The crude product was separated by column chromatography using petroleum ether/dichloromethane (1:1) as eluent to give compound 3(0.99g, 88% yield) as an orange solid, 5- (5- (5-bromo-4- (2-ethylhexyl) thiophen-2-yl) thiazolo [5,4-d ] thiazolo-2-yl) -3- (2-ethylhexyl) thiophene-2-carbaldehyde.
The structure validation 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) synthesis of the compound 5,5, 5'- (5,5' - (5,5'- (4,8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) benzo [1,2-b:4,5-b' ] dithiophene-2, 6-diyl) bis (4- (2-ethylhexyl) thiophen-5, 2-diyl)) bis (thiazolo [5,4-d ] thiazolo-5, 2-diyl)) bis (3- (2-ethylhexyl) thiophen-2-carbaldehyde);
in a dried 100ml two-necked round-bottom flask, compound 3(0.87g,1.36mmol), compound 4(4, 8-bis (5- (2-ethylhexyl) -4-hexane)Thien-2-yl) benzo [1,2-b:4,5-b']Dithiophene-2, 6-diyl) bis (trimethylstannyl) (0.59g,0.55mmol) (Compound 4 was purchased from Nakay Co.) and tetrakis (triphenylphosphine) palladium [ Pd (PPh) as a catalyst3)4](0.047g,0.04mmol) were dissolved together in dry purified toluene. The reaction mixture was placed in an oil bath under argon protection (the temperature in the oil bath was slowly raised to 110 ℃) and reacted for 24 hours with stirring. After completion of the reaction, the reaction mixture was poured into a mixture of water and methylene chloride (100ml) and extracted three times. Drying the organic layer with anhydrous magnesium sulfate, removing the solvent by rotary evaporation to obtain a crude product, and separating by column chromatography silica gel method, wherein the specific polarity of the column chromatography separation eluent is petroleum ether: chloroform-1: 1, compound 5 was finally obtained as a red solid (0.75g, 73% yield), i.e., 5'- (5,5' - (5,5'- (4,8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) benzo [1,2-b:4,5-b']Dithiophene-2, 6-diyl) bis (4- (2-ethylhexyl) thiophene-5, 2-diyl)) bis (thiazole [5,4-d]Benzothiazole-5, 2-diyl)) bis (3- (2-ethylhexyl) thiophene-2-carbaldehyde).
The structure validation 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) synthesis of BTTzR, (5Z,5'Z) -5,5' - ((5,5'- (5,5' - (5,5'- (4,8-bis (5- (2-ethylhexyl) -4-hexylthiophen-2-yl) benzo [1,2-b:4,5-b' ] dithiophene-2, 6-diyl) bis (4- (2-ethylhexyl) thiophen-5, 2-diyl)) bis (thiazolo [5,4-d ] benzothiazole-5, 2-diyl)) bis (3- (2-ethylhexyl) thiophen-5, 2-diyl)) bis (methylidene)) bis (3-ethyl-rhodanine);
compound 5(0.39g,0.21mmol) was dissolved in a clean and purified chloroform solvent (40 ml). Then Lawstronic end-group rhodanine (0.34g,2.1mmol) and 5 drops of piperidine were added. The reaction mixture was then stirred under an inert atmosphere of argon for 12 hours. After stirring the reaction for 12 hours, the reaction mixture was extracted three times with chloroform. The organic layer was washed with water three times and then dried over anhydrous magnesium sulfate. And (3) after removing the anhydrous magnesium sulfate by suction filtration, removing the organic solvent by rotary evaporation to obtain a crude product, and separating the crude product by using a column chromatography silica gel method, wherein the specific polarity of an eluent for column chromatography separation is petroleum ether: chloroform 2:3, the final product BTTzR was obtained as a black solid (0.32g, 71% yield).
The structure validation 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.
preparing a solar photovoltaic device and testing the performance of the solar photovoltaic device:
commercially available Indium Tin Oxide (ITO) glass is firstly cleaned by a detergent, then is sequentially cleaned by water, deionized water, acetone and isopropanol through ultrasonic cleaning, and is dried and then is spin-coated with a layer of polyethylene dioxythiophene with the thickness of 40 nm: and (3) drying the anode modification layer of the polystyrene sulfonate PEDOT: PSS (weight ratio of 1:1) (AL 4083) at 150 ℃ for 15 minutes for later use. The active layer of the device is formed by dripping the blending solution of the A-D-A conjugated molecule BTTzR based on thiazole as the bridging unit and the small molecule acceptor material IT-4F (weight ratio is 1.5:1,1:1 and 1:1.5) on the anode modification layer of PEDOT: PSS (AL 4083) respectively, and the concentration of the donor small molecule BTTzR is 10mg ml-1. Then, zinc oxide (ZnO-NPs) with nano particles is spin-coated on the active layer to be used as a cathode interface layer. The effective area of each cell in the active layer of the photovoltaic device is 0.2cm-2. Vacuum (1X 10) on the active layer-4Pa) evaporating metal aluminum with the thickness of about 100nm as a cathode of the photovoltaic device.
SS-F5-3A (Enli Technology CO., Ltd.) xenon lamp equipped with AM 1.5 filter was used as the simulated solar light source at 100mWcm-2Carrying out photovoltaic performance test on the device under light intensity, wherein the light intensity is calibrated through a standard monocrystalline silicon solar cell; the J-V curve was measured using Keithley 2450.
Referring to FIG. 5, FIG. 5 shows a thiazole-containing organic small molecule in organic solar cell according to the present inventionJ-V curve of the cell. As shown in FIG. 5, the short-circuit current J of the device was measuredscIs 17.84mA cm-1Open circuit voltage VocAt 0.89V, a fill factor FF of 66.45% and an energy conversion efficiency PCE of 10.59%.
The structure of the small molecule receptor IT-4F used in the invention is as follows:
Figure BDA0001616687860000151
compared with the prior art, the invention has the beneficial effects that: according to the organic micromolecules containing thiazole, a high-performance benzodithiophene unit (BDT) is used as an electron donor core, thiazole is used as a bridging unit, and a series of brand-new A-D-A conjugated molecules which are good in solubility and thermal stability and take the thiazole as the bridging unit are synthesized by changing the design of a terminal electron withdrawing unit.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (6)

1. The organic micromolecule containing thiazole is an A-D-A conjugated organic micromolecule which takes a benzodithiophene unit as a core and takes thiazole as a bridging unit and is characterized by having the following structure:
Figure FDA0002941658540000011
wherein,
x is selected from any one of O, S or Se;
R1～R3independently selected from hydrogen, C1～C30Alkyl of (C)1～C30Any one of alkoxy or 4-alkylphenyl;
Ar1and Ar2Independently represents any one of the following unsubstituted or substituted groups:
an ethenylene group, an ethynylene group, a monocyclic arylene group, a bicyclic arylene group, an arylene group containing at least three rings, a monocyclic heteroarylene group, a bicyclic heteroarylene group or a heteroarylene group containing at least three rings, wherein in the bicyclic arylene group, the arylene group containing at least three rings, the bicyclic heteroarylene group or the heteroarylene group containing at least three rings, the rings are fused with each other or connected through a single bond;
when Ar is1And Ar2When any one or two of them are substituted at the same time, Ar1Or Ar2Each having 1 to 2 substituents of aryl group and C1～C30Or with C1～C30Any one of the alkoxy groups of (a);
the electron withdrawing group A is selected from one of the following structures:
Figure FDA0002941658540000012
r in the above A structure4Is C1～C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1～C8Any one of the alkyl groups of (1).
2. A thiazole-containing small organic molecule according to claim 1, wherein: said X ═ S; the R is1～R3Independently of one another is hydrogen, C1～C8In alkyl or 4-hexylphenyl ofAny one of (a); r in the structure of A4Is C1～C8Any one of the alkyl groups of (1).
3. A preparation method of thiazole-containing organic micromolecules is characterized by comprising the following steps:
Figure FDA0002941658540000021
(1) dissolving the compound 1 in a mixed solvent of chloroform and glacial acetic acid, slowly adding N-bromosuccinimide in an ice-water bath under the condition of keeping out of the sun, removing the ice-water bath after half an hour, carrying out normal-temperature stirring reaction for 10 hours, and separating and purifying to obtain a compound 2;
(2) stirring phosphorus oxychloride and N, N-dimethylformamide to react for 1-2 hours under the condition of ice-water bath, removing the ice-water bath, dissolving the compound 2 in chloroform, adding the chloroform into the product obtained by the reaction of the phosphorus oxychloride and the N, N-dimethylformamide by using an injector, stirring at 70 ℃, refluxing for 12 hours, separating and purifying to obtain a compound 3;
(3) stirring and reacting the compound 3, the compound 4 and a catalyst tetrakis (triphenylphosphine) palladium in toluene at 110 ℃ for 20-30 hours, and separating and purifying to obtain a compound 5;
(4) stirring the compound 5, an electron withdrawing group A and piperidine or pyridine in chloroform at 70 ℃ for 12 hours, and finally separating and purifying to obtain an A-D-A conjugated molecular product 6 which has the following general structure and takes benzodithiophene as a core and thiazole as a bridging unit;
wherein,
x is selected from any one of O, S or Se;
R1～R3independently selected from hydrogen, C1～C30Alkyl of (C)1～C30Any one of alkoxy or 4-alkylphenyl;
Ar1and Ar2Independently represent any of the following groups which are unsubstituted or have a substituentOne of them is:
an ethenylene group, an ethynylene group, a monocyclic arylene group, a bicyclic arylene group, an arylene group containing at least three rings, a monocyclic heteroarylene group, a bicyclic heteroarylene group or a heteroarylene group containing at least three rings, wherein in the bicyclic arylene group, the arylene group containing at least three rings, the bicyclic heteroarylene group or the heteroarylene group containing at least three rings, the rings are fused with each other or connected through a single bond;
when Ar is1And Ar2When any one or two of them are substituted at the same time, Ar1Or Ar2Each having 1 to 2 substituents of aryl group and C1～C30Or with C1～C30Any one of the alkoxy groups of (a);
the electron withdrawing group A is selected from one of the following structures:
Figure FDA0002941658540000031
r in the above A structure4Is C1～C30Any one of the alkyl groups of (a);
the alkyl group in the 4-alkylphenyl group is C1～C8Any one of the alkyl groups of (1).
4. A method for preparing thiazole-containing small organic molecules as claimed in claim 3, wherein: the molar ratio of the added piperidine or pyridine to the compound 5 is 1: 0.001-0.5.
5. A method for preparing thiazole-containing small organic molecules as claimed in claim 3, wherein: and (3) and (4) are stirred to react under the inert gas atmosphere.
6. A method for preparing thiazole-containing small organic molecules as claimed in claim 3, wherein: the molar ratio of the catalyst tetrakis (triphenylphosphine) palladium to the compound 4 is 1: 10-100.
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