CN105906652A - Thiophene/selenophene acene fused perylene bisimide derivative and application thereof in organic solar cells - Google Patents

Thiophene/selenophene acene fused perylene bisimide derivative and application thereof in organic solar cells Download PDF

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CN105906652A
CN105906652A CN201610257237.7A CN201610257237A CN105906652A CN 105906652 A CN105906652 A CN 105906652A CN 201610257237 A CN201610257237 A CN 201610257237A CN 105906652 A CN105906652 A CN 105906652A
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aryl
thiophene
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acene
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CN105906652B (en
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杨楚罗
张晨
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Wuhan University WHU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a compound with thiophene/selenophene acene fused perylene bisimide as a skeleton. A synthesis method is simple and easy to operate, and is suitable for wide application. The thiophene/selenophene acene fused perylene bisimide derivative can be used as a receptor material for preparing organic solar cell devices, has high efficiency and high open circuit voltage, and can be widely applied in the field of organic solar cells.

Description

The imide derivative that thiophene/selenophen acene condenses and the application on organic solar batteries thereof
Technical field
The present invention relates to imide derivative that a kind of thiophene/selenophen acene condenses and at organic solar electricity Application on the material of pond, belongs to organic photoelectric functional material and device preparing technical field thereof.
Background technology
Bulk heteroj joint solar cell has low cost, and weight is little, flexible machinable feature, by extensively Concern and research.Bulk heteroj joint solar cell includes donor material and acceptor material.Wherein, fullerene Derivant (PCBM) due to its electron affinity good, electron mobility is high, has direction-free electric charge and passes The advantages such as defeated characteristic and nanoscale network structure, are in leading position in current solar energy acceptor material (Acc.Chem.Res.2015,48,2803-2812；J.Mater.Chem.A 2015,3,20516-20526). But, fullerene acceptor also has some defects, such as: absorption region is narrow in visible region, molecule energy Level adjustability is poor, preparation cost height, purification difficult etc. (Energy.Environ.Sci.2012,5,8343-8350). Now, organic molecule and polymer get the attention as solar energy acceptor material, its solaode Energy conversion efficiency (PCE) have also been obtained and significantly improve (Adv.Energy Mater.2015,5,1500032； Adv.Mater.2014,26,4313-4319；Adv.Mater.2015,27,3266-3272).
For small molecule receptor material, there is suitable micron-scale phase separation yardstick and enough electron mobilities are them Solar cell device has the key (Adv.Mater.2015,27,1015-1020) of good efficiencies.Acid imide It is a kind of wide variety of solar energy acceptor material, but, owing to imido big planar molecule configuration makes it There is strong molecule and assemble tendency, thus cause serious being separated, affect device efficiency.Imido Dimer has nonplanar molecular configuration, can suppress the gathering of the molecule of receptor, the suitable phase of induced synthesis Separate yardstick, thus receive extensive concern.Based on acid imide dimer as the solar-electricity of acceptor material Pond efficiency has had as the solaode of acceptor material compared to acid imide molecule and has been obviously improved, its PCE Reach 6% (Adv.Mater.2015,27,1015-1020；J.Am.Chem.Soc.2015,11156- 11162)。
But, acid imide dimeric lowest unoccupied molecular orbital (LUMO) energy level is mostly-3.9～-4.1eV Between, its deeper lumo energy is close with the lumo energy of fullerene acceptor.Therefore, with based on richness The solaode strangling alkene receptor is the same, opening of the solar cell device of most of acid imide dimer receptors Road voltage, 0.7～0.85eV, which has limited the further of solar battery efficiency based on acid imide receptor Promote.Therefore, exploitation has the acyl of higher lumo energy, relatively high open circuit voltage and energy conversion efficiency Imine derivative, for application and the development of non-fullerene solaode, significant.
Summary of the invention
The problem to be solved in the present invention is the imide derivative providing a class novel and at organic sun Application in energy battery.
The technical solution used in the present invention is:
The imide derivative that one class thiophene/selenophen acene condenses, its chemical general formula is as follows:
In formula, X is selected from sulphur atom, selenium atom.R1Selected from hydrogen atom, carbon number is the alkyl of 1-50, alkene Base, carbon number is the substituted or unsubstituted aryl of 6-50, biaryl, fused ring aryl, and carbon number is 4-50 replaces or unsubstituted heterocyclic aryl containing nitrogen-atoms, benzheterocycle aryl, and carbon number is The linking group being made up of alkyl, thiazolinyl, aryl or heterocyclic aryl of 1-50.R in formula2Selected from carbon atom Number is the substituted or unsubstituted aryl of 6-50, biaryl, fused ring aryl, and carbon number is the replacement of 4-50 Or unsubstituted heterocyclic aryl containing nitrogen-atoms, benzheterocycle aryl, carbon number be 1-50 by alkene Base, aryl or the linking group of heterocyclic aryl composition.
In particular, X is sulphur atom, selenium atom, R1For 2-octyldodecyl or 1-amyl group hexyl, R2 For a series of substituent groups containing aromatic ring.Molecular structure the most out is as follows:
In the present invention, our design is with to have synthesized the acid imide that a class thiophene/selenophen acene condenses derivative Thing.They have the characteristics that and beneficial effect:
(1) due to thiophene/selenophen acene to electronic effect, and the acid imide phase that thiophene/selenophen acene condenses The bigger conjugated system that acid imide is had, the imide derivative tool that thiophene/selenophen acene condenses There is higher lumo energy, also make the solaode of the imide derivative that thiophene/selenophen acene condenses Device has relatively high open circuit voltage；
(2) other groups can be further introduced on imido thiophene/selenophen that thiophene/selenophen acene condenses Modify, and other substituent groups on imido nitrogen-atoms, can also be further introduced into, carry for further expanding For condition.
Accompanying drawing explanation
The structural representation of the organic solar batteries of Fig. 1 embodiment of the present invention 28-30.
The J-V curve of the organic solar batteries device of Fig. 2 embodiment of the present invention 28.
The J-V curve of the organic solar batteries device of Fig. 3 embodiment of the present invention 29.
The J-V curve of the organic solar batteries device of Fig. 4 embodiment of the present invention 30.
Detailed description of the invention
Raw material used by the embodiment of the present invention is known compound, is commercially available, or available this area is normal The method synthesis of rule.
Embodiment 1: the preparation of compound 1
(1) synthesis of compound M2.
2.0g M1 is dissolved in 100mL CHCl3In, add 7.0g K2CO3, drip 10mLBr2,50℃ Stirring 12h.It is cooled to room temperature, drips saturated N2SO3Solution removes the bromine of excess, uses saturated NHCO successively3 Aqueous solution, water washing organic facies, it is spin-dried for.With dichloromethane: petroleum ether=3:2 (v/v) is that eluent carries out post Chromatography, obtains red solid, productivity 68%.Mass spectrum: 1031.7.Elementary analysis: theoretical value C:74.61%, H:8.71%, N:2.72% experiment value C:74.49%, H:8.86%, N:2.88%.
(2) synthesis of compound M3.
5.0g copper powder is placed in 500 milliliters of beakers, adds 100mL acetone, adds 3g I2, it is stirred at room temperature 30 Minute.Sucking filtration, gained solid is poured in beaker, adds 100mL acetone: concentrated hydrochloric acid=1:1's (v/v) is molten Liquid, stirs 10 minutes.Sucking filtration, drying for standby in obtained red copper powder vacuum tank.1.5g M2,2.0g The copper powder processed, in argon gas atmosphere, joins in 250mL there-necked flask.Add 80mL and be dried deoxygenation Toluene and 100mL be dried the DMSO of deoxygenation, stir 24h at 85 DEG C.Pour reactant mixture into 200mL In water, chloroform extracts, and saturated aqueous common salt washs.Organic facies separates, and is dried, is spin-dried for, with dichloromethane: stone Oil ether=3:1 (v/v) carries out column chromatography, obtains aubergine solid, productivity 71%.Mass spectrum: 1901.6.Element Analyze: theoretical value C:80.88%, H:9.44%, N:2.95% experiment value C:80.66%, H: 9.27%, N:2.92%.
(3) synthesis of compound M4.
1.0g M3 is dissolved in 50mL CHCl3In, add 7.0g K2CO3, drip 10mL Br2, 55 DEG C are stirred Mix 30h.It is cooled to room temperature, drips saturated N2SO3Solution removes the bromine of excess, uses saturated NHCO successively3 Aqueous solution, water washing organic facies, it is spin-dried for.With dichloromethane: petroleum ether=2:1 (v/v) is that eluent carries out post Chromatography, obtains dark red solid, productivity 26%.Mass spectrum: 2057.9.Elementary analysis: theoretical value C:74.68%, H:8.62%, N:2.72 experiment value C:74.72%, H:8.82%, N:2.78%.
(4) synthesis of compound M5.
By 280mg M4,400mg (2-tributyl tinbase) thiophene, 10mg Pd2(dba)3And 20mg P(o-tol)3Join in 150mL single necked round bottom flask under nitrogen atmosphere, add the toluene of 40mL deoxygenation, 36h is stirred under the conditions of 110 DEG C.It is spin-dried for, with dichloromethane: petroleum ether=2:1 (v/v) is that eluent is carried out Column chromatography, obtains violet solid, productivity 93%.Mass spectrum: 2064.8.Elementary analysis: theoretical value C:79.10%, H:8.88%, N:2.71 experiment value C:79.22%, H:8.76%, N:2.64%.
(5) synthesis of compound 1.
260mg M5 is dissolved in 100mL toluene.1.5g FeCl3It is dissolved in 25 acetonitriles, is added drop-wise to the first of M5 In benzole soln, 50 DEG C are stirred 30 minutes.Washing, separatory, organic facies is spin-dried for.With dichloromethane: oil Ether=2:1 (v/v) is that eluent carries out column chromatography, obtains red solid, productivity 43%.Mass spectrum: 2060.6. Elementary analysis: theoretical value C:79.25%, H:8.71%, N:2.72% experiment value C:79.22%, H:8.97%, N:2.85%.1H NMR(300MHz,CDCl3)δ(ppm):9.93(br,2H),9.17(br, 2H),8.70(m,4H),8.41-7.75(m,6H),4.11-3.86(m,8H),1.89(m,4H),1.60-1.06(m, 128H),0.86(m,24H).
Embodiment 2: the preparation of compound 2
Compound 2 uses the method identical with compound 1 to prepare, and difference is to change raw material M1 into N Upper substituent group is the acid imide of 11 carbon alkyl chains, and corresponding raw material 1-amyl group-1-hexylamine is from Beijing unicorn benefactor Department buys and obtains.Mass spectrum: 1556.1.Elementary analysis: theoretical value C:77.19%, H:6.87%, N:3.60% Experiment value C:77.28%, H:6.68%, N:3.65%.
Embodiment 3: the preparation of compound 3
Compound 3 uses the method identical with compound 1 to prepare, and difference is to change raw material M1 into N Upper substituent group is the acid imide of corresponding alkyl chain.Mass spectrum: 2230.5.Elementary analysis: theoretical value C:79.66%, H:9.22%, N:2.51% experiment value C:79.68%, H:9.24%, N:2.52%.
Embodiment 4: the preparation of compound 4
Compound 4 uses the method identical with compound 1 to prepare, and difference is to change raw material M1 into phase Answer the acid imide of alkyl chain.Mass spectrum: 1669.9.Elementary analysis: theoretical value C:77.66%, H:7.48%, N:3.35% experiment value C:77.67%, H:7.44%, N:3.32%.
Embodiment 5: the preparation of compound 5
Compound 5 uses the method identical with compound 1 to prepare, and difference is to change raw material M1 into phase Answer the acid imide of alkyl chain.Mass spectrum: 2286.6.Elementary analysis: theoretical value C:79.81%, H:9.34%, N:2.45% experiment value C:79.84%, H:9.28%, N:2.52%.
Example example 6: the preparation of compound 6
(1) synthesis of intermediate M6
By 1.0g M2,800mg (2-tributyl tinbase) thiophene, 10mg Pd2(dba)3With 20mg P (o-tol)3In nitrogen Join in 150mL single necked round bottom flask under gas atmosphere, add the toluene of 40mL deoxygenation, in 110 DEG C of bars 36h is stirred under part.It is spin-dried for, with dichloromethane: petroleum ether=3:1 (v/v) is that eluent carries out column chromatography, To aubergine solid, productivity 97%.Mass spectrum: 1033.5.Elementary analysis: theoretical value C:79.02%, H: 8.97%, N:2.71% experiment value C:79.16%, H:8.86%, N:2.68%.1H NMR(300 MHz,CDCl3) δ (ppm): 8.65 (m, 3H), 8.49 (m, 2H), 8.21 (d, J=8.1Hz, 1H), 8.01 (d, J= 8.1Hz, 1H), 7.52 (d, J=4.8Hz, 1H), 7.20 (m, 2H), 4.13 (m, 4H), 2.01 (m, 2H), 1.60-1.06(m,64H),0.86(m,12H).
(2) synthesis of intermediate M7
1.0g M6 is dissolved in 100mL toluene.1.5g FeCl3It is dissolved in 25 acetonitriles, is added drop-wise to the toluene of M6 In solution, 50 DEG C are stirred 30 minutes.Washing, separatory, organic facies is spin-dried for.With dichloromethane: petroleum ether= 3:1 (v/v) is that eluent carries out column chromatography, obtains red solid, productivity 75%.Mass spectrum: 1031.2.Element Analyze: theoretical value C:79.18%, H:8.79%, N:3.11 experiment value C:79.04%, H:8.77%, N:3.04%.1H NMR(300MHz,CDCl3)δ(ppm):8.48(s,1H),8.33(m,3H),8.12(d,J =4.8Hz, 2H), 7.66 (d, J=4.5Hz, 1H), 7.58 (d, J=4.5Hz, 1H), 4.17 (m, 4H), 2.01 (m, 2H),1.60-1.06(m,64H),0.86(m,12H).
(3) synthesis of intermediate M8
700mg M7 is dissolved in 50mL chloroform, adds 10mg FeCl3, drip 1mLBr2, 40 DEG C of stirring 5h. It is cooled to room temperature, drips saturated N2SO3Solution removes the bromine of excess, uses saturated NHCO successively3Aqueous solution, Water washing organic facies, is spin-dried for.With dichloromethane: petroleum ether=3:1 (v/v) is that eluent carries out column chromatography, To Orange red solid, productivity 83%.Mass spectrum: 1110.4.Elementary analysis: theoretical value C:73.55%, H: 8.08%, N:2.52 experiment value C:73.54%, H:8.12%, N:2.33%.1H NMR(300 MHz,CDCl3)δ(ppm):8.73(m,5H),8.46(s,1H),7.74(s,1H),4.22(m,4H),2.02(m, 2H),1.60-1.06(m,64H),0.86(m,12H).
(4) synthesis of compound 6
5.0g copper powder is placed in 500 milliliters of beakers, adds 100mL acetone, adds 3g I2, it is stirred at room temperature 30 points Clock.Sucking filtration, gained solid is poured in beaker, addition 100mL acetone: the solution of concentrated hydrochloric acid=1:1 (v/v), Stir 10 minutes.Sucking filtration, drying for standby in obtained red copper powder vacuum tank.300mg M8,1.0g The copper powder processed, in argon gas atmosphere, joins in 250mL there-necked flask.Add 80mL and be dried deoxygenation Toluene and 100mL be dried the DMSO of deoxygenation, stir 24h at 85 DEG C.Pour reactant mixture into 200mL In water, chloroform extracts, and saturated aqueous common salt washs.Organic facies separates, and is dried, is spin-dried for, with dichloromethane: stone Oil ether=3:1 (v/v) carries out column chromatography, obtains aubergine solid, productivity 65%.Mass spectrum: 2059.4.Unit Element is analyzed: theoretical value C:79.25%, H:8.71%, N:2.72% experiment value C:79.22%, H: 8.69%, N:2.78%.1H NMR(300MHz,CDCl3)δ(ppm):8.42(m,4H),8.27(m,4H), 8.04(m,4H),7.78(s,2H),4.09(m,8H),1.98(m,4H),1.60-1.06(m,128H),0.86(m, 24H).
Embodiment 7: the preparation of compound 7
Compound 7 uses the method identical with compound 6 to prepare, and only difference is that and takes on selection N The raw material of the corresponding alkyl chain of Dai Jiwei.Mass spectrum: 2284.6.Elementary analysis: theoretical value C:79.88%, H: 9.26%, N:2.45% experiment value C:79.68%, H:9.25%, N:2.46%.
Embodiment 8: the preparation of compound 8
Compound 8 uses the method identical with compound 6 to prepare, and only difference is that and takes on selection N The raw material of the corresponding alkyl chain of Dai Jiwei.Mass spectrum: 1668.3.Elementary analysis: theoretical value C:77.75%, H: 7.37%, N:3.36% experiment value C:77.78%, H:7.36%, N:3.42%.
Example example 9: the preparation of compound 10
By commercially available to 222mg M8,123mg IDT tin reagent (M9), 10mg Pd2(dba)3And 20mg P(o-tol)3Join in 150mL single necked round bottom flask under nitrogen atmosphere, add the toluene of 40mL deoxygenation, 48h is stirred under the conditions of 110 DEG C.It is spin-dried for, with dichloromethane: petroleum ether=2:1 (v/v) is that eluent is carried out Column chromatography, obtains greenish yellow solid, productivity 97%.Mass spectrum: 2966.41.Elementary analysis: theoretical value C: 80.98%, H:8.49%, N:1.89% experiment value C:80.94%, H:8.52%, N:1.86%.1H NMR(300MHz,CDCl3)δ(ppm):9.16(br,2H),8.85(m,10H),7.99(m,2H),7.63(m, 4H),7.35(m,8H),7.13(m,8H),4.26(m,8H),2.61(m,8H),2.03(m,4H),1.82-1.06 (m,160H),0.86(m,36H).
The preparation of example example 10 compound 11
The preparation method of compound 11 is identical with compound 10, only difference is that on selection N, substituent group is The initiation material of corresponding alkyl chain.Mass spectrum: 3134.8.Elementary analysis: theoretical value C:81.23%, H: 8.81%, N:1.79% experiment value C:81.24%, H:8.80%, N:1.74%.
The preparation of example example 11 compound 12
The preparation method of compound 12 is identical with compound 10, only difference is that on selection N, substituent group is The initiation material of corresponding alkyl chain.Mass spectrum: 2572.4.Elementary analysis: theoretical value C:80.27%, H: 7.60%, N:2.18% experiment value C:80.26%, H:7.52%, N:2.23%.
The preparation of example example 12 compound 13
The preparation method of compound 13 is identical with compound 10, only difference is that and selects relevant tin reagent. Mass spectrum: 2572.4.Elementary analysis: theoretical value C:80.27%, H:7.60%, N:2.18% experiment value C: 80.26%, H:7.52%, N:2.23%.
The preparation of example example 13 compound 14
The preparation method of compound 14 is identical with compound 10, only difference is that and selects relevant tin reagent. Mass spectrum: 3078.6.Elementary analysis: theoretical value C:79.59%, H:8.19%, N:1.82%.Experiment Value C:80.04%, H:8.10%, N:1.85%.
The preparation of example example 14 compound 17
The preparation method of compound 17 is identical with compound 10, only difference is that and selects relevant tin reagent. Mass spectrum: 2626.5.Elementary analysis: theoretical value C:77.40%, H:8.33%, N:2.12%.Experiment value C:77.36%, H:8.32%, N:2.26%.
The preparation of example example 15 compound 22
The preparation method of compound 17 is identical with compound 10, only difference is that and selects relevant tin reagent. Mass spectrum: 2200.3.Elementary analysis: theoretical value C:77.48%, H:8.33%, N:2.55%.Experiment Value C:77.46%, H:8.34%, N:2.36%.
The preparation of example example 16 compound 28
The preparation method of compound 28 is essentially identical with example example 1, only difference is that thiophene used Tin reagent replaces with the tin reagent of selenophen.Mass spectrum: 2154.8.Elementary analysis: theoretical value C:75.81%, H: 8.33%, N:2.60% experiment value C:75.82%, H:8.37%, N:2.56%.
The preparation of example example 17 compound 29
The preparation method of compound 29 is identical with compound 28, only difference is that selection has relevant alkyl The initiation material of chain.Mass spectrum: 2382.5.Elementary analysis: theoretical value C:76.67%, H:8.97%, N: 2.35%.Experiment value C:76.62%, H:8.87%, N:2.43%.
The preparation of example example 18 compound 30
The preparation method of compound 30 is identical with compound 28, only difference is that selection has relevant alkyl The initiation material of chain.Mass spectrum: 1651.9.Elementary analysis: theoretical value C:72.71%, H:6.59%, N: 3.39% experiment value C:72.77%, H:6.32%, N:3.44%.
The preparation of example example 19 compound 33
The preparation method of compound 33 is essentially identical with example example 2, only difference is that thiophene used Tin reagent replaces with the tin reagent of selenophen.Mass spectrum: 2154.8.Elementary analysis: theoretical value C:75.81%, H: 8.33%, N:2.60%.Experiment value C:75.86%, H:8.31%, N:2.58%.
The preparation of example example 20 compound 34
The preparation method of compound 34 is identical with compound 33, only difference is that selection has relevant alkyl The initiation material of chain.Mass spectrum: 2380.4.Elementary analysis: theoretical value C:76.33%, H:8.90%, N: 2.35% experiment value C:76.32%, H:8.83%, N:2.41%.
The preparation of example example 21 compound 35
The preparation method of compound 35 is identical with compound 33, only difference is that selection has relevant alkyl The initiation material of chain.Mass spectrum: 1763.8.Elementary analysis: theoretical value C:73.62%, H:6.98%, N: 3.18% experiment value C:73.42%, H:6.88%, N:3.09%.
The preparation of example example 22 compound 38
The preparation method of compound 38 is identical with compound 10, only difference is that selection has selenium atom Initiation material.Mass spectrum: 1763.8.Elementary analysis: theoretical value C:73.62%, H:6.98%, N:3.18% Experiment value C:73.42%, H:6.88%, N:3.09%.
The preparation of example example 23 compound 39
The preparation method of compound 39 is identical with compound 38, only difference is that selection has relevant alkyl The initiation material of chain.Mass spectrum: 3228.9.Elementary analysis: theoretical value C:78.87%, H:8.55%, N: 1.74% experiment value C:78.84%, H:8.46%, N:1.68%.
The preparation of example example 24 compound 40
The preparation method of compound 40 is identical with compound 38, only difference is that selection has relevant alkyl The initiation material of chain.Mass spectrum: 2667.3.Elementary analysis: theoretical value C:77.45%, H:7.33%, N: 2.10% experiment value C:77.34%, H:7.36%, N:2.12%.
The preparation of example example 25 compound 42
The preparation method of compound 42 is identical with compound 38, only difference is that selection has the examination of relevant stannum Agent.Mass spectrum: 2731.7.Elementary analysis: theoretical value C:74.74%, H:8.04%, N:2.05% are real Test value C:74.64%, H:7.96%, N:2.08%.
The preparation of example example 26 compound 43
The preparation method of compound 43 is identical with compound 38, only difference is that selection has the examination of relevant stannum Agent.Mass spectrum: 2518.4.Elementary analysis: theoretical value C:75.32%, H:8.56%, N:2.22% are real Test value C:75.34%, H:8.52%, N:2.18%.
The preparation of example example 27 compound 44
The preparation method of compound 44 is identical with compound 38, only difference is that selection has the examination of relevant stannum Agent.Mass spectrum: 2453.2.Elementary analysis: theoretical value C:73.44%, H:7.56%, N:3.43% are real Test value C:73.46%, H:7.55%, N:3.42%.
Embodiment 28: the embodiment of compound application:
Compound 1 involved in the present invention can serve as the acceptor material of organic bulk hetero-junctions.Device architecture is ITO/PEDOT:PSS/PDBT-T1: compound 1/Ca/Al.
On the glass substrate that an indium oxide-tin oxide cleaned (ITO) covers, by solution spin coating one Then PEDOT:PSS thick for layer 40nm is dried under vacuum 10 minutes in 140 DEG C.By PDBT-T1: The ratio of compound 1 1:1 in mass ratio is dissolved in o-dichlorohenzene (containing 3% (v/v) 1,8-bis-iodohexane (DIO)) In, it is then spin coated onto on PEDOT:PSS layer, in nitrogen atmosphere, 100 DEG C process 5 minutes removing solvents. Finally with the method for vacuum sublimation, Ca, Al it is deposited with successively with vapour deposition method PDBT-T1/ compound 1 mixed layer On.The test result of solar cell device is: open-circuit voltage 0.95V, and short-circuit current density is 10.31 mA/cm2, fill factor, curve factor is 0.687, and PCE is 6.71%.As a comparison, the acyl being connected with singly-bound in document Imines dimer SdiPBI, is blended the mutually isostructural solaode of preparation with same donor PDBT-T1 Device, its open-circuit voltage be 0.87V, PCE be 5.4% (J.Am.Chem.Soc.2015,11156-11162). Visible, the acid imide dimer that thiophene acene condenses has the open-circuit voltage apparently higher than SdiPBI and PCE, Illustrate that the present invention has positive meaning to solaode.
Embodiment 29: the embodiment of compound application:
Compound 6 involved in the present invention can serve as the acceptor material of organic bulk hetero-junctions.Device architecture is ITO/PEDOT:PSS/PDBT-T1: compound 1/Ca/Al.
On the glass substrate that one indium oxide-tin oxide cleaned (ITO) covers, by solution spin coating one layer Then PEDOT:PSS thick for 40nm is dried under vacuum 10 minutes in 140 DEG C.By PDBT-T1: chemical combination The ratio of thing 6 1:1 in mass ratio is dissolved in o-dichlorohenzene, is then spin coated onto on PEDOT:PSS layer, In nitrogen atmosphere, 100 DEG C process 5 minutes removing solvents.Finally with the method for vacuum sublimation by Ca, Al to steam Plating method is deposited with on PDBT-T1/ compound 6 mixed layer successively.The open-circuit voltage 0.98 of solar cell device V.Visible, the imide derivative that thiophene acene condenses has apparently higher than SdiPBI (0.87V, J.Am. Chem.Soc.2015,11156-11162) open-circuit voltage, illustrate the present invention to promote solaode open circuit electricity Pressing element has positive meaning.
Embodiment 30: the embodiment of compound application:
Compound 10 involved in the present invention can serve as the acceptor material of organic bulk hetero-junctions.Device architecture is ITO/PEDOT:PSS/PDBT-T1: compound 1/Ca/Al.
On the glass substrate that one indium oxide-tin oxide cleaned (ITO) covers, by solution spin coating one layer Then PEDOT:PSS thick for 40nm is dried under vacuum 10 minutes in 140 DEG C.By PDBT-T1: chemical combination The ratio of thing 10 1:1 in mass ratio is dissolved in o-dichlorohenzene, is then spin coated onto on PEDOT:PSS layer, In nitrogen atmosphere, 100 DEG C process 5 minutes removing solvents.Finally with the method for vacuum sublimation by Ca, Al to steam Plating method is deposited with on PDBT-T1/ compound 10 mixed layer successively.The open-circuit voltage 0.97 of solar cell device V.Visible, the imide derivative that thiophene acene condenses has apparently higher than SdiPBI (0.87V, J.Am. Chem.Soc.2015,11156-11162) open-circuit voltage, illustrate the present invention to promote solaode open circuit electricity Pressing element has positive meaning.
Although describing the present invention in conjunction with preferred embodiment, but the invention is not limited in above-mentioned reality Execute example.Under the design of the present invention guides, it will be appreciated by the person skilled in the art that and the present invention is implemented Certain change that each scheme of example is carried out, all will be covered by the spirit and scope of the present invention.

Claims (4)

1. the imide derivative that thiophene/selenophen acene condenses, its structure such as in logical formula (I)-(III) Kind:
In logical formula (I)-(III), X is selected from sulphur atom or selenium atom, R1Selected from hydrogen atom, carbon number is 1-50's Alkyl, thiazolinyl and the alkyl containing halogen atom, carbon number is the substituted or unsubstituted aryl of 6-50, connection Aryl, fused ring aryl, carbon number be 4-50 replace or unsubstituted heterocyclic aryl containing nitrogen-atoms, Benzheterocycle aryl, or carbon number is being made up of alkyl, thiazolinyl, aryl or heterocyclic aryl of 1-50 Linking group, R2It is the substituted or unsubstituted aryl of 6-50, biaryl, fused ring aryl selected from carbon number, Carbon number is replacing or unsubstituted heterocyclic aryl containing nitrogen-atoms, benzheterocycle aryl of 4-50, Or the linking group being made up of thiazolinyl, aryl or heterocyclic aryl that carbon number is 1-50.
Imide derivative the most according to claim 1, it is characterised in that R1For in following group One:
Imide derivative the most according to claim 1, it is characterised in that R2For following group In one:
4. imide derivative according to any one of claims 1 to 3 is as in organic photoelectric functional device The purposes of solaode acceptor material.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106892917A (en) * 2017-03-07 2017-06-27 武汉工程大学 A kind of Fu Dai perylene diimides derivative and its application
CN108840876A (en) * 2018-07-11 2018-11-20 上海交通大学 A kind of synthesis and its application of halogenated condensed ring acid imide electron transport material
CN109575243A (en) * 2018-11-07 2019-04-05 王勇 Conjugated polymer of the alkoxyl phenyl containing meta position and its preparation method and application
CN111777580A (en) * 2019-04-03 2020-10-16 上海和辉光电有限公司 Furan derivative, application thereof and OLED device comprising furan derivative

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101709109A (en) * 2009-12-28 2010-05-19 大连理工大学 Trapezoidal conjugated polymer and method for preparing same
CN105037400A (en) * 2015-06-03 2015-11-11 中国科学院化学研究所 Novel heterocycle perylene imide dimer compound as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101709109A (en) * 2009-12-28 2010-05-19 大连理工大学 Trapezoidal conjugated polymer and method for preparing same
CN105037400A (en) * 2015-06-03 2015-11-11 中国科学院化学研究所 Novel heterocycle perylene imide dimer compound as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YANG ZOU,ET AL.,: "SYNTHESIS, PROPERTIES AND ELECTROPOLYMERIZATION OF STAR-STARSHAPED OLIGOTHIOPHENES WITH HEXAKIS(FLUOREN-2-YL)BENZENE AS CORE", 《CHINESE JOURNAL OF POLYMER SCIENCE》 *
王洪宇，等，: "含苝酰亚胺衍生物太阳电池材料", 《化学进展》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106892917A (en) * 2017-03-07 2017-06-27 武汉工程大学 A kind of Fu Dai perylene diimides derivative and its application
CN106892917B (en) * 2017-03-07 2019-07-23 武汉工程大学 A kind of fluoro imide derivative and its application
CN108840876A (en) * 2018-07-11 2018-11-20 上海交通大学 A kind of synthesis and its application of halogenated condensed ring acid imide electron transport material
CN109575243A (en) * 2018-11-07 2019-04-05 王勇 Conjugated polymer of the alkoxyl phenyl containing meta position and its preparation method and application
CN111777580A (en) * 2019-04-03 2020-10-16 上海和辉光电有限公司 Furan derivative, application thereof and OLED device comprising furan derivative

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