CN106831815A - A kind of A-D-A type organic molecule acceptors of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof - Google Patents
A kind of A-D-A type organic molecule acceptors of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof Download PDFInfo
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Abstract
A-D-A type organic molecule acceptors the invention discloses a kind of seven yuan of condensed ring (DTCC) of carbazoles containing thieno and preparation method and application.The structure of the small molecule receptor is shown in formula I.The intermediate and its synthetic route of interesting small organic molecules acceptor that the present invention is provided have the advantages that simple efficient, raw material are cheap and easy to get, universality is high, reproducible, and can promote the use of that all kinds of DTCC bases A-D-A type organic molecules receive synthesizes.The organic micromolecule acceptor have the advantages that Stability Analysis of Structures, raw material be commonly easy to get, production cost it is relatively low.This organic micromolecule acceptor is used to prepare non-fullerene polymer solar cell, 4.8-6% or so energy conversion efficiency can be obtained, the excellent potentiality that such small molecule receptor is applied in organic solar batteries are fully illustrated, with certain actual application value.
Description
Technical field
The invention belongs to organic semiconductor material field, it is related to the organic molecule acceptor material for organic solar batteries
Material and preparation method thereof.
Background technology
Solar energy has inexhaustible, nexhaustible and the features such as without limitations, is that a class is most potential
Regenerative resource.In recent years, due to organic solar batteries (Organic Solar Cells, OSCs) have lightweight, flexibility,
Low cost and can the advantage such as solwution method large area processing, thus enjoy people to pay close attention to.Wherein, the organic sun of bulk heteroj junction type
Energy battery achieves fast development.At present, the energy conversion effect of the unijunction OSCs devices based on fullerene derivate receptor structure
Rate (PCE) is more than 10%.However, there are some essential defects in fullerene derivate acceptor, for example：Caught in the light of visible region
Capacitation power is weak, synthesis and purification difficult and intermolecular aggregation tendency are strong etc., dramatically limits entering for fowler alkenyl OSCs
One step develops.Therefore, it is the disadvantages mentioned above of solution fullerene acceptor, develops new non-fullerene acceptor (for example：Organic small point
Sub- acceptor) there is important Research Significance, it is the substitute of most promising fullerene derivate acceptor to have been found to.
Seven yuan of condensed ring (Dithienocyclopentacarbazole, DTCC) of thieno carbazoles are the classical ladders of a class
Shape conjugation and ring element, there is strong electron donation, good coplanarity and molecular structure to be easy to cut out for it
Advantage, thus it is widely used in the p-type polymer semiconducting material of design, synthesized high-performance.Wherein, based on DTCC- bases
The hole mobility of the organic field effect tube of polymer film construction is up to 0.001~0.14cm2V–1s–1
(Macromolecules,2013,46,7687-7695).Fowler alkenyl OSCs's based on DTCC- based polymer films construction
PCE is up to 3.7~4.6% (Chem.Commun., 2010,46,3259-3261；Adv.Funct.Mater.,2012,22,1711–
1722).Although p-type DTCC derivative units are widely used in the p-type polymer semiconducting material of synthesized high-performance,
It is that DTCC- base n-type organic molecule acceptor materials are not reported still.The present invention is by the thiophene end of DTCC derivatives position
Two strong electrophilic end groups of upper introducing, design has synthesized a kind of A-D-A type organic molecule acceptors of unit of derivative containing DTCC,
Obtain the electronic transmission performance of excellent combination property.As acceptor material, have in non-fullerene solar cell good
Application potential.By molecular structure and organic solar batteries device optimization, it is expected to obtain photoelectric transformation efficiency high.
The content of the invention
In view of problem above, a kind of A-D-A type organic molecules of seven yuan of condensed ring of carbazoles containing thieno of present invention offer
Acceptor and preparation method thereof.
The technical scheme is that：
A kind of A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles, with below general formula (I)：
Wherein, R1It is C1-C16Straight or branched alkyl；
In formula (I), R2For in formula (II), formula (III), formula (IV), formula (VI), formula (VII), structure shown in formula (VIII)
It is a kind of；
Wherein, R can be C1-C16Straight or branched alkyl；
The preparation method of the above-mentioned A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles, including such as
Lower synthesis step：
(1) carbazole borate reacts with thiophene ester halogenated compound, obtains intermediate a：
The structural formula of the carbazole borate is:
Wherein, R1It is C1-C16Straight or branched alkyl；
The thiophene ester halogenated compound structural formula is:
The structural formula of the intermediate a is:
Wherein, R1It is C1-C16Straight or branched alkyl；
(2) at high temperature, intermediate a elder generations and R2Grignard reagent reaction, then through peracetic acid cyclization, obtain intermediate b：
The R2Grignard reagent structural formula be R2MgBr；
The R2For in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII), structure shown in formula (VIII)
It is a kind of；Wherein, R can be C1-C16Straight or branched alkyl；
The structural formula of the intermediate b is：
Wherein, R1Can be C1-C16Straight or branched alkyl；
The R2For in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII) or structure shown in formula (VIII)
One kind；Wherein, R can be C1-C16Straight or branched alkyl；
(3) at high temperature, intermediate b and POCl3 and N, N '-dimethyl formamide obtain intermediate c：
The structural formula of the intermediate c is：
Wherein, R1Can be C1-C16Straight or branched alkyl；
The R2For in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII), structure shown in formula (VIII)
It is a kind of；Wherein, R can be C1-C16Straight or branched alkyl；
(4) at high temperature, intermediate c and intermediate d reacts, and obtains the final product shown in following structures：
The structural formula of the intermediate d is：
The structural formula of the final product is：
Wherein, R1Can be C1-C16Straight or branched alkyl；
The R2For in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII) or structure shown in formula (VIII)
One kind；Wherein, R can be C1-C16Straight or branched alkyl；
Preferably, the preparation method of the above-mentioned A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles,
Wherein step (1) is carried out as follows：By 10mmol carbazole borates, 20-100mmol thiophene esters halogenated compounds are (through business
Approach is bought, if other chemical reagent are not explained clearly, is commercially available), 10-100mmol anhydrous Ks2CO3, in right amount
Water, 1-10mmol TBABs, 0.1-0.5g palladium catalysts, 200mL toluene is added in reaction bulb.Nitrogen is protected,
Lucifuge, reacts 5-15 hours at 100 DEG C.Room temperature is cooled to, is extracted with dichloromethane and water, anhydrous MgSO4Dry, be spin-dried for
Post, obtains yellow solid, as intermediate a.
Preferably, the preparation method of the above-mentioned A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles,
Wherein step (2) is carried out as follows：By 10mmol magnesium chips, appropriate iodine as catalyst, 10-30mmol bromo chemical combination
Thing, the THF of 50-150mL, is added in reaction bulb.Nitrogen is protected, and is triggered at 100 DEG C.React 8-20 hours at this temperature
Afterwards, the THF solution of 1-3mmol intermediates a is added in reaction system at normal temperatures, and subsequent temperature rises to 110 DEG C of stirrings 10-15
Hour.Room temperature is cooled to, is extracted with dichloromethane and water, through anhydrous MgSO4Dry, after being spin-dried for post, add 50-150mL second
Acid, in nitrogen protection, stirs 3-8 hours at 100 DEG C.Reaction stop after, directly carry out suction filtration, obtain yellow solid, as in
Mesosome b.
Preferably, the preparation method of the above-mentioned A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles,
Wherein step (3) is carried out as follows：By 0.5mmol intermediate products c, 10-30mmol POCl3s, the N of 30-100mL, N '-
Dimethylformamide reacts, and is added in reaction bulb.Nitrogen is protected, and is stirred 15-30 hours at 110 DEG C.Room temperature is cooled to, with two
Chloromethanes and water are extracted, anhydrous MgSO4Dry, be spin-dried for post, obtain yellow solid, as intermediate c.
Preferably, the preparation method of the above-mentioned A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles,
Wherein step (4) is carried out as follows：By 0.5mmol intermediates c, 1-10mmol intermediate the d ,-4mL of pyridine 1,20-40mL chlorine
It is imitative, it is added in reaction bulb.Nitrogen is protected, and is reacted 8-15 hours at 100 DEG C.After stopping reaction, post is crossed, obtain navy blue and consolidate
Body, as final goal product.
Using commercially available PCE10 as solar cell donor, with seven yuan of A of condensed ring of carbazoles containing thieno-
D-A type organic molecules acceptor is the acceptor of solar cell, using classical sandwich device architecture (ITO/PEDOT:PSS/
PCE10:DTCC-IC/Ca/Al solar device) is constructed.
The advantage of the invention is that：
(1) synthesis of organic molecule acceptor shown in the present invention is simple, and raw material can be easy to get, and its synthetic method has generalization
High and reproducible the advantages of；
(2) organic molecule acceptor shown in the present invention is used to prepare non-fullerene polymer solar cell, can obtain 6%
The energy conversion efficiency of left and right, with certain actual application value.
Brief description of the drawings
Fig. 1 is the ultraviolet-visible-near-infrared of the organic molecule acceptor that chemical structural formula shown in the present invention is DTCC-IC
Abosrption spectrogram.
Fig. 2 is the ultraviolet-visible-near-infrared of the organic molecule acceptor that chemical structural formula shown in the present invention is DTCC8-IC
Abosrption spectrogram.
Fig. 3 is that the organic molecule acceptor that chemical structural formula shown in the present invention is DTCC-IC and DTCC8-IC prepares non-lipid
Strangle the J-V curves of alkene solar cell.
Specific embodiment
With reference to specific embodiment, the present invention will be further described, but the present invention and is only not limited to following examples
Described structure.
Embodiment 1
A kind of chemical structural formula is the organic molecule acceptor of DTCC-IC, and its synthetic route is as follows：
(1) chemical structural formula is the synthesis of the intermediate of a：By (2.7g, 5.1mmol) carbazole borate, (3.7g,
15.3mmol) thiophene ester halogenated compound, (13.8g, 100.0mmol) anhydrous K2CO3, appropriate water, 2 drop TBABs,
0.5g palladium catalysts, 100mL toluene, are added in reaction bulb.Nitrogen is protected, lucifuge, is reacted 24 hours at 100 DEG C.It is cooled to
Room temperature, is extracted, anhydrous MgSO with dichloromethane and water4Dry, be spin-dried for post, obtain yellow solid, as intermediate a, yield
It is 75%.1H NMR(400MHz,CDCl3),δ(ppm):8.08–8.10(d,2H),7.54–7.56(m,4H),7.36–7.38
(dd,2H),7.27–7.28(d,2H),4.30(t,2H),4.17–4.22(m,4H),1.85–1.91(m,2H),1.23–1.42
(m,10H),1.12–1.16(t,3H),0.82–0.86(t,3H)；13C NMR(100MHz,CDCl3),δ(ppm):163.59,
151.79,140.60,131.04,130.08,128.41,124.02,122.76,121.29,119.87,110.26,60.49,
43.29,31.81,29.38,29.19,29.06,27.31,22.62,14.11,14.07.
(2) chemical structural formula is the synthesis of the intermediate of b：By (0.48g, 20mmol) magnesium chips, appropriate iodine is used as urging
Agent, (5.0g, 17.0mmol) is added in reaction bulb to bromooctane epoxide benzene, 120mL THF.Nitrogen is protected, at 100 DEG C
Triggered.After reacting 12 hours at this temperature, the THF solution of (1.0g, 1.7mmol) intermediate a is added to instead at normal temperatures
Answer in system, subsequent temperature rises to 110 DEG C and stirs 12 hours.Room temperature is cooled to, is extracted with dichloromethane and water, through anhydrous
MgSO4Dry, after being spin-dried for post, add 100mL acetic acid, in nitrogen protection, stirred 6 hours at 100 DEG C.After reaction stops, directly
Row suction filtration is tapped into, yellow solid, as intermediate b is obtained, yield is 73%.1H NMR(400MHz,CDCl3),δ(ppm):
7.80(s,2H),7.37(s,2H),7.27–7.29(d,2H),7.16–7.19(d,8H),6.99–7.01(d,2H),6.73–
6.75(d,8H),4.30–4.34(t,2H),3.86–3.89(t,8H),1.90–1.94(m,2H),1.69–1.75(m,12H),
1.26–1.47(m,46H),0.85–0.88(m,15H)；13C NMR(100MHz,CDCl3),δ(ppm):157.87,156.93,
145.84,141.45,140.67,137.66,135.04,129.04,127.53,123.17,121.28,117.66,114.16,
99.43,67.93,61.53,43.43,31.91,31.85,29.47,29.39,29.36,29.26,27.38,26.11,
22.68,14.13.
(3) chemical structural formula is the synthesis of the intermediate of c：By (0.9g, 0.7mmol) intermediate b, (1.7g,
10.5mmol) POCl3,50mL DMF, is added in reaction bulb.Nitrogen is protected, and is stirred 24 hours at 110 DEG C.It is cooled to room
Temperature, is extracted, anhydrous MgSO with dichloromethane and water4Dry, be spin-dried for post, obtain yellow solid, as intermediate c, yield is
78%.1H NMR(400MHz,CDCl3),δ(ppm):9.87(s,2H),7.90(s,2H),7.68(s,2H),7.55(s,2H),
7.18–7.20(d,8H),6.78–6.81(d,8H),4.39(t,2H),3.90–3.93(t,8H),1.96(m,2H),1.72–
1.77(m,8H),1.29–1.44(m,50H),0.88–0.89(m,15H)；13C NMR(100MHz,CDCl3),δ(ppm):
182.84,158.24,157.34,151.38,146.84,145.91,141.18,136.44,133.99,132.20,128.88,
123.14,118.10,114.40,101.32,68.01,61.74,43.51,31.83,29.44,29.37,29.31,29.24,
27.32,26.09,22.66,14.11.
(4) chemical structural formula is the synthesis of the organic molecule acceptor of DTCC-IC：By (0.4g, 0.3mmol) intermediate c,
(0.4g, 2.1mmol) intermediate d, pyridine 1.5mL, 30mL chloroform, is added in reaction bulb.Nitrogen is protected, and is reacted at 100 DEG C
12 hours.After stopping reaction, stirring a period of time in methyl alcohol is poured the mixture into, then carry out suction filtration, cross post, obtain navy blue
Solid, as final goal product DTCC-IC, yield is 73%.1H NMR(400MHz,CDCl3),δ(ppm):8.70–8.73
(t,4H),7.97(s,2H),7.93(d,2H),7.79–7.81(m,4H),7.69(s,2H),7.29–7.33(t,8H),7.18
(s,2H),6.87–6.89(d,8H),3.94–3.97(t,8H),3.72(t,2H),1.74–1.81(m,8H),1.67(m,2H),
1.29–1.45(m,50H),0.86–0.91(m,15H)；13C NMR(100MHz,CDCl3),δ(ppm):187.88,160.82,
159.70,158.46,158.24,148.06,141.41,141.15,139.75,136.79,136.36,135.28,134.63,
134.50,129.15,124.06,123.78,121.36,114.52,101.98,68.40,68.10,61.50,31.94,
31.82,29.57,29.39,29.34,29.24,29.17,28.85,27.25,26.10,22.65,14.09.
Embodiment 2
Chemical structural formula is as follows for the synthetic route of the organic molecule acceptor of DTCC8-IC：
(1) chemical structural formula is the synthesis of the intermediate of a with embodiment 1
(2) chemical structural formula is the synthesis of the intermediate of e：By (0.6g, 25mmol) magnesium chips, appropriate iodine is used as catalysis
Agent, (5.0g, 18.6mmol) is added in reaction bulb to bromooctane base benzene, 120mL THF.Nitrogen is protected, by it at 100 DEG C
Trigger.After reacting 12 hours at this temperature, the THF solution of (1.5g, 2.6mmol) intermediate a is added to reactant at normal temperatures
In system, subsequent temperature rises to 110 DEG C and stirs 12 hours.Room temperature is cooled to, is extracted with dichloromethane and water, through anhydrous MgSO4It is dry
It is dry, after being spin-dried for post, 100mL acetic acid is added, in nitrogen protection, stirred 6 hours at 100 DEG C.After reaction stops, directly being taken out
Filter, obtains peak green solid, as intermediate e, and yield is 73%.1H NMR(400MHz,CDCl3),δ(ppm):7.83(s,
2H),7.38(s,2H),7.27–7.29(d,4H),7.16–7.18(d,4H),7.01–7.03(d,10H),4.30–4.33(t,
2H),2.50–2.54(t,8H),1.87–1.93(m,2H),1.53–1.57(m,8H),1.24–1.28(m,50H),0.84–
0.87(m,15H)；13C NMR(100MHz,CDCl3),δ(ppm):156.60,145.40,142.98,141.65,141.13,
140.68,135.12,128.25,127.90,127.44,123.35,121.27,117.92,99.41,62.28,43.42,
35.62,31.94,31.44,29.56,29.51,29.29,29.09,27.39,22.72,14.17.
(3) chemical structural formula is the synthesis of the intermediate of f：By (1.3g, 1.1mmol) intermediate e, (4.2g,
27.3mmol) POCl3,50mL DMF, is added in reaction bulb.Nitrogen is protected, and is stirred 24 hours at 110 DEG C.It is cooled to room
Temperature, is extracted, anhydrous MgSO with dichloromethane and water4Dry, be spin-dried for post, obtain orange/yellow solid, as intermediate f, yield
It is 76%.1H NMR(400MHz,CDCl3),δ(ppm):9.84(s,2H),7.90(s,2H),7.68(s,2H),7.54(s,
2H),7.15–7.17(d,8H),7.04–7.06(d,8H),4.35–4.39(t,2H),2.52–2.56(t,8H),1.92–1.95
(m,2H),1.52–1.58(m,8H),1.25–1.28(m,50H),0.84–0.88(m,15H)；13C NMR(100MHz,
CDCl3),δ(ppm):182.92,157.01,151.60,146.39,145.79,141.83,141.79,141.21,134.07,
132.46,128.51,127.72,123.16,118.39,101.33,62.46,43.54,35.58,31.91,31.87,
31.41,29.51,29.48,29.27,29.24,29.06,27.35,22.70,22.66,14.15.
(4) chemical structural formula is the synthesis of the organic molecule acceptor of DTCC8-IC：By (0.4g, 0.3mmol) intermediate
F, the intermediate d of (0.4g, 2.1mmol), pyridine 1.5mL, 30mL chloroform, are added in reaction bulb.Nitrogen is protected, at 100 DEG C
Reaction 12 hours.After stopping reaction, stirring a period of time in methyl alcohol is poured the mixture into, then carry out suction filtration, cross post, obtain depth
Blue solid, as final goal product DTCC8-IC, yield is 73%.1H NMR(400MHz,CDCl3),δ(ppm):8.68
(s,2H),8.66(d,2H),7.96(s,2H),7.85–7.87(d,2H),7.73–7.79(t,4H),7.67(s,2H),7.33
(s,2H),7.24–7.26(d,8H),7.12–7.14(d,8H),3.84(t,2H),2.55–2.59(t,8H),1.70(m,2H),
1.59–1.51(m,8H),1.25–1.29(m,50H),0.84–0.87(m,15H)；13C NMR(100MHz,CDCl3),δ
(ppm):187.96,160.97,159.81,157.93,147.55,142.06,141.74,141.54,140.99,140.19,
139.79,138.17,136.77,135.22,134.60,128.65,127.96,125.18,124.19,123.78,121.32,
118.38,114.56,114.46,102.13,68.38,62.30,42.78,35.65,31.92,31.46,29.55,29.51,
29.29,28.88,27.35,22.70,14.14.
Above-described embodiment 1 and 2 prepare gained organic molecule acceptor DTCC-IC and DTCC8-IC absorption spectra property and
Non- fullerene solar cell properties are determined：
(1) absorption spectra property of organic molecule acceptor DTCC-IC and DTCC8-IC
Fig. 1 is ultraviolet-visible-near-infrared of organic molecule acceptor DTCC-IC films on chloroformic solution and quartz plate
Absorption spectrum.As shown in Figure 1, DTCC-IC solution and film show absorption region wide, its film absorption absorption maximum side
Band value is all 778nm or so, and corresponding optical band gap is that (optical band gap is according to formula E for 1.59eVg=1240/ λ is calculated, wherein Eg
It is optical band gap, λ is film absorption absorption maximum sideband value).
Fig. 2 is ultraviolet-visible-near-infrared of organic molecule acceptor DTCC8-IC films on chloroformic solution and quartz plate
Absorption spectrum.As shown in Figure 2, DTCC8-IC solution and film show absorption region wide, its film absorption absorption maximum
Sideband value is all 765nm or so, and corresponding optical band gap is that (optical band gap is according to formula E for 1.62eVg=1240/ λ is calculated, its
Middle EgIt is optical band gap, λ is film absorption absorption maximum sideband value).
(2) the non-fullerene solar cell properties of organic molecule acceptor DTCC-IC are determined：
Using commercially available PCE10 as solar cell donor, the gained DTCC-IC of embodiment 1 be solar-electricity
The acceptor in pond, using classical sandwich device architecture (ITO/PEDOT:PSS/PCE10:DTCC-IC/Ca/Al solar energy) is constructed
Device.Wherein, indium oxide (ITO) glass (sheet resistance=10-15 Ω–1), being successively placed in acetone and isopropanol is carried out
Ultrasonic prerinse, then processed 20 minutes in UV ozone case.Using solution spin-coating method by PEDOT：The PSS aqueous solution is spin-coated on
On ITO electro-conductive glass, it is subsequently placed in air to be dried 15 minutes under the conditions of 150 DEG C and forms one layer of PEDOT：PSS films (40nm).
In nitrogen glove box, using solution spin-coating method by PCE10：DTCC-IC (w/w=1:1) dichlorobenzene solution spin-on deposition exists
PEDOT：On PSS films, the photosensitive activity layer film that a layer thickness is about 100-150nm is formed.Under the conditions of condition of high vacuum degree, first
The Al of the Ca and 100nm of evaporation 20nm is used as anode electrode afterwards.Effective work area of prepared solar cell is about
4mm2.In simulated solar radiant, (light intensity is 100mW/cm2) under irradiation, the J-V curves of solar cell are measured, such as Fig. 3 institutes
Show.
Test result is as shown in Figure 3：Short circuit current JscIt is 11.23mA/cm2, open-circuit voltage VocIt is 0.95V, fill factor, curve factor
FF is 0.56, and the energy conversion efficiency for thus calculating battery is 6%.
(3) the non-fullerene solar cell properties of organic molecule acceptor DTCC-IC are determined：
Prepared with the methods described of embodiment 1 and condition and test is based on DTCC8-IC for acceptor and PCE10 are the non-of donor
Fullerene solar cell.Test result is as shown in Figure 3：Short circuit current JscIt is 10.74mA/cm2, open-circuit voltage VocIt is 0.95V,
Fill factor, curve factor FF is 0.47, and the energy conversion efficiency for thus calculating battery is 4.8%.
Claims (9)
1. A-D-A type organic molecule acceptors of seven yuan of condensed ring of a kind of carbazoles containing thieno, it is characterised in that with formula (I) institute
The structure shown：
Wherein, R1It is C1-C16Straight or branched alkyl；R2It is formula (II), formula (III), formula (IV), formula (VI), formula (VII), formula
(VIII) one kind in structure shown in, wherein, R is C1-C16Straight or branched alkyl；
2. A-D-A types organic molecule acceptor according to claim 1, it is characterised in that R1It is that formula (IX) or formula (X) are described
Structure, R2It is C8Straight or branched alkyl：
3. the preparation side of the A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles described in claim 1
Method, it is characterised in that including following synthesis step：
(1) carbazole borate reacts with thiophene ester halogenated compound, obtains intermediate a, and the structural formula of the carbazole borate is:
Wherein, R1It is C1-C16Straight or branched alkyl；The thiophene ester halogenated compound structural formula is:
The structural formula of the intermediate a is:
Wherein, R1It is C1-C16Straight or branched alkyl；
(2) at high temperature, intermediate a elder generations and R2Grignard reagent reaction, then through peracetic acid cyclization, obtain intermediate b：In described
The structural formula of mesosome b is：
Wherein, R2Grignard reagent structural formula be R2- MgBr, R2It is above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula
(VII), one kind in structure shown in formula (VIII)；R1Can be C1-C16Straight or branched alkyl；
(3) at high temperature, intermediate b and POCl3 and N, N '-dimethyl formamide obtain intermediate c, the centre
The structural formula of body c is：
Wherein, R1It is C1-C16Straight or branched alkyl；
The R2It is the one kind in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII), structure shown in formula (VIII)；
(4) at high temperature, intermediate c and intermediate d reacts, and obtaining the A-D-A types containing seven yuan of condensed ring of thieno carbazoles has
Machine small molecule receptor, the structural formula of the intermediate d is：
4. the system of the A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles according to claim 3
Preparation Method, it is characterised in that the concrete operations of the step (1) are：By 10mmol carbazole borates, 20-100mmol thiophene esters
Halogenated compound, 10-100mmol anhydrous Ks2CO3, appropriate water, 1-10mmol TBABs, 0.1-0.5g palladium catalysts,
200mL toluene, is added in reaction bulb.Nitrogen is protected, lucifuge, is reacted 10-15 hours at 100 DEG C.Room temperature is cooled to, dichloro is used
Methane and water are extracted, anhydrous MgSO4Dry, be spin-dried for post, obtain yellow solid, as intermediate a.
5. the system of the A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles according to claim 3
Preparation Method, it is characterised in that the concrete operations of the step (2) are：By 10mmol magnesium chips, appropriate iodine as catalyst,
10-30mmol bromo compounds, 50-150mL THF, are added in reaction bulb.Nitrogen is protected, and is triggered at 100 DEG C.The temperature
After the lower reaction of degree 8-20 hours, the THF solution of 1-3mmol intermediates a is added in reaction system at normal temperatures, subsequent temperature liter
Stirred 10-15 hours to 110 DEG C.Room temperature is cooled to, is extracted with dichloromethane and water, through anhydrous MgSO4Dry, be spin-dried for post
Afterwards, 50-150mL acetic acid are added, in nitrogen protection, is stirred 3-8 hours at 100 DEG C.After reaction stops, suction filtration is directly carried out, obtained
To yellow solid, as intermediate b.
6. the system of the A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles according to claim 3
Preparation Method, it is characterised in that the concrete operations of the step (3) are：By 0.5mmol intermediate products c, 10-30mmol trichlorine oxygen
Phosphorus, 30-100mL DMF, is added in reaction bulb.Nitrogen is protected, and is stirred 15-30 hours at 110 DEG C.Room temperature is cooled to, with two
Chloromethanes and water are extracted, anhydrous MgSO4Dry, be spin-dried for post, obtain yellow solid, as intermediate c.
7. the system of the A-D-A type organic molecule acceptors containing seven yuan of condensed ring of thieno carbazoles according to claim 3
Preparation Method, it is characterised in that the concrete operations of the step (4) are：By 0.5mmol intermediates c, 1-10mmol intermediate d, pyrrole
- the 4mL of pyridine 1,20-40mL chloroforms are added in reaction bulb.Nitrogen is protected, and is reacted 8-15 hours at 100 DEG C.After stopping reaction, mistake
Post, obtains blue solid, the A-D-A type organic molecule acceptors as containing seven yuan of condensed ring of thieno carbazoles.
8. A-D-A type organic molecules containing seven yuan of condensed ring of thieno carbazoles in claim 1 or 2 described in any one
Acceptor application in solar cells, is made with the A-D-A type organic molecules acceptor containing seven yuan of condensed ring of thieno carbazoles
It is the acceptor of solar cell.
9. A-D-A type organic molecules containing seven yuan of condensed ring of thieno carbazoles in claim 1 or 2 described in any one
Acceptor prepare solar cell device, using commercially available PCE10 as solar cell donor, with click containing thieno
A-D-A type organic molecules the acceptor of seven yuan of condensed ring of azole is the acceptor of solar cell, using classical sandwich device architecture
(ITO/PEDOT:PSS/PCE10:DTCC-IC/Ca/Al solar device) is constructed.
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| CN107573722A (en) * | 2017-08-03 | 2018-01-12 | 湘潭大学 | A kind of D-A-π-A type organic photosensitizing dyestuffs of the carbazole of ring containing Dithiophene penta and preparation method and application |
| CN107573722B (en) * | 2017-08-03 | 2019-06-28 | 湘潭大学 | A kind of D-A-π-A type organic photosensitizing dyestuff of penta carbazole of ring containing Dithiophene and the preparation method and application thereof |
| WO2019052935A1 (en) * | 2017-09-13 | 2019-03-21 | Merck Patent Gmbh | Organic semiconducting compounds |
| CN111418079A (en) * | 2018-01-10 | 2020-07-14 | 香港科技大学 | Aromatic systems based on condensed ring thiophenes |
| CN111418079B (en) * | 2018-01-10 | 2023-05-16 | 香港科技大学 | Aromatic systems based on fused ring thiophenes |
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| CN108299449B (en) * | 2018-01-15 | 2020-08-25 | 华南协同创新研究院 | Electroluminescent material based on carbazole five-membered heterocyclic unit and preparation method and application thereof |
| CN108299408A (en) * | 2018-01-23 | 2018-07-20 | 西安近代化学研究所 | Condensed ring A-D-A type conjugated molecules based on carbazole and preparation method thereof |
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| CN110256460A (en) * | 2019-07-09 | 2019-09-20 | 湘潭大学 | A kind of efficient small organic molecule acceptor material and its preparation method and application |
| CN110256460B (en) * | 2019-07-09 | 2021-06-15 | 湘潭大学 | Organic small molecule receptor material and preparation method and application thereof |
| CN110606857A (en) * | 2019-09-25 | 2019-12-24 | 湘潭大学 | A-D-A type organic small molecule based on nine-ring fused aromatic hydrocarbon and preparation method and application thereof |
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