CN107778319A - One kind contains seven and condensed cyclic structure indacene A D A type micromolecular compounds and preparation method thereof - Google Patents
One kind contains seven and condensed cyclic structure indacene A D A type micromolecular compounds and preparation method thereof Download PDFInfo
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Abstract
The invention discloses indacene A D A type of the one kind containing seven and condensed cyclic structure to be conjugated micromolecular compound and preparation method thereof, and the application as photoactive layer material in organic photovoltaic devices.Such compound has below general formula structure：It is based on seven and condensed ring as electron unit (D), using thiphene ring as bridging unit, 4, thiophene is drawing electronic unit (A), utilize the difference of A units the position of substitution on bridging thiophene, adjust the level structure and optical absorption characteristics of material, so as to adjust the parameters such as the open-circuit voltage of photovoltaic cell, short circuit current, and then improve the photoelectric transformation efficiency of device.
Description
Technical field
The invention belongs to organic photoelectric functional material field, and in particular to a kind of indacene A-D- containing seven and condensed cyclic structure
A types conjugation micromolecular compound and preparation method thereof, and the quasi-molecule as the n-type material in photoactive layer in organic photovoltaic
(OPV) application in device.
Background technology
In solar cells, organic solar batteries are because its is in light weight, cost is low, preparation process is simple, can be prepared into
The advantages that flexible device, have become one of field the most active in photovoltaic research.Photoactive layer material is organic solar
The crucial photosensitive layer of battery, its property decides the generation of exciton and diffusion, the separation of electric charge and transported, and finally decides electricity
The photoelectric transformation efficiency in pond.
Photoactive layer forms body heterojunction by electron donor material and electron acceptor material, and electricity is used as using conjugated polymer
Sub- donor, fullerene derivate (PC61BM、PC71BM, ICBA etc.) electron acceptor is used as, make the effect of organic solar batteries
Rate breaks through 11% [Nature Energy, 2016,1,15027], it is meant that the huge application potential of organic solar batteries.But
It is fullerene and its derivative has certain shortcoming, including：Prepare and purification condition is harsh, visible region absorption is on the weak side, energy level is adjusted
Control is difficult, the dissolubility in common solvents is poor, easily aggregation etc. [Nat.Photonics 2012,6,153], and these shortcomings restrict
The further breakthrough of organic solar batteries performance.In recent years, non-fullerene small molecule electron-acceptor material is because its system
It is standby simple, have the advantages that strong absorption, structure in long wave direction and energy level is adjustable, superior solubility, attract scientific research personnel's
Concern.Mainly have based on the new n-type electronics such as acid imide, fluorenyl derivative, benzene thiazole, pyrrolo-pyrrole-dione, pentacene by
Body material is used for photovoltaic cell.Imidodicarbonic diamide (PDI) is that earliest a kind of material is studied in solar cell, is had excellent
Optical absorption characteristics, wider sunshine wave spectrum, higher electron mobility, adjustable highest occupied molecular orbital(HOMO) (HOMO) and most
Low-altitude track (LUMO) energy level, the electron affinity energy suitable with fullerene, and in structure, can be changed by simply modifying
Become acid imide parent nucleus and side bit substituent, so as to can obtain a series of n-type electron acceptor materials with excellent photoelectric properties
[Adv.Mater.2010,22,3876], but the wider band gap of such material limits the further lifting of device performance；And
Pentaphene class and its derivative are easy to regulate and control film morphology by chemical modification, to improve charge transport rate
[Adv.Energy.Mater.2011,1,431]；The photovoltaic device made based on diazosulfide class material, is shown good
Electronic transmission performance [Adv.Energy Mater.2013,3,54].Pyrrolo-pyrrole-dione (DPP)
[J.Mater.Chem.2010,20,3626] has wide light abstraction width, while has excellent chemical property, thermodynamics
Stability and machining property, the technological requirement for making organic electronic device can be met.Account for Xiao Wei etc.
[J.Mater.Chem.A.2015,3,1910] develops to be extended π and is total to based on dithieno Yin up to receptoroid molecule, condensed ring is saved
Yoke framework, high electron mobility is obtained, in addition, because of the electronics push-pull configuration of its molecule, more efficient intramolecular electricity can be induced
Lotus shifts, and so as to widen the absorption spectrum of material, the donor polymer material PTB7-Th of itself and arrowband system is blended, device efficiency
Reach 6.31%.Such small molecule receptor material generally have five and condensed ring or seven and condensed ring structure, because of its excellent property
Can and attract wide attention, as electron acceptor be used for prepare organic photovoltaic battery, its performance has reached or even surmounted richness
Strangle alkenes electron acceptor [Adv.Mater.2016,28,1884；Adv.Mater.2016,28,4734；Adv.Mater.2016,
28,9423].In addition, in these structures for having reported, it can also pass through thiophene or connection thiophene between center condensed ring and both sides short of electricity unit
Fen has more excellent photoelectric properties [CN 105315298A as bridging unit；Adv.Mater.2016,28,8283；
Angew.Chem.Int.Ed.2017,56,1].The short of electricity unit of these materials is confined to be connected to the 5- of thiophene bridging unit
Position, molecular skeleton is mostly planar structure, although this structure promote some of materials absorption spectrum can red shift to near-infrared
Wave band, but be difficult to look for absorption spectrum matching good single polymers donor material and form spectrum complementation therewith, based on this
The individual layer organic photovoltaic battery of the two-spot blending of a little small molecule receptors, its photoelectric transformation efficiency are generally less than 10%.
The content of the invention
The defects of existing for prior art or deficiency, the present invention provide one kind seven and small point of condensed ring indacene A-D-A types
Sub- compound, the both sides short of electricity unit of the micromolecular are connected to the 4- positions of thiophene bridging unit, and the structure has no report, this
Structure can realize the regulation to photoelectric properties, to meet the needs of photovoltaic cell photoactive layers electron acceptor material.Will be this kind of
Micromolecular compound is used for high efficiency organic photovoltaic cells, using steric effect, the push-and-pull characteristic electron etc. of substituent, adjusts material
Energy level and spectral region, realize the lifting of device photoelectric conversion efficiency.
In order to realize above-mentioned task, seven and the condensed ring indacene A-D-A type micromolecular compounds structure that the present invention designs are such as
Under：
Wherein, R1Independently be alkyl-substituted phenyl that alkyl, carbon number that carbon number is 1~20 are 1~20,
The alkylated substituted thiazoline fen base that phenyl, the carbon number for the alkoxy substitution that carbon number is 1~20 are 1~20, or carbon number
For 1~20 alkoxy substituted thiophene base, R2It independently is hydrogen atom, the alkyl that carbon number is 1~20, carbon number 1
~20 alkoxy or carbon number is 1~20 alkyl ester group, wherein drawing electronic unit A1And A2For independent free following knot
One of structure：
A1And A2R in structure3The alkyl for being 1~12 for carbon number.
Its preparation method is carried out using reaction equation as follows：
Specific synthesis step is as follows：
R will be carried1Substituent seven and condensed ring organotin reagent, and with R2The bromo- 3- thiophenecarboxaldehydes of 5- of substituent, add
Into reaction vessel, the lower catalyst four (triphenylphosphine) for adding 5%-10% of argon gas protection closes palladium or two (triphenylphosphine) dichloros
Change palladium, using toluene as solvent, micro- backflow 12-24h, after reaction completely, stopping heating making system be cooled to room temperature, adds water and terminates
Reaction, with toluene aqueous phase extracted, organic layer is through liquid separation, drying and filters, and is spin-dried for filtrate and obtains crude product, is carried by column chromatography
It is pure, seven accordingly containing dialdehyde base and condensed ring are obtained, then by the aldehyde and the 4-6 times of drawing electronic unit A measured1Or A2In chloroform
Pyridine backflow 6-12 hours are added in solution, are settled after cooling by methanol, silica gel column chromatography, chloroform elution, you can obtain mesh
Product is marked, or contains A by what above-mentioned seven and condensed ring containing dialdehyde base and 1-1.5 times were measured1Unit draws electron donating monomer in chloroform
Solution adds pyridine backflow 6-10 hours, and column chromatography purifying, what resulting intermediate was measured with 2-4 times again contains A2Unit draws electronics
Monomer adds pyridine backflow 6-12 hours, chloroform extraction, methanol sedimentation, silica gel column chromatography, chloroform elution in chloroformic solution, you can
Obtain the A-D-A conjugated molecule products shown in formula I.
The preferred scheme of the present invention, R1Carbon number is 1~20 4- alkyl phenyls, or the alkane that carbon number is 1~20
Base, or the 5- alkylthrophene bases that carbon number is 1~20, or the 4- alkoxyl phenyls that carbon number is 1~20；R2For carbon atom
Number is 1~20 alkoxy, or the alkyl that carbon number is 1~20, or the alkyl ester group that carbon number is 1~20.
Indacene A-D-A type micromolecular compounds provided by the invention containing seven and condensed cyclic structure, can be used as photolytic activity
Layer material, prepared applied to organic photovoltaic battery.
Beneficial effects of the present invention：Short of electricity subelement is incorporated into the 4- positions of thiphene ring by the present invention, draws on molecular backbone
Enter certain distortion, effectively adjust the absorption spectrum and energy level of material.This kind of indacene type A-D-A micromolecular compounds have
Broad-adjustable absorption spectrum, strong absorptivity, preferable charge transport properties and suitable level structure, with optics
The polymer-electronics donor that band gap is 1.7~1.9eV is blended, and makes individual layer two-spot photovoltaic device, and photoelectric transformation efficiency exceedes
10%.The polymer-electronics donor of these broad-band gaps includes the D-A type donor polymer based on double fluorine BTAs, based on thiazole
And the D-A type donor polymer of thiazole, based on benzo [1,2-C:4,5-C'] Dithiophene -4,8- diketone D-A type donor polymerization
Thing etc..
Brief description of the drawings
Fig. 1 is the compound A1 of the embodiment of the present invention 1 UV-visible-near infrared absorption.
Fig. 2 is the compound A1 of the embodiment of the present invention 1 and a kind of double fluorine benzotriazole type polymer J52 I-V curve.
Embodiment
Specific embodiment of the invention given below is, it is necessary to which explanation is that the invention is not limited in implement in detail below
Example, all equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
Embodiment 1：Compound A1
Synthetic route is as follows:
(1) synthesis of compound 3：
Compound 1 672.5mg/0.5mmol, 2- bromo- 3- (2- ethyl hexyl oxies) thiophene -4- is added in 100ml there-necked flasks
Formaldehyde 478mg/1.5mmol, Pd (PPh3)440mg, toluene 30ml, nitrogen protection is lower to open heating, and flow back 24h, product extraction,
Washing, column chromatography (n-hexane：Ethyl acetate=100:1) (the liquid content of 550mg compounds 3, is obtained>99%), yield
73.5%.1H NMR(500MHz,CDCl3),δ9.93(s,2H),7.94(s,2H),7.45(s,2H),7.18(d,8H),7.10
(d,8H),6.88(s,2H),4.10(d,4H),2.57(t,8H),1.76(m,2H),1.66-1.58(m,16H),1.50-1.26
(m,32H),0.95-0.86(m,24H).13C NMR(125MHz,CDCl3),δ181.09,164.32,157.11,153.37,
146.23,142.93,141.91,139.04,137.06,135.16,129.62,128.45,127.68,126.39,122.71,
119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,31.28,30.32,29.07,29.01,
23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for(C94H110O4S6):C 75.45,H 7.41,
Found:C 75.23,H 7.27。
(2) A1 synthesis
658mg/0.44mmol above-claimed cpds 3 are taken, 575mg/2.5mmol compound as, are placed in 100ml there-necked flasks, it is molten
In 40ml chloroforms, pyridine 1.5ml is then added, is heated to reflux 10h, stops heating, cooling, extraction, washing, is sunk with methanol
Drop, by gained solid column chromatographic purifying after filtering, chloroform elution, black-and-blue solid 531mg is obtained, yield 65%, liquid phase contains
Amount>99%.1H NMR(500MHz,CDCl3), δ 9.17 (s, 2H), 8.66 (d, 2H), 7.85 (d, 2H), 7.73 (m, 4H), 7.21
(d,8H),7.14(d,8H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,
16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.35,170.37,
158.72,158.82,155.69,154.78,154.14,148.06,146.00,142.22,140.69,139.37,135.76,
134.25,132.83,127.80,123.88,122.69,118.31,117.40,117.19,115.14,114.57,109.18,
75.85,67.36,63.21,39.31,35.59,31.77,31.38,30.01,29.13,28.97,23.48,23.02,
22.63,14.11,10.92.Anal.Calcd for(C118H114F4N4O4S6):C 73.79,H 5.98,Found:C 76.35,
H 5.79。
The UV-visible-near infrared absorption of compound A1 solution and film is as shown in Figure 1.According to lambert Bill
Law, the compound A1 of measure solution molar extinction coefficient is 3.94 × 105M-1cm-1, surveyed using film absorption side (843nm)
The optical energy gap for trying to obtain is 1.47eV.
Photovoltaic performance is studied：Using ITO/ZnO/J52:Acceptor material/MoO3/ Al battery structure, by polymer J52 with
Polymer photovoltaic cell, effective area 0.16cm is made in acceptor material2, in simulated solar light source (Oriel model 91192；
100mW/cm2) under carry out current-voltage test, using the source table collections of Keithley 2400, measure the short circuit current J of devicesc
For 21.17mA cm-2, open-circuit voltage VocFor 0.84V, fill factor, curve factor 66.4%, energy conversion efficiency PCE is 11.83%.Accompanying drawing
2 be the compound A1 of the embodiment of the present invention 1 and J52 according to I-V curve of certain weight than polymer photovoltaic cell is made.
J52 structural formula is as follows：
Embodiment 2：Compound A2
Synthetic route is as follows:
658mg/0.44mmol above-claimed cpds 3 are taken, 485mg/2.5mmol compound b, are placed in 100ml there-necked flasks, it is molten
In 40ml chloroforms, pyridine 1.5ml is then added, is heated to reflux 6h, stops heating, cooling, extraction, washing, is settled with methanol,
By gained solid column chromatographic purifying after filtering, chloroform elution, black-and-blue solid 582mg, yield 69%, liquid content are obtained>
99%.1H NMR(500MHz,CDCl3), δ 9.17 (s, 2H), 8.66 (d, 2H), 7.85 (d, 2H), 7.72 (m, 4H), 7.53 (d,
Hz,4H),7.19(d,8H),7.14(d,8H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),
1.62-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ
187.25,170.27,158.71,158.82,154.78,154.14,145.99,142.22,140.69,139.37,137.06,
135.76,134.25,132.83,128.69,127.79,123.88,122.69,118.31,117.40,117.19,115.14,
114.57,109.18,75.85,67.36,63.20,39.31,35.58,31.77,31.38,30.01,29.13,28.97,
23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C118H118N4O4S6):C 76.67,H 6.43,
Found:C 76.15,H 6.28.
Embodiment 3：The synthesis of compound A-13
Synthetic route is as follows:
(1) synthesis of compound 5：
Different monooctyl ester -4- the formaldehyde of the bromo- thenoic acid of compound 1 672.5mg/0.5mmol, 2- is added in 100ml there-necked flasks
521mg/1.5mmol, Pd (PPh3)440mg, toluene 30ml, nitrogen protection is lower to open heating, and flow back 24h, product extraction, washes
Wash, column chromatography (n-hexane：Ethyl acetate=100:1) (the liquid content of 543mg compounds 5, is obtained>99%), yield 70%.1H
NMR(500MHz,CDCl3),δ9.93(s,2H),7.94(s,2H),7.46(s,2H),7.19(d,8H),7.11(d,8H),
6.89(s,2H),4.30(d,4H),2.57(t,8H),1.81(m,2H),1.68-1.58(m,16H),1.50-1.26(m,
32H),0.95-0.86(m,24H).13C NMR(125MHz,CDCl3),δ181.10,165.29,160.10,157.11,
153.39,146.23,142.93,141.92,139.04,137.06,135.16,129.62,128.45,127.68,126.39,
122.71,119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,31.28,30.32,29.07,
29.01,23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for(C96H110O6S6):C 74.28,H
7.14,Found:C 73.97,H 6.96.
(2) synthesis of compound A-13
683mg/0.44mmol above-claimed cpds 5 are taken, 485mg/2.5mmol compound b, are placed in 100ml there-necked flasks, it is molten
In 40ml chloroforms, pyridine 1.5ml is then added, is heated to reflux 8h, stops heating, cooling, extraction, washing, is settled with methanol,
By gained solid column chromatographic purifying after filtering, chloroform elution, black-and-blue solid 562mg, yield 67%, liquid content are obtained>
99%.1H NMR(500MHz,CDCl3), δ 9.17 (s, 2H), 8.66 (d, 2H), 7.85 (d, 2H), 7.72 (m, 4H), 7.53 (d,
Hz,4H),7.19(d,8H),7.14(d,8H),6.93(s,2H),4.31(q,4H),2.63(t,8H),2.01(m,2H),
1.63-1.56(m,16H),1.38-1.30(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ
187.27,170.28,160.11,158.71,158.83,154.78,154.15,146.00,142.23,140.69,139.37,
137.06,135.76,134.25,132.83,128.69,127.79,123.89,122.69,118.31,117.40,117.19,
115.14,114.57,109.18,75.85,67.36,63.20,39.31,35.58,31.77,31.38,30.01,29.13,
28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C120H118N4O6S6):C 75.67,H
6.24,Found:C 75.46,H 6.09.
Embodiment 4：Compound A4
Synthetic route is as follows:
(1) synthesis of compound 7：
Compound 6 520.5mg/0.5mmol, 2- bromo- 3- (2- ethyl hexyl oxies) thiophene -4- is added in 100ml there-necked flasks
Formaldehyde 478mg/1.5mmol, Pd (PPh3)440mg, toluene 30ml, nitrogen protection is lower to open heating, and flow back 24h, product extraction,
Washing, column chromatography (n-hexane：Ethyl acetate=100:1) (the liquid content of 423mg compounds 7, is obtained>99%), yield 71%
。1H NMR(500MHz,CDCl3),δ9.92(s,2H),7.91(s,2H),7.43(s,2H),6.87(s,2H),4.11(d,4H),
2.57(t,8H),1.76(m,2H),1.66-1.58(m,16H),1.50-1.26(m,32H),0.95-0.86(m,24H).13C
NMR(125MHz,CDCl3),δ181.09,164.32,157.11,153.37,146.23,142.93,139.04,129.62,
128.45,126.39,121.76,119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,
31.28,30.32,29.07,29.01,23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for
(C70H94O4S6):C 70.54,H 7.95,Found:C 70.32,H 7.68.
(2) A4 synthesis
524mg/0.44mmol above-claimed cpds 7 are taken, 575mg/2.5mmol compound as, are placed in 100ml there-necked flasks, it is molten
In 40ml chloroforms, pyridine 1.5ml is then added, is heated to reflux 10h, stops heating, cooling, extraction, washing, is sunk with methanol
Drop, by gained solid column chromatographic purifying after filtering, chloroform elution, black-and-blue solid 484mg is obtained, yield 68%, liquid phase contains
Amount>99%.1H NMR(500MHz,CDCl3), δ 9.17 (s, 2H), 8.66 (d, 2H), 7.85 (d, 2H), 7.73 (m, 4H), 6.93
(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,16H),1.36-1.29(m,32H),
0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.35,170.37,158.72,158.82,155.69,
154.78,154.14,148.06,146.00,140.69,139.37,132.83,127.80,122.69,118.31,117.40,
117.19,115.14,114.57,109.18,75.85,67.36,63.21,39.31,35.59,31.77,31.38,30.01,
29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C94H98F4N4O4S6):C
69.86,H 6.11,Found:C 69.57,H5.92.
Embodiment 5：Compound A-45
Synthetic route is as follows:
658mg/0.44mmol above-claimed cpds 3 are taken, 152mg/0.66mmol compound as, are placed in 100ml there-necked flasks,
It is dissolved in 40ml chloroforms, then adds pyridine 1.5ml, be heated to reflux 6h, stops heating, stopped reaction, by products therefrom post layer
Analysis purifying, and added with 351mg/1.32mmol compounds c in 100ml there-necked flasks, 40ml chloroforms are added, then add pyridine
1.5ml, 8h is heated to reflux, stops heating, cooling, extraction, washing, settled with methanol, by gained solid column chromatography after filtering
Purifying, chloroform elution, obtains black-and-blue solid 335mg, yield 39%, liquid content>99%.1H NMR(500MHz,CDCl3),
δ 9.17 (s, 2H), 8.66 (d, 2H), 7.85 (d, 2H), 7.73 (m, 2H), 7.21 (d, 8H), 7.14 (d, 8H), 6.93 (s,
2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,16H),1.36-1.29(m,32H),0.96-
0.86(m,24H).13C NMR(125 MHz,CDCl3),δ187.35,170.37,158.72,158.82,155.69,154.78,
154.14,148.06,146.00,142.22,140.69,139.37,137.21,136.17,132.83,127.80,123.88,
122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.21,39.31,
35.59,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd
for(C118H112F6N4O4S6):C 72.44,H 5.77,Found:C 72.31,H 5.69.
Claims (9)
1. a kind of indacene A-D-A type micromolecular compounds containing seven and condensed cyclic structure, it is characterised in that general structure such as formula I
It is shown：
In formula, R1It independently is phenyl, the alkyl of alkyl, alkyl-substituted phenyl, the alkoxy substitution that carbon number is 1~20
Substituted thiophene base, or alkoxy substituted thiophene base；R2Independently be hydrogen atom, carbon number be 1~20 alkyl, alkoxy,
Or alkyl ester group, wherein drawing electronic unit A1And A2For one of independent free following structure：
A1And A2R in structure3The alkyl for being 1~12 for carbon number.
2. the indacene A-D-A type micromolecular compounds containing seven and condensed cyclic structure as claimed in claim 1, it is characterised in that
The R1The 4- alkyl phenyls for being 1~20 for carbon number, R2The alkoxy for being 1~20 for carbon number.
3. the indacene A-D-A type micromolecular compounds containing seven and condensed cyclic structure as claimed in claim 1, it is characterised in that
The R1The alkyl for being 1~20 for carbon number, R2The alkoxy for being 1~20 for carbon number.
4. the indacene A-D-A type micromolecular compounds containing seven and condensed cyclic structure as claimed in claim 1, it is characterised in that
The R1The 5- alkylthrophene bases for being 1~20 for carbon number, R2The alkoxy for being 1~20 for carbon number.
5. the indacene A-D-A type micromolecular compounds containing seven and condensed cyclic structure as claimed in claim 1, it is characterised in that
The R1The 4- alkoxyl phenyls for being 1~20 for carbon number, R2The alkoxy for being 1~20 for carbon number.
6. the indacene A-D-A type micromolecular compounds containing seven and condensed cyclic structure as claimed in claim 1, it is characterised in that
The R1The 4- alkyl phenyls for being 1~20 for carbon number, R2The alkyl for being 1~20 for carbon number.
7. the indacene A-D-A type micromolecular compounds containing seven and condensed cyclic structure as claimed in claim 1, it is characterised in that
The R1The 4- alkyl phenyls for being 1~20 for carbon number, R2The alkyl ester group for being 1~20 for carbon number.
8. the indacene A-D-A type small molecule chemical combination containing seven and condensed cyclic structure described in claim 1-7 wherein any one
Thing, it is characterised in that it individually or with other materials is blended, and as photoactive layer material, is prepared applied to organic photovoltaic battery.
9. the preparation method containing seven and the indacene A-D-A type micromolecular compounds of condensed cyclic structure described in a kind of claim 1,
It is characterized in that comprise the following steps：
R will be carried1Substituent seven and condensed ring organotin reagent, and with R2The bromo- 3- thiophenecarboxaldehydes of 5- of substituent, it is added to anti-
Answer in container, the lower catalyst four (triphenylphosphine) for adding 5%-10% of argon gas protection closes palladium or two (triphenylphosphine) dichlorides
Palladium, using toluene as solvent, micro- backflow 12-24h, after reaction completely, stopping heating making system be cooled to room temperature, and it is anti-to add water termination
Should, with toluene aqueous phase extracted, organic layer is through liquid separation, drying and filters, and is spin-dried for filtrate and obtains crude product, by chromatography over CC,
Seven accordingly containing dialdehyde base and condensed ring are obtained, then by the aldehyde and the 4-6 times of drawing electronic unit A measured1Or A2In chloroformic solution
Middle addition pyridine backflow 6-12 hours, settled after cooling by methanol, silica gel column chromatography, chloroform elution, you can obtain target production
Thing, or contain A by what above-mentioned seven and condensed ring containing dialdehyde base and 1-1.5 times were measured1Unit draws electron donating monomer in chloroformic solution
Pyridine backflow 6-10 hours are added, column chromatography purifying, what resulting intermediate was measured with 2-4 times again contains A2Unit draws electron donating monomer
Pyridine backflow 6-12 hours, chloroform extraction, methanol sedimentation, silica gel column chromatography, chloroform elution, you can obtain are added in chloroformic solution
A-D-A conjugated molecule products shown in formula I.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265468A (en) * | 2018-09-18 | 2019-01-25 | 四川大学 | Small molecule containing anti-aromaticity indacene unit and its application in photovoltaic |
| CN109776566A (en) * | 2019-01-23 | 2019-05-21 | 深圳大学 | A kind of A-D-A conjugated molecule and its application based on polysubstituted benzo cyclopentanedione derivative |
| 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 |
| WO2020062254A1 (en) * | 2018-09-30 | 2020-04-02 | Southern University Of Science And Technology | Chlorine atoms induced molecular interlocked network in a non-fullerene acceptor |
| CN112209946A (en) * | 2020-09-15 | 2021-01-12 | 西安近代化学研究所 | Benzo-dithiophene-containing hepta-condensed ring main chain twisted small-molecule near-infrared absorption material, and preparation method and application thereof |
| CN112409375A (en) * | 2020-11-21 | 2021-02-26 | 东华理工大学 | Organic small-molecule photovoltaic material based on tetrazine derivative |
| CN115073488A (en) * | 2021-03-12 | 2022-09-20 | 中国科学院化学研究所 | Full-condensed ring organic photovoltaic receptor and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150114418A (en) * | 2014-03-27 | 2015-10-12 | 주식회사 엘지화학 | Heterocyclic compound and organic solar cell comprising the same |
| CN105315298A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules |
| CN106883247A (en) * | 2017-02-24 | 2017-06-23 | 武汉大学 | A D A conjugated molecules based on thieno cyclopentanedione derivative and preparation method thereof |
-
2017
- 2017-11-06 CN CN201711077458.7A patent/CN107778319B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150114418A (en) * | 2014-03-27 | 2015-10-12 | 주식회사 엘지화학 | Heterocyclic compound and organic solar cell comprising the same |
| CN105315298A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules |
| CN106883247A (en) * | 2017-02-24 | 2017-06-23 | 武汉大学 | A D A conjugated molecules based on thieno cyclopentanedione derivative and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HUA-CHUN WANG: "Investigating the crystalline nature, charge transport properties and photovoltaic performances of ladder-type donor based small molecules", 《RSC ADVANCES》 * |
| ZHONGQIANG ZHANG: "Energy-level modulation of non-fullerene acceptors to achieve high-efficiency polymer solar cells at a diminished energy offset", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (10)
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| CN109265468A (en) * | 2018-09-18 | 2019-01-25 | 四川大学 | Small molecule containing anti-aromaticity indacene unit and its application in photovoltaic |
| CN109265468B (en) * | 2018-09-18 | 2021-06-08 | 四川大学 | Small molecule containing anti-aromatic indacenodithiophene unit and application thereof in organic photovoltaics |
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| CN109776566A (en) * | 2019-01-23 | 2019-05-21 | 深圳大学 | A kind of A-D-A conjugated molecule and its application based on polysubstituted benzo cyclopentanedione derivative |
| CN109776566B (en) * | 2019-01-23 | 2021-12-28 | 深圳大学 | A-D-A conjugated molecule based on multi-substituted benzocyclopentadienone derivative and application thereof |
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| CN115073488A (en) * | 2021-03-12 | 2022-09-20 | 中国科学院化学研究所 | Full-condensed ring organic photovoltaic receptor and preparation method and application thereof |
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