CN105713185A - Regular polymer containing monofluorine-substituted benzo-hetero[1,3]diazole and preparation and application of regular polymer - Google Patents

Regular polymer containing monofluorine-substituted benzo-hetero[1,3]diazole and preparation and application of regular polymer Download PDF

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CN105713185A
CN105713185A CN201610064405.0A CN201610064405A CN105713185A CN 105713185 A CN105713185 A CN 105713185A CN 201610064405 A CN201610064405 A CN 201610064405A CN 105713185 A CN105713185 A CN 105713185A
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CN105713185B (en
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黄飞
周城
张桂传
曹镛
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South China University of Technology SCUT
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Abstract

The invention belongs to the field of organic photoelectric materials, and discloses a regular polymer containing monofluorine-substituted benzo-hetero[1,3]diazole, a preparation method of the regular polymer and application of the regular polymer in the field of organic photoelectric technologies. The structural formula of the polymer is shown as the first formula (please see the formula in the description), wherein x, y and z are separately independent and represent integers ranging from 0 to 5, n represents a positive integer ranging from 3 to 100,000, X1, X2 and X3 are separately independent and are selected from O or S or Se or Te or N-R or R-C-R or R-Si-R or R-Ge-R or R-Sn-R, R represents straight chains or branch chains or circular alkyl chains of C1-C30, R1, R2, R3 and R4 are separately independent and are selected from hydrogen, an alkyl group with 1-30 carbon atoms and an alkoxy group with 1-30 carbon atoms, an alkenyl group, an aryl group, a carboxyl group, a carbonyl group, an amino group, a cyano group, a nitryl group, an ester group, halogen and a halogenated alkyl group, and Ar is selected from a non-substituted or substituted electron-deficient conjugate unit group, an electron-rich conjugate group and a conjugate unit group formed by the units. The polymer can be applied to organic solar cell devices.

Description

Regular polymer and the preparation and application thereof of benzo miscellaneous [1,3] diazole are replaced containing single fluorine
Technical field
The invention belongs to organic photoelectrical material field, contain single fluorine regular polymer replacing benzo miscellaneous [1,3] diazole and preparation method thereof with it in the application of organic photoelectric technical field particularly to one.
Background technology
Organic photoelectrical material, by feat of the Photophysics of its uniqueness, has a light weight, and processing is simple, low cost and can make the plurality of advantages such as large-area flexible device, has obtained vast concern during the decade at this.
In terms of organic photovoltaic cell, there is this year seminar's report single polymer layer cell power conversion efficiency to have been over 10% (DOI:10.1038/ncomms6293) in Nature Communication, this imply that organic photovoltaic cell has wide commercial promise.But relative to inorganic solar cell, the energy conversion efficiency of organic photovoltaic cell is the most on the low side, this forces each Research Team still to put into a lot of energy for this.Except continuing to optimize device architecture, processing technology, scientific research personnel the most constantly researches and develops new photoactive layer material, fundamentally to improve the efficiency of organic photovoltaic cell.
The most efficient active layer polymeric material often by traditional electron deficiency monomer (A) and two kinds of monomers of electron rich monomer (D), is obtained by a single metal catalytic coupling polymerization.If these monomers contain as single fluorine substituted thiophene also [3,4-b] thiophene, single fluorine replace diazosulfide or pyridine thiadiazoles etc. these time there is asymmetric monomer, after polymerization, the features group of these unsymmetrical monomers will be in main polymer chain arbitrary orientation.The main chain randomness that this arbitrary orientation causes from the point of view of report at present, will limit the photovoltaic conversion efficiency (DOI:10.1021/ja500935d) of material greatly.One these unsymmetrical monomer next regular being reported towards method, be to prepare D-A-D or A-D-A intermediate by first coupling, then be polymerized (DOI:10.1021/ja500935d) with A or D monomer with these intermediate.This method can make the most regular arrangement of asymmetric cell, and their arrangement is regular but alternate arrangement.Also has another solution, it is simply that allow the feature of these asymmetric monomers replace functional group and unanimously arrange along main chain direction.The research of regular consistent arrangement along main chain direction of benzo miscellaneous [1,3] diazole unit is not the most replaced based on single fluorine.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide one to replace the regular polymer material of benzo miscellaneous [1,3] diazole containing single fluorine.
Another object of the present invention is to provide the preparation method of a kind of above-mentioned regular polymer replacing benzo miscellaneous [1,3] diazole containing single fluorine.
Still a further object of the present invention is to provide the above-mentioned regular polymer application in organic photoelectric technical field replacing benzo miscellaneous [1,3] diazole containing single fluorine.
The purpose of the present invention is realized by following proposal:
A kind of regular polymer replacing benzo miscellaneous [1,3] diazole containing single fluorine, its structural formula as shown in Equation 1:
Wherein:
X, y, z the most each stand alone as the integer of 0 to 5；
N is the positive integer of 3 to 100000.
X1, X2, X3The most each standing alone as O, S, Se, Te, N-R, R-C-R, R-Si-R, R-Ge-R or R-Sn-R, wherein R is C1～C30Straight chain, side chain or cyclic alkyl chain；
R1, R2, R3, R4The most each stand alone as: hydrogen；There is the alkyl of 1～30 carbon atom；There is the alkoxyl of 1～30 carbon atom, thiazolinyl, alkynyl, aryl, carboxyl, hydroxyl, carbonyl, amino, cyano group, nitro, ester group, halogen, haloalkyl；
nullAr is unsubstituted or substituted group: benzo miscellaneous [1,3] di azoly、Pyrido miscellaneous [1,3] di azoly、Benzotriazole base、Naphtho-miscellaneous [1,3] di azoly、Aphthotriazoles base、Pyrrolo-pyrrole-dione base、Indigo base、Bioxindol base、Quinoxalinyl、Naphthalene diimide group、Imidodicarbonic diamide base、Thieno imide、The electron deficiency conjugate unit bases such as quinoxalinyl，And phenyl、Naphthyl、Anthryl、Phenanthryl、Pyrenyl、Naphthacenyl、Pentacenyl、Fluorenyl、Spirofluorene-based、Indane fluorenyl、Pyrrole radicals、Benzopyrrole base、Hexichol amido，Triphenylamine base、Carbazyl、Indole carbazole base、Thienyl、Bithiophene base、Three bithiophene bases、Benzothienyl、Thieno diphenyl、The double thienyl of benzo、Furyl、Benzofuranyl、Benzo difuryl、Stannum fen base、Bithiophene base、The double stannum fen base of benzo、Benzothiophene furyl、The double thienyl of benzo、The conjugate unit base of the electron riches such as aphthothiophenes base，And the conjugate unit base of composition between above group；
The described substituent group in substituted group independently be: hydrogen；There is the alkyl of 1～30 carbon atom；There is the alkoxyl of 1～30 carbon atom, thiazolinyl, alkynyl, aryl, carboxyl, hydroxyl, carbonyl, amino, cyano group, nitro, ester group, halogen, haloalkyl；
Preferably, above-mentioned Ar is selected from the group of structure as shown below:
Wherein X1, X2, X3, R1, R2, R3, R4There is implication described above.
The effect of Ar group and five-membered ring π bridge unit is: uses different Ar groups and five-membered ring π bridge unit, can effectively regulate and control the optical property of obtained organic semiconducting materials；The high performance regular polymer replacing benzo miscellaneous [1,3] diazole containing single fluorine can be prepared by making to modify further to Ar group in derivant and five-membered ring π unit.
The preparation method of a kind of above-mentioned regular polymer replacing benzo miscellaneous [1,3] diazole containing single fluorine, comprises the following steps:
Have logical formula I single fluorine replace benzo miscellaneous [1,3] diazole has logical formula II with at least one, the compound of (III) or (IV) reacts, and must have the compound shown in formula (V)；Then the compound generation metal catalytic self-polymerization reaction shown in formula (V), obtains the regular polymer replacing benzo miscellaneous [1,3] diazole containing single fluorine shown in formula 1.
Wherein x, y, z, X1, X2, X3, R1, R2, R3, R4There is implication described above；X is halogen atom；M is tin trimethyl, tributyl tin, boric acid, borate etc..
The above-mentioned regular polymer replacing benzo miscellaneous [1,3] diazole containing single fluorine, wherein fluorine atom is regular along main polymer chain direction orientation.Due to fluorine atom strong draw electronic capability, the fluorine atom of regular arrangement will produce a net dipole moment.This characteristic, will make polymer morphology more orderly, and beneficially light swashs separation of charge, and then the photoelectric conversion efficiency of raising material, thus can effectively apply in organic photovoltaic cell device.
The mechanism of the present invention is:
The difference of the product characteristics that this patent is obtained by the difference and different the position of substitution that make use of different loci reactivity dexterously, carrys out design path preparation and purification obtains subject polymer monomer.This polymerization monomer is characteristically connected two kinds of different coupling functional groups simultaneously.So guaranteeing that single fluorine replaces benzo miscellaneous [1,3] diazole unit and keeps being orientated consistent connected in order in the course of the polymerization process, fluorine atom rule in the polymer backbone is orientated.And the synthetic schemes that the present invention provides has extraordinary versatility, it can adjust kind and the quantity of aromatic group Ar and the π bridge unit introducing different functionalization, synthesize photovoltaic active layers material miscellaneous, regulation photophysical property and photovoltaic conversion performance.Single fluorine that the present invention obtains replaces benzo miscellaneous [1,3] diazole unit, and along main chain direction, the polymeric material of regular consistent arrangement demonstrates more preferable crystalline arrangement, the beneficially material separation of charge in solar cell device and the raising of photoelectric conversion efficiency.
The present invention, relative to prior art, has such advantages as and beneficial effect:
(1) present invention make use of the difference of product characteristics that the difference of different loci reactivity and different the position of substitution obtain cleverly, carrys out design path preparation and purification obtains subject polymer monomer.Synthetic route is simple, is easily purified.
(2) present invention coupling functional group that two kinds different is characteristically received one polymerization monomer on, so guarantee molecule keep in the course of the polymerization process end to end-the most connected in order, make fluorine atom rule in the polymer backbone be orientated.
(3) the regular semiconducting organic polymer material replacing benzo miscellaneous [1,3] diazole unit containing single fluorine of the present invention, introduces aromatic group Ar and the π bridge unit of functionalization, successfully by this kind of materials application in organic photovoltaic cell.
(4) fluorine atom regular orientation in the polymer backbone is utilized so that polymeric material has more preferable crystalline arrangement, the beneficially material separation of charge in solar cell device and the raising of photoelectric conversion efficiency.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of gained compound 5 in embodiment 1.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of gained compound 6 in embodiment 1.
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of gained compound 7 in embodiment 1.
Fig. 4 is the film absorption spectrogram of embodiment 1 resulting polymers 1.
Fig. 5 is the thermogravimetric analysis spectrogram of embodiment 1 resulting polymers 1.
Fig. 6 is the dsc analysis spectrogram of embodiment 1 resulting polymers 1.
Fig. 7 is the electro chemical analysis spectrogram of embodiment 1 resulting polymers 1.
Fig. 8 is the GIXD analysis of spectra of embodiment 1 resulting polymers 1.
Fig. 9 is the GIXD analysis of spectra of embodiment 1 resulting polymers 1 and PCBM blend film.
Figure 10 is the nucleus magnetic hydrogen spectrum figure of compound 10 in example 2.
Figure 11 is the nucleus magnetic hydrogen spectrum figure of compound 11 in example 2.
Figure 12 is chlorobenzene solution and the film absorption spectrogram of polymer 2 in example 2.
Figure 13 is the film absorption spectrogram of polymer 3 in example 3.
Figure 14 is the dsc analysis spectrogram of polymer 3 in example 3.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
The routine techniques of the polymer chemistry in the practice of the present invention can use art technology in this enforcement.In the examples below, endeavour to ensure the accuracy in numeral used (amount of including, temperature, response time etc.), it is contemplated that some experimental erroies and deviation.Temperature used in the examples below is DEG C to represent, pressure is atmospheric pressure or close to atmospheric pressure.Agents useful for same all can be buied from market routine, and agents useful for same is analytical pure or chromatographically pure, is responded and carries out the most under an inert atmosphere.
Embodiment 1
In embodiment 1, chemical process formula is shown below, and concrete reactions steps and reaction condition are as follows:
(1) compound 1 (4,7-bis-bromo-5-fluorobenzene [c] [1,2,5] thiadiazoles) it is according to document [Adv.Mater.2012,24,3646 3649] method disclosed in prepares, and concretely comprises the following steps: by 4-fluorobenzene-1, and 2-diamidogen is dissolved in the mixed solvent of dichloromethane and triethylamine, thionyl chloride solvent is dripped under ice-water bath stirring, crude product purified by silica gel post purifies and obtains 5-fluorobenzene also [c] [1,2,5] thiadiazoles.5-fluorobenzene also [c] [1,2,5] thiadiazoles is dissolved in hydrobromic acid aqueous solution, drips bromine post-heating under stirring at normal temperature and reflux overnight.Crude product purified by silica gel post purifies available compound 1 (4,7-bis-bromo-5-fluorobenzene [c] [1,2,5] thiadiazoles).
(2) by 4,7-bis-bromo-5-fluorobenzene [c] [1,2,5] thiadiazoles (compound 1,6.24g, 20mmol), tributyl (4-(2-hexyl decyl) thiophene-2-base) stannum (10.8g, 18mmol), toluene (150mL) and DMF (20mL) add in two neck flasks, and argon air-blowing processes 15 minutes.Catalyst Pd (PPh is rapidly joined under argon stream3)4(200mg) in reaction bulb, then process 15 minutes in argon air-blowing.Then, reaction is heated to backflow, keeps temperature stirring reaction 6 hours.Afterwards reactant liquor is cooled to room temperature, then is poured into water, extract with dichloromethane.Purifying with silica gel chromatographic column after organic layer solution being spin-dried for, petroleum ether and dichloromethane flow phase as gradient elution.Finally obtain yellow product (compound 2,8.21g, productivity 84.5%).Aerofluxus in subsequent experimental procedure and reaction postprocessing method, describe with reference to this section.
The nuclear magnetic data of compound 2 is specific as follows:1H NMR(CDCl3, 600MHz) and δ (ppm): 7.94 (d, J=1.3,1H), 7.66 (d, J=10.0,1H), 7.08 (br, 1H), 2.62 (d, J=6.9,2H), 1.71-1.66 (m, 1H), 1.34-1.22 (m, 24H), 0.89-0.85 (m, 6H).13C NMR(CDCl3,150MHz)δ(ppm):161.9,160.2,154.6,149.3,143.8,137.0,131.4,128.2,124.5,116.3,116.1,96.2,96.1,39.3,35.3,33.7,32.3,30.4,30.0,29.7,27.0,23.0,14.5。
(3) compound 2 (5.40g, 10mmol) is dissolved in THF (50mL), then adds N-bromo-succinimide (NBS) (2.14g, 12mmol).Reactant liquor is stirred at room temperature 4 hours.It is poured into water afterwards, extracts with dichloromethane.Crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, finally give yellow product (compound 3,5.59g, 90.4%).
The nuclear magnetic data of compound 3 is specific as follows:1H NMR(CDCl3, 600MHz) and δ (ppm): 7.73 (s, 1H), 7.61 (d, J=9.9,1H), 2.56 (d, J=7.15,2H), 1.76-1.71 (m, 1H), 1.35-1.22 (m, 24H), 0.89-0.84 (m, 6H).13C NMR(CDCl3,150MHz)δ(ppm):161.9,160.2,149.0,142.9,136.6,130.3,127.1,127.0,115.8,115.6,114.4,96.7,96.5,38.9,34.6,33.7,32.3,32.2,30.3,30,0,29.7,26.9,23.0,14.5,14.4.
(4) by compound 3 (3.09g, 5mmol), tributyl (thiophene-2-base) stannum (1.68g, 4.5mmol), two (triphenylphosphine) palladium chloride (140mg), toluene (50mL) and DMF (10mL) under an argon atmosphere, are heated to reflux stirring 6 hours.Being extracted by dichloromethane, crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, obtain red body product (compound 4,1.22g, 39.2%).
The nuclear magnetic data of compound 4 is specific as follows:1H NMR(CDCl3, 500MHz) and δ (ppm): 7.94 (s, 1H), 7.65 (d, J=10.1,1H), 7.37 (dd, J=5.1,1.0Hz, 1H), 7.23 (dd, J=3.6,1.0Hz, 1H), 7.10 (dd, J=5.0,3.7Hz, 1H), 2.77 (d, J=7.2Hz, 2H), 1.79-1.73 (m, 1H), 1.35-1.20 (m, 24H), 0.88-0.84 (m, 6H).13C NMR(CDCl3,125MHz)δ(ppm):162.1,154.6,149.3,140.3,135.8,134.9,132.9,127.9,127.8,127.6,127.5,127.1,126.5,116.0,115.8,96.3,96.1,39.1,34.2,33.77,33.7,32.3,32.2,30.4,30.1,20.0,29.7,26.8,26.8,23.0,14.5.
(5) by compound 4 (1.24g, 2mmol), tributyl (4-(2-hexyl decyl) thiophene-2-base) stannum (2.99g, 5mmol), catalyst Pd (PPh3)4(80mg), toluene (20mL) and DMF (5mL) under an argon atmosphere, are heated to reflux stirring 24 hours.Being extracted by dichloromethane, crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, obtain red product (compound 5,1.51g, 88.9%)
Wherein the nucleus magnetic hydrogen spectrum figure of compound 5 is as it is shown in figure 1, number from spectrogram peak, position, coupling constant are it can be seen that compound 5 is successfully prepared and purification.
The nuclear magnetic data of compound 5 is specific as follows:1H NMR(CDCl3, 500MHz) and δ (ppm): 8.08 (d, J=0.93,1H), 7.95 (s, 1H), 7.71 (d, J=12.8Hz, 1H), 7.36 (dd, J=5.2,1.1Hz, 1H), 7.24 (dd, J=3.6,1.0Hz, 1H), 7.12 (br, 1H), 7.10 (dd, J=5.2,3.7Hz, 1H), 2.78 (d, J=7.2Hz, 2H), 2.65 (d, J=6.7Hz, 2H), 1.81-1.76 (m, 1H), 1.73-1.68 (m, 1H), 1.36-1.22 (m, 48H), 0.90-0.85 (m, 12H).13C NMR(CDCl3,125MHz)δ(ppm):160.2,158.2,153.9,153.8,150.1,142.5,140.2,136.1,135.7,134.3,132.5,132.4,132.3,132.2,127.8,127.0,126.3,125.6,125.5,124.3,124.2,116.8,116.6,111.7,111.6,39.3,39.2,35.3,34.2,33.8,33.7,32.3,30.4,30.1,30.0,29.7,27.0,26.8,23.1,23.0,14.5.
(6) compound 5 (1.70g, 2mmol) is dissolved in THF (50mL), solution is cooled to-50 DEG C.Afterwards NBS (0.36g, 2mmol) is joined in reactant liquor.After keeping low temperature-50 DEG C to stir 1 hour, then it is warmed to room temperature stirring 12 hours.It is poured into water afterwards, extracts with dichloromethane.Crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, finally give red product (compound 6,0.93g, 50.1%).
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of compound 6, and number from spectrogram peak, position, coupling constant are it can be seen that compound 6 is successfully prepared and purification.
The nuclear magnetic data of compound 6 is specific as follows:1H NMR(CDCl3, 500MHz) and δ (ppm): 7.95 (s, 1H), 7.92 (s, 1H), 7.68 (d, J=13.0Hz, 1H), 7.36 (dd, J=5.2,1.1Hz, 1H), 7.23 (dd, J=3.6,1.1Hz, 1H), 7.10 (dd, J=5.2,3.5Hz, 1H), (2.77 d, J=7.3Hz, 2H), (2.59 d, J=7.2Hz, 2H), 1.81-1.73 (m, 2H), 1.36-1.20 (m, 48H), 0.89-0.84 (m, 12H).13C NMR(CDCl3,125MHz)δ(ppm):160.3,158.3,153.5,153.4,150.0,141.8,140.3,136.0,135.5,134.6,132.5,132.4,131.9,131.8,127.8,127.0,126.3,125.9,116.6,116.4,114.1,114.0,110.8,110.7,39.2,38.9,34.5,34.2,33.8,33.7,32.3,30.4,30.1,30.0,29.7,27.0,26.9,26.8,23.1,23.0,14.5.
(7) compound 6 (0.928g, 1mmol) is dissolved in THF (10mL), and reactant liquor is cooled to-80 DEG C.Under argon atmosphere, the THF solution (2mol/L, 2mL) of dropping lithium diisopropylamine.After low temperature stirs 4 hours, add the THF solution (1mol/L, 5mL) of trimethyltin chloride.Reactant liquor is warming up to room temperature, and is stirred at room temperature 12 hours and falls back.After petroleum ether extraction, it is dried with anhydrous magnesium sulfate.Purified by gel column the most again and obtain red product (compound 7,0.96g, 88.0%).
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of compound 7, and number from spectrogram peak, position, coupling constant are it can be seen that compound 7 is successfully prepared and purification.
The nuclear magnetic data of compound 7 is specific as follows:1H NMR(CDCl3, 500MHz) and δ (ppm): 7.96 (s, 1H), 7.92 (s, 1H), 7.68 (d, J=13.1Hz, 1H), 7.35 (d, J=3.4Hz, 1H), 7.17 (d, J=3.4Hz, 1H), 2.79 (d, J=7.3Hz, 2H), 2.59 (d, J=7.0Hz, 2H), 1.82-1.73 (m, 2H), 1.37-1.21 (m, 48H), 0.90-0.84 (m, 12H), 0.42 (s, 9H).13C NMR(CDCl3,125MHz)δ(ppm):160.4,158.3,153.5,150.0,141.8,141.7,139.8,139.4,135.9,135.2,135.1,132.7,132.5,131.8,131.7,129.4,128.6,128.0,127.8,126.1,126.0, 116.5,116.2,114.0,113.9,110.7,110.5,39.12,38.9,34.5,34.3,33.9,33.8,33.7,32.3,30.4,30.1,30.0,29.7,26.9,26.8,23.0,14.5,-7.8.
(8) compound 7 (0.327g, 0.3mmol), three (dibenzalacetone) two palladium (0) (Pd2dba3) (4.0mg), tri-o-tolyl phosphine (P (o Tol)3) (10.0mg) and be dried toluene (4mL) join in microwave reaction pipe.Microwave reaction 45 minutes at 160 DEG C.Solution is precipitated in methanol solution, solid is collected by filtration.Crude solid, again in apparatus,Soxhlet's, washes away little molecule and oligomer with normal hexane, dichloromethane successively.Finally obtain resulting polymer 1 (polymer 1,0.215g, 84.6%) .GPC (1,2,4-trichloro-benzenes, 150 DEG C, polystyrene reference): number-average molecular weight Mn=24.4kDa, PDI=1.50.
Fig. 4 is the film absorption spectrogram of embodiment 1 resulting polymers 1.It can be seen that polymer 1 absorption region width, assemble acromion obvious.The crystalline arrangement excellent performance of polymer 1 is described.
Fig. 5 is the thermogravimetric analysis spectrogram of embodiment 1 resulting polymers 1.It can be seen that polymer 1 has extraordinary heat stability.
Fig. 6 is the dsc analysis spectrogram of embodiment 1 resulting polymers 1.As can be seen from the figure polymer 1 has obvious melting peak and peak crystallization, illustrates that polymer 1 has good crystal property.
Fig. 7 is the electro chemical analysis spectrogram of embodiment 1 resulting polymers 1.Can to calculate the HOMO of polymer 1 be-5.29eV in the peak position that aoxidized according to polymer 1, and the LUMO that can obtain polymer 1 further according to optical band gap is-3.70.Energy level and PCBM good match.
Fig. 8 is the GIXD analysis of spectra of embodiment 1 resulting polymers 1.It can be seen that polymer 1 thin film shows good crystalline arrangement, strand is face accumulation mode arrangement, is conducive to promoting photoelectric conversion efficiency.
Fig. 9 is the GIXD analysis of spectra of embodiment 1 resulting polymers 1 and PCBM blend film.It can be seen that the accumulation peak, face of polymer 1 is the most clearly.Illustrate that polymer 1 has the potential quality becoming an outstanding organic photovoltaic active layer material.
Embodiment 2
In embodiment 2, chemical process formula is shown below, and concrete reactions steps and reaction condition are as follows:
(1) by compound 1 (6.24g, 20mmol), tributyl (thiophene-2-base) stannum (6.71g, 18mmol), toluene (50mL), DMF (10mL) and catalyst Pd (PPh3)4(200mg) under argon atmosphere, it is heated to reflux stirring 6 hours.Being extracted by dichloromethane, crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, obtains yellow solid product (compound 8, productivity 88.7%).
The nuclear magnetic data of compound 8 is specific as follows:1H NMR(CDCl3, 600MHz) and δ (ppm): 8.08 (dd, J=3.7,1.1Hz, 1H), 7.67 (d, J=10.0Hz, 1H), 7.51 (dd, J=5.0,1.1Hz, 1H), 7.19 (dd, J=5.0,3.8Hz, 1H).
(2) by compound 8 (1.78g, 5.0mmol), tributyl (4-(2-decyl myristyl) thiophene-2-base) stannum (10.65g, 15.0mmol), catalyst Pd (PPh3)4(100mg), toluene (50mL) and DMF (10mL), under argon atmosphere, are heated to reflux stirring 24 hours.Being extracted by dichloromethane, crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, obtain orange solid product (compound 9,2.84g, 86.7%).
The nuclear magnetic data of compound 9 is specific as follows:1H NMR(CDCl3, 600MHz) and δ (ppm): 8.12 (dd, J=3.7,1.0Hz, 1H), 8.08 (d, J=0.9Hz, 1H), 7.77 (d, J=12.8Hz, 1H), 7.50 (dd, J=5.1,1.0Hz, 1H), 7.22 (dd, J=5.1,3.7Hz, 1H), (7.13 d, J=0.8Hz, 1H), (2.65 d, J=6.8Hz, 2H), 1.73-1.67 (m, 1H), 1.37-1.21 (m, 40H), 0.89-0.85 (m, 6H).13C NMR(CDCl3,150MHz)δ(ppm):160.0,158.3,153.8,150.2,142.5,138.4,132.6,132.5,132.2,128.6,128.5,128.1,125.9,124.3,117.6,117.3,111.9,111.8,39.3,35.3,33.7,32.3,30.4,30.1,30.0,29.7,27.0,23.0,14.5.
(3) compound 9 is dissolved in THF (50mL) ice bath and is cooled to-20 DEG C.After adding NBS (0.71g, 4mmol) in reactant liquor, then low temperature stirring 1h is warmed to room temperature stirring 12 hours again.It is poured into water afterwards, extracts with dichloromethane.Crude product purified by silica gel chromatographic column purifies, and finally gives orange product (compound 10,2.80g, 95.2%).
Figure 10 is the nucleus magnetic hydrogen spectrum figure of compound 10.Number from spectrogram peak, position, coupling constant are it can be seen that compound 10 is successfully prepared and purification.
The nuclear magnetic data of compound 10 is specific as follows:1H NMR(CDCl3, 500MHz) and δ (ppm): 8.12 (dd, J=3.8,1.1Hz, 1H), 7.92 (s, 1H), 7.73 (d, J=13.0Hz, 1H), 7.50 (dd, J=5.0,1.1Hz, 1H), 7.21 (dd, J=5.1,3.7Hz, 1H), 2.59 (d, J=7.2Hz, 2H), 1.80-1.72 (m, 1H), 1.37-1.21 (m, 40H), 0.90-0.84 (m, 6H).13C NMR(CDCl3,125MHz)δ(ppm):160.2,158.2,153.5,153.4,150.0,141.8,138.2,132.3,132.0,131.9,128.8,128.5,128.3,126.3,126.2,117.4,117.1,114.1,114.0,111.0,110.9,38.9,34.5,33.7,32.3,30.4,30.1,30.0,29.7,26.9,23.0,14.5.
(4) compound 10 (0.734g, 1mmol) is dissolved in THF (10ml) it is cooled to-80 DEG C.Under argon atmosphere, the THF solution (2mol/L, 2mL) of dropping lithium diisopropylamine.After low temperature stirs 4 hours, add the THF solution (1mol/L, 5mL) of trimethyltin chloride.Reactant liquor is warming up to room temperature, and is stirred at room temperature 12 hours and falls back.After petroleum ether extraction, it is dried with anhydrous magnesium sulfate.Purified by gel column the most again and obtain orange product (compound 11,0.76g, 84.7%).
Figure 11 is the nucleus magnetic hydrogen spectrum figure of compound 11.Number from spectrogram peak, position, coupling constant are it can be seen that compound 11 is successfully prepared and purification.
The nuclear magnetic data of compound 11 is specific as follows:1H NMR(CDCl3, 600MHz) and δ (ppm): 8.19 (d, J=3.4Hz, 1H), 7.92 (s, 1H), 7.73 (d, J=13.0Hz, 1H), 7.29 (d, J=3.5Hz, 1H), 2.58 (d, J=7.1Hz, 2H), 1.79-1.72 (m, 1H), 1.39-1.19 (m, 40H), 0.91-0.84 (m, 6H), 0.44 (s, 9H).13C NMR(CDCl3,150MHz)δ(ppm):160.2,158.5,153.5,153.4,150.1,143.8,142.5,141.8,136.6,132.5,131.8,129.8,126.4,126.3,117.1,116.9,113.9,110.7,110.6,38.9,34.5,33.7,32.3,30.4,30.1,30.0,29.7,26.9,23.0,14.5,-7.8.
(5) compound 11 (0.269g, 0.3mmol), three (dibenzalacetone) two palladium (0) (Pd2dba3) (4.0mg), tri-o-tolyl phosphine (P (o Tol)3) (10.0mg) and be dried toluene (4 mL) join in microwave reaction pipe.Microwave reaction 45 minutes at 160 DEG C.Solution is precipitated in methanol solution, solid is collected by filtration.Crude solid, again in apparatus,Soxhlet's, washes away little molecule and oligomer with normal hexane, dichloromethane successively.Finally obtain cyan polymer product (polymer 2,0.166g, 84.7%) .GPC (1,2,4-trichloro-benzenes, 150 DEG C, polystyrene reference): number-average molecular weight Mn=16.4kDa, PDI=3.07.
Figure 12 is chlorobenzene solution and the film absorption spectrogram of polymer 2 in example 2.It can be seen that polymer 2 absorption region width, it is obvious that film absorption assembles acromion.The crystalline arrangement excellent performance of polymer 2 is described.
Embodiment 3
In embodiment 3, chemical process formula is shown below, and concrete reactions steps and reaction condition are as follows:
(1) compound 1 (4,7-bis-bromo-5-fluorobenzene [c] [1,2,5] thiadiazoles) it is according to document (Adv.Mater.2012,24,3646 3649) prepared by the method disclosed in, concretely comprise the following steps commercially available 4-fluorobenzene-1, and 2-diamidogen is dissolved in the mixed solvent of dichloromethane and triethylamine, thionyl chloride solvent is dripped under ice-water bath stirring, crude product purified by silica gel post purifies and obtains 5-fluorobenzene also [c] [1,2,5] thiadiazoles.5-fluorobenzene also [c] [1,2,5] thiadiazoles is dissolved in hydrobromic acid aqueous solution, drips bromine post-heating under stirring at normal temperature and reflux overnight.Crude product purified by silica gel post purifies available compound 1 [4,7-bis-bromo-5-fluorobenzene [c] [1,2,5] thiadiazoles].
(2) 4,7-bis-bromo-5-fluorobenzene [c] [1,2,5] thiadiazoles (compound 1,6.24g, 20mmol), tributyl (4-(2-hexyl decyl) thiophene-2-base) stannum (10.8g, 18mmol), toluene (150mL) and DMF (20mL) add in two neck flasks, and argon air-blowing processes 15 minutes.Catalyst Pd (PPh is rapidly joined under argon stream3)4(200mg) in reaction bulb, then process 15 minutes in argon air-blowing.Then, reaction is heated to backflow, keeps temperature stirring reaction 6 hours.Afterwards reactant liquor is cooled to room temperature, then is poured into water, extract with dichloromethane.Purifying with silica gel chromatographic column after organic layer solution being spin-dried for, petroleum ether and dichloromethane flow phase as gradient elution.Finally obtain yellow product (compound 2,8.21g, productivity 84.5%).
The nuclear magnetic data of compound 2 is specific as follows:1H NMR(CDCl3, 600MHz) and δ (ppm): 7.94 (d, J=1.3,1H), 7.66 (d, J=10.0,1H), 7.08 (br, 1H), 2.62 (d, J=6.9,2H), 1.71-1.66 (m, 1H), 1.34-1.22 (m, 24H), 0.89-0.85 (m, 6H).13C NMR(CDCl3,150MHz)δ(ppm):161.9,160.2,154.6,149.3,143.8,137.0,131.4,128.2,124.5,116.3,116.1,96.2,96.1,39.3,35.3,33.7,32.3,30.4,30.0,29.7,27.0,23.0,14.5。
(3) compound 2 (5.40g, 10mmol) is dissolved in THF (50mL), then adds N-bromo-succinimide (NBS) (2.14g, 12mmol).Reactant liquor is stirred at room temperature 4 hours.It is poured into water afterwards, extracts with dichloromethane.Crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, finally give yellow product (compound 3,5.59g, 90.4%).
The nuclear magnetic data of compound 3 is specific as follows:1H NMR(CDCl3, 600MHz) and δ (ppm): 7.73 (s, 1H), 7.61 (d, J=9.9,1H), 2.56 (d, J=7.15,2H), 1.76-1.71 (m, 1H), 1.35-1.22 (m, 24H), 0.89-0.84 (m, 6H).13C NMR(CDCl3,150MHz)δ(ppm):161.9,160.2,149.0,142.9,136.6,130.3,127.1,127.0,115.8,115.6,114.4,96.7,96.5,38.9,34.6,33.7,32.3,32.2,30.3,30,0,29.7,26.9,23.0,14.5,14.4.
(4) compound 3 (3.09g, 5mmol), [2,2'-bis-thiophene]-5-base tributyl tin (2.05g, 4.5mmol), two (triphenylphosphine) palladium chloride (140mg), toluene (50mL) and DMF (10mL), under argon atmosphere, are heated to reflux stirring 6 hours.Being extracted by dichloromethane, crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, obtain red solid product (compound 12,1.36g, 42.9%)
The nuclear magnetic data of compound 12 is specific as follows:1H NMR(CDCl3, 500MHz) and δ (ppm): 7.93 (s, 1H), 7.64 (d, J=10.1Hz, 1H), 7.24 (dd, J=3.5,1.1Hz, 1H), 7.20 (dd, J=5.1,1.1Hz, 1H), 7.14 (d, J=3.8Hz, 1H), 7.13 (d, J=3.8Hz, 1H), 7.03 (dd, J=5.1,3.6Hz, 1H), (2.79 d, J=7.3Hz, 2H), 1.83 1.75 (m, 1H), 1.34 1.18 (m, 24H), 0.87 0.81 (m, 6H).13C NMR(CDCl3,125MHz)δ(ppm):162.1,160.1,154.6,149.3,140.4,138.3,137.3,134.9,134.8,134.6,133.1,128.2,127.6,127.5,127.4,125.0,124.3,124.2,124.1,116.0,115.7,96.3,96.2,39.2,34.4,33.8,32.3,30.4,30.1,30.0,29.7,26.8,23.0,14.5.
(5) compound 12 (1.41g, 2mmol), tributyl (4-(2-hexyl decyl) thiophene-2-base) stannum (2.99g, 5mmol), catalyst Pd (PPh3)4(80mg), toluene (20mL) and DMF (5mL), under argon atmosphere, are heated to reflux stirring 24 hours.Being extracted by dichloromethane, crude product purified by silica gel chromatographic column purifies, and petroleum ether and dichloromethane flow phase as gradient elution, obtain red solid product (compound 13,1.74g, 93.4%)
The nuclear magnetic data of compound 13 is specific as follows:1H NMR(CDCl3null,500MHz)δ(ppm):8.06(d,J=1.1Hz,1H),7.89(s,1H),7.63(d,J=12.8Hz,1H),7.21(dd,J=5.1,1.1Hz,1H),7.17(dd,J=3.6,1.1Hz,1H),7.12(d,J=3.7Hz,1H),7.10(d,J=3.8Hz,1H),7.09(d,J=1.1Hz,1H),7.01(dd,J=5.1,3.6Hz,1H),2.77(d,J=7.3Hz,2H),2.63(d,J=6.7Hz,2H),1.83–1.75(m,1H),1.74–1.65(m,1H),1.37–1.18(m,48H),0.91–0.81(m,12H).13C NMR(CDCl3,125MHz)δ(ppm):160.1,158.1,153.8,153.7,150.0,142.4,140.1,138.0,137.4,135.6,135.0,134.1,132.5,132.4,132.3,128.2,127.3,125.3,124.9,124.3,124.2,124.0,116.6,116.4,111.7,111.6,39.3,39.1,35.2,34.4,33.8,33.7,32.3,30.5,30.4,30.1,30.0,29.7,27.0,26.8,23.1,23.0,14.5.
(6) compound 13 (1.86g, 2mmol) is dissolved in THF (50mL), solution is cooled to-50 DEG C.Afterwards NBS (0.36g, 2mmol) is joined in reactant liquor.After keeping low temperature-50 DEG C to stir 1 hour, then it is warmed to room temperature stirring 12 hours.It is poured into water afterwards, extracts with dichloromethane.Crude product purified by silica gel chromatographic column purifies, and finally gives red product (compound 14,1.01g, 50.0%).
The nuclear magnetic data of compound 14 is as follows:1H NMR(CDCl3, 500MHz) and δ (ppm): 7.94 (s, 1H), 7.92 (s, 1H), 7.68 (d, J=13.1Hz, 1H), (7.24 dd, J=5.1,1.1Hz, 1H), (7.21 dd, J=3.7,1.1Hz, 1H), 7.15 (d, J=3.8Hz, 1H), 7.14 (d, J=3.8Hz, 1H), 7.04 (dd, J=5.1,3.6Hz, 1H), 2.80 (d, J=7.2Hz, 2H), 2.59 (d, J=7.2Hz, 2H), 1.84 1.73 (m, 2H), 1.38 1.19 (m, 48H), 0.91 0.82 (m, 12H).13C NMR(CDCl3,125MHz)δ(ppm):160.3,158.3,153.5,153.4,150.0,141.8,140.3,138.2,137.4,135.5,134.9,134.4,132.6,132.5,132.4,131.9,131.8,128.3,127.5,125.8,125.7,125.0,124.4,124.1,116.6,116.3,114.1,114.0,110.9,110.7,39.2,38.9,34.5,34.4,33.9,33.8,33.7,32.3,30.4,30.1,30.0,29.7,26.9,26.8,23.1,23.0,14.5.
(7) compound 14 (1.01g, 1mmol) is dissolved in THF (10ml), and reactant liquor is cooled to-80 DEG C.Under argon atmosphere, the THF solution (2mol/L, 2mL) of dropping lithium diisopropylamine.After low temperature stirs 4 hours, add the THF solution (1mol/L, 5mL) of trimethyltin chloride.Reactant liquor is warming up to room temperature, and is stirred at room temperature 12 hours and falls back.After petroleum ether extraction, it is dried with anhydrous magnesium sulfate.Purified by gel column the most again and obtain red product (compound 15,1.03g, 87.8%).
The nuclear magnetic data of compound 15 is specific as follows:1H NMR(CDCl3, 500MHz) and δ (ppm): 7.93 (s, 1H), 7.92 (s, 1H), 7.66 (d, J=13.0Hz, 1H), 7.31 (d, J=3.3Hz, 1H), 7.14 (d, J=3.9Hz, 1H), 7.14 (d, J=3.9Hz, 1H), 7.11 (d, J=3.3Hz, 1H), 2.80 (d, J=7.3Hz, 2H), 2.59 (d, J=7.2Hz, 2H), 1.83 1.73 (m, 2H), 1.39 1.19 (m, 48H), 0.92 0.81 (m, 12H), 0.41 (s, 9H).13C NMR(CDCl3,125MHz)δ(ppm):160.3,158.3,153.5,153.4,150.0,142.8,141.8,140.2,138.3,136.3,135.4,135.3,134.6,132.6,132.5,131.9,131.8,127.5,125.8,125.7,125.3,124.2,116.5,116.2,114.0,110.8,110.6,39.1,38.9,34.5,34.4,33.9,33.8,33.7,32.3,30.4,30.1,30.0,29.7,26.9,26.8,23.1,23.0,14.5,-7.8.
(8) by compound 15 (0.352g, 0.3mmol), three (dibenzalacetone) two palladium (0) (Pd2dba3) (4.0mg), tri-o-tolyl phosphine (P (o Tol)3) (10.0mg) and be dried toluene (4mL) join in microwave reaction pipe.Microwave reaction 45 minutes at 160 DEG C.Solution is precipitated in methanol solution, solid is collected by filtration.Crude solid, again in apparatus,Soxhlet's, washes away little molecule and oligomer with normal hexane, dichloromethane successively.Finally obtain polymer product (polymer 3,0.231g, 82.8%). GPC (1,2,4-trichloro-benzenes, 150 DEG C, polystyrene reference): number-average molecular weight 36.8kDa, PDI=1.49.
Figure 13 is the film absorption spectrogram of polymer 3 in example 3.It can be seen that polymer 3 absorption region width, assemble acromion obvious.The crystalline arrangement excellent performance of polymer 3 is described.
Figure 14 is the dsc analysis spectrogram of polymer 3 in example 3.From figure, obvious melting peak and peak crystallization are it can be seen that polymer 3 has good crystal property.
Above-described embodiment 1, embodiment 2 and the polymer 1 prepared by embodiment 3, polymer 2, polymer 3 be respectively prepared preliminary photovoltaic device (device architecture: ITO/PEDOT:PSS/Polymer:PC71BM/Ca/Al), and embodiment 1, example 2, the polymer 1 of example 3 gained, polymer 2, that the preliminary photovoltaic device of polymer 3 characterizes data is as shown in table 1:
The sign data of preliminary photovoltaic device prepared by made polymer in table 1 embodiment 1～3
From table, 1 it can be seen that the photoelectric conversion efficiency of polymer 1 reaches 7%, and the photoelectric conversion efficiency of polymer 2 reaches 4.6%, and the photoelectric conversion efficiency of polymer 3 reaches 6.8%, all demonstrates excellent photovoltaic performance.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (4)

1. the regular polymer replacing benzo miscellaneous [1,3] diazole containing single fluorine, it is characterised in that have such as formula Structural formula shown in 1:
Wherein:
X, y, z the most each stand alone as the integer of 0 to 5；
N is the positive integer of 3 to 100000；
X1, X2, X3The most each stand alone as O, S, Se, Te, N-R, R-C-R, R-Si-R, R-Ge-R or R-Sn-R, wherein R is C1～C30Straight chain, side chain or cyclic alkyl chain；
R1, R2, R3, R4The most each stand alone as: hydrogen；There is the alkyl of 1～30 carbon atom；Have The alkoxyl of 1～30 carbon atom, thiazolinyl, alkynyl, aryl, carboxyl, hydroxyl, carbonyl, amino, cyanogen Base, nitro, ester group, halogen, haloalkyl；
Ar is unsubstituted or substituted group: benzo miscellaneous [1,3] di azoly, pyrido miscellaneous [1,3] di azoly, Benzotriazole base, naphtho-miscellaneous [1,3] di azoly, aphthotriazoles base, pyrrolo-pyrrole-dione base, indigo base, Bioxindol base, quinoxalinyl, naphthalene diimide group, imidodicarbonic diamide base, thieno imide, quinoline Quinoline base, and phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, naphthacenyl, pentacenyl, fluorenyl, spiral shell Fluorenyl, indane fluorenyl, pyrrole radicals, benzopyrrole base, hexichol amido, triphenylamine base, carbazyl, Yin Diindyl carbazyl, thienyl, bithiophene base, three bithiophene bases, benzothienyl, thieno diphenyl, benzene And double thienyl, furyl, benzofuranyl, benzo difuryl, stannum fen base, bithiophene base, benzo The double thienyl of double stannum fen bases, benzothiophene furyl, benzo, group between aphthothiophenes base, and above group The conjugate unit base become；
The described substituent group in substituted group independently be: hydrogen；There is the alkyl of 1～30 carbon atom； There is the alkoxyl of 1～30 carbon atom, thiazolinyl, alkynyl, aryl, carboxyl, hydroxyl, carbonyl, amino, Cyano group, nitro, ester group, halogen, haloalkyl.
The regular polymer replacing benzo miscellaneous [1,3] diazole containing single fluorine the most according to claim 1, its It is characterised by:
Described Ar is selected from the group of structure as shown below:
Wherein X1, X2, X3, R1, R2, R3, R4There is implication described above.
3. the rule replacing benzo miscellaneous [1,3] diazole according to the fluorine containing list described in any one of claim 1～2 The preparation method of whole polymer, it is characterised in that comprise the following steps:
Have logical formula I single fluorine replace benzo miscellaneous [1,3] diazole with at least one have logical formula II, (III) or (IV) compound reaction, must have the compound shown in formula (V)；Then formula (V) Shown compound generation metal catalytic self-polymerization reaction, obtains the fluorine replacement benzo containing list shown in formula 1 miscellaneous [1,3] regular polymer of diazole；
Wherein x, y, z, X1, X2, X3, R1, R2, R3, R4There is implication described above；X is halogen Element atom；M is tin trimethyl, tributyl tin, boric acid or borate.
4. according to regular the gathering containing single fluorine replacement benzo miscellaneous [1,3] diazole described in any one of claim 1～2 Compound is in the application of organic photoelectric technical field.
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