CN105315298B - A D A conjugated molecules and its preparation method and application based on seven and condensed ring unit - Google Patents
A D A conjugated molecules and its preparation method and application based on seven and condensed ring unit Download PDFInfo
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- CN105315298B CN105315298B CN201410380113.9A CN201410380113A CN105315298B CN 105315298 B CN105315298 B CN 105315298B CN 201410380113 A CN201410380113 A CN 201410380113A CN 105315298 B CN105315298 B CN 105315298B
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Abstract
Seven are based on the present invention relates to a class and condensed ring unit is core, oligomerisation 5-membered aromatic heterocycle is bridging unit, the A D A conjugated molecules of end to draw electronic unit and preparation method thereof, and application of the quasi-molecule as active layer electron donor or electron acceptor material in organic solar batteries (OPV).The present invention based on seven and condensed ring unit A D A conjugated molecules can solwution method processing, possess suitable energy level, and possess preferable sunshine capture ability and heat endurance, be the ideal material of electron donor or electron acceptor in organic solar batteries.It has below general formula structure：
Description
Technical field
Seven are based on the present invention relates to a class and condensed ring unit is core, and oligomerisation 5-membered aromatic heterocycle is bridging unit, and end is
Draw A-D-A conjugated molecules and preparation method thereof of electronic unit, and the quasi-molecule as active layer electron donor or electronics by
Application of the body material in organic solar batteries (OPV).
Background technology
Organic solar batteries are possessed low, lightweight, flexible cost, solution processable and can prepared with large area
Advantage, therefore widely paid close attention in academia.In recent years, polymer and small molecule solar cell are quickly grown, and are taken
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processable electron acceptor based on dibenzosilole and diketopyrrolopyrrole
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Y.Li,D.Zhu,X.Zhan,A Star-shaped perylene diimide electron acceptor for high-
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Chem.Commun.,2014,50,1024；S.Rajaram,R.Shivanna,S.K.Kandappa,K.S.Narayan,
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(D.Mori,H.Benten,I.Okada,H.Ohkita,S.Ito,Low-bandgap donor/acceptor polymer
Blend solar cells with efficiency exceeding 4%, Adv.Energy Mater., 2014,4,
1301006；Y.Zhou,T.Kurosawa,W.Ma,Y.Guo,L.Fang,K.Vandewal,Y.Diao,C.Wang,Q.Yan,
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chain engineering,Adv Mater,2014,DOI:10.1002/adma.201306242.) and based on polymeric donor
With the organic solar batteries of the non-fullerene acceptor of small molecule (X.Zhang, Z.Lu, L.Ye, C.Zhan, J.Hou, S.Zhang,
B.Jiang,Y.Zhao,J.Huang,S.Zhang,Y.Liu,Q.Shi,Y.Liu,J.Yao,A potential perylene
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Non-fullerene organic solar cells with4.03%efficiency, Adv.Mater., 2013,25,
5791；Z.Lu,B.Jiang,X.Zhang,A.Tang,L.Chen,C.Zhan,J.Yao,Perylene–Diimide Based
Non-fullerene solar cells with4.34%efficiency through engineering surface
donor/acceptor compositions,Chem.Mater.,2014,DOI:10.1021/cm5006339.) photoelectricity turn
Change efficiency more than 4%.This explanation, develops high performance non-fullerene acceptor material and is not only highly desirable to, and be also
It is very feasible.
Due to its rigid planar structure, it is mutual that the conjugated polymer containing condensed ring unit possesses very strong intermolecular π-π
Effect, so as to obtain higher carrier mobility；Conjugated polymer electronics based on indacene class seven and condensed ring unit is given
Body photovoltaic material shows wider absorption spectrum and higher molar absorption coefficient, can when thus be accordingly used in solar cell
Obtain higher short circuit current flow (JSC).So far, the A-D-A conjugation of any document or patent report based on seven and condensed ring unit is had no
Application of the small molecule as electron donor or electron acceptor material in organic solar batteries.
Design feature based on seven and condensed ring unit, four substituents above it can outside conjugate planes due to propping up
The aggregation between acceptor molecule is efficiently reduced, and regulates and controls it by haling electronic unit in the introducing of the two ends of seven and condensed ring unit
Energy level, can be used as electron acceptor.
Simultaneously condensed ring unit is as core by the use of seven with high carrier mobility by the present invention, and oligomerisation 5-membered aromatic heterocycle is bridge
Connect unit, the drawing electronic unit design for changing end has synthesized a series of A-D-A conjugated molecules based on seven and condensed ring unit, this
Quasi-molecule possesses stronger absorption, preferable charge transport properties and suitable electron energy level, can as electron donor or
Electron acceptor material is applied to organic solar batteries device.
The content of the invention
An object of the present invention is to provide a class with stronger absorption, higher charge transport properties and suitable
The A-D-A conjugated molecules based on seven and condensed ring unit of electron energy level.
The second object of the present invention is to provide a kind of preparation method based on seven and the A-D-A conjugated molecules of condensed ring unit.
The third object of the present invention be to provide based on seven and condensed ring unit A-D-A conjugated molecules as electron donor or electricity
Application of the sub- acceptor material in organic solar batteries.
The present invention is prepared for that a series of brand-new, dissolubilities are good, the good A-D-A based on seven and condensed ring unit of heat endurance
Conjugated molecule.Due to seven and the rigid planar structure of condensed ring unit, what electronic unit was drawn in end hales electronic capability, therefore this kind of
Molecule possesses strong visible absorption ability, high charge transport properties and suitable electron energy level, is adapted as electronics
Donor or electron acceptor material are applied to prepare organic solar batteries.
With elementary analysis, nuclear magnetic resonance, the A-D-A conjugated molecules of the mass spectral characteristi present invention chemical constitution, use thermogravimetric
The heat endurance of the A-D-A conjugated molecules of the analysis and characterization present invention, characterizes with cyclic voltammetric the A-D-A conjugation point of the present invention
The electrochemical properties of son, the photophysical property of the A-D-A conjugated molecules of the present invention is have studied with ultra-violet absorption spectrum.
The A-D-A conjugated molecules based on seven and condensed ring unit of the present invention have below general formula structure：
N is 0~6；
Z=C, Si or N；
X=O, S or Se；
R1~R3It independently is hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl.
Alkyl in described 4- alkyl phenyls is C1~C8Alkyl.
The present invention based on seven and condensed ring unit A-D-A conjugated molecules in, preferred scheme is：Described n is 0~3；Institute
The Z=C stated；X=S；R1~R3It independently is hydrogen, C1~C8Alkyl or 4- hexyl phenyl；R in A structures4For C1~C8Alkane
Base.
The present invention based on seven and condensed ring unit A-D-A conjugated molecules in, preferred scheme is：Described n is 0~3；R1
~R3It independently is hydrogen, C1~C12Alkyl, C1~C12Alkoxy or 4- hexyl phenyl；R in A structures4For C1~C8's
Alkyl.
The preparation method based on seven and the A-D-A conjugated molecules of condensed ring unit of the present invention comprises the following steps：
R will be carried1, R2, R3Seven and condensed ring unit aldehyde compound of substituent hold with drawing electronic unit A to be added to reaction
In device, wherein：With R1, R2, R3Seven and condensed ring unit aldehyde compound of substituent are with drawing electronic unit A mol ratio to be 1：2
~100；Using chloroform as solvent, lead to after inert gas excludes the air in reaction vessel and add piperidines or pyridine, be 30 in temperature
Reaction is stirred at~80 DEG C；After reaction terminates, gained reaction product is poured into methanol, filtration drying obtains solid, led to
Cross chromatography over CC and obtain the A-D-A conjugated molecule products based on seven and condensed ring unit with below general formula structure；Or：
R will be carried1Seven and condensed ring unit tin trimethyl compound of substituent are with carrying R2, R3Substituent and electron withdrawing group
Group A single bromine oligomerisation five-membered aromatic heterocyclic compounds are added in reaction vessel, wherein：With R1Seven and condensed ring list of substituent
First tin trimethyl compound is with carrying R2, R3Substituent and drawing electron group A single bromine oligomerisation five-membered aromatic heterocyclic compounds rub
You are than being 1：2~5；Using toluene as solvent, lead to inert gas and exclude the four (triphens that catalytic amount is added after the air in reaction vessel
Base phosphine) palladium catalyst, it is stirred reaction in the case where temperature is 100~120 DEG C；Reaction is added relative to R after terminating1Substitution
The potassium fluoride aqueous solution of seven and condensed ring unit tin trimethyl compound the mole excess of base, extraction is dried and filtered, and is spin-dried for filter
Liquid obtains solid, and the A-D-A conjugation point based on seven and condensed ring unit with below general formula structure is obtained by chromatography over CC
Sub- product；
N is 0~6；
Z=C, Si or N；
X=O, S or Se；
R1~R3It independently is hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl.
Described piperidines or the addition of pyridine be described piperidines or pyridine with R1, R2, R3Substituent seven and it is thick
The mol ratio of ring element aldehyde compound is 1：0.001~0.5.
Described is that to be stirred time of reaction at 30~80 DEG C be 6~48 hours in temperature.
The addition of described tetrakis triphenylphosphine palladium catalyst be preferably described tetrakis triphenylphosphine palladium catalyst with
With R1Substituent seven and condensed ring unit tin trimethyl compound mol ratio be 1：10~100.
Described is that to be stirred time of reaction at 100~120 DEG C be 12~48 hours in temperature.
The A-D-A conjugated molecules based on seven and condensed ring unit of the present invention possess stronger absorption, higher electric charge transmission
Performance and suitable electron energy level, the active layer electron donor or electron acceptor material that can be captured as light are in organic solar
Applied in battery.
Main advantages of the present invention are：
1. synthesis based on seven and condensed ring unit A-D-A conjugated molecules can solwution method processing, be dissolved in dichloromethane, chlorine
The organic solvent such as imitative, tetrahydrofuran and chlorobenzene.
2. the A-D-A conjugated molecules heat endurance based on seven and condensed ring unit of synthesis is good, starting heat decomposition temperature exceedes
300℃。
3. the A-D-A conjugated molecules light absorptive based on seven and condensed ring unit of synthesis is good, it is adapted to do organic solar batteries
Material.
4. the A-D-A conjugated molecules based on seven and condensed ring unit of synthesis possess suitable electron energy level, it is suitable for having
Electron donor material or electron acceptor material in machine solar cell.
5. the A-D-A conjugated molecules based on seven and condensed ring unit of synthesis are used as electron donor material or electron acceptor material
Very high electricity conversion is shown in organic solar batteries.
Brief description of the drawings
Fig. 1 is the ultraviolet-ray visible absorbing based on seven and the A-D-A conjugated molecules 1 of condensed ring unit of the embodiment of the present invention 1
Spectrum.
Fig. 2 is the cyclic voltammetry curve based on seven and the A-D-A conjugated molecules 1 of condensed ring unit of the embodiment of the present invention 1.
Fig. 3 is the thermogravimetric curve based on seven and the A-D-A conjugated molecules 1 of condensed ring unit of the embodiment of the present invention 1.
Fig. 4 is the ultraviolet-ray visible absorbing based on seven and the A-D-A conjugated molecules 2 of condensed ring unit of the embodiment of the present invention 2
Spectrum.
Fig. 5 is the cyclic voltammetry curve based on seven and the A-D-A conjugated molecules 2 of condensed ring unit of the embodiment of the present invention 2.
Fig. 6 is the thermogravimetric curve based on seven and the A-D-A conjugated molecules 2 of condensed ring unit of the embodiment of the present invention 2.
Fig. 7 is the ultraviolet-ray visible absorbing based on seven and the A-D-A conjugated molecules 3 of condensed ring unit of the embodiment of the present invention 3
Spectrum.
Fig. 8 is the cyclic voltammetry curve based on seven and the A-D-A conjugated molecules 3 of condensed ring unit of the embodiment of the present invention 3.
Fig. 9 is the thermogravimetric curve based on seven and the A-D-A conjugated molecules 3 of condensed ring unit of the embodiment of the present invention 3.
Figure 10 is the organic solar batteries based on seven and the A-D-A conjugated molecules 1 of condensed ring unit of the embodiment of the present invention 1
I-V curve；Measure the short circuit current flow J of devicescFor 15.89mA cm-2, open-circuit voltage VocIt is for 0.81V, fill factor, curve factor FF
59.2%, energy conversion efficiency PCE are 7.62%.
Figure 11 is the organic solar batteries based on seven and the A-D-A conjugated molecules 2 of condensed ring unit of the embodiment of the present invention 2
I-V curve；Measure the short circuit current flow J of devicescFor 16.65mA cm-2, open-circuit voltage VocIt is for 0.93V, fill factor, curve factor FF
42.3%, energy conversion efficiency PCE are 6.56%.
Figure 12 is the organic solar batteries based on seven and the A-D-A conjugated molecules 3 of condensed ring unit of the embodiment of the present invention 3
I-V curve；Measure the short circuit current flow J of devicescFor 12.53mA cm-2, open-circuit voltage VocIt is for 0.83V, fill factor, curve factor FF
60.1%, energy conversion efficiency PCE are 6.25%.
Embodiment
Embodiment 1
Synthetic route based on seven and the A-D-A conjugated molecules 1 of condensed ring unit is as follows：
Compound a (200mg, 0.19mmol), compound b (279mg, 1.4mmol), chlorine are added in three neck round bottom flask
Imitative (50mL), logical argon gas adds 1mL pyridines in 30 minutes to remove after the air in three neck round bottom flask；Enter in the case where temperature is 65 DEG C
Row stirring reaction 12 hours, is then cooled to room temperature；Gained reaction solution is poured into 200mL methanol, the precipitation being filtrated to get is simultaneously
Silica gel (200~300 mesh) pillar layer separation is used after drying, eluant, eluent is that (volume ratio is 1 to petroleum ether/dichloromethane:1), product
It is the A-D-A conjugated molecules 1 based on seven and condensed ring unit for blue solid (57mg, 21%).1H NMR(400MHz,
CDCl3):δ 8.87 (s, 2H), 8.70 (d, J=7.6Hz, 2H), 8.22 (s, 2H), 7.93 (d, J=6.4Hz, 2H), 7.79 (m,
4H), 7.63 (s, 2H), 7.23 (d, J=8.4Hz, 8H), 7.15 (d, J=8.4Hz, 8H), 2.58 (m, 8H), 1.61 (m, 8H),
1.33(m,24H),0.87(m,12H).13C NMR(100MHz,CDCl3):δ188.18,160.36,155.65,152.86,
147.65,147.06,143.64,142.51,140.02,139.60,138.94,138.24,136.95,136.86,135.19,
134.49,128.87,127.89,125.32,123.76,122.73,118.53,114.63,114.57,69.38,63.24,
35.61,31.70,31.27,29.20,22.59,14.10.MS(MALDI):m/z1427.4(M+1).Anal.Calcd for
C94H82N4O2S4:C,79.07；H,5.79；N,3.92.Found:C,78.93；H,5.70；N, 3.85%.
Uv-visible absorption spectra based on seven and the A-D-A conjugated molecules 1 of condensed ring unit is as shown in Figure 1；Circulation volt
Pacify curve as shown in Figure 2；Thermogravimetric curve is as shown in Figure 3；The I-V curve of prepared organic solar batteries is as shown in Figure 10.
Embodiment 2
Synthetic route based on seven and the A-D-A conjugated molecules 2 of condensed ring unit is as follows：
Compound c (165mg, 0.11mmol), compound b (219mg, 1.1mmol), chlorine are added in three neck round bottom flask
Imitative (50mL), logical argon gas adds 0.5mL pyridines in 30 minutes to remove after the air in three neck round bottom flask；In the case where temperature is 65 DEG C
Reaction 12 hours is stirred, room temperature is then cooled to；Gained reaction solution is poured into 200mL methanol, the precipitation being filtrated to get
And silica gel (200~300 mesh) pillar layer separation is used after drying, eluant, eluent is that (volume ratio is 1 to petroleum ether/dichloromethane:1), produce
Thing is dark green solid (152mg, 74%), is the A-D-A conjugated molecules 2 based on seven and condensed ring unit.1H NMR
(400MHz,CDCl3):δ 8.78 (s, 2H), 8.70 (d, J=7.2Hz, 2H), 7.93 (d, J=7.2Hz, 2H), 7.77 (m,
4H), 7.69 (s, 2H), 7.60 (s, 2H), 7.56 (s, 2H), 7.21 (d, J=8.0Hz, 8H), 7.14 (d, J=8.0Hz, 8H),
(m, the 24H) of 2.78 (d, J=7.2Hz, 4H), 2.60 (m, 8H), 1.64 (m, 14H), 1.35 (m, 36H), 0.8813C NMR
(100MHz,CDCl3):δ118.86,160.76,154.67,150.11,149.50,147.13,146.27,143.47,
142.74,140.62,140.50,140.39,137.70,137.38,136.92,136.83,136.52,135.56,134.96,
129.30,128.59,125.79,124.28,122.90,121.88,118.02,115.16,69.84,63.64,40.02,
36.25,34.73,34.26,33.05,32.33,32.21,31.93,29.82,29.14,26.35,23.58,14.69,
11.26.MS(MALDI):m/z1815.6(M+1).Anal.Calcd for C118H118N4O2S6:C,78.02；H,6.55；N,
3.08.Found:C,77.93；H,6.45；N, 3.12%.
Uv-visible absorption spectra based on seven and the A-D-A conjugated molecules 2 of condensed ring unit is as shown in Figure 4；Circulation volt
Pacify curve as shown in Figure 5；Thermogravimetric curve is as shown in Figure 6；The I-V curve of prepared organic solar batteries is as shown in figure 11.
Embodiment 3
Synthetic route based on seven and the A-D-A conjugated molecules 3 of condensed ring unit is as follows：
Compound d (200mg, 0.148mmol), compound e (100mg, 0.345mmol) are added in three neck round bottom flask
With 20mL toluene, logical argon gas adds Pd (PPh in 15 minutes to remove the air in three neck round bottom flask3)4(40mg,
0.034mmol), it is stirred reaction 48 hours in the case where temperature is 110 DEG C；It is cooled to room temperature；Add 40mL (0.1g mL-1)KF
The aqueous solution, is stirred overnight at room temperature, to remove tin impurity；150mL water, CH are added in gained reactant2Cl2(2×150mL)
Extracted, the anhydrous MgSO of gained organic phase4It is dried；Filter and be spin-dried for removing after solvent, with petroleum ether/dichloromethane
(volume ratio is 1 to mixed solvent:1) eluent is made, the purification of silica gel (200~300 mesh) pillar layer separation obtains black-and-blue solid
(30mg, 14.1%), is the A-D-A conjugated molecules 3 based on seven and condensed ring unit.1H-NMR(400MHz,CD2Cl2):δ8.79
(s, 2H), 8.73 (s, 2H), 8.69 (d, J=8.0Hz, 2H), 7.92 (d, J=8.0Hz, 2H), 7.66 (s, 2H), 7.26 (d, J
=8.4Hz, 8H), 7.17 (d, J=8.0Hz, 8H), 2.60 (m, 8H), 1.56 (m, 8H), 1.27 (m, 24H), 0.85 (m,
12H).MS(MALDI):m/z1438.6(M+)。
Uv-visible absorption spectra based on seven and the A-D-A conjugated molecules 3 of condensed ring unit is as shown in Figure 7；Circulation volt
Pacify curve as shown in Figure 8；Thermogravimetric curve is as shown in Figure 9；The I-V curve of prepared organic solar batteries is as shown in figure 12.
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, Polyglycolic acid fibre thick one layer of 30 nm of spin coating after drying：Poly styrene sulfonate PEDOT:PSS
(weight compares 1：1) (4083) anode modification layer, is dried 15 minutes at 150 DEG C, standby.By embodiment 1~3 based on seven and condensed ring
(weight is than being all 1 with polymer donor material PTB7-TH respectively for the A-D-A conjugated molecules 1~3 of unit：0.5~blending 4)
Solution (20~30mg/ml) is spun on PEDOT:The active layer of device is formed in PSS (4083) anode modification layer.Photovoltaic device is lived
Property layer effective area be 4mm2.Vacuum (3 × 10 on active layer-5Pa) evaporation thickness 50nm or so metallic aluminium is used as photovoltaic device
The negative electrode of part.
With the Newport500W xenon lamps equipped with AM1.5 optical filters as simulated solar light source, in 100mW/cm2Under light intensity
Photovoltaic performance test is carried out to device, light intensity is calibrated by standard monocrystalline silicon solar cell；J-V curves are used
Keithley236 is measured, and is controlled by Labview softwares by computer.
Based on seven and condensed ring unit A-D-A conjugated molecules 1~3 organic solar batteries I-V curve such as Figure 10~
Shown in 12.
The structure of polymeric donor PTB7-TH used in the present invention is as follows：
。
Claims (8)
1. a kind of A-D-A conjugated molecules based on seven and condensed ring unit, it is characterized in that, the A- based on seven and condensed ring unit
D-A conjugated molecules have below general formula structure：
N is 0~6；
Z=C, Si or N；
X=O, S or Se；
R1~R3It independently is hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl；
Alkyl in described 4- alkyl phenyls is C1~C8Alkyl.
2. the A-D-A conjugated molecules according to claim 1 based on seven and condensed ring unit, it is characterized in that：Described n is 0
~3；Described Z=C；X=S；R1~R3It independently is hydrogen, C1~C8Alkyl or 4- hexyl phenyl；R in A structures4For C1~
C8Alkyl.
3. the A-D-A conjugated molecules according to claim 1 based on seven and condensed ring unit, it is characterized in that：Described n is 0
~3；R1~R3It independently is hydrogen, C1~C12Alkyl, C1~C12Alkoxy or 4- hexyl phenyl；R in A structures4For C1~
C8Alkyl.
4. the preparation side based on seven and the A-D-A conjugated molecules of condensed ring unit described in a kind of claims 1 to 3 any one
Method, it is characterized in that, described preparation method comprises the following steps：
R will be carried1, R2, R3Seven and condensed ring unit aldehyde compound of substituent are added in reaction vessel with drawing electronic unit A,
Wherein：With R1, R2, R3Seven and condensed ring unit aldehyde compound of substituent are with drawing electronic unit A mol ratio to be 1：2~
100；Using chloroform as solvent, lead to after inert gas excludes the air in reaction vessel and add piperidines or pyridine, temperature be 30~
Reaction is stirred at 80 DEG C；After reaction terminates, gained reaction product is poured into methanol, filtration drying obtains solid, passed through
Chromatography over CC obtains the A-D-A conjugated molecule products based on seven and condensed ring unit with below general formula structure；Or：
R will be carried1Seven and condensed ring unit tin trimethyl compound of substituent are with carrying R2, R3Substituent and drawing electron group A's
Single bromine oligomerisation five-membered aromatic heterocyclic compounds are added in reaction vessel, wherein：With R1Seven and condensed ring unit three of substituent
Methyl tin compound is with carrying R2, R3The mol ratio of substituent and drawing electron group A single bromine oligomerisation five-membered aromatic heterocyclic compounds
For 1：2~5；Using toluene as solvent, lead to inert gas and exclude the four (triphenyls that catalytic amount is added after the air in reaction vessel
Phosphine) palladium catalyst, it is stirred reaction in the case where temperature is 100~120 DEG C；Reaction is added relative to R after terminating1Substituent
The excessive potassium fluoride aqueous solution of seven and condensed ring unit tin trimethyl compound mole, extraction, which is dried, simultaneously filters, and is spin-dried for filtrate
Solid is obtained, the A-D-A conjugated molecules based on seven and condensed ring unit with below general formula structure are obtained by chromatography over CC
Product；
N is 0~6；
Z=C, Si or N；
X=O, S or Se；
R1~R3It independently is hydrogen, C1~C30Alkyl, C1~C30Alkoxy or 4- alkyl phenyls；
Drawing electron group A is selected from one of following structures：
R in above-mentioned A structures4For C1~C30Alkyl；
Alkyl in described 4- alkyl phenyls is C1~C8Alkyl.
5. preparation method according to claim 4, it is characterized in that：Described piperidines or the addition of pyridine are described piperazines
Pyridine or pyridine are with carrying R1, R2, R3Substituent seven and condensed ring unit aldehyde compound mol ratio be 1：0.001~0.5.
6. preparation method according to claim 4, it is characterized in that：Described being stirred in the case where temperature is 30~80 DEG C is anti-
The time answered is 6~48 hours；Described is that to be stirred time of reaction at 100~120 DEG C be 12~48 hours in temperature.
7. preparation method according to claim 4, it is characterized in that：The addition of described tetrakis triphenylphosphine palladium catalyst
It is described tetrakis triphenylphosphine palladium catalyst and carries R1Substituent seven and condensed ring unit tin trimethyl compound mole
Than for 1：10~100.
8. the application based on seven and the A-D-A conjugated molecules of condensed ring unit described in a kind of claims 1 to 3 any one, its
It is characterized in：Active layer electron donor or electronics that the described A-D-A conjugated molecules based on seven and condensed ring unit are captured as light
Acceptor material is applied in organic solar batteries.
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